Processable molecularly imprinted polymers

• US 7,678,870 B2
• Filed: 10/04/2004
• Issued: 03/16/2010
• Est. Priority Date: 04/08/2004
• Status: Active Grant

• Current Assignee: Johns Hopkins University, DaimlerChrysler AG (Mercedes-Benz Group AG)
• Original Assignee: Johns Hopkins University
• Inventors: Southard, Glen E., Murray, George M.
• Primary Examiner(s): Teskin; Fred M
• Application Number:
  US10/599,062
• Publication Number:
  US 20070197746A1
• Time in Patent Office: 1,989 Days
• Field of Search: 436/164, 436/166, 436/172, 534/16, 526/172, 526/240, 526/274, 526/279, 526/320, 526/336, 525/245
• US Class Current: 526/172
• CPC Class Codes: G01N 2600/00 Assays involving molecular imprinted polymers/polymers created around a molecular template
• CPC Class Codes: G01N 33/53 Immunoassay; Biospecific binding assay; Materials therefor
• CPC Class Codes: G01N 33/543 with an insoluble carrier for immobilising immunochemicals

Abstract

A process is provided herein for preparing molecularly imprinted polymers for detecting a target analyte by Reversible Addition Fragmentation Chain Transfer (RAFT). The process includes providing a complex having the formula L₃M wherein L is a β-diketone ligand containing a chain transfer moiety and L₃ can be the same or different ligands, and M is a lanthanide element; reacting the complex with the target analyte to provide an adduct containing the target analyte; co-polymerizing the adduct with a monomer and cross-linking agent to provide a polymer; and removing the target analyte from the polymer to provide the molecularly imprinted polymer.

Claims

1. A process for preparing a molecularly imprinted polymer for detecting a target analyte comprising the steps of:

(a) providing a complex comprising a compound of the general formula L₃M wherein L is the same or different and is a β

-diketone ligand containing the same or different chain transfer moiety and M is a lanthanide element;

(b) reacting the complex with a target analyte to provide an adduct containing the target analyte;

(c) co-polymerizing the adduct with a monomer and cross-linking agent to provide a polymer; and

,

(d) removing the target analyte from the polymer to provide the molecularly imprinted polymer.

2. The process of claim 1, wherein the lanthanide element M is europium.

3. The process of claim 1, wherein the ligands L₃ are each the same ligand.

4. The process of claim 1, where in two ligands of L₃ are the same and the third ligand is different.

5. The process of claim 1, wherein the β

-diketone ligands have the structure;

R¹—

C(O)—

CR²₂—

C(O)—

R³

wherein R¹ is a hydrocarbon group having 1 to about 20 carbons containing a chain transfer moiety;

R² can be the same or different and is hydrogen or a hydrocarbon group having from 1 to about 12 carbon atoms and R³ is a straight or branched chain alkyl group of 1 to about 12 carbon atoms optionally containing one or more halogen atoms.

6. The process of claim 5, wherein R³ is an alkyl halide.

7. The process of claim 6, wherein the alkyl halide is —

CF₃.

8. The process of claim 1, wherein the chain transfer moiety is selected from the group consisting of dithiocarboxylic ester, trithiocarbonate and benzyl iodide.

9. The process of claim 8, wherein the dithiocarboxylic ester is of the general formula —

S—

C(S)R wherein R is a hydrocarbon group having from 1 to about 20 carbon.

10. The process of claim 1, wherein the analyte is an organophosphorus compound.

11. The process of claim 10, wherein the organophosphorus compound has the formula (R⁵)(R⁶)(R⁷)P═

O, wherein R⁵, R⁶ and R⁷ can be the same or different and are individually selected from inorganic or organic groups, provided that at least one group is organic.

12. The process of claim 11, wherein the inorganic groups are selected from the group consisting of H, —

OH, F, Cl, Br, I, —

CN and —

NO₂, and the organic groups are substituted or unsubstituted aliphatic or aromatic groups with or without heteroatoms.

13. The process of claim 10, wherein the organophosphorus compound is selected from the group consisting of dimethyl hydrogen phosphate and pinacolyl methyl phosphonate.

14. The process of claim 1, wherein each ligand L is a fluorinated β

-diketone having the structure;

R¹—

C(O)—

CH₂—

C(O)—

CF₃

wherein R¹ is a hydrocarbon group which includes as the chain transfer moiety a moiety selected from the group consisting of dithiocarboxylic ester, trithiocarbonate and benzyl iodide.

15. The process of claim 1, wherein the crosslinking agent is selected from the group consisting of difunctional acrylates, difunctional methacrylates, trifunctional acrylates, trifunctional methacrylates, tetrafunctional acrylates, tetrafunctional methacrylates, divinylbenzene, alkylene glycol diacrylates, alkylene glycol methacrylates, polyalkylene glycol diacrylates, polyalkylane glycol methacrylates, vinyl acrylates, vinyl methacrylates, allyl acrylates, allyl methacrylates, divinylbenzene, diallyldiglycol dicarbonate, diallyl maleate, diallyl fumarate, diallyl itaconate, divinyl oxalate, divinyl malonate, diallyl succinate, triallyl isocyanurate, bis-phenol A dimethacrylate, bis-phenol A diacrylate, ethoxylated bis-phenol A dimethacrylate, ethoxylated bis-phenol A diacrylate, methylene bisacrylamide, methylene bismethylacrylamide, polymethylene bisacrylamide, polymethylene bismethacrylamide, di(alkene) tertiary amines, trimethylol propane triacrylate, pentaerythritol tetraacrylate, divinyl ether, divinyl sulfone, diallyl phthalate, triallyl melamine, 2-isocyanatoethyl methacrylate, 2-isocyanatoethylacrylate, 3-isocyanatopropylacrylate, 1-methyl-2-isocyanatoethyl methacrylate, 1,1-dimethyl-2-isocyanaotoethyl acrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, hexanediol diacrylate, divinyl benzene;

1,3-divinyltetramethyl disiloxane;

8,13-divinyl-3,7,12,17-tetramethyl-21H,23H-porphine;

8,13-divinyl-3,7,12,17-tetramethyl-21H,23H-propionic acid;

8,13-divinyl-3,7,12,17-tetramethyl-21H,23H-propionic acid disodium salt;

3,9-divinyl-2,4,8,10-tetraoraspiro[5,5]undecane;

divinyl tin dichloride and mixtures.

