Polyelectrolyte complex films for analytical and membrane separation of chiral compounds

• US 20040044100A1
• Filed: 06/16/2003
• Published: 03/04/2004
• Est. Priority Date: 06/14/2002
• Status: Active Grant

• Current Assignee: Florida State University Research Foundation, Inc. (State University System of Florida)
• Original Assignee: Florida State University Research Foundation, Inc. (State University System of Florida)
• Inventors: Schlenoff, Joseph B., Rmaile, Hassan
• Granted Patent: US 7,101,947 B2
• Time in Patent Office: Days
• US Class Current: 523/206
• CPC Class Codes: C07B 57/00 Separation of optically-active compounds
• CPC Class Codes: C08L 25/18 Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• CPC Class Codes: Y10T 428/31743 Next to addition polymer from unsaturated monomer[s]
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers

Abstract

The present invention is directed to enantioselective polyelectrolyte complex films. Further, said films may be free or isolated membranes, or coatings on substrates such a porous substrates, capillary tubes, chromatographic packing material, and monolithic stationary phases and used to separate chiral compounds. The present invention is also directed to a method for forming such enantioselective polyelectrolyte complex films.

Claims

10. A polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, wherein each polyelectrolyte is formed from a synthetic monomer and at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

11. A polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, wherein at least one of the polyelectrolytes comprises a chiral cyclodextrin moiety.

12. The polyelectrolyte complex of claim 11 wherein comprising the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte comprise a chiral cyclodextrin moiety.

24. The supported film of claim 23 polyelectrolyte complex of claim 11 wherein comprising the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte comprise a chiral cyclodextrin moiety.

13-1. The supported film of claim 23 wherein at least one of the polyelectrolytes comprises a charged repeat unit selected from the group diallyldimethylammonium, vinylbenzyltrimethylammonium, ionene, acryloxyethyltrimethyl ammonium chloride, methacryloxy(2-hydroxy)propyltrimethyl ammonium chloride, N-alkylvinylpyridinium,allylamine hydrochloride, ethyleneimmine, and salts thereof, styrenesulfonate, 2-acrylamido-2-methyl-1-propane sulfonate, sulfonated ether ether ketone, ethylenesulfonic acid, methacryloxyethylsulfonic acid, acrylic acid, methacrylic acid, and salts thereof.

14. A polyelectrolyte film comprising:

a first stratum having a front surface and a back surface, the first stratum comprising a first positively-charged polyelectrolyte and a first negatively-charged polyelectrolyte, wherein at least one of the first polyelectrolytes is formed from a natural monomer;

a second stratum on the front surface of the first stratum, the second stratum comprising a second positively-charged polyelectrolyte and a second negatively-charged polyelectrolyte, wherein the second positively- and negatively-charged polyelectrolytes are formed from synthetic monomers; and

at least one of the first positively-charged polyelectrolyte, the first negatively-charged polyelectrolyte, the second positively-charged polyelectrolyte, and the second negatively-charged polyelectrolyte comprises an enantiomeric excess of chiral repeat units.

15. The polyelectrolyte film of claim 14 wherein the first positively-charged polyelectrolyte is formed from a natural monomer and comprises an enantiomeric excess of chiral repeat units, and the first negatively-charged polyelectrolyte is formed from a natural monomer and comprises an enantiomeric excess of chiral repeat units.

16. The polyelectrolyte film of claim 15 wherein first positively-charged polyelectrolyte is poly(lysine) and the first negatively-charged polyelectrolyte is poly(glutamic acid).

17. The polyelectrolyte film of claim 14 wherein the second positively-charged polyelectrolyte comprises a quaternary ammonium group, a pyridinium group, or a protonated polyamine, and the second negatively-charged polyelectrolyte comprises a sulfonate group, a carboxylate, or a sulfate.

18. The polyelectrolyte film of claim 14 wherein second positively-charged polyelectrolyte is selected from the group consisting of poly(diallyldimethylammonium chloride), poly(vinylbenzyltrimethylammonium), ionenes, poly(acryloxyethyltrimethyl ammonium chloride), poly(methacryloxy(2-hydroxy)propyltrimethyl ammonium chloride), a poly(N-alkylvinylpyridinium), a poly(N-aryl vinyl pyridinium), poly(allylaminehydrochloride), polyethyleneimine, and salts and copolymers thereof, and the second negatively-charged polyelectrolyte is selected from the group consisting of poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propane sulfonic acid), sulfonated poly (ether ether ketone), poly(ethylenesulfonic acid), poly(methacryloxyethylsulfonic acid), poly(acrylic acid), poly(methacrylic acid), and salts and copolymers thereof.

