Photochromic water harvesting platform

Abstract

The application discloses compounds, compositions, films and devices comprising the compounds and compositions, and their methods of use for harvesting water.

Claims

1. A method for the condensation of water on a surface of a film deposited on a surface of a device, comprising: exposing the device comprising photoactive, thermally or electrically-active or a combination of a photoactive, thermally active and/or electrically-active film, wherein the film comprises a compound having a ground state that reversibly converts to its activated state upon exposure to light, heat or an electric field, or a combination of light, heat and/or electric field, wherein the activated state of the compound is more polar than the ground state of the compound; wherein the device is exposed for a sufficient period of time to condense moisture on or capture and adhere water droplets on the surface of the film; and continuously collecting the water formed or collected on the surface of the device.

2. The method of claim 1, wherein the compound is of the formula I: ##STR00016## wherein: m is 0, 1, 2, 3 or 4; n is 0, 1, 2, 3 or 4; R is H or is selected from the group consisting of substituted or unsubstituted C.sub.1-22 alkyl, substituted or unsubstituted C.sub.6-10 aryl, substituted or unsubstituted alkyl-C.sub.6-10 aryl, substituted or unsubstituted C.sub.1-22 alkylC(O)—, substituted or unsubstituted C.sub.1-22 alkylS(O).sub.1-2—, substituted or unsubstituted C.sub.1-22 alkylNR′C(O)— and substituted or unsubstituted C.sub.1-22 alkoxyC(NR″)—, or a polymer; each X is independently H or is selected from the group consisting of halo, —CN, —NO.sub.2, —COOH, —SH, —OH, substituted or unsubstituted C.sub.1-6 alkyl, substituted or unsubstituted C.sub.6-10 aryl, substituted or unsubstituted —C.sub.1-6 alkyl-C.sub.6-10 aryl, substituted or unsubstituted —C.sub.1-6alkylC(O)—, substituted or unsubstituted —C.sub.1-6alkylS(O).sub.1-2—, substituted or unsubstituted —C.sub.1-6 alkylNR′C(O)— and substituted or unsubstituted C.sub.1-6 alkoxyC(NR″)—; each Y is independently H or is selected from the group consisting of halo, —CN, —NO.sub.2, —COOH, —SH, —OH, substituted or unsubstituted C.sub.1-6 alkyl, substituted or unsubstituted C.sub.6-10 aryl, substituted or unsubstituted —C.sub.1-6 alkyl-C.sub.6-10 aryl, substituted or unsubstituted C.sub.1-6 alkylC(O)—, substituted or unsubstituted C.sub.1-6 alkylS(O).sub.1-2—, substituted or unsubstituted C.sub.1-6 alkylNR′C(O)— and substituted or unsubstituted C.sub.1-6 alkoxyC(NR″)—; Z is —O—, —S—, —C(O)—, —C(S)—, —C(NR′)—, —S(O).sub.1-2—, —NR′— and —CR′R″—; and R′ and R″ are each independently selected from the group consisting of H, substituted or unsubstituted C.sub.1-6 alkyl and substituted and unsubstituted —C.sub.1-6 alkyl-C.sub.6-10 aryl.

3. The method of claim 1, wherein R is a polymer deposited on the surface of the device.

4. The method of claim 3, wherein the polymer is selected from the group consisting of polyethylene (LDPE or HDPE), polypropylene, poly(vinyl chloride), poly(vinylidene chloride), polystyrene, polyacrylonitrile, polytetrafluoroethylene (PTFE, Teflon), poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), polyisoprene, polychloroprene, poly(oxyethylene) (POE), poly(oxy-1,2-ethanediyloxycarbonyl-1,4-phenylenecarbony (PET), poly[amino(1-oxo-1,6-hexanediyl)], polystyrene, ethyl-vinyl-acetate (EVA), polylactide (PLA), polyhydroxyalkanoates (PHA), polyhydroxybutyrate (PHB), poly-L-lactide (PLLA), PDLA (poly-D-lactide) or mixtures thereof.

5. The method of claim 1, wherein the device is configured for harvesting water from humid air and/or fog.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: FIG. 1A is a schematic illustration of water droplets beading up on a hydrophilic film in the ground state and spreading out on an activated hydrophilic film; FIG. 1B shows that, in a bead of water on a hydrophilic film in the ground state, the contact angle is greater than 90°, while on an activated hydrophilic film, the contact angle is less than 90°.

(2) FIG. 2: FIG. 2 is a schematic illustration showing a thin film as described herein, which oscillates between the ground(hydrophobic) state and the activated (hydrophilic) state depending on the light contacting the surface.