16. The process of claim 1, wherein the co-polymerization step (c) is performed in the presence of an initiator.

17. The process of claim 16, wherein the initiator is selected from the group consisting of benzoyl peroxide, acetyl peroxide, lauryl peroxide, azobisisobutyronitrile, t-butyl peracetate, cumyl peroxide, t-butyl peroxide;

t-butyl hydroperoxide, bis(isopropyl)peroxy-dicarbonate, benzoin methyl ether, 2,2′

-azobis(2,4-dimethylvaleronitrile), tertiarybutyl peroctoate, phthalic peroxide, diethoxyacetophenone, and tertiarybutyl peroxypivalate, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethyoxy-2-phenylacetophenone, phenothiazine, diisopropylxanthogen disulfide, 2,2′

-azobis-(2-amidinopropane), 4,4′

-azobis-(4-cyanovaleric acid), 1,1′

-azobis-(cyclohexanecarbonitrile)-, and mixtures thereof.

18. The process of claim 1, wherein the step of removing the target analyte comprises washing the polymer with a solution capable of leaching the analyte.

19. The process of claim 18, wherein the leaching solution includes a compound selected from the group consisting of acetone, isopropanol, methanol, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidinone, and mixtures thereof.

20. The process of claim 1, wherein the copolymerization step (c) is performed neat or in a solvent.

21. The process of claim 1, wherein the monomer is selected from the group consisting of acrylic acid, methacrylic acid, alkyl methacrylates, alkyl acrylates, allyl acrylates, allyl methacrylates, aryl acrylates, aryl methacrylates, cyanoacrylate, styrene, -methyl styrene, vinyl acetate, vinyl chloride, methyl vinyl ketone, vinylidene chloride, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, 2-acetamido acrylic acid;

2-(acetoxyacetoxy)ethyl methacrylate 1-acetoxy-1,3-butadiene;

2-acetoxy-3-butenenitrile;

4-acetoxystyrene;

acrolein;

acrolein diethyl acetal;

acrolein dimethyl acetal;

acrylamide;

2-acrylamidoglycolic acid;

2-acrylamido-2-methyl propane sulfonic acid;

acrylic acid;

acrylic anhydride;

acrylonitrile;

acryloyl chloride;

(R)-acrylox, ′

-dimethyl-g-butyrolactone;

N-acryloxy succinimide-acryloxytris(hydroxymethyl)aminomethane;

N-acryloly chloride;

N-acryloyl pyrrolidinone;

N-acryloyl-tris(hydroxymethyl)amino methane;

2-amino ethyl methacrylate;

N-(3-aminopropyl)methacrylamide;

(o, m, or p)-amino-styrene;

t-amyl methacrylate;

2-(1-aziridinyl)ethyl methacrylate;

4-benzyloxy-3-methoxystyrene;

2-bromoacrylic acid;

4-bromo-1-butene;

3-bromo-3,3-difluoropropane;

6-bromo-1-hexene;

3-bromo-2-methacrylonitrile;

2-(bromomethyl)acrylic acid;

8-bromo-1-octene;

5-bromo-1-pentene;

cis-1-bromo-1-propene;

.-bromostyrene;

p-bromostyrene;

bromotrifluoro ethylene;

(±

)-3-buten-2-ol;

1,3-butadiene;

1,3-butadiene-1,4-dicarboxylic acid 3-butenal diethyl acetal;

1-butene;

3-buten-2-ol;

3-butenyl chloroformate;

2-butylacrolein;

-t-butylacrylamide;

butyl acrylate;

butyl methacrylate;

(o,m,p)-bromostyrene;

t-butyl acrylate;

(R)-carvone;

(S)-carvone;

(−

)-carvyl acetate;

cis 3-chloroacrylic acid;

2-chloroacrylonitrile;

2-chloroethyl vinyl ether;

2-chloromethyl-3-trimethylsilyl-1-propene;

3-chloro-1-butene;

3-chloro-2-chloromethyl-1-propene;

3-chloro-2-methyl propene;

2,2-bis(4-chlorophenyl)-1,1-dichloroethylene;

3-chloro-1-phenyl-1-propene;

m-chlorostyrene;

o-chlorostyrene;

p-chlorostyrene;

1-cyanovinyl acetate;

1-cyclopropyl-1-(trimethylsiloxy)ethylene;

2,3-dichloro-1-propene;

2,6-dichlorostyrene;

1,3-dichloropropene;

2,4-diethyl-2,6-heptadienal;

1,9-decadiene;

1-decene;

1,2-dibromoethylene;

1,1-dichloro-2,2-difluoroethylene;

1,1-dichloropropene;

2,6-difluorostyrene;

dihydrocarveol;

(±

)-dihydrocarvone;

(−

)-dihydrocarvyl acetate;

3,3-dimethylacrylaldehyde;

N,N′

-dimethylacrylamide;

3,3-dimethylacrylic acid;

3,3-dimethylacryloyl chloride;

2,3-dimethyl-1-butene;

3,3-dimethyl-1-butene;

2-dimethyl aminoethyl methacrylate;

2,4-dimethyl-2,6-heptadien-1-ol;

2,4-dimethyl-2,6-heptadienal;

2,5-dimethyl-1,5-hexadiene;

2,4-dimethyl-1,3-pentadiene;

2,2-dimethyl-4-pentenal;

2,4-dimethylstyrene;

2,5-dimethylstyrene;

3,4-dimethylstryene;

