Nano-sized particles, processes of making, compositions and uses thereof

• US 20070140951A1
• Filed: 06/12/2006
• Published: 06/21/2007
• Est. Priority Date: 12/11/2003
• Status: Active Grant

• Current Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Original Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Inventors: Yin, Ming, O'Brien, Stephen
• Granted Patent: US 8,182,786 B2
• Time in Patent Office: Days
• US Class Current: 423/592.100
• CPC Class Codes: A61K 2800/413 Nanosized, i.e. having sizes below 100 nm
• CPC Class Codes: A61K 8/19 containing inorganic ingredients
• CPC Class Codes: A61K 8/27 Zinc; Compounds thereof
• CPC Class Codes: A61Q 1/00 Make-up preparations; Body powders; Preparations for removing make-up
• CPC Class Codes: A61Q 1/12 Face or body powders for grooming, adorning or absorbing
• CPC Class Codes: A61Q 13/00 Formulations or additives for perfume preparations essential oils or perfumes per se C11B9/00
• CPC Class Codes: A61Q 15/00 Anti-perspirants or body deodorants deodorisation of air A61L9/00
• CPC Class Codes: A61Q 17/04 Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: A61Q 19/08 Anti-ageing preparations
• CPC Class Codes: A61Q 19/10 Washing or bathing preparations
• CPC Class Codes: A61Q 5/02 Preparations for cleaning the hair
• CPC Class Codes: A61Q 5/10 Preparations for permanently dyeing the hair
• CPC Class Codes: A61Q 5/12 Preparations containing hair conditioners
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 5/00 Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• CPC Class Codes: C01B 13/18 by thermal decomposition of compounds, e.g. of salts or hydroxides
• CPC Class Codes: C01G 1/02 Oxides
• CPC Class Codes: C01G 3/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 49/02 : Oxides; Hydroxides C01G49/0018 takes precedence
• CPC Class Codes: C01G 49/04 : Ferrous oxide [FeO]
• CPC Class Codes: C01G 49/06 : Ferric oxide [Fe2O3]
• CPC Class Codes: C01G 49/08 : Ferroso-ferric oxide [Fe3O4]
• CPC Class Codes: C01G 9/02 : Oxides; Hydroxides
• CPC Class Codes: C01P 2002/70 : defined by measured X-ray, neutron or electron diffraction data
• CPC Class Codes: C01P 2002/72 : by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/76 : by a space-group or by other symmetry indications
• CPC Class Codes: C01P 2002/77 : by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2002/82 : by IR- or Raman-data
• CPC Class Codes: C01P 2004/03 : obtained by SEM
• CPC Class Codes: C01P 2004/04 : obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/52 : highly monodisperse size distribution
• CPC Class Codes: C01P 2004/64 : Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/42 : Magnetic properties

Abstract

The present invention describes methods for preparing high quality nanoparticles, i.e., metal oxide based nanoparticles of uniform size and monodispersity. The nanoparticles advantageously comprise organic alkyl chain capping groups and are stable in air and in nonpolar solvents. The methods of the invention provide a simple and reproducible procedure for forming transition metal oxide nanocrystals, with yields over 80%. The highly crystalline and monodisperse nanocrystals are obtained directly without further size selection; particle size can be easily and fractionally increased by the methods. The resulting nanoparticles can exhibit magnetic and/or optical properties. These properties result from the methods used to prepare them. Also advantageously, the nanoparticles of this invention are well suited for use in a variety of industrial applications, including cosmetic and pharmaceutical formulations and compositions.

Claims

1. A method of preparing metal oxide nanoparticles, comprising:

(a) mixing a metal acetate precursor with a non-aqueous organic solvent comprising at least one organic stabilizing ligand to form a reaction mixture;

(b) subjecting the mixture of step (a) to a temperature greater than about 100°

C. for a time sufficient to allow formation of metal oxide nanoparticles and decomposition of the metal acetate; and

(c) extracting the metal oxide nanoparticles into a hydrocarbon solvent at a temperature lower than the temperature of step (b) by precipitation with a flocculating agent.

2. The method according to claim 1, wherein the organic solvent of step (a) comprises a trialkylamine.

3. The method according to claim 2 wherein the solvent is trioctylamine.

4. The method according to claim 1, wherein the organic stabilizing ligand is selected from the group consisting of sulfonic acid, sulfinic acid, phosphonic acid, phosphoric acid, a carboxylic acid and a thiol.