DETAILED DESCRIPTION

Definitions

(3) Unless specifically noted otherwise herein, the definitions of the terms used are standard definitions used in the art of organic synthesis and chemical sciences. Exemplary embodiments, aspects and variations are illustrative in the figures and drawings, and it is intended that the embodiments, aspects and variations, and the figures and drawings disclosed herein are to be considered illustrative and not limiting.

(4) An “alkyl” group is a straight, branched, saturated or unsaturated, aliphatic group having a chain of carbon atoms, optionally with oxygen, nitrogen or sulfur atoms inserted between the carbon atoms in the chain or as indicated. A (C.sub.1-20)alkyl, for example, includes alkyl groups that have a chain of between 1 and 20 carbon atoms, and include, for example, the groups methyl, ethyl, propyl, isopropyl, vinyl, allyl, 1-propenyl, isopropenyl, ethynyl, 1-propynyl, 2-propynyl, 1,3-butadienyl, penta-1,3-dienyl, penta-1,4-dienyl, hexa-1,3-dienyl, hexa-1,3,5-trienyl, and the like. An alkyl group may also be represented, for example, as a —(CR.sup.1R.sup.2)m- group where R.sup.1 and R.sup.2 are independently hydrogen or are independently absent, and for example, m is 1 to 8, and such representation is also intended to cover both saturated and unsaturated alkyl groups.

(5) An alkyl as noted with another group such as an aryl group, represented as “arylalkyl” for example, is intended to be a straight, branched, saturated or unsaturated aliphatic divalent group with the number of atoms indicated in the alkyl group (as in (C.sub.1-20)alkyl, for example) and/or aryl group (as in (C.sub.5-14)aryl or (C.sub.6-14)aryl, for example) or when no atoms are indicated means a bond between the aryl and the alkyl group. Nonexclusive examples of such group include benzyl, phenethyl and the like.

(6) An “alkylene” group is a straight, branched, saturated or unsaturated aliphatic divalent group with the number of atoms indicated in the alkyl group; for example, a —(C.sub.1-3)alkylene- or —(C.sub.1-3)alkylenyl-.

(7) A “cyclyl” such as a monocyclyl or polycyclyl group includes monocyclic, or linearly fused, angularly fused or bridged polycycloalkyl, or combinations thereof. Such cyclyl groups include the heterocyclyl analogs. A cyclyl group may be saturated, partially saturated or aromatic.

(8) “Halogen” or “halo” means fluorine, chlorine, bromine or iodine.

(9) A “heterocyclyl” or “heterocycle” is a cycloalkyl wherein one or more of the atoms forming the ring is a heteroatom that is a N, O, or S. Non-exclusive examples of heterocyclyl include piperidyl, 4-morpholyl, 4-piperazinyl, pyrrolidinyl, 1,4-diazaperhydroepinyl, 1,3-dioxanyl, and the like.

(10) “Substituted or unsubstituted” or “optionally substituted” means that a group such as, for example, alkyl, aryl, heterocyclyl, (C.sub.1-8)cycloalkyl, heterocyclyl(C.sub.1-8)alkyl, aryl(C.sub.1-8)alkyl, heteroaryl, heteroaryl(C.sub.1-8)alkyl, and the like, unless specifically noted otherwise, may be unsubstituted or, may substituted by 1, 2 or 3 substituents selected from the group such as halo, nitro, trifluoromethyl, trifluoromethoxy, methoxy, carboxy, —NH.sub.2, —OH, —SH, —NHCH.sub.3, —N(CH.sub.3).sub.2, —SMe, cyano and the like.

(11) The following procedures may be employed for the preparation of the compounds of the present invention. The starting materials and reagents used in preparing these compounds are either available from commercial suppliers such as the Aldrich Chemical Company (Milwaukee, Wis.), Bachem (Torrance, Calif.), Sigma (St. Louis, Mo.), or are prepared by methods well known to a person of ordinary skill in the art, following procedures described in such references as Fieser and Fieser's Reagents for Organic Synthesis, vols. 1-17, John Wiley and Sons, New York, N.Y., 1991; Rodd's Chemistry of Carbon Compounds, vols. 1-5 and supps., Elsevier Science Publishers, 1989; Organic Reactions, vols. 1-40, John Wiley and Sons, New York, N.Y., 1991; March J.: Advanced Organic Chemistry, 4th ed., John Wiley and Sons, New York, N.Y.; and Larock: Comprehensive Organic Transformations, VCH Publishers, New York, 1989.

