Nanoparticles

Abstract

Nanoparticle compositions comprising nanoparticles formed from -conjugated cross-linked polymers are disclosed, together with their methods of manufacture and their applications. Owing to the nature of the cross-links formed therein, the nanoparticle compositions afford a high degree of manufacturing flexibility and control, as well as being amenable to facile purification for the purpose of imaging and electronics applications.

Claims

1. A nanoparticle composition comprising a plurality of nanoparticles formed from a -conjugated cross-linked polymer, the -conjugated cross-linked polymer comprising a) 80-99.9 mol. % of -conjugated monomers, and b) 3-10 mol. % of a cross-linker having the formula I shown below: ##STR00056## wherein Z.sub.1 and Z.sub.2 are monomeric moieties, and Y is absent, a bond, or a linking group.

2. The nanoparticles composition of claim 1, wherein the cross-linker has the formula II shown below: ##STR00057## wherein Y is absent, a bond, or a linking group.

3. The nanoparticle composition of claim 1, wherein Y is absent.

4. The nanoparticle composition of claim 1, wherein the cross linker has the formula III shown below: ##STR00058##

5. The nanoparticle composition of claim 1, wherein the -conjugated monomers each independently comprise a moiety having the formula IV shown below: ##STR00059## wherein R.sub.1 and R.sub.2 are each independently a group:
X-Q wherein X is selected from the group consisting of (1-30C)alkylene, (2-30C)alkenylene, (2-30C)alkynylene, [(CH.sub.2).sub.2O].sub.n, [O(CH.sub.2).sub.2].sub.n, (CH.sub.2).sub.m(CF.sub.2).sub.n, and [OSi(R.sub.z).sub.2].sub.n (wherein R.sub.z is (1-4C)alkyl, n is 1 to 30, and m is 0 to 30), and Q is a terminal group selected from hydrogen, methyl, hydroxyl, carboxy, (1-4C)alkoxycarbonyl, amino, CCH.sub.2, CCH, SH, -biotin, -streptavidin, CF.sub.3 and a polymerisable group selected from acrylates, epoxy and styrene; or R.sub.1 and R.sub.2 are linked so that, together with the carbon atom to which they are attached, they form a ring.

6. The nanoparticle composition of claim 1, wherein the -conjugated monomers each independently have a structure according to formula V shown below: ##STR00060## wherein R.sub.1 and R.sub.2 are as defined in claim 5; and A.sub.1 and A.sub.2 are independently absent or selected from any one of the following moieties: ##STR00061## ##STR00062## ##STR00063## wherein R.sub.3 and R.sub.4 are each independently a group:
X.sup.1-Q.sup.1 wherein X.sup.1 is selected from the group consisting of (1-30C)alkylene, (2-30C)alkenylene, (2-30C)alkynylene, [(CH.sub.2).sub.2O].sub.n, [O(CH.sub.2).sub.2].sub.n, (CH.sub.2).sub.m(CF.sub.2).sub.n, and [OSi(R.sub.z).sub.2].sub.n (wherein R.sub.z is (1-4C)alkyl, n is 1 to 30, and m is 0 to 30), and Q.sup.1 is a terminal group selected from hydrogen, methyl, hydroxyl, carboxy, (1-4C)alkoxycarbonyl, amino, CCH.sub.2, CCH, SH, -biotin, -streptavidin, CF.sub.3, and a polymerisable group selected from acrylates, epoxy and styrene; M is a metal selected from Ir, Pt, Rh, Re, Ru, Os, Cr, Cu, Pd and Au; L is a ligand independently selected from the group consisting of halo, (1-30C)hydrocarbyl optionally comprising one or more heteroatoms selected from N, O, S, Si or P, or an aryl or heteroaryl group optionally substituted with one or more substituents selected from (1-4C)alkyl, halo, aryl or heteroaryl; and p is 1 to 4.

7. The nanoparticle composition of claim 1, wherein the -conjugated monomers each independently have a structure defined by formula VI below: ##STR00064## wherein R.sub.1 and R.sub.2 are as defined in claim 5; and A.sub.1 and A.sub.2 are as defined in claim 6.

8. The nanoparticle composition of claim 7, wherein A.sub.1 and A.sub.2 are independently absent or selected from any one of the following moieties: ##STR00065## wherein R.sub.3, R.sub.4, M, L and p are as defined in claim 6.

9. The nanoparticle composition of claim 6, wherein one or both of A.sub.1 and A.sub.2 is absent.

10. The nanoparticle composition of claim 5, wherein R.sub.1 and R.sub.2 are each independently a group:
X-Q wherein X and Q are as defined in claim 5.

11. The nanoparticle composition of claim 6, wherein when present X.sup.1 is independently selected from the group consisting of (1-30C)alkylene, (2-30C)alkenylene, (2-30C)alkynylene, [(CH.sub.2).sub.2O].sub.n or [O(CH.sub.2).sub.2].sub.n (wherein n is 1 to 30); Q.sup.1 is independently a terminal group selected from hydrogen, methyl, hydroxyl, carboxy, (1-4C)alkoxycarbonyl, amino, CCH.sub.2 or CCH; M is a metal selected from Ir, Pt, Rh, Re, Ru, Os, Cr, Cu, Pd and Au; L is a ligand independently selected from the group consisting of halo, (1-30C)hydrocarbyl optionally comprising one or more heteroatoms selected from N, O, S, Si or P, or an aryl or heteroaryl group optionally substituted with one or more substituents selected from (1-4C)alkyl, halo, aryl or heteroaryl; and p is 1 to 4.

