BOTTLEBRUSH POLYMERS AND USES THEREOF

Abstract

Provided are new bottlebrush polymers and diblock bottlebrush copolymers, which can self-assemble into structures of desired morphology (e.g., hexagonal cylindrical, gyroid). The self-assembled structures of the bottlebrush polymers and copolymers provide useful materials such as photonics (e.g., photonic crystals), functional materials, chromatography media, stimuli-responsive materials, lubricants, nanolithography, films, and coatings. In certain embodiments, the backbone repeating units of the bottlebrush polymers and copolymers have two different polymeric sidechains covalently attached to the backbone repeating unit through a branched linker, wherein one of the polymeric sidechain is a polysiloxane. Also provided are methods of preparing the bottlebrush polymers and copolymers described herein.

Claims

1. A bottlebrush polymer comprising a backbone of repeating units covalently linked to polymeric sidechains, wherein the polymer is capable of self-assembling into structures having a hexagonal cylindrical or gyroid morphology.

2-3. (canceled)

4. The polymer of claim 1, wherein each repeating unit of the backbone is linked to at least two different polymeric sidechains.

5. The polymer of claim 1, wherein at least one polymeric sidechain is a polysiloxane.

6. The polymer of claim 5, wherein the polysiloxane is of the formula: ##STR00266## wherein: R.sup.1 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy; R.sup.2 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy; and q is an integer between 1 and 1000, inclusive.

7. The polymer of claim 5, wherein the polysiloxane is polydimethylsiloxane (PDMS).

8. The polymer of claim 1, wherein the bottlebrush polymer is of Formula (I): ##STR00267## or a salt thereof, wherein: G.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof; each of L.sup.1, L.sup.2, L.sup.3, L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof; each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio; n is an integer between 1 and 4000, inclusive; A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20,000 Da; and B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.

9-10. (canceled)

11. The polymer of claim 8, wherein the bottlebrush polymer is of Formula (I-a): ##STR00268## or a salt thereof.

12-19. (canceled)

20. The polymer of claim 8, wherein A is polydimethylsiloxane.

21. (canceled)

22. The polymer of claim 8, wherein B is a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer.

23. (canceled)

24. The polymer of claim 8, wherein B is polystyrene.

25. (canceled)

26. The polymer of claim 8, wherein A is polydimethylsiloxane; and B is polystyrene; wherein the ratio of dimethylsiloxane repeating units to styrene repeating units is about 2:1.

27. The polymer of claim 8, wherein B is a polyacrylate.

28-29. (canceled)

30. The polymer of claim 8, wherein A is polydimethylsiloxane; and B is poly(tert-butyl acrylate); wherein the ratio of dimethylsiloxane repeating units to tert-butyl acrylate) repeating units is about 2.6:1.

31. The polymer of claim claim 1, wherein the bottlebrush polymer is of Formula (I-c): ##STR00269## or a salt thereof, wherein: each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl; n is an integer between 10 and 100, inclusive; p is an integer between 10 and 100, inclusive; and q is an integer between 25 and 260, inclusive; wherein the ratio of q:p is about 2.6:1; or wherein the bottlebrush polymer is of Formula (I-d): ##STR00270## or a salt thereof, wherein: each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl: n is an integer between 10 and 100, inclusive; r is an integer between 20 and 200, inclusive; and q is an integer between 20 and 200, inclusive; wherein the ratio of q:r is about 1:1.2 to about 1:1.3.

32. (canceled)

33. A bottlebrush polymer, wherein the polymer is of Formula (I): ##STR00271## or a salt thereof, wherein: G.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof; each of L.sup.1, L.sup.2, L.sup.3, L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof; each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio; n is an integer between 1 and 4000, inclusive; A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20,000 Da; and B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.

34-38. (canceled)

39. A bottlebrush copolymer comprising a backbone of repeating units covalently linked to polymeric sidechains; wherein the copolymer is a diblock copolymer, and at least one block of the copolymer comprises polysiloxane sidechains.

40-69. (canceled)

70. A bottlebrush polymer, wherein the bottlebrush polymer is of Formula (I): ##STR00272## or a salt thereof, wherein: G.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof; each of L.sup.1, L.sup.2, L.sup.3, L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof; each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio; n is an integer between 1 and 4000, inclusive; A is a polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da; and B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da; wherein the bottlebrush polymer has a gyroid morphology.

71-93. (canceled)

94. A self-assembled material comprising the polymer of claim 1.

95. (canceled)

96. A method of preparing a self-assembled material, the method comprising annealing the polymer of claim 1.

97. A method of preparing a bottlebrush polymer of claim 1, the method comprising forming the bottlebrush polymer via polymerization reactions.

98-112. (canceled)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0117] The accompanying drawings, which constitute a part of this specification, illustrate several embodiments of the invention and together with the description, serve to explain the principles of the invention.

[0118] FIG. 1A shows graft-through polymerization methods for traditional diblock BBCPs. FIG. 1B shows graft-through polymerization methods for core-shell BBCPs. FIG. 1C shows graft-through polymerization methods for A-branch-B BBCPs.

[0119] FIG. 2 includes Scheme 1, the synthesis of pseudo-alternating BBCPs.

[0120] FIG. 3 shows one-dimensional SAXS profiles of PS-branch-PDMS BBCPs containing different PS/PDMS volume fractions.

[0121] FIGS. 4A to 4D show top-view SEM images of the self-assembled morphology after etching of drop-cast bulk film of (PS-15.3k-branch-PDMS-5k)30 (FIG. 4A); spin-cast 28 nm thin film (FIG. 4B); 50 nm film treated with solvent annealing (FIG. 4C); and 50 nm film treated with thermal annealing (FIG. 4D). Scale bars are 100 nm.

[0122] FIG. 5A shows SAXS profiles of PDMS-5k-branch-PtBA-3.6k BMM and BBCPs. FIG. 5B shows a SCFT simulation of A-branch-B BBCP gyroid. The color scale represents the density of A blocks. B blocks are transparent for clarity.

[0123] FIG. 6A shows SAXS profiles of PS 4.6k-branch-PtBA 4.6k BMM and BBCPs. FIG. 6B shows the plot of N and sidechain length (L.sub.0) vs backbone DP. Increasing backbone DP leads to stretching of the sidechains, and facilitates phase separation.

[0124] FIG. 7 shows representative AFM images of (PDMS-5k-branch-PS-3.3k).sub.25.

[0125] FIG. 8 shows phase plots as a function of the total volume fraction f.sub.A and m=4, at .sub.ABN=12 and .sub.ABN=17. The low .sub.ABN show defective bicontinuous morphologies for f.sub.A<0.44. Gyroid structure is observed f.sub.A=0.44-0.46 after which lamellar structure is formed. The bicontinuous structures are suppressed at high .sub.ABN where the structure goes from cylinders to lamellae at f.sub.A0.36.

[0126] FIG. 9 shows <R.sup.2> vs. DP (m) for BBCP normal and parallel to the interface. Root mean square end-to-end distance of the backbone chain C as a function of the number of backbone segments m. The chain size normal to the interface rapidly reaches a plateau determining the interface width. However, parallel to interface, the chain size continuously increases as m grows. The curve accurately follows <R.sup.2>N.sup.0.54. This shows that the backbone chain is slightly stretched due the large density packing of the AB side chains.

[0127] FIG. 10 shows the normalized density of block A (.sub.A) for a lamella forming structure as a function of the normalized width of the system. The degree of segregation rises sharply as the number of side-chains increase till m=9. After which it reaches a plateau at 96%.

[0128] FIG. 11 shows the probability distribution of finding the end of the last segment of backbone. Concentric ovals are the probability distribution of finding the end of the last segment of the backbone chain C mapped for m=4 (top) and m=29 (bottom). The chains extend along the interface while maintaining the confinement normal to the interface. The spread of probability distribution is estimated to a fitted Gaussian (see inset).

[0129] FIG. 12 shows differential refractive index GPC traces of PSBr.

[0130] FIG. 13 shows differential refractive index GPC traces of PSN3.

[0131] FIG. 14 shows differential refractive index GPC traces of NbPS-branch-PDMS macromonomers.

[0132] FIG. 15 shows differential refractive index GPC traces of (PS-2.3k-branch-PDMS-5k).sub.n.

[0133] FIG. 16 shows differential refractive index GPC traces of (PS-3.3k-branch-PDMS-5k).sub.n.

[0134] FIG. 17 shows differential refractive index GPC traces of (PS4.6k-branch-PDMS5k).sub.n.

[0135] FIG. 18 shows differential refractive index GPC traces of (PS-6.4k-branch-PDMS-5k).sub.n.

[0136] FIG. 19 shows differential refractive index GPC traces of (PS-8.2k-branch-PDMS-5k).sub.n.

[0137] FIG. 20 shows differential refractive index GPC traces of (PS-9.2k-branch-PDMS-5k).sub.n.

[0138] FIG. 21 shows differential refractive index GPC traces of (PS-10.3k-branch-PDMS-5k).sub.n.

[0139] FIG. 22 shows differential refractive index GPC traces of (PS-15.3k-branch-PDMS-5k).sub.n.

[0140] FIG. 23 shows differential refractive index GPC traces of of PtBA-N.sub.3.

[0141] FIG. 24 shows differential refractive index GPC traces of (PtBA-3.6k-branch-PDMS-5k).sub.n.

[0142] FIG. 25 shows differential refractive index GPC traces of starting materials and intermediates for 3.

[0143] FIG. 26 shows differential refractive index GPC traces of (PS-4.6k-branch-PtBA-4.6k).sub.n.

[0144] FIG. 27 shows that BBCP containing monodisperse PLA and PDMS with molecular weight of 1000 were synthesized. A ultra-small d-spacing of 5.68 nm. i.e., 2.84 nm single phase domain size, was observed in the long range ordered phase separation of PLA.sub.8-branch-PDMS 1000 BBCP. Subscript stands for the degree of polymerization (DP) of a monodisperse sidechain polymer. SAXS patterns of BBCP containing PDMS 1000 and PLA.sub.12 sidechains (left) and PDMS 1000 and PLA.sub.8 sidechains (right). (DP) in the plots are the DP of a backbone; the broad peaks around q0.4 .sup.1 originate from Kapton tape used to hold liquid samples.

[0145] FIG. 28 shows 1D SAXS profile for (PS4.7k-br-PLA3.8k).sub.n. This polymer exhibited gyroid morphology with d=13.6 nm.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

[0146] Provided herein are bottlebrush polymers and bottlebrush copolymers. The bottlebrush polymers and copolymers may comprise multiple polymeric sidechains that, in part, confer certain unexpected and advantageous properties. For example, when the repeating unit of the bottlebrush polymer backbone is linked to two different polymeric sidechains (e.g., polysiloxane and polyacrylate sidechains), the bottlebrush polymers are capable of self-assembly into structures that have a gyroid morphology. Accordingly, the pseudo-alternating bottlebrush polymer structure provides several unique advantages in the context of bottlebrush polymer assembly, including access to the first examples of gyroid phases. In other embodiments, the bottlebrush polymers and copolymers are capable of self-assembly into structures that have a hexagonal cylindrical morphology. In other embodiments, the bottlebrush polymers and copolymers are capable of self-assembly into structures that have a lamellar morphology. In other embodiments, the bottlebrush polymers and copolymers are capable of self-assembly into structures that have a spherical morphology.

[0147] The bottlebrush polymers and copolymers may be capable of self-assembling into useful materials, such as photonic crystals. In other embodiments, the bottlebrush polymers and copolymers may be chemically manipulated to provide useful materials, such as nanofiltration devices. In another aspect, the present disclosure provides self-assembled materials comprising the bottlebrush polymers and copolymers described herein. Also provided are methods of preparing the bottlebrush polymers and copolymers and self-assembled materials comprising the bottlebrush polymers and copolymers.

Bottlebrush Polymers

[0148] One aspect of the present disclosure relates to bottlebrush polymers. In certain embodiments, the bottlebrush polymers comprise a backbone of repeating units covalently linked to polymeric sidechains, wherein the polymer is capable of self-assembling into structures having a hexagonal cylindrical or gyroid morphology. In some embodiments, the bottlebrush polymers are capable of self-assembling into structures having a hexagonal cylindrical morphology. In some embodiments, the bottlebrush polymers are capable of self-assembling into structures having a gyroid morphology.

[0149] In certain embodiments, the bottlebrush polymers provided herein have the same backbone repeating units, meaning that the polymer sidechains covalently linked to the repeating units of the backbone are the same for each repeating unit. In certain embodiments, the repeating units may be covalently linked to more than one polymeric sidechain. For example, in certain embodiments, the polymeric sidechains may be connected to the backbone repeating unit through a linker that branches such that two polymeric sidechains are connected through the same linker. In some embodiments, the branched linker connects the backbone repeating unit to two or more polymeric sidechains that are each of a different polymer class. In certain embodiments, at least one polymeric sidechain is a polysiloxane. In certain embodiments, the polysiloxane is polydimethylsiloxane (PDMS). Further, the polymeric sidechains may be of the same or different lengths, and/or of the same or different molecular weights.

[0150] In embodiments where two different polymeric sidechains are connected to the backbone repeating unit at a branching point through a linker, the bottlebrush copolymer may be referred to as an A-branch-B bottlebrush copolymer or a Janus bottlebrush polymer.

[0151] The bottlebrush polymers provided herein comprise a backbone of repeating units (backbone units). In some embodiments, the repeating backbone units are the same throughout the polymer. In other embodiments, the polymer may comprise two or more blocks of different repeating backbone units. In certain embodiments, the bottlebrush polymers comprise 1 to 4000 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 2 to 4000 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 2 to 2000 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 2 to 1000 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 2 to 500 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 2 to 200) repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 2 to 100 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 5 to 1(0) repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 10 to 100 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 25 to 100 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 10 to 50 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 25 to 50 repeating backbone units, inclusive. In certain embodiments, the bottlebrush polymers comprise 10, 25, 50, or 100 repeating backbone units. In certain embodiments, the bottlebrush polymers comprise 10 repeating backbone units. In certain embodiments, the bottlebrush polymers comprise 25 repeating backbone units. In certain embodiments, the bottlebrush polymers comprise 50 repeating backbone units. In certain embodiments, the bottlebrush polymers comprise 100 repeating backbone units. In certain embodiments, each repeating backbone unit of the bottlebrush polymer is covalently linked to a polymeric sidechain. In certain embodiments, each repeating backbone unit of the bottlebrush polymer is covalently linked to two polymeric sidechains. In certain embodiments, each repeating backbone unit of the bottlebrush polymer is covalently linked to two polymeric sidechains that are connected to the repeating backbone unit through the same linker. In certain embodiments, some but not all repeating backbone units are covalently linked to polymeric sidechains.

[0152] The backbone units may be derived from polymerization of a monomer including, but not limited to, substituted or unsubstituted norbomene, olefin, cyclic olefin, norbomene anhydride, cyclooctene, cyclopentadiene, styrene, or acrylate. In other embodiments, the repeating backbone units are derived from monomers not listed here. Some backbone units useful in the present disclosure may be obtained from a ring opening metathesis polymerization (ROMP) reaction.

[0153] The polymer sidechains of the bottlebrush polymer may comprise any polymer. Examples of classes of polymers include, but are not limited to, vinyl polymers (e.g., polystyrene), polyethylenes (e.g., polyethylene, polytetrafluoroethylene), polypropylenes, polyacetylenes, polyethers (e.g., polyethylene glycol, polyoxymethylene, polypropylene glycol, polytetramethylene glycol, poly(ethyl ethylene) phosphate, poly(oxazoline)), polyamines, polyesters (e.g., polyglycolic acid, polylactic acid, poly(lactic-co-glycolic acid), polycaprolactone, polyhydroxyalkanoate, polyhydroxybutryate, polyethylene adipate, polybutylene succinate, poly(3-hydroxybutyrate-co-3-hydroxy valerate), polysilanes, polysiloxanes (e.g., polydimethylsiloxane), polyacrylates (e.g., polymethacrylate, poly(n-butyl acrylate), poly(tert-butyl acrylate)), polylactides (e.g., polylactic acid), polyamino acids, polypeptides, polyamides, polyacrylamides (e.g., polymethylacrylamide), and polysaccharides. The polymer sidechains may be homopolymers or copolymers. The polymer sidechains may be linear or branched. In certain embodiments, the polymer sidechains are linear. In certain embodiments, the polymer sidechains are branched.

[0154] In certain embodiments, the bottlebrush polymer comprises polyether, polyester, polyacrylamide, polyacrylate, polysiloxane, or vinyl polymer sidechains, or a combination thereof. In certain embodiments, the bottlebrush polymer comprises polyester, polyacrylate, or vinyl polymer sidechains, or a combination thereof.

[0155] In certain embodiments, the bottlebrush polymer comprises polyester sidechains. Examples of polyesters include, but are not limited to, polyglycolic acid (PGA), polylactic acid (PLA), poly(lactic-co-glycolic acid) (PLGA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutryate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), or poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). In certain embodiments, the bottlebrush polymer comprises polylactic acid (PLA) sidechains.

[0156] In certain embodiments, the bottlebrush polymer comprises polyether sidechains. Examples of polyethers include, but are not limited to, polyethylene glycol (PEG), polyoxymethylene (POM), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), poly(ethyl ethylene) phosphate (PEEP), and poly(oxazoline). In certain embodiments, the bottlebrush polymer comprises polyethylene glycol (PEG) sidechains.

[0157] In certain embodiments, the bottlebrush polymer comprises polysiloxane sidechains. In certain embodiments, the polysiloxane is polydimethylsiloxane (PDMS). In certain embodiments, the bottlebrush polymer comprises polydimethylsiloxane sidechains.

[0158] In certain embodiments, the bottlebrush polymer comprises vinyl polymer sidechains. Examples of vinyl polymers include, but are not limited to, polystyrene, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyvinyl acetate, polyvinyl alcohol, and polyacrylonitrile. In certain embodiments, the bottlebrush polymer comprises polystyrene sidechains.

[0159] In certain embodiments, the bottlebrush polymer comprises polyacrylate sidechains. Examples of polyacrylates include, but are not limited to, poly(methyl methacrylate), poly(methyl acrylate), poly(methacrylate), poly(hydroxyethyl methacrylate), poly(n-butyl acrylate), and poly(tert-butyl acrylate). In certain embodiments, the bottlebrush polymer comprises poly(tert-butyl acrylate) sidechains.

[0160] In certain embodiments, the bottlebrush polymer comprises polysiloxane sidechains and vinyl polymer sidechains. In certain embodiments, the bottlebrush polymer comprises polydimethylsiloxane sidechains and polystyrene sidechains. In certain embodiments, the bottlebrush polymer comprises polysiloxane sidechains and polyacrylate sidechains. In certain embodiments, the bottlebrush polymer comprises polydimethylsiloxane sidechains and poly(tert-butyl acrylate) sidechains. In certain embodiments, the bottlebrush polymer comprises polysiloxane sidechains and polyester sidechains. In certain embodiments, the bottlebrush polymer comprises polydimethylsiloxane sidechains and poly(lactic acid) sidechains.

[0161] The polymer sidechains may be of any molecular weight. In certain embodiments, the polymer sidechains each independently have a number average molecular weight ranging from about 50 to about 10000 Da, about 100 to about 10000 Da, about 500 to about 10000 Da, about 1000 to about 10000 Da, about 2000 to about 10000 Da, about 2000 to about 7000 Da, about 2000 to about 4000 Da, about 3000 to about 4000) Da. or about 4000 to about 6000 Da; each range being inclusive.

[0162] In certain embodiments, the bottlebrush polymer is of Formula (I):

##STR00010##

or salts thereof, wherein:

[0163] G.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof:

[0164] each of L.sup.1, L.sup.2, L.sup.3, L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;

[0165] each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;

[0166] n is an integer between 1 and 4000, inclusive;

[0167] A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20,000 Da; and

[0168] B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.

[0169] As described herein, in certain embodiments, the bottlebrush polymer may have a gyroidal or hexagonal cylindrical morphology.

[0170] In certain embodiments, G.sup.A is optionally substituted carbocyclylene, optionally substituted heterocyclylene, or a combination thereof. In certain embodiments, G.sup.A is optionally substituted carbocyclylene. In certain embodiments, G.sup.A is optionally substituted heterocyclylene. In certain embodiments, G.sup.A comprises optionally substituted 5-membered carbocyclylene or 5-membered heterocyclylene. In certain embodiments, G.sup.A comprises optionally substituted cyclopentylene, cyclohexylene, tetrahydrofuranylene, tetrahydrothiophenylene, or pyrrolidinylene. In certain embodiments, G.sup.A is optionally substituted bicyclic heterocyclylene. In certain embodiments, G.sup.A is substituted bicyclic heterocyclylene. In certain embodiments, G.sup.A is of the following formula:

##STR00011##

wherein X.sup.A is CH.sub.2, CH.sub.2CH.sub.2, O, or S; and A.sup.R is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In certain embodiments, G.sup.A is of the following formula:

##STR00012##

wherein A.sup.R is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In certain embodiments, G.sup.A is of the following formula:

##STR00013##

wherein X.sup.A is CH.sub.2, CH.sub.2CH.sub.2, O, or S. In certain embodiments. G.sup.A is of the following formula:

##STR00014##

[0171] In certain embodiments, each of L.sup.1 and L.sup.3 is independently a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and combinations thereof. In certain embodiments, each of L.sup.1 and L.sup.3 is optionally substituted alkylene. In certain embodiments, each of L.sup.1 and L.sup.3 is optionally substituted heteroalkylene. In certain embodiments, each of L.sup.1 and L.sup.3 is optionally substituted alkynylene. In certain embodiments, each of L.sup.1 and L.sup.3 is optionally substituted alkenylene. In certain embodiments, each of L.sup.1 and L.sup.3 is substituted alkenylene. In certain embodiments, each of L.sup.1 and L.sup.3 is unsubstituted alkenylene. In certain embodiments, each of L.sup.1 and L.sup.3 is of the formula:

##STR00015##

In certain embodiments, each of L.sup.1 and L.sup.3 is of the formula:

##STR00016##

In certain embodiments, each of L.sup.1 and L.sup.3 is of the formula:

##STR00017##

[0172] In certain embodiments, L.sup.1 is optionally substituted alkylene. In certain embodiments. L.sup.1 is optionally substituted heteroalkylene. In certain embodiments, L.sup.1 is optionally substituted alkynylene. In certain embodiments. L.sup.1 is optionally substituted alkenylene. In certain embodiments, L.sup.1 substituted alkenylene. In certain embodiments, L.sup.1 is unsubstituted alkenylene. In certain embodiments, L.sup.1 is of the formula:

##STR00018##

In certain embodiments, L.sup.1 is of the formula:

##STR00019##

In certain embodiments, L.sup.1 is of the formula:

##STR00020##

[0173] In certain embodiments, L.sup.3 is optionally substituted alkylene. In certain embodiments, L.sup.3 is optionally substituted heteroalkylene. In certain embodiments, L.sup.3 is optionally substituted alkynylene. In certain embodiments, L.sup.3 is optionally substituted alkenylene. In certain embodiments, L.sup.3 substituted alkenylene. In certain embodiments, L.sup.3 is unsubstituted alkenylene. In certain embodiments, L.sup.3 is of the formula:

##STR00021##

In certain embodiments, L.sup.3 is of the formula:

##STR00022##

In certain embodiments, L.sup.3 is of the formula:

##STR00023##

[0174] In certain embodiments, L.sup.2 is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.2 is optionally substituted alkylene or optionally substituted heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted alkylene. In certain embodiments, L.sup.2 is optionally substituted heteroalkylene. In certain embodiments, L.sup.2 is unsubstituted alkylene. In certain embodiments, L.sup.2 is unsubstituted heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is unsubstituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is of the formula:

##STR00024##

[0175] In certain embodiments, L.sup.A is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.A is optionally substituted alkylene. In certain embodiments, L.sup.A is optionally substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted heteroarylene. In certain embodiments, L.sup.A is unsubstituted alkylene. In certain embodiments, L.sup.A is unsubstituted heteroalkylene. In certain embodiments, L.sup.A is substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments. L.sup.A is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.A is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.A is of the formula:

##STR00025##

[0176] In certain embodiments, L.sup.A is of the formula:

##STR00026##

In certain embodiments, L.sup.A is unsubstituted heteroarylalkylene. In certain embodiments, L.sup.A is optionally substituted heteroarylalkylene. In certain embodiments, L.sup.A is an unsubstituted 5-membered heteroarylalkylene. In certain embodiments, L.sup.A comprises a triazole. In certain embodiments, L.sup.A comprises a group of the formula:

##STR00027##

In certain embodiments, L.sup.A is of the formula:

##STR00028##

[0177] In certain embodiments, L.sup.B is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.B is optionally substituted alkylene. In certain embodiments, L.sup.B is optionally substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted heteroarylene. In certain embodiments, L.sup.B is unsubstituted alkylene. In certain embodiments, L.sup.B is unsubstituted heteroalkylene. In certain embodiments, L.sup.B is substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.B is of the formula:

##STR00029##

In certain embodiments, L.sup.B is of the formula:

##STR00030##

In certain embodiments, L.sup.B is unsubstituted heteroarylalkylene. In certain embodiments, L.sup.B is optionally substituted heteroarylalkylene. In certain embodiments, L.sup.B is an unsubstituted 5-membered heteroarylalkylene. In certain embodiments, L.sup.B comprises a triazole. In certain embodiments, L.sup.B comprises a group of the formula:

##STR00031##

In certain embodiments, L.sup.B is of the formula:

##STR00032##

[0178] In certain embodiments, L.sup.2 is optionally substituted alkylene or optionally substituted heteroalkylene; L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene; and L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene. In certain embodiments, L.sup.2 is optionally substituted heteroalkylene; L.sup.A is optionally substituted heteroalkylene; and L.sup.B is optionally substituted heteroarylalkylene. In certain embodiments, L.sup.2 is unsubstituted heteroalkylene; L.sup.A is unsubstituted heteroalkylene; and L.sup.B is substituted heteroarylalkylene. In certain embodiments. L.sup.2 is unsubstituted C.sub.1-10 heteroalkylene; L.sup.A is substituted C.sub.1-10 heteroalkylene; and L.sup.B is an unsubstituted 5-membered heteroarylalkylene.

[0179] In certain embodiments, L.sup.2 is of the formula:

##STR00033##

L.sup.A is of the formula:

##STR00034##

and L.sup.B is of the formula:

##STR00035##

[0180] In certain embodiments, L.sup.2 is of the formula:

##STR00036##

L.sup.A is of the formula:

##STR00037##

and L.sup.B is of the formula:

##STR00038##

[0181] In certain embodiments, L.sup.2 is of the formula:

##STR00039##

L.sup.A is of the formula:

##STR00040##

and L.sup.B is of the formula:

##STR00041##

[0182] In certain embodiments, L.sup.2 is of the formula:

##STR00042##

L.sup.A is of the formula:

##STR00043##

and LB is of the formula:

##STR00044##

[0183] In certain embodiments, n is an integer between 1 and 4000, inclusive. In certain embodiments, n is an integer between 5 and 4000, inclusive. In certain embodiments, n is an integer is between 50 and 4000, inclusive. In certain embodiments, n is an integer between 100 and 4000, inclusive. In certain embodiments, n is an integer between 1000 and 4000, inclusive. In certain embodiments, n is an integer between 2000 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 2000, inclusive. In certain embodiments, n is an integer between 2 and 1000, inclusive. In certain embodiments, n is an integer between 10 and 1000, inclusive. In certain embodiments, n is an integer between 2 and 100, inclusive. In certain embodiments, n is an integer between 10 and 100, inclusive. In certain embodiments, n is an integer between 10 and 50, inclusive. In certain embodiments, n is an integer between 25 and 50, inclusive. In certain embodiments, n is an integer between 25 and 100, inclusive. In certain embodiments, n is about 10, about 25, about 50, or about 100. In certain embodiments, the average of n is about 10, about 25, about 50, or about 100. In certain embodiments, the average of n is about 25 or about 50. In certain embodiments, the average of n is about 10. In certain embodiments, the average of n is about 25. In certain embodiments, the average of n is about 50. In certain embodiments, the average of n is about 100. In certain embodiments, n is the same as the degree of polymerization of the polymer.