19. The polyelectrolyte film of claim 14 wherein the second positively- and negatively-charged polyelectrolytes comprise an enantiomeric excess of chiral repeat units.

20. The polyelectrolyte film of claim 14 wherein the second positively- and negatively-charged polyelectrolytes comprise an enantiomeric excess of L-chiral repeat units or the second positively- and negatively-charged polyelectrolytes comprise an enantiomeric excess of D-chiral repeat units.

21. A free membrane, the free membrane comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, wherein at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

22. A supported membrane, the supported membrane comprising a porous substratum having a surface and a polyelectrolyte complex on the surface of the porous substratum, the polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, and at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

23. A supported film, the supported film comprising a porous substratum having a surface and a polyelectrolyte complex on the surface of the porous substratum, the polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, and at least one of the polyelectrolytes comprises a chiral cyclodextrin moiety.

1. An optically active polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, wherein each polyelectrolyte is formed from a synthetic monomer and at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

2. The optically active polyelectrolyte complex of claim 1 wherein the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte comprise an enantiomeric excess of chiral repeat units.

3. The optically active polyelectrolyte complex of claim 1 wherein the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte comprise an enantiomeric excess of L-chiral repeat units or the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte comprise an enantiomeric excess of D-chiral repeat units.

4. The optically active polyelectrolyte complex of claim 1 wherein the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte are selected from the group consisting of linear polyelectrolytes, branched polyelectrolytes, dendritic polyelectrolytes, graft polyelectrolytes, comb polyelectrolytes and copolymers thereof.

5. The optically active polyelectrolyte complex of claim 1 wherein the polyelectrolyte comprising an enantiomeric excess of chiral repeat units is formed from chiral monomer units.

6. The optically active polyelectrolyte complex of claim 1 wherein the polyelectrolyte comprising an enantiomeric excess of a chiral repeat units is the reaction product of a non-chiral polymer and a chiral reagent or a non-chiral reagent which introduces chirality.

7. The optically active polyelectrolyte complex of claim 6 wherein the positively-charged polyelectrolyte is the polyelectrolyte comprising an enantiomeric excess of chiral repeat units and the non-chiral polymer comprises an amine group, a pyridine group, or a benzyl halogen group.

8. The optically active polyelectrolyte complex of claim 7 wherein the chiral reagent or the non-chiral reagent which introduces chirality is selected from the group consisting of a chiral alkyl halide and a chiral aryl halogen.

9. The optically active polyelectrolyte complex of claim 1 wherein the negatively-charged polyelectrolyte is the polyelectrolyte comprising an enantiomeric excess of chiral repeat units, the negatively-charged polyelectrolyte comprises a sulfonate group or a carboxylate group.

13. The polyelectrolyte complex of claim 11 wherein at least one of the polyelectrolytes comprises a charged repeat unit selected from the group diallyldimethylammonium, vinylbenzyltrimethylammonium, ionene, acryloxyethyltrimethyl ammonium chloride, methacryloxy(2-hydroxy)propyltrimethyl ammonium chloride, N-alkylvinylpyridinium,allylamine hydrochloride, ethyleneimmine, and salts thereof, styrenesulfonate, 2-acrylamido-2-methyl-1-propane sulfonate, sulfonated ether ether ketone, ethylenesulfonic acid, methacryloxyethylsulfonic acid, acrylic acid, methacrylic acid, and salts thereof.

25. A chromatographic stationary phase, the chromatographic stationary phase comprising a substratum having a surface and a polyelectrolyte complex on the surface of the substratum, the polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, and at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

26. The chromatographic stationary phase of claim 25 wherein the substratum is selected from the group consisting of a particulate chromatographic packing material, a capillary tube, and a porous continuous solid.