12. The nanoparticle composition of claim 6, wherein when present X.sup.1 is independently selected from the group consisting of (4-12C)alkylene or [(CH.sub.2).sub.2O].sub.n (wherein n is 1 to 15); Q.sup.1 is independently a terminal group selected from hydrogen, (1-2C)alkoxycarbonyl and methyl; M is Ir; L is a ligand independently selected from the group consisting of phenyl or 6-membered heteroaryl, optionally substituted with one or more substituents selected from phenyl or 6-membered heteroaryl; and p is 1 to 2.

13. The nanoparticle composition of claim 1 wherein the -conjugated cross-linked polymer comprises 80-99.9 mol. % of -conjugated monomers selected from at least one of the following structures: ##STR00066##

14. The nanoparticle composition of claim 1, wherein the cross-linker has the following structure: ##STR00067##

15. A method of forming a nanoparticle composition as claimed in claim 1, the method comprising the step of forming the nanoparticles by emulsion polymerisation, miniemulsion polymerisation or dispersion polymerisation techniques to provide an aqueous suspension of nanoparticles.

16. The method of claim 15, wherein the nanoparticles are formed by a cross-coupling polymerisation reaction (e.g. a Suzuki and/or Stille reaction).

17. The method of claim 15, further comprising the step of purifying the aqueous suspension of nanoparticles by contacting the aqueous suspension of nanoparticles with at least one organic solvent.

18. The method of claim 17, wherein the at least one organic solvent is selected from the group consisting of polar and non-polar solvents.

19. The method of claim 17, wherein the at least one organic solvent is methanol.

20. A nanoparticle dispersion comprising a nanoparticle composition as claimed in claim 1 dispersed throughout a dispersing medium.

Description

EXAMPLES

(1) Examples of the invention will now be described, for the purpose of reference and illustration only, with reference to the accompanying figures, in which:

(2) FIG. 1 shows DLS particle size histograms of the cross-linked nanoparticles of Example 1 in water (solid line) or THF (broken line).

(3) FIG. 2 shows UV/Vis spectra of the cross-linked nanoparticles of Example 1 in water (solid line) or THF (broken line).

(4) FIG. 3 shows PL spectra of the cross-linked nanoparticles of Example 1 in water (solid line) or THF (broken line).

(5) FIG. 4 shows DLS particle size histograms of the cross-linked nanoparticles of Example 2 in water (solid line) and THF (broken line) dispersants.

(6) FIG. 5 shows UV/Vis (broken line) and PL (solid line) spectra of the cross-linked nanoparticles of Example 2.

(7) FIG. 6 shows DLS sizing histograms of cross-linked phosphorescent nanoparticles in water (solid line) or THF (broken line) of the cross-linked nanoparticles of Example 3.

(8) FIG. 7 shows UV/Vis spectra of the cross-linked nanoparticles of Example 3 in water (solid line) or THF (broken line).

(9) FIG. 8 shows PL spectra of the cross-linked nanoparticles of Example 3 in water (solid line) or THF (broken line).

(10) FIG. 9 shows DLS sizing histograms of the cross-linked nanoparticles of Example 4 in water (solid line) and THF (broken line).

(11) FIG. 10 shows DLS sizing histograms of the cross-linked nanoparticles of Example 5 in water.

(12) FIG. 11 shows DLS sizing histograms of the cross-linked nanoparticles of Example 6 in water (broken line) and THF (solid line).

(13) FIG. 12 shows absorption and emission spectra of the cross-linked nanoparticles of Examples 4 (FIG. 12a), 5 (FIG. 12b) and 6 (FIG. 12c).

EXAMPLE 1

Cross-Linked PFO Nanoparticles

(14) Synthesis

(15) Referring to Scheme 1 and Table 1 shown below, sodium dodecyl sulphate (SDS) (50.0 mg) and deionised water (10 mL) were transferred to a Schlenk tube and the resultant solution was degassed by bubbling with argon for 20 minutes. Monomer A (see Table 1), crosslinker B (see Table 1) and monomer C (58.6 mg, 9.1210.sup.2 mmol) were dissolved in toluene (1 mL), to which hexadecane (78 L) was also added, and this solution was degassed for 5 minutes in the same manner. Tetrakis(triphenylphosphine)palladium(0) (2.2 mg, 9.1310.sup.3 mmol) was added to the monomer solution, which was then transferred to the reaction vessel. The reaction mixture was emulsified by ultrasonication (Cole Parmer 750 W ultasonicator, fitted with microtip, on 22% power) for 2 minutes while cooling with an ice bath. The Schlenk tube was resealed and the miniemulsion was heated to 72 C., followed by addition of 1M aqueous sodium hydroxide solution (365 L), and the reaction mixture was stirred for 16 hours. After cooling to room temperature, the cap of the reaction vessel was removed and the emulsion was stirred for 5 hours to remove the residual toluene.

(16) ##STR00035##

(17) TABLE-US-00001 TABLE 1 Reaction variables for synthesis of cross-linked PFO nanoparticles Monomer A Crosslinker B Sample Name (mass, moles) (mass, moles) NP-X2.5 45.0 mg 2.9 mg 8.21 10.sup.2 mmol 4.6 10.sup.3 mmol NP-X5 40.0 mg 5.8 mg 7.29 10.sup.2 mmol 9.1 10.sup.3 mmol NP-X10 30.0 mg 11.6 mg 5.47 10.sup.2 mmol 1.82 10.sup.2 mmol
Surfactant Removal and DLS Analysis (Nanoparticles in Water)

(18) A 400 L aliquot of the crude nanoparticle suspension was diluted with 1.6 mL of deionised water, to which Amberlite XAD-2 resin (20 mg, pre-washed with 22 mL of water) was added. The suspension was shaken at room temperature for 15 minutes before decanting off the nanoparticle suspension. This Amberlite XAD-2 purification step was repeated, after which time the suspension no longer foamed upon shaking and was filtered through glass wool prior to dynamic light scattering (DLS) analysis of particle size using a Malvern Zetasizer Nano ZS. Results are shown in Table 2 and FIG. 1.

