METHODS FOR CONTROLLING SURFACE FUNCTIONALITY OF METAL OXIDE NANOPARTICLES, METAL OXIDE NANOPARTICLES HAVING CONTROLLED FUNCTIONALITY, AND USES THEREOF

• US 20080299046A1
• Filed: 10/16/2007
• Published: 12/04/2008
• Est. Priority Date: 10/16/2006
• Status: Abandoned Application

• 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: Turro, Nicholas J., Koberstein, Jeffrey T., White, Meghann A.
• Application Number:
  US11/873,163
• Publication Number:
  US 20080299046A1
• Time in Patent Office: Days
• US Class Current: 424/9.32
• CPC Class Codes: A61K 47/542 Carboxylic acids, e.g. a fatty acid or an amino acid
• CPC Class Codes: A61K 47/548 Phosphates or phosphonates, e.g. bone-seeking phospholipids A61K47/544
• CPC Class Codes: A61K 47/6923 the form being an inorganic particle, e.g. ceramic particles, silica particles, ferrite or synsorb
• CPC Class Codes: A61K 49/1839 the small organic molecule being a lipid, a fatty acid having 8 or more carbon atoms in the main chain, or a phospholipid
• CPC Class Codes: A61K 49/1842 the small organic molecule being a phosphate or a phosphonate, not being a phospholipid
• CPC Class Codes: A61P 35/00 Antineoplastic agents
• 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: C07F 9/091 with hydroxyalkyl compounds with further substituents on alkyl
• CPC Class Codes: C07F 9/6518 Five-membered rings
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: C09D 7/62 modified by treatment with other compounds
• CPC Class Codes: C09D 7/67 Particle size smaller than 100 nm
• CPC Class Codes: C09D 7/68 Particle size between 100-1000 nm
• CPC Class Codes: C09D 7/70 characterised by shape, e.g. fibres, flakes or microspheres

Abstract

Methods for controlling surface functionality of metal oxide nanoparticles, nanoparticles having controlled surface functionality, and uses thereof are described herein. Methods for controlling the surface functionality of a metal oxide nanoparticle are can include attaching a ligand to a metal oxide nanoparticle, where the ligand can include a functional portion that is capable of forming an irreversible bond with an object at a site that is complementary to the functional portion without reacting with other reactive sites that may be present. Moreover, metal oxide nanoparticles having versatile ligands can include an anchoring portion that binds to the surface of the metal oxide nanoparticle and a functional portion that is capable of forming an irreversible bond with an object at a site that is complementary to the functional portion without reacting with other reactive sites that may be present. Uses thereof can include cancer detection, electronics, cosmetics, cellular delivery carriers, magnetic storage media, drug delivery carriers, nanocomposite formation for improved mechanical properties, and the like.

Claims

14. A metal oxide nanoparticle comprising:

a ligand which comprises

an anchoring portion that attaches to a surface of the metal oxide nanoparticle; and

a functional portion that is capable of forming an irreversible bond with an object at one or more reactive sites that are complementary to the functional portion without reacting with other reactive sites that may be present.

1. A method for controlling the surface functionality of metal oxide nanoparticle, the method comprising:

attaching a ligand to metal oxide nanoparticle, the ligand comprising a functional portion that is capable of forming an irreversible bond with an object at one or more reactive sites that are complementary to the functional portion without reacting with other reactive sites that may be present.

2. The method of claim 1, further comprising:

reacting the ligand with the object.

3. The method of claim 1, further comprising:

reacting the ligand with the object using a click chemistry.

6. The method of claim 1, wherein the ligand further comprises an anchoring portion that attaches to the metal oxide nanoparticle, the anchoring portion being selected from the group consisting of carboxylates, alcohols, phosphonates, phosphonic acid esters, siloxanes, enediols, diols, and catechols.