1-dodecene;

3,4-epoxy-1-butene;

2-ethyl acrolein;

ethyl acrylate;

2-ethyl-1-butene;

(±

)-2-ethylhexyl acrylate;

(±

)-2-ethylhexyl methacrylate;

2-ethyl-2-(hydroxymethyl)-1,3-propanediol triacrylate;

2-ethyl-2-(hydroxymethyl)-1,3-propanediol trimethacrylate;

ethyl methacrylate;

ethyl vinyl ether, ethyl vinyl ketone;

ethyl vinyl sulfone;

(1-ethylvinyl)tributyl tin;

m-fluorostyrene;

o-fluorostyrene;

p-fluorostyrene;

glycol methacrylate (hydroxyethyl methacrylate);

GA GMA;

1,6-heptadiene;

1,6-heptadienoic acid;

1,6-heptadien-4-ol;

1-heptene;

1-hexen-3-ol;

1-hexene;

hexafluoropropene;

1,6-hexanediol diacrylate;

1-hexadecene;

1,5-hexadien-3,4-diol;

1,4-hexadiene;

1,5-hexadien-3-ol;

1,3,5-hexatriene;

5-hexen-1,2-diol;

5-hexen-1-ol;

hydroxypropyl acrylate;

3-hydroxy-3,7,11-trimethyl-1,6,10-dodecatriene;

isoamyl methacrylate;

isobutyl methacrylate;

isoprene;

2-isopropenylaniline;

isopropenyl chloroformate;

4,4′

-isopropylidene dimethacrylate;

3-isopropyl-a-a-dimethylbenzene isocyanate;

isopulegol;

itaconic acid;

itaconalyl chloride;

(±

)-;

linalool;

linalyl acetate;

p-mentha-1,8-diene;

p-mentha-6,8-dien-2-ol;

methyleneamino acetonitrile;

methacrolein;

[3-(methacryloylamino)-propyl]trimethylammonium chloride;

methacrylamide;

methacrylic acid;

methacrylic anhydride;

methacrylonitrile;

methacryloyl chloride;

2-(methacryloyloxy)ethyl acetoacetate;

(3-methacryloxypropyl)trimethoxy silane;

2-(methacryloxy)ethyl trimethyl ammonium methylsulfate;

2-methoxy propene (isopropenyl methyl ether);

methyl-2-(bromomethyl)acrylate;

5-methyl-5-hexen-2-one;

methyl methacrylate;

N,N′

-methylene bisacrylamide;

2-methylene glutaronitrite;

2-methylene-1,3-propanediol;

3-methyl-1,2-butadiene;

2-methyl-1-butene;

3-methyl-1-butene;

3-methyl-1-buten-1-ol;

2-methyl-1-buten-3-yne;

2-methyl-1,5-heptadiene;

2-methyl-1-heptene;

2-methyl-1-hexene;

3-methyl-1,3-pentadiene;

2-methyl-1,4-pentadiene;

(±

)-3-methyl-1-pentene;

(±

)-4-methyl-1-pentene;

(±

)-3-methyl-1-penten-3-ol;

2-methyl-1-pentene;

-methyl styrene;

t-methylstyrene;

t-methylstyrene;

3-methylstyrene;

methyl vinyl ether;

methyl vinyl ketone;

methyl-2-vinyloxirane;

4-methylstyrene;

methyl vinyl sulfone;

4-methyl-5-vinylthiazole;

myrcene;

t-nitrostyrene;

3-nitrostyrene;

1-nonadecene;

1,8-nonadiene;

1-octadecene;

1,7-octadiene;

7-octene-1,2-diol;

1-octene;

1-octen-3-ol;

1-pentadecene;

1-pentene;

1-penten-3-ol;

t-2,4-pentenoic acid;

1,3-pentadiene;

1,4-pentadiene;

1,4-pentadien-3-ol;

4-penten-1-ol;

4-penten-2-ol;

4-phenyl-1-butene;

phenyl vinyl sulfide;

phenyl vinyl sulfonate;

2-propene-1-sulfonic acid sodium salt;

phenyl vinyl sulfoxide;

1-phenyl-1-(trimethylsiloxy)ethylene;

propene;

safrole;

styrene (vinyl benzene);

4-styrene sulfonic acid sodium salt;

styrene sulfonyl chloride;

3-sulfopropyl acrylate potassium salt;

3-sulfopropyl methacrylate sodium salt;

tetrachloroethylene;

tetracyano ethylene;

trans 3-chloroacrylic acid;

2-trifluoromethyl propene;

2-(trifluoromethyl)propenoic acid;

2,4,4′

-trimethyl-1-pentene;

3,5-bis(trifluoromethyl)styrene;

2,3-bis(trimethylsiloxy)-1,3-butadiene;

1-undecene;

vinyl acetate;

vinyl acetic acid;

4-vinyl anisole;

9-vinyl anthracene;

vinyl behenate;

vinyl benzoate;

vinyl benzyl acetate;

vinyl benzyl alcohol;

3-vinyl benzyl chloride;

3-(vinyl benzyl)-2-chloroethyl sulfone;

4-(vinyl benzyl)-2-chloroethyl sulfone;

N-(p-vinyl benzyl)-N,N′

-dimethyl amine;

4-vinyl biphenyl (4-phenyl styrene);

vinyl bromide;

2-vinyl butane;

vinyl butyl ether;

9-vinyl carbazole;

vinyl carbinol;

vinyl cetyl ether;

vinyl chloroacetate;

vinyl chloroformate;

vinyl crotanoate;

vinyl cyclohexane;

4-vinyl-1-cyclohexene;

4-vinylcyclohexene dioxide;

vinyl cyclopentene;

vinyl dimethylchlorosilane;

vinyl dimethylethoxysilane;

vinyl diphenylphosphine;

vinyl 2-ethyl hexanoate;

vinyl 2-ethylhexyl ether;

vinyl ether ketone;

vinyl ethylene;

vinyl ethylene iron tricarbonyl;

vinyl ferrocene;

vinyl formate;

vinyl hexadecyl ether;

vinylidene fluoride;