(19) TABLE-US-00002 TABLE 2 DLS analysis of cross-linked PFO nanoparticles in water Z- Size by St. Sample Average Intensity Dev. Name (d .Math. nm) (d .Math. nm) (nm) PdI NP-X2.5 128 154 69 0.16 NP-X5 130 151 60 0.14 NP-X10 129 150 56 0.13
DLS Analysis (Nanoparticles in THF)

(20) A 200 L aliquot of the crude nanoparticle suspension was flocculated through addition of 1.3 mL toluene and the polymer was isolated by centrifugation (14,000 rpm, 1 minute) and decantation of the supernatant. The polymer was dried in air to remove residual methanol before dissolving in tetrahydrofuran (THF, 1 mL). The resultant suspension was measured directly using a Malvern Zetasizer Nano ZS. Results are shown in Table 3 and FIG. 1.

(21) TABLE-US-00003 TABLE 3 DLS analysis of cross-linked PFO nanoparticles in THF Sample Z-Average Size by Intensity St. Dev. name (d .Math. nm) (d .Math. nm) (nm) PdI NP-X2.5 n/a.sup.[a] NP-X5 174 .sup.198 (99.6%) 74 (99.6%) 0.13 4827 (0.4%).sup.[b] 711 (0.4%).sup.[a] NP-X10 147 175 73 0.15 .sup.[a]secondary peak likely to result from a small proportion of aggregated nanoparticles
UV/Vis Analysis (Nanoparticles in Water or THF)

(22) Following surfactant removal via treatment with Amberlite XAD-2, 40 L of the nanoparticle suspension was diluted with 3 mL of water. UV-Vis absorption spectra of the nanoparticles at this concentration were recorded on a Varian Cary 55 5000UV-Vis-NIR spectrophotometer at room temperature. FIG. 2 shows UV/Vis spectra of the cross-linked PFO nanoparticles.

(23) Photoluminescence (PL) Analysis (Nanoparticles in Water or THF)

(24) Following surfactant removal via treatment with amberlite XAD-2, 40 L of the nanoparticle suspension was diluted with 3 mL of water. PL spectra were recorded on a Varian Cary Eclipse fluorimeter. FIG. 2 shows PL spectra of the cross-linked PFO nanoparticles

(25) Photoluminescence (PL) Analysis (Nanoparticles in Water)

(26) Photoluminescencemeasurements were obtained using a Fluoromax-4 spectrofluorometer. Measurements were carried out on dilute dispersions of the nanoparticles in water (800 L, abs>1), using the same volume of water for background measurements. The results are provided in Table 4.

(27) TABLE-US-00004 TABLE 4 Optical properties of PFO nanoparticles in water Sample Name .sub.max .sub.em.sup.[a] NP-X2.5 390 440 NP-X5 390 438 NP-X10 390 437 .sup.[a].sub.ex = 380 nm

EXAMPLE 2

Ethyl Ester-Functionalised Cross-Linked PFO Nanoparticles

(28) Synthesis

(29) Referring to Scheme 2 shown below, sodium dodecyl sulfate (50.0 mg) and deionised water (10 mL) were transferred to a Schlenk tube and the resultant solution was degassed by bubbling with argon for 20 minutes. Crosslinker A (5.8 mg, 9.1210.sup.3 mmol), monomer B (44.4 mg, 7.3010.sup.2 mmol) and monomer C (58.6 mg, 9.1210.sup.2 mmol) were dissolved in toluene (1 mL), to which hexadecane (78 L) was also added, and this solution was degassed for 5 minutes in the same manner. Tetrakis(triphenylphosphine)palladium(0) (2.2 mg, 9.1310.sup.3 mmol) was added to the monomer solution, which was then transferred to the reaction vessel. The reaction mixture was emulsified by ultrasonication (Cole Parmer 750 W ultasonicator, fitted with microtip, on 22% power) for 2 minutes while cooling with an ice bath. The Schlenk tube was resealed and the miniemulsion was heated to 72 C., followed by addition of 1M aqueous sodium hydroxide solution (365 L), and the reaction mixture was stirred for 16 hours. After cooling to room temperature, the cap of the reaction vessel was removed and the emulsion was stirred for 5 hours to remove the residual toluene.

(30) ##STR00036##
DLS Analysis (Nanoparticles in Water or THF)

(31) Surfactant removal was carried out using the general procedure described in Example 1. Flocculation and resuspension in THF were carried out using the general procedure described in Example 1. DLS analysis was carried out as in Example 1, using either water or THF as the dispersant. The results are provided in Table 5 and FIG. 4.

(32) TABLE-US-00005 TABLE 5 DLS analysis of ethyl ester-functionalised nanoparticles in water or THF Sample Z-Average Size by Intensity St. Dev Name Dispersant (d .Math. nm) (d .Math. nm) (nm) PdI NP-X5E40 Water 118 139 56 0.14 NP-X5E40 THF 170 204 82 0.16
Vis and PL Analysis (Nanoparticles in Water)

(33) The general UV/Vis and PL analytical_procedures described in Example 1 were used to record the UV/Vis and PL spectra of the nanoparticles in dilute aqueous dispersion. The results are provided in FIG. 5.