27. A method for preparing an optically active polyelectrolyte complex, the method comprising:

a. providing a substratum comprising a surface;

b. applying a first solution comprising a first polyelectrolyte onto at least a portion of the substratum surface whereby the polyelectrolyte in the first solution is deposited onto the portion of the substratum surface to form a first polymer layer comprising the first polyelectrolyte;

c. applying a second solution comprising a second polyelectrolyte that is oppositely-charged from the first polyelectrolyte whereby the second polyelectrolyte is deposited onto the first polymer layer to form a second polymer layer comprising the second polyelectrolyte;

d. performing steps b and c until the desired number of first and second polymer layers are formed; and

e. wherein each polyelectrolyte is formed from a synthetic monomer and at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

28. The method as set forth in claim 27 wherein the first and second polyelectrolytes comprise an enantiomeric excess of chiral repeat units.

29. The method as set forth in claim 27 wherein the first and second polyelectrolytes comprise an enantiomeric excess of L-chiral repeat units or first and second polyelectrolytes comprise an enantiomeric excess of D-chiral repeat units.

30. The method as set forth in claim 27 wherein the first and second polyelectrolytes are selected from the group consisting of linear polyelectrolytes, branched polyelectrolytes, dendritic polyelectrolytes, graft polyelectrolytes, comb polyelectrolytes and copolymers thereof.

31. The method as set forth in claim 27 wherein the polyelectrolyte comprising an enantiomeric excess of chiral repeat units is formed from chiral monomer units.

32. The method as set forth in claim 27 wherein the polyelectrolyte comprising an enantiomeric excess of chiral repeat units is the reaction product of a non-chiral polymer and a chiral reagent or a non-chiral reagent which introduces chirality.

33. The method as set forth in claim 32 wherein the polyelectrolyte comprising an enantiomeric excess of chiral repeat units is a positively-charged polyelectrolyte and the non-chiral polymer comprises an amine group or pyridine group.

34. The method as set forth in claim 27 wherein the polyelectrolyte comprising an enantiomeric excess of a chiral repeat units is a negatively-charged polyelectrolyte comprising a sulfonate group or a carboxylate.

35. The method as set forth in claim 27 wherein the first polyelectrolyte or the second polyelectrolyte does not comprise an enantiomeric excess of chiral repeat units and is selected from the group consisting of poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propane sulfonic acid), sulfonated poly (ether ether ketone), poly(ethylenesulfonic acid), poly(methacryloxyethylsulfonic acid), their salts, and copolymers thereof, poly(acrylic acid) and poly(methacrylic acid), or is selected from the group consisting of poly(diallyldimethylammonium chloride), poly(vinylbenzyltrimethylammonium), ionenes, poly(acryloxyethyltrimethyl ammonium chloride), poly(methacryloxy(2-hydroxy)propyltrimethyl ammonium chloride) and copolymers thereof, a poly(N-methylvinylpyridium), a poly(N-aryl vinyl pyridinium), poly(N-octyl-4-vinyl pyridinium iodide, poly(N-octadecyl-2-ethynyl pyridinium bromide), poly(N-alkyl pyridines) and copolymers thereof, poly(allylamine hydrochloride), poly(ethyleneimmine), and poly(vinyl amine).

36. The method as set forth in claim 27 comprising rinsing each first and second polymer layer with a rinsing liquid prior to applying the next first or second solution, the rinsing liquid being free of polyelectrolyte and comprising a solvent for the polyelectrolyte in the layer being rinsed.

37. The method as set forth in claim 36 wherein the polyelectrolyte rinsed from each layer is reintroduced into the solution from which it came.

38. The method as set forth in claim 36 comprising drying each rinsed layer prior to applying the next layer.

39. The method as set forth in claim 36 wherein the first and second solutions comprise about 0.01% to about 40% by weight of the first and second polyelectrolytes, respectively.

40. The method as set forth in claim 36 wherein the first and second solutions comprise about 0.1% to about 10% by weight of the first and second polyelectrolytes, respectively.

