Molecularly imprinted polymers grafted on solid supports

• US 6,759,488 B1
• Filed: 02/21/2002
• Issued: 07/06/2004
• Est. Priority Date: 09/17/1999
• Status: Expired due to Term

• Current Assignee: Mip Technologies AB
• Original Assignee: Mip Technologies AB
• Inventors: Rückert, Bärbel, Sulitzky, Claudia, Sellergren, Börje
• Primary Examiner(s): PEZZUTO, HELEN LEE
• Application Number:
  US10/069,068
• Time in Patent Office: 866 Days
• Field of Search: 526/218.1, 526/67, 526/199, 526/200
• US Class Current: 526/67
• CPC Class Codes: B01D 15/3852 using imprinted phases or molecular recognition; using imprinted phases
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/261 obtained by reactions only involving carbon to carbon unsaturated bonds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F
• CPC Class Codes: B01J 20/268 Polymers created by use of a template, e.g. molecularly imprinted polymers
• CPC Class Codes: B01J 20/285 based on polymers
• CPC Class Codes: B01J 20/3057 Use of a templating or imprinting material molecularly imprinted polymers B01J20/268; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: C08F 285/00 Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00

Abstract

The invention refers to a molecularly imprinted polymer, a method of preparing a molecularly imprinted polymer material, and the use thereof. According to the invention a support comprising at least one monomer, and a template, in a polymerization medium is polymerized with a free radical initiator, whereafter the template is removed from the molecularly imprinted polymer obtained. The polymerization is confined to the surface of the support, preferably by confining the free radical initiator to the support by bonding adsorption. The molecularly imprinted polymer may be used in chromatography, for separations, in chemical sensors, in molecular recognition as stationary phase in capillaries, in selected sample enrichment or in catalysis.

Claims

1. A supported molecularly imprinted polymer, characterised in that it is obtainable by

(a) providing a composition comprising a polymerisation medium with at least one functional monomer, a template, a support, and a free radical initiator;

(b) polymerisation of the composition while confining the polymerisation to the surface of the support, thereby providing a molecularly imprinted polymer on the support;

(c) separation of the supported molecularly imprinted polymer from the polymerisation medium;

(d) removal of the template from the supported molecularly imprinted polymer;

(e) reuse of the polymerisation medium for preparing further supported molecularly imprinted polymer by repeating steps (a)-(d).

2. A supported molecularly imprinted polymer according to claim 1, wherein the polymerisation is confined to the surface of the support by confining the free radical initiator to the support.

3. A supported molecularly imprinted polymer according to claim 2, wherein the free radical initiator is bound or adsorbed to the surface of the support.

4. A supported molecularly imprinted polymer according to claim 1, wherein the support is selected from the group consisting of porous and non-porous, planar and non-planar inorganic and organic supports.

5. A supported molecularly imprinted polymer according to claim 1, wherein the support is a particle and the free radical initiator is an azo-initiator that is bound to the surface of the particle.

6. A supported molecularly imprinted polymer according to claim 5, wherein the azoinitiator is bound to the surface of the particle by a two point attachment.

7. A supported molecularly imprinted polymer according to claim 1, wherein the initiator is an azo-bis-amidine initiator that is adsorbed to the surface of the support and is insoluble in the polymerisation medium.

8. A supported molecularly imprinted polymer according to claim 7, wherein the initiator is 2,2′

-azo-bis (2-amidinopropane) or 2,2′

-azobis (N,N′

-dimethyleneisobutyramidine).

9. A supported molecularly imprinted polymer according to claim 1, wherein the polymerisation is confined to the surface of the support by subjecting the composition to microwave irradiation which selectively heats the support and thereby initiates a polymerisation reaction at the surface of the support.

10. A supported molecularly imprinted polymer according to claim 1, wherein the polymerisation on the support is repeated at least once with a different composition to obtain at least one further layer of a molecularly imprinted polymer;

a layer of different polarity;

or a layer of other functional properties.

11. A supported molecularly imprinted polymer according to claim 1, wherein the template is selected from the group consisting of organic or inorganic molecule entities, ions, antibodies, antigens, amino acids, peptides, proteins, nucleotides, DNA-bases, carbohydrates, drugs, pesticides, and derivatives thereof.

23. A supported molecularly imprinted polymer according to claim 2, wherein the support is selected from the group consisting of porous and non-porous, planar and non-planar inorganic and organic supports.