5. The method according to claim 1, wherein the organic stabilizing ligand is oleic acid.

6. The method according to claim 1, wherein the metal acetate of step (a) is selected from the group consisting of zinc (Zn) acetate, iron (Fe) acetate, manganese (Mn) acetate, cobalt (Co) acetate, ruthenium (Ru), copper (Cu) acetate, scandium (Sc) acetate, titanium (Ti) acetate, vanadium (V) acetate, chromium (Cr) acetate, chromium (Cr) acetate dimer, molybdenum (Mo) acetate, molybdenum (Mo) acetate dimer, yttrium (Y) acetate, zirconium (Zr) acetate, hafnium (Hf) acetate, nickel (Ni) acetate, or a mixture thereof.

7. The method according to claim 1, wherein the temperature of step (b) is from about 50°

C. to about 400°

C.

8. The method according to claim 7, wherein the temperature of step (b) is from about 250°

C. to about 400°

C.

9. The method according to claim 1, wherein the nanoparticles of step (c) are selected from the group consisting of zinc oxide nanoparticles, iron oxide nanoparticles, manganese oxide nanoparticles, cobalt oxide nanoparticles, ruthenium oxide nanoparticles, copper oxide nanoparticles, scandium oxide nanoparticles, titanium oxide nanoparticles, vanadium oxide nanoparticles, chromium oxide nanoparticles, molybdenum oxide nanoparticles, yttrium oxide nanoparticles, zirconium oxide nanoparticles, hafnium oxide nanoparticles, nickel oxide nanoparticles, or a mixture thereof.

10. The method according to claim 9, wherein the nanoparticles are selected from zinc oxide, manganese oxide, or iron oxide nanoparticles.

11. The method according to claim 1, wherein, in step (a), the anhydrous metal acetate precursor is mixed with the organic solvent to form the reaction mixture at room temperature.

12. The method according to claim 1, wherein, in step (b), the mixture is brought to said temperature in a time period of from about 10 minutes to about 30 minutes.

13. The method according to claim 12, wherein, in step (b), the mixture is brought to said temperature in a time period of from about 10 minutes to about 15 minutes.

14. The method according to claim 1, wherein the mixture of step (b) is maintained at said temperature for about 45 minutes to about 1 hour to allow the formation of nanoparticles.

15. The method according to claim 1, wherein in step (c) the hydrocarbon solvent is selected from pentane, hexane, heptane, octane, or dodecane.

16. The method according to claim 1, wherein in step (c) the flocculating agent comprises a polar organic solvent.

17. The method according to claim 16, wherein the polar organic solvent is methanol, ethanol, propanol, or butanol.

18. The method according to claim 1, wherein, in step (c), the nanoparticles are extracted into an alkane solvent by precipitation with an alcohol or ketone.

19. The method according to claim 18, wherein the nanoparticles are extracted into hexane solvent by precipitation with ethanol, followed by centrifugation and redispersion in hydrocarbon solvent.

20. The method according to claim 1, wherein the extracted nanoparticles of step (c) are stable, monodisperse, and have uniform size.

21. The method according to claim 1, wherein the extracted nanoparticles of step (c) have an organic outside coating.

22. The method according to claim 1, wherein the nanoparticles have a size from about 3 nm to about 20 nm.

23. The method according to claim 1, wherein, following step (b), the organic solvent is subjected to a second temperature of at least about 100°

C. for a time sufficient to obtain nanocrystals having a specific diameter of from about 10 nm to about 40 nm.

24. The method according to claim 1, further comprising the step of subjecting the extracted metal oxide nanoparticles obtained in step (c) to oxidation to obtain further oxidized metal oxide nanoparticles.

25. Monodisperse and stable nanoparticles produced by the method according to claim 1.

26. A composition comprising the nanoparticles according to claim 25 for use in the preparation of a formulation to prevent, reduce, retard, ameliorate, or eliminate photodamage and/or photoaging in a human or animal due to exposure to sunlight.

27. A composition comprising the nanoparticles according to claim 25 for use in the preparation of a pharmaceutical formulation, drug formulation, or medicament, and further comprising a physiologically acceptable carrier, vehicle, or excipient.

28. A composition comprising the nanoparticles according to claim 25 for use in the preparation of a cosmetic formulation.

29. The composition according to claim 28, wherein the cosmetic formulation is selected from makeups, topical skin care products, soaps, powders, lotions, creams, ointments, sunblocks, sunscreens, conditioners, shampoos, fragrances, deodorants, deodorizers, hair colors, or hair dyes.

75. The method of any one of claims 1, 30, 31, 32, 57, 58 or 59, wherein the metal acetate precursor is anhydrous.

30. A method of preparing iron oxide nanoparticles, comprising:

(a) mixing an iron acetate precursor with an organic solvent comprising at least one organic stabilizing ligand to form a reaction mixture;

(b) subjecting the mixture of step (a) to a temperature of from about 200°

C. to about 260°

C. for a time sufficient to allow formation of iron oxide nanoparticles and decomposition of the iron acetate; and

(c) extracting the iron oxide nanoparticles of step (b) into a hydrocarbon solvent at a temperature lower than the temperature of step (b) by precipitation with a flocculating agent.