(34) PL Analysis (Nanoparticles in Water)

(35) PL measurements were obtained using the general method described in Example 1. The results are provided in Table 6.

(36) TABLE-US-00006 TABLE 6 Optical properties of ethyl ester- functionalised nanoparticles in water Sample Name .sub.max .sub.em.sup.[a] NP-X5E40 391 432 .sup.[a].sub.ex = 380 nm

EXAMPLE 3

Cross-Linked Phosphorescent Nanoparticles

(37) Method

(38) Referring to Scheme 3 and Table 7 shown below, sodium dodecyl sulfate (50.0 mg) and deionised water (10 mL) were transferred to a Schlenk tube and the resultant solution was degassed by bubbling with argon for 20 minutes. Monomers A (see Table 7), C (20.5 mg, 1.8210.sup.2 mmol) and D (58.6 mg, 9.1210.sup.2 mmol) and crosslinker B (5.8 mg, 9.1210.sup.3 mmol) were dissolved in toluene (1 mL), to which hexadecane (78 L) was also added, and this solution was degassed for 5 minutes in the same manner. Tetrakis(triphenylphosphine)palladium(0) (2.2 mg, 9.1310.sup.3 mmol) was added to the monomer solution, which was then transferred to the reaction vessel. The reaction mixture was emulsified by ultrasonication (Cole Parmer 750 W ultasonicator, fitted with microtip, on 22% power) for 2 minutes while cooling with an ice bath. The Schlenk tube was resealed and the miniemulsion was heated to 72 C., followed by addition of 1M aqueous sodium hydroxide solution (365 L), and the reaction mixture was stirred for 16 hours. After cooling to room temperature, the cap of the reaction vessel was removed and the emulsion was stirred for 5 hours to remove the residual toluene.

(39) ##STR00037##

(40) TABLE-US-00007 TABLE 7 Reaction variables for synthesis of cross- linked phosphorescent nanoparticles Sample Monomer A Monomer A Name Side Chain (R.sup.1) (mass, moles) NP-XIr1 Octyl 30.0 mg NP-XIr2 MeO-PEG3 5.47 10.sup.2 mmol 33.7 mg 5.57 10.sup.2 mmol
DLS Analysis (Nanoparticles in Water or THF)

(41) Surfactant removal was carried out using the general procedure described in Example 1. Flocculation and resuspension in THF were carried out using the general procedure described in Example 1. DLS analysis was carried out as in Example 1, using either water or THF as the dispersant. The results are provided in Table 8 and FIG. 6.

(42) TABLE-US-00008 TABLE 8 DLS analysis of cross-linked phosphorescent nanoparticles in water or THF Size by Sample Z-Average Intensity St. Dev Name Dispersant (d .Math. nm) (d .Math. nm) (nm) PdI NP-XIr1 Water 131 158 69 0.15 NP-XIr1 THF 167 210 109 0.18 NP-XIr2 Water 126 150 (99.3%) 70 (99.3%) 0.19 4709 (0.7%).sup.[a] 774 (0.7%).sup.[a] NP-XIr2 THF 165 205 98 0.18 .sup.[a]Secondary peak likely to result from a small proportion of aggregated nanoparticles
UV/Vis and PL Analysis (Nanoparticles in Water or THF)

(43) The general UV/Vis and PL analytical_procedures described in Example 1 were used to record the UV/Vis (FIG. 7) and PL (FIG. 8) spectra of the nanoparticles in dilute aqueous dispersion or THF.

(44) PL Analysis (Nanoparticles in Water)

(45) PL measurements were obtained using the general method described in Example 1. The results are provided in Table 9.

(46) TABLE-US-00009 TABLE 9 Optical properties of cross-linked phosphorescent nanoparticles in water Sample Name .sub.max .sub.em.sup.[a] NP-Ir1 392 609 NP-Ir2 392 609 .sup.[a].sub.ex = 390 nm

EXAMPLE 4

PEG3 Functionalised 10% Cross-Linked PFO Nanoparticles

(47) Synthesis

(48) Referring to Scheme 4 shown below, tetraethylammonium hydroxide solution (40% in water) (0.1567 g, 0.4 mmol), was added to an aqueous solution (50 ml) of non-ionic surfactant, Triton x-102 (2.5 g, 5 wt % in de-ionised water) in a 100 ml three necked round bottom flask. Then contents were then through degassed for 30 mins by bubbling nitrogen gas through the stirred solution. Then a separate 10 ml two necked round bottom flask was used to mix together the monomers in the organic solvent prior to addition to the reaction flask. 9,9-dioctylfluorene-2,7-di-boronic acid-bis(1,3-propanediol)ester (0.1151 g, 0.2 mmol), 2,7-dibromo-9,9-bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)fluorene (0.0967 g, 0.16 mmol) and 2,2,7,7-tetrabromo-9,9-spirobifluorene (0.0126 g, 0.02 mmol) were dissolved in xylene (2 ml). The monomer solution was degassed and then the catalyst IPr*PdTEACl.sub.2 (0.0095 g, 0.008 mmol) was added, followed by further degassing of the resultant solution. A syringe was used to transfer the monomer/catalyst into the stirred surfactant/base solution in the main reaction flask now maintained at 30 C. with stirring and maintaining under nitrogen gas for 24 h.