7. The method of claim 1, wherein the ligand is selected from the group consisting of trioctylphosphine oxide, oleic acid, myristic acid, caprylic acid, 2-bromo-2-methylpropionic acid, dodecanol, 2,2′

-didodecyl-1,3-dihydroxypropane, 2-dodecyl-1,3-dihydroxypropane, tridodecylcarbinol, didodecylcarbinol, octadecylphosphonic acid, lauric acid-liposome, trioctylamine, octylamine, dodecylamine, hexadecylamine, oleylamine, octanethiol, and dodecanethiol.

8. The method of claim 1, wherein the metal oxide nanoparticle is selected from the group consisting of iron oxide, titanium oxide, silicon oxide, aluminum oxide, vanadium oxide, copper oxide, cobalt oxide, manganese oxide, zinc oxide, europium oxide, gadolinium oxide, indium oxide, barium titanium oxide, manganese iron oxide, cobalt iron oxide, nickel iron oxide, zinc iron oxide, and mixtures thereof.

9. The method of claim 1, wherein the metal oxide nanoparticles are greater than approximately 1 nm and less than approximately 1000 nm.

10. The method of claim 9, wherein the metal oxide nanoparticles are greater than approximately 10 nm and less than approximately 100 nm.

11. The method of claim 1, wherein the metal oxide nanoparticles are spherical, rod-like, plate-like, ellipsoidal, hemispherical, hemiellipsoidal, tripod-like, or tetrapod-like in shape.

12. The method of claim 1, wherein the ligand is 2-azido-2-methyl-propionic acid 2-phosphonooxy-ethyl ester or 5-hexynoic acid and the nanoparticle is iron oxide.

13. The method of claim 1, wherein the ligand is dodec-11-ynyl-phosphonic acid diethyl ester and the nanoparticle is titanium dioxide.

15. The metal oxide nanoparticle of claim 14, further comprising:

the object bonded with the functional portion of the ligand.

16. The metal oxide nanoparticle of claim 15, wherein

the object was bonded with the functional portion of the ligand via click chemistry.

17. The metal oxide nanoparticle of claim 15, wherein the functional portion comprises an azide or an alkyne group.

18. The metal oxide nanoparticle of claim 17, wherein the complementary site comprises an alkyne group when the functional portion comprises an azide group or the complementary site comprises an azide group when the function portion comprises an alkyne group.

19. The metal oxide nanoparticle of claim 14, wherein the anchoring portion is selected from the group consisting of carboxylates, alcohols, phosphonates, phosphonic acid esters, siloxanes, enediols, diols, and catechols.

20. The metal oxide nanoparticle of claim 14, wherein the ligand is selected from the group consisting of trioctylphosphine oxide, oleic acid, myristic acid, caprylic acid, 2-bromo-2-methylpropionic acid, dodecanol, 2,2′

-didodecyl-1,3-dihydroxypropane, 2-dodecyl-1,3-dihydroxypropane, tridodecylcarbinol, didodecylcarbinol, octadecylphosphonic acid, lauric acid-liposome, trioctylamine, octylamine, dodecylamine, hexadecylamine, oleylamine, octanethiol, and dodecanethiol.

21. The metal oxide nanoparticle of claim 14, wherein the metal oxide nanoparticle is selected from the group consisting of iron oxide, titanium oxide, silicon oxide, aluminum oxide, vanadium oxide, copper oxide, cobalt oxide, manganese oxide, zinc oxide, europium oxide, gadolinium oxide, indium oxide, barium titanium oxide, manganese iron oxide, cobalt iron oxide, nickel iron oxide, zinc iron oxide and mixtures thereof.

22. The metal oxide nanoparticle of claim 14, wherein the metal oxide nanoparticles are greater than approximately 1 nm and less than approximately 1000 nm.

23. The metal oxide nanoparticle of claim 22, wherein the metal oxide nanoparticles are greater than approximately 10 nm and less than approximately 100 nm.

24. The metal oxide nanoparticle of claim 14, wherein the metal oxide nanoparticles are spherical, rod-like, plate-like, ellipsoidal, hemispherical, hemiellipsoidal, tripod-like, or tetrapod-like in shape.