(12) In some cases, protective groups may be introduced and finally removed. Suitable protective groups for amino, hydroxy, and carboxy groups are described in Greene et al., Protective Groups in Organic Synthesis, Second Edition, John Wiley and Sons, New York, 1991. Standard organic chemical reactions can be achieved by using a number of different reagents, for examples, as described in Larock: Comprehensive Organic Transformations, VCH Publishers, New York, 1989.

EXAMPLES

Example 1

Preparation of a Photo-Switchable Surface

(13) A photo-switchable surface was prepared by a 2-step synthesis of the spiropyran 3′,3′-dimethyl-6-nitro-I′-octadecylspiro[chromene-2,2′-indoline], III or “C-18-spiropyran,” which is then followed by a third step in which the spiropyran III and a polymer were dissolved in solvent, coated onto a substrate, and the resultant polymer film dried. The photo-switchable polymer surface was characterized by drop-shape analysis of water on the surface.

(14) ##STR00006##

(15) Compound III is a specific compound of formula I, in which X=4-nitro (4-NO.sub.2); m is 1; n=0 (no Y substituents other than H); R=n-octadecyl (n-C.sub.18H37); and Z═C(CH.sub.3).sub.2.

A. Synthesis of intermediate 3-dimethyl-2-methylene-1-octadecylindoline

(16) To a 500-mL, three-necked, round bottom flask was added 10.0 mL 2,3,3-trimethylindolenine (62 mmol, 1.0 equivalent), 9.34 g sodium iodide (62 mmol, 1.0 equivalent) and 200 mL of acetonitrile. The mixture was heated to reflux with stirring. To the refluxing solution, 19.2 mL of bromooctadecane (56 mmol, 0.9 equivalent) was added dropwise. The solution was refluxed for 7 days (158 hours), with occasional additions of acetonitrile to maintain solvent volume.

(17) The solvent was removed by evaporation with heating, and the residue was cooled to room temperature. The residue was extracted into acetonitrile. The filtrate was concentrated under reduced pressure. The residue was dissolved in methylene chloride and transferred to a separatory funnel. The solution was washed with saturated sodium bicarbonate solution two times and water once. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The crude yield of 3-dimethyl-2-methylene-1-octadecylindoline was 23.43 grams. The material was used in the next step without purification.

B. Synthesis of C-18-Spiropyran, Compound III

(18) 6.71 grams of 5-nitrosalicylaldehyde (40 mmol, 1.0 equivalent) was added to 150 mL ethanol in a round bottom flask and brought to reflux. To the refluxing solution was added dropwise 16.54 grams of the crude product from step 1, namely, 3-dimethyl-2-methylene-1-octadecylindoline (40 mmol, 1.0 equivalent). The mixture was refluxed overnight. After refluxing, the solution was cooled to room temperature and filtered. The solid was washed with ice-cold ethanol and dried under vacuum, to yield 12.80 grams of purple crystals of C-18-spiropyran III.

C. Preparation of C-18-Spiropyran Films

(19) 0.5 grams of C-18-spiropyran (III) was dissolved in a solution consisting 0.225 grams of poly(methyl methacrylate) (PMMA) (Alfa Aesar Z007-239, average molecular weight 550,000 g/mol) dissolved in 6.5 grams of ethyl acetate. The resulting solution was coated 0.005-inch thick onto Dupont 6638 polyethylene terephthalate substrate using a wire-wound rod (#5 Meyer rod). The resulting wet film was dried at ambient temperature in the dark. The dried film is composed of 68% C-18-spiropyran (III) and 32% PMMA.

(20) A “control” film consisting of 100% poly(methyl methacrylate) was prepared by coating a solution of 0.225 grams PMMA dissolved in 6.5 grams of ethyl acetate. The resulting solution was coated 0.005-inch thick onto Dupont 6638 polyethylene terephthalate substrate using a wire-wound rod (#5 Meyer rod). The resulting wet film was dried at ambient temperature in the dark. The dried film is composed of 100% PMMA.

(21) Determination of hydrophilic/hydrophobic character of films by contact angle measurement: Three 5-microliter aliquots of de-ionized water droplets were deposited on the surface of each of the two resulting dried films. Contact angles were measured for each droplet using a KRÜSS DSA100 Drop Shape Analyzer. Each film was then exposed to 365-nanometer (ultraviolet) light for 5 minutes in a Spectrolinker XL-1500 UV crosslinker (Spectronics Corporation).

(22) The control film remained colorless after exposure to ultraviolet light. The film composed of 68% C-18-spiropyran (III)/32% PMMA was colored purple as a result of the ultraviolet light exposure. Immediately after ultraviolet light exposure, three 5-microliter aliquots of de-ionized water droplets were deposited on the surface of each of the two films, and the contact angles measured. The film composed of 68% C-18-spiropyran (III)/32% PMMA was then stored in the dark at ambient temperature for two days. Contact angles of three 5-microliter water droplets on the now-deactivated film were then determined.