(49) ##STR00038##
DLS Analysis (Nanoparticles in Water or THF)

(50) 500 l of sample was transferred to centrifuge vial the 1.5 ml of methanol was added. The sample vial was centrifuged at 14,000 rpm for 5 min then the liquid was decanted. Crude sample was washed with methanol 3 times and re-dispersed in THF in order to measure the size of particles. Neat products without further purification were also investigated. The results are shown in FIG. 9 and Table 10. Concentrations of polymer in water was 23 g/ml.

(51) TABLE-US-00010 TABLE 10 Particle sizes of CPNs in water and THF at 25 C. Size Dz STD Sample (nm) (nm) (nm) PdI LM55 Neat 50 44 26.81 0.244 LM55 in THF 108 218 51.80 0.217
Optical Properties

(52) Referring to Table 11 and FIG. 12, LM55 exhibited maxima band at 370 nm but no -phase was observed.

(53) TABLE-US-00011 TABLE 11 Summarized optical properties of cross-linked polymer in water Final polymer Size .sub.abs .sub.em Sample conc. (mg/ml) (nm) (nm) (nm) E.sub.g* LM55 2.5 50 370 420, 441 2.91

EXAMPLE 5

PEG3 Functionalised 5% Cross-Linked PFO Nanoparticles

(54) Synthesis

(55) Referring to Scheme 5 shown below, tetraethylammonium hydroxide solution (40% in water) (0.1567 g, 0.4 mmol), was added to an aqueous solution (50 ml) of non-ionic surfactant, Triton x-102 (2.5 g, 5 wt % in de-ionised water) in a 100 ml three necked round bottom flask. Then contents were then through degassed for 30 mins by bubbling nitrogen gas through the stirred solution. Then a separate 10 ml two necked round bottom flask was used to mix together the monomers in the organic solvent prior to addition to the reaction flask. 9,9-dioctylfluorene-2,7-di-boronic acid-bis(1,3-propanediol)ester (0.1151 g, 0.2 mmol), 2,7-dibromo-9,9-dioctylfluorene (0.0768 g, 0.14 mmol), 2,7-dibromo-9,9-bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)fluorene (0.0242 g, 0.04 mmol) and 2,2,7,7-tetrabromo-9,9-spirobifluorene (0.0063 g, 0.01 mmol) were dissolved in xylene (2 ml). The monomer solution was degassed and then the catalyst IPr*PdTEACl.sub.2 (0.0095 g, 0.008 mmol) was added, followed by further degassing of the resultant solution. A syringe was used to transfer the monomer/catalyst into the stirred surfactant/base solution in the main reaction flask now maintained at 30 C. with stirring and maintaining under nitrogen gas for 24 h.

(56) ##STR00039##
DLS Analysis (Nanoparticles in Water or THF)

(57) 500 l of sample was transferred to centrifuge vial the 1.5 ml of methanol was added. The sample vial was centrifuged at 14,000 rpm for 5 min then the liquid was decanted. Crude sample was washed with methanol 3 times and re-dispersed in THF in order to measure the size of particles. Neat products without further purification were also investigated. The results are shown in FIG. 10 and Table 12. Concentrations of polymer in water was 23 g/ml.

(58) TABLE-US-00012 TABLE 12 Particle sizes of CPNs in water at 25 C. Size Dz STD Sample (nm) (nm) (nm) PdI LM56 Neat 55 41 26.23 0.381
Optical Properties

(59) Referring to Table 13 and FIG. 12, LM56 showed absorption peak at 378 nm.

(60) TABLE-US-00013 TABLE 13 Summarized optical properties of cross-linked polymer in water Final polymer Size .sub.abs .sub.em Sample conc. (mg/ml) (nm) (nm) (nm) E.sub.g* LM56 2.5 55 378, 435 421, 436, 453 2.78

EXAMPLE 6

PEG12 Functionalised 10% Cross-Linked PFO Nanoparticles

(61) Synthesis

(62) Referring to Scheme 6 below, tetraethylammonium hydroxide solution (40% in water) (0.1567 g, 0.4 mmol), was added to an aqueous solution (50 ml) of non-ionic surfactant, Triton x-102 (2.5 g, 5 wt % in de-ionised water) in a 100 ml three necked round bottom flask. Then contents were then through degassed for 30 mins by bubbling nitrogen gas through the stirred solution. Then a separate 10 ml two necked round bottom flask was used to mix together the monomers in the organic solvent prior to addition to the reaction flask. 9,9-dioctylfluorene-2,7-di-boronic acid-bis(1,3-propanediol)ester (0.1151 g, 0.2 mmol), 2,7-dibromo-9,9-bis(polyethylene glycol monoether)fluorene (0.2255 g, 0.16 mmol) and 2,2,7,7-tetrabromo-9,9-spirobifluorene (0.0126 g, 0.02 mmol) were dissolved in xylene (2 ml). The monomer solution was degassed and then the catalyst IPr*PdTEACl.sub.2 (0.0095 g, 0.008 mmol) was added, followed by further degassing of the resultant solution. A syringe was used to transfer the monomer/catalyst into the stirred surfactant/base solution in the main reaction flask now maintained at 30 C. with stirring and maintaining under nitrogen gas for 24 h.

(63) ##STR00040##
DLS Analysis (Nanoparticles in Water or THF)

(64) 500 l of sample was transferred to centrifuge vial the 1.5 ml of methanol was added. The sample vial was centrifuged at 14,000 rpm for 5 min then the liquid was decanted. Crude sample was washed with methanol 3 times and re-dispersed in THF in order to measure the size of particles. Neat products without further purification were also investigated. The results are shown in FIG. 11 and Table 14. Concentrations of polymer in water was 23 g/ml.

