Metal oxide compositions and methods

• US 6,417,244 B1
• Filed: 10/13/2000
• Issued: 07/09/2002
• Est. Priority Date: 04/13/1993
• Status: Expired due to Term

• Current Assignee: Southwest Research Institute, Board of Regents of the University of Texas System (University of Texas System)
• Original Assignee: Southwest Research Institute, Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Dixon, Hong, Wellinghoff, Stephen T., Norling, Barry K., Rawls, Henry R.
• Primary Examiner(s): Zitomer, Fred
• Application Number:
  US09/687,447
• Time in Patent Office: 634 Days
• Field of Search: 522/104, 526/116, 526/277, 526/260, 526/258, 526/262, 526/263
• US Class Current: 522/104
• CPC Class Codes: A61K 2800/413 Nanosized, i.e. having sizes below 100 nm
• CPC Class Codes: A61K 6/831 comprising non-metallic elements or compounds thereof, e.g. carbon
• CPC Class Codes: A61K 6/887 Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61K 8/0204 Specific forms not provided for by any of groups A61K8/0208 - A61K8/14
• CPC Class Codes: A61K 8/29 Titanium; Compounds thereof
• CPC Class Codes: A61K 8/365 Hydroxycarboxylic acids; Ketocarboxylic acids
• CPC Class Codes: A61Q 17/04 Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• CPC Class Codes: B01J 13/02 Making microcapsules or microballoons for medical preparations A61K9/50
• 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 13/32 by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
• CPC Class Codes: C01G 23/003 Titanates C01G23/001 takes precedence
• CPC Class Codes: C01G 35/00 Compounds of tantalum
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Abstract

Metal oxide and metal oxide-silica nanoparticles are disclosed wherein the surfaces thereof are complexed with a polymerizable, biocompatible, heterocyclic base. Polymerizable compositions are prepared by loading such nanoparticles into acrylate based monomer matrices, which compositions can then be photocured into X-ray opaque, transparent or translucent solids. Methods are disclosed for forming such complexed nanoparticles and compositions and for using such compositions as medical or dental restoratives.

Claims

1. A composition photopolymerizable into transparent or translucent solids comprising:

a matrix comprising monomers selected from the group consisting of bisacrylate, bis-methacrylate, and a combination thereof;

particles comprising an amphoteric metal oxide, said particles selected from the group consisting of amphoteric metal oxide particles and amphoteric metal oxide-silica particles, said particles having a diameter in nanometers of about 50 to 100;

wherein said particles comprise a surface comprising acid sites complexed with or bound to a functionality selected from the group consisting of a phosphate group, a phosphonate group, and a heterocyclic basic atom of an alkene substituted polymerizable, biocompatible, monomeric, heterocyclic base.

2. The composition of claim 1 wherein said metal is tantalum and said base is selected from the group consisting of an alkene-terminated imidazole and an alkene-terminated phosphate.

3. The composition of claim 1 wherein said base is selected from the group consisting of 1-vinyl imidazole and (C₂H₅O)₂P(O)═

O(CH₂)₂(C(O)—

O—

Me)C═

CH₂.

4. The composition of claim 2 wherein said base is selected from the group consisting of 1-vinyl imidazole and (C₂H₅O)₂P(O)═

O(CH₂)₂(C(O)—

O—

Me)C═

CH₂.

5. The composition of claim 1 wherein said amphoteric metal oxide particles comprise tantalum oxide.

6. The composition of claim 2 wherein said amphoteric metal oxide particles comprise tantalum oxide.

7. The composition of claim 3 wherein said amphoteric metal oxide particles comprise tantalum oxide.

8. The composition of claim 4 wherein said amphoteric metal oxide particles comprise tantalum oxide.

27. A method of dental repair comprising applying to a dentin surface the photopolymerizable composition of claim 1.

28. A method of dental repair comprising applying to a dentin surface the photopolymerizable composition of claim 8.

9. A method of making photopolymerizable, transparent or translucent X-ray opaque compositions comprising admixing a matrix comprising monomers selected from the group consisting of bisacrylate monomers and bis-methacrylate monomers with X-ray opaque metal oxide particles comprising an amphoteric metal oxide, said particles having a diameter in nanometers of about 50 to 100, said metal oxide particles comprising a surface comprising acid sites complexed with or bound to a functionality selected from the group consisting of a phosphate group, a phosphonate group, and the heterocyclic basic atom of an alkene substituted polymerizable, biocompatible, monomeric, heterocyclic base.

10. The method of claim 9 wherein said metal is tantalum and said base is selected from the group consisting of an alkene-terminated imidazole and an alkene-terminated phosphate.

11. The method of claim 9 wherein said base is selected from the group consisting of 1-vinyl imidazole or (C₂H₅O)₂P(O)═

O(CH₂)₂(C(O)—

O—

Me)C═

CH₂.

12. The method of claim 9 wherein said amphoteric metal oxide comprises tantalum oxide.

13. The method of claim 10 wherein said amphoteric metal oxide comprises tantalum oxide.

14. The method of claim 11 wherein said amphoteric metal oxide comprises tantalum oxide.

15. A composition photopolymerizable into transparent or translucent solids comprising:

a matrix comprising monomers having the following general structure;

 

wherein

n is from about 6 to about 12;

R1 and R3 are selected from the group consisting of hydrogen and a methyl group; and

R2 is an organic group having greater bulk than R1 and R3, wherein said bulk is sufficient upon polymerization to produce a transparent or translucent solid which consists essentially of a nematic state at room temperature; and

particles comprising an amphoteric metal oxide, said particles selected from the group consisting of amphoteric metal oxide particles and amphoteric metal oxide-silica particles, said particles having a diameter in nanometers of about 50 to 100;

wherein said particles comprise a surface comprising acid sites complexed with an alkene terminated polymerizable, biocompatible, monomeric, heterocyclic base.

16. The composition of claim 15 wherein said metal is tantalum and said base is selected from the group consisting of an alkene-terminated imidazole and an alkene-terminated phosphate.

17. The composition of claim 15 wherein said base is 1-vinyl imidazole or (C₂H₅O)₂P(O)═

O(CH₂)₂(C(O)—

O—

Me)C═

CH₂.

18. The composition of claim 15 wherein said amphoteric metal oxide particles comprise tantalum oxide.

19. The composition of claim 16 wherein said amphoteric metal oxide particles comprise tantalum oxide.

20. The composition of claim 17 wherein said amphoteric metal oxide particles comprise tantalum oxide.

21. The composition of claim 15 wherein said matrix comprises a mixture of said monomers.

22. The composition of claim 16 wherein said matrix comprises a mixture of said monomers.

23. The composition of claim 17 wherein said matrix comprises a mixture of said monomers.

24. The composition of claim 18 wherein said matrix comprises a mixture of said monomers.

25. The composition of claim 19 wherein said matrix comprises a mixture of said monomers.

26. The composition of claim 20 wherein said matrix comprises a mixture of said monomers.

29. A method of dental repair comprising applying to a dentin surface the photopolymerizable composition of claim 21.

30. A method of dental repair comprising applying to a dentin surface the photopolymerizable composition of claim 26.