Nanoparticles

Abstract

Nanoparticle compositions comprising nanoparticles formed from π-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.

1 .- 26 . (canceled) 
     
     
         27 . A nanoparticle composition comprising a plurality of nanoparticles formed from a π-conjugated cross-linked polymer, the π-conjugated cross-linked polymer comprising
 a) 80-99.9 mol. % of π-conjugated monomers, and 
 b) 0.1-20 mol. % of a cross-linker having the formula I shown below: 
 
       
         
           
           
               
               
           
         
         wherein
 Z 1  and Z 2  are monomeric moieties, 
 Y is absent, a bond, or a linking group; and 
 
         wherein the π-conjugated monomers comprise a moiety having the formula IV shown below: 
       
       
         
           
           
               
               
           
         
         wherein 
         R 1  and R 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, —[O—(CH 2 ) 2 ] n —, —(CH 2 ) m (CF 2 ) n —, and —[O—Si(R z ) 2 ] n —, wherein R z  is (1-4C)alkyl, n is 1 to 30, and m is 0 to 30); and 
         Q is a terminal group selected from hydroxyl, carboxyl, amino, —C═CH 2 , —C≡CH, —SH, -biotin, -streptavidin and epoxy. 
       
     
     
         28 . The nanoparticle composition of  claim 27 , wherein X is (1-30C)alkylene and Q is carboxyl or amino. 
     
     
         29 . The nanoparticle composition of  claim 27 , wherein the π-conjugated monomers comprise a moiety having the formula: 
       
         
           
           
               
               
           
         
       
     
     
         30 . The nanoparticle composition of  claim 27 , wherein the π-conjugated monomers further comprise one or more of the following moieties: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein R 3  and R 4  are each independently a group:
   —X 1 -Q 1  
 
 
         wherein 
         X 1  is selected from the group consisting of (1-30C)alkylene, (2-30C)alkenylene, (2-30C)alkynylene, —[(CH 2 ) 2 —O] n —, —[O—(CH 2 ) 2 ] n —, —(CH 2 ) m (CF 2 ) n —, and —[O—Si(R z ) 2 ] n —, wherein R z  is (1-4C)alkyl, n is 1 to 30, and m is 0 to 30); and 
         Q 1  is a terminal group selected from hydrogen, methyl, hydroxyl, carboxyl, (1-4C)alkoxycarbonyl, amino, —C═CH 2 , —C≡CH, —SH, -biotin, -streptavidin, —CF 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. 
       
     
     
         31 . The nanoparticle composition of  claim 30 , wherein
 X 1  is selected from the group consisting of (1-20C)alkylene, —[(CH 2 ) 2 —O] n — or —[O—(CH 2 ) 2 ] n — (wherein n is 1 to 20);   Q 1  is a terminal group selected from hydrogen, methyl, (1-2C)alkoxycarbonyl and hydroxyl;   M is Ir;   L is a ligand independently selected from the group consisting of aryl or heteroaryl, optionally substituted with one or more substituents selected from aryl or heteroaryl; and   p is 1 to 2.   
     
     
         32 . The nanoparticle composition of  claim 30 , wherein
 X 1  is selected from the group consisting of (4-12C)alkylene or —[(CH 2 ) 2 —O] n — (wherein n is 1 to 15);   Q 1  is 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.   
     
     
         33 . The nanoparticle composition of  claim 30 , wherein the π-conjugated monomers further comprise one or more of the following moieties: 
       
         
           
           
               
               
           
         
       
     
     
         34 . The nanoparticle composition of  claim 27 , wherein the cross-linker has the formula II shown below: 
       
         
           
           
               
               
           
         
         wherein
 Y is absent, a bond, or a linking group. 
 
       
     
     
         35 . The nanoparticle composition of  claim 34 , wherein the cross linker has the formula III shown below: 
       
         
           
           
               
               
           
         
       
     
     
         36 . The nanoparticle composition of  claim 34 , wherein the cross-linker has the following structure: 
       
         
           
           
               
               
           
         
       
     
     
         37 . A method of forming a nanoparticle composition as claimed in  claim 27 , 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. 
     
     
         38 . The method of  claim 37 , wherein the nanoparticles are formed by a cross-coupling polymerisation reaction. 
     
     
         39 . The method of  claim 38 , wherein the polymerisation reaction is a Suziki reaction. 
     
     
         40 . The method of  claim 38 , wherein the polymerisation reaction is a Stille reaction. 
     
     
         41 . The method of  claim 38 , further comprising the step of purifying the aqueous suspension of nanoparticles. 
     
     
         42 . The method of  claim 41 , wherein the aqueous suspension of nanoparticles is purified by contacting the aqueous suspension of nanoparticles with at least one organic solvent. 
     
     
         43 . The method of  claim 42 , wherein the at least one organic solvent is selected from the group consisting of polar and non-polar solvents. 
     
     
         44 . The method of  claim 43 , wherein the at least one organic solvent is methanol. 
     
     
         45 . Use of a nanoparticle composition as defined in  claim 27  in one or more applications selected from the group consisting of biological or non-biological imaging or sensing, down-conversion of LED light, anti-counterfeit encoding, displays, cell-sorting/flow cytometry, long-term cell tracking, and flow visualisation. 
     
     
         46 . A nanoparticle dispersion comprising a nanoparticle composition as claimed in  claim 27  dispersed throughout a dispersing medium.