31. A method of preparing manganese oxide nanoparticles, comprising:

(a) mixing a manganese acetate precursor with an organic solvent comprising at least one organic stabilizing ligand to form a reaction mixture;

(b) subjecting the mixture of step (a) to a temperature of from about 300°

C. to about 350°

C. for a time sufficient to allow formation of monodisperse manganese oxide nanoparticles and decomposition of the manganese acetate; and

(c) extracting the manganese oxide nanoparticles of step (b) into a hydrocarbon solvent at a temperature lower than the temperature of step (b) by precipitation with a flocculating agent.

32. A method of preparing zinc oxide nanoparticles, comprising:

(a) mixing a zinc acetate precursor with an organic solvent comprising at least one organic stabilizing ligand to form a reaction mixture;

(b) subjecting the mixture of step (a) to a temperature of from about 300°

C. to about 400°

C. for a time sufficient to allow formation of zinc oxide nanoparticles and decomposition of the zinc acetate; and

(c) extracting the zinc oxide nanoparticles of step (b) into a hydrocarbon solvent at a temperature lower than the temperature of step (b) by precipitation with a flocculating agent.

33. The method according to claim 32, wherein the temperature of step (b) is about 360°

C.

34. The method according to claim 32, wherein the organic solvent of step (a) comprises a trialkylamine.

35. The method according to claim 34, wherein the trialkylamine is trioctylamine.

36. The method according to claim 32, wherein the organic stabilizing ligand is selected from the group consisting of sulfonic acid, sulfinic acid, phosphonic acid, phosphoric acid, a carboxylic acid and a thiol.

37. The method according to claim 32, wherein the organic stabilizing ligand is oleic acid.

38. The method according to claim 32, wherein, in step (a), the anhydrous zinc acetate precursor is mixed with the organic solvent to form the reaction mixture at room temperature.

39. The method according to claim 32, wherein, in step (b), the mixture is brought to said temperature in a time period of from about 10 minutes to about 30 minutes.

40. The method according to claim 39, wherein, in step (b), the mixture is brought to said temperature in a time period of from about 10 minutes to about 15 minutes.

41. The method according to claim 32, wherein the mixture of step (b) is maintained at said temperature for a time period of from about 45 minutes to about 1 hour to allow the formation of the zinc oxide nanoparticles.

42. The method according to claim 32, wherein in step (c) the hydrocarbon solvent is selected from pentane, hexane, heptane, octane, or dodecane.

43. The method according to claim 32, wherein in step (c) the flocculating agent comprises a polar organic solvent.

44. The method according to claim 43, wherein the polar organic solvent is methanol, ethanol, propanol or butanol.

45. The method according to claim 32, wherein, in step (c), the zinc oxide nanoparticles are extracted into an alkane solvent by precipitation with an alcohol or ketone.

46. The method according to claim 45, wherein the zinc oxide nanoparticles are extracted into hexane solvent by precipitation with ethanol, followed by centrifugation and redispersion in hydrocarbon solvent.

47. The method according to claim 32, wherein the extracted zinc oxide nanoparticles of step (c) are stable, monodisperse, and have uniform size.

48. The method according to claim 32, wherein the extracted zinc oxide nanoparticles of step (c) have an organic outside coating.

49. The method according to claim 32, wherein the zinc oxide nanoparticles have a size of from about 2 nm to about 20 nm.

50. The method according to claim 49, wherein the zinc oxide nanoparticles have a size of from about 12 nm to about 20 nm.

51. The method according to claim 32, wherein, following step (b), the organic solvent is subjected to a second temperature of at least about 100°

C. for a time sufficient to obtain zinc oxide nanoparticles having a specific diameter of from about 10 nm to about 40 nm.

52. The method according to claim 32, further comprising the step of subjecting the extracted zinc oxide nanoparticles obtained in step (c) to oxidation to obtain further oxidized zinc oxide nanoparticles.

53. The method according to claim 52, wherein the further oxidized zinc oxide nanoparticles have a crystal size from about 2 nm to about 20 nm.

54. The method according to claim 32, wherein the extracted zinc oxide nanoparticles comprise nanorods, nanotriangles or nanospheres.

55. Monodisperse and stable zinc oxide nanoparticles produced by the method according to claim 32.

56. The zinc oxide nanoparticles according to claim 54.

71. A composition comprising the nanoparticles according to claim 32 for use in the preparation of a formulation to prevent, reduce, retard, ameliorate, or eliminate photodamage and/or photoaging in a human or animal due to exposure to sunlight.