25. The metal oxide nanoparticle of claim 14, wherein the ligand is 2-azido-2-methyl-propionic acid 2-phosphonooxy-ethyl ester or 5-hexynoic acid and the nanoparticle is iron oxide.

26. The metal oxide nanoparticle of claim 14, wherein the ligand is dodec-11-ynyl-phosphonic acid diethyl ester and the nanoparticle is titanium dioxide.

27. A method for treating cancer, the method comprising:

attaching a ligand to a metal oxide nanoparticle, the ligand comprising a functional portion that is capable of forming an irreversible bond with an marker that has an affinity to cancer cells at one or more reactive sites that are complementary to the functional portion without reacting with other reactive sites that may be present;

reacting the ligand with the marker to form a metal oxide nanoparticle having affinity to cancer cells;

administering a sufficient quantity of the nanoparticle having affinity to cancer cells to a patient in need thereof, and

detecting the cancer cells through magnetic resonance imaging.

25-1. The method of claim 24, wherein the metal oxide nanoparticle comprises an iron oxide nanoparticle.

26-2. The method of claim 25, wherein the marker comprises anti-vascular endothelial growth factor.

27-3. The method of claim 26, further comprising carrying out magnetic heating to kill the cancerous cells.

28. A method for forming a dielectric material in an electronic device, the method comprising:

attaching a ligand to a metal oxide nanoparticle having a dielectric constant that is at least 2, the ligand comprising a functional portion that is capable of forming an irreversible bond with a resin that is compatible with electronic device manufacturing requirements at one or more reactive sites that are complementary to the functional portion without reacting with other reactive sites that may be present;

reacting the ligand with the resin to form a metal oxide nanoparticle that is compatible with electronic device manufacturing requirements; and

depositing the metal oxide nanoparticle that is compatible with electronic device manufacturing requirements onto at least a portion of an electronic device.

4. The method of claim 3, wherein the functional portion comprises an azide or an alkyne group.

5. The method of claim 4, wherein the reacting comprises adding a copper catalyst to carry out an azide-alkyne cycloaddition.

29. The method of claim 28, wherein the dielectric constant is from about 30 to about 100.

30. The method of claim 28, wherein the metal oxide nanoparticle comprises titanium dioxide nanoparticle.

29-4. The method of claim 28, further comprising:

pattering the metal oxide nanoparticle that is compatible with electronic device manufacturing requirements using lithography.

30-5. The method of claim 28, wherein the depositing is carried out by printing.

31. A method for delivering a drug, the method comprising:

attaching a ligand to a metal oxide nanoparticle, the ligand comprising a functional portion that is capable of forming an irreversible bond with a block copolymer at one or more reactive sites that are complementary to the functional portion without reacting with other reactive sites that may be present;

reacting the ligand with the block copolymer to form a metal oxide nanoparticle;

incorporating the drug with the block copolymer;

administering a sufficient quantity of the nanoparticle having the block copolymer and the drug to a patient in need thereof.

32. The method of claim 31, wherein the block copolymer comprises at least one block which is hydrophilic and at least one block which is hydrophobic.

33. The method of claim 32, wherein the hydrophilic block is biocompatible and the hydrophobic block is capable is carrying a drug.

34. A composition comprising metal oxide nanoparticles, the metal oxide nanoparticles comprising:

a ligand which comprises

an anchoring portion that attaches to a surface of the metal oxide nanoparticle; and

a functional portion that is capable of forming an irreversible bond with a hydrophilic molecule at one or more reactive sites that are complementary to the functional portion without reacting with other reactive sites that may be present.

35. The composition of claim 34, wherein the metal oxide nanoparticles are capable of absorbing at least some ultraviolet radiation.

36. The composition of claim 35, wherein the composition is included in a sunscreen.

37. The composition of claim 35, wherein the composition is included in a paint formulation.