41. The method as set forth in claim 27 wherein the first and the second solutions are applied by spraying.

42. The method as set forth in claim 27 wherein the first and the second solutions are applied by dip coating.

43. The method as set forth in claim 27 wherein the first and the second solutions are applied by spin coating.

44. A method for preparing a polyelectrolyte complex, the method comprising:

a. providing a substratum comprising a surface;

b. applying a first solution comprising a first polyelectrolyte onto at least a portion of the substratum surface whereby the polyelectrolyte in the first solution is deposited onto the portion of the substratum surface to form a first polymer layer comprising the first polyelectrolyte;

c. applying a second solution comprising a second polyelectrolyte that is oppositely-charged from the first polyelectrolyte whereby the second polyelectrolyte is deposited onto the first polymer layer to form a second polymer layer comprising the second polyelectrolyte;

d. performing steps b and c until the desired number of first and second polymer layers are formed; and

e. wherein each polyelectrolyte is formed from a synthetic monomer, and at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

45. A method for depositing a polyelectrolyte complex on a surface of a substratum, the method comprising applying a solution that comprises the polyelectrolyte complex onto at least a portion of the surface of the substratum whereby the polyelectrolyte complex is deposited onto the portion of the surface of the substratum, wherein the polyelectrolyte complex comprises a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, each polyelectrolyte is formed from a synthetic monomer, and at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

46. A method for depositing a polyelectrolyte complex on a surface of a substratum, the method comprising applying a solution that comprises the polyelectrolyte complex onto at least a portion of the surface of the substratum whereby the polyelectrolyte complex is deposited onto the portion of the surface of the substratum, wherein the polyelectrolyte complex comprises a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, and at least one of the polyelectrolytes comprises a chiral cyclodextrin moiety.

47. A method of chromatographically separating test enantiomers, the method comprising using an optically active polyelectrolyte complex as a chiral surface which interacts with the test enantiomers in an enantioselective manner, the optically active polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, wherein at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

48. The method of claim 47 wherein the optically active polyelectrolyte complex is on the surface of particles.

49. The method of claim 47 wherein the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte comprise an enantiomeric excess of chiral repeat units.

50. The method of claim 47 wherein the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte comprise an enantiomeric excess of L-chiral repeat units or the positively-charged polyelectrolyte and the negatively-charged polyelectrolyte comprise an enantiomeric excess of D-chiral repeat units.

51. The method of claim 47 wherein the positively-charged polyelectrolyte and the negatively-charge polyelectrolyte are selected from the group consisting of linear polyelectrolytes, branched polyelectrolytes, dendritic polyelectrolytes, graft polyelectrolytes, comb polyelectrolytes, and copolymers thereof.

52. The method of claim 47 wherein the polyelectrolyte comprising an enantiomeric excess of chiral repeat units is formed from chiral monomer units.

53. The method of claim 52 wherein the polyelectrolyte comprising an enantiomeric excess of chiral repeat units is poly(lysine) or poly(glutamic acid).

54. The method of claim 47 wherein the polyelectrolyte comprising an enantiomeric excess of chiral repeat units is the reaction product of a non-chiral polymer and a chiral reagent or a non-chiral reagent which introduces chirality.

55. The method of claim 54 wherein the positively-charged polyelectrolyte is the polyelectrolyte comprising an enantiomeric excess of chiral repeat units and the non-chiral polymer comprises a quaternary ammonium group, an amine group, a pyridine group, or a benzyl halogen group.

56. The method of claim 55 wherein the chiral reagent or the non-chiral reagent which introduces chirality is selected from the group consisting of a chiral alkyl halide and a chiral aryl halogen.

57. The method of claim 54 wherein the negatively-charged polyelectrolyte is the polyelectrolyte comprising an enantiomeric excess of chiral repeat units, and the negatively-charged polyelectrolyte comprises a sulfonate group or a carboxylate group.

58. A method of separating test enantiomers, the method comprising using polyelectrolyte complex as a chiral surface which interacts with the test enantiomers in an enantioselective manner, the polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, wherein at least one of the polyelectrolytes comprises an enantiomeric excess of chiral repeat units.

59. The method of claim 58 wherein the polyelectrolyte complex is a thin film membrane and is permeably enantioselective.

60. A method of separating test enantiomers, the method comprising using polyelectrolyte complex as a chiral surface which interacts with the test enantiomers in an enantioselective manner, the polyelectrolyte complex comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte, wherein at least one of the polyelectrolytes comprises a chiral cyclodextrin moiety.