1-vinyl imidizole;

vinyl iodide;

vinyl laurate;

vinyl magnesium bromide;

vinyl mesitylene;

vinyl 2-methoxy ethyl ether;

vinyl methyl dichlorosilane;

vinyl methyl ether;

vinyl methyl ketone;

2-vinyl naphthalene;

5-vinyl-2-norbornene;

vinyl pelargonate;

vinyl phenyl acetate;

vinyl phosphonic acid, bis(2-chloroethyl)ester;

vinyl propionate;

4-vinyl pyridine;

2-vinyl pyridine;

1-vinyl-2-pyrrolidinone;

2-vinyl quinoline;

1-vinyl silatrane;

vinyl sulfone;

vinyl sulfonic acid sodium salt;

o-vinyl toluene;

p-vinyl toluene;

vinyl triacetoxysilane;

vinyl tributyl tin;

vinyl trichloride;

vinyl trichlorosilane;

vinyl trichlorosilane (trichlorovinylsilane);

vinyl triethoxysilane;

vinyl triethylsilane;

vinyl trifluoroacetate;

vinyl trimethoxy silane;

vinyl trimethyl nonylether;

vinyl trimethyl silane;

vinyl triphenyphosphonium bromide (triphenyl vinyl phosphonium bromide);

vinyl tris-(2-methoxyethoxy) silane, vinyl 2-valerate, 1-(3-butenyl)-4-vinylbenzene and mixtures thereof.

22. The process of claim 1, wherein the polymer is a block copolymer.

23. A polymer comprising the reaction product of(a) a complex comprising a compound of the general formula L₃M wherein L is the same or different and is a β

-diketone ligand containing the same or different chain transfer moiety and M is a lanthanide element, the complex being capable of binding an analyte to be detected;

(b) a monomer; and

(c) optional crosslinking agent, wherein said polymer undergoes a detectable luminescence change upon exposure to the analyte to be detected.

24. The polymer of claim 23, wherein the β

-diketone ligands have the structure;

R¹—

C(O)—

CR²₂—

C(O)—

R³

wherein R¹ is a hydrocarbon group having 1 to about 20 carbons containing a chain transfer moiety;

R² can be the same or different and is hydrogen or a hydrocarbon group having from 1 to about 12 carbon atoms and R³ is a straight or branched chain alkyl group of 1 to about 12 carbon atoms optionally containing one or more halogen atoms.

25. The polymer of claim 24, wherein R³ is an alkyl halide.

26. The polymer of claim 25, wherein the alkyl halide is —

CF₃.

27. The polymer of claim 23, wherein the chain transfer moiety is selected from the group consisting of dithiocarboxylic ester, trithiocarbonate and benzyl iodide.

28. The polymer of claim 23, wherein the lanthanide element M is europium and the chain transfer moiety is a dithiocarboxylic ester of the general formula —

S—

C(S)R wherein R is a hydrocarbon group having from 1 to about 20 carbon.

29. The polymer of claim 23, wherein the analyte is an organophosphorus compound.

30. The polymer of claim 29, wherein the organophosphorus compound is selected from the group consisting of dimethyl hydrogen phosphate and pinacolyl methyl phosphonate.

31. The polymer of claim 23, wherein each ligand L is a fluorinated β

-diketone having the structure;

R¹—

C(O)—

CH₂—

C(O)—

CF₃

wherein R¹ is a hydrocarbon group which includes as the chain transfer moiety a dithiocarboxylic ester and the lanthanide element M is europium.

32. The polymer of claim 23, wherein monomer is selected from the group consisting of acrylic acid, methacrylic acid, alkyl methacrylates, alkyl acrylates, allyl acrylates, allyl methacrylates, aryl acrylates, aryl methacrylates, cyanoacrylate, styrene, -methyl styrene, vinyl acetate, vinyl chloride, methyl vinyl ketone, vinylidene chloride, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, 2-acetamido acrylic acid;

2-(acetoxyacetoxy)ethyl methacrylate 1-acetoxy-1,3-butadiene;

2-acetoxy-3-butenenitrile;

4-acetoxystyrene;

acrolein;

acrolein diethyl acetal;

acrolein dimethyl acetal;

acrylamide;

2-acrylamidoglycolic acid;

2-acrylamido-2-methyl propane sulfonic acid;

acrylic acid;

acrylic anhydride;

acrylonitrile;

acryloyl chloride;

(R)-acryloxy, ′

-dimethyl-g-butyrolactone;

N-acryloxy succinimide-acryloxytris(hydroxymethyl)aminomethane;

N-acryloly chloride;

N-acryloyl pyrrolidinone;

N-acryloyl-tris(hydroxymethyl)amino methane;

2-amino ethyl methacrylate;

N-(3-aminopropyl)methacrylamide;

(o, m, or p)-amino-styrene;

t-amyl methacrylate;

2-(1-aziridinyl)ethyl methacrylate;

4-benzyloxy-3-methoxystyrene;

2-bromoacrylic acid;

4-bromo-1-butene;

3-bromo-3,3-difluoropropane;

6-bromo-1-hexene;

3-bromo-2-methacrylonitrile;

2-(bromomethyl)acrylic acid;

8-bromo-1-octene;

5-bromo-1-pentene;

cis-1-bromo-1-propene;

-bromostyrene;

p-bromostyrene;

bromotrifluoro ethylene;

(±

)-3-buten-2-ol;

1,3-butadiene;

1,3-butadiene-1,4-dicarboxylic acid 3-butenal diethyl acetal;

1-butene;

3-buten-2-ol;

3-butenyl chloroformate;

2-butylacrolein;

-t-butylacrylamide;

butyl acrylate;

butyl methacrylate;

(o,m,p)-bromostyrene;

t-butyl acrylate;

