Ionic liquid reconstituted cellulose composites as solid support matrices

• US 20070006774A1
• Filed: 06/27/2006
• Published: 01/11/2007
• Est. Priority Date: 06/29/2005
• Status: Abandoned Application

• Current Assignee: University of Alabama (University of Alabama System)
• Original Assignee: University of Alabama (University of Alabama System)
• Inventors: Rogers, Robin, Turner, Megan, Holbrey, John, Spear, Scott, Daly, Daniel
• Application Number:
  US11/475,630
• Publication Number:
  US 20070006774A1
• Time in Patent Office: Days
• US Class Current: 106/200.200
• CPC Class Codes: C08L 1/02 Cellulose; Modified cellulose
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 2666/20 Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
• CPC Class Codes: C08L 2666/26 Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: C08L 79/02 Polyamines
• CPC Class Codes: C08L 89/00 Compositions of proteins; Compositions of derivatives thereof foodstuff preparations A23J3/00

Abstract

Disclosed are composites comprising regenerated cellulose, a first active substance, a second active substance, and a linker. Methods for preparing the composites that involve the use of ionic liquids are also disclosed. Articles prepared from the disclosed composites and further disclosed.

Claims

1. A cellulose/active substance composite, comprising a regenerated cellulose matrix, a first active substance substantially homogeneously distributed within the matrix of regenerated cellulose, a linker, and a second active substance, wherein the linker is bonded to the first and second active substances.

2. The composite of claim 1, wherein the regenerated cellulose has substantially the same molecular weight as a starting cellulose from which the regenerated cellulose is prepared, wherein the regenerated cellulose is substantially free of an increased amount of substituent groups relative to the starting cellulose, and wherein the regenerated cellulose is substantially free of entrapped ionic liquid degradation products.

3. The composite of claim 1, wherein the weight ratio of regenerated cellulose to first active substance is from about 1000:

1 to about 1;

2.

4. The composite of claim 1, wherein the first active substance prior to being bonded to the linker comprises a nucleophilic functional group.

5. The composite of claim 1, wherein the first active substance prior to being bonded to the linker comprises a polymeric amine.

10. The composite of claim 1, wherein the first active substance prior to being bonded to the linker comprises an electrophilic functional group.

11. The composite of claim 1, wherein the linker prior to being bonded to the first and second active substances comprises at least two electrophilic functional groups.

12. The composite of claim 1, wherein the linker prior to being bonded to the first and second active substances comprises a diester.

13. The composite of claim 1, wherein the linker prior to being bonded to the first and second active substances comprises a dialdehyde.

14. The composite of claim 1, wherein the linker prior to being bonded to the first and second active substances comprises gluteraldehyde.

15. The composite of claim 1, wherein the linker prior to being bonded to the first and second active substances comprises at least one nucleophilic functional group and at least one electrophilic functional group.

16. The composite of claim 1, wherein the linker comprises at least two nucleophilic functional groups.

17. The composite of claim 1, wherein the weight ratio of regenerated cellulose to second active substance is from about 1000:

1 to about 1;

2.

18. The composite of claim 1, wherein the second active substance comprises a nucleophilic fuictional group.

19. The composite of claim 1, wherein the second active substance comprises an electrophilic fimctional group.

20. The composite of claim 1, wherein the second active substance comprises a microbial cell, herbicide, an insecticide, a fungicide, a microbial cell, a repellent for an animal or insect, a plant growth regulator, a fertilizer, a flavor or odor composition, a catalyst, a photoactive agent, an indicator, a dye, an UV adsorbent, or a mixture thereof.

21. The composite of claim 1, wherein the second active substance comprises an antibacterial agent.

22. The composite of claim 1, wherein the second active substance comprises an antiviral agent.

23. The composite of claim 1, wherein the second active substance comprises a biomolecule.

24. The composite of claim 1, wherein the second active substance comprises a peptide, protein, enzyme, or antibody.

25. The composite of claim 1, wherein the second active substance comprises a nucleic acid, aptamer, or ribozyme.

73. An article comprising the composition of any of claims 1.

74. The article of claim 73, wherein the article comprises paper.

75. The article of claim 73, wherein the article comprises a textile.

76. The article of claim 73, where the article comprises protective clothing.

77. The article of claim 73, wherein the clothing comprises a surgical gown, glove, mask, or bandage.

6. The composite of claim 6, wherein polymeric amine comprises a protein or peptide.

7. The composite of claim 6, wherein the polymeric amine comprises bovine serum albumin.

8. The composite of claim 6, wherein the polymeric amine comprises polylysine, polyamine, or polyalkyleneimine.

9. The composite of claim 6, wherein the polymeric amine comprises a polyether amine.

26. A method for preparing a cellulose/active substance composite, comprising:

a. providing a composition comprising a regenerated cellulose matrix and a first active substance, wherein the first active substance is substantially homogeneously distributed within the regenerated cellulose matrix;

b. contacting the first active substance with a linker to bond the linker to the first active substance; and

c. contacting a second active substance with the linker to bond the linker to the second active substance,

thereby providing a cellulose/active substance composite.

27. The method of claim 26, wherein the linker is contacted to the first active substance prior to contacting the second active substance to the linker.

28. The method of claim 26, wherein the linker is contacted to the first active substance prior to providing the regenerated cellulose composition.

29. The method of claim 26, wherein the linker is contacted to the second active substance prior to contacting the first active substance to the linker.

30. The method of claim 26, wherein prior to providing the regenerated cellulose composition the linker is contacted to the first active substance and then contacted to the second active substance.