[0184] In certain embodiments, each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thiol. In certain embodiments, T.sup.1 is hydrogen. In certain embodiments, T.sup.1 is halogen. In certain embodiments, T.sup.1 is optionally substituted alkyl. In certain embodiments, T.sup.1 is optionally substituted alkenyl. In certain embodiments, T.sup.1 is optionally substituted alkynyl. In certain embodiments, T.sup.1 is optionally substituted carbocyclyl. In certain embodiments, T.sup.1 is optionally substituted heterocyclyl. In certain embodiments, T.sup.1 is optionally substituted aryl. In certain embodiments, T.sup.1 is optionally substituted heteroaryl. In certain embodiments, T.sup.1 is optionally substituted acyl. In certain embodiments, T.sup.1 is optionally substituted hydroxyl. In certain embodiments, T.sup.1 is optionally substituted amino. In certain embodiments, T.sup.1 is optionally substituted thiol. In certain embodiments, T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is halogen. In certain embodiments. T.sup.2 is optionally substituted alkyl. In certain embodiments, T.sup.2 is optionally substituted alkenyl. In certain embodiments, T.sup.2 is optionally substituted alkynyl. In certain embodiments, T.sup.2 is optionally substituted carbocyclyl. In certain embodiments, T.sup.2 is optionally substituted heterocyclyl. In certain embodiments, T.sup.2 is optionally substituted aryl.

[0185] In certain embodiments, T.sup.2 is optionally substituted heteroaryl. In certain embodiments, T.sup.2 is optionally substituted acyl. In certain embodiments, T.sup.2 is optionally substituted hydroxyl. In certain embodiments, T.sup.2 is optionally substituted amino. In certain embodiments, T.sup.2 is optionally substituted thiol. In certain embodiments, both T.sup.1 and T.sup.2 are hydrogen.

[0186] In certain embodiments, T.sup.1 is optionally substituted aryl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.1 is phenyl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is optionally substituted aryl, and T.sup.1 is hydrogen. In certain embodiments. T.sup.2 is phenyl, and T.sup.1 is hydrogen.

[0187] In certain embodiments, A is a polysiloxane and B is a different polymer. In certain embodiments, A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20.000 Da; and B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.

[0188] In certain embodiments, A is a polysiloxane. In certain embodiments, the polysiloxane is of the formula:

##STR00045##

wherein:

[0189] R.sup.1 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy:

[0190] R.sup.2 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy; and

[0191] q is an integer between 5 and 2000, inclusive.

[0192] In certain embodiments, R.sup.1 is optionally substituted alkyl. In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.1 is methyl.

[0193] In certain embodiments, R.sup.2 is optionally substituted alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-20 alkyl. In certain embodiments. R.sup.2 is unsubstituted C.sub.1-20 alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.2 is n-butyl.

[0194] In certain embodiments, q is an integer between 5 and 500, inclusive. In certain embodiments, q is an integer between 5 and 100, inclusive. In certain embodiments, q is an integer between 10 and 100, inclusive. In certain embodiments, q is an integer between 30 and 80, inclusive. In certain embodiments, q is an integer between 50 and 80, inclusive. In certain embodiments, q is an integer between 60 and 70, inclusive.

[0195] In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl; R.sup.2 is optionally substituted C.sub.1-6 alkyl; and q is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl; R.sup.2 is unsubstituted C.sub.1-6 alkyl; and q is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.1 is methyl; R.sup.2 is n-butyl; and q is an integer between 50 and 100, inclusive.

[0196] In certain embodiments. R.sup.1 is C.sub.1-6 alkyl, and the polysiloxane has a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, or about 4,000 Da to about 6,000 Da. or about 4,500 Da to about 5,500 Da.

[0197] In certain embodiments, the polysiloxane is polydimethylsiloxane (PDMS) having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, or about 4,000 Da to about 6,000 Da, or about 4,500 Da to about 5,500 Da.

[0198] In certain embodiments, B is a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer. The polyacrylate may be any polyester described herein. The polyester may be any polyester described herein. The polyether may be any polyether described herein. The polyacrylamide may be any polyacrylamide described herein. Additionally, the vinyl polymer may be any vinyl polymer described herein.

[0199] In certain embodiments, B is a polyether selected from the group consisting of polyethylene glycol (PEG), polyoxymethylene (POM), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), poly(ethyl ethylene) phosphate (PEEP), and poly(oxazoline). In certain embodiments, B is polyethylene glycol (PEG). In certain embodiments. B is a polyester. In certain embodiments, B is a polyester selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), poly(lactic-co-glycolic acid) (PLGA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutryate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). In certain embodiments, B is polylactic acid (PLA). In certain embodiments, B is polyglycolic acid (PGA) or poly(lactic-co-glycolic acid) (PLGA). In certain embodiments, B is a polyacrylamide. In certain embodiments, B is a poly(N-alkylacrylamide). In certain embodiments, B is poly(N-isopropylacrylamide). In certain embodiments, B is a vinyl polymer. In certain embodiments, B is a vinyl polymer selected from the group consisting of polystyrene, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyvinyl acetate, polyvinyl alcohol, and polyacrylonitrile. In certain embodiments, B is polystyrene. In certain embodiments, B is a polyacrylate. In certain embodiments, B is a polyacrylate selected from the group consisting of poly(methyl methacrylate), poly(methyl acrylate), poly(methacrylate), poly(hydroxyethyl methacrylate), poly(n-butyl acrylate), and poly(tert-butyl acrylate). In certain embodiments, B is poly(tert-butyl acrylate).

[0200] In certain embodiments, B is a vinyl polymer of the following formula:

##STR00046##

wherein:

[0201] R.sup.3 is optionally substituted alkyl, halogen, hydrogen, cyano, OR.sup.a, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0202] R.sup.4 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl:

[0203] R.sup.a is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0204] r is an integer between 5 and 2000, inclusive.

[0205] In certain embodiments, R.sup.3 is hydrogen. In certain embodiments, R.sup.3 is optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted alkenyl. In certain embodiments, R.sup.3 is optionally substituted alkynyl. In certain embodiments, R.sup.3 is optionally substituted aryl. In certain embodiments, R.sup.3 is optionally substituted heteroaryl. In certain embodiments, R.sup.3 is cyano. In certain embodiments, R.sup.3 is halogen. In certain embodiments, R.sup.3 is OR.sup.a, wherein R.sup.a is hydrogen or optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted phenyl. In certain embodiments. R.sup.3 is unsubstituted phenyl.

[0206] In certain embodiments, R.sup.4 is optionally substituted alkyl. In certain embodiments, R.sup.4 is optionally substituted alkenyl. In certain embodiments, R.sup.4 is optionally substituted alkynyl. In certain embodiments, R.sup.4 is optionally substituted aryl. In certain embodiments. R.sup.4 is optionally substituted heteroaryl. In certain embodiments, R.sup.4 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is C.sub.1-6 alkyl substituted with an ester group.

[0207] In certain embodiments, r is an integer between 5 and 500, inclusive. In certain embodiments, r is an integer between 5 and 100, inclusive. In certain embodiments, r is an integer between 10 and 100, inclusive. In certain embodiments, r is an integer between 10 and 50, inclusive. In certain embodiments, r is an integer between 20 and 40, inclusive. In certain embodiments, r is an integer between 30 and 40, inclusive.

[0208] In certain embodiments, R.sup.3 is optionally substituted aryl; R.sup.4 is optionally substituted C.sub.1-6 alkyl; and r is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.3 is unsubstituted aryl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive. In certain embodiments, R.sup.3 is unsubstituted phenyl; R.sup.4 is substituted C.sub.10.6 alkyl; and r is an integer between 10 and 50, inclusive.

[0209] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 10,000 Da to about 15,000 Da, about 2,000 Da to about 10,000 Da, about 7.000 Da to about 10,000 Da, about 8,000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3.000 Da, or about 2,500 Da to about 3,600 Da.

[0210] In certain embodiments. B is a polyacrylate of the following formula:

##STR00047##

wherein:

[0211] R.sup.5 is optionally substituted alkyl, hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0212] R.sup.6 is optionally substituted alkyl, hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0213] R.sup.7 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0214] p is an integer between 5 and 2000, inclusive.

[0215] In certain embodiments, R.sup.5 is hydrogen. In certain embodiments, R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted alkenyl. In certain embodiments, R.sup.5 is optionally substituted alkynyl. In certain embodiments, R.sup.5 is optionally substituted aryl. In certain embodiments, R.sup.5 is optionally substituted heteroaryl. In certain embodiments, R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.5 is tert-butyl.

[0216] In certain embodiments, R.sup.6 is optionally substituted alkyl. In certain embodiments, R.sup.6 is hydrogen. In certain embodiments, R.sup.6 is optionally substituted alkenyl. In certain embodiments, R.sup.6 is optionally substituted alkynyl. In certain embodiments, R.sup.6 is optionally substituted aryl. In certain embodiments, R.sup.6 is optionally substituted heteroaryl. In certain embodiments, R.sup.6 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is methyl.

[0217] In certain embodiments, R.sup.7 is optionally substituted alkyl. In certain embodiments, R.sup.7 is optionally substituted alkenyl. In certain embodiments, R.sup.7 is optionally substituted alkynyl. In certain embodiments, R.sup.7 is optionally substituted aryl. In certain embodiments, R.sup.7 is optionally substituted heteroaryl. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-6 alkyl. In certain embodiments. R.sup.7 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is C.sub.1-6 alkyl substituted with an ester group.

[0218] In certain embodiments, p is an integer between 5 and 500, inclusive. In certain embodiments, p is an integer between 5 and 100, inclusive. In certain embodiments, p is an integer between 10 and 100, inclusive. In certain embodiments, p is an integer between 10 and 50, inclusive. In certain embodiments, p is an integer between 20 and 40, inclusive. In certain embodiments, p is an integer between 25 and 35, inclusive.

[0219] In certain embodiments, R.sup.5 is optionally substituted alkyl; R.sup.6 is hydrogen; R.sup.7 is optionally substituted C.sub.1-6 alkyl; and p is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl; R.sup.6 is hydrogen; R.sup.7 is substituted C.sub.1-6 alkyl; and p is an integer between 10 and 50, inclusive. In certain embodiments, R.sup.5 is tert-butyl; R.sup.6 is hydrogen; R.sup.4 is substituted C.sub.1-6 alkyl; and p is an integer between 20 and 40, inclusive.

[0220] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 10,000 Da to about 15,000 Da, about 2,000 Da to about 10,000 Da, about 7,000 Da to about 10,000 Da, about 8,000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3,000 Da, or about 2,500 Da to about 3,600 Da.

[0221] In certain embodiments, B is a polyester of the following formula:

##STR00048##

wherein:

[0222] R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl;

[0223] R.sup.9 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group; and

[0224] s is an integer between 5 and 2000, inclusive.

[0225] In certain embodiments, R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl. In certain embodiments, R.sup.8 is hydrogen. In certain embodiments, R.sup.8 is optionally substituted alkyl. In certain embodiments. R.sup.8 is optionally substituted alkenyl. In certain embodiments. R.sup.8 is optionally substituted alkynyl. In certain embodiments, R.sup.8 is optionally substituted aryl. In certain embodiments, R.sup.8 is optionally substituted heteroaryl In certain embodiments, R.sup.8 is optionally substituted carbocyclyl. In certain embodiments, R.sup.8 is optionally substituted heterocyclyl. In certain embodiments, R.sup.8 is optionally substituted acyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-6 alkyl. In certain embodiments. R.sup.8 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-3 alkyl. In certain embodiments. R.sup.8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.8 is methyl.

[0226] In certain embodiments, R.sup.9 hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group. In certain embodiments, R.sup.9 is hydrogen. In certain embodiments, R.sup.9 is optionally substituted alkyl. In certain embodiments, R.sup.9 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.9 is optionally substituted alkenyl. In certain embodiments, R.sup.9 is optionally substituted alkynyl. In certain embodiments, R.sup.9 is optionally substituted aryl. In certain embodiments, R.sup.9 is optionally substituted heteroaryl. In certain embodiments, R.sup.9 is optionally substituted carbocyclyl. In certain embodiments, R.sup.9 is optionally substituted heterocyclyl. In certain embodiments. R.sup.9 is optionally substituted acyl. In certain embodiments, R.sup.9 is an oxygen protecting group.

[0227] In certain embodiments, s is an integer between 5 and 2000, inclusive. In certain embodiments, s is an integer between 5 and 1000, inclusive. In certain embodiments, s is an integer between 5 and 500, inclusive. In certain embodiments, s is an integer between 5 and 200, inclusive. In certain embodiments, s is an integer between 5 and 100, inclusive.

[0228] In certain embodiments, B is a polyether of the following formula:

##STR00049##

wherein:

[0229] R.sup.10 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group; and

[0230] t is an integer between 5 and 2000, inclusive.

[0231] As generally defined herein, t is an integer between 5 and 2000, inclusive. In certain embodiments, t is an integer between 5 and 1000, inclusive. In certain embodiments, t is an integer between 5 and 500, inclusive. In certain embodiments, t is an integer between 5 and 200, inclusive. In certain embodiments, t is an integer between 5 and 100, inclusive.

[0232] In certain embodiments. B is a polyacrylamide group of the following formula:

##STR00050##

wherein:

[0233] each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or a nitrogen protecting group; or optionally two R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl:

[0234] R.sup.11 is hydrogen, halogen, CN, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, optionally substituted amino, optionally substituted hydroxyl, or optionally substituted thiol; and

[0235] u is an integer between 5 and 2000, inclusive.

[0236] In certain embodiments, each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or a nitrogen protecting group; or optionally two R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl. In certain embodiments, R.sup.N is hydrogen. In certain embodiments, R.sup.N is optionally substituted alkyl. In certain embodiments, R.sup.N is optionally substituted alkenyl. In certain embodiments, R.sup.N is optionally substituted alkynyl. In certain embodiments, R.sup.N is optionally substituted carbocyclyl. In certain embodiments, R.sup.N is optionally substituted heterocyclyl. In certain embodiments, R.sup.N is optionally substituted aryl. In certain embodiments, R.sup.N is optionally substituted heteroaryl. In certain embodiments, R.sup.N is or a nitrogen protecting group. In certain embodiments, R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl. In certain embodiments, R.sup.N is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.N is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.N is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.N is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.N is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.N is iso-propyl.

[0237] In certain embodiments, R.sup.11 is hydrogen, halogen, CN, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, optionally substituted amino, optionally substituted hydroxyl, or optionally substituted thiol. In certain embodiments, R.sup.11 is hydrogen. In certain embodiments, R.sup.11 is halogen. In certain embodiments, R.sup.11 is CN. In certain embodiments, R.sup.11 is optionally substituted alkyl. In certain embodiments, R.sup.11 is optionally substituted alkenyl. In certain embodiments, R.sup.11 is optionally substituted alkynyl. In certain embodiments, R.sup.11 is optionally substituted aryl. In certain embodiments, R.sup.11 is optionally substituted heteroaryl. In certain embodiments, R.sup.11 is optionally substituted carbocyclyl. In certain embodiments, R.sup.11 is optionally substituted heterocyclyl. In certain embodiments, R.sup.11 is optionally substituted acyl. In certain embodiments, R.sup.11 is optionally substituted amino. In certain embodiments, R.sup.C is optionally substituted hydroxyl. In certain embodiments, R.sup.11 is optionally substituted thiol. In certain embodiments, R.sup.11 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.11 is substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.11 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.11 is substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.11 is of the formula:

##STR00051##

[0238] In certain embodiments, u is an integer between 5 and 2000, inclusive. In certain embodiments, u is an integer between 5 and 1000, inclusive. In certain embodiments, u is an integer between 5 and 500, inclusive. In certain embodiments, u is an integer between 5 and 200, inclusive. In certain embodiments, u is an integer between 5 and 100, inclusive.

[0239] In certain embodiments, the bottlebrush polymer of Formula (I) is of Formula (I-a):

##STR00052##

or salts thereof, wherein:

[0240] each of L.sup.2, L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;

[0241] each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;

[0242] n is an integer between 1 and 4000, inclusive;

[0243] A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20,000 Da; and

[0244] B is a different polymer having a number average molecular weight of about 1.000 Da to about 20,000 Da.

[0245] In certain embodiments, L.sup.2 is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.2 is optionally substituted alkylene or optionally substituted heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted alkylene. In certain embodiments, L.sup.2 is optionally substituted heteroalkylene. In certain embodiments, L.sup.2 is unsubstituted alkylene. In certain embodiments, L.sup.2 is unsubstituted heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is unsubstituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is of the formula:

##STR00053##

[0246] In certain embodiments, L.sup.A is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L is optionally substituted alkylene. In certain embodiments, L.sup.A is optionally substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted heteroarylene. In certain embodiments, L.sup.A is unsubstituted alkylene. In certain embodiments, L.sup.A is unsubstituted heteroalkylene. In certain embodiments, L.sup.A is substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments. L.sup.A is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.A is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.A is of the formula:

##STR00054##

In certain embodiments, L.sup.A is of the formula:

##STR00055##

##STR00056##

In certain embodiments, L.sup.A is of the formula:

##STR00057##

[0247] In certain embodiments. L.sup.B is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments. L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.B is optionally substituted alkylene. In certain embodiments, L.sup.B is optionally substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted heteroarylene. In certain embodiments, L.sup.B is unsubstituted alkylene. In certain embodiments, L.sup.B is unsubstituted heteroalkylene. In certain embodiments, L.sup.B is substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.B is of the formula:

##STR00058##

In certain embodiments, L.sup.B is of the formula:

##STR00059##

##STR00060##

In certain embodiments, L.sup.B is of the formula:

##STR00061##

[0248] In certain embodiments, L.sup.2 is optionally substituted alkylene or optionally substituted heteroalkylene; L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene; and L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene. In certain embodiments, L.sup.2 is optionally substituted heteroalkylene; L.sup.A is optionally substituted heteroalkylene; and L.sup.B is optionally substituted heteroarylalkylene. In certain embodiments, L.sup.2 is unsubstituted heteroalkylene; L.sup.A is unsubstituted heteroalkylene; and L.sup.B is substituted heteroarylalkylene. In certain embodiments, L.sup.2 is unsubstituted C.sub.1-10 heteroalkylene; L.sup.A is substituted C.sub.1-10 heteroalkylene; and L.sup.B is an unsubstituted 5-membered heteroarylalkylene.

[0249] In certain embodiments, L.sup.2 is of the formula:

##STR00062##

L.sup.A is of the formula:

##STR00063##

and L.sup.B is of the formula:

##STR00064##

[0250] In certain embodiments, L.sup.2 is of the formula:

##STR00065##

L.sup.A is of the formula:

##STR00066##

and L.sup.B is of the formula:

##STR00067##

[0251] In certain embodiments, L.sup.2 is of the formula:

##STR00068##

L.sup.A is of the formula:

##STR00069##

and L.sup.B is of the formula:

##STR00070##

[0252] In certain embodiments, L.sup.2 is of the formula:

##STR00071##

L.sup.A is of the formula:

##STR00072##

and L.sup.B is of the formula:

##STR00073##

[0253] In certain embodiments, n is an integer between 1 and 4000, inclusive. In certain embodiments, n is an integer between 5 and 4000, inclusive. In certain embodiments, n is an integer is between 50 and 4000, inclusive. In certain embodiments, n is an integer between 100 and 4000, inclusive. In certain embodiments, n is an integer between 1000 and 4000, inclusive. In certain embodiments, n is an integer between 2000 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 2000, inclusive. In certain embodiments, n is an integer between 2 and 1000, inclusive. In certain embodiments, n is an integer between 10 and 1000, inclusive. In certain embodiments, n is an integer between 2 and 100, inclusive. In certain embodiments, n is an integer between 10 and 100, inclusive. In certain embodiments, n is an integer between 10 and 50, inclusive. In certain embodiments, n is an integer between 25 and 50, inclusive. In certain embodiments, n is an integer between 25 and 100, inclusive. In certain embodiments, n is about 10, about 25, about 50, or about 100. In certain embodiments, n is 10, 25, 50, or 100. In certain embodiments, n is 25 or 50. In certain embodiments, n is 10. In certain embodiments, n is 25. In certain embodiments, n is 50. In certain embodiments, n is 100.

[0254] In certain embodiments, each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thiol. In certain embodiments, T.sup.1 is hydrogen. In certain embodiments, T.sup.1 is halogen. In certain embodiments, T.sup.1 is optionally substituted alkyl. In certain embodiments, T.sup.1 is optionally substituted alkenyl. In certain embodiments, T.sup.1 is optionally substituted alkynyl. In certain embodiments, T.sup.1 is optionally substituted carbocyclyl. In certain embodiments, T.sup.1 is optionally substituted heterocyclyl. In certain embodiments, T.sup.1 is optionally substituted aryl. In certain embodiments, T.sup.1 is optionally substituted heteroaryl. In certain embodiments, T.sup.1 is optionally substituted acyl. In certain embodiments, T.sup.1 is optionally substituted hydroxyl. In certain embodiments, T.sup.1 is optionally substituted amino. In certain embodiments, T.sup.1 is optionally substituted thiol. In certain embodiments, T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is halogen. In certain embodiments, T.sup.2 is optionally substituted alkyl. In certain embodiments, T.sup.2 is optionally substituted alkenyl. In certain embodiments. T.sup.2 is optionally substituted alkynyl. In certain embodiments, T.sup.2 is optionally substituted carbocyclyl. In certain embodiments, T.sup.2 is optionally substituted heterocyclyl. In certain embodiments, T.sup.2 is optionally substituted aryl. In certain embodiments, T.sup.2 is optionally substituted heteroaryl. In certain embodiments, T.sup.2 is optionally substituted acyl. In certain embodiments, T.sup.2 is optionally substituted hydroxyl. In certain embodiments, T.sup.2 is optionally substituted amino. In certain embodiments, T.sup.2 is optionally substituted thiol. In certain embodiments, both T.sup.1 and T.sup.2 are hydrogen.

[0255] In certain embodiments, T.sup.1 is optionally substituted aryl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.1 is phenyl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is optionally substituted aryl, and T.sup.1 is hydrogen. In certain embodiments, T.sup.2 is phenyl, and T.sup.1 is hydrogen.

[0256] In certain embodiments, A is a polysiloxane and B is a different polymer. In certain embodiments, A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20.000 Da; and B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.

[0257] In certain embodiments, A is a polysiloxane. In certain embodiments, the polysiloxane is of the formula:

##STR00074##

wherein:

[0258] R.sup.1 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy;

[0259] R.sup.2 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy; and

[0260] q is an integer between 5 and 2000, inclusive.

[0261] In certain embodiments, R.sup.1 is optionally substituted alkyl. In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.1 is methyl.

[0262] In certain embodiments, R.sup.1 is C.sub.1-6 alkyl, and the polysiloxane has a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, or about 4,000 Da to about 6,000 Da, or about 4,500 Da to about 5,500 Da.

[0263] In certain embodiments, R.sup.2 is optionally substituted alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-20 alkyl. In certain embodiments. R.sup.2 is unsubstituted C.sub.1-20 alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is unsubstituted C.sub.1-6alkyl. In certain embodiments, R.sup.2 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.2 is n-butyl.

[0264] In certain embodiments, q is an integer between 5 and 500, inclusive. In certain embodiments, q is an integer between 5 and 100, inclusive. In certain embodiments, q is an integer between 10 and 100, inclusive. In certain embodiments, q is an integer between 30 and 80, inclusive. In certain embodiments, q is an integer between 50 and 80, inclusive. In certain embodiments, q is an integer between 60 and 70, inclusive.

[0265] In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl; R.sup.2 is optionally substituted C.sub.1-6 alkyl; and q is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl; R.sup.2 is unsubstituted C.sub.1-6 alkyl; and q is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.1 is methyl; R.sup.2 is n-butyl; and q is an integer between 50 and 100, inclusive.

[0266] In certain embodiments, R.sup.1 is C.sub.1-6 alkyl, and the polysiloxane has a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, or about 4,000 Da to about 6,000 Da. or about 4,500 Da to about 5,500 Da.

[0267] In certain embodiments, the polysiloxane is polydimethylsiloxane (PDMS) having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, about 4,000 Da to about 6,000 Da, or about 4,500 Da to about 5,500 Da.

[0268] In certain embodiments, B is a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer. The polyacrylate may be any polyester described herein. The polyester may be any polyester described herein. The polyether may be any polyether described herein. The polyacrylamide may be any polyacrylamide described herein. Additionally, the vinyl polymer may be any vinyl polymer described herein.

[0269] In certain embodiments, B is a polyether selected from the group consisting of polyethylene glycol (PEG), polyoxymethylene (POM), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), poly(ethyl ethylene) phosphate (PEEP), and poly(oxazoline). In certain embodiments, B is polyethylene glycol (PEG). In certain embodiments. B is a polyester. In certain embodiments, B is a polyester selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), poly(lactic-co-glycolic acid) (PLGA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutryate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). In certain embodiments, B is polylactic acid (PLA). In certain embodiments, B is polyglycolic acid (PGA) or poly(lactic-co-glycolic acid) (PLGA). In certain embodiments. B is a polyacrylamide. In certain embodiments, B is a poly(N-alkylacrylamide). In certain embodiments, B is poly(N-isopropylacrylamide). In certain embodiments, B is a vinyl polymer. In certain embodiments, B is a vinyl polymer selected from the group consisting of polystyrene, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyvinyl acetate, polyvinyl alcohol, and polyacrylonitrile. In certain embodiments, B is polystyrene. In certain embodiments, B is a polyacrylate. In certain embodiments, B is a polyacrylate selected from the group consisting of poly(methyl methacrylate), poly(methyl acrylate), poly(methacrylate), poly(hydroxyethyl methacrylate), poly(n-butyl acrylate), and poly(tert-butyl acrylate). In certain embodiments. B is poly(tert-butyl acrylate).

[0270] In certain embodiments, B is a vinyl polymer of the following formula:

##STR00075##

wherein:

[0271] R.sup.3 is optionally substituted alkyl, halogen, hydrogen, cyano, OR.sup.a, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0272] R.sup.4 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0273] R.sup.a is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0274] r is an integer between 5 and 2000, inclusive.

[0275] In certain embodiments, R.sup.3 is hydrogen. In certain embodiments, R.sup.3 is optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted alkenyl. In certain embodiments, R.sup.3 is optionally substituted alkynyl. In certain embodiments, R.sup.3 is optionally substituted aryl. In certain embodiments, R.sup.3 is optionally substituted heteroaryl. In certain embodiments, R.sup.3 is cyano. In certain embodiments, R.sup.3 is halogen. In certain embodiments, R.sup.3 is OR.sup.a, wherein R.sup.a is hydrogen or optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted phenyl. In certain embodiments, R.sup.3 is unsubstituted phenyl.