(R)-carvone;

(S)-carvone;

(−

)-carvyl acetate;

cis 3-chloroacrylic acid;

2-chloroacrylonitrile;

2-chloroethyl vinyl ether;

2-chloromethyl-3-trimethylsilyl-1-propene;

3-chloro-1-butene;

3-chloro-2-chloromethyl-1-propene;

3-chloro-2-methyl propene;

2,2-bis(4-chlorophenyl)-1,1-dichloroethylene;

3-chloro-1-phenyl-1-propene;

m-chlorostyrene;

o-chlorostyrene;

p-chlorostyrene;

1-cyanovinyl acetate;

1-cyclopropyl-1-(trimethylsiloxy)ethylene;

2,3-dichloro-1-propene;

2,6-dichlorostyrene;

1,3-dichloropropene;

2,4-diethyl-2,6-heptadienal;

1,9-decadiene;

1-decene;

1,2-dibromoethylene;

1,1-dichloro-2,2-difluoroethylene;

1,1-dichloropropene;

2,6-difluorostyrene;

dihydrocarveol;

(±

)-dihydrocarvone;

(−

)-dihydrocarvyl acetate;

3,3-dimethylacrylaldehyde;

N,N′

-dimethylacrylamide;

3,3-dimethylacrylic acid;

3,3-dimethylacryloyl chloride;

2,3-dimethyl-1-butene;

3,3-dimethyl-1-butene;

2-dimethyl aminoethyl methacrylate;

2,4-dimethyl-2,6-heptadien-1-ol;

2,4-dimethyl-2,6-heptadienal;

2,5-dimethyl-1,5-hexadiene;

2,4-dimethyl-1,3-pentadiene;

2,2-dimethyl-4-pentenal;

2,4-dimethylstyrene;

2,5-dimethylstyrene;

3,4-dimethylstryene;

1-dodecene;

3,4-epoxy-1-butene;

2-ethyl acrolein;

ethyl acrylate;

2-ethyl-1-butene;

(±

)-2-ethylhexyl acrylate;

(±

)-2-ethylhexyl methacrylate;

2-ethyl-2-(hydroxymethyl)-1,3-propanediol triacrylate;

2-ethyl-2-(hydroxymethyl)-1,3-propanediol trimethacrylate;

ethyl methacrylate;

ethyl vinyl ether;

ethyl vinyl ketone;

ethyl vinyl sulfone;

(1-ethylvinyl)tributyl tin;

m-fluorostyrene;

o-fluorostyrene;

p-fluorostyrene;

glycol methacrylate (hydroxyethyl methacrylate);

GA GMA;

1,6-heptadiene;

1,6-heptadienoic acid;

1,6-heptadien-4-ol;

1-heptene;

1-hexen-3-ol;

1-hexene;

hexafluoropropene;

1,6-hexanediol diacrylate;

1-hexadecene;

1,5-hexadien-3,4-diol;

1,4-hexadiene;

1,5-hexadien-3-ol;

1,3,5-hexatriene;

5-hexen-1,2-diol;

5-hexen-1-ol;

hydroxypropyl acrylate;

3-hydroxy-3,7,11-trimethyl-1,6,10-dodecatriene;

isoamyl methacrylate;

isobutyl methacrylate;

isoprene;

2-isopropenylaniline;

isopropenyl chloroformate;

4,4′

-isopropylidene dimethacrylate;

3-isopropyl-a-a-dimethylbenzene isocyanate;

isopulegol;

itaconic acid;

itaconalyl chloride;

(±

)-;

linalool;

linalyl acetate;

p-mentha-1,8-diene;

p-mentha-6,8-dien-2-ol;

methyleneamino acetonitrile;

methacrolein;

[3-(methacryloylamino)-propyl]trimethylammonium chloride;

methacrylamide;

methacrylic acid;

methacrylic anhydride;

methacrylonitrile;

methacryloyl chloride;

2-(methacryloyloxy)ethyl acetoacetate;

(3-methacryloxypropyl) trimethoxy silane;

2-(methacryloxy)ethyl trimethyl ammonium methylsulfate;

2-methoxy propene (isopropenyl methyl ether);

methyl-2-(bromomethyl)acrylate;

5-methyl-5-hexen-2-one;

methyl methacrylate;

N,N′

-methylene bisacrylamide;

2-methylene glutaronitrite;

2-methylene-1,3-propanediol;

3-methyl-1,2-butadiene;

2-methyl-1-butene;

3-methyl-1-butene;

3-methyl-1-buten-1-ol;

2-methyl-1-buten-3-yne;

2-methyl-1,5-heptadiene;

2-methyl-1-heptene;

2-methyl-1-hexene;

3-methyl-1,3-pentadiene;

2-methyl-1,4-pentadiene;

(±

)-3-methyl-1-pentene;

(±

)-4-methyl-1-pentene;

(±

)-3-methyl-1-penten-3-ol;

2-methyl-1-pentene;

-methyl styrene;

t-methylstyrene;

t-methylstyrene;

3-methylstyrene;

methyl vinyl ether;

methyl vinyl ketone;

methyl-2-vinyloxirane;

4-methylstyrene;

methyl vinyl sulfone;

4-methyl-5-vinyithiazole;

myrcene;

t-nitrostyrene;

3-nitrostyrene;

1-nonadecene;

1,8-nonadiene;

1-octadecene;

1,7-octadiene;

7-octene-1,2-diol;

1-octene;

1-octen-3-ol;

1-pentadecene;

1-pentene;

1-penten-3-ol;

t-2,4-pentenoic acid;

1,3-pentadiene;

1,4-pentadiene;

1,4-pentadien-3-ol;

4-penten-1-ol;

4-penten-2-ol;

4-phenyl-1-butene;

phenyl vinyl sulfide;

phenyl vinyl sulfonate;

2-propene-1-sulfonic acid sodium salt;

phenyl vinyl sulfoxide;