(65) TABLE-US-00014 TABLE 14 Particle sizes of CPNs in water and THF at 25 C. Size Dz STD Sample (nm) (nm) (nm) PdI LM02-6 Neat 244 13 103.2 0.359 LM02-6 in THF 74 847 10.97 0.489
Optical Properties

(66) Table 15 and FIG. 12 show summarized optical properties for LM02-6 in water.

(67) TABLE-US-00015 TABLE 15 Summarized optical properties of cross-linked polymer in water Final polymer Size .sub.abs .sub.em Sample conc. (mg/ml) (nm) (nm) (nm) E.sub.g* LM02-6 2.5 244 N/A 419, 441 N/A

EXAMPLE 7

5% 1,3-Diphenoxypropane Cross-Linked Polyfluorene Nanoparticles

(68) Synthesis

(69) ##STR00041##

(70) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (87.8 mg, 160 mol), 1,3-bis(3,5-dibromophenoxy)propane (10.9 mg, 20 mol), tris(dibenzylideneacetone) dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 16 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL using deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky light green solution. DLS (water): Z-average=110 nm, PdI=0.156, D.sub.n=69 nm and SD=21.0 nm. UV-Vis Abs. (water): .sub.max=379 nm, .sub.sec.=432 nm, .sub.onset=455 nm. UV-Vis PL (water): .sub.max=439 nm, .sub.sec.=467 nm, .sub.sec.=499 nm, .sub.sec.=534 nm.

EXAMPLE 8

5% 1,1-Biphenyl Cross-Linked Polyfluorene Nanoparticles

(71) Synthesis

(72) ##STR00042##

(73) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (87.8 mg, 160 mol), 3,3,5,5-tetrabromo-1,1-biphenyl (9.4 mg, 20 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 16 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL using deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky light green solution. DLS (water): Z-average=110 nm, PdI=0.134, D.sub.n=61 nm and SD=21.7 nm. UV-Vis Abs. (water): .sub.max=378 nm, .sub.sec.=432 nm, .sub.onset=451 nm. UV-Vis PL (water): .sub.max=438 nm, .sub.sec.=466 nm, .sub.sec.=497 nm, .sub.sec.=534 nm.

EXAMPLE 9

5% 9,9-(1,3-Propanediyl)bis[9-octyl-9H-fluorene] Cross-Linked Polyfluorene Nanoparticles

(74) Synthesis

(75) ##STR00043##

(76) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (87.8 mg, 160 mol), 9,9-(1,3-propyldiyl)bis[2,7-dibromo-9H-Fluorene-9-octyl] (18.3 mg, 20 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 16 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL using deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky light green solution. DLS (water): Z-average=118 nm, PdI=0.133, D.sub.n=71.7 nm and SD=24.6 nm. UV-Vis Abs. (water): .sub.max=383 nm, .sub.sec.=433 nm, .sub.onset=451 nm. UV-Vis PL (water): .sub.max=439 nm, .sub.sec.=466 nm, .sub.sec.=498 nm, .sub.sec.=535 nm.

EXAMPLE 10

5% 5-Phenyl-1,1:3,1-terphenyl Cross-Linked Polyfluorene Nanoparticles

(77) Synthesis

(78) ##STR00044##

(79) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (76.8 mg, 140 mol), 3,3,5,5-tetrabromo-5-(3,5-dibromophenyl)-1,1:3,1-terphenyl (15.6 mg, 20 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 16 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL using deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky light green solution. DLS (water): Z-average=108 nm, PdI=0.148, D.sub.n=66 nm and SD=22.5 nm. UV-Vis Abs. (water): .sub.max=380 nm, .sub.sec.=433 nm, .sub.onset=452 nm. UV-Vis PL (water): .sub.max=439 nm, .sub.sec.=467 nm, .sub.sec.=499 nm, .sub.sec.=535 nm.

EXAMPLE 11

5% 2,1,3-Benzothiadiazole, 35% 9,9-Di(undecanoic acid)fluorene and 5% 9,9-Spirobifluorene Cross-Linked Polyfluorene Nanoparticles

(80) Synthesis

(81) ##STR00045##

(82) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (1080 L, 1080 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 2,7-dibromo-9,9-di(undecanoic acid)fluorene (96.9 mg, 140 mol), 2,2,7,7-tetrabromo-9,9-spirobifluorene (12.6 mg, 20 mol), 4,7-dibromobenzo[c]-1,2,5-thiadiazole (5.9 mg, 20 mol) tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 20 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL with deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky dark green solution. DLS (water): Z-average=79.0 nm, PdI=0.117, D.sub.n=52.4 nm and SD=15.3 nm. UV-Vis Abs. (water): .sub.max=380 nm, .sub.sec.=450 nm, .sub.onset=520 nm. UV-Vis PL (water): .sub.max=535 nm, .sub.sec.=424 nm.

EXAMPLE 12

40% Di(t-Butyl Hexanoate)Fluorene and 5% 9,9-Spirobifluorene Cross-Linked Polyfluorene Nanoparticles

(83) Synthesis

(84) ##STR00046##

(85) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctyl-9H-fluorene-2,7-diboronic acid bis(pinacol) ester (128.5 mg, 200 mol), 2,7-dibromo-9,9-di(t-butyl hexanoate)fluorene (106.3 mg, 160 mol), 2,2,7,7-tetrabromo-9,9-spirobifluorene (12.6 mg, 20 mop, tetrakis (triphenylphosphine)palladium(0) (5.8 mg, 5 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 72 C. and stirred for 20 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL with deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky light green solution. DLS (water): Z-average=129 nm, PdI=0.226, D.sub.n=64 nm and SD=23.4 nm. UV-Vis Abs. (water): .sub.max=384 nm, .sub.onset=441 nm. UV-Vis PL (water): .sub.max=430 nm, .sub.sec.=453 nm, .sub.sec.=484 nm.