[0276] In certain embodiments, R.sup.4 is optionally substituted alkyl. In certain embodiments, R.sup.4 is optionally substituted alkenyl. In certain embodiments, R.sup.4 is optionally substituted alkynyl. In certain embodiments. R.sup.4 is optionally substituted aryl. In certain embodiments, R.sup.4 is optionally substituted heteroaryl. In certain embodiments, R.sup.4 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is C.sub.1-6 alkyl substituted with an ester group.

[0277] In certain embodiments, r is an integer between 5 and 500, inclusive. In certain embodiments, r is an integer between 5 and 100, inclusive. In certain embodiments, r is an integer between 10 and 100, inclusive. In certain embodiments, r is an integer between 10 and 50, inclusive. In certain embodiments, r is an integer between 20 and 40, inclusive. In certain embodiments, r is an integer between 30 and 40, inclusive.

[0278] In certain embodiments. R.sup.3 is optionally substituted aryl; R.sup.4 is optionally substituted C.sub.1-6 alkyl; and r is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.3 is unsubstituted aryl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive. In certain embodiments, R.sup.3 is unsubstituted phenyl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive.

[0279] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2,000 Da to about 20.000 Da, about 10,000 Da to about 15,000 Da, about 2,000 Da to about 10,000 Da, about 7,000 Da to about 10,000 Da, about 8,000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3,000 Da, or about 2,500 Da to about 3,600 Da.

[0280] In certain embodiments, B is a polyacrylate of the following formula:

##STR00076##

wherein:

[0281] R.sup.5 is optionally substituted alkyl, hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0282] R.sup.6 is optionally substituted alkyl, hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0283] R.sup.7 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0284] p is an integer between 5 and 2000, inclusive.

[0285] In certain embodiments, R.sup.5 is hydrogen. In certain embodiments, R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted alkenyl. In certain embodiments, R.sup.5 is optionally substituted alkynyl. In certain embodiments, R.sup.5 is optionally substituted aryl. In certain embodiments, R.sup.5 is optionally substituted heteroaryl. In certain embodiments. R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.5 is tert-butyl.

[0286] In certain embodiments, R.sup.6 is optionally substituted alkyl. In certain embodiments, R.sup.6 is hydrogen. In certain embodiments, R.sup.6 is optionally substituted alkenyl. In certain embodiments, R.sup.6 is optionally substituted alkynyl. In certain embodiments, R.sup.6 is optionally substituted aryl. In certain embodiments, R.sup.6 is optionally substituted heteroaryl. In certain embodiments, R.sup.6 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is methyl.

[0287] In certain embodiments, R.sup.7 is optionally substituted alkyl. In certain embodiments, R.sup.7 is optionally substituted alkenyl. In certain embodiments, R.sup.7 is optionally substituted alkynyl. In certain embodiments, R.sup.7 is optionally substituted aryl. In certain embodiments, R.sup.7 is optionally substituted heteroaryl. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is C.sub.1-6 alkyl substituted with an ester group.

[0288] In certain embodiments, p is an integer between 5 and 500, inclusive. In certain embodiments, p is an integer between 5 and 100, inclusive. In certain embodiments, p is an integer between 10 and 100, inclusive. In certain embodiments, p is an integer between 10 and 50, inclusive. In certain embodiments, p is an integer between 20 and 40, inclusive. In certain embodiments, p is an integer between 25 and 35, inclusive.

[0289] In certain embodiments. R.sup.5 is optionally substituted alkyl; R.sup.6 is hydrogen; R.sup.7 is optionally substituted C.sub.1-6 alkyl; and p is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl; R.sup.6 is hydrogen; R.sup.7 is substituted C.sub.1-6 alkyl; and p is an integer between 10 and 50, inclusive. In certain embodiments. R.sup.5 is tert-butyl; R.sup.6 is hydrogen; R.sup.4 is substituted C.sub.1-6 alkyl; and p is an integer between 20 and 40, inclusive.

[0290] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 10,000 Da to about 15,000 Da, about 2,000 Da to about 10,000 Da, about 7,000 Da to about 10,000 Da, about 8,000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3,000 Da. or about 2,500 Da to about 3,600 Da.

[0291] In certain embodiments, B is a polyester of the following formula:

##STR00077##

wherein:

[0292] R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl:

[0293] R.sup.9 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group; and

[0294] s is an integer between 5 and 2000, inclusive.

[0295] In certain embodiments, R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl. In certain embodiments, R.sup.8 is hydrogen. In certain embodiments. R.sup.8 is optionally substituted alkyl. In certain embodiments, R.sup.8 is optionally substituted alkenyl. In certain embodiments, R.sup.8 is optionally substituted alkynyl. In certain embodiments, R.sup.8 is optionally substituted aryl. In certain embodiments, R.sup.8 is optionally substituted heteroaryl In certain embodiments, R.sup.8 is optionally substituted carbocyclyl. In certain embodiments, R.sup.8 is optionally substituted heterocyclyl. In certain embodiments, R.sup.8 is optionally substituted acyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.8 is methyl.

[0296] In certain embodiments, R.sup.9 hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group. In certain embodiments, R.sup.9 is hydrogen. In certain embodiments. R.sup.9 is optionally substituted alkyl. In certain embodiments, R.sup.9 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.9 is optionally substituted alkenyl. In certain embodiments, R.sup.9 is optionally substituted alkynyl. In certain embodiments, R.sup.9 is optionally substituted aryl. In certain embodiments, R.sup.9 is optionally substituted heteroaryl. In certain embodiments, R.sup.9 is optionally substituted carbocyclyl. In certain embodiments, R.sup.9 is optionally substituted heterocyclyl. In certain embodiments, R.sup.9 is optionally substituted acyl. In certain embodiments, R.sup.9 is an oxygen protecting group.

[0297] In certain embodiments, s is an integer between 5 and 2000, inclusive. In certain embodiments, s is an integer between 5 and 1000, inclusive. In certain embodiments, s is an integer between 5 and 500, inclusive. In certain embodiments, s is an integer between 5 and 200, inclusive. In certain embodiments, s is an integer between 5 and 100, inclusive.

[0298] In certain embodiments, B is a polyether of the following formula:

##STR00078##

wherein:

[0299] R.sup.10 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group; and

[0300] t is an integer between 5 and 2000, inclusive.

[0301] In certain embodiments, t is an integer between 5 and 2000, inclusive. In certain embodiments, t is an integer between 5 and 1000, inclusive. In certain embodiments, t is an integer between 5 and 500, inclusive. In certain embodiments, t is an integer between 5 and 200, inclusive. In certain embodiments, t is an integer between 5 and 100, inclusive.

[0302] In certain embodiments, B is a polyacrylamide group of the following formula:

##STR00079##

wherein:

[0303] each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or a nitrogen protecting group; or optionally two R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl;

[0304] R.sup.11 is hydrogen, halogen, CN, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, optionally substituted amino, optionally substituted hydroxyl, or optionally substituted thiol; and

[0305] u is an integer between 5 and 2000, inclusive.

[0306] In certain embodiments, each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or a nitrogen protecting group; or optionally two R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl. In certain embodiments, R.sup.N is hydrogen. In certain embodiments, R.sup.N is optionally substituted alkyl. In certain embodiments. R.sup.N is optionally substituted alkenyl. In certain embodiments, R.sup.N is optionally substituted alkynyl. In certain embodiments, R.sup.N is optionally substituted carbocyclyl. In certain embodiments, R.sup.N is optionally substituted heterocyclyl. In certain embodiments, R.sup.N is optionally substituted aryl. In certain embodiments. R.sup.N is optionally substituted heteroaryl. In certain embodiments, R.sup.N is or a nitrogen protecting group. In certain embodiments, R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl. In certain embodiments, R.sup.N is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.N is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.N is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.N is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.N is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.N is iso-propyl.

[0307] In certain embodiments, R.sup.11 is hydrogen, halogen, CN, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, optionally substituted amino, optionally substituted hydroxyl, or optionally substituted thiol. In certain embodiments, R.sup.11 is hydrogen. In certain embodiments, R.sup.11 is halogen. In certain embodiments, R.sup.11 is CN. In certain embodiments, R.sup.11 is optionally substituted alkyl. In certain embodiments. R.sup.11 is optionally substituted alkenyl. In certain embodiments. R.sup.11 is optionally substituted alkynyl. In certain embodiments. R.sup.11 is optionally substituted aryl. In certain embodiments, R.sup.11 is optionally substituted heteroaryl. In certain embodiments, R.sup.11 is optionally substituted carbocyclyl. In certain embodiments, R.sup.11 is optionally substituted heterocyclyl. In certain embodiments, R.sup.11 is optionally substituted acyl. In certain embodiments, R.sup.11 is optionally substituted amino. In certain embodiments, R.sup.C is optionally substituted hydroxyl. In certain embodiments, R.sup.11 is optionally substituted thiol. In certain embodiments, R.sup.11 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.11 is substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.11 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.11 is substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.11 is of the formula:

##STR00080##

[0308] In certain embodiments, u is an integer between 5 and 2000, inclusive. In certain embodiments, u is an integer between 5 and 1000, inclusive. In certain embodiments, u is an integer between 5 and 500, inclusive. In certain embodiments, u is an integer between 5 and 200, inclusive. In certain embodiments, u is an integer between 5 and 100, inclusive.

[0309] In certain embodiments, the bottlebrush polymer is of Formula (I-b):

##STR00081##

or salts thereof, wherein:

[0310] each L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;

[0311] each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;

[0312] n is an integer between 1 and 4000, inclusive;

[0313] A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20,000 Da; and

[0314] B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.

[0315] In certain embodiments. L.sup.A is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.A is optionally substituted alkylene. In certain embodiments, L.sup.A is optionally substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted heteroarylene. In certain embodiments, L.sup.A is unsubstituted alkylene. In certain embodiments, L.sup.A is unsubstituted heteroalkylene. In certain embodiments, L.sup.A is substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.A is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.A is C-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.A is of the formula:

##STR00082##

In certain embodiments, L.sup.A is of the formula:

##STR00083##

##STR00084##

In certain embodiments. L.sup.A is of the formula:

##STR00085##

[0316] In certain embodiments, L.sup.B is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.B is optionally substituted alkylene. In certain embodiments, L.sup.B is optionally substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted heteroarylene. In certain embodiments. L.sup.B is unsubstituted alkylene. In certain embodiments, L.sup.B is unsubstituted heteroalkylene. In certain embodiments, L.sup.B is substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments. L.sup.B is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.B is of the formula:

##STR00086##

In certain embodiments, L.sup.B is of the formula:

##STR00087##

In certain embodiments, L.sup.B is unsubstituted heteroarylalkylene. In certain embodiments, L.sup.B is optionally substituted heteroarylalkylene. In certain embodiments, L.sup.B is an unsubstituted 5-membered heteroarylalkylene. In certain embodiments. L.sup.B comprises a triazole. In certain embodiments, L.sup.B comprises a group of the formula:

##STR00088##

In certain embodiments, L.sup.B is of the formula:

##STR00089##

[0317] In certain embodiments, L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene; and L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene. In certain embodiments, L.sup.A is optionally substituted heteroalkylene; and L.sup.B is optionally substituted heteroarylalkylene. In certain embodiments, L.sup.A is unsubstituted heteroalkylene; and L.sup.B is substituted heteroarylalkylene. In certain embodiments, L.sup.A is substituted C.sub.1-10 heteroalkylene; and L.sup.B is an unsubstituted 5-membered heteroarylalkylene.

[0318] In certain embodiments, L.sup.A is of the formula:

##STR00090##

and L.sup.B is of the formula:

##STR00091##

[0319] In certain embodiments. L.sup.A is of the formula:

##STR00092##

and L.sup.B is of the formula:

##STR00093##

[0320] In certain embodiments, L.sup.A is of the formula:

##STR00094##

and L.sup.B is of the formula:

##STR00095##

[0321] In certain embodiments, L.sup.A is of the formula:

##STR00096##

and L.sup.B is of the formula:

##STR00097##

[0322] In certain embodiments, n is an integer between 1 and 4000, inclusive. In certain embodiments, n is an integer between 5 and 4000, inclusive. In certain embodiments, n is an integer is between 50 and 4000, inclusive. In certain embodiments, n is an integer between 100 and 4000, inclusive. In certain embodiments, n is an integer between 1000 and 4000, inclusive. In certain embodiments, n is an integer between 2000 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 2000, inclusive. In certain embodiments, n is an integer between 2 and 1000, inclusive. In certain embodiments, n is an integer between 10 and 1000, inclusive. In certain embodiments, n is an integer between 2 and 100, inclusive. In certain embodiments, n is an integer between 10 and 100, inclusive. In certain embodiments, n is an integer between 10 and 50, inclusive. In certain embodiments, n is an integer between 25 and 50, inclusive. In certain embodiments, n is an integer between 25 and 100, inclusive. In certain embodiments, n is about 10, about 25, about 50, or about 100. In certain embodiments, the average of n is about 10, about 25, about 50, or about 100. In certain embodiments, the average of n is about 25 or about 50. In certain embodiments, the average of n is about 10. In certain embodiments, the average of n is about 25. In certain embodiments, the average of n is about 50. In certain embodiments, the average of n is about 100. In certain embodiments, n is the same as the degree of polymerization of the polymer.

[0323] In certain embodiments, each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thiol. In certain embodiments, T.sup.1 is hydrogen. In certain embodiments, T.sup.1 is halogen. In certain embodiments, T.sup.1 is optionally substituted alkyl. In certain embodiments, T.sup.1 is optionally substituted alkenyl. In certain embodiments, T.sup.1 is optionally substituted alkynyl. In certain embodiments, T.sup.1 is optionally substituted carbocyclyl. In certain embodiments, T.sup.1 is optionally substituted heterocyclyl. In certain embodiments. T.sup.1 is optionally substituted aryl. In certain embodiments, T.sup.1 is optionally substituted heteroaryl. In certain embodiments, T.sup.1 is optionally substituted acyl. In certain embodiments, T.sup.1 is optionally substituted hydroxyl. In certain embodiments, T.sup.1 is optionally substituted amino. In certain embodiments, T.sup.1 is optionally substituted thiol. In certain embodiments, T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is halogen. In certain embodiments, T.sup.2 is optionally substituted alkyl. In certain embodiments, T.sup.2 is optionally substituted alkenyl. In certain embodiments, T.sup.2 is optionally substituted alkynyl. In certain embodiments. T.sup.2 is optionally substituted carbocyclyl. In certain embodiments, T.sup.2 is optionally substituted heterocyclyl. In certain embodiments, T.sup.2 is optionally substituted aryl. In certain embodiments, T.sup.2 is optionally substituted heteroaryl. In certain embodiments, T.sup.2 is optionally substituted acyl. In certain embodiments, T.sup.2 is optionally substituted hydroxyl. In certain embodiments, T.sup.2 is optionally substituted amino. In certain embodiments, T.sup.2 is optionally substituted thiol. In certain embodiments, both T.sup.1 and T.sup.2 are hydrogen.

[0324] In certain embodiments, T.sup.1 is optionally substituted aryl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.1 is phenyl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is optionally substituted aryl, and T.sup.1 is hydrogen. In certain embodiments, T.sup.2 is phenyl, and T.sup.1 is hydrogen.

[0325] In certain embodiments, A is a polysiloxane and B is a different polymer. In certain embodiments, A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20.000 Da; and B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.

[0326] In certain embodiments, A is a polysiloxane. In certain embodiments, the polysiloxane is of the formula:

##STR00098##

wherein:

[0327] R.sup.1 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy;

[0328] R.sup.2 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy; and

[0329] q is an integer between 5 and 2000, inclusive.

[0330] In certain embodiments, R.sup.1 is optionally substituted alkyl. In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl.

[0331] In certain embodiments, R.sup.1 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.1 is methyl. In certain embodiments, R.sup.1 is C.sub.1-6 alkyl, and the polysiloxane has a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, or about 4,000 Da to about 6,000 Da, or about 4,500 Da to about 5,500 Da.

[0332] In certain embodiments, R.sup.2 is optionally substituted alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-20 alkyl. In certain embodiments. R.sup.2 is unsubstituted C.sub.1-20 alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl.

[0333] In certain embodiments, R.sup.2 is n-butyl. In certain embodiments, q is an integer between 5 and 500, inclusive. In certain embodiments, q is an integer between 5 and 100, inclusive. In certain embodiments, q is an integer between 10 and 100, inclusive. In certain embodiments, q is an integer between 30 and 80, inclusive. In certain embodiments, q is an integer between 50 and 80, inclusive. In certain embodiments, q is an integer between 60 and 70, inclusive.

[0334] In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl; R.sup.2 is optionally substituted C.sub.1-6 alkyl; and q is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl; R.sup.2 is unsubstituted C.sub.1-6 alkyl; and q is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.1 is methyl; R.sup.2 is n-butyl; and q is an integer between 50 and 100, inclusive.

[0335] In certain embodiments, R.sup.1 is C.sub.1-6 alkyl, and the polysiloxane has a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, or about 4,000 Da to about 6,000 Da. or about 4,500 Da to about 5,500 Da.

[0336] In certain embodiments, the polysiloxane is polydimethylsiloxane (PDMS) having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, about 4,000 Da to about 6,000 Da, about 4,500 Da to about 5,500 Da.

[0337] In certain embodiments, B is a vinyl polymer of the following formula:

##STR00099##

wherein:
R.sup.3 is optionally substituted alkyl, halogen, hydrogen, cyano, OR.sup.a, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0338] R.sup.4 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0339] R.sup.a is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0340] r is an integer between 5 and 2000, inclusive.

[0341] In certain embodiments, R.sup.3 is hydrogen. In certain embodiments, R.sup.3 is optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted alkenyl. In certain embodiments, R.sup.3 is optionally substituted alkynyl. In certain embodiments, R.sup.3 is optionally substituted aryl. In certain embodiments, R.sup.3 is optionally substituted heteroaryl. In certain embodiments, R.sup.3 is cyano. In certain embodiments, R.sup.3 is halogen. In certain embodiments, R.sup.3 is OR.sup.a, wherein R.sup.a is hydrogen or optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted phenyl. In certain embodiments, R.sup.3 is unsubstituted phenyl.

[0342] In certain embodiments, R.sup.4 is optionally substituted alkyl. In certain embodiments, R.sup.4 is optionally substituted alkenyl. In certain embodiments, R.sup.4 is optionally substituted alkynyl. In certain embodiments, R.sup.4 is optionally substituted aryl. In certain embodiments, R.sup.4 is optionally substituted heteroaryl. In certain embodiments, R.sup.4 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is C.sub.1-6 alkyl substituted with an ester group.

[0343] In certain embodiments, r is an integer between 5 and 500, inclusive. In certain embodiments, r is an integer between 5 and 100, inclusive. In certain embodiments, r is an integer between 10 and 100, inclusive. In certain embodiments, r is an integer between 10 and 50, inclusive. In certain embodiments, r is an integer between 20 and 40, inclusive. In certain embodiments, r is an integer between 30 and 40, inclusive.

[0344] In certain embodiments, R.sup.3 is optionally substituted aryl; R.sup.4 is optionally substituted C.sub.1-6 alkyl; and r is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.3 is unsubstituted aryl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive. In certain embodiments, R.sup.3 is unsubstituted phenyl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive.

[0345] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2.000 Da to about 20,000 Da, about 10,000 Da to about 15.000 Da, about 2.000 Da to about 10,000 Da, about 7,000 Da to about 10,000 Da, about 8,000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3,000 Da, or about 2,500 Da to about 3,600 Da.

[0346] In certain embodiments. B is a polyacrylate of the following formula:

##STR00100##

wherein:

[0347] R.sup.5 is optionally substituted alkyl, hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0348] R.sup.6 is optionally substituted alkyl, hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0349] R.sup.7 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0350] p is an integer between 5 and 2000, inclusive.

[0351] In certain embodiments, R.sup.5 is hydrogen. In certain embodiments, R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted alkenyl. In certain embodiments, R.sup.5 is optionally substituted alkynyl. In certain embodiments, R.sup.5 is optionally substituted aryl. In certain embodiments, R.sup.5 is optionally substituted heteroaryl. In certain embodiments, R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments. R.sup.5 is tert-butyl.

[0352] In certain embodiments. R.sup.6 is optionally substituted alkyl. In certain embodiments, R.sup.6 is hydrogen. In certain embodiments, R.sup.6 is optionally substituted alkenyl. In certain embodiments, R.sup.6 is optionally substituted alkynyl. In certain embodiments, R.sup.6 is optionally substituted aryl. In certain embodiments, R.sup.6 is optionally substituted heteroaryl. In certain embodiments, R.sup.6 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is methyl.

[0353] In certain embodiments, R.sup.7 is optionally substituted alkyl. In certain embodiments, R.sup.7 is optionally substituted alkenyl. In certain embodiments, R.sup.7 is optionally substituted alkynyl. In certain embodiments, R.sup.7 is optionally substituted aryl. In certain embodiments, R.sup.7 is optionally substituted heteroaryl. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is C.sub.1-6 alkyl substituted with an ester group.

[0354] In certain embodiments, p is an integer between 5 and 500, inclusive. In certain embodiments, p is an integer between 5 and 100, inclusive. In certain embodiments, p is an integer between 10 and 100, inclusive. In certain embodiments, p is an integer between 10 and 50, inclusive. In certain embodiments, p is an integer between 20 and 40, inclusive. In certain embodiments, p is an integer between 25 and 35, inclusive.

[0355] In certain embodiments, R.sup.5 is optionally substituted alkyl; R.sup.6 is hydrogen; R.sup.7 is optionally substituted C.sub.1-6 alkyl; and p is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl; R.sup.6 is hydrogen; R.sup.7 is substituted C.sub.1-6 alkyl; and p is an integer between 10 and 50, inclusive. In certain embodiments, R.sup.5 is tert-butyl; R.sup.6 is hydrogen; R.sup.4 is substituted C.sub.1-6 alkyl; and p is an integer between 20 and 40, inclusive.

[0356] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2,000 Da to about 20.000 Da, about 10,000 Da to about 15,000 Da, about 2,000 Da to about 10,000 Da, about 7,000 Da to about 10.000 Da, about 8.000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3.000 Da, or about 2,500 Da to about 3,600 Da.

[0357] In certain embodiments, B is a polyester of the following formula:

##STR00101##

wherein:

[0358] R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl;

[0359] R.sup.9 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group; and

[0360] s is an integer between 5 and 2000), inclusive.

[0361] In certain embodiments, R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl. In certain embodiments, R.sup.8 is hydrogen. In certain embodiments, R.sup.8 is optionally substituted alkyl. In certain embodiments, R.sup.8 is optionally substituted alkenyl. In certain embodiments, R.sup.8 is optionally substituted alkynyl. In certain embodiments, R.sup.8 is optionally substituted aryl. In certain embodiments, R.sup.8 is optionally substituted heteroaryl In certain embodiments, R.sup.8 is optionally substituted carbocyclyl. In certain embodiments, R.sup.8 is optionally substituted heterocyclyl. In certain embodiments. R.sup.8 is optionally substituted acyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.8 is methyl.

[0362] In certain embodiments, R.sup.9 hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group. In certain embodiments, R.sup.9 is hydrogen. In certain embodiments, R.sup.9 is optionally substituted alkyl. In certain embodiments, R.sup.9 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.9 is optionally substituted alkenyl. In certain embodiments, R.sup.9 is optionally substituted alkynyl. In certain embodiments, R.sup.9 is optionally substituted aryl. In certain embodiments, R.sup.9 is optionally substituted heteroaryl. In certain embodiments, R.sup.9 is optionally substituted carbocyclyl. In certain embodiments, R.sup.9 is optionally substituted heterocyclyl. In certain embodiments. R.sup.9 is optionally substituted acyl. In certain embodiments, R.sup.9 is an oxygen protecting group.

[0363] In certain embodiments, s is an integer between 5 and 2000, inclusive. In certain embodiments, s is an integer between 5 and 1000, inclusive. In certain embodiments, s is an integer between 5 and 500, inclusive. In certain embodiments, s is an integer between 5 and 200, inclusive. In certain embodiments, s is an integer between 5 and 100, inclusive.

[0364] In certain embodiments, the polyester is poly(lactic acid). In certain embodiments, the polyester is poly(lactic acid) having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 7,000 Da, or about 2,000 Da to about 4,000 Da.

[0365] In certain embodiments, A is of the formula:

##STR00102##

and B is of the formula:

##STR00103##

wherein R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, q, and p are as defined in the embodiments of Formula (I); and the ratio of q:r is about 1:1, about 1.5:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0366] In certain embodiments, A is of the formula:

##STR00104##

and B is of the formula:

##STR00105##

wherein R.sup.2, R.sup.7, q, and p are as defined in the embodiments of Formula (I); and the ratio of q:r is about 1:1, about 1.5:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0367] In certain embodiments, A is of the formula:

##STR00106##

and B is of the formula:

##STR00107##

wherein R.sup.2, R.sup.7, q, and p are as defined in the embodiments of Formula (I); and the ratio of q:r is about 2.6:1. In certain embodiments, these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, these parameters lead to a BBCP with gyroid morphology.

[0368] In certain embodiments, A is of the formula:

##STR00108##

and B is of the formula:

##STR00109##

wherein R.sup.2 and R.sup.7 are as defined in the embodiments of Formula (I); q is about 65 to about 70; p is about 25 to about 30; and the ratio of q:r is about 2.6:1. In certain embodiments, any of these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0369] In certain embodiments, A is of the formula:

##STR00110##

and B is of the formula:

##STR00111##

wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, q, and r are as defined in the embodiments of Formula (I); and the ratio of q:r is about 1:1.1, about 1:1.2, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.1, about 1:2.2, about 1:2.3, about 1:2.4, about 1:2.5, about 1:2.6, about 1:2.7, about 1:2.8, about 1:2.9, about 1:3, about 1:4, about 1:5, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0370] In certain embodiments, A is of the formula:

##STR00112##

and B is of the formula:

##STR00113##

wherein R.sup.2, R.sup.4, q, and r are as defined in the embodiments of Formula (I); and wherein the ratio of q:r is about 1:1.1, about 1:1.2, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.1, about 1:2.2, about 1:2.3, about 1:2.4, about 1:2.5, about 1:2.6, about 1:2.7, about 1:2.8, about 1:2.9, about 1:3, about 1:4, about 1:5, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0371] In certain embodiments, A is of the formula:

##STR00114##

and B is of the formula:

##STR00115##

wherein R.sup.2, R.sup.4, q, and r are as defined in the embodiments of Formula (I); and the ratio of q:r is about 2:1. In certain embodiments, these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, these parameters lead to a BBCP with gyroid morphology.

[0372] In certain embodiments, A is of the formula:

##STR00116##

and B is of the formula:

##STR00117##

wherein R.sup.2, R.sup.4, q, and r are as defined in the embodiments of Formula (I); and the ratio of q:r is about 3:1. In certain embodiments, these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, these parameters lead to a BBCP with gyroid morphology.

[0373] In certain embodiments, A is of the formula:

##STR00118##

and B is of the formula:

##STR00119##

wherein R.sup.2, R.sup.4, q, and r are as defined in the embodiments of Formula (I); and the ratio of q:r is about 1:1.5. In certain embodiments, these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, these parameters lead to a BBCP with gyroid morphology.