1-phenyl-1-(trimethylsiloxy)ethylene;

propene;

safrole;

styrene (vinyl benzene);

4-styrene sulfonic acid sodium salt;

styrene sulfonyl chloride;

3-sulfopropyl acrylate potassium salt;

3-sulfopropyl methacrylate sodium salt;

tetrachloroethylene;

tetracyano ethylene;

trans 3-chloroacrylic acid;

2-trifluoromethyl propene;

2-(trifluoromethyl)propenoic acid;

2,4,4′

-trimethyl-1-pentene;

3,5-bis(trifluoromethyl)styrene;

2,3-bis(trimethylsiloxy)-1,3-butadiene;

1-undecene;

vinyl acetate;

vinyl acetic acid;

4-vinyl anisole;

9-vinyl anthracene;

vinyl behenate;

vinyl benzoate;

vinyl benzyl acetate;

vinyl benzyl alcohol;

3-vinyl benzyl chloride;

3-(vinyl benzyl)-2-chloroethyl sulfone;

4-(vinyl benzyl)-2-chloroethyl sulfone;

N-(p-vinyl benzyl)-N,N′

-dimethyl amine;

4-vinyl biphenyl (4-phenyl styrene);

vinyl bromide;

2-vinyl butane;

vinyl butyl ether;

9-vinyl carbazole;

vinyl carbinol;

vinyl cetyl ether;

vinyl chloroacetate;

vinyl chloroformate;

vinyl crotanoate;

vinyl cyclohexane;

4-vinyl-1-cyclohexene;

4-vinylcyclohexene dioxide;

vinyl cyclopentene;

vinyl dimethylchlorosilane;

vinyl dimethylethoxysilane;

vinyl diphenylphosphine;

vinyl 2-ethyl hexanoate;

vinyl 2-ethylhexyl ether;

vinyl ether ketone;

vinyl ethylene;

vinyl ethylene iron tricarbonyl;

vinyl ferrocene;

vinyl formate;

vinyl hexadecyl ether;

vinylidene fluoride;

1-vinyl imidizole;

vinyl iodide;

vinyl laurate;

vinyl magnesium bromide;

vinyl mesitylene;

vinyl 2-methoxy ethyl ether;

vinyl methyl dichlorosilane;

vinyl methyl ether;

vinyl methyl ketone;

2-vinyl naphthalene;

5-vinyl-2-norbornene;

vinyl pelargonate;

vinyl phenyl acetate;

vinyl phosphonic acid, bis(2-chloroethyl)ester;

vinyl propionate;

4-vinyl pyridine;

2-vinyl pyridine;

1-vinyl-2-pyrrolidinone;

2-vinyl quinoline;

1-vinyl silatrane;

vinyl sulfone;

vinyl sulfonic acid sodium salt;

o-vinyl toluene;

p-vinyl toluene;

vinyl triacetoxysilane;

vinyl tributyl tin;

vinyl trichloride;

vinyl trichlorosilane;

vinyl trichlorosilane (trichlorovinylsilane);

vinyl triethoxysilane;

vinyl triethylsilane;

vinyl trifluoroacetate;

vinyl trimethoxy silane;

vinyl trimethyl nonylether;

vinyl trimethyl silane;

vinyl triphenyphosphonium bromide (triphenyl vinyl phosphonium bromide);

vinyl tris-(2-methoxyethoxy) silane, vinyl 2-valerate, 1-(3-butenyl)-4-vinylbenzene and mixtures thereof.

33. The polymer of claim 23, wherein the polymer is a block copolymer.

34. A molecularly imprinted polymer obtained by the steps of (a) providing a reaction product of(i) a complex comprising a compound of the general formula L₃M wherein L is the same or different and is a β

-diketone ligand containing the same or different chain transfer moiety and M is a lanthanide element and (ii) a target analyte;

(b) copolymerizing the reaction product of step (a) with monomer and optional crosslinking agent to form a polymer; and

(c) removing the target analyte from the polymer to provide a molecularly imprinted polymer which selectively binds to the target analyte and undergoes a detectable luminescence change when the target analyte binds thereto.

35. The molecularly imprinted polymer of claim 34, wherein the ligands L₃ are each the same ligand.

36. The molecularly imprinted polymer of claim 34, wherein the β

-diketone ligands have the structure;

R¹—

C(O)—

CR²₂—

C(O)—

R³

wherein R¹ is a hydrocarbon group having 1 to about 20 carbons containing a chain transfer moiety;

R² can be the same or different and is hydrogen or a hydrocarbon group having from 1 to about 12 carbon atoms and R³ is a straight or branched chain alkyl group of 1 to about 12 carbon atoms optionally containing one or more halogen atoms.

37. The molecularly imprinted polymer of claim 36, wherein R³ is an alkyl halide.

38. The molecularly imprinted polymer of claim 37, wherein the alkyl halide is —

CF₃.

39. The molecularly imprinted polymer of claim 34, wherein the chain transfer moiety is selected from the group consisting of dithiocarboxylic ester, trithiocarbonate and benzyl iodide.

40. The molecularly imprinted polymer of claim 34, wherein the lanthanide element M is europium and the chain transfer moiety is a dithiocarboxylic ester of the general formula —

S—

C(S)R wherein R is a hydrocarbon group having from 1 to about 20 carbon.

41. The molecularly imprinted polymer of claim 34, wherein the analyte is an organophosphorus compound.

42. The molecularly imprinted polymer of claim 41, wherein the organophosphorus compound is selected from the group consisting of dimethyl hydrogen phosphate and pinacolyl methyl phosphonate.

43. The molecularly imprinted polymer of claim 34, wherein each ligand L is a fluorinated β

-diketone having the structure;

R¹—

C(O)—

CH₂—

C(O)—

CF₃

wherein R¹ is a hydrocarbon group which includes as the chain transfer moiety a moiety selected from the group consisting of dithiocarboxylic ester, trithiocarbonate and benzyl iodide and the lanthanide element M is europium.