(23) Results of the series of contact angle measurements are given in Table 1.

(24) TABLE-US-00001 TABLE 1 Contact angles for 5-microliter deionized water droplets on 100% poly(methyl methacrylate) (PMMA) films and 68% C-18-spiropyran (III)/32% PMMA film pre- and post-ultraviolet light exposure. 68% C-18- 68% C-18- spiropyran spiropyran (III)/ 100% 68% (III)/32% 32% PMMA PMMA C-18- PMMA film post- film spiropyran film ultraviolet 100% post- (III)/32% post- exposure PMMA ultraviolet PMMA ultraviolet followed by 2 film exposure film exposure days in darkness Droplet 1 77.1° 75.5° 102.2° 79.4° 89.4° Droplet 2 85.4° 79.4°  97.9° 76.2° 85.1° Droplet 3 82.7° 80.0°  98.1° 74.4° 84.4° Average ± 81.7° ± 78.3° ± 99.4° ± 76.7° ± 86.3° ± 2.7° standard  4.2°  2.4°  2.4°  2.5° deviation

(25) Water droplets on the film composed of 100% PMMA show an average contact angle of 81.7°±4.2°. Following exposure to ultraviolet light, the average contact angle is 78.3°±2.4°, a change which shows little statistical significance (p=0.31). The contact angles are all slightly less than 90°, indicating that the 100% PMMA film is slightly hydrophilic.

(26) Water droplets on the film composed of 68% C-18-spiropyran (III)/32% PMMA show an average contact angle of 99.4°±2.4°. The angle is greater than 90°, indicating the film is hydrophobic. Following exposure to ultraviolet light, the average contact angle is 76.7°±2.5°, a statistically-significant (p=0.0003) decrease of 22.7°. The post-ultraviolet exposure contact angle is less than 90°, indicating the ultraviolet-exposed 68% C-18-spiropyran (III)/32% PMMA film has an increased hydrophilicity.

(27) After two subsequent days in the dark, the previously-exposed 68% C-18-spiropyran (V)/32% PMMA film shows an average contact angle of 86.3°±2.7°. The dark-reversed film shows a recovery of the hydrophobicity, as measured by a significant (p=0.01) increase of the contact angle by 9.6° as compared to the contact angle measured for the film immediately after exposure to ultraviolet light. After two days in the dark, the film does not show complete recovery of the hydrophobicity, as measured by a still significantly (p=0.003) reduced contact angle, 13.1° less than the film pre-exposure.

Example 2

Synthesis of C1-H, C4-H, C4-OMe, C8-H, and C18-OMe Spiropyrans and Solution Preparation

A. General Synthetic Route to Spiropyrans

(28) ##STR00007##

(29) These spiropyrans were prepared using an adapted version of the procedure in Tomasulo, Massimiliano et al., Journal of Organic Chemistry (2007), 72(2):595-605.

B. 5′-methoxy-3′,3′-dimethyl-6-nitro-1′-octadecyl-spiro[chromene-2,2′-indoline] (C18-OMe)

(30) ##STR00008##

(31) C18-OMe spiropyran is a specific compound of formula I, in which X=4-nitro (4-NO2); m is 1; Y=methoxy (OCH3); n=1; R=n-octadecyl (n-C.sub.18H.sub.37); and Z═C(CH.sub.3).sub.2, and was prepared as follows.

(32) A solution of the iodide salt of 5-methoxy-3,3-dimethyl-2-methylene-1-octadecyl-indoline (2 g, 3.72 mmol), 2-hydroxy-5-nitro-benzaldehyde (0.65 g, 3.91 mmol, Ark Pharm Inc., Libertyville, Ill.), and triethylamine (0.8 mL, 5.56 mmol, Sigma Aldrich, St. Louis, Mo.) in ethanol (20 mL) was heated for 12 h under reflux and a nitrogen blanket. After cooling down to room temperature, the solvent was removed under reduced pressure. The residue was extracted with dichloromethane (2×20 mL) and washed with distilled water (20 mL). The organic layer was dried over anhydrous Na2SO4 and removed under reduced pressure to get the crude product. The crude was suspended in hexane and the solid was filtered to afford the desired product (1.48 g, 68%). .sup.1H NMR (400 MHz, DMSO-d6): δ 10.18 (br s, 1H), 8.60 (s, 1H), 8.29-8.28, m, 2H), 7.80 (d, J=8.28, 1H), 7.53 (d, J=8.28, 1H), 7.09 (d, J=2.44, 1H), 6.90 (d, J=9.8, 1H), 6.25 (d, J=9.8, 1H), 3.11 (m, 2H), 1.78-1.76 (m, 2H), 1.68 (s, 6H), 1.50-1.20 (m, 13H). LCMS (M+1): 442.4.