[0374] In certain embodiments, A is of the formula:

##STR00120##

and B is of the formula:

##STR00121##

wherein R.sup.2, R.sup.4, q, and r are as defined in the embodiments of Formula (I); and the ratio of q:r is about 1:2.2. In certain embodiments, these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, these parameters lead to a BBCP with gyroid morphology.

[0375] In certain embodiments, A is of the formula:

##STR00122##

and B is of the formula:

##STR00123##

wherein R.sup.2, R.sup.4, q, and r are as defined in the embodiments of Formula (I); and the ratio of q:r is about 1:1.2 to about 1:1.3. In certain embodiments, these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, these parameters lead to a BBCP with gyroid morphology.

[0376] In certain embodiments, A is of the formula:

##STR00124##

and B is of the formula:

##STR00125##

wherein R.sup.2 and R.sup.4 are as defined in the embodiments of Formula (I); q is about 65 to about 70; r is about 80 to about 90; and the ratio of q:r is about 1:1.2 to about 1:1.3. In certain embodiments, these parameters lead to a BBCP with hexagonal cylindrical morphology. In certain embodiments, these parameters lead to a BBCP with gyroid morphology.

[0377] In certain embodiments, the bottlebrush polymer of Formula (I) is of Formula (I-c):

##STR00126##

or salts thereof, wherein:

[0378] each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl;

[0379] n is an integer between 10 and 100, inclusive;

[0380] p is an integer between 10 and 100, inclusive; and

[0381] q is an integer between 25 and 260, inclusive; wherein the ratio of q:p is about 2.6:1. In certain embodiments, the polymer has a hexagonal cylindrical morphology. In certain embodiments, the polymer has a gyroid morphology.

[0382] In certain embodiments, the bottlebrush polymer of Formula (I) is of Formula (I-d):

##STR00127##

or salts thereof, wherein:

[0383] each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl:

[0384] n is an integer between 10 and 100, inclusive;

[0385] r is an integer between 20 and 200, inclusive; and

[0386] q is an integer between 20 and 200, inclusive; wherein the ratio of q:r is about 1:1.2 to about 1:1.3. In certain embodiments, the polymer has a hexagonal cylindrical morphology. In certain embodiments, the polymer has a gyroid morphology.

[0387] In certain embodiments, the bottlebrush polymer of Formula (I) is of Formula (I-e):

##STR00128##

or salts thereof, wherein each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl; n is an integer between 10 and 100, inclusive; s is an integer between 20 and 200, inclusive; and q is an integer between 20 and 200, inclusive. In certain embodiments, the polymer has a hexagonal cylindrical morphology. In certain embodiments, the polymer has a gyroid morphology.

[0388] As described herein, in certain embodiments, a bottlebrush polymer of the present invention has a bottlebrush or comb structure. In certain embodiments, the polymer has a bottlebrush structure. In certain embodiments, the polymer has a comb structure. A bottlebrush polymer described herein may self-assemble to form any type of polymer network or nanostructure. In certain embodiments, a bottlebrush polymer described herein self-assembles to form photonic crystals. In certain embodiments, a bottlebrush polymer described herein self-assembles to form a spherical, lamellar, cylindrical, ellipsoidal, polyhedral, or gyroid shape.

[0389] In certain embodiments, the bottlebrush polymer described herein self-assembles to form a structure with a hexagonal cylindrical morphology. In certain embodiments, the bottlebrush polymer described herein self-assembles to form a structure with a gyroid morphology. In certain embodiments, the bottlebrush polymer described herein self-assembles to form a spherical morphology. In certain embodiments, the bottlebrush polymer described herein self-assembles to form a lamellar morphology. In certain embodiments, the bottlebrush polymer described herein self-assembles to form an ellipsoidal morphology. In certain embodiments, the bottlebrush polymer described herein self-assembles to form a polyhedral morphology.

Additional Bottlebrush Polymers Having Gyroid Morphologies

[0390] As described herein, the present invention provides new bottlebrush polymers having gyroid morphologies. In certain embodiments, provided herein are bottlebrush polymers of Formula (I):

##STR00129##

and salts thereof, wherein:

[0391] G.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof:

[0392] each of L.sup.1, L.sup.2, L.sup.3, L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;

[0393] each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;

[0394] n is an integer between 1 and 4000, inclusive;

[0395] A is a polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da; and

[0396] B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da;

[0397] wherein the bottlebrush polymer has a gyroid morphology.

[0398] In certain embodiments, G.sup.A is optionally substituted carbocyclylene, optionally substituted heterocyclylene, or a combination thereof. In certain embodiments, G.sup.A is optionally substituted carbocyclylene. In certain embodiments, G.sup.A is optionally substituted heterocyclylene. In certain embodiments, G.sup.A comprises optionally substituted 5-membered carbocyclylene or 5-membered heterocyclylene. In certain embodiments, G.sup.A comprises optionally substituted cyclopentylene, cyclohexylene, tetrahydrofuranylene, tetrahydrothiophenylene, or pyrrolidinylene. In certain embodiments, G.sup.A is optionally substituted bicyclic heterocyclylene. In certain embodiments, G.sup.A is substituted bicyclic heterocyclylene. In certain embodiments, G.sup.A is of the following formula:

##STR00130##

wherein X.sup.A is CH.sub.2, CH.sub.2CH.sub.2, O, or S; and A.sup.R is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In certain embodiments. G.sup.A is of the following formula:

##STR00131##

wherein A.sup.R is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In certain embodiments, G.sup.A is of the following formula:

##STR00132##

wherein X.sup.A is CH.sub.2, CH.sub.2CH.sub.2 O, or S. In certain embodiments, G.sup.A is of the following formula:

##STR00133##

[0399] In certain embodiments, each of L.sup.1 and L.sup.3 is independently a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and combinations thereof. In certain embodiments, each of L.sup.1 and L.sup.3 is optionally substituted alkylene. In certain embodiments, each of L.sup.1 and L.sup.3 is optionally substituted heteroalkylene. In certain embodiments, each of L.sup.1 and L.sup.3 is optionally substituted alkynylene. In certain embodiments, each of L.sup.1 and L.sup.3 is optionally substituted alkenylene. In certain embodiments, each of L.sup.1 and L.sup.3 is substituted alkenylene. In certain embodiments, each of L.sup.1 and L.sup.3 is unsubstituted alkenylene. In certain embodiments, each of L.sup.1 and L.sup.3 is of the formula:

##STR00134##

In certain embodiments, each of L.sup.1 and L.sup.3 is of the formula:

##STR00135##

In certain embodiments, each of L.sup.1 and L.sup.3 is of the formula:

##STR00136##

[0400] In certain embodiments, L.sup.1 is optionally substituted alkylene. In certain embodiments, L.sup.1 is optionally substituted heteroalkylene. In certain embodiments, L.sup.1 is optionally substituted alkynylene. In certain embodiments, L.sup.1 is optionally substituted alkenylene. In certain embodiments, L.sup.1 substituted alkenylene. In certain embodiments, L.sup.1 is unsubstituted alkenylene. In certain embodiments, L.sup.1 is of the formula:

##STR00137##

In certain embodiments, L.sup.1 is of the formula:

##STR00138##

In certain embodiments, L.sup.1 is of the formula:

##STR00139##

[0401] In certain embodiments, L.sup.3 is optionally substituted alkylene. In certain embodiments, L.sup.3 is optionally substituted heteroalkylene. In certain embodiments, L.sup.3 is optionally substituted alkynylene. In certain embodiments, L.sup.3 is optionally substituted alkenylene. In certain embodiments, L.sup.3 substituted alkenylene. In certain embodiments, L.sup.3 is unsubstituted alkenylene. In certain embodiments, L.sup.3 is of the formula:

##STR00140##

In certain embodiments, L.sup.3 is of the formula:

##STR00141##

certain embodiments, L.sup.3 is of the formula:

##STR00142##

[0402] In certain embodiments. L.sup.2 is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.2 is optionally substituted alkylene or optionally substituted heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted alkylene. In certain embodiments, L.sup.2 is optionally substituted heteroalkylene. In certain embodiments, L.sup.2 is unsubstituted alkylene. In certain embodiments, L.sup.2 is unsubstituted heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is unsubstituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is of the formula:

##STR00143##

[0403] In certain embodiments, the bottlebrush polymer of Formula (I) is of Formula (I-a):

##STR00144##

or salts thereof, wherein:

[0404] each of L.sup.2, L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;

[0405] each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;

[0406] n is an integer between 1 and 4000, inclusive;

[0407] A is a polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da; and

[0408] B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da;

[0409] wherein the bottlebrush polymer has a gyroid morphology.

[0410] In certain embodiments, the bottlebrush polymer is of Formula (I-b):

##STR00145##

or salts thereof, wherein:

[0411] each L.sup.A, and L.sup.B is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;

[0412] each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;

[0413] n is an integer between 1 and 4000, inclusive;

[0414] A is a polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da; and

[0415] B is a different polymer having a number average molecular weight of about 1.000 Da to about 20,000 Da:

[0416] wherein the bottlebrush polymer has a gyroid morphology.

[0417] In certain embodiments, L.sup.A is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.A is optionally substituted alkylene. In certain embodiments, L.sup.A is optionally substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted heteroarylene. In certain embodiments, L.sup.A is unsubstituted alkylene. In certain embodiments, L.sup.A is unsubstituted heteroalkylene. In certain embodiments, L.sup.A is substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.A is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.A is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.A is of the formula:

##STR00146##

In certain embodiments, L.sup.A is of the formula:

##STR00147##

##STR00148##

In certain embodiments, L.sup.A is of the formula:

##STR00149##

[0418] In certain embodiments, L.sup.B is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.B is optionally substituted alkylene. In certain embodiments, L.sup.B is optionally substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted heteroarylene. In certain embodiments, L.sup.B is unsubstituted alkylene. In certain embodiments, L.sup.B is unsubstituted heteroalkylene. In certain embodiments, L.sup.B is substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments. L.sup.B is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.B is of the formula:

##STR00150##

In certain embodiments, L.sup.B is of the formula:

##STR00151##

In certain embodiments, L.sup.B is unsubstituted heteroarylalkylene. In certain embodiments, L.sup.B is optionally substituted heteroarylalkylene. In certain embodiments. L.sup.B is an unsubstituted 5-membered heteroarylalkylene. In certain embodiments. L.sup.B comprises a triazole. In certain embodiments, L.sup.B comprises a group of the formula:

##STR00152##

In certain embodiments, L.sup.B is of the formula:

##STR00153##

[0419] In certain embodiments, L.sup.2 is optionally substituted alkylene or optionally substituted heteroalkylene; L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene; and L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene. In certain embodiments, L.sup.2 is optionally substituted heteroalkylene; L.sup.A is optionally substituted heteroalkylene; and L.sup.B is optionally substituted heteroarylalkylene. In certain embodiments, L.sup.2 is unsubstituted heteroalkylene; L.sup.A is unsubstituted heteroalkylene; and L.sup.B is substituted heteroarylalkylene. In certain embodiments, L.sup.2 is unsubstituted C.sub.1-10 heteroalkylene; L.sup.A is substituted C.sub.1-10 heteroalkylene; and L.sup.B is an unsubstituted 5-membered heteroarylalkylene.

[0420] In certain embodiments, L.sup.2 is of the formula:

##STR00154##

L.sup.A is of the formula:

##STR00155##

and L.sup.B is of the formula:

##STR00156##

[0421] In certain embodiments, L.sup.2 is of the formula:

##STR00157##

L.sup.A is of the formula:

##STR00158##

and L.sup.B is of the formula:

##STR00159##

[0422] In certain embodiments, L.sup.2 is of the formula:

##STR00160##

L.sup.A is of the formula:

##STR00161##

and L.sup.B is of the formula:

##STR00162##

[0423] In certain embodiments, L.sup.2 is of the formula:

##STR00163##

L.sup.A is of the formula:

##STR00164##

and L.sup.B is of the formula:

##STR00165##

[0424] In certain embodiments, n is an integer between 1 and 4000, inclusive. In certain embodiments, n is an integer between 5 and 4000, inclusive. In certain embodiments, n is an integer is between 50 and 4000, inclusive. In certain embodiments, n is an integer between 100 and 4000, inclusive. In certain embodiments, n is an integer between 1000 and 4000, inclusive. In certain embodiments, n is an integer between 2000 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 2000, inclusive. In certain embodiments, n is an integer between 2 and 1000, inclusive. In certain embodiments, n is an integer between 10 and 1000, inclusive. In certain embodiments, n is an integer between 2 and 100, inclusive. In certain embodiments, n is an integer between 10 and 100, inclusive. In certain embodiments, n is an integer between 10 and 50, inclusive. In certain embodiments, n is an integer between 25 and 50, inclusive. In certain embodiments, n is an integer between 25 and 100, inclusive. In certain embodiments, n is about 10, about 25, about 50, or about 100. In certain embodiments, the average of n is about 10, about 25, about 50, or about 100. In certain embodiments, the average of n is about 25 or about 50. In certain embodiments, the average of n is about 10. In certain embodiments, the average of n is about 25. In certain embodiments, the average of n is about 50. In certain embodiments, the average of n is about 100. In certain embodiments, n is the same as the degree of polymerization of the polymer.

[0425] In certain embodiments, each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thiol. In certain embodiments, T.sup.1 is hydrogen. In certain embodiments, T.sup.1 is halogen. In certain embodiments, T.sup.1 is optionally substituted alkyl. In certain embodiments, T.sup.1 is optionally substituted alkenyl. In certain embodiments, T.sup.1 is optionally substituted alkynyl. In certain embodiments, T.sup.1 is optionally substituted carbocyclyl. In certain embodiments, T.sup.1 is optionally substituted heterocyclyl. In certain embodiments, T.sup.1 is optionally substituted aryl. In certain embodiments, T.sup.1 is optionally substituted heteroaryl. In certain embodiments, T.sup.1 is optionally substituted acyl. In certain embodiments, T.sup.1 is optionally substituted hydroxyl. In certain embodiments, T.sup.1 is optionally substituted amino. In certain embodiments, T.sup.1 is optionally substituted thiol. In certain embodiments, T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is halogen. In certain embodiments. T.sup.2 is optionally substituted alkyl. In certain embodiments, T.sup.2 is optionally substituted alkenyl. In certain embodiments, T.sup.2 is optionally substituted alkynyl. In certain embodiments, T.sup.2 is optionally substituted carbocyclyl. In certain embodiments, T.sup.2 is optionally substituted heterocyclyl. In certain embodiments, T.sup.2 is optionally substituted aryl. In certain embodiments, T.sup.2 is optionally substituted heteroaryl. In certain embodiments, T.sup.2 is optionally substituted acyl. In certain embodiments, T.sup.2 is optionally substituted hydroxyl. In certain embodiments, T.sup.2 is optionally substituted amino. In certain embodiments, T.sup.2 is optionally substituted thiol. In certain embodiments, both T.sup.1 and T.sup.2 are hydrogen.

[0426] In certain embodiments, T.sup.1 is optionally substituted aryl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.1 is phenyl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is optionally substituted aryl, and T.sup.1 is hydrogen. In certain embodiments. T.sup.2 is phenyl, and T.sup.1 is hydrogen.

[0427] As defined herein, A is a polymer. In certain embodiments, A is a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer. The polyacrylate may be any polyester described herein. The polyester may be any polyester described herein. The polyether may be any polyether described herein. The polyacrylamide may be any polyacrylamide described herein. Additionally, the vinyl polymer may be any vinyl polymer described herein.

[0428] In certain embodiments, A is a polyether selected from the group consisting of polyethylene glycol (PEG), polyoxymethylene (POM), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), poly(ethyl ethylene) phosphate (PEEP), and poly(oxazoline). In certain embodiments, A is polyethylene glycol (PEG). In certain embodiments, A is a polyester. In certain embodiments, A is a polyester selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), poly(lactic-co-glycolic acid) (PLGA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutryate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). In certain embodiments, A is polylactic acid (PLA). In certain embodiments, A is polyglycolic acid (PGA) or poly(lactic-co-glycolic acid) (PLGA). In certain embodiments, A is a polyacrylamide. In certain embodiments, A is a poly(N-alkylacrylamide). In certain embodiments, A is poly(N-isopropylacrylamide). In certain embodiments, A is a vinyl polymer. In certain embodiments, A is a vinyl polymer selected from the group consisting of polystyrene, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyvinyl acetate, polyvinyl alcohol, and polyacrylonitrile. In certain embodiments, A is polystyrene. In certain embodiments, A is a polyacrylate. In certain embodiments, A is a polyacrylate selected from the group consisting of poly(methyl methacrylate), poly(methyl acrylate), poly(methacrylate), poly(hydroxyethyl methacrylate), poly(n-butyl acrylate), and poly(tert-butyl acrylate). In certain embodiments, A is poly(tert-butyl acrylate).

[0429] As defined herein, B is a polymer (e.g., a different polymer than polymer A). In certain embodiments, B is a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer. The polyacrylate may be any polyester described herein. The polyester may be any polyester described herein. The polyether may be any polyether described herein. The polyacrylamide may be any polyacrylamide described herein. Additionally, the vinyl polymer may be any vinyl polymer described herein.

[0430] In certain embodiments, B is a polyether selected from the group consisting of polyethylene glycol (PEG), polyoxymethylene (POM), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), poly(ethyl ethylene) phosphate (PEEP), and poly(oxazoline). In certain embodiments. B is polyethylene glycol (PEG). In certain embodiments, B is a polyester. In certain embodiments, B is a polyester selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), poly(lactic-co-glycolic acid) (PLGA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutryate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). In certain embodiments. B is polylactic acid (PLA). In certain embodiments, B is polyglycolic acid (PGA) or poly(lactic-co-glycolic acid) (PLGA). In certain embodiments, B is a polyacrylamide. In certain embodiments, B is a poly(N-alkylacrylamide). In certain embodiments. B is poly(N-isopropylacrylamide). In certain embodiments, B is a vinyl polymer. In certain embodiments, B is a vinyl polymer selected from the group consisting of polystyrene, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyvinyl acetate, polyvinyl alcohol, and polyacrylonitrile. In certain embodiments, B is polystyrene. In certain embodiments. B is a polyacrylate. In certain embodiments. B is a polyacrylate selected from the group consisting of poly(methyl methacrylate), poly(methyl acrylate), poly(methacrylate), poly(hydroxyethyl methacrylate), poly(n-butyl acrylate), and poly(tert-butyl acrylate). In certain embodiments, B is poly(tert-butyl acrylate).

[0431] In certain embodiments, A is a polyester; and B is a different polymer. In certain embodiments. A is a polyester having a number average molecular weight of about 1,000 Da to about 20,000 Da; and B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da. In certain embodiments, A is PLA; and B is a different polymer. In certain embodiments, A is PLA having a number average molecular weight of about 1,000 Da to about 20,000 Da; and B is a different polymer having a number average molecular weight of about 1.000 Da to about 20,000 Da.

[0432] In certain embodiments, B is a vinyl polymer; and A is a different polymer. In certain embodiments, B is a vinyl polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da; and A is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da. In certain embodiments, B is polystyrene; and A is a different polymer. In certain embodiments, B is polystyrene having a number average molecular weight of about 1,000 Da to about 20,000 Da; and A is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.

[0433] In certain embodiments, A is a polyester; and B is a vinyl polymer. In certain embodiments, A is a polyester having a number average molecular weight of about 1,000 Da to about 20,000 Da; and B is vinyl polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da. In certain embodiments, A is PLA; and B is polystyrene. In certain embodiments, A is PLA having a number average molecular weight of about 1,000 Da to about 20,000 Da; and B is polystyrene having a number average molecular weight of about 1,000 Da to about 20,000 Da.

[0434] In certain embodiments, A is a polyester of the following formula:

##STR00166##

wherein:

[0435] R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl:

[0436] R.sup.9 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group; and

[0437] s is an integer between 5 and 2000, inclusive.

[0438] In certain embodiments, R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl. In certain embodiments, R.sup.8 is hydrogen. In certain embodiments, R.sup.8 is optionally substituted alkyl. In certain embodiments, R.sup.8 is optionally substituted alkenyl. In certain embodiments, R.sup.8 is optionally substituted alkynyl. In certain embodiments, R.sup.8 is optionally substituted aryl. In certain embodiments, R.sup.8 is optionally substituted heteroaryl In certain embodiments, R.sup.8 is optionally substituted carbocyclyl. In certain embodiments, R.sup.8 is optionally substituted heterocyclyl. In certain embodiments, R.sup.8 is optionally substituted acyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.8 is methyl.

[0439] In certain embodiments, R.sup.9 hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group. In certain embodiments, R.sup.9 is hydrogen. In certain embodiments. R.sup.9 is optionally substituted alkyl. In certain embodiments, R.sup.9 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.9 is optionally substituted alkenyl. In certain embodiments, R.sup.9 is optionally substituted alkynyl. In certain embodiments, R.sup.9 is optionally substituted aryl. In certain embodiments, R.sup.9 is optionally substituted heteroaryl. In certain embodiments, R.sup.9 is optionally substituted carbocyclyl. In certain embodiments, R.sup.9 is optionally substituted heterocyclyl. In certain embodiments, R.sup.9 is optionally substituted acyl. In certain embodiments, R.sup.9 is an oxygen protecting group.

[0440] In certain embodiments, s is an integer between 5 and 2000, inclusive. In certain embodiments, s is an integer between 5 and 1000, inclusive. In certain embodiments, s is an integer between 5 and 500, inclusive. In certain embodiments, s is an integer between 5 and 200, inclusive. In certain embodiments, s is an integer between 5 and 100, inclusive. In certain embodiments, s is an integer between 10 and 100, inclusive.

[0441] In certain embodiments, the polyester is poly(lactic acid). In certain embodiments, the polyester is poly(lactic acid) having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2.000 Da to about 10,000 Da, about 2,000 Da to about 7,000 Da, or about 2,000 Da to about 4,000 Da. In certain embodiments, the number average molecular weight is 3,000 to 4,000 Da.

[0442] In certain embodiments, B is a vinyl polymer of the following formula:

##STR00167##

wherein:

[0443] R.sup.3 is optionally substituted alkyl, halogen, hydrogen, cyano, OR.sup.a, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0444] R.sup.4 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0445] R.sup.a is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0446] r is an integer between 5 and 2000, inclusive.

[0447] In certain embodiments. R.sup.3 is hydrogen. In certain embodiments, R.sup.3 is optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted alkenyl. In certain embodiments, R.sup.3 is optionally substituted alkynyl. In certain embodiments, R.sup.3 is optionally substituted aryl. In certain embodiments, R.sup.3 is optionally substituted heteroaryl. In certain embodiments, R.sup.3 is cyano. In certain embodiments. R.sup.3 is halogen. In certain embodiments, R.sup.3 is OR.sup.a, wherein R.sup.a is hydrogen or optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted phenyl. In certain embodiments, R.sup.3 is unsubstituted phenyl.

[0448] In certain embodiments, R.sup.4 is optionally substituted alkyl. In certain embodiments, R.sup.4 is optionally substituted alkenyl. In certain embodiments, R.sup.4 is optionally substituted alkynyl. In certain embodiments. R.sup.4 is optionally substituted aryl. In certain embodiments, R.sup.4 is optionally substituted heteroaryl. In certain embodiments, R.sup.4 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is C.sub.1-6 alkyl substituted with an ester group.

[0449] In certain embodiments, r is an integer between 5 and 500, inclusive. In certain embodiments, r is an integer between 5 and 100, inclusive. In certain embodiments, r is an integer between 10 and 100, inclusive. In certain embodiments, r is an integer between 10 and 50, inclusive. In certain embodiments, r is an integer between 20 and 40, inclusive. In certain embodiments, r is an integer between 30 and 40, inclusive.

[0450] In certain embodiments, R.sup.3 is optionally substituted aryl; R.sup.4 is optionally substituted C.sub.1-6 alkyl; and r is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.3 is unsubstituted aryl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive. In certain embodiments, R.sup.3 is unsubstituted phenyl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive.

[0451] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 10.000 Da to about 15,000 Da, about 2,000 Da to about 10.000 Da, about 7,000 Da to about 10,000 Da, about 8,000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3,000 Da, or about 2,500 Da to about 3,600 Da. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 4,000 Da to about 5,000 Da.

[0452] In certain embodiments, the ratio of A:B, by weight, is about 1:1, about 1:1.1, about 1:1.2, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.5, about 1:3, about 1:3.5, about 1:4, about 1:1.4, or about 1:5. In certain embodiments, the ratio of A:B, by weight, is about 1:1.2, 1:1.21, 1:1.23, 1:1.24, 1:1.25, 1:1.26, 1:1.27, or 1:1.29. In certain embodiments, the ratio of A:B, by weight, is about 1:1.25.

[0453] In certain embodiments, the ratio of PLA:PS, by weight, is about 1:1, about 1:1.1, about 1:1.2, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.5, about 1:3, about 1:3.5, about 1:4, about 1:1.4, or about 1:5. In certain embodiments, the ratio of PLA:PS, by weight, is about 1:1.2, 1:1.21, 1:1.23, 1:1.24, 1:1.25, 1:1.26, 1:1.27, or 1:1.29. In certain embodiments, the ratio of PLA:PS, by weight, is about 1:1.25.

[0454] In certain embodiments, A is of the formula:

##STR00168##

and B is of the formula:

##STR00169##

wherein R.sup.3, R.sup.4, R.sup.8, R.sup.9, s and r are as defined in the embodiments of Formula (I); and the ratio of s:r is about 1:1.1, about 1:1.2, about 1:1.25, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.1, about 1:2.2, about 1:2.3, about 1:2.4, about 1:2.5, about 1:2.6, about 1:2.7, about 1:2.8, about 1:2.9, about 1:3, about 1:4, about 1:5, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0455] In certain embodiments, A is of the formula:

##STR00170##

and B is of the formula:

##STR00171##

wherein R.sup.3, R.sup.4. R.sup.9, s and r are as defined in the embodiments of Formula (I); and the ratio of s:r is about 1:1.1, about 1:1.2, about 1:1.25, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.1, about 1:2.2, about 1:2.3, about 1:2.4, about 1:2.5, about 1:2.6, about 1:2.7, about 1:2.8, about 1:2.9, about 1:3, about 1:4, about 1:5, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0456] In certain embodiments, A is of the formula:

##STR00172##

and B is of the formula:

##STR00173##

wherein R.sup.4, R.sup.8, R.sup.9, s and r are as defined in the embodiments of Formula (I); and the ratio of s:r is about 1:1.1, about 1:1.2, about 1:1.25, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.1, about 1:2.2, about 1:2.3, about 1:2.4, about 1:2.5, about 1:2.6, about 1:2.7, about 1:2.8, about 1:2.9, about 1:3, about 1:4, about 1:5, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0457] In certain embodiments, A is of the formula:

##STR00174##

and B is of the formula:

##STR00175##

wherein R.sup.4, R.sup.9, s and r are as defined in the embodiments of Formula (I); and the ratio of s:r is about 1:1.1, about 1:1.2, about 1:1.25, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.1, about 1:2.2, about 1:2.3, about 1:2.4, about 1:2.5, about 1:2.6, about 1:2.7, about 1:2.8, about 1:2.9, about 1:3, about 1:4, about 1:5, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0458] In certain embodiments, A is of the formula:

##STR00176##

and B is of the formula:

##STR00177##

wherein s and r are as defined in the embodiments of Formula (I); and the ratio of s:r is about 1:1.1, about 1:1.2, about 1:1.25, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, about 1:1.9, about 1:2, about 1:2.1, about 1:2.2, about 1:2.3, about 1:2.4, about 1:2.5, about 1:2.6, about 1:2.7, about 1:2.8, about 1:2.9, about 1:3, about 1:4, about 1:5, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 4:1, or about 5:1. In certain embodiments, any of these parameters lead to a BBCP with gyroid morphology.

