Controllable ion-exchange membranes

• US 6,468,657 B1
• Filed: 12/04/1998
• Issued: 10/22/2002
• Est. Priority Date: 12/04/1998
• Status: Expired due to Fees

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Stroeve, Pieter, Hou, Zhizhong, Abbott, Nicholas
• Primary Examiner(s): Le, Hoa T.
• Application Number:
  US09/206,084
• Time in Patent Office: 1,418 Days
• Field of Search: 428/403, 428/404, 428/407, 428/450, 428/457, 428/699, 428/701, 428/702, 427/2.11, 427/2.14, 427/217, 427/220, 435/7.1, 435/7.7, 435/7.8, 435/7.9, 435/287.1, 435/287.2, 435/287.9, 436/73, 436/72, 436/80, 436/120, 436/127, 436/501, 514/495, 514/499, 514/501, 514/706, 514/770
• US Class Current: 428/403
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: B32B 15/14 next to a fibrous or filamentary layer
• CPC Class Codes: B32B 2311/04 Gold
• CPC Class Codes: B32B 3/26 characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids foam layer B32B5/18; layer of synthetic resin characterised by fillers that create voids or cavities B32B27/205; characterised by an apertured layer
• CPC Class Codes: B32B 7/04 Interconnection of layers
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: G01N 27/40 Semi-permeable membranes or partitions
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2993 Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer
• CPC Class Codes: Y10T 436/182 Organic or sulfhydryl containing [e.g., mercaptan, hydrogen, sulfide, etc.]
• CPC Class Codes: Y10T 436/20 Oxygen containing

Abstract

Multilayered porous materials are formed by coating a porous substrate with a metal and adsorbing an organic layer comprising a recognition moiety onto the metal film. The recognition moiety interacts with an analyte of interest allowing for its detection, purification, etc. Suitable recognition moieties can be selected from a range of species including, small molecules, polymers and biomolecules and the like. The novel porous materials of the invention can be utilized in an array of methods including, ion-exchange, ion-selective ion-exchange, assays, affinity dialysis, size exclusion dialysis and the like.

Claims

1. A multilayered porous membrane comprising:

(a) a porous substrate;

(b) a metal film adhered onto said substrate; and

(c) an organic layer attached to said metal film, said organic layer having a recognition moiety attached thereto,

wherein said membrane is porous.

2. The material according to claim 1, wherein said substrate is a member selected from the group consisting of optically opaque substrates, optically transparent substrates, insulating substrates, conducting substrates, semiconducting substrates, magnetic substrates and combinations thereof.

3. The material according to claim 1, wherein said substrate is a member selected from the group consisting of metals, inorganic oxides, inorganic glasses, organic polymers and combinations thereof.

4. The material according to claim 3, wherein said organic polymer is a member selected from the group consisting of polypropylene, nylon, fluorocarbon, polyester, polyethylene, polysulfone, polyether sulfone, cellulose, cellulose ester, ethyl vinyl acetate, polycarbonate, polyaramide, polyimide and combinations thereof.

5. The material according to claim 3, wherein said metal is a member selected from the group consisting of nickel, copper, silver, gold, platinum, palladium and combinations thereof.

6. The material according to claim 3, wherein said inorganic oxide is a member selected from the group consisting of silicon polymers, ZnO, TiO₂, Fe₂O₃, Al₂O₃, CeO₂, SnO₂, CuO, Cr₂O₃, SiO₂ and combinations thereof.

7. The material according to claim 1, wherein said substrate is track-etched.

8. The material according to claim 1, wherein said metal film is a member selected from the group consisting of nickel film, copper film, silver film, gold film, platinum film, palladium film and combinations thereof.

9. The material according to claim 8, wherein said metal film is a gold film.

10. The material according to claim 1, wherein said metal film is layered onto said substrate by electroless deposition.

11. The material according to claim 1, wherein said organic layer is attached to said metal film through a mechanism which is a member selected from the group consisting of covalent bonding, ionic bonding, coordination, van der Waals interactions, chemisorption, physisorption and combinations thereof.

12. The material according to claim 1, wherein said organic layer comprises an organosulfur moiety.

13. The material according to claim 12, wherein said organic layer comprises a group having the structure:

14. The material according to claim 13, wherein R¹ is a member selected from the group consisting of stable linking groups and cleaveable linking groups.

