Methods For Preparation of Molecularly Imprinted Polymers For Wine Extraction

• US 20150232598A1
• Filed: 10/15/2013
• Published: 08/20/2015
• Est. Priority Date: 10/15/2012
• Status: Active Grant

• Current Assignee: The Trustees of Dartmounth College (Dartmouth College)
• Original Assignee: The Trustees of Dartmounth College (Dartmouth College)
• Inventors: Belbruno, Joseph J.
• Granted Patent: US 10,000,598 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08F 220/20 of polyhydric alcohols or phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08F 222/10 Esters
• CPC Class Codes: C08F 226/10 N-Vinyl-pyrrolidone
• CPC Class Codes: C12H 1/0424 with the aid of a polymer
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

Disclosed herein are compositions of, synthesis methods and methods of use for improved molecularly imprinted polymers useful for extracting target molecule compounds of wine.

Claims

1. A crosslinked molecularly imprinted polymer (MIP) for extraction of at least one target molecule component of wine, the MIP comprising polyvinylpolypyrrolidone (PVPP) or poly(hydroxyethylmethacrylate) (pHEMA).

2. The MIP of claim 1, wherein the PVPP is formed by polymerization of N-vinyl pyrrolidone with a crosslinker molecule.

3. The MIP of claim 1, wherein the crosslinked pHEMA is formed by polymerization of hydroxyethylmethacrylate with a crosslinker molecule.

4. The MIP of claim 2 wherein the molar ratio of crosslinker to monomer is 1.5:

1 to 6;

1.

5. The MIP of claim 2 wherein the crosslinker molecule is ethylene dimethacrylate.

6. The MIP of claim 1 wherein the MIP has been imprinted with 2-isobutyl-3-methoxypyrazine (IBMP), 2 methoxypyrazine or 2-phenyl ethyl alcohol.

7. The MIP of claim 1 wherein the MIP has been imprinted with guaiacaol or 4-methyl guaiacol.

8. The MIP of claim 1, wherein the MIP is in the form of particles having an average size from 100 nm to 1 micrometer.

9. The MIP of claim 8 wherein the particles have an average size from 100 nm to 500 nm.

10. The MIP of any of claim 1 wherein 1 g of the MIP removes 80-100% of the target molecule from 100 ml of wine or synthetic wine containing 20 ng/L of the target molecule.

11. The MIP of claim 10, wherein the MIP has been imprinted with 2-isobutyl-3-methoxypyrazine (IBMP), 2 methoxypyrazine or 2-phenyl ethyl alcohol and the target molecule is IBMP.

12. The MIP of claim 10, wherein the MIP has been imprinted with guaiacaol or 4-methyl guaiacol and the target molecule is guaiacaol.

23. A method comprising flowing wine through a solid phase extraction column comprising a solid phase comprising the MIP of claim 1.

24. The method of claim 23 further comprising the step of collecting the wine after it exits the solid phase extraction column.

25. The method of claim 23, wherein the wine comprises an initial concentration of a target molecule as it enters the solid phase extraction column, the wine comprises a final concentration of a target molecule as it exits the solid phase extraction column, and the ratio of the final concentration to the initial concentration of the target molecule is from 0 to 0.4.

26. The method of claim 25 wherein the ratio of the final concentration to the initial concentration of the target molecule is from 0 to 0.2.

27. A method of regenerating a MIP comprising washing the MIP of claim 1 with a solvent.

28. The method of claim 27 wherein the solvent comprises a mixture of an alcohol and water.

29. The MIP of claim 3 wherein the molar ratio of crosslinker to monomer is 1. 5:

1 to 6;

1.

30. The MIP of claim 3 wherein the crosslinker molecule is ethylene dimethacrylate.

13. A method of making a molecularly imprinted polymer (MIP) for extraction of at least one target molecule component of wine comprising;

a) Forming a first solution comprising a solvent, a monomer and a target molecule or a target molecule analog to form a first solution;

b) stirring said first solution;

c) adding a cross linker to said stirred first solution to form a second solution; and

d) stirring said second solution for 5 to 18 hours; and

e) adding a polymerization initiator to said stirred second solution to form a third solution;

f) forming the MIP by polymerization of the monomer and the crosslinker, the MIP being associated with the target molecule or target molecule analog; and

g) isolating the MIP from said third solution; and

h) removing at least some of the target molecule or target molecule analog from the MIP.

14. The method of claim 13 wherein said solvent is a polar protic solvent other than water.

15. The method of claim 13 wherein the monomer is selected from the group consisting of N-vinyl pyrrolidone and hydroxyethylmethacrylate.

16. The method of claim 13 wherein the cross linker is ethylene dimethacrylate.

17. The method of claim 13 wherein the molar ratio of crosslinker to monomer is 1.5:

1 to 6;

1.

18. The method of claim 13 wherein the target molecule is 2-isobutyl-3-methoxypyrazine, 2-methoxypyrazine, 2-phenylethyl alcohol, guaiacol, or 4-methylguaiacol.

19. The method of claim 13 wherein the second solution is stirred from 5 to 12 hours.

20. The method of claim 13 wherein the polymerization initiator is a dialkyldiazine.

21. The method of claim 13 wherein the MIP is in the form of particles having an average size from 100 nm to 1 micrometer

22. The method of claim 21 wherein the MIP is in the form of particles having an average size from 100 nm to 500 nm.