C. 1′,3′-dihydro-3′,3′-dimethyl-6-nitro-1′-octyl-spiro[2H-1-benzopyran-2,2′-[2H]indole] (C8-H)

(33) ##STR00009##

(34) C8-H spiropyran is a specific compound of formula I, in which X=4-nitro (4-NO.sub.2); m is 1; n=0 (no Y substituents other than H); R=n-octyl (n-C.sub.8H.sub.17); and Z═C(CH.sub.3).sub.2. C8-H was prepared in accordance with the procedure in Wu, Yusong et al., Journal of Physical Chemistry B (2008), 112(25): 7530-7536.

D. 1′-butyl-1′,3′-dihydro-3′,3′-dimethyl-6-nitro-spiro[2H-1-benzopyran-2,2′-[2H]indole] (C4-H)

(35) ##STR00010##

(36) C4-H spiropyran is a specific compound of formula I, in which X=4-nitro (4-NO.sub.2); m is 1; n=0 (no Y substituents other than H); R=n-butyl (n-C.sub.4H.sub.9); and Z═C(CH.sub.3).sub.2. C8-H was prepared as in C above.

E. 5′-methoxy-3′,3′-dimethyl-6-nitro-1′-octadecyl-spiro[chromene-2,2′-indoline] (C.SUB.4.—OMe)

(37) ##STR00011##

(38) C4-OMe spiropyran is a specific compound of formula I, in which X=4-nitro (4-NO.sub.2); m is 1; Y=methoxy (OCH.sub.3); n=1; R=n-butyl (n-C.sub.4H9); and Z═C(CH.sub.3).sub.2. C4-OMe was prepared as in B above.

(39) A solution of the iodide salt of 1′-butyl-5′-methoxy-3′,3′-dimethyl-6-nitro-spiro[chromene-2,2′-indoline] (2.21 g, 9.39 mmol), 2-hydroxy-5-nitro-benzaldehyde (1.64 g, 9.86 mmol) and triethylamine (2.62 mL, 18.79 mmol) in ethanol (20 mL) was heated for 12 h under reflux and a nitrogen blanket. After cooling down to room temperature, the solvent was removed under reduced pressure. The residue was extracted with dichloromethane (2×20 mL) and washed with distilled water (20 mL). The organic layer was dried over anhydrous Na.sub.2SO.sub.4 and removed under reduced pressure to get the crude product. The crude was suspended in hexane and the solid was filtered to afford the desired product (1.48 g, 48%). .sup.1H NMR (400 MHz, DMSO-d6): δ 10.18 (br s, 1H), 8.60 (s, 1H), 8.29-8.28, m, 2H), 7.80 (d, J=8.28, 1H), 7.53 (d, J=8.28, 1H), 7.09 (d, J=2.44, 1H), 6.90 (d, J=9.8, 1H), 6.25 (d, J=9.8, 1H), 3.11 (m, 2H), 1.78-1.76 (m, 2H), 1.68 (s, 6H), 1.50-1.20 (m, 13H). LCMS (M+1): 395.2

F. 1′,3′,3′-trimethyl-6-nitro-spiro[chromene-2,2′-indoline] (C1-H)

(40) ##STR00012##

(41) C1-H spiropyran is a specific compound of formula I, in which X=4-nitro (4-NO.sub.2); m is 1; n=0 (no Y substituents other than H); R=methyl (CH.sub.3); and Z═C(CH.sub.3).sub.2. C1-H was prepared in accordance with the procedure in Shiraishi, Yasuhiro et al., Organic Letters (2009), 11(15): 3482-3485.

G. 3′,3′-dimethyl-6-nitro-1′-[(4-vinylphenyl)methyl]spiro[chromene-2,2′-indoline] (Styrene-H)

(42) ##STR00013##

(43) Styrene-H spiropyran is a specific compound of formula I, in which X=4-nitro (4-NO.sub.2); m is 1; n=0 (no Y substituents other than H); R=styrene; and Z═C(CH.sub.3).sub.2. Styrene-H was prepared in accordance with the procedures in Tan, Chunbin et al., Huaxue Xuebao (2012), 70(9): 1095-1103 and Tian, Zhiyuan et al., Journal of the American Chemical Society (2011), 133(40): 16092-16100.