15. The material according to claim 14, wherein R¹ is a stable linking group which is a member selected from the group consisting of alkyl, substituted alkyl, aryl, arylalkyl, substituted aryl, substituted arylalkyl, saturated cyclic hydrocarbon, unsaturated cyclic hydrocarbon, heteroaryl, heteroarylalkyl, substituted heteroaryl, substituted heteroarylalkyl, heterocyclic, substituted heterocyclic and heterocyclicalkyl groups.

16. The material according to claim 15, wherein R¹ is a member selected from the group consisting of alkyl and substituted alkyl groups.

17. The material according to claim 14, wherein R¹ is a cleaveable linking group comprising a cleaveable moiety which is a member selected from group consisting of disulfide, ester, imide, carbonate, nitrobenzyl, phenacyl and benzoin groups.

18. The material according to claim 13, wherein said organic layer comprises:

19. The material according to claim 18, wherein Q, Q¹ and Q² are independently members selected from the group consisting of H and fluorine.

20. The material according to claim 13, wherein said organic layer comprises:

21. The material according to claim 20, wherein R² is a member selected from H and CH₃.

22. The material according to claim 20, wherein u is a number between 5 and 20.

23. The material according to claim 13, wherein said organic layer forms a self-assembled monolayer.

24. The material according to claim 1, wherein said organosulfur layer comprises a moiety that undergoes a change in state upon exposing said moiety to an external agent.

25. The material according to claim 24, wherein said external agent is a member selected from the group consisting of light, electrical field, magnetic field, heat, change in fluid pH, change in fluid ionic strength and combinations thereof.

26. The material according to claim 1, wherein said recognition moiety is a member selected from the group consisting of biomolecules, organic groups, metal chelates and organometallic moieties.

27. The material according to claim 26, wherein said organic group is a member selected from the group consisting of amines, sulfonamides, quaternary phosphonium, tertiary sulfonium, acids, drugs, chelating agents, crown ethers, cyclodextrins and combinations thereof.

28. The material according to claim 27, wherein said amine is a member selected from the group consisting of quaternary amines, heterocyclic amines and combinations thereof.

29. The material according to claim 27, wherein said acid is a member selected from the group consisting of sulfonic acids, carboxylic acids, phosphonic acids and combinations thereof.

30. The material according to claim 26, wherein said biomolecule is a member selected from the group consisting of antibodies, antigens, carbohydrates, nucleic acids, peptides, enzymes and receptors.

31. A multilayered porous membrane comprising:

(a) a porous polycarbonate track-etched substrate;

(b) a metal film adhered onto said substrate; and

(c) an organic layer attached to said metal film, said organic layer having a recognition moiety attached thereto

wherein said membrane is porous.

32. The material according to claim 31, wherein said metal film is a member selected from the group consisting of nickel film, copper film, silver film, gold film, platinum film, palladium film and combinations thereof.

33. The material according to claim 31, wherein said organic layer comprises a group having the structure:

34. The material according to claim 33, wherein R¹ is a member selected from the group consisting of alkyl and substituted alkyl groups.

35. The material according to claim 31, wherein said recognition moiety is a member selected from acids and amines.

36. The material according to claim 35, wherein said amine is a member selected from quaternary amines, heterocyclic amines and combinations thereof.

37. The material according to claim 35, wherein said acid is a member selected from the group consisting of carboxylic acids, sulfonic acids, phosphonic acids and combinations thereof.

38. A multilayered porous ion exchange membrane comprising:

(a) a porous substrate;

(b) a metal film adhered onto said substrate; and

(c) an organic layer attached to said metal film, said organic layer comprising a recognition moiety that binds or repels an ion

wherein said membrane is porous.

39. The material according to claim 38, wherein said substrate is a member selected from the group consisting of metals, inorganic oxides, inorganic glasses, organic polymers and combinations thereof.

40. The material according to claim 39, wherein said organic polymer is a member selected from the group consisting of polypropylene, nylon, fluorocarbon, polyester, polyethylene, polysulfone, polyether sulfone, cellulose, cellulose ester, ethyl vinyl acetate, polycarbonate, polyaramide, polyimide and combinations thereof.

41. The material according to claim 39, wherein said metal is a member selected from the group consisting of nickel, copper, silver, gold, platinum, palladium and combinations thereof.

42. The material according to claim 39, wherein said inorganic oxide is a member selected from the group consisting of ZnO, TiO₂, Fe₂O₃, Al₂O₃, CeO₂, SnO₂, CuO, Cr₂O₃, SiO₂ and combinations thereof.