[0459] In certain embodiments, the bottlebrush polymer of Formula (I), having a gyroid morphology, is of Formula (I-aa):

##STR00178##

or a salt thereof, wherein:

[0460] each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl:

[0461] n is an integer between 10 and 100, inclusive;

[0462] s is an integer between 10 and 100, inclusive; and

[0463] r is an integer between 10 and 100, inclusive.

[0464] In certain embodiments, the bottlebrush polymer of Formula (I), having a gyroid morphology, is of Formula (I-bb):

##STR00179##

or a salt thereof, wherein:

[0465] each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl:

[0466] n is an integer between 10 and 100, inclusive;

[0467] s is an integer between 10 and 100, inclusive; and

[0468] r is an integer between 10 and 100, inclusive.

Diblock Bottlebrush Copolymers

[0469] Another aspect of the present invention relates to diblock bottlebrush copolymers. In certain embodiments, the polymer is an AB diblock bottlebrush copolymer comprising a Block A polymer, and a Block B polymer. A diblock bottlebrush copolymer of the present disclosure comprises a backbone polymer of repeating units covalently linked to polymeric sidechains; wherein Block A and Block B of the copolymer comprise polymeric sidechains covalently linked to the repeating units of the backbone polymer. In certain embodiments, at least one of Block A and Block B comprise repeating units linked to at least two different polymeric sidechains.

[0470] The diblock bottlebrush copolymers provided herein are AB diblock bottlebrush copolymers, meaning that at least one polymeric sidechain of Block A is different from the polymeric sidechains of Block B. In the converse, at least one polymeric sidechain of Block B is different from the polymeric sidechains of Block A. In certain embodiments, Block A comprises repeating units covalently linked to at least two polymeric sidechains and Block B comprises repeating units covalently linked to at least two polymeric sidechains. In other embodiments. Block A comprises repeating units covalently linked to one polymeric sidechain and Block B comprises repeating units covalently linked to at least two polymeric sidechains. In other embodiments, Block B comprises repeating units covalently linked to one polymeric sidechain and Block A comprises repeating units covalently linked to at least two polymeric sidechains. In other embodiments, the polymeric sidechains of Blocks A and B each are of a different polymer class. Further, any two polymeric sidechains of Blocks A and B may be of the same or different length, or of the same or different molecular weight.

[0471] The diblock bottlebrush copolymers provided herein comprise a backbone polymer of repeating units (backbone units). The repeating backbone units of any two of Blocks A and B may be the same or different. Further, any two of Blocks A and B may comprise the same or a different number of repeating backbone units. In certain embodiments, each of Blocks A and B independently comprise 1 to 4000 repeating backbone units, inclusive. In certain embodiments, each of Blocks A and B independently comprise 2 to 4000 repeating backbone units, inclusive. In certain embodiments, each of Blocks A and B independently comprise 2 to 2000 repeating backbone units, inclusive. In certain embodiments, each of Blocks A and B independently comprise 2 to 1000 repeating backbone units, inclusive. In certain embodiments, each of Blocks A and B independently comprise 2 to 500 repeating backbone units, inclusive. In certain embodiments, each of Blocks A and B independently comprise 2 to 200 repeating backbone units, inclusive. In certain embodiments, each of Blocks A and B independently comprise 2 to 100 repeating backbone units, inclusive. In certain embodiments, each of Blocks A and B independently comprise 10 to 100 repeating backbone units, inclusive. In certain embodiments, each of Blocks A and B independently comprise 10 to 50 repeating backbone units, inclusive.

[0472] The backbone units may be derived from polymerization of a monomer including substituted or unsubstituted norbomene, olefin, cyclic olefin, norbomene anhydride, cyclooctene, cyclopentadiene, styrene or acrylate. Some backbone units useful in the present disclosure may be obtained from a ring opening metathesis polymerization (ROMP) reaction.

[0473] The polymeric sidechains of Block A, and Block B of the diblock bottlebrush copolymer may comprise any polymer. Examples of classes of polymers include, but are not limited to, vinyl polymers (e.g., polystyrene), polyethylenes (e.g., polyethylene, polytetrafluoroethylene), polypropylenes, polyacetylenes, polyethers (e.g., polyethylene glycol, polyoxymethylene, polypropylene glycol, polytetramethylene glycol, poly(ethyl ethylene) phosphate, poly(oxazoline)), polyamines, polyesters (e.g., polyglycolic acid, polylactic acid, poly(lactic-co-glycolic acid), polycaprolactone, polyhydroxyalkanoate, polyhydroxybutryate, polyethylene adipate, polybutylene succinate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polysilanes, polysiloxanes (e.g., polydimethylsiloxane), polyacrylates (e.g., polymethacrylate, poly(n-butyl acrylate), poly(tert-butyl acrylate)), polylactides (e.g., polylactic acid), polyamino acids, polypeptides, polyamides, polyacrylamides (e.g., polymethylacrylamide), and polysaccharides. The polymeric sidechains may be homopolymers or copolymers. The polymeric sidechains may be linear or branched. In certain embodiments, the polymeric sidechains are linear. In certain embodiments, the polymeric sidechains are branched.

[0474] In certain embodiments, one or more of Block A and Block B of the diblock bottlebrush copolymer comprise polyester sidechains. In certain embodiments, Block A of the diblock bottlebrush copolymer comprises polyester sidechains. In certain embodiments, Block B of the diblock bottlebrush copolymer comprises polyester sidechains. Examples of polyesters include, but are not limited to, polyglycolic acid (PGA), polylactic acid (PLA), poly(lactic-co-glycolic acid) (PLGA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutryate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), or poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). In certain embodiments, the diblock bottlebrush copolymer comprises polylactic acid (PLA) sidechains. In certain embodiments, the diblock bottlebrush copolymer comprises polyglycolic acid (PGA) or poly(lactic-co-glycolic acid) (PLGA) sidechains. In certain embodiments, Block A of the diblock bottlebrush copolymer comprises a polylactic acid (PLA), polyglycolic acid (PGA), or poly(lactic-co-glycolic acid) (PLGA) sidechain. In certain embodiments, Block A of the diblock bottlebrush copolymer comprises PLA sidechains. In certain embodiments, Block B of the diblock bottlebrush copolymer comprises PLA sidechains.

[0475] In certain embodiments, one or more of Block A and Block B of the diblock bottlebrush copolymer comprise polyether sidechains. In certain embodiments. Block B of the diblock bottlebrush copolymer comprises polyether sidechains. In certain embodiments, Block A of the diblock bottlebrush copolymer comprises polyether sidechains. Examples of polyethers include, but are not limited to, polyethylene glycol (PEG), polyoxymethylene (POM), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), poly(ethyl ethylene) phosphate (PEEP), and poly(oxazoline). In certain embodiments, the diblock bottlebrush copolymer comprises polyethylene glycol (PEG) sidechains.

[0476] In certain embodiments, at least one of Block A and Block B of the diblock bottlebrush copolymer comprises polysiloxane sidechains. In certain embodiments, the polysiloxane is polydimethylsiloxane (PDMS). In certain embodiments. Block A comprises polydimethylsiloxane sidechains. In certain embodiments, Block B comprises polydimethylsiloxane sidechains.

[0477] In certain embodiments, the diblock bottlebrush copolymer comprises polyacrylamide sidechains. In certain embodiments, the diblock bottlebrush copolymer comprises poly(N-alkylacrylamide) sidechains. In certain embodiments, the diblock bottlebrush copolymer comprises poly(N-isopropylacrylamide) (PNIPAM) sidechains. In certain embodiments, Block A comprises poly(N-alkylacrylamide) sidechains. In certain embodiments, Block B comprises poly(N-alkylacrylamide) sidechains.

[0478] In certain embodiments, the diblock bottlebrush copolymer comprises vinyl polymer sidechains. Examples of vinyl polymers include, but are not limited to, polystyrene, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyvinyl acetate, polyvinyl alcohol, and polyacrylonitrile. In certain embodiments, Block A comprises polystyrene sidechains. In certain embodiments, Block B comprises polystyrene sidechains.

[0479] In certain embodiments, the diblock bottlebrush copolymer comprises polyacrylate sidechains. Examples of polyacrylates include, but are not limited to, poly(methyl methacrylate), poly(methyl acrylate), poly(methacrylate), poly(hydroxyethyl methacrylate), poly(n-butyl acrylate), and poly(tert-butyl acrylate). In certain embodiments, Block A comprises poly(tert-butyl acrylate) sidechains. In certain embodiments, Block B comprises poly(tert-butyl acrylate) sidechains.

[0480] In certain embodiments, the diblock bottlebrush copolymer comprises polysiloxane sidechains, polyester sidechains, and vinyl polymer sidechains. In certain embodiments, the diblock bottlebrush copolymer comprises polysiloxane sidechains, polyacrylate sidechains, polyester sidechains, and vinyl polymer sidechains. In certain embodiments, the diblock bottlebrush copolymer comprises polydimethylsiloxane sidechains, poly(lactic acid) sidechains, and polystyrene sidechains. In certain embodiments, the diblock bottlebrush copolymer comprises polydimethylsiloxane sidechains, poly(tert-butylacrylate) sidechains, poly(lactic acid) sidechains, and polystyrene sidechains.

[0481] The polymeric sidechains of Blocks A and B may be of any molecular weight. In certain embodiments, the polymeric sidechains of Blocks A and B each independently have a number average molecular weight of about 50 to about 10000 Da, about 100 to about 10000 Da, about 500 to about 10000 Da, about 1000 to about 10000 Da, about 2000 to about 10000 Da, about 2000 to about 7000 Da, about 2000 to about 4000 Da, about 3000 to about 4000 Da. or about 4000 to about 6000 Da; each range being inclusive.

[0482] In certain embodiments, one block of the copolymer comprises repeating units of the backbone linked to at least two different polymeric sidechains. In certain embodiments, each block of the copolymer comprises repeating units of the backbone linked to at least two different polymeric sidechains.

[0483] In certain embodiments, the diblock bottlebrush copolymer is of Formula (II):

##STR00180##

or salts thereof, wherein:

[0484] each of G.sup.A and G.sup.B is independently optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof;

[0485] each of L.sup.1, L.sup.2, L.sup.3, L.sup.4, and L.sup.5 is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof:

[0486] each of L.sup.A, L.sup.B, L.sup.C, and L.sup.D is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;

[0487] each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;

[0488] n is an integer between 1 and 4000, inclusive;

[0489] m is an integer between 1 and 4000, inclusive; and

[0490] each of A, B, C, and D is independently a polymer or hydrogen.

[0491] In certain embodiments, no more than one of A, B, C. or D is hydrogen. In certain embodiments, no more than two of A, B, C, or D is the same polymer. In certain embodiments, none of A, B, C, or D is the same polymer. In certain embodiments, at least one of A, B, C, or D is a polysiloxane.

[0492] In certain embodiments, G.sup.A is optionally substituted carbocyclylene, optionally substituted heterocyclylene, or a combination thereof. In certain embodiments, G.sup.A is optionally substituted carbocyclylene. In certain embodiments, G.sup.A is optionally substituted heterocyclylene. In certain embodiments, G.sup.A comprises optionally substituted 5-membered carbocyclylene or 5-membered heterocyclylene. In certain embodiments, G.sup.A comprises optionally substituted cyclopentylene, cyclohexylene, tetrahydrofuranylene, tetrahydrothiophenylene, or pyrrolidinylene. In certain embodiments, G.sup.A is optionally substituted bicyclic heterocyclylene. In certain embodiments, G.sup.A is substituted bicyclic heterocyclylene. In certain embodiments, G.sup.A is of the following formula:

##STR00181##

wherein X.sup.A is CH.sub.2, CH.sub.2CH.sub.2, O, or S; and AR is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In certain embodiments, G.sup.A is of the following formula:

##STR00182##

wherein A.sup.R is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In certain embodiments, G.sup.A is of the following formula:

##STR00183##

wherein X.sup.A is CH.sub.2, CH.sub.2CH.sub.2, O, or S. In certain embodiments. G.sup.A is of the following formula:

##STR00184##

[0493] In certain embodiments. G.sup.B is optionally substituted carbocyclylene, optionally substituted heterocyclylene, or a combination thereof. In certain embodiments, G.sup.B is optionally substituted carbocyclylene. In certain embodiments, G.sup.B is optionally substituted heterocyclylene. In certain embodiments, G.sup.B is optionally substituted bicyclic heterocyclylene. In certain embodiments, G.sup.B comprises optionally substituted 5-membered carbocyclylene or 5-membered heterocyclylene. In certain embodiments, G.sup.B comprises optionally substituted cyclopentylene, cyclohexylene, tetrahydrofuranylene, tetrahydrothiophenylene, or pyrrolidinylene. In certain embodiments, G.sup.B is substituted bicyclic heterocyclylene. In certain embodiments, G.sup.B is of the following formula:

##STR00185##

wherein X.sup.B is CH.sub.2, CH.sub.2CH.sub.2, O, or S; and B.sup.R is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In certain embodiments, G.sup.B is of the following formula:

##STR00186##

wherein B.sup.R is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In certain embodiments, G.sup.B is of the following formula:

##STR00187##

wherein X.sup.B is CH.sub.2, CH.sub.2CH.sub.2, O, or S. In certain embodiments, G.sup.B is of the following formula:

##STR00188##

[0494] In certain embodiments, G.sup.A and G.sup.B are the same. In certain embodiments, each of G.sup.A and G.sup.B is independently optionally substituted carbocyclylene, optionally substituted heterocyclylene, or a combination thereof. In certain embodiments, each of G.sup.A and G.sup.B is of the following formula:

##STR00189##

[0495] In certain embodiments, G.sup.A and G.sup.B are different, as defined in the embodiments of Formula (II) above.

[0496] In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is independently a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, and combinations thereof. In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is optionally substituted alkylene. In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is optionally substituted heteroalkylene. In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is optionally substituted alkynylene. In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is optionally substituted alkenylene. In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is substituted alkenylene. In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is unsubstituted alkenylene. In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is of the formula:

##STR00190##

In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is of the formula:

##STR00191##

In certain embodiments, each of L.sup.1, L.sup.3, and L.sup.5 is of the formula:

##STR00192##

[0497] In certain embodiments, L.sup.1 is optionally substituted alkylene. In certain embodiments, L.sup.1 is optionally substituted heteroalkylene. In certain embodiments, L.sup.1 is optionally substituted alkynylene. In certain embodiments, L.sup.1 is optionally substituted alkenylene. In certain embodiments, L.sup.1 substituted alkenylene. In certain embodiments. L.sup.1 is unsubstituted alkenylene. In certain embodiments. L.sup.1 is of the formula:

##STR00193##

In certain embodiments, L.sup.1 is of the formula:

##STR00194##

In certain embodiments, L.sup.1 is of the formula:

##STR00195##

[0498] In certain embodiments, L.sup.3 is optionally substituted alkylene. In certain embodiments. L.sup.3 is optionally substituted heteroalkylene. In certain embodiments, L.sup.3 is optionally substituted alkynylene. In certain embodiments, L.sup.3 is optionally substituted alkenylene. In certain embodiments, L.sup.3 substituted alkenylene. In certain embodiments, L.sup.3 is unsubstituted alkenylene. In certain embodiments, L.sup.3 is of the formula:

##STR00196##

In certain embodiments, L.sup.3 is of the formula:

##STR00197##

In certain embodiments, L.sup.3 is of the formula

##STR00198##

[0499] In certain embodiments, L.sup.5 is optionally substituted alkylene. In certain embodiments, L.sup.5 is optionally substituted heteroalkylene. In certain embodiments, L.sup.5 is optionally substituted alkynylene. In certain embodiments, L.sup.5 is optionally substituted alkenylene. In certain embodiments, L.sup.5 substituted alkenylene. In certain embodiments, L.sup.5 is unsubstituted alkenylene. In certain embodiments, L.sup.5 is of the formula:

##STR00199##

In certain embodiments, L.sup.5 is of the formula:

##STR00200##

In certain embodiments, L.sup.5 is of the formula:

##STR00201##

[0500] In certain embodiments, L.sup.2 is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.2 is optionally substituted alkylene or optionally substituted heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted alkylene. In certain embodiments, L.sup.2 is optionally substituted heteroalkylene. In certain embodiments, L.sup.2 is unsubstituted alkylene. In certain embodiments, L.sup.2 is of the formula:

##STR00202##

certain embodiments, L.sup.2 is unsubstituted heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.2 is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is unsubstituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is of the formula:

##STR00203##

In certain embodiments, L.sup.2 is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.2 is of the formula:

##STR00204##

[0501] In certain embodiments. L.sup.4 is a linker selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.4 is optionally substituted alkylene or optionally substituted heteroalkylene. In certain embodiments, L.sup.4 is optionally substituted alkylene. In certain embodiments, L.sup.4 is optionally substituted heteroalkylene. In certain embodiments, L.sup.4 is unsubstituted alkylene. In certain embodiments. L.sup.4 is of the formula:

##STR00205##

In certain embodiments, L.sup.4 is unsubstituted heteroalkylene. In certain embodiments, L is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.4 is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.4 is unsubstituted C.sub.1-10 heteroalkylene. In certain embodiments. L.sup.4 is of the formula:

##STR00206##

In certain embodiments, L.sup.4 is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.4 is of the formula:

##STR00207##

[0502] In certain embodiments, each of L.sup.2 and L.sup.4 is independently optionally substituted alkylene or optionally substituted heteroalkylene.

[0503] In certain embodiments, L.sup.2 is substituted C.sub.1-10 heteroalkylene, and L.sup.4 is unsubstituted C.sub.1-10 heteroalkylene.

[0504] In certain embodiments, L.sup.2 is of the formula:

##STR00208##

and L.sup.4 is of the formula:

##STR00209##

[0505] In certain embodiments. L.sup.A is a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.A is a bond. In certain embodiments, L.sup.A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.A is optionally substituted alkylene. In certain embodiments, L.sup.A is optionally substituted heteroalkylene. In certain embodiments, L.sup.A is optionally substituted heteroarylene. In certain embodiments, L.sup.A is unsubstituted alkylene. In certain embodiments, L.sup.A is unsubstituted heteroalkylene. In certain embodiments. L.sup.A is substituted heteroalkylene. In certain embodiments, L is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.A is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.A is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.A is of the formula:

##STR00210##

certain embodiments. L.sup.A is of the formula:

##STR00211##

##STR00212##

In certain embodiments, L.sup.A is of the formula:

##STR00213##

[0506] In certain embodiments. L.sup.B is a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments. L.sup.B is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.B is optionally substituted alkylene. In certain embodiments, L.sup.B is optionally substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted heteroarylene. In certain embodiments, L.sup.B is unsubstituted alkylene. In certain embodiments, L.sup.B is unsubstituted heteroalkylene. In certain embodiments, L.sup.B is substituted heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.B is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.B is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.B is of the formula:

##STR00214##

In certain embodiments, L.sup.B is of the formula:

##STR00215##

##STR00216##

In certain embodiments. L.sup.B is of the formula:

##STR00217##

[0507] In certain embodiments, L.sup.C is a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.C is a bond. In certain embodiments, L.sup.c is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.C is optionally substituted alkylene. In certain embodiments, L.sup.c is optionally substituted heteroalkylene. In certain embodiments, L.sup.C is optionally substituted heteroarylene. In certain embodiments, L.sup.C is unsubstituted alkylene. In certain embodiments, L.sup.c is unsubstituted heteroalkylene. In certain embodiments, L.sup.C is substituted heteroalkylene. In certain embodiments, L.sup.c is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.A is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.C is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.C is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.C is of the formula:

##STR00218##

In certain embodiments, L.sup.c is of the formula:

##STR00219##

In certain embodiments, L.sup.c is unsubstituted heteroarylalkylene. In certain embodiments, L.sup.c is optionally substituted heteroarylalkylene. In certain embodiments, L.sup.C is an unsubstituted 5-membered heteroarylalkylene. In certain embodiments, L.sup.C comprises a triazole. In certain embodiments, L.sup.C comprises a group of the formula:

##STR00220##

In certain embodiments, L.sup.c is of the formula:

##STR00221##

[0508] In certain embodiments, L.sup.D is a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. In certain embodiments, L.sup.D is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene. In certain embodiments, L.sup.D is optionally substituted alkylene. In certain embodiments, L.sup.D is optionally substituted heteroalkylene. In certain embodiments, L.sup.D is optionally substituted heteroarylene. In certain embodiments, L.sup.D is unsubstituted alkylene. In certain embodiments, L.sup.D is unsubstituted heteroalkylene. In certain embodiments, L.sup.D is substituted heteroalkylene. In certain embodiments, L.sup.D is optionally substituted C.sub.1-20 heteroalkylene. In certain embodiments, L.sup.D is optionally substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.D is substituted C.sub.1-10 heteroalkylene. In certain embodiments, L.sup.D is C.sub.1-10 heteroalkylene substituted with at least one oxo (O) group. In certain embodiments, L.sup.D is of the formula:

##STR00222##

In certain embodiments, L.sup.D is of the formula:

##STR00223##

In certain embodiments, L.sup.D is unsubstituted heteroarylalkylene. In certain embodiments, L.sup.D is optionally substituted heteroarylalkylene. In certain embodiments. L.sup.D is an unsubstituted 5-membered heteroarylalkylene. In certain embodiments, L.sup.D comprises a triazole. In certain embodiments, L.sup.D comprises a group of the formula:

##STR00224##

In certain embodiments, L.sup.D is of the formula:

##STR00225##

[0509] In certain embodiments, L.sup.2 and L.sup.4 are each independently optionally substituted alkylene or optionally substituted heteroalkylene; and L.sup.A, L.sup.B, L.sup.c, and L.sup.D are each independently a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylalkylene, or optionally substituted heteroarylene; wherein no more than one of L.sup.A. L.sup.B, L.sup.C, and L.sup.D is a bond.

[0510] In certain embodiments, L.sup.2 is optionally substituted alkylene; L.sup.4 is optionally substituted heteroalkylene; L.sup.A is a bond; L.sup.B is optionally substituted heteroalkylene; L.sup.C is optionally substituted heteroalkylene; and L.sup.D is optionally substituted heteroarylalkylene.

[0511] In certain embodiments, L.sup.2 is unsubstituted alkylene; L.sup.4 is unsubstituted heteroalkylene; L.sup.A is a bond; L.sup.B is substituted heteroalkylene; L.sup.c is substituted heteroalkylene; and L.sup.D is unsubstituted heteroarylalkylene.

[0512] In certain embodiments, L.sup.2 is of the formula:

##STR00226##

L.sup.4 is of the formula:

##STR00227##

L.sup.A is a bond; L.sup.B is of the formula:

##STR00228##

L.sup.C is of the formula:

##STR00229##

and L.sup.D is of the formula:

##STR00230##

[0513] In certain embodiments, L.sup.2 and L.sup.4 are each independently optionally substituted alkylene or optionally substituted heteroalkylene; and L.sup.A, L.sup.B, L.sup.c, and L.sup.D are each independently optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted heteroarylene, or optionally substituted heteroarylalkylene.

[0514] In certain embodiments, L.sup.2 is optionally substituted heteroalkylene; L.sup.4 is optionally substituted heteroalkylene; L.sup.A is optionally substituted heteroarylene; L.sup.B is optionally substituted heteroalkylene; L.sup.C is optionally substituted heteroalkylene; and L.sup.D is optionally substituted heteroarylalkylene.

[0515] In certain embodiments, L.sup.2 is of the formula:

##STR00231##

L.sup.4 is of the formula:

##STR00232##

L.sup.A is of the formula:

##STR00233##

L.sup.B is of the formula:

##STR00234##

L.sup.C of the formula:

##STR00235##

and L.sup.D is of the formula:

##STR00236##

[0516] In certain embodiments, n is an integer between 1 and 4000, inclusive. In certain embodiments, n is an integer between 5 and 4000, inclusive. In certain embodiments, n is an integer is between 50 and 4000, inclusive. In certain embodiments, n is an integer between 100 and 4000, inclusive. In certain embodiments, n is an integer between 1000 and 4000, inclusive. In certain embodiments, n is an integer between 2000 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 4000, inclusive. In certain embodiments, n is an integer between 2 and 2000, inclusive. In certain embodiments, n is an integer between 2 and 1000, inclusive. In certain embodiments, n is an integer between 10 and 1000, inclusive. In certain embodiments, n is an integer between 2 and 100, inclusive. In certain embodiments, n is an integer between 10 and 100, inclusive. In certain embodiments, n is an integer between 10 and 50, inclusive. In certain embodiments, n is an integer between 25 and 50, inclusive. In certain embodiments, n is an integer between 25 and 100, inclusive. In certain embodiments, n is about 10, about 25, about 50, or about 100. In certain embodiments, the average of n is about 10, about 25, about 50, or about 100. In certain embodiments, the average of n is about 25 or about 50. In certain embodiments, the average of n is about 10. In certain embodiments, the average of n is about 25. In certain embodiments, the average of n is about 50. In certain embodiments, the average of n is about 100. In certain embodiments, n is the same as the degree of polymerization of the polymer.

[0517] In certain embodiments, m is an integer between 1 and 4000, inclusive. In certain embodiments, m is an integer between 5 and 4000, inclusive. In certain embodiments, m is an integer is between 50 and 4000, inclusive. In certain embodiments, m is an integer between 100 and 4000, inclusive. In certain embodiments, m is an integer between 1000 and 4000, inclusive. In certain embodiments, n is an integer between 2000 and 4000, inclusive. In certain embodiments, m is an integer between 2 and 4000, inclusive. In certain embodiments, m is an integer between 2 and 2000, inclusive. In certain embodiments, m is an integer between 2 and 100, inclusive. In certain embodiments, m is an integer between 10 and 1000, inclusive. In certain embodiments, m is an integer between 2 and 100, inclusive. In certain embodiments, m is an integer between 10 and 100, inclusive. In certain embodiments, m is an integer between 10 and 50, inclusive. In certain embodiments, m is an integer between 25 and 50, inclusive. In certain embodiments, m is an integer between 25 and 100, inclusive. In certain embodiments, m is about 10, about 25, about 50, or about 100. In certain embodiments, the average of m is about 10, about 25, about 50, or about 100. In certain embodiments, the average of m is about 25 or about 50. In certain embodiments, the average of m is about 10. In certain embodiments, the average of m is about 25. In certain embodiments, the average of m is about 50. In certain embodiments, the average of m is about 100. In certain embodiments, m is the same as the degree of polymerization of the polymer.