H. Preparing Small Molecule Solutions

(44) Poly(methyl methacrylate) (450 mg, PMMA, Alfa Aesar, Ward Hill, Mass.) was added to 13 g (14.4 mL) of ethyl acetate. The PMMA was dissolved in ethyl acetate under agitation for 12 h. 250 mg of each SP (including C18-H, as prepared in Example 1) was added to 3.375 g of the PMMA/ethyl acetate solution and agitated until dissolved. The resulting solutions were 10% solids by mass and 69:31 SP/PMMA by mass.

Example 3

Synthesis of P(SP-homo), P(SP-co-MMA) (1:1), P(SP-co-MMA) (1:3), P(SP-co-MMA) (1:5), and P(SP-co-MMA) (1:10) and Solution Preparation

A. P(SP-homo)

(45) ##STR00014## P(SP-homo) is a specific compound of formula II, in which X=4-nitro(4-NO.sub.2); m is 1, n=0 (no Y substituents other than H); Z=C(CH.sub.3).sub.2; and p=unknown. R′″ and q are not applicable.

(46) A 50 mL round bottom flask was charged with Styrene-H (1 g, 0.0259 mol), as prepared in Example 2G, and isopropanol (10 mL). The mixture was degassed with nitrogen for 5 minutes, then heated and stirred at 75° C. In a separate vial, 40 mg of 2,2′-Azobis(2-methylpropionitrile) (AIBN, Sigma Aldrich, St. Louis, Mo.) was dissolved in 2 mL of isopropanol and degassed with nitrogen. The AIBN solution was added to the hot Styrene-H and isopropanol reaction mixture and heated and stirred at 75° C. for 15 h. The reaction mixture was cooled to room temperature. The resulting solid was filtered, washed with hexanes, and dried in a vacuum oven at 40° C. for 4 h (0.57 g).

(47) .sup.1H NMR (CDCl.sub.3) showed 70% polymer and about 30% unreacted monomer. To remove the unreacted monomer, the solid was washed with 1:1 ether/hexanes and ether. The .sup.1H NMR still showed about 20% monomer. The solid was taken back into ether and stirred at room temperature overnight. The solid was filtered and washed with ether. .sup.1H NMR before drying the sample showed pure homopolymer. The solid was dried in a vacuum oven at 40° C. for 8 h (isolated weight 0.25 g).

B. P(SP-co-MMA) (1:1), P(SP-co-MMA) (1:3), P(SP-co-MMA) (1:5), and P(SP-co-MMA) (1:10)

(48) ##STR00015##

(49) P(SP-co-MMA) (1:1), P(SP-co-MMA) (1:3), P(SP-co-MMA) (1:5), and P(SP-co-MMA) (1:10) are variants of compound II, in which X=4-nitro (4-NO2); m is 1, n=0 (no 7 substituents other than H); Z=C(CH3)2; p=unknown; R′″=methyl methacrylate (MMA); and q=unknown. The (1:1), (1:3), (1:5), and (1:10) note the molar rations of Styrene-H to MMA in the copolymers.

(50) A 50 mL round bottom flask was charged with Styrene-H (1 g, 0.0024 mol), as prepared in Example 2G, and isopropanol (8 mL). The resulting slurry was degassed with nitrogen for 5 minutes. Methyl methacrylate (0.26 mL, 0.0024 mol, 1 eqv., Sigma Aldrich, St. Louis, Mo.) was added to the solution. The resulting mixture was degassed for another 5 minutes, then heated and stirred at 75° C. In a separate vial, 40 mg of AIBN was dissolved in 2 mL of isopropanol and degassed with nitrogen. The AIBN solution was added to the hot reaction mixture and heated and stirred at 75° C. for 15-24 h. The reaction mixture was cooled to room temperature and stirred for another 24 h. Hexanes (20 mL) were added and the solution was stirred for 1 h. The resulting solid was filtered, washed with 25% EtOAc/hexanes (10 mL×3), and dried at 45° C. in a vacuum oven for 20 h. This method was repeated for the P(SP-co-MMA) (1:3), (1:5), and (1:10) equivalents using (0.77 mL, 0.0072 mol, 3 eqv.), (1.26 mL, 0.012 mol, 5 eqv.), and (2.57 mL, 0.024 mol, 10 eqv.) of methyl methacrylate, respectively. .sup.1H NMRs of all solids appeared clean and showed broad peaks, revealing polymer formation.

C. Preparing Polymer Solutions

(51) The 10% solids by mass P(SP-co-MMA) solutions were prepared by adding 50 mg of each copolymer to 450 mg (0.34 mL) dichloromethane and stirring until dissolved.