EXAMPLE 13

5% 4,7-Bis(4-hexylthiophen-2-yl)benzo[c][1,2,5]thiadiazole and 5% 9,9-Spirobifluorene Cross-Linked Polyfluorene Nanoparticles

(86) Synthesis

(87) ##STR00047##

(88) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (76.8 mg, 140 mop, 2,2,7,7-tetrabromo-9,9-spirobifluorene (12.6 mg, 20 mol), 4,7-bis(5-bromo-4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (12.5 mg, 20 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 20 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL with deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky bright red solution. DLS (water): Z-average=105 nm, PdI=0.125, D.sub.n=64.4 nm and SD=20.8 nm. UV-Vis Abs. (water): .sub.max=382 nm, .sub.sec=433 nm, .sub.sec.=514 nm, .sub.onset=620 nm. UV-Vis PL (water): .sub.max=621 nm, .sub.sec.=437 nm.

EXAMPLE 14

10% 4,7-Bis(4-hexylthiophen-2-yl)benzo[c][1,2,5]thiadiazole and 5% 9,9-Spirobifluorene Cross-Linked Polyfluorene Nanoparticles

(89) Synthesis

(90) ##STR00048##

(91) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (65.8 mg, 120 mol), 2,2,7,7-tetrabromo-9,9-spirobifluorene (12.6 mg, 20 mol), (25.1 mg, 40 mol), tris(dibenzylideneacetone) dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 20 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL with deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky bright red solution. DLS (water): Z-average=130 nm, PdI=0.264, D.sub.n=58.4 nm and SD=20.9 nm. UV-Vis Abs. (water): .sub.max=382 nm, .sub.sec.=432 nm, .sub.sec.=515 nm, .sub.onset=623 nm. UV-Vis PL (water): .sub.max=625 nm.

EXAMPLE 15

2% 9,9-Di(undecanoic acid)fluorene, 5% 2,1,3-Benzothiadiazole, 33% Di(hex-5-en-1-yl)fluorene and 5% 9,9-Spirobifluorene Cross-Linked Polyfluorene Nanoparticles

(92) Synthesis

(93) ##STR00049##

(94) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (816 L, 816 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 2,7-dibromo-9,9-di(undecanoic acid)fluorene (5.5 mg, 8 mol), 2,2,7,7-tetrabromo-9,9-spirobifluorene (12.6 mg, 20 mol), 4,7-dibromobenzo[c]-1,2,5-thiadiazole (5.9 mg, 20 mol), 2,7-dibromo-9,9-di(hex-5-en-1-yl)fluorene (64.5 mg, 132 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 20 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL with deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky dark green solution. DLS (water): Z-average=101 nm, PdI=0.166, D.sub.n=55.1 nm and SD=18.1 nm. UV-Vis Abs. (water): .sub.max=381 nm, .sub.sec.=453 nm, .sub.onset=522 nm. UV-Vis PL (water): .sub.max=530 nm.

EXAMPLE 16

CL-F8T2 CPNs

(95) Synthesis

(96) ##STR00050##

(97) In a Schlenk tube, sodium dodecyl sulfate (50 mg) was dissolved in deionised water (10 mL) under argon. The solution was degassed by bubbling with argon for 30 minutes. In a separate vial, monomer A (58.6 mg, 9.1210.sup.2 mmol), monomer B, monomer C (see amounts in Table 1), monomer D (5.8 mg, 9.1210.sup.3 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.9 mg, 0.9810.sup.3 mmol) and tri(o-tolyl)phosphine (1.2 mg, 3.910.sup.3 mmol) were dissolved in toluene (1 mL). Hexadecane was added (78 L) and the mixture was degassed by bubbling with argon for 5 min. After this time, the monomer mixture was then injected to the SDS solution. To promote the miniemulsion, the Schlenk tube was taken to an ice bath and the mixture was sonicated using an ultrasonicator fitted with microtip (Cole Parmer 750 W ultrasonicator, 22% amplitude) for 2 minutes. The tube was resealed and then heated up to 72 C. Once reached this temperature, an aqueous solution of sodium hydroxide 1M (365 L) was added and the reaction mixture was stirred for 16 h. After cooling down to room temperature, the Schlenk tube was opened and the mixture was stirred for 5 h to remove the residual toluene. To remove SDS, 400 L of the resulting miniemulsion was diluted with 1.6 mL of deionised water and Amberlite XAD-2 (20 mg) previously washed with water (22 mL) was added. The mixture was stirred for 2 hours at room temperature and the Amberlite XAD-2 was removed. Treatment with Amberlite XAD-2 was repeated until the mixture was shaken and no foam formation was longer observed.

(98) Table 15 below shows the amount of monomers B and C used. Table 16 below shows the particle size of the CL-F8T2 CPNs. Table 17 shows the optical properties of CL-F8T2 CPNs in water & THF.