31. The method of claim 26, wherein providing the composition comprising the regenerated cellulose matrix and the first active substance, comprises:

a. providing a composition comprising a starting cellulose, the first active substance, and a hydrophilic ionic liquid, wherein the starting cellulose is dissolved in the ionic liquid and wherein the ionic liquid is substantially free of water, organic solvent, and nitrogen-containing bases; and

b. admixing the composition of step (a) with a liquid non-solvent for the cellulose, wherein the non-solvent is miscible with the ionic liquid and wherein the first active substance is substantially insoluble in the non-solvent,

wherein a composition comprising the regenerated cellulose matrix and an ionic liquid phase is provided.

32. The method of claim 31, wherein the regenerated cellulose has substantially the same molecular weight as the starting cellulose from which the regenerated cellulose is prepared, wherein the regenerated cellulose is substantially free of an increased amount of substituent groups relative to the starting cellulose, and wherein the regenerated cellulose is substantially free of entrapped ionic liquid degradation products.

33. The method of claim 31, wherein the admixing step is carried out by extruding the composition of step (a) through a die and into the non-solvent.

34. The method of claim 31, further comprising collecting the regenerated cellulose matrix.

35. The method of claim 31, wherein the starting cellulose comprises fibrous cellulose, wood pulp, linters, cotton, or paper.

36. The method of claim 31, wherein the ionic liquid is molten at a temperature of less than about 150°

C.

37. The method of claim 31, wherein the ionic liquid is molten at a temperature of from about −

44°

C. to about 120°

C.

38. The method of claim 31, wherein the ionic liquid comprises one or more cations and one or more anions and wherein the one or more cations comprise one or more compounds having the formula

wherein R¹ and R² are independently a C₁-C₆ alkyl group or a C₁-C₆ alkoxyalkyl group, and R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are independently H, a C₁-C₆ alkyl, a C₁-C₆ alkoxyalkyl group, or a C₁-C₆ alkoxy group, and the one or more anions comprise one or more of a halogen, perchlorate, pseudohalogen, or C₁-C₆ carboxylate.

39. The method of claim 31, wherein ionic liquid comprises one or more cations and one or more anions and wherein the one or more cations comprise one or more compounds having the formula:

wherein R¹ and R² are independently a C₁-C₆ alkyl group or a C₁-C₆ alkoxyalkyl group, and R³, R⁴, and R⁵ are independently H, a C₁-C₆ alkyl group, a C₁-C₆ alkoxyalkyl group, or a C₁-C₆ alkoxy group, and the one or more anions comprise one or more of a halogen or pseudohalogen.

40. The method of claim 31, wherein the one or more cations comprise an imidazolium ion having the formula:

wherein R¹ and R² are C₁-C₆ alkyl.

41. The method of claim 40, wherein R¹ or R² is methyl.

42. The method of claim 40, wherein R¹ is C₁-C₄-alkyl and R² is methyl.

43. The method of claim 40, wherein R³, R⁴, and R⁵ each are H.

44. The method of claim 31, wherein ionic liquid comprises one or more cations and one or more anions and the one or more anions comprise one or more of a halogen, perchlorate, pseudohalogen, or C₁-C₆ carboxylate.

45. The method of claim 31, wherein the one or more anions is chloride.

46. The method of claim 31, wherein the non-solvent is miscible with water.

47. The method of claim 31, wherein the non-solvent is water, an alcohol, or a ketone.

48. The method of claim 31, wherein the non-solvent is water.

49. The method of claim 31, wherein the starting cellulose is initially present in the composition of step (a) in an amount of about 10 to about 25 weight percent of the composition of step (a).

50. The method of claim 26, wherein the first active substance comprises a nucleophilic functional group.

51. The method of claim 26, wherein the first active substance comprises a polymeric amine.

52. The method of claim 51, wherein the polymeric amine comprises a protein or peptide.

53. The method of claim 51, wherein the polymeric amine comprises bovine serum albumin.

54. The method of claim 51, wherein the polymeric amine comprises polylysine, polyamine, or polyalkyleneimine.

55. The method of claim 51, wherein the polymeric amine comprises a polyether amine.

56. The method of claim 26, wherein the first active substance comprises an electrophilic functional group.

57. The method of claim 26, wherein the linker comprises at least two electrophilic functional groups.

58. The method of claim 57, wherein the linker comprises a diester.

59. The method of claim 57, wherein the linker comprises a dialdehyde.

60. The method of claim 57, wherein the linker comprises gluteraldehyde.

61. The method of claim 26, wherein the linker comprises at least two nucleophilic functional groups.

62. The method of claim 26, wherein the linker comprises at least one nucleophilic functional group and at least one electrophilic functional group.

63. The method of claim 26, wherein the second active substance comprises a nucleophilic functional group.

64. The method of claim 26, wherein the second active substance comprises an electrophilic functional group.

65. The method of claim 26, wherein the second active substance comprises a microbial cell, herbicide, an insecticide, a fungicide, a microbial cell, a repellent for an animal or insect, a plant growth regulator, a fertilizer, a flavor or odor composition, a catalyst, a photoactive agent, an indicator, a dye, an UV adsorbent, or a mixture thereof.

66. The method of claim 26, wherein the second active substance comprises an antibacterial agent.

67. The method of claim 26, wherein the second active substance comprises an antiviral agent.

68. The method of claim 26, wherein the second active substance comprises a biomolecule.

69. The method of claim 26, wherein the second active substance comprises a peptide, protein, enzyme, or antibody.

70. The method of claim 26, wherein the second active substance comprises a nucleic acid, aptamer, or ribozyme.

71. The method of claim 26, wherein the first active substance is coated with a hydrophobic ionic liquid prior to being dissolved or dispersed in the hydrophilic ionic liquid, and wherein the hydrophobic ionic liquid is not miscible with the non-solvent.

72. A cellulose/active substance composite prepared by the method of claim 26.