[0518] In certain embodiments, each of T.sup.1 and T.sup.2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thiol. In certain embodiments, T.sup.1 is hydrogen. In certain embodiments, T.sup.1 is halogen. In certain embodiments, T.sup.1 is optionally substituted alkyl. In certain embodiments, T.sup.1 is optionally substituted alkenyl. In certain embodiments, T.sup.1 is optionally substituted alkynyl. In certain embodiments, T.sup.1 is optionally substituted carbocyclyl. In certain embodiments, T.sup.1 is optionally substituted heterocyclyl. In certain embodiments, T.sup.1 is optionally substituted aryl. In certain embodiments, T.sup.1 is optionally substituted heteroaryl. In certain embodiments, T.sup.1 is optionally substituted acyl. In certain embodiments, T.sup.1 is optionally substituted hydroxyl. In certain embodiments, T.sup.1 is optionally substituted amino. In certain embodiments, T.sup.1 is optionally substituted thiol. In certain embodiments. T.sup.2 is hydrogen. In certain embodiments. T.sup.2 is halogen. In certain embodiments, T.sup.2 is optionally substituted alkyl. In certain embodiments, T.sup.2 is optionally substituted alkenyl. In certain embodiments, T.sup.2 is optionally substituted alkynyl. In certain embodiments, T.sup.2 is optionally substituted carbocyclyl. In certain embodiments, T.sup.2 is optionally substituted heterocyclyl. In certain embodiments, T.sup.2 is optionally substituted aryl. In certain embodiments, T.sup.2 is optionally substituted heteroaryl. In certain embodiments, T.sup.2 is optionally substituted acyl. In certain embodiments, T.sup.2 is optionally substituted hydroxyl. In certain embodiments, T.sup.2 is optionally substituted amino. In certain embodiments, T.sup.2 is optionally substituted thiol. In certain embodiments, both T.sup.1 and T.sup.2 are hydrogen.

[0519] In certain embodiments, T.sup.1 is optionally substituted aryl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.1 is phenyl, and T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is optionally substituted aryl, and T.sup.1 is hydrogen. In certain embodiments, T.sup.2 is phenyl, and T.sup.1 is hydrogen.

[0520] At least one of A, B, C, or D is a polysiloxane. In certain embodiments, the polysiloxane is of the formula:

##STR00237##

wherein:

[0521] R.sup.1 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy;

[0522] R.sup.2 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy; and

[0523] q is an integer between 5 and 2000, inclusive.

[0524] In certain embodiments, R.sup.1 is optionally substituted alkyl. In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.1 is methyl.

[0525] In certain embodiments, R.sup.2 is optionally substituted alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-20alkyl. In certain embodiments, R.sup.2 is unsubstituted C.sub.1-20 alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1, alkyl. In certain embodiments, R.sup.2 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.2 is n-butyl.

[0526] In certain embodiments, q is an integer between 5 and 500, inclusive. In certain embodiments, q is an integer between 5 and 100, inclusive. In certain embodiments, q is an integer between 10 and 100, inclusive. In certain embodiments, q is an integer between 30 and 80, inclusive. In certain embodiments, q is an integer between 50 and 80, inclusive. In certain embodiments, q is an integer between 60 and 70, inclusive.

[0527] In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl; R.sup.2 is optionally substituted C.sub.1-6 alkyl; and q is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl; R.sup.2 is unsubstituted C.sub.1-6 alkyl; and q is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.1 is methyl; R.sup.2 is n-butyl; and q is an integer between 50 and 100, inclusive.

[0528] In certain embodiments, R.sup.1 is C.sub.1-6 alkyl, and the polysiloxane has a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, or about 4,000 Da to about 6,000 Da. or about 4,500 Da to about 5,500 Da.

[0529] In certain embodiments, the polysiloxane is polydimethylsiloxane (PDMS) having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 2,000 Da to about 10,000 Da, about 2,000 Da to about 6,000 Da, about 4,000 Da to about 6,000 Da, or about 4,500 Da to about 5,500 Da.

[0530] In certain embodiments, one of A, B, C, or D is a polysiloxane and the remaining are selected from the group consisting of a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer. The polyacrylate may be any polyester described herein. The polyester may be any polyester described herein. The polyether may be any polyether described herein. The polyacrylamide may be any polyacrylamide described herein. Additionally, the vinyl polymer may be any vinyl polymer described herein.

[0531] In certain embodiments, A, B, C, or D is a polyester. In certain embodiments, A, B, C, or D is a polyester selected from the group consisting of polyglycolic acid (PGA), polylactic acid (PLA), poly(lactic-co-glycolic acid) (PLGA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyhydroxybutryate (PHB), polyethylene adipate (PEA), polybutylene succinate (PBS), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). In certain embodiments, A, B, C, or D is polylactic acid (PLA). In certain embodiments, A, B, C, or D is a vinyl polymer. In certain embodiments, A, B, C, or D is a vinyl polymer selected from the group consisting of polystyrene, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyvinyl acetate, polyvinyl alcohol, and polyacrylonitrile. In certain embodiments, A, B, C, or D is polystyrene. In certain embodiments, B is a polyacrylate. In certain embodiments, A, B, C, or D is a polyacrylate selected from the group consisting of poly(methyl methacrylate), poly(methyl acrylate), poly(methacrylate), poly(hydroxyethyl methacrylate), poly(n-butyl acrylate), and poly(tert-butyl acrylate). In certain embodiments, A, B, C, or D is poly(tert-butyl acrylate).

[0532] In certain embodiments, A, B, C, or D is a vinyl polymer of the following formula

##STR00238##

wherein:

[0533] R.sup.3 is optionally substituted alkyl, halogen, hydrogen, cyano, OR.sup.a, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0534] R.sup.4 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0535] R.sup.a is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0536] r is an integer between 5 and 2000, inclusive.

[0537] In certain embodiments, R.sup.3 is hydrogen. In certain embodiments, R.sup.3 is optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted alkenyl. In certain embodiments, R.sup.3 is optionally substituted alkynyl. In certain embodiments, R.sup.3 is optionally substituted aryl. In certain embodiments, R.sup.3 is optionally substituted heteroaryl. In certain embodiments, R.sup.3 is cyano. In certain embodiments, R.sup.3 is halogen. In certain embodiments, R.sup.3 is OR.sup.a, wherein R.sup.a is hydrogen or optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted phenyl. In certain embodiments, R.sup.3 is unsubstituted phenyl.

[0538] In certain embodiments. R.sup.4 is optionally substituted alkyl. In certain embodiments, R.sup.4 is optionally substituted alkenyl. In certain embodiments, R.sup.4 is optionally substituted alkynyl. In certain embodiments, R.sup.4 is optionally substituted aryl. In certain embodiments, R.sup.4 is optionally substituted heteroaryl. In certain embodiments, R.sup.4 is optionally substituted C.sub.1-6 alkyl. In certain embodiments. R.sup.4 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is C.sub.1-6 alkyl substituted with an ester group.

[0539] In certain embodiments, r is an integer between 5 and 500, inclusive. In certain embodiments, r is an integer between 5 and 100, inclusive. In certain embodiments, r is an integer between 10 and 100, inclusive. In certain embodiments, r is an integer between 10 and 50, inclusive. In certain embodiments, r is an integer between 20 and 40, inclusive. In certain embodiments, r is an integer between 30 and 40, inclusive.

[0540] In certain embodiments, R.sup.3 is optionally substituted aryl; R.sup.4 is optionally substituted C.sub.1-6 alkyl; and r is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.3 is unsubstituted aryl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive. In certain embodiments, R.sup.3 is unsubstituted phenyl; R.sup.4 is substituted C.sub.1-6 alkyl; and r is an integer between 10 and 50, inclusive.

[0541] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2,000 Da to about 20,000 Da, about 10.000 Da to about 15,000 Da, about 2,000 Da to about 10.000 Da, about 7,000 Da to about 10,000 Da, about 8,000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3,000 Da, or about 2,500 Da to about 3,600 Da.

[0542] In certain embodiments, A, B, C, or D is a polyacrylate of the following formula:

##STR00239##

wherein:

[0543] R.sup.5 is optionally substituted alkyl, hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0544] R.sup.6 is optionally substituted alkyl, hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0545] R.sup.7 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl; and

[0546] p is an integer between 5 and 2000, inclusive.

[0547] In certain embodiments, R.sup.5 is hydrogen. In certain embodiments, R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted alkenyl. In certain embodiments, R.sup.5 is optionally substituted alkynyl. In certain embodiments, R.sup.5 is optionally substituted aryl. In certain embodiments, R.sup.5 is optionally substituted heteroaryl. In certain embodiments. R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.5 is tert-butyl.

[0548] In certain embodiments, R.sup.6 is optionally substituted alkyl. In certain embodiments, R.sup.6 is hydrogen. In certain embodiments, R.sup.6 is optionally substituted alkenyl. In certain embodiments, R.sup.6 is optionally substituted alkynyl. In certain embodiments, R.sup.6 is optionally substituted aryl. In certain embodiments, R.sup.6 is optionally substituted heteroaryl. In certain embodiments. R.sup.6 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is methyl.

[0549] In certain embodiments, R.sup.7 is optionally substituted alkyl. In certain embodiments, R.sup.7 is optionally substituted alkenyl. In certain embodiments, R.sup.7 is optionally substituted alkynyl. In certain embodiments. R.sup.7 is optionally substituted aryl. In certain embodiments, R.sup.7 is optionally substituted heteroaryl. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is C.sub.1-6 alkyl substituted with an ester group.

[0550] In certain embodiments, p is an integer between 5 and 500, inclusive. In certain embodiments, p is an integer between 5 and 100, inclusive. In certain embodiments, p is an integer between 10 and 100, inclusive. In certain embodiments, p is an integer between 10 and 50, inclusive. In certain embodiments, p is an integer between 20 and 40, inclusive. In certain embodiments, p is an integer between 25 and 35, inclusive.

[0551] In certain embodiments, R.sup.5 is optionally substituted alkyl; R.sup.6 is hydrogen; R.sup.7 is optionally substituted C.sub.1-6 alkyl; and p is an integer between 10 and 100, inclusive. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl; R.sup.6 is hydrogen; R.sup.7 is substituted C.sub.1-6 alkyl; and p is an integer between 10 and 50, inclusive. In certain embodiments, R.sup.5 is tert-butyl; R.sup.6 is hydrogen; R.sup.4 is substituted C.sub.1-6 alkyl; and p is an integer between 20 and 40, inclusive.

[0552] In certain embodiments, the vinyl polymer is polystyrene. In certain embodiments, the vinyl polymer is polystyrene having a number average molecular weight of about 2,000 Da to about 20.000 Da, about 10,000 Da to about 15,000 Da, about 2,000 Da to about 10,000 Da, about 7,000 Da to about 10,000 Da, about 8,000 Da to about 9,500 Da, about 2,000 Da to about 7,000 Da, about 2,000 Da to about 4,000 Da, about 2,000 Da to about 3,000 Da, or about 2,500 Da to about 3,600 Da.

[0553] In certain embodiments, A, B, C, or D is a polyester of the following formula:

##STR00240##

wherein:

[0554] R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl;

[0555] R.sup.9 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group; and

[0556] s is an integer between 5 and 2000, inclusive.

[0557] In certain embodiments, R.sup.8 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, or optionally substituted acyl. In certain embodiments, R.sup.8 is hydrogen. In certain embodiments, R.sup.8 is optionally substituted alkyl. In certain embodiments, R.sup.8 is optionally substituted alkenyl. In certain embodiments, R.sup.8 is optionally substituted alkynyl. In certain embodiments, R.sup.8 is optionally substituted aryl. In certain embodiments, R.sup.8 is optionally substituted heteroaryl In certain embodiments, R.sup.8 is optionally substituted carbocyclyl. In certain embodiments. R.sup.8 is optionally substituted heterocyclyl. In certain embodiments, R.sup.8 is optionally substituted acyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.8 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.8 is methyl.

[0558] In certain embodiments, R.sup.9 hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group. In certain embodiments. R.sup.9 is hydrogen. In certain embodiments, R.sup.9 is optionally substituted alkyl. In certain embodiments, R.sup.9 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.9 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.9 is optionally substituted alkenyl. In certain embodiments, R.sup.9 is optionally substituted alkynyl. In certain embodiments, R.sup.9 is optionally substituted aryl. In certain embodiments, R.sup.9 is optionally substituted heteroaryl. In certain embodiments, R.sup.9 is optionally substituted carbocyclyl. In certain embodiments, R.sup.9 is optionally substituted heterocyclyl. In certain embodiments, R.sup.9 is optionally substituted acyl. In certain embodiments, R.sup.9 is an oxygen protecting group.

[0559] In certain embodiments, s is an integer between 5 and 2000, inclusive. In certain embodiments, s is an integer between 5 and 1000, inclusive. In certain embodiments, s is an integer between 5 and 500, inclusive. In certain embodiments, s is an integer between 5 and 200, inclusive. In certain embodiments, s is an integer between 5 and 100, inclusive.

[0560] In certain embodiments, A, B, C, or D is a polyether of the following formula:

##STR00241##

wherein:

[0561] R.sup.10 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group; and

[0562] t is an integer between 5 and 2000, inclusive.

[0563] As generally defined herein, t is an integer between 5 and 200), inclusive. In certain embodiments, t is an integer between 5 and 1000, inclusive. In certain embodiments, t is an integer between 5 and 500, inclusive. In certain embodiments, t is an integer between 5 and 200, inclusive. In certain embodiments, t is an integer between 5 and 100, inclusive.

[0564] In certain embodiments, A, B, C. or D is a polyacrylamide group of the following formula:

##STR00242##

wherein:

[0565] each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or a nitrogen protecting group; or optionally two R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl;

[0566] R.sup.11 is hydrogen, halogen, CN, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, optionally substituted amino, optionally substituted hydroxyl, or optionally substituted thiol; and

[0567] u is an integer between 5 and 2000, inclusive.

[0568] In certain embodiments, each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or a nitrogen protecting group; or optionally two R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl. In certain embodiments, R.sup.N is hydrogen. In certain embodiments, R.sup.N is optionally substituted alkyl. In certain embodiments, R.sup.N is optionally substituted alkenyl. In certain embodiments, R.sup.N is optionally substituted alkynyl. In certain embodiments, R.sup.N is optionally substituted carbocyclyl. In certain embodiments, R.sup.N is optionally substituted heterocyclyl. In certain embodiments, R.sup.N is optionally substituted aryl. In certain embodiments, R.sup.N is optionally substituted heteroaryl. In certain embodiments, R.sup.N is or a nitrogen protecting group. In certain embodiments, R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl. In certain embodiments. R.sup.N is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.N is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.N is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.N is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.N is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.N is iso-propyl.

[0569] In certain embodiments. R.sup.11 is hydrogen, halogen, CN, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, optionally substituted amino, optionally substituted hydroxyl, or optionally substituted thiol. In certain embodiments, R.sup.11 is hydrogen. In certain embodiments, R.sup.11 is halogen. In certain embodiments, R.sup.11 is CN. In certain embodiments, R.sup.11 is optionally substituted alkyl. In certain embodiments, R.sup.11 is optionally substituted alkenyl. In certain embodiments, R.sup.11 is optionally substituted alkynyl. In certain embodiments, R.sup.11 is optionally substituted aryl. In certain embodiments, R.sup.11 is optionally substituted heteroaryl. In certain embodiments, R.sup.11 is optionally substituted carbocyclyl. In certain embodiments, R.sup.11 is optionally substituted heterocyclyl. In certain embodiments, R.sup.11 is optionally substituted acyl. In certain embodiments, R.sup.11 is optionally substituted amino. In certain embodiments, R.sup.C is optionally substituted hydroxyl. In certain embodiments, R.sup.11 is optionally substituted thiol. In certain embodiments, R.sup.11 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.11 is substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.11 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.11 is substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.11 is of the formula:

##STR00243##

[0570] In certain embodiments, u is an integer between 5 and 2000, inclusive. In certain embodiments, u is an integer between 5 and 1000, inclusive. In certain embodiments, u is an integer between 5 and 500, inclusive. In certain embodiments, u is an integer between 5 and 200, inclusive. In certain embodiments, u is an integer between 5 and 100, inclusive.

[0571] In certain embodiments, one of A, B, C, or D is hydrogen; and one of the remaining is a polysiloxane. In certain embodiments, A is hydrogen; and one of B, C, or D is a polysiloxane. In certain embodiments, A is hydrogen; B is a polysiloxane; and C and D are independently selected from the group consisting of a polyether, a polyester, a polyacrylamide, a polyacrylate, and a vinyl polymer. In certain embodiments, A is hydrogen; B is a polysiloxane; C and D are independently selected from the group consisting of a polyester, a polyacrylate, and a vinyl polymer. In certain embodiments, A is hydrogen; B is a polysiloxane; C is a polyester; and D is a vinyl polymer. In certain embodiments, A is hydrogen; B is a polydimethylsiloxane; C is poly(lactic acid); and D is polystyrene.

[0572] In certain embodiments, one of A, B, C, or D is polysiloxane; and the remaining are independently selected from the group consisting of a polyether, a polyester, a polyacrylamide, a polyacrylate, and a vinyl polymer. In certain embodiments, B is a polysiloxane; and A, C, and D are independently selected from the group consisting of a polyester, a polyacrylate, and a vinyl polymer. In certain embodiments, A is a polyacrylate; B is a polysiloxane; C is a polyester; and D is a vinyl polymer. In certain embodiments, A is poly(tert-butylacrylate); B is polydimethylsiloxane; C is poly(lactic acid); and D is polystyrene.

[0573] In certain embodiments, the diblock bottlebrush copolymer is of Formula (II-a):

##STR00244##

or salts thereof, wherein each of T.sup.1, T.sup.2, L.sup.2, L.sup.4, L.sup.A, L.sup.B, L.sup.C, L.sup.D, A, B, C, D, n, and m are as defined in any of the embodiments of Formula (II).

[0574] In certain embodiments, the diblock bottlebrush copolymer is of Formula (II-b):

##STR00245##

or salts thereof, wherein each of T.sup.1, T.sup.2, L.sup.A, L.sup.B, L.sup.C, L.sup.D, A, B, C, D, n, and m are as defined in any of the embodiments of Formula (II).

[0575] In certain embodiments, the diblock bottlebrush copolymer is of Formula (II-c):

##STR00246##

or salts thereof, wherein each of T.sup.1, T.sup.2, L.sup.A, L.sup.B, L.sup.C, L.sup.D, A, B, C, D, n, and m are as defined in any of the embodiments of Formula (II).

[0576] In certain embodiments, the diblock bottlebrush copolymer of Formula (II) is of Formula (II-d):

##STR00247##

or salts thereof, wherein:

[0577] each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl:

[0578] n is an integer between 10 and 100, inclusive;

[0579] m is an integer between 10 and 100, inclusive;

[0580] q is an integer between 50 and 100, inclusive;

[0581] p is an integer between 30 and 70, inclusive; and

[0582] r is an integer between 10 and 50, inclusive.

[0583] In certain embodiments, the bottlebrush polymer of Formula (II) is of Formula (I-c):

##STR00248##

or salts thereof, wherein:

[0584] each of T.sup.1 and T.sup.2 is independently hydrogen or phenyl;

[0585] n is an integer between 10 and 100, inclusive;

[0586] m is an integer between 10 and 100, inclusive;

[0587] p is an integer between 10 and 50, inclusive;

[0588] q is an integer between 50 and 100, inclusive;

[0589] s is an integer between 30 and 70, inclusive; and

[0590] r is an integer between 10 and 50, inclusive.

[0591] The properties of a diblock bottlebrush copolymer described herein may be dependent upon the ratio of Block A to Block B in the copolymer. In certain embodiments, the ratio of Block A to Block B repeating backbone units in the diblock bottlebrush copolymer is about 1:1, about 3:2, about 4:3, about 5:4, about 6:4, about 7:3, about 4:1, or about 9:1.

[0592] As described herein, in certain embodiments, a diblock bottlebrush copolymer of the present invention has a bottlebrush, comb, or graft-copolymer structure. In certain embodiments, the copolymer has a bottlebrush structure. In certain embodiments, the copolymer has a comb structure. In certain embodiments, the copolymer has a graft-copolymer structure. A diblock bottlebrush copolymer described herein may self-assemble to form any type of polymer network or nanostructure. In certain embodiments, a diblock bottlebrush copolymer described herein self-assembles to form a spherical, lamellar, cylindrical, ellipsoidal, polyhedral, hexagonal cylindrical, or gyroid shape.

[0593] In certain embodiments, the diblock bottlebrush copolymer described herein self-assembles to form a structure with a hexagonal cylindrical morphology. In certain embodiments, the diblock bottlebrush copolymer described herein self-assembles to form a structure with a gyroid morphology. In certain embodiments, the diblock bottlebrush copolymer described herein self-assembles to form a spherical morphology. In certain embodiments, the diblock bottlebrush copolymer described herein self-assembles to form a lamellar morphology. In certain embodiments, the diblock bottlebrush copolymer described herein self-assembles to form an ellipsoidal morphology. In certain embodiments, the diblock bottlebrush copolymer described herein self-assembles to form a polyhedral morphology.

[0594] Diblock bottlebrush copolymers described herein may comprise one or more additional blocks (e.g., to form a triblock bottlebrush copolymer in the case of one additional block).

Methods for Preparing Bottlebrush Polymers and Diblock Bottlebrush Copolymers

[0595] In one aspect, the present invention provides methods for preparing the bottlebrush polymers and copolymers described herein. The methods comprise forming the polymers and copolymers via a polymerization reaction or series of subsequent polymerization reactions, and any polymerization reactions known in the art may be employed. Examples of polymerization reactions include, but are not limited to, free-radical polymerization, cationic polymerization, anionic polymerization, and olefin metathesis polymerization (e.g., ring-opening metathesis polymerization (abbreviated ROMP)).

[0596] A method of preparing a bottlebrush polymer or diblock bottlebrush copolymer described herein may comprise two or more sequential polymerization steps. For instance, a first macromonomer may be polymerized to form a homopolymer or copolymer. Then, the homopolymer or copolymer can be polymerized with itself to form a bottlebrush polymer, or it can be polymerized with a second macromonomer to form a diblock copolymer.

[0597] Provided herein is a method of producing a bottlebrush polymer described herein, the method comprising the steps of:

[0598] (a) providing a first macromonomer comprising one or more polymeric sidechains and one or more reactive moieties;

[0599] (b) reacting the macromonomer provided in step (a) under conditions suitable to effect a polymerization reaction and yield a bottlebrush polymer;

[0600] In certain embodiments, the method of preparing a bottlebrush polymer described herein comprises one or more olefin metathesis polymerization steps (e.g., step (b)). In certain embodiments, the method of preparing a bottlebrush polymer described herein comprises one or more ROMP steps (e.g., step (b)). Ring-opening metathesis polymerization (ROMP) is an olefin metathesis strategy for chain-growth polymerization that utilizes ring strain of cyclic olefins (e.g., norbomene or cyclopentane; or heterocyclic analogs thereof) to drive the polymerization reaction. For olefin metathesis polymerization, the one or more reactive moieties on the macromonomers are olefins. For ROMP reactions, the one or more reactive moieties are cyclic olefins (e.g., norbomene or cyclopentane; or heterocyclic analogs thereof).

[0601] Therefore, in certain embodiments, the method of producing a bottlebrush polymer described herein comprises steps of:

[0602] (a) providing a macromonomer comprising two polymeric sidechains (e.g., polymeric sidechains described herein) and one or more olefins (e.g., a cyclic olefin);

[0603] (b) reacting the macromonomer provided in step (a) under conditions suitable to effect a polymerization reaction and yield a bottlebrush polymer.

[0604] Also provided herein is a method of producing a diblock bottlebrush copolymer described herein, the method comprising the steps of:

[0605] (a) providing a first macromonomer comprising one or more polymeric sidechains and one or more reactive moieties;

[0606] (b) providing a second macromonomer comprising one or more polymeric sidechains and one or more reactive moieties;

[0607] (c) reacting the macromonomer provided in step (a) under conditions suitable to effect a polymerization reaction and yield a polymer;

[0608] (d) reacting the polymer in step (c) with the macromonomer provided in step (b) under conditions suitable to effect a polymerization reaction and yield a diblock bottlebrush copolymer.

[0609] In certain embodiments, the method of preparing a diblock bottlebrush copolymer described herein comprises one or more olefin metathesis polymerization steps (e.g., steps (c) and (d)). In certain embodiments, the method of preparing a diblock bottlebrush copolymer described herein comprises one or more ROMP steps (e.g., steps (c) and (d)). Ring-opening metathesis polymerization (ROMP) is a olefin metathesis strategy for chain-growth polymerization that utilizes ring strain of cyclic olefins (e.g., norbomene or cyclopentane; or heterocyclic analogs thereof) to drive the polymerization reaction. For olefin metathesis polymerization, the one or more reactive moieties on the macromonomers are olefins. For ROMP reactions, the one or more reactive moieties are cyclic olefins (e.g., norbomene or cyclopentane; or heterocyclic analogs thereof).

[0610] Therefore, in certain embodiments, the method of producing a diblock bottlebrush copolymer described herein comprises steps of:

[0611] (a) providing a first macromonomer comprising one or two polymeric sidechains (e.g., polymeric sidechains described herein) and one or more olefins (e.g., a cyclic olefin);

[0612] (b) providing a second macromonomer comprising two polymeric sidechains (e.g., polymeric sidechains described herein) and one or more olefins (e.g., a cyclic olefin);

[0613] (c) reacting the macromonomer provided in step (a) under conditions suitable to effect a polymerization reaction and yield a polymer;

[0614] (d) reacting the polymer in step (c) with the macromonomer provided in step (b) under conditions suitable to effect a polymerization reaction and yield a diblock bottlebrush copolymer.

[0615] A macromonomer is a monomer comprising one or more polymer groups (e.g., polymeric sidechains described herein) and a reactive moiety (e.g., an olefin such as a cyclic olefin). In general, a macromonomer is a polymer comprising a reactive group that allows it to act as a monomer in a polymerization reaction. In certain embodiments, the macromonomer contains two polymeric sidechains covalently linked through a branching linker. The reactive group may be anywhere on the polymer and may be at the end/terminus of the polymer chain. Macromonomers function as monomers in polymerization reactions and, after polymerization, are the repeating units in the larger diblock bottlebrush copolymer.

[0616] In certain embodiments, macromonomers for the preparation of bottlebrush polymers of the present disclosure are of the following formulae:

##STR00249##

or salts thereof, wherein X.sup.A, A.sup.R, L.sup.2. L.sup.A, L.sup.B, L.sup.C, A, and B are as defined in embodiments of Formula (I). In the exemplary macromonomer shown above, the cyclic olefins represent reactive moieties and A and B represent polymeric sidechains.

[0617] In certain embodiments, the reactive moieties are cyclic olefins such as norbomene (or variants thereof). For example, in certain embodiments, macromonomers for the preparation of bottlebrush polymers of the present disclosure are of the following formulae:

##STR00250##

or salts thereof, wherein L.sup.2, L.sup.A, L.sup.B, A, and B are as defined in embodiments of Formula (I). Further examples of macromonomers of the present disclosure are provided in the Examples below.

[0618] In certain embodiments, macromonomers for the preparation of diblock bottlebrush copolymers of the present disclosure are of the following formulae:

##STR00251##

or salts thereof, wherein X.sup.A, X.sup.B, A.sup.R, B.sup.R, L.sup.2, L.sup.4. L.sup.A, L.sup.B, L.sup.C, A, B, C, and D are as defined in embodiments of Formula (II). In the exemplary macromonomers shown above, the cyclic olefins represent reactive moieties and A, B, C, and D represent polymeric sidechains.

[0619] In certain embodiments, the reactive moieties are cyclic olefins such as norbomene (or variants thereof). For example, in certain embodiments, macromonomers of the present invention are of the following formulae:

##STR00252##

or salts thereof, wherein L.sup.A, L.sup.B, L.sup.c, A, B. and C are as defined in embodiments of Formula (II). Further examples of macromonomers of the present disclosure are provided in the Examples below.