(99) ##STR00051##

(100) TABLE-US-00016 TABLE 15 Initial loading of monomers B and C in CL-F8T2 CPNs Monomer C Monomer B Monomer C Polymer (% mol) (mass, moles) (mass, moles) CL-F8T2/20 20 20 mg 11.8 mg (3.65 10.sup.2 mmol) (3.65 10.sup.3 mmol) CL-F8T2/30 30 10 mg 17.8 mg (1.82 10.sup.2 mmol) (5.48 10.sup.2 mmol)

(101) TABLE-US-00017 TABLE 16 Particle size of CL-F812 CPNs in water & THF Water THF d.sub.z D.sub.Num d.sub.z D.sub.Num Polymer (nm) PdI (nm) (nm) PdI (nm) CL-F8T2/20 105 0.158 64 124 0.212 62 CL-F8T2/30 103 0.178 53 120 0.223 63

(102) TABLE-US-00018 TABLE 17 optical properties of CL-F8T2 CPNs in water & THF Water THF Absorption Fluorescence Absorption Fluorescence Polymer .sub.max (nm) .sub.max (nm) .sub.max (nm) .sub.max (nm) CL-F8T2/20 386 554 394 525 CL-F8T2/30 431 541 438 498

EXAMPLE 17

5% N,N,N,N-Tetraphenylbenzidine Cross-Linked Polyfluorene Nanoparticles

(103) Synthesis

(104) ##STR00052##

(105) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (87.8 mg, 160 mol), N.sup.4,N.sup.4,N.sup.4,N.sup.4-tetrakis(4-bromophenyl)-[1,1-biphenyl]-4,4-diamine (16.1 mg, 20 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 16 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL using deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky light green solution. DLS (water): Z-average=112 nm, PdI=0.150, D.sub.n=72.5 nm and SD=22.3 nm. UV-Vis Abs. (water): .sub.max=384 nm, .sub.sec.=433 nm, .sub.onset=452 nm. UV-Vis PL (water): .sub.max=438 nm, .sub.sec.=467 nm, .sub.sec.=496 nm, .sub.sec.=535 nm.

EXAMPLE 18

5% Pyrene Cross-Linked Polyfluorene Nanoparticles

(106) Synthesis

(107) ##STR00053##

(108) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctyl-9H-fluorene-2,7-diboronic acid bis(pinacol) ester (128.5 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (87.8 mg, 160 mol), 1,3,6,8-tetrabromopyrene (10.4 mg, 20 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 72 C. and stirred for 20 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL with deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky light green solution. DLS (water): Z-average=103 nm, PdI=0.141, D.sub.n=71.5 nm and SD=21.8 nm. UV-Vis Abs. (water): .sub.max=376 nm, .sub.sec.=432 nm, .sub.onset=452 nm. UV-Vis PL (water): .sub.max=439 nm, .sub.sec.=466 nm, .sub.sec.=498 nm, .sub.sec.=532 nm.

EXAMPLE 19

5% 5,10,15,20-tetrakis(4-bromophenyl)-21H,23H-porphine (Zinc) Cross-Linked Polyfluorene Nanoparticles

(109) Synthesis

(110) ##STR00054##

(111) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (87.8 mg, 160 mol), 5,10,15,20-tetrakis(4-bromophenyl)-21H,23H-porphine (zinc) (19.9 mg, 20 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 16 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL using deionised water and filtered through a glass wool plug. The emulsion was obtained as a dark green solution. DLS (water): Z-average=95.0 nm, PdI=0.135, D.sub.n=64.1 nm and SD=19.7 nm. UV-Vis Abs. (water): .sub.max=380 nm, .sub.sec.=396 nm, .sub.sec.=433 nm, .sub.sec.=550 nm, .sub.sec.=596 nm, .sub.onset=625 nm. UV-Vis PL (water): .sub.max=440 nm, .sub.sec.=466 nm, .sub.sec.=498 nm.

EXAMPLE 20

5% 5,10,15,20-Tetraphenyl-21H,23H-porphine (Zinc) Cross-Linked Polyfluorene Nanoparticles

(112) Synthesis

(113) ##STR00055##

(114) In a Schlenk tube was added water (22.0 mL), sodium dodecyl sulfate (110 mg, 382 mol) and 1M aqueous sodium hydroxide (800 L, 800 mol). The solution was purged with argon for 2 hours. In a vial was weighed 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester (111.7 mg, 200 mol), 9,9-dioctyl-2,7-dibromofluorene (65.8 mg, 120 mol), 5,10,15,20-tetrakis(3,5-dibromophenyl)-21H,23H-porphine (zinc) (26.2 mg, 20 mol), tris(dibenzylideneacetone)dipalladium(0) (4.6 mg, 5 mol), tri(o-tolyl)phosphine (9.1 mg, 30 mol) and hexadecane (171 L, 585 mol). The vial was transferred to an argon filled glovebox, sealed with a rubber septum and removed. Toluene (2.19 mL) was added to the vial and the suspension sonicated until a homogenous solution was achieved. The initial aqueous solution was cooled to 0 C. in an ice bath, the ultrasonic probe inserted and the toluene solution injected rapidly into the water. The solution was ultrasonicated for 1 minute, stirred for 30 seconds and ultrasonicated for 1 further minute. The Schlenk tube was sealed, placed in a preheated oil bath at 50 C. and stirred for 16 hours. The Schlenk was opened and a stream of nitrogen gas passed over the emulsion at 50 C., with stirring. The emulsion was cooled to room temperature, the volume increased to 23.0 mL using deionised water and filtered through a glass wool plug. The emulsion was obtained as a milky dark green solution. DLS (water): Z-average=98.4 nm, PdI=0.151, D.sub.n=59.9 nm and SD=19.4 nm. UV-Vis Abs. (water): .sub.max=377 nm, .sub.sec.=432 nm, .sub.onset=451 nm. UV-Vis PL (water): .sub.max=439 nm, .sub.sec.=466 nm, .sub.sec.=499 nm, .sub.sec.=534 nm, .sub.sec.=596 nm, .sub.sec.=644 nm.

(115) While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims.