Sol-gel precursors and products thereof

Patent metadata

Field	Value
Publication number	US-9567353-B2
Application number	US-44051607-A
Country	US
Kind code	B2
Filing date	Sep 10, 2007
Priority date	Sep 8, 2006
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

The present invention provides a generalizable single-source sol-gel precursor capable of introducing a wide range of functionalities to metal oxides such as silica. The sol-gel precursor facilitates a one-molecule, one-step approach to the synthesis of metal-silica hybrids with combinations of biological, catalytic, magnetic, and optical functionalities. The single-source precursor also provides a flexible route for simultaneously incorporating functional species of many different types. The ligands employed for functionalizing the metal oxides are derived from a library of amino acids, hydroxy acids, or peptides and a silicon alkoxide, allowing many biological functionalities to be built into silica hybrids. The ligands can coordinate with a wide range of metals via a carboxylic acid, thereby allowing direct incorporation of inorganic functionalities from across the periodic table. Using the single-source precursor a wide range of functionalized nanostructures such as monolith structures, mesostructures, multiple metal gradient mesostructures and Stober-type nanoparticles can be synthesized.

First claim

What is claimed is:

1. A sol-gel precursor comprising a cross-linkable molecule including a first metal M 1 , wherein the first metal is directly bonded to carbon and the cross-linkable molecule is further conjugated to a first functional group capable of being conjugated to the first metal M 1 , and a second functional group comprising a carboxylate group and a side chain R selected from a benzyl group, methyl group, ethyl group, propyl group, and butyl group that is a substituent on a carbon in the alpha position to the carbonyl carbon, wherein at least one of the oxygen atoms in the carboxylate group is ligated to a second metal M 2 selected from the group consisting of Ag, Bi, Co, Cr, Cu, Er, Eu, Gd, In, Mn, Mo, Pb, Pd, Pt, Rh, Y, Zn, B, Si, Ge, As, Sb, Te, and Po, and
wherein the first metal M 1 is a semimetal selected from the group consisting of Bi, Si, Ge, and Sb.

2. The sol-gel precursor of claim 1 , wherein the second metal M 2 is any metal selected from the group consisting of Ag, Co, Cr, Cu, Er, Eu, Gd, In, Mn, Mo, Pb, Pd, Pt, Rh, Y, and Zn.

3. The sol-gel precursor of claim 1 , wherein the second metal M 2 is a semi-metal selected from the group consisting of Bi, Si, Ge, As, Sb and Te.

4. The sol-gel precursor of claim 1 , wherein the functional group capable of being conjugated to the first metal M 1 , and the second functional group comprising the carboxylate group and the side chain R together form a compound selected from the group consisting of organic compounds, bioorganic compounds and organometallic compounds.

5. The sol-gel precursor of claim 4 , wherein the organic compound is selected from the group consisting of carboxylic acids, hydroxy acids, azide acids, isocyanate acids, isothiocyanate acids, thiol acids, maleimide acids and aldehyde acids.

6. The sol-gel precursor of claim 4 , wherein the organic compound is a polyester.

7. The sol-gel precursor of claim 4 , wherein the bioorganic compound is selected from the group consisting of amino acids, peptides and peptide fragments.

8. The sol-gel precursor of claim 4 , wherein the side chain R is sterically hindering.

9. The sol-gel precursor of claim 4 , wherein the side chain R has a chiral portion.

10. The sol-gel precursor of claim 4 , wherein the side chain R comprises one or more alkyl side-chains.

11. The sol-gel precursor of claim 10 , wherein the alkyl side-chain comprises a benzyl, methyl, ethyl, butyl or t-butyl derivative.

12. The sol-gel precursor of claim 4 , wherein the side chain R comprises a functional group.

13. The sol-gel precursor of claim 1 , wherein the sol-gel precursor comprises C, H, N, O and S and the mass of C, H, N, O and S in said sol-gel precursor is between about 40% and 90% of the total mass of the sol-gel precursor.

14. The sol-gel precursor of claim 1 , wherein the sol-gel precursor has the following structure:

wherein n+ is the oxidation state of M 2 .

15. A sol-gel precursor comprising a cross-linkable molecule including a first metal M 1 , wherein the first metal is directly bonded to carbon and the cross-linkable molecule is further conjugated to a first functional group capable of being conjugated to the first metal M 1 , and a second functional group comprising a carboxylate group and a side chain R, wherein at least one of the oxygen atoms in the carboxylate group is ligated to a second metal M 2 selected from the group consisting of Bi, Si, Ge, As, Sb and Te.

16. The sol-gel precursor of claim 15 , wherein the first metal M 1 is any metal on the periodic table.

17. The sol-gel precursor of claim 16 , wherein the first metal M 1 is any metal selected from the group consisting of Ti, Al, Ga, Zn, Cd, Sn, Zr and Pb.

18. The sol-gel precursor of claim 16 , wherein the first metal M 1 is a semimetal selected from the group consisting of Bi, Si, Ge, and Sb.

19. The sol-gel precursor of claim 15 , wherein the functional group capable of being conjugated to the first metal M 1 , and the second functional group comprising a carboxylate group and a side chain R together form a compound selected from the group consisting of organic compounds, bioorganic compounds and organometallic compounds.

20. The sol-gel precursor of claim 19 , wherein the organic compound is selected from the group consisting of carboxylic acids, hydroxy acids, azide acids, isocyanate acids, isothiocyanate acids, thiol acids, maleimide acids and aldehyde acids.

21. The sol-gel precursor of claim 19 , wherein the organic compound is a polyester.

22. The sol-gel precursor of claim 19 , wherein the bioorganic compound is selected from the group consisting of amino acids, peptides and peptide fragments.

23. The sol-gel precursor of claim 15 , wherein the side chain R is sterically hindering.

24. The sol-gel precursor of claim 15 , wherein the side chain R has a chiral portion.

25. The sol-gel precursor of claim 15 , wherein the side chain R comprises one or more alkyl side-chains.

26. The sol-gel precursor of claim 25 , wherein the alkyl side-chain comprises a benzyl, methyl, ethyl, butyl or t-butyl derivative.

27. The sol-gel precursor of claim 15 , wherein the side chain R comprises a functional group.

28. The sol-gel precursor of claim 27 , wherein the functional group is selected from the group consisting of a therapeutic agent, a peptide, a polymer, an alcohol, an amine, a nanoparticle and a fluorescent dye.

29. The sol-gel precursor of claim 15 , wherein the sol-gel precursor comprises C, H, N, O and S and the mass of C, H, N, O and S in said sol-gel precursor is between about 40% and 90% of the total mass of the sol-gel precursor.

30. The sol-gel precursor of claim 15 , wherein the sol-gel precursor has the following structure:

wherein n+ is the oxidation state of M 2 .

31. A sol-gel precursor comprising a cross-linkable molecule including a first metal M 1 , wherein the first metal is directly bonded to carbon and the cross-linkable molecule is further conjugated to a first functional group capable of being conjugated to the first metal M 1 , and a second functional group comprising a carboxylate group and a side chain R, wherein at least one of the oxygen atoms in the carboxylate group is ligated to a second metal M 2 that is a semimetal selected from the group consisting of Bi, Si, Ge, As, Sb, and Te,
wherein the functional group capable of being conjugated to the first metal M 1 , and the second functional group comprising a carboxylate group and a side chain R together form a polyester.

32. The sol-gel precursor of claim 31 , wherein the first metal M 1 is any metal on the periodic table.

33. The sol-gel precursor of claim 32 , wherein the first metal M 1 is any metal selected from the group consisting of Ti, Al, Ga, Zn, Cd, Sn, Zr and Pb.

34. The sol-gel precursor of claim 32 , wherein the first metal M 1 is a semimetal selected from the group consisting of Bi, Si, Ge, and Sb.

35. A sol-gel precursor comprising a cross-linkable molecule including a first metal M 1 , wherein the first metal is directly bonded to c

Assignees

• Warren Scott C
• Disalvo Jr Francis J
• Weisner Ulrich B
• Cornell Res Foundation Inc

Inventors

• Warren Scott C
• Disalvo Jr Francis J
• Weisner Ulrich B

Classifications

• C07F7/1836 Primary

  Chemistry & Metallurgy · mapped topic

• C07F7/1804 Primary

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · CPC title