Method for functionalizing carbon nanoparticles and compositions

Patent metadata

Field	Value
Publication number	US-10995004-B2
Application number	US-201716336709-A
Country	US
Kind code	B2
Filing date	Sep 29, 2017
Priority date	Sep 30, 2016
Publication date	May 4, 2021
Grant date	May 4, 2021

Abstract

A method of increasing a density of carboxylic acids on a surface of a carbon nanoparticle is disclosed. The method includes contacting an oxygen-containing functional group on a surface of a carbon nanoparticle with a reducing agent to provide a hydroxyl group; reacting the hydroxyl group with a diazoacetate ester in the presence of a transition metal catalyst to provide an ester, the diazoacetate ester having the structure wherein R is a C1-8 hydrocarbyl, preferably tert-butyl, methyl, ethyl, isopropyl, allyl, benzyl, pentafluorophenyl, or N-succinimidyl; and cleaving the ester to provide a carboxylic acid group. Surface-functionalized carbon nanoparticles made by the method are also disclosed.

First claim

What is claimed is:

1. A method of increasing a density of carboxylic acids on a surface of a carbon nanoparticle, the method comprising
contacting an oxygen-containing functional group on a surface of a carbon nanoparticle with a reducing agent to provide a hydroxyl group;
reacting the hydroxyl group with a diazoacetate ester in the presence of a transition metal catalyst to provide an ester coupled to the carbon nanoparticle by an ether linkage, the diazoacetate ester having the structure

wherein R is a C 1-8 hydrocarbyl; and
cleaving the ester to provide a carboxylic acid group.

2. The method of claim 1 , wherein the reducing agent is a metal hydride.

3. The method of claim 1 , wherein the carbon nanoparticle is a carbon nanotube, a fullerene, a graphene, graphene oxide, a nanodiamond, or a combination thereof.

4. The method of claim 1 , wherein R is tert-butyl, methyl, ethyl, isopropyl, allyl, benzyl, pentafluorophenyl, or N-succinimidyl.

5. The method of claim 1 , further comprising
oxidizing the surface of the carbon nanoparticle.

6. The method of claim 1 , wherein the transition metal catalyst is Rh 2 (OAc) 4 , Rh 2 (NHAc) 4 , Rh 2 (NHCOCF 3 ) 4 , Rh 2 (NHCOC 3 F 7 ) 4 , Cu(Otf) 2 , CuI.P(OMe) 3 , Ni(acac) 2 , BF 3 -Et 2 O, or a combination thereof.

7. The method of claim 6 , wherein the transition metal catalyst is Rh 2 (OAc) 4 , Rh 2 (NHAc) 4 , or a combination thereof.

8. The method of claim 1 , further comprising:
functionalizing the carboxylic acid group to a second functional group.

9. The method of claim 8 , wherein the second functional group is an acyl chloride, an amide, a pegylate, a biotinylate, a folate, a thiol, a maleimide, an active ester, an amine, a chelated gadolinium, an azide, an alkyne, a protein tag ligand, or a dendrimer linkage.

10. The method of claim 8 , wherein functionalizing the carboxylic acid group comprises
covalently coupling the second functional group to the carboxylic acid group, optionally wherein the second functional group is coupled via a linker, wherein the second functional group is an alkyne, a dibenzocyclooctyne, an alkylating group, a protected thiol, or a protein tag system ligand.

11. A surface-functionalized carbon nanoparticle comprising
a first functional group attached to a surface of the carbon nanoparticle by an ether linkage,
wherein the first functional group is present in an amount of at least 1×10 17 first functional group/g of carbon nanoparticle, at least 100 first functional group/carbon nanoparticle, or at least 1 first functional group/210 nm 2 of the surface.

12. The carbon nanoparticle of claim 11 , which is a carbon nanotube, a fullerene, graphene, graphene oxide, a nanodiamond, or a combination thereof.

13. The carbon nanoparticle of claim 11 , wherein the first functional group is an acyl chloride, an amide, a pegylate, a biotinylate, or an amine.

14. The carbon nanoparticle of claim 11 , comprising
an alkyne covalently coupled to the surface of the carbon nanoparticle, optionally the alkyne is coupled via a linker; or
a dibenzocyclooctyne covalently coupled to the surface of the carbon nanoparticle, optionally the dibenzocyclooctyne is coupled via a linker.

15. The carbon nanoparticle of claim 11 , comprising
an alkylating group covalently coupled to the surface of the carbon nanoparticle, optionally the alkylating group is coupled via a linker; or
a protected thiol covalently coupled to the surface of the carbon nanoparticle, optionally the protected thiol is coupled via a linker.

16. The carbon nanoparticle of claim 11 , comprising a protein tag system ligand covalently coupled to the surface of the carbon nanoparticle, optionally the protein tag system ligand is coupled via a linker.

17. The carbon nanoparticle of claim 16 , wherein the protein tag system ligand comprises a haloalkane, an O 6 -alkylguanine, or an O 2 -benzylcytosine.

18. The carbon nanoparticle of claim 11 , wherein the first functional group is a carboxylic acid.

19. The carbon nanoparticle of claim 18 , wherein the carboxylic acid group is further functionalized to a second functional group.

20. The carbon nanoparticle of claim 19 , wherein the second functional group is an acyl chloride, an amide, a pegylate, a biotinylate, a folate, a thiol, a maleimide, an active ester, an amine, a chelated gadolinium, an azide, an alkyne, a protein tag ligand, or a dendrimer linkage.

Assignees

• Us Health

Inventors

• Neuman Keir Cajal
• Shenoy Ganesh
• Mushti Chandrasekhar
• Swenson Rolf E

Classifications

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title

• C07D207/448

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide · CPC title

• C07C51/347

  by reactions not involving formation of carboxyl groups · CPC title

• C01P2002/82

  by IR- or Raman-data · CPC title

• C07D473/18

  one oxygen and one nitrogen atom, e.g. guanine · CPC title