Water-Soluble Functionalized Fullerenes

• US 20120183468A1
• Filed: 01/17/2012
• Published: 07/19/2012
• Est. Priority Date: 01/17/2011
• Status: Active Grant

• Current Assignee: Marelle LLC
• Original Assignee: Marelle LLC
• Inventors: Farrell, Mark, Guaragno, Michelle
• Granted Patent: US 9,085,463 B2
• Time in Patent Office: Days
• US Class Current: 423/415.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 32/15 Nano-sized carbon materials
• CPC Class Codes: C07C 231/12 by reactions not involving the formation of carboxamide groups
• CPC Class Codes: C07C 233/25 having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
• CPC Class Codes: C07C 2601/16 the ring being unsaturated
• CPC Class Codes: C07C 2604/00 Fullerenes, e.g. C60 buckminsterfullerene or C70
• CPC Class Codes: C07C 29/12 of esters of mineral acids
• CPC Class Codes: C07C 29/62 by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• CPC Class Codes: C07C 303/02 of sulfonic acids or halides thereof
• CPC Class Codes: C07C 309/25 having sulfo groups bound to carbon atoms of rings other than six-membered aromatic rings of a carbon skeleton
• CPC Class Codes: C07C 35/44 with a hydroxy group on a condensed ring system having more than three rings
• CPC Class Codes: C07C 35/52 Alcohols with a condensed ring system
• CPC Class Codes: C07C 45/70 by reaction with functional groups containing oxygen only in singly bound form
• CPC Class Codes: C07C 46/00 Preparation of quinones
• CPC Class Codes: C07C 49/84 containing ether groups, groups, groups, or groups
• CPC Class Codes: C07C 50/26 containing groups having oxygen atoms singly bound to carbon atoms
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 69/013 Esters of alcohols having the esterified hydroxy group bound to a carbon atom of a ring other than a six-membered aromatic ring
• CPC Class Codes: C07C 69/52 Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
• CPC Class Codes: C07C 69/587 : Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
• CPC Class Codes: C07D 495/04 : Ortho-condensed systems
• CPC Class Codes: C07J 5/0053 : not substituted in position 16

Abstract

Provided herein are water-soluble, functionalized fullerenes, and processes for producing water-soluble, functionalized fullerenes. The process includes sulfonating a fullerene in an acidic solution comprising sulfuric acid to produce a sulfonated fullerene, isolating the sulfonated fullerene from the acidic solution without neutralizing the acidic solution, reacting the sulfonated fullerene with hydrogen peroxide to form a reaction product, and isolating a polyhydroxylated fullerene from the reaction product produced from reacting the sulfonated fullerene with the hydrogen peroxide. The process of producing water-soluble fullerenes further includes functionalizing a polyhydroxylated fullerene with one or more pendant functional groups by reacting the polyhydroxylated fullerene with one or more functional group precursors.

Claims

1. A process of producing water-soluble fullerenes, comprising:

a. sulfonating a fullerene in an acidic solution comprising sulfuric acid to produce a sulfonated fullerene;

b. isolating the sulfonated fullerene from the acidic solution without neutralizing the acidic solution;

c. reacting the sulfonated fullerene with hydrogen peroxide to form a reaction product; and

d. isolating a polyhydroxylated fullerene from the reaction product of step (c).

2. The process according to claim 1, wherein the fullerene is a C₆₀ spherical fullerene.

3. The process according to claim 1, wherein the acidic solution comprises sulfuric acid and one or more of SO₃, HNO₃, P₂O₅, and V₂O₅.

4. The process according to claim 1, wherein the sulfonated fullerene comprises a ratio of sulfate groups to carbon atoms of at least (4-7):

60.

5. The process according to claim 1, wherein the polyhydroxylated fullerene comprises a ratio of hydroxyl groups to carbon atoms of at least 2:

3.

6. The process according to claim 1, wherein step (b) comprises isolating the sulfonated fullerene by centrifugation.

7. The process according to claim 1, wherein the step (d) of isolating a hydroxylated fullerene comprises precipitating the reaction product of step (c) in an organic solvent.

8. The process according to claim 7, wherein the organic solvent is a mixture of an alcohol, an aliphatic organic compound, and an ether.

9. The process according to claim 7, wherein the organic solvent is a mixture of isopropanol, hexane, and diethyl ether.

10. The process according to claim 8, wherein the organic solvent mixture comprises a volume ratio range of about 10-70:

10-70;

10-70 of alcohol to aliphatic hydrocarbon to ether.

11. The process of claim 1, further comprising functionalizing the polyhydroxylated fullerene with one or more pendant functional groups by reacting the polyhydroxylated fullerene with one or more functional group precursors.

12. The process according to claim 11, in which the one or more functional group precursors is a hydrogen halide to produce a halogen-functionalized polyhydroxylated fullerene.

13. The process according to claim 12, wherein the halogen is selected from the group consisting of F, Cl, Br, I, and At.

14. The process according to claim 12, wherein the halogen-functionalized polyhydroxylated fullerene comprises a ratio of halogen functional groups to carbon atoms of at least 1:

60.

15. The process according to claim 11, wherein the functionalized polyhydroxylated fullerene comprises a ratio of at least 2:

3 of hydroxyl groups to carbon atoms.