72. A composition comprising the nanoparticles according to claim 32 for use in the preparation of a pharmaceutical formulation, drug formulation, or medicament, and further comprising a physiologically acceptable carrier, vehicle, or excipient.

73. A composition comprising the nanoparticles according to claim 32 for use in the preparation of a cosmetic formulation.

74. The composition according to claim 73, wherein the cosmetic formulation is selected from makeups, topical skin care products, soaps, powders, lotions, creams, ointments, conditioners, shampoos, fragrances, deodorants, deodorizers, hair colors, or hair dyes.

57. A method of preparing monodisperse, stable metal oxide nanoparticles, comprising:

(a) mixing a metal acetate precursor with a non-aqueous organic solvent comprising at least one organic stabilizing ligand to form a reaction mixture;

(b) subjecting the mixture of step (a) to a temperature of from about 150°

C. to about 400°

C. for a time sufficient to allow formation of metal oxide nanoparticles and decomposition of the metal acetate; and

(c) extracting the metal oxide nanoparticles into a hydrocarbon solvent at a temperature of about 100°

C. or lower by precipitation with a polar organic solvent.

60. The method according to any one of claims 57, 58 or 59, wherein the trialkylamine is trioctylamine.

61. The method according to any one of claims 57, 58 or 59, wherein the organic stabilizing ligand is oleic acid.

62. The method according to any one of claims 57, 58 or 59, wherein the metal acetate of step (a) is selected from the group consisting of zinc (Zn) acetate, iron (Fe) acetate, manganese (Mn) acetate, cobalt (Co) acetate, ruthenium (Ru), copper (Cu) acetate, scandium (Sc) acetate, titanium (Ti) acetate, vanadium (V) acetate, chromium (Cr) acetate, chromium (Cr) acetate dimer, molybdenum (Mo) acetate, molybdenum (Mo) acetate dimer, yttrium (Y) acetate, zirconium (Zr) acetate, hafnium (Hf) acetate, nickel (Ni) acetate, or a mixture thereof.

63. The method according to any one of claims 57, 58 or 59, wherein, in step (a), the anhydrous metal acetate precursor is mixed with the organic solvent to form the reaction mixture at room temperature.

64. The method according to any one of claims 57, 58 or 59, wherein, in step (b), the mixture is brought to said temperature in a time period of from about 10 minutes to about 30 minutes.

65. The method according to any one of claims 57, 58 or 59, wherein the mixture of step (b) is maintained at said temperature for a time period of from about 45 minutes to about 1 hour to allow the formation of metal oxide nanoparticles.

66. The method according to any one of claims 57, 58 or 59, wherein in step (c) the hydrocarbon solvent is selected from pentane, hexane, heptane, octane, or dodecane.

67. The method according to any one of claims 57, 58 or 59, wherein the polar organic solvent is methanol, ethanol, propanol, or butanol.

68. The method according to any one of claims 57, 58 or 59, wherein the extracted metal oxide nanoparticles of step (c) have an organic outside coating.

69. The method according to any one of claims 57, 58 or 59, wherein the nanoparticles have a size of from about 2 nm to about 20 nm.

70. Monodisperse and stable nanoparticles produced by the method according to any one of claims 57, 58 or 59.

58. A method of preparing monodisperse, stable metal oxide nanoparticles, comprising:

(a) mixing a metal acetate precursor with a trialkylamine solvent comprising at least one organic stabilizing ligand comprising a long chain alkyl with one or more carboxylic acid functional groups to form a reaction mixture;

(b) subjecting the mixture of step (a) to a temperature of from about 150°

C. to about 400°

C. for a time sufficient to allow formation of metal oxide nanoparticles and decomposition of the metal acetate; and

(c) extracting the metal oxide nanoparticles into a hydrocarbon solvent at a temperature of about 100°

C. or lower by precipitation with a polar organic solvent.

59. A method of preparing monodisperse, stable metal oxide nanoparticles, comprising:

(a) mixing a metal acetate precursor with a trialkylamine solvent comprising at least one organic stabilizing ligand comprising a long chain alkyl with one or more carboxylic acid functional groups to form a reaction mixture;

(b) subjecting the mixture of step (a) to a temperature of from about 250°

C. to about 400°

C. for a time sufficient to allow formation of metal oxide nanoparticles and decomposition of the metal acetate; and

(c) extracting the metal oxide nanoparticles into a hydrocarbon solvent at a temperature of about 100°

C. or lower by precipitation with a polar organic solvent.