[0620] In order to effect a polymerization reaction to form a bottlebrush polymer or diblock bottlebrush copolymer described herein, macromonomers are reacted in the presence of a polymerization initiator. In certain embodiments, when polymerization reaction is an olefin metathesis polymerization reaction (e.g. ROMP), the polymerization initiator is a catalyst or promoter of olefin metathesis. In certain embodiments, a ROMP polymerization involves reacting macromonomers in the presence of a ruthenium complex. In certain embodiments, the ruthenium complex is what is known in the art as a Grubbs or Grubbs-Hoveyda catalyst. Examples of commercially available ruthenium complexes useful in the polymerization reactions described herein can be found on the internet (See, e.g., www.sigmaaldrich.com/chemistry/chemical-synthesis/technology-spotlights/metathesis.html).

[0621] In certain embodiments, a ruthenium complex useful in a ROMP reaction described herein is of the following formula:

##STR00253##

wherein X is a halogen (e.g., Br) or hydrogen.

[0622] For examples of olefin metathesis reagents, catalysts, and reaction conditions useful in the present methods, see, e.g., Schrodi, Y.; Pederson, R. L. Aldrichimnica Acta 2007, 40, 45; Adv. Synth. Catal, 2007, 349, 1-268; Grubbs, R. H. Tetrahedron 2004, 60, 7117; Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim, 2003; Vols. 1-3: Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18; Frstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012; Schuster, M.; Blechert. S. Angew. Chem., Int. Ed. 1997, 36, 2036; Ritter, T. et al. Organometallics 2006, 25, 5740; Chatterjee, A. K. et al. J. Am. Chem. Soc. 2000, 122, 3783; Chatterjee, A. K.; Grubbs, R. H. Org. Lett. 1999, 1, 1751; Murelli, R. P.; Snapper, M. L. Org. Lett. 2007, 9, 1749; Stewart, I. C. et al. Org. Lett. 2007, 9, 1589; Ung, T. et al. Organometallics 2004, 23, 5399; Benitez, D.; Goddard, W. A., III. J. Am. Chem. Soc. 2005, 127, 12218; Love, J. A. et al. Angew. Chem., Int. Ed. 2002, 41, 4035; Sanford, M. S. et al. Organometallics 2001, 20, 5314; Choi. T.-L.; Grubbs, R. H. Angew. Chem. 2003, 115, 1785; Ritter, T. et al. Organometallics 2006, 25, 5740; and references cited therein; each of which is incorporated herein by reference.

Uses of the Bottlebrush Polymers and Copolymers

[0623] The bottlebrush polymers and diblock bottlebrush copolymers described herein may be useful in a variety of applications. For example, self-assembly of the bottlebrush polymers and copolymers can provide useful materials such as photonics (e.g., photonic crystals), functional materials, drug delivery systems, therapeutic vehicles, chromatography media, stimuli-responsive materials, lubricants, nanolithography, films, and coatings.

[0624] In certain embodiments, the bottlebrush polymers are capable of self assembling into materials useful for nanofiltration. In particular, bottlebrush polymers that self assemble into hexagonal cylindrical or gyroid morphologies are useful materials for nanofiltration.

[0625] In certain embodiments, the bottlebrush polymers are capable of self assembling into materials useful for photonics such as photonic crystals. In particular, bottlebrush polymers that self assemble into gyroid morphologies can provide useful photonic crystals.

[0626] In certain embodiments, a self-assembled material deriving from a bottlebrush polymer or copolymer of the present disclosure may be chemically modified to provide useful materials. For example, a self-assembled material deriving from a bottlebrush polymer or copolymer comprising polysiloxane sidechains may be treated with a fluoride ion source to chemically degrade the polysiloxane sidechains. The chemical degradation of the polysiloxane can result in the formation of a porous material useful for nanofiltration. In another example, a self-assembled material deriving from a bottlebrush polymer or copolymer comprising poly(tert-butylacrylate) sidechains may be subjected to conditions that hydrolyze the tert-butyl ester, resulting in polyacrylic acid sidechains, which can function as an anionic polymer and create porous channels useful for ion exchange and/or filtration.

[0627] Additional uses will be self-evident to one of ordinary skill in the art.

EXAMPLES

[0628] These and other aspects of the present invention will be further appreciated upon consideration of the following Examples, which are intended to illustrate certain particular embodiments of the invention but are not intended to limit its scope, as defined by the claims.

Graft-Through Synthesis and Assembly of Janus Bottlebrush Polymers from A-Branch-B Diblock Macromonomers

[0629] Branched macromolecules (BMMs) were synthesized with different A and B polymer combinations: (1) polystyrene (PS) and polydimethylsiloxane (PDMS); (2) PDMS and poly(tert-butyl acrylate) (PtBA); and (3) PS and PtBA (FIG. 2). The assembly of linear PS-b-PDMS has been particularly well-studied.sup.10; for comparison eight different variants of BMM 1 with differing number average molecular weight (MW) of PS were synthesized. These BMMs are referred to as norbomene PS-x-branch-PDMS-y, where x and y are the MW of PS and PDMS, respectively. ROMP of these BMMs produced A-branch-B BBCPs of tunable backbone degree of polymerization (DP).

[0630] The structures of thermally annealed samples (145 C. in a vacuum oven for 6 h) of the PS-PDMS BMMs and their corresponding BBCPs were studied using small-angle X-ray scattering (SAXS) at 20 C. In the bulk state, the BMMs readily formed ordered lamellar (LAM) or hexagonal cylinder (HEX) morphologies. In contrast, the resultant BBCPs spanned a wider range of morphologies. Interestingly, the bulk morphology of the BMMs was not necessarily the same morphology as the resulting BBCP. For example, the PS-2.3k-branch-PDMS-5k BMM formed lamellae with a domain size of 13.0 nm by SAXS, while the DP=10, 20, 30, and 40 BBCPs (0.30 PS volume fraction in all cases) formed highly ordered HEX morphologies with domain sizes of 12.9 or 13.0 nm (FIG. 3A and Table 1). Similar behavior was observed for the PS-3.3k-branch-PDMS-5k BMM (0.38 PS volume fraction) and its resultant BBCPs (FIG. 3A). Atomic force microscopy (AFM) phase images of drop-cast thick films of the (PS-3.3k-branch-PDMS-5k).sub.25. BBCP confirmed the HEX phase (FIG. 7). Furthermore, self-consistent field theory (SCFT) confirmed the HEX morphology at PS volume fractions between 0.30 and 0.36 (FIG. 8).

TABLE-US-00001 TABLE 1 Principal q and d for BMMs and BBCPs. Sample Composition Backbone DP Principal q (nm.sup.1) d (nm) PS-2.3k-branch-PDMS-5k MM 0.482 13.0 10 0.489 12.9 20 0.489 12.9 30 0.486 12.9 40 0.489 12,9 PS-3.3k-branch-PDMS-5k MM 0.476 13.2 25 0.456 13.8 50 0.459 13.7 100 0.459 13.7 PS-4.6k-branch-PDMS-5k MM 0.421 14.9 10 0.380 16.5 20 0.378 16.6 30 0.378 16,6 40 0.380 16.5 50 0.375 16.7 70 0.378 16.6 80 0.375 16.7 PS-6.4k-branch-PDMS-5k MM 0.387 16.2 10 0.348 18.1 20 0.348 18.1 40 0.335 18.7 80 0.345 18.2 IPS-8.2k-branch-PDMS-5k MM 0.363 17.3 10 0.321 19,5 20 0.301 20.9 40 0.315 20.0 80 0.312 20.1 PS-9.2k-branch-PDMS-5k MM 0.358 17.6 10 0.321 19.5 20 0.301 20.8 40 0.317 19.8 80 0.312 20.1 PS-10.3k-branch-PDMS-5k MM 0.327 19.2 10 0.321 19.6 20 0.317 19,8 30 0.316 19.9 40 0.316 19.9 50 0.314 20.0 60 0.321 19.6 PS-15.3k-branch-PDMS-5k MM 0.324 19.4 10 0.292 21.5 30 0.287 21.9 40 0.287 21.9 PtBA-3.6k-branch-PDMS- MM 0.555 11.3 5k 25 0.483 13.0 50 0.473 13,3 100 0.471 13.3 PS-4.6k-branch-PtBA-4.6k MM N/A 10 0.498 12.6 20 0.477 13.2 30 0.473 13.3 40 0.465 13.5

[0631] The small increase in domain spacing observed for the BBCPs relative to their corresponding BMMs is likely due to the A-branch-B BBCP architecture: the confinement of PS and PDMS on the densely grafted backbone stretches the two immiscible chains. However, when the DP was above a certain value10 in this caselittle increase in the domain size was observed. Simulation results using SCFT capture this behavior: the close packing of the side chains forces the ends to stretch away from the interface as inferred from the increase of sidechain length, L0, beyond the ideal value of a linear BCP (FIG. 9, L.sub.ideal03.86Rg, Rg=radius of gyration). FIG. 9 depicts the increase of root mean squared end-to-end distance as a function of DP; in the simulations, the effect is prominent until DP9 after which it plateaus. Overall, the equilibrium spacing increased45% from 3.37Rg (for the BMM) to 4.87Rg (at backbone DP=29).

[0632] For BBCPs prepared from PS-8.2k-branch-PDMS-5k and PS-9.2k-branch-PDMS-5k BMMs, a coexistence of two phases that were indexed to lamellar and gyroidal morphologies was observed. Despite the fact that phase separation is dominated by the sidechains of these polymers, which are quite uniform, this coexistence could arise from the somewhat broad molecular weight distribution for the polymer backbone, especially at higher backbone DP (FIGS. 12 to 26). While the BMM with PS of MW=8.2k itself formed ordered lamellar structures, the DP=10, 20, and 40 BBCPs exhibited multiple sets of peaks. The principal and second order diffraction peaks in the DP=20 BBCP were indexed to a gyroid morphology, while the third, fourth, and fifth order diffraction peaks were indexed to lamellae. BBCPs formed from 9.2k PS appeared to have a greater fraction of gyroid phase.

[0633] The thin film morphologies of (PS-15.3k-branch-PDMS-5k).sub.30 was also characterized. Well-ordered periodic cylindrical microdomains with 20 nm period and 10 nm line width were obtained for a sample drop-cast from toluene, slowly evaporated for 72 h, and plasma etched (FIG. 4A). FIG. 4B shows the annealed thin film morphology of a 28 nm as-cast film consisting of cylinders and spheres with average domain spacing of 25 nm. Hole formation suggested that the thickness of the film was insufficient to form a monolayer of microdomains. The structure is believed to consist of a wetting layer of PDMS blocks at the substrate and air interface surrounding a layer of PS, with poorly ordered rounded or linear microdomains protruding from the wetting layer. For a film with as-cast thickness of 50 nm, cylindrical microdomains oriented parallel to the substrate were achieved without terrace formation over macroscopic areas (FIG. 4C). Each microdomain appeared to be split longitudinally, which may be attributed to oxygen etching of the butyl terminus of the PDMS sidechain. In contrast, a thermally annealed 50 nm thick film produced a kinetically trapped state consisting of poorly ordered cylinders or an interpenetrated gyroid-like structure (FIG. 4D), with average domain spacing of 20 nm similar to the period of the drop-cast bulk BBCP.

[0634] These results indicate that solvent vapor annealing promotes microphase separation with improved ordering compared to thermal annealing. The large leads to a high thermodynamic driving force for microphase separation and a high order-disorder transition (ODT) temperature..sup.11 During solvent vapor annealing, solvent uptake by the film screens the strong interaction between blocks and lowers the diffusion barrier of the polymer chains, enhancing the microphase separation kinetics..sup.12 Additionally, in contrast to the conventional linear BCP systems with comparable high MW, the reduced chain entanglement arising from the steric hindrance between the densely grafted side chains in the BBCP system expedites the self-assembly..sup.13

[0635] Next, the bulk assembly of BMM 2 (FIG. 2, Scheme 1), PDMS-5k-branch-PtBA-3.6k (0.41 PtBA volume fraction), which was polymerized to form DP=25, 50, and 100 BBCPs was investigated. The BMM itself phase-separated, but only a single peak was observed by SAXS, which suggested limited ordering. Furthermore, freshly annealed BBCP samples also displayed one broad peak; they could not be indexed to any morphology. After eight months at ambient conditions, however, the scattering profiles of the DP=25 and 50 BBCPs had become highly ordered. As shown in FIG. 5A, the ratio of q.sub.i/q.sub.1, where q.sub.i is the scattering vector at the ith order diffraction peak, precisely matched that of the gyroid phase (6, 29 8, 14, 16, 20, 22, 24), where q.sub.1=0.481 nm.sup.1 and 0.472 nm.sup.1 for the 25 and 50 unit BBCPs, respectively. The DP=100 BBCP also displayed higher order peaks, but could not be indexed accurately due to the peak broadness. Nonetheless, these data represent observation of a pure gyroid phase in BBCP assembly, which is made possible by the unique A-branch-B BBCP architecture. SCFT simulation of a low N=12 A-branch-B BBCP recapitulated a bicontinuous gyroid window for f.sub.A=0.44-0.46 (FIG. 5B).

[0636] BMM 3 with PS of MW=4.6k and PtBA of MW=4.6k and resulting BBCPs was investigated also. In this case, the BMM was disordered, but the SAXS profile of the DP=10 BBCP displayed broad principal and higher-order peaks that were indexed as lamellae (FIG. 6A). The SAXS patterns of the DP=20, 30, and 40 BBCPs displayed sharp peaks that were also indexed to a lamellar morphology. In this system, the BMM components (PS and PtBA) were chosen to have lower than the examples above. The fact that the BMM itself does not phase-separate while the BBCPs do, i.e., the ODT is shifted upon polymerization, suggests that pre-organization of the sidechains along the dense BBCP backbone reduces the entropic penalty of self-assembly that the BMM suffers.

[0637] However, polymerization of the BMM lowered the critical A.sub.0N to 11.03 at DP=29, and lead to stretching of the sidechains (increase in L.sub.0), which facilitates phase separation. These results suggest that the A-branch-B BBCP structure could enhance the assembly of short BCPs, and thereby provide access to ultra-small domains sizes via an architectural approach..sup.14

[0638] The synthesis of the disclosed families of A-branch-B BBCPs demonstrate that these polymers have several unique advantages in the context of self-assembly. For example, polymerization-induced changes in bulk morphology and the ODT were observed, along with gyroid phases in BBCPs. Furthermore, the achievement of 20 nm domain spacing in thin film assemblies from the high molecular weight BBCP breaks the conventional N limitation..sup.11

Experimental Procedures

[0639] All anhydrous and HPLC grade solvents were purchased from Sigma Aldrich or Alfa Aesar and used as supplied unless otherwise stated. Anhydrous, degassed dichloromethane (DCM) and tetrahydrofuran (THF) were used from a J. C. Meyer solvent purification system. HPLC grade DCM and THF were sparged vigorously with argon for at least one hour before being connected to the solvent purification system. All reagents were purchased from Sigma Aldrich or Alfa Aesar unless otherwise stated. All chromatography was performed on EMD Millipore silica gel 60, particle size 0.040-0.063 mm (230-400 mesh) on a BIOTAGE ISOLERA PRIME flash purification system. Gel Permeation Chromatography (GPC) was performed with a concentration of 0.1-1.0 mg/mL on an Agilent 1260 Infinity system in THF, calibrated with monodisperse linear polystyrene standards and equipped with a UV diode array detector and a differential refractive index (dRI) detector. The GPC was run at a flow rate of 1 mL/minute at 35 C. and the .sup.1H nuclear magnetic resonance (.sup.1H NMR) spectra were acquired on 500 MHz Varian INOVA or 400 MHz Bruker AVANCE spectrometers. Spectra were calibrated by the residual solvent signal in deuterated solvent (CDCl.sub.3), which was purchased from Cambridge Isotope Laboratories, Inc. NMR spectra were processed in MestReNova 10.0.2, 2D SAXS data were azimuthally averaged and plotted using RAW 0.99.9.13b or by the EPICS system in MatLab at the Advanced Photon Source.

SAXS Sample Preparation and Measurements

[0640] Dried samples from ROMPs were wet with 15-50 L of THF to form thick, barely dissolved solutions. A small amount of the material was removed with a spatula or pipet tip and used to fill the hole of a circular washer that acted as a sample holder (outer diameter: 24 mm, inner diameter: 2 mm, thickness: 1 mm). Samples were then placed in a vacuum oven, evacuated, and heated to 145 C. for six hours. The vacuum oven was allowed to cool overnight and then vented to the atmosphere.

[0641] Transmission SAXS was conducted at the Cornell High Energy Synchrotron Source (CHESS) at the G1 beamline or beamline 12-ID-B at the Advanced Photon Source at Argonne National Lab. The sample to detector distance used at CHESS was 1.250 m and the wavelength of the beam was 1.268 . At APS, the sample to detector distance used was 1.9081 m and the wavelength of the beam was 0.886 .

AFM Imaging

[0642] Atomic force microscopy (AFM) imaging was performed using an Asylum Research MFP-3D. Samples were drop cast from a 10 mg/mL solution in toluene on a silicon wafer that was washed sequentially with hexane and acetone three times each. The silicon wafer was fixed to a glass microscope slide using a piece of double sided tape and the sample was allowed to slowly dry in a petri dish for one hour. Then the sample was annealed in a 140 C. oven for 30 minutes.

SEM Imaging

[0643] The BBCP was spin-coated from a 2 wt % toluene solution onto silicon substrates with a native oxide layer and then solvent annealed under toluene vapor, which is a partially selective solvent for the PS block The as-cast film thickness is measured by spectral reflectometry (Filmetrics F20). To induce microphase separation at room temperature, the BBCP thin films were solvent annealed under toluene vapor, which is a partially selective solvent for the PS block, at 298 K for 30 min. Solvent vapor annealing was performed in an 80 cm.sup.3 chamber filled with 3 cm.sup.3 of toluene liquid at ambient temperature for 30 min. During the solvent annealing process, the vapor pressure decreased as the solvent liquid gradually evaporated. After a total process time of 30 min, the lid was slowly removed and the film dried completely. For comparison, thermal annealing was implemented at 130 C. for 30 min in a vacuum oven. The annealed samples were subjected to a two-step reactive ion etching process in a Plasma-Therm 790 consisting of 5 sec, 50 W CF.sub.4 plasma at 15 mTorr to remove the top surface layer of PDMS, followed by a 30 sec, 90 W O.sub.2 plasma at 6 mTorr to remove the PS and produce robust oxidized PDMS microdomains on the substrate. Image analysis was performed with a Zeiss Merlin high-resolution scanning electron microscope at 3 kV as shown in FIG. 4.

Computation and Modeling

[0644] The effect of the polymer architecture of an (AB).sub.mC.sub.m+1 block polymer on the characteristics of self-assembly was studied. The backbone polymer C is assumed to be neutral when interacting with the AB side chains (.sub.AC=.sub.BC=0) where x is the Flory Huggins parameter. This is motivated by noting that AB chains will be already extended away from the interface by the effect of .sub.AB. Hence, the interaction between side chains AB and the backbone C should be minimal. By doing so, the role of chain architecture on the self-assembled morphologies compared to simple AB diblock copolymers can be elucidated.

[0645] The backbone C and the AB side chains are modeled as flexible Gaussian chains.sup.15 with degree of polymerization N.sub.i (i=A, B, or C). Along the contour of the backbone C, there are m AB junctions dividing the backbone into m+1 equal segments. For simplicity, all molecules are assumed to have equal statistical segment length b and the melt is incompressible. In this regards, a reference radius of gyration R.sub.g=b(N/6).sup.1/2, which is that of a linear triblock N=N.sub.A+N.sub.B+2NC. Rg sets the length scale of the polymer morphology. In addition, N.sub.tot is the whole molecule degree of polymerization where N.sub.tot=m(N.sub.A+N.sub.B)+(m+1)NC..sup.16 Hence, the total block volume fractions are calculated as follows f.sub.i=mN.sub.i/N.sub.tot for i=A and B and f.sub.C=(m+1)N.sub.C/N.sub.tot. The geometric ratio =N/N.sub.tot acts as a scaling factor for the free energy expression as discussed below..sup.16

[0646] The canonical partition function of a melt of a bottlebrush polymer with ABC blocks, in the field representation can be written..sup.17

[00001] $\begin{matrix} Z = {DW}_{A} .Math. {DW}_{B} .Math. {DW}_{C} .Math. DPD .Math. .Math._{A} .Math. D .Math. .Math._{B} .Math. D .Math. .Math._{C} .Math. e^{- F [W_{i}, .Math. .Math. i, P] / k_{B} .Math. T} .Math. .Math. And, & (S1) \\ \frac{.Math. .Math. F}{{nk}_{B} .Math. T} = \frac{1}{V} .Math. dr (\underset{i < j}{.Math.} .Math._{ij} .Math. N .Math. .Math._{i} .Math._{j} - \underset{i}{.Math.} .Math. W_{i} .Math._{i} + P (\underset{i}{.Math.} .Math. (_{i} - 1))) - \ln .Math. .Math. Q [W_{i}] & (S2) \end{matrix}$

[0647] Where n is the number of molecules in the melt. V is the system volume and .sub.ij is the Flory Huggins parameter between species i and j. Q[Q.sub.i] is the single chain partition function describing the conformational entropy of the Gaussian chain in W fields.

[0648] The architecture of the molecule is constructed using six propagators q.sub.i(r, s.sub.i, k) and q.sub.i.sup.+(r, s.sub.i, k) where s, is a variable parameterizing the contour of chain of type i and k is the segment number. The polymer probability distributions q, and q.sub.i.sup.+ satisfy the modified diffusion equation

[00002] $\begin{matrix} \frac{}{s_{i}} .Math. q = R_{g}^{2} .Math.^{2} .Math. q - W_{i} .Math. q & (S3) \end{matrix}$

[0649] Hence, the applied field W.sub.i matches the block type of contour variable s.sub.i when solving equation S3. The key step in constructing the polymer structure is identifying the initial conditions for every propagator. In this regard, q.sub.A(r,0,k)=q.sub.B(r,0,k)=1; q.sub.C(r,0,1)=q.sup.+.sub.C(r,N.sub.C,m+1)=1; q.sub.C(r,0,k)=q.sub.A(r,N.sub.A,k)*q.sub.B(r,N.sub.B,k)*q.sub.C(r,N.sub.C,k1); q.sup.+.sub.A(r,N.sub.A,k)=q.sub.B(r,N.sub.B,k)*q.sub.C(r,N.sub.C,k)*q.sup.+.sub.C(r,N.sub.C,m+1k); q.sub.B.sup.+(r,N.sub.B,k)=q.sub.A(r,N.sub.A,k)*q.sub.C(r,N.sub.C,k)*q.sup.+.sub.C(r,N.sub.C,m+1k); q.sup.+.sub.C(r,N.sub.C,k)=q.sub.A(r,N.sub.A,k)*q.sub.B(r,N.sub.B,k)*q.sup.+.sub.C(r,0,k1) where k[1,m]. The modified diffusion equation is solved using the pseudospectral method with operator splitting scheme..sup.18 Accordingly, the single chain partition function can be written as Q=1/Vdr q.sub.C(r, N.sub.C,m+1).

[0650] Minimization of the free energy F to the fields, density, and pressure leads to the following set of equations that have to be solved self-consistently..sup.18

[00003] $\begin{matrix} _{A} = \frac{1}{QN} .Math. {.Math.}_{k = 1}^{m} .Math._{0}^{N_{A}} .Math. {dsq}_{A} (r, s_{A}, k) .Math. q_{A}^{+} (r, s_{A}, k) .Math. .Math._{B} = \frac{1}{QN} .Math. {.Math.}_{k = 1}^{m} .Math._{0}^{N_{B}} .Math. {dsq}_{B} (r, s_{B}, k) .Math. q_{B}^{+} (r, s_{B}, k) .Math. .Math._{C} = \frac{1}{QN} .Math. {.Math.}_{k = 1}^{m + 1} .Math._{0}^{N_{C}} .Math. {dsq}_{C} (r, s_{C}, k) .Math. q_{C}^{+} (r, s_{C}, k) .Math. .Math. W_{A} (r) =_{AB} .Math. N .Math. .Math._{B} (r) +_{AC} .Math. N .Math. .Math._{C} (r) + P (r) .Math. .Math. W_{B} (r) =_{AB} .Math. N .Math. .Math._{A} (r) +_{BC} .Math. N .Math. .Math._{C} (r) + P (r) .Math. .Math. W_{C} (r) =_{AC} .Math. N .Math. .Math._{A} (r) +_{BC} .Math. N .Math. .Math._{B} (r) + P (r) .Math. .Math._{A} (r) +_{B} (r) +_{C} (r) = 1 & (S4) \end{matrix}$

[0651] The numerical solution of the SCFT equations to study phase separation of the bottlebrush polymer is initialized through random fields W.sub.i 's that are used to solve the modified diffusion equation (S3). The calculated propagators are employed to estimate Q and accordingly the density distributions. The fields W.sub.i 's and P are updated using a numerical relaxation scheme..sup.19

[0652] In order to explore the effect of polymer architecture on the characteristics of self-assembly, a series of simulations of a lamellar structure (projected to striped domains in 2D) maintaining N.sub.i the same while changing the number of segments m were conducted. By doing so, the bottlebrush volume fractions f.sup.0.sub.i=N.sub.i/N are fixed, while the total block volume fractions are changing f.sub.i. In this work the degree of polymerization of the equivalent linear triblock at N=100 was maintained. The composition profile is first calculated to analyze the degree of segregation. The computation cell has a pixel size of 0.2Rg, while the number of pixels is changed for every m to achieve a relaxed structure with a minimum in the system free energy (S2). The striped structure is formed at f.sup.0.sub.A=f.sup.0.sub.B=0.48, f.sup.0.sub.C=0.02.

[0653] FIG. 10 compares the normalized density profile of block A (.sub.A) for five different polymers with increasing number of segments m at a relatively low degree of segregation .sub.ABN=13. It is shown that the degree of segregation is quite low for a single AB chain as .sub.A peaks at 80%. This is expected for the low magnitude of .sub.ABN driving the phase separation; However, increasing the magnitude of m from one to nine segments causes O.sub.A to sharply rise, after which it reaches almost a constant value of .sub.A96%. It is interesting to note that the interface remains diffuse despite the increase in the effect strength of segregation. In addition, the improvement in the degree of segregation is reflected in the equilibrium domain spacing L.sub.0 as was shown in FIG. 10. FIG. 10 demonstrates the increase of L.sub.0 as a function of m. The effect is quite prominent when the number segments m9 after which it plateaus. Tethering more AB chains to the backbone increased the equilibrium spacing from 3.37R.sub.g (m=1) to 4.87R.sub.g at (m=29) with an increase of 45%.

[0654] Studying the onset of phase separation for the lamellar structure revealed a shift in the critical .sub.ABN to a higher value of 11.25 for m=1. This is significantly larger than the case of pure AB diblock copolymer of 50/50 volume fraction that phase separates at 10.49. However, the increase of number of segments m improves the onset of phase separation to 11.03 at m=29.

[0655] The SCFT results shed light on the unique features of the new architecture of the bottlebrush polymer. The ability to regulate the spacing between the brush chains adds an extra constraint on the chain accessible volume. The close packing of the side chains forces the ends to stretch away from the interface. This is inferred from the increase of L.sub.0 beyond the ideal value of a diblock (L.sup.ideal.sub.03.86Rg).sup.1(a). The behavior becomes more prominent as the number of side chains increase where the polymer deviates from a star like structure to a bottlebrush structure. In the SCFT analysis, the transition occurs as the number of segments increases above nine. The chain distribution can be better understood if we analyze a single chain propagating in an applied field. In this regard, we freeze the equilibrium W.sub.i fields and change the initial condition of qc(r.sub.o,0,1)=1, where r.sub.o is any point in space with a large relative density of C (C). In the current polymer structure, C is maximum at the AB interface. FIG. 11 compares the probability distribution of a short (m=4) and long (m=29) chains propagating along the AB interface. The probability of finding the chain end can be accurately fit by two Gaussians to determine the spread as shown in the insets. The dotted background lines are for A.