16. The process according to claim 11, wherein the functionalized polyhydroxylated fullerene comprises a ratio of at least 1:

60 functional groups to carbon atoms.

17. The process of claim 11, further comprising functionalizing the polyhydroxylated fullerenes with one or more pendant functional groups by reacting the polyhdroxylated fullerene with one or more functional group precursors in the presence of a Lewis acid catalyst.

18. The process according to claim 17, wherein the Lewis acid catalyst is BF₃.

19. The process according to claim 17, in which the one or more functional group precursors are chosen from an aromatic compound, a fatty acid, a peptide, a corticosteroid, an anti-oxidant, and a vitamin.

20. The process according to claim 17, in which the one or more functional group precursors is an organic acid comprising a carboxylic acid group.

21. The process according to claim 17, wherein the one or more functional group precursors is an aromatic compound selected from the group consisting of propanil and avobenzone.

22. The process according to claim 17, wherein the one or more functional group precursors is a fatty acid and is selected from the group consisting of omega-3 fatty acids and omega-6 fatty acids.

23. The process according to claim 22, wherein the fatty acid is linoleic acid, α

-linolenic acid, and/or arachidonic acid.

24. The process according to claim 11, comprising reacting the polyhydroxylated fullerene with two or more functional group precursors, thereby producing a composition comprising polyhydroxylated fullerenes functionalized with two or more functional groups.

25. The process according to claim 24, in which the two or more functional group precursors are chosen from an aromatic compound, a fatty acid, a peptide, a corticosteroid, an anti-oxidant, a vitamin, and hydrogen halide.

45. A product manufactured by the process of claim 1.

26. A method of making a water-insoluble composition soluble in an aqueous solution, comprising reacting a water-insoluble composition containing a carboxylic acid group with a polyhydroxylated fullerene, thereby linking the water-insoluble composition to the polyhydroxylated fullerene to produce a fullerene conjugate.

27. The method of claim 26, in which the polyhydroxylated fullerene is prepared by a method comprising:

a. sulfonating a fullerene in an acidic solution comprising sulfuric acid to produce a sulfonated fullerene;

b. isolating the sulfonated fullerene from the acidic solution without neutralizing the acidic solution;

c. reacting the sulfonated fullerene with hydrogen peroxide to form a reaction product; and

d. isolating a polyhydroxylated fullerene from the reaction product of step (c).

28. The method of claim 27, further comprising preparing the polyhydroxylated fullerene by a process comprising:

a. sulfonating a fullerene in an acidic solution comprising sulfuric acid to produce a sulfonated fullerene;

b. isolating the sulfonated fullerene from the acidic solution without neutralizing the acidic solution;

c. reacting the sulfonated fullerene with hydrogen peroxide to form a reaction product; and

d. isolating a polyhydroxylated fullerene from the reaction product of step (c).

29. A water-soluble polyhydroxylated fullerene having the general formula:

R—

(OH)_x

wherein R is a fullerene and x is a number of at least ⅔

the number of carbon atoms in R.

30. The water-soluble polyhydroxylated fullerene of claim 29, wherein R is a C₆₀ spherical fullerene.

31. A water-soluble functionalized polyhydroxylated fullerene having the general formula:

R—

(R′

)_y(OH)_x

wherein R is a fullerene, R′

is a functional group, x is a number of at least ⅔

the number of carbon atoms in R, and y is a number in the range from about 1% to about 7% of the number of carbon atoms in R.

32. The water-soluble fullerene according to claim 31, wherein R′

is chosen from an aromatic compound, a fatty acid ester, a peptide, a corticosteroid, an anti-oxidant, a vitamin, and a halogen.

33. The water-soluble fullerene according to claim 31, wherein R′

is chosen from prednisone, arachidonic acid, biotin, avobenzone, glutathione, propanil, hydrocortisone, linoleic acid, α

-linolenic acid, Coenzyme Q₁₀, an avobenzone/glutathione mixture, and mixtures thereof.

34. The water-soluble fullerene according to claim 31, wherein R′

is prednisone.

35. The water-soluble fullerene according to claim 31, wherein R′

is arachidonic acid.

36. The water-soluble fullerene according to claim 31, wherein R′

is biotin.

37. The water-soluble fullerene according to claim 31, wherein R′

is avobenzone.

38. The water-soluble fullerene according to claim 31, wherein R′

is glutathione.

39. The water-soluble fullerene according to claim 31, wherein R′

is propanil.

40. The water-soluble fullerene according to claim 31, wherein R′

is hydrocortisone.

41. The water-soluble fullerene according to claim 31, wherein R′

is linoleic acid.

42. The water-soluble fullerene according to claim 31, wherein R′

is α

-linolenic acid.

43. The water-soluble fullerene according to claim 31, wherein R′

is Coenzyme Q₁₀.

44. The water-soluble fullerene according to claim 31, wherein R′

is a mixture of avobenzone and glutathione.

46. A process of producing a polyhydroxylated fullerene, comprising reacting a fullerene with greater than 30% H₂O₂, thereby producing a polyhydroxylated fullerene.

47. The process of claim 46, in which the fullerene is reacted with at least 50% H₂O₂.