44. The molecularly imprinted polymer of claim 34, wherein monomer is selected from the group consisting of acrylic acid, methacrylic acid, alkyl methacrylates, alkyl acrylates, allyl acrylates, allyl methacrylates, aryl acrylates, aryl methacrylates, cyanoacrylate, styrene, -methyl styrene, vinyl acetate, vinyl chloride, methyl vinyl ketone, vinylidene chloride, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, 2-acetamido acrylic acid;

2-(acetoxyacetoxy)ethyl methacrylate 1-acetoxy-1,3-butadiene;

2-acetoxy-3-butenenitrile;

4-acetoxystyrene;

acrolein;

acrolein diethyl acetal;

acrolein dimethyl acetal;

acrylamide;

2-acrylamidoglycolic acid;

2-acrylamido-2-methyl propane sulfonic acid;

acrylic acid;

acrylic anhydride;

acrylonitrile;

acryloyl chloride;

(R)-acryloxy, ′

-dimethyl-g-butyrolactone;

N-acryloxy succinimide acryloxytris(hydroxymethyl)aminomethane;

N-acryloly chloride;

N-acryloyl pyrrolidinone;

N-acryloyl-tris(hydroxymethyl)amino methane;

2-amino ethyl methacrylate;

N-(3-aminopropyl)methacrylamide;

(o, m, or p)-amino-styrene;

t-amyl methacrylate;

2-(1-aziridinyl)ethyl methacrylate;

4-benzyloxy-3-methoxystyrene;

2-bromoacrylic acid;

4-bromo-1-butene;

3-bromo-3,3-difluoropropane;

6-bromo-1-hexene;

3-bromo-2-methacrylonitrile;

2-(bromomethyl)acrylic acid;

8-bromo-1-octene;

5-bromo-1-pentene;

cis-1-bromo-1-propene;

-bromostyrene;

p-bromostyrene;

bromotrifluoro ethylene;

(±

)-3-buten-2-ol;

1,3-butadiene;

1,3-butadiene-1,4-dicarboxylic acid 3-butenal diethyl acetal;

1-butene;

3-buten-2-ol;

3-butenyl chloroformate;

2-butylacrolein;

-t-butylacrylamide;

butyl acrylate;

butyl methacrylate;

(o,m,p)-bromostyrene;

t-butyl acrylate;

(R)-carvone;

(S)-carvone;

(−

)-carvyl acetate;

cis 3-chloroacrylic acid;

2-chloroacrylonitrile;

2-chloroethyl vinyl ether;

2-chloromethyl-3-trimethylsilyl-1-propene;

3-chloro-1-butene;

3-chloro-2-chloromethyl-1-propene;

3-chloro-2-methyl propene;

2,2-bis(4-chlorophenyl)-1,1-dichloroethylene;

3-chloro-1-phenyl-1-propene;

m-chlorostyrene;

o-chlorostyrene;

p-chlorostyrene;

1-cyanovinyl acetate;

1-cyclopropyl-1-(trimethylsiloxy)ethylene;

2,3-dichloro-1-propene;

2,6-dichlorostyrene;

1,3-dichloropropene;

2,4-diethyl-2,6-heptadienal;

1,9-decadiene;

1-decene;

1,2-dibromoethylene;

1,1-dichloro-2,2-difluoroethylene;

1,1-dichloropropene;

2,6-difluorostyrene;

dihydrocarveol;

(±

)-dihydrocarvone;

(−

)-dihydrocarvyl acetate;

3,3-dimethylacrylaldehyde;

N,N′

-dimethylacrylamide;

3,3-dimethylacrylic acid;

3,3-dimethylacryloyl chloride;

2,3-dimethyl-1-butene;

3,3-dimethyl-1-butene;

2-dimethyl aminoethyl methacrylate;

2,4-dimethyl-2,6-heptadien-1-ol;

2,4-dimethyl-2,6-heptadienal;

2,5-dimethyl-1,5-hexadiene;

2,4-dimethyl-1,3-pentadiene;

2,2-dimethyl-4-pentenal;

2,4-dimethylstyrene;

2,5-dimethylstyrene;

3,4-dimethylstryene;

1-dodecene;

3,4-epoxy-1-butene;

2-ethyl acrolein;

ethyl acrylate;

2-ethyl-1-butene;

(±

)-2-ethylhexyl acrylate;

(±

)-2-ethylhexyl methacrylate;

2-ethyl-2-(hydroxymethyl)-1,3-propanediol triacrylate;

2-ethyl-2-(hydroxymethyl)-1,3-propanediol trimethacrylate;

ethyl methacrylate;

ethyl vinyl ether;

ethyl vinyl ketone;

ethyl vinyl sulfone;

(1-ethylvinyl)tributyl tin;

m-fluorostyrene;

o-fluorostyrene;

p-fluorostyrene;

glycol methacrylate (hydroxyethyl methacrylate);

GA GMA;

1,6-heptadiene;

1,6-heptadienoic acid;

1,6-heptadien-4-ol;

1-heptene;

1-hexen-3-ol;

1-hexene;

hexafluoropropene;

1,6-hexanediol diacrylate;

1-hexadecene;

1,5-hexadien-3,4-diol;

1,4-hexadiene;

1,5-hexadien-3-ol;

1,3,5-hexatriene;

5-hexen-1,2-diol;

5-hexen-1-ol;

hydroxypropyl acrylate;

3-hydroxy-3,7,11-trimethyl-1,6,10-dodecatriene;

isoamyl methacrylate;

isobutyl methacrylate;

isoprene;

2-isopropenylaniline;

isopropenyl chloroformate;

4,4′

-isopropylidene dimethacrylate;

3-isopropyl-a-a-dimethylbenzene isocyanate;

isopulegol;

itaconic acid;

itaconalyl chloride;