[0656] By plotting the propagator of the end point q.sub.C(r,N.sub.C,m+1), the root mean square end-to-end <R2> distance can be calculated. FIG. 8 showed the evolution of the <R2> as a function of the size of the backbone C. Normal to the AB interface, the chain size remains almost constant with increasing the backbone size. This is consistent with the diffuse interface observed in the density profile of FIG. 9. However, the chain size was observed to continuously grow along the interface as the number of segments m increases. The chain growth closely follows a power law of <R2>N.sup.0.54 which is slightly larger than the ideal chain model of <R2>N.sup.0.5, see FIG. 8. The increase of the power law hints on the fact that chain C is also stretched in order to accommodate the dense packing of the side AB chains.

[0657] The 3D analysis of the bottlebrush structure can provide more information on chain packing and the conditions under which particular morphologies might emerge. Here, a simple phase diagram at m=4 and at two degrees of segregation .sub.ABN=12 and .sub.ABN=17 was constructed. The resulting morphologies when changing f.sub.A between 0.3 and 0.5 was studied. This goes slightly beyond the f.sub.A=f.sub.B point due to the presence of C. f.sup.0.sub.C is kept constant at the previously mentioned value. A cubic computational cell of 60 pixels a side was used. Every pixel has magnitude of 0.2R.sub.g. FIG. 9 shows the resulting phases, where the .sub.ABN=17 exhibits only two phases of lamellae and cylinders. The transition happens at f.sub.A0.36. No gyroid structure was observed. In addition, spherical BCC structure was not generated in the range of f.sub.A studied. On the other hand, the low .sub.ABN=12 demonstrated a different behavior where the lamellar structure persisted in the range of f.sub.A>0.46. Below which a window of gyroid structure emerged at f.sub.A=0.44-0.46. Lower than that, defective bicontinuous domains were generated till the disordered phase appeared below. f.sub.A=0.4. The results indicate that the bottlebrush structure can stabilize a gyroid phase at low .sub.ABN. This can be expected with the ability of structure of introduce curvature in the case of unequal side-chain size.

Synthetic Procedures

[0658] Bromide-terminated polystyrene (PSBr) was synthesized according to literature procedure, using the activator regenerated by electron transfer (ARGET) ATRP protocol..sup.20 Bromide-terminated poly(tert-butyl acrylate) (PtBA-Br) was synthesized according to literature procedure, using standard ATRP conditions..sup.21

Grubbs Catalyst

[0659] A modified 3rd generation Grubbs' catalyst was synthesized according to literature procedure from the second generation Grubbs' catalyst, provided by Materia, Inc..sup.23 The catalyst was weighed into 4 mL vials under ambient conditions and stored in the glovebox. The catalyst was then dissolved in the requisite amount of THF to produce a 5 mg/mL stock solution inside the glovebox. The correct volume of stock solution was then dispensed to each reaction vial using a micropippetor. After 2.5 hours, the reactions were removed from the glovebox and quenched with three to five drops of ethyl vinyl ether. An aliquot of the reaction mixture was removed for GPC analysis.

Synthesis of PSN.SUB.3

[0660] PSBr was converted to azide-terminated polystyrene (PSN.sub.3) using the procedure below. The starting material was not completely purified before proceeding to the azidation; anisole and trace styrene were carried through and removed during the step below. The procedure below is based on PS of M.sub.n: 4600.

[0661] To a dry 500 mL round bottom flask was added 23.3 g of PSBr and 1.33 g of sodium azide. The flask was evacuated and backfilled with nitrogen three times. Then, approximately 130 mL of anhydrous DMF was cannulated into the flask under nitrogen. The reaction was then heated to 50 C. overnight under aluminum foil. After 18 hours, the reaction was cooled to room temperature and diluted with 200 mL of toluene. The organic layer was washed five times with water and once with brine. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The material was then redissolved in THF and precipitated by dropwise addition to a stirring beaker of methanol (80-100 mL/g of PS). The product was collected by filtration through a medium fritted glass funnel.

PS2300: The product was collected as a white powder. 9.76 g
PS3300: The product was collected as a white powder. 13.70 g
PS4600: The product was collected as a white powder. 21.18 g
PS6400: The product was collected as a white powder. 25.30 g
PS8200: The product was collected as a white powder. 10.1 g
PS9200: The product was collected as a white powder. 11.02 g
PS 10300: The product was collected as a white powder. 10.50 g
PS 15300: The product was collected as a white powder. 9.19 g

Synthesis of PtBA-N.SUB.3

[0662] PtBA-Br was converted to azide-terminated PtBA (PtBA-Ns) using the procedure below. The starting material was not completely purified before proceeding to the azidation; anisole and trace tert-butyl acrylate were carried through and removed during the step below. The procedure below is based on PtBA of M.sub.n: 4600.

[0663] To a dry 500 mL round bottom flask was added 16 g of PtBA-Br and 1.33 g of sodium azide. The flask was evacuated and backfilled with nitrogen three times. Then, approximately 130 mL of anhydrous DMF was cannulated into the flask under nitrogen. The reaction was then heated to 50 C. overnight under aluminum foil. After 18 hours, the reaction was cooled to room temperature and diluted with 200 mL of ethyl acetate. The organic layer was washed five times with water and once with brine. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The material was then redissolved in DCM and chromatographed on silica using a 0 to 8% methanol/DCM gradient. The product eluted at approximately 5-6% methanol. The product was collected and the solvent was evaporated on a rotary evaporator. The rotation and vacuum were controlled such that the product dried as a foam inside the flask. The flask was then dried on a vacuum line overnight. Foaming during concentration and drying allows for facile collection of the product by scraping from the inside of the flask.

PtBA 3.6k: 8.5 g

PtBA 4.6k: 11 g

Synthesis of Compound S1

[0664] ##STR00254##

[0665] This compound was synthesized from cis-endo-Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride according to literature procedure..sup.6(a)

Nb-PDMS-alkyne (Compound S2)

[0666] ##STR00255##

[0667] To a flame-dried 100 mL round bottom flask was added 844.6 mg (2.1 mmol, 1 equiv) of compound S1, 9.74 g (2.1 mmol, 1 equiv) of PDMS (M.sub.n: 5000) monocarbinol (from Gelest MCR-C18), 1.2 g (6.3 mmol, 3 equiv) of EDC-HCl, and 51 mg (0.42 mmol, 0.2 equiv) of DMAP. The flask was evacuated and backfilled with nitrogen three times, after which 20 mL of anhydrous dichloromethane was added via syringe. The reaction mixture was stirred for 16 hours at room temperature under nitrogen. The reaction mixture was concentrated under reduced pressure, and loaded directly onto a silica gel column. The column was first flushed with 100% dichloromethane to remove excess PDMS monocarbinol and the polarity was increased with a gradient to 8% methanol in dichloromethane to elute the desired product at approximately 6-7% methanol. The product was isolated as a viscous, slightly yellow oil. 8.03 g, 71% yield.

Nb-PLA-Alkyne

[0668] Nb-PLA-alkyne could also be prepared from compound S1 by incorporation of poly(lactic acid).

##STR00256##

Synthesis of Macromonomers 1 and 2

[0669] ##STR00257##

[0670] Macromonomer 1 was synthesized with eight different Mn of PSN3: 2300, 3300, 4600, 6400, 8200, 9200, 10,300, and 15,300. The same procedure was used for each molecular weight combination. Below is a representative protocol with PS of 4600 Mn.

[0671] To a 20 mL microwave vial was added 1.251 g (0.23 mmol, 1 equiv) of compound S2 via syringe. Then 1.53 g (0.33 mmol, 1.33 equiv) of PSN.sub.3 (M.sub.n: 4600) was added. The mixture was dissolved in 8 mL of THF and the vial was sealed with a PTFE-lined septum and aluminum crimp-top cap. The septum was pierced with a nitrogen inlet needle and an outlet needle and the solution was sparged for 45 minutes with nitrogen. The needles were carefully removed and the holes were sealed with electrical tape. The vial was brought into a nitrogen atmosphere glovebox, after which 1 mL of a stock solution of CuBr/Me.sub.6 TREN in toluene was added. The vial was then heated to 52 C. in the glovebox for 24 hours. In order to remove excess PSN.sub.3 and/or Nb-PDMS-alkyne, the vial was opened in the glovebox and 300 mg of azide-functionalized PS beads (average 4 mmol/gram), 300 mg of alkyne-functionalized PS beads (average 4 mmol/gram), and an extra 0.5 mL of the same CuBr/Me.sub.6 TREN catalyst solution were added. The reaction was resealed and stirred for a minimum of 24 extra hours. To quench the reaction, the vial was removed from the glovebox, opened to air, and 5-10 mL of HPLC grade (not anhydrous or deoxygenated) THF was added and allowed to stir for at least 5 minutes. A 1 inch diameter column was packed with 4-5 inches of activated neutral alumina and equilibrated with HPLC-grade THF. To remove the majority of the copper, the reaction mixture, including the beads, were directly applied to the column, which was then flushed with approximately three column volumes of THF. The solvent was removed under reduced pressure at 40 C. to remove as much residual THF and toluene as possible. The product was redissolved in dichloromethane and chromatographed on silica gel using a 0.fwdarw.8% methanol/DCM gradient. The majority of the product eluted at approximately 6-7% methanol. The product was collected and dried under vacuum. 2.17 g, 98% yield.

PS2300/PDMS5000: The product was collected as a waxy solid. 2.1 g, 65% yield
PS3300/PDMS5000: The product was collected as a white, waxy solid. 2.42 g, 72% yield
PS4600/PDMS5000: The product was collected as a slightly waxy, white solid. 1.69 g, 70% yield
PS6400/PDMS5000: The product was collected as a white solid. 1.70 g, 93% yield
PS8200/PDMS5000: The product was collected as a white solid. 1.50 g, 87% yield
PS9200/PDMS5000: The product was collected as a white solid. 1.82 g, 68% yield
PS10300/PDMS5000: The product was collected as a white solid. 1.35 g, 38% yield
PS15300/PDMS5000: The product was collected as a white solid. 1.09 g, 72% yield

Preparation of CuBr/Me.SUB.6 .TREN Catalyst Solution

[0672] CuBr was first purified according to literature procedure to remove Cu(II) salts..sup.22 CuBr was first weighed in a 40 mL scintillation vial inside a glovebox. The CuBr was then dispersed in toluene to a concentration of 20 mg/mL. Then, 1.1 equivalents of Me.sub.6 TREN was added dropwise to the solution. The solution was stable for several weeks at a time. Some Cu(0) precipitated due to disproportionation, but did not seem to affect the reaction.

Synthesis of Macromonomer 2

[0673] ##STR00258##

[0674] Macromonomer 2 was synthesized in the same manner as macromonomer 1 but with PtBA-N3 as the azide for the copper catalyzed azide-alkyne cycloaddition. The product was isolated a sticky, gummy wax that initially foamed under vacuum. 1.727 g, 92% yield.

Synthesis of Compound S3

[0675] ##STR00259##

[0676] To a 20 mL microwave vial was added 2.09 g (0.45 mmol, 1 equiv) of PSN.sub.3 (Mn: 4600). The mixture was dissolved in 8 mL of THF and the vial was sealed with a PTFE-lined septum and aluminum crimp-top cap. The septum was pierced with a nitrogen inlet needle and an outlet needle and the solution was sparged for 45 minutes with nitrogen. The needles were carefully removed and the holes were sealed with electrical tape. The vial was brought into a nitrogen atmosphere glovebox, after which 250 L (244 mg, 4.5 mmol, 10 equiv) of propargyl alcohol and 1 mL of a stock solution of CuBr/Me.sub.6 TREN in toluene was added (vide infra). The vial was then heated to 52 C. in the glovebox for 24 hours. In order to remove excess PSN.sub.3, the vial was opened in the glovebox and 300 mg of alkyne-functionalized polystyrene beads (average 4 mmol/gram), and an extra 0.5 mL of the same CuBr/Me.sub.6 TREN catalyst solution were added. The reaction was resealed and stirred for a minimum of 24 extra hours. To quench the reaction, the vial was removed from the glovebox, opened to air, and 5-10 mL of HPLC grade (not anhydrous or deoxygenated) THF was added and allowed to stir for at least 5 minutes. A 1 inch diameter column was packed with 4-5 inches of activated neutral alumina and equilibrated with HPLC-grade THF. To remove the majority of the copper, the reaction mixture, including the beads, were directly applied to the column, which was then flushed with approximately three column volumes of THF. The solvent was removed under reduced pressure at 40 C. to remove as much residual THF and toluene as possible. The product was redissolved in dichloromethane and chromatographed on silica gel using a 0.fwdarw.8% methanol/DCM gradient. The majority of the product eluted at approximately 4-5% methanol. The product, compound S3, was collected and dried under vacuum. 1.513 g, 72% yield.

Synthesis of Compound S4

[0677] ##STR00260##

[0678] To a flame-dried 50 mL round bottom flask was added 128 mg (0.322 mmol, 1 equiv) of compound S1, 1.513 g (0.322 mmol, 1 equiv) of compound S3, 154 mg (0.805 mmol, 2.5 equiv) of EDC.HCl, and 11.8 mg (0.1 mmol, 0.3 equiv) of DMAP. The flask was evacuated and backfilled with nitrogen three times, after which 10 mL of anhydrous dichloromethane was added via syringe. The reaction mixture was stirred for 16 hours at room temperature under nitrogen. The reaction mixture was concentrated under reduced pressure, and loaded directly onto a silica gel column. The column was first flushed with 100%/o dichloromethane to remove excess PDMS monocarbinol and the polarity was increased with a gradient to 8% methanol in dichloromethane to elute the desired product at approximately 6-7% methanol. The product was isolated as white solid. 1.26 g, 78% yield.

Synthesis of Macromonomer 3

[0679] ##STR00261##

[0680] To a 20 mL microwave vial was added 1.267 g (0.253 mmol, 1 equiv) of compound S4 and 1.170 g (0.253 mmol, equiv) of PtBA-N.sub.3 (M.sub.n: 4600). The mixture was dissolved in 8 mL of THF and the vial was sealed with a PTFE-lined septum and aluminum crimp-top cap. The septum was pierced with a nitrogen inlet needle and an outlet needle and the solution was sparged for 45 minutes with nitrogen. The needles were carefully removed and the holes were sealed with electrical tape. The vial was brought into a nitrogen atmosphere glovebox, after which 1 mL of a stock solution of CuBr/Me.sub.6 TREN in toluene was added (vide infra). The vial was then heated to 52 C. in the glovebox for 24 hours. In order to remove excess PtBA-N.sub.3 and S4 the vial was opened in the glovebox and 300 mg of alkyne-functionalized polystyrene beads (average 4 mmol/gram), 300 mg of azide-functionalized PS beads (average 4 mmol/gram), and an extra 0.5 mL of the same CuBr/Me.sub.6 TREN catalyst solution were added. The reaction was resealed and stirred for a minimum of 24 extra hours. To quench the reaction, the vial was removed from the glovebox, opened to air, and 5-10 mL of HPLC grade (not anhydrous or deoxygenated) THF was added and allowed to stir for at least 5 minutes. A 1 inch diameter column was packed with 4-5 inches of activated neutral alumina and equilibrated with HPLC-grade THF. To remove the majority of the copper, the reaction mixture, including the beads, were directly applied to the column, which was then flushed with approximately three column volumes of THF. The solvent was removed under reduced pressure at 40 C. to remove as much residual THF and toluene as possible. The product was redissolved in dichloromethane and chromatographed on silica gel using a 0.fwdarw.8% methanol/DCM gradient. The majority of the product eluted at approximately 7% methanol. The product was collected and dried under vacuum. 1.941 g, 77% yield.

Synthesis of NbPS-Branch-PLA

[0681] In analogous fashion, NbPS-branch-PLA was prepared from Nb-PLA-alkyne.

##STR00262##

ROMP of Macromonomers

[0682] All ROMPs were performed in 2 mL vials equipped with Teflon stir bars and PTFE-lined caps. For macromonomers that could be easily scraped (i.e. 1 for PS 3300 and above and 3), 50 mg of the material were weighed out into glass vials. The vials were brought into the glovebox and then dissolved in 50 L of THF while stirring. For macromonomers that were too waxy or intractable to handle with a spatula (i.e. 1 for PS 2300 and 2), the macromonomers were first dried under vacuum in a 20 mL scintillation vial and then brought into a glovebox. Anhydrous THF was added to dissolve the macromonomer at a concentration of 500 mg/mL; the density of the polymer was taken to be 1 g/mL in order to account for its volume. The macromonomer stock solution was then dispensed to 2 mL vials using a micropipettor.

[0683] In addition to the synthesis of 1-3, the following bottlebrush polymer (4) was synthesized in analogous fashion:

##STR00263##

[0684] Bottlebrush polymer 4 (n=50) exhibited a larger periodicity than the macromonomer employed for its preparation. AFM of surface bulk samples showed ordered morphology.

[0685] Diblock bottlebrush copolymers (5) and (6) were also prepared in analogous fashion, but employing standard techniques of sequential polymerization for formation of the diblock copolymers. The following sets of diblock copolymers were prepared accordingly:

##STR00264##

[0686] Bottlebrush copolymer 5 (n=25, 50, 100) showed ordered lamellar morphology Brushes of higher DP appeared to be photonic crystals. Bottlebrush copolymer 6 (n=25) was visible by SAXS, but internal sidechain features were not highly ordered (annealed at 120 C.). Brushes appeared to be photonic crystals.

[0687] BBCP containing monodisperse PLA and PDMS with molecular weight of 1000 were also synthesized. A ultra-small d-spacing of 5.68 nm, i.e., 2.84 nm single phase domain size, was observed in the long range ordered phase separation of PLA.sub.8-branch-PDMS 1000 BBCP. Subscript stands for the degree of polymerization (DP) of a monodisperse sidechain polymer (FIG. 27).

[0688] BBCP containing both monodisperse PLA and PDMS sidechains were also synthesized and characterized. d-Spacings BBCP samples with backbone DP of 100 are summarized in Table 2. The morphology of each sample is provided in the parenthesis. DIS: disordered. L: lamellae.

TABLE-US-00002 TABLE 2 d-Spacings of BBCP containing monodisperse PLA and PDMS sidechains PLA.sub.8 PLA.sub.12 PLA.sub.16 PDMS.sub.7 4.24 nm (DIS) 5.15 nm (DIS) 5.93 nm (DIS/L) PDMS.sub.11 5.11 nm (DIS) 6.30 nm (L) 7.03 nm (L) PDMS.sub.15 5.82 nm (DIS) 6.85 nm (L) 7.73 nm (L)
PS/PLA Bottlebrush Polymers with Gyroid Morphologies

[0689] In addition to the PDMS/PS, PDMS/PtBA AB branched bottlebrush polymers PS/PLA AB branched bottlebrush polymers were also prepared as shown in the scheme below. These BBCPs had surprising gyroid morphologies; in particular, (PS4.7k-br-PLA3.8k).sub.n as shown in FIG. 28.

##STR00265##

REFERENCES

[0690] (1) (a) Bates, F. S.; Fredrickson, G. H. Physics Today 1999, 52, 32; (b) Verduzco, R.; Li, X.; Pesek. S. L.; Stein, G. E. Chem. Soc. Rev. 2015, 44, 2405. [0691] (2) (a) Hawker, C. J.; Frechet, J. M. J. J. Am. Chem. Soc. 1990, 112, 7638; (b) Frechet, J. M. Science 1994, 263, 1710; (c) Zheng, W.; Wang, Z.-G. Macromolecules 1995, 28, 7215; (d) Bohbot-Raviv, Y.; Wang, Z.-G. Phys. Rev. Lett. 2000, 85, 3428; (e) Gao, H.; Matyjaszewski, K. Prog. Polym. Sci. 2009, 34, 317; (f) Lutz, J.-F.; Lehn, J.-M.; Meijer, E. W.: Matyjaszewski, K. Nature Reviews Materials 2016, 1, 16024. [0692] (3) (a) Sheiko, S. S.; Sumerlin, B. S.; Matyjaszewski, K. Prog. Polym. Sci. 2008, 33, 759; (b) Lee, H.-i.; Pietrasik, J.; Sheiko, S. S.; Matyjaszewski, K. Prog. Polym. Sci. 2010, 35, 24; (c) Rzayev, J. ACS Macro Letters 2012, 1, 1146. [0693] (4) (a) Xia, Y.; Olsen, B. D.; Kornfield, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2009, 131, 18525; (b) Xia Y.; Komfield, J. A.; Grubbs, R. H. Macromolecules 2009, 42, 3761; (c) Miyake, G. M.; Piunova, V. A.; Weitekamp, R. A.; Grubbs, R. H. Angew. Chem. Int. Ed. 2012, 51, 11246; (d) Sveinbjoemsson, B. R.; Weitekamp, R. A.; Miyake, G. M.; Xia, Y.; Atwater, H. A.; Grubbs. R. H. Proc. Natl. Acad. Sci. U.S.A 2012, 109, 14332. [0694] (5) (a) Hroguez, V.; Amedro, E.; Grande, D.; Fontanille, M.; Gnanou, Y. Macromolecules 2000, 33, 7241; (b) Li, Z.; Ma, J., Lee, N. S.; Wooley, K. L. J. Am. Chem. Soc. 2011, 133, 1228. [0695] (6) (a) Johnson, J. A.; Lu, Y. Y.; Burts, A. O.; Xia, Y.; Durrell, A. C.; Tirrell, D. A.; Grubbs, R. H. Macromolecules 2010, 43, 10326; (b) Johnson, J. A.; Lu, Y. Y.; Burts, A. O.; Lim, Y.-H.; Finn, M. G.; Koberstein, J. T.; Turro, N. J.; Tirrell, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133, 559; (c) Liu, J.; Burts, A. O.; Li, Y.; Zhukhovitskiy, A. V.; Ottaviani, M. F.: Turro, N. J.; Johnson. J. A. J. Am. Chem. Soc. 2012, 134, 16337; (d) Burts, A. O.; Li, Y.; Zhukhovitskiy, A. V.; Patel, P. R.; Grubbs, R. H.; Ottaviani, M. F.; Turro, N. J.; Johnson, J. A. Macromolecules 2012, 45, 8310; (e) Liao, L.; Liu, J.; Dreaden, E. C.; Morton, S. W.; Shopsowitz, K. E.; Hammond, P. T.; Johnson, J. A. J. Am. Chem. Soc. 2014, 136, 5896; (f) Sowers, M. A.; McCombs, J. R.; Wang, Y.; Paletta, J. T.; Morton. S. W.; Dreaden. E. C.; Boska, M. D.; Ottaviani, M. F.; Hammond, P. T.; Rajca, A.; Johnson, J. A. Nat Commun 2014, 5; (g) Mahanthappa, M. K.; Speetjens, F. W.; Wisconsin Alumni Research Foundation, USA. 2016, p 31pp. [0696] (7) (a) Kale, T. S.; Klaikherd, A.; Popere, B.; Thayumanavan, S. Langmuir 2009, 25, 9660: (b) Cheng, C.; Yang, N.-L. Macromolecules 2010, 43, 3153; (c) Li, Y.; Themistou, E.; Zou, J.; Das, B. P.; Tsianou, M.; Cheng, C. ACS Macro Letters 2012, 1, 52; (d) Luo, H.; Santos, J. L.; Herrera-Alonso, M. Chem. Commun. 2014, 50, 536; (e) Burts, A. O. Gao, A. X.; Johnson, J. A. Macromol. Rapid Commun. 2014, 35, 168; (f) Rangadurai, P.; Molla, M. R.; Prasad. P.; Caissy, M.; Thayumanavan, S. J. Am. Chem. Soc. 2016, 138, 7508; (g) Li, H.; Miao, H.; Gao, Y.; Li, H.; Chen, D. Polymer Chemistry 2016, 7, 4476. [0697] (8) (a) Zhao, L.; Byun, M.; Rzayev, J.; Lin, Z. Macromolecules 2009, 42, 9027; (b) Yuan, Y.-Y.; Du, Q.; Wang, Y.-C.; Wang, J. Macromolecules 2010, 43, 1739; (c) Li, Y.; Zou, J.; Das, B. P.; Tsianou, M.; Cheng, C. Macromolecules 2012, 45, 4623; (d) Li, Y.; Christian-Tabak, L.; Fuan, V. L. F.; Zou, J. Cheng, C. J. Polym. Sci., Part A; Polym. Chem. 2014, 52, 3250. [0698] (9) (a) Bowden, N. B.; Runge, M. B.; Dutta, S.; American Chemical Society; 2005, p PMSE; (b) Theodorakis, P. E.; Paul, W.; Binder, K. Macromolecules 2010, 43, 5137; (c) Dalsin, S. J.; Rions-Maehren, T. G.; Beam, M. D.; Bates, F. S.; Hillmyer, M. A.; Matsen, M. W. ACS Nano 2015, 9, 12233. [0699] (10) Jung, Y. S.; Ross, C. A. Nano Lett. 2007, 7, 2046. [0700] (11) Sinturel, C.; Bates, F. S.; Hillmyer, M. A. ACS Macro Letters 2015, 4, 1044. [0701] (12) Jeong, J. W.; Park, W. I.; Kim, M.-J.; Ross, C. 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Macromolecules 2000, 33, 4039. [0711] (22) Kawamoto, K.; Zhong, M.; Wang, R.; Olsen, B. D.; Johnson, J. A. Macromolecules 2015, 48, 8980. [0712] (23) Liu, J.; Gao, A. X.; Johnson, J. A. 2013, e50874

EQUIVALENTS AND SCOPE

[0713] In the claims, articles such as a, an, and the may mean one or more than one unless indicated to the contrary or otherwise evident from the context. Claims or descriptions that include or between one or more members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The invention includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The invention includes embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.

[0714] Furthermore, the invention encompasses all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include one or more limitations found in any other claim that is dependent on the same base claim. Where elements are presented as lists, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should it be understood that, in general, where the invention, or aspects of the invention, is/are referred to as comprising particular elements and/or features, certain embodiments of the invention or aspects of the invention consist, or consist essentially of, such elements and/or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein.

[0715] It is also noted that the terms comprising and containing are intended to be open and permits the inclusion of additional elements or steps. Where ranges are given, endpoints are included. Furthermore, unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the invention, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.

[0716] This application refers to various issued patents, published patent applications, journal articles, and other publications, all of which are incorporated herein by reference. If there is a conflict between any of the incorporated references and the instant specification, the specification shall control. In addition, any particular embodiment of the present invention that falls within the prior art may be explicitly excluded from any one or more of the claims. Because such embodiments are deemed to be known to one of ordinary skill in the art, they may be excluded even if the exclusion is not set forth explicitly herein. Any particular embodiment of the invention can be excluded from any claim, for any reason, whether or not related to the existence of prior art.

[0717] Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation many equivalents to the specific embodiments described herein. The scope of the present embodiments described herein is not intended to be limited to the above Description, but rather is as set forth in the appended claims. Those of ordinary skill in the art will appreciate that various changes and modifications to this description may be made without departing from the spirit or scope of the present invention, as defined in the following claims.

BOTTLEBRUSH POLYMERS AND USES THEREOF

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Abstract

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