24. A supported molecularly imprinted polymer according to claim 3 wherein the support is selected from the group consisting of porous and non-porous, planar and non-planar inorganic and organic supports.

25. A supported molecularly imprinted polymer according to claim 2, wherein the support is a particle and the free radical initiator is an azo-initiator that is bound to the surface of the particle.

26. A supported molecularly imprinted polymer according to claim 2, wherein the initiator is an azo-bis-amidine initiator that is adsorbed to the surface of the support and is insoluble in the polymerisation medium.

27. A supported molecularly imprinted polymer according to claim 2, wherein the polymerisation on the support is repeated at least once with a different composition to obtain at least one further layer of a molecularly imprinted polymer;

a layer of different polarity;

or a layer of other functional properties.

28. A supported molecularly imprinted polymer according to claim 2, wherein the template is selected from the group consisting of organic or inorganic molecule entities, ions, antibodies, antigens, amino acids, peptides, proteins, nucleotides, DNA-bases, carbohydrates, drugs, pesticides, and derivatives thereof.

31. A chromatography process wherein the supported molecularly imprinted polymer of claim 1 is utilized.

32. A separation process wherein the supported molecularly imprinted polymer of claim 1 is utilized.

33. A chemical sensor comprising the supported molecularly imprinted polymer of claim 1.

34. A process for molecular recognition as stationary phase in capillaries wherein the supported molecularly imprinted polymer of claim 1 is utilized.

35. A process for selective sample enrichment wherein the supported molecularly imprinted polymer of claim 1 is utilized.

36. A catalysis process wherein the molecularly imprinted polymer of claim 1 is utilized.

37. A molecularly imprinted polymer according to claim 1, wherein the duration of polymerisation is adjusted in a manner that optimizes the mass transfer properties of the resulting thin layer film.

12. A method for preparing a supported molecularly imprinted polymer, characterised by

(a) providing a composition comprising a polymerisation medium with at least one functional monomer, a template, a support, and a free radical initiator;

(b) polymerising the composition while confining the polymerisation to the surface of the support, thereby providing a molecularly imprinted polymer on the support;

(c) separating the supported molecularly imprinted polymer from the polymerisation medium;

(d) removing the template from the supported molecularly imprinted polymer;

(e) reusing the polymerisation medium for preparing further supported molecularly imprinted polymer by repeating steps (a)-(d).

13. A method according to claim 12, wherein the polymerisation is confined to the surface of the support by confining the free radical initiator to the support.

14. A method according to claim 13, wherein the free radical initiator is bound or adsorbed to the surface of the support.

15. A method according to claim 14, wherein the support is a particle and the initiator is an azoinitiator that is bound to the surface of the particle.

16. A method according to claim 15, wherein the azoinitiator is bound to the surface of the particle by a two point attachment.

17. A method according to claim 16, wherein the azoinitiator is the reaction product of glyxidoxypropyltrimethoxysilane (GPS) and azo-bis (cyanopentanoic acid) (ACPA).

18. A method according to claim 14, wherein the initiator is an azo-bis-amidine initiator that is adsorbed to the surface of the support and is insoluble in the polymerisation medium.

19. A method according to claim 18, wherein the initiator is 2,2′

-azo-bis(2-amidinopropane) or 2,2′

-azobis (N,N′

-dimethyleneisobutyramidine).

20. A method according to claim 12, wherein the polymerisation is confined to the surface of the support by subjecting the composition to microwave irradiation which selectively heats the support and thereby initiates a polymerisation reaction at the surface of the support.

21. A method according to claim 12, wherein the polymerisation on the support is repeated at least once with a different composition to obtain at least one further layer of a molecularly imprinted polymer;

a layer of different polarity;

or a layer of other functional properties.

22. Azoinitiator as a means of carrying out the method of claim 12, characterised in that it is the reaction product of glyxidoxypropyltrimethoxysilane (GPS) and azo-bis-(cyanopentanoic acid) (ACPA).

29. A method according to claim 13, wherein the polymerisation on the support is repeated at least once with a different composition to obtain at least one further layer of a molecularly imprinted polymer;

a layer of different polarity;

or a layer of other functional properties.

30. Azoinitiator as a means of carrying out the method of claim 13, characterised in that it is the reaction product of glyxidoxypropyltrimethoxysilane (GPS) and azo-bis-(cyanopentanoic acid) (ACPA).

38. A method according to claim 12, wherein the duration of the polymerisation is adjusted in a matter that optimizes the mass transfer properties of the resulting thin layer film.