(±

)-;

linalool;

linalyl acetate;

p-mentha-1,8-diene;

p-mentha-6,8-dien-2-ol;

methyleneamino acetonitrile;

methacrolein;

[3-(methacryloylamino)-propyl]trimethylammonium chloride;

methacrylamide;

methacrylic acid;

methacrylic anhydride;

methacrylonitrile;

methacryloyl chloride;

2-(methacryloyloxy)ethyl acetoacetate;

(3-methacryloxypropyl) trimethoxy silane;

2-(methacryloxy)ethyl trimethyl ammonium methylsulfate;

2-methoxy propene (isopropenyl methyl ether);

methyl-2-(bromomethyl)acrylate;

5-methyl-5-hexen-2-one;

methyl methacrylate;

N,N′

-methylene bisacrylamide;

2-methylene glutaronitrite;

2-methylene-1,3-propanediol;

3-methyl-1,2-butadiene;

2-methyl-1-butene;

3-methyl-1-butene;

3-methyl-1-buten-1-ol;

2-methyl-1-buten-3-yne;

2-methyl-1,5-heptadiene;

2-methyl-1-heptene;

2-methyl-1-hexene;

3-methyl-1,3-pentadiene;

2-methyl-1,4-pentadiene;

(±

)-3-methyl-1-pentene;

(±

)-4-methyl-1-pentene;

(±

)-3-methyl-1-penten-3-ol;

2-methyl-1-pentene;

-methyl styrene;

t-methylstyrene;

t-methylstyrene;

3-methylstyrene;

methyl vinyl ether;

methyl vinyl ketone;

methyl-2-vinyloxirane;

4-methylstyrene;

methyl vinyl sulfone;

4-methyl-5-vinylthiazole;

myrcene;

t-nitrostyrene;

3-nitrostyrene;

1-nonadecene;

1,8-nonadiene;

1-octadecene;

1,7-octadiene;

7-octene-1,2-diol;

1-octene;

1-octen-3-ol;

1-pentadecene;

1-pentene;

1-penten-3-ol;

t-2,4-pentenoic acid;

1,3-pentadiene;

1,4-pentadiene;

1,4-pentadien-3-ol;

4-penten-1-ol;

4-penten-2-ol;

4-phenyl-1-butene;

phenyl vinyl sulfide;

phenyl vinyl sulfonate;

2-propene-1-sulfonic acid sodium salt;

phenyl vinyl sulfoxide;

1-phenyl-1-(trimethylsiloxy)ethylene;

propene;

safrole;

styrene (vinyl benzene);

4-styrene sulfonic acid sodium salt;

styrene sulfonyl chloride;

3-sulfopropyl acrylate potassium salt;

3-sulfopropyl methacrylate sodium salt;

tetrachloroethylene;

tetracyano ethylene;

trans 3-chloroacrylic acid;

2-trifluoromethyl propene;

2-(trifluoromethyl)propenoic acid;

2,4,4′

-trimethyl-1-pentene;

3,5-bis(trifluoromethyl)styrene;

2,3-bis(trimethylsiloxy)-1,3-butadiene;

1-undecene;

vinyl acetate;

vinyl acetic acid;

4-vinyl anisole;

9-vinyl anthracene;

vinyl behenate;

vinyl benzoate;

vinyl benzyl acetate;

vinyl benzyl alcohol;

3-vinyl benzyl chloride;

3-(vinyl benzyl)-2-chloroethyl sulfone;

4-(vinyl benzyl)-2-chloroethyl sulfone;

N-(p-vinyl benzyl)-N,N′

-dimethyl amine;

4-vinyl biphenyl (4-phenyl styrene);

vinyl bromide;

2-vinyl butane;

vinyl butyl ether;

9-vinyl carbazole;

vinyl carbinol;

vinyl cetyl ether;

vinyl chloroacetate;

vinyl chloroformate;

vinyl crotanoate;

vinyl cyclohexane;

4-vinyl-1-cyclohexene;

4-vinylcyclohexene dioxide;

vinyl cyclopentene;

vinyl dimethylchlorosilane;

vinyl dimethylethoxysilane;

vinyl diphenylphosphine;

vinyl 2-ethyl hexanoate;

vinyl 2-ethylhexyl ether;

vinyl ether ketone;

vinyl ethylene;

vinyl ethylene iron tricarbonyl;

vinyl ferrocene;

vinyl formate;

vinyl hexadecyl ether;

vinylidene fluoride;

1-vinyl imidizole;

vinyl iodide;

vinyl laurate;

vinyl magnesium bromide;

vinyl mesitylene;

vinyl 2-methoxy ethyl ether;

vinyl methyl dichlorosilane;

vinyl methyl ether;

vinyl methyl ketone;

2-vinyl naphthalene;

5-vinyl-2-norbornene;

vinyl pelargonate;

vinyl phenyl acetate;

vinyl phosphonic acid, bis(2-chloroethyl)ester;

vinyl propionate;

4-vinyl pyridine;

2-vinyl pyridine;

1-vinyl-2-pyrrolidinone;

2-vinyl quinoline;

1-vinyl silatrane;

vinyl sulfone;

vinyl sulfonic acid sodium salt;

o-vinyl toluene;

p-vinyl toluene;

vinyl triacetoxysilane;

vinyl tributyl tin;

vinyl trichloride;

vinyl trichlorosilane;

vinyl trichlorosilane (trichlorovinylsilane);

vinyl triethoxysilane;

vinyl triethylsilane;

vinyl trifluoroacetate;

vinyl trimethoxy silane;

vinyl trimethyl nonylether;

vinyl trimethyl silane;

vinyl triphenyphosphonium bromide (triphenyl vinyl phosphonium bromide);

vinyl tris-(2-methoxyethoxy) silane, vinyl 2-valerate, 1-(3-butenyl)-4-vinylbenzene and mixtures thereof.

45. The molecularly imprinted polymer of claim 34, wherein the polymer is a block copolymer.