43. The material according to claim 38, wherein said substrate is track-etched.

44. The material according to claim 38, wherein said metal film is a member selected from the group consisting of nickel film, copper film, silver film, gold film, platinum film, palladium film and combinations thereof.

45. The material according to claim 44, wherein said metal film is a gold film.

46. The material according to claim 38, wherein said metal film is layered onto said substrate by electroless deposition.

47. The material according to claim 38, wherein said organic layer is attached to said metal film through a mechanism which is a member selected from the group consisting of covalent bonding, ionic bonding, coordination, van der Waals interactions, chemisorption, physisorption and combinations thereof.

48. The material according to claim 38, wherein said organic layer comprises an organosulfur moiety.

49. The material according to claim 48, wherein said organosulfur layer comprises a moiety that undergoes a change in conformation upon exposing said moiety to a member selected from the group consisting of light, heat or combinations thereof.

50. The material according to claim 48, wherein said organic layer comprises a group having the structure:

51. The material according to claim 50, wherein R¹ is a member selected from the group consisting of stable linking groups and cleaveable linking groups.

52. The material according to claim 51, wherein R¹ is a stable linking group which is a member selected from the group consisting of alkyl, substituted alkyl, aryl, arylalkyl, substituted aryl, substituted arylalkyl, saturated cyclic hydrocarbon, unsaturated cyclic hydrocarbon, heteroaryl, heteroarylalkyl, substituted heteroaryl, substituted heteroarylalkyl, heterocyclic, substituted heterocyclic and heterocyclicalkyl groups.

53. The material according to claim 52, wherein R¹ is a member selected from the group consisting of alkyl and substituted alkyl groups.

54. A method of producing a multilayered porous membrane comprising:

(a) contacting a porous substrate with a metal plating solution to form a porous substrate having a metal film adhered thereto;

(b) contacting said metal coated substrate from step (a) with a solution comprising nitric acid, thereby activating said metal film;

(c) contacting said metal coated substrate from step (b) with a plurality of organic molecules that associate with the activated metal film, thereby forming an organic layer on said particle, wherein at least a portion of said plurality of organic molecules comprise a member selected from the group consisting of recognition moieties, reactive groups, protected reactive groups and combinations thereof

wherein said membrane is porous.

55. The material according to claim 54, wherein said metal plating solution comprises a member selected from the group consisting of nickel, copper, silver, gold, platinum, palladium and combinations thereof.

56. The method according to claim 55, wherein said plating solution comprises a reducible gold salt.

57. The method according to claim 56, wherein said sensitizer is a transition metal salt.

58. The method according to claim 57, wherein said transition metal salt is a salt of Sn⁺².

59. The method according to claim 56, wherein said gold plating solution comprises a reducible gold salt.

60. The method according to claim 59, wherein said gold plating solution further comprises a reducing agent.

61. The method according to claim 60, wherein said reducing agent is formaldehyde.

62. The method according to claim 59, wherein said reducible gold salt is Na₃Au(SO₃)₂.

63. The method according to claim 54, further comprising, prior to step (a), contacting a particulate substrate with a sensitizer to form a sensitized particulate substrate.

64. The method according to claim 54, further comprising, prior to step (a), contacting said sensitized particulate substrate with a silver solution to form a silver coated particle.

65. The method according to claim 64, wherein said silver solution comprises AgNO₃.

66. The method according to claim 64, wherein said silver solution further comprises ammonia.

67. The method according to claim 54, wherein said plurality of organic molecules comprises an organosulfur.

68. The method according to claim 54, wherein said plurality of organic molecules comprises a moiety selected from the group consisting of recognition moieties, reactive moieties, protected reactive moieties and combinations thereof.

69. The method according to claim 68, wherein said plurality of organic molecules comprises a reactive moiety and said method further comprises:

(d) reacting said reactive moiety with a recognition moiety.

70. The method according to claim 68, wherein said plurality of organic molecules comprises a protected reactive moiety and said method further comprises:

(d) deprotecting said protected reactive moiety to form a reactive moiety;

(e) reacting said reactive moiety with a recognition moiety.

71. A drug delivery device comprising:

(a) a porous substrate;

(b) a metal film adhered onto said substrate;

(c) an organic layer attached to said metal film, said organic layer comprising a recognition moiety; and

(d) a drug moiety reversibly associated with said recognition moiety.