Example 4

C18-H Spiropyran Water Uptake and Release Studies

A. C18-H Spiropyran Film on PET Preparation

(52) The C18-H spiropyran solution, as prepared in Example 1H, was cast into films on PET substrate (500 gauge, Melinex 454, DuPont Teijin Films) using a 5 mil coating bar and allowed to dry in the dark under ambient conditions for 12 h.

B. Water Uptake of C18-H Film on PET

(53) All FTIR spectra for this experiment were taken using a diamond ATR crystal. FTIR spectra of the uncoated PET substrate and the C18-H film were taken as controls. The first C18-H film sample was exposed to water vapor for 10 min and FTIR spectra were taken. The second C18-H film sample was exposed to 365 nm UV irradiation for 5 min in the Spectrolinker XL-1000 (Spectronics Corporation) and FTIR spectra were taken immediately after. After UV irradiation, the film was exposed to water vapor for 10 min and FTIR spectra were taken again.

(54) As determined by Florea, L. et al., Sensors and Actuators B: Chemical (2012), 175: 92-99, the formation of an absorption band at 1593 cm.sup.−1 indicates the presence of C═N.sup.+ stretching vibrations in the merocyanine form. In the FTIR spectra, both controls and the first sample showed no absorption in this region. However, the second sample showed absorption at 1593 cm.sup.−1 both before and after exposure to water, with a stronger absorption before exposure.

C. Water Uptake of C18-H Film with Shorter Evaporation Time and Longer Irradiation Time

(55) A 50 μL aliquot of C18-H spiropyran solution was deposited onto the surface of a germanium ATR crystal. The ethyl acetate was allowed to evaporate for 10 min, resulting in a film. The C18-H film was then irradiated for 20 min with a 405 nm violet laser. After 20 min, while irradiation continued, 1 mL water was added on top of the film. FTIR spectra were taken at various intervals from t=0 min, the moment the solution was deposited on the crystal, to t=47 min.

(56) In the FTIR spectra, a broad band begins to appear at 3400 cm.sup.−1 after the addition of water and gradually grows as time goes on. This band corresponds to the hydroxyl stretching vibrations in the water adsorbed to the film.

(57) In order to quantify the water retention of the films, the instrumental drift in the FTIR spectra was corrected for and the difference in absorbance between 3385 cm.sup.−1 and 4000 cm.sup.−1 (Δ.sub.Abs) was plotted as a function of time. The Δ.sub.Abs was then fitted to an exponential decay equation where t is time, and A, t.sub.0, and τ are the fitting parameters:

(58) ${\Delta }_{\mathrm{Abs}}=A\times \left(1-e^{-\frac{t-t_0}{\tau }}\right)$
The Δ.sub.Abs showed a sharp increase after the addition of water, resulting in a Δ.sub.Abs (1 min) irradiated of 1.88×10.sup.−3.

D. Water Uptake of C18-H Film with Longer Evaporation Time and Shorter Irradiation Time

(59) A 50 μL aliquot of C18-H spiropyran solution was deposited onto the surface of a germanium ATR crystal. The ethyl acetate was allowed to evaporate for 45 min, resulting in a film. The film was irradiated for 3 min with a 405 nm violet laser. After 3 min, while irradiation continued, 1 mL water was added on top of the film. FTIR spectra were taken at various intervals from t=0 min, the moment the solution was deposited on the crystal, to t=79 min.

(60) Next, 50 μL of the C18-H solution was deposited onto the surface of another germanium ATR crystal. The ethyl acetate was allowed to evaporate for 47 min, after which 1 mL water was added on top of the film. FTIR spectra were taken at various intervals from t=0 min, the moment the solution was deposited on the crystal, to t=58 min.

(61) The Δ.sub.Abs was plotted as a function of time and fitted to an exponential decay equation. The Δ.sub.Abs (1 min) irradiated for the film irradiated for 3 min, at 0.438×10.sup.−3, was less pronounced than the film irradiated for 20 min. The film that was not irradiated at all had the smallest Δ.sub.Abs (1 min) irradiated at 0.342×10.sup.−3.

E. Water Release in Pre-wetted C18-H Film

(62) To prepare the pre-wetted film, 20 μL of water was added to 180 μL of C18-H solution and mixed until homogeneous. A 50 μL aliquot of the resulting solution was deposited onto the surface of a germanium ATR crystal. The film was allowed to dry under ambient light for 5 min, while FTIR spectra were taken at 1 min intervals. The experiment was repeated using a 405 nm violet laser instead of ambient light.

(63) The FTIR spectra show a steep decrease in absorbance from 0 to 5 min in the sample without irradiation and a steadier decrease in absorbance in the sample with irradiation.

F. Water Contact Angle on C18-H Film

(64) A C18-H film on PET was fabricated as described in part A. A control droplet of water was deposited onto the surface of the film and its contact angle was monitored using a KRÜSS DSA100 Drop Shape Analyzer for 80 s.

(65) Another droplet was deposited onto the surface of the film and left to stabilize for 30 s. After 30 s, the film was irradiated in situ with a 405 nm violet laser for 40 s, then allowed to sit for another 10 s. The contact angle of the droplet was monitored the entire time.

(66) The contact angle data show that the 40 sec irradiation results in a 2-degree decrease compared to the control, from 85.5 degrees to 83.5 degrees. Using the Young-Dupré equation, it was estimated that the adhesion energy of the irradiated droplet increased by about 2.5 mN/m.

Example 5

Spiropyran Small Molecule and Polymer Water Uptake Screening Studies

(67) A 20 μL aliquot of SP solution was added onto the surface of a diamond ATR crystal. The solvent was allowed to evaporate for 10 min under ambient light, after which 1 mL of water was added on top of the film. The water uptake was monitored by FTIR. The experiment was performed using each of the SP solutions prepared in Examples 1H and 2F. The experiment was repeated with the film under continuous irradiation in situ by a 405 nm violet laser from the moment of deposition to water uptake.

(68) The Δ.sub.Abs of each SP small molecule and polymer was plotted as a function of time and fitted to an exponential decay equation. The fitting parameters A and τ were used to calculate Δ.sub.Abs (1 min). Next, the ratio R was calculated, where:

(69) $R=\frac{{\Delta }_{\mathrm{Abs}}\left(1\min \right)\mathrm{irradiated}}{{\Delta }_{\mathrm{Abs}}\left(1\min \right)\mathrm{not}\mathrm{irradiated}}$

(70) SP small molecules and polymers with the highest values of R and Δ.sub.Abs (1 min) irradiated were judged as the most promising candidates for a light-powered reversible water harvesting system. Greater Δ.sub.Abs (1 min) irradiated values indicated efficient water uptake and greater R values indicated a larger difference in the water uptake efficiencies of the irradiated and non-irradiated SP forms, suggesting better water retention and release.

(71) For the SP small molecules, the resulting R and Δ.sub.Abs (1 min) irradiated values showed that both irradiated and non-irradiated SPs with shorter alkyl chains held water better than those with longer alkyl chains. However, while the water uptake of non-irradiated SPs decreased rapidly with the size of the alkyl chain, the water uptake of the irradiated SPs decreased more gradually.

(72) The effect of the (Y).sub.n—H and —OMe substituents on the R and Δ.sub.Abs (1 min) irradiated values was also investigated. The electron donating methoxy group in the (Y).sub.n position was expected to stabilize the zwitterionic, hydrophilic merocyanine form. The C4-OMe and C18-OMe compounds showed increased Δ.sub.Abs (1 min) irradiated compared to C4-H and C18-H, respectively, but lower R values.

(73) Of the SP small molecules, C4-H demonstrated the most promise, followed by C18-OMe, C8-H, and C18-H, respectively. C1-H and Styrene-H showed the least desirable results for this application.

(74) For the SP polymers, the P(SP-co-MMA) (1:3), P(SP-homo), and P(SP-co-MMA) (1:5) copolymers respectively show the most efficient water uptake based on their R and Δ.sub.Abs (1 min) irradiated values. The P(SP-co-MMA) (1:3) exhibited the largest R value, accompanied by the second largest Δ.sub.Abs (1 min) irradiated values. The P(SP-homo) demonstrated the highest Δ.sub.Abs (1 min) irradiated values, but low R value. The P(SP-co-MMA) (1:5) has a relatively large R value, but its Δ.sub.Abs (1 min) irradiated values are not as high as those of P(SP-co-MMA) (1:3) or P(SP-homo).

(75) Of the SP polymers, the P(SP-co-MMA) (1:3) and (1:5) copolymers appear to have the most potential as water harvesting systems. Although the P(SP-homo) showed promising Δ.sub.Abs min) and R values, the quality of the film was not desirable. The (1:3) and (1:5) copolymers showed better coating properties. The P(SP-co-MMA) (1:1) and (1:10) copolymers showed the least desirable results for this application.

(76) While a number of exemplary embodiments, aspects and variations have been provided herein, those of skill in the art will recognize certain modifications, permutations, additions and combinations and certain sub-combinations of the embodiments, aspects and variations. It is intended that the following claims are interpreted to include all such modifications, permutations, additions and combinations and certain sub-combinations of the embodiments, aspects and variations are within their scope.

(77) The entire disclosures of all documents cited throughout this application are incorporated herein by reference.