Method for functionalizing materials and devices comprising such materials

• US 20100028559A1
• Filed: 05/28/2009
• Published: 02/04/2010
• Est. Priority Date: 03/12/2007
• Status: Active Grant

• Current Assignee: Oregon State University (Oregon University System)
• Original Assignee: Oregon State University (Oregon University System)
• Inventors: Wang, Xin, Ramström, Olof, Lerner, Michael M., Liu, Li-Hong, Maluangnont, Tosapol, Yan, Mingdi
• Granted Patent: US 8,679,859 B2
• Time in Patent Office: Days
• US Class Current: 427/558
• CPC Class Codes: B82Y 25/00 Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
• CPC Class Codes: C01B 32/19 by exfoliation
• CPC Class Codes: H01F 1/0054 Coated nanoparticles, e.g. nanoparticles coated with organic surfactant

Abstract

Devices comprising functionalized materials, and embodiments of a method for making and using such devices, are disclosed. Exemplary devices include ophthalmic devices, nanoparticles, quartz crystal microbalances, microarrays, and nanocomposites. In particular embodiments, device surfaces are modified with monomers and/or polymers, typically carbohydrate monomers and/or polymers. Embodiments of a method for making and using such devices are disclosed. Monomers and/or polymers are covalently bonded to surfaces using functionalized perhalophenylazides. In some embodiments, device surfaces are functionalized with a perhalophenylazide. One or more monomers and/or polymers subsequently are covalently bonded to the device surface using the perhalophenylazide. In other embodiments, monomers and/or polymers are derivatized with a functionalized perhalophenylazide. The derivatized monomers and/or polymers then are covalently bonded to the device surface using the perhalophenylazide. In some embodiments, graphite is functionalized with perhalophenylazide to produce a functionalized graphene sheet. In other embodiments, graphene sheets are covalently attached to functionalized substrates.

Claims

1. A device, comprising:

at least a substrate; and

at least one carbohydrate monomer or carbohydrate polymer covalently bonded to at least a portion of a surface of the substrate using a perhalophenylazide.

2. The device of claim 1 where the device is a contact lens and the substrate comprises at least one polymer selected from filcon polymers, focon polymers, silicone hydrogels, siloxanes, poly(2-hydroxyethyl methacrylate), poly(methyl methacrylate), and combinations thereof, and the carbohydrate polymer is hydrophilic.

3. The device of claim 1, where the substrate is a hematite nanoparticle and the perhalophenylazide comprises a phosphate-perfluorophenylazide.

4. The device of claim 1 where the substrate is a silica nanoparticle and the perhalophenylazide is a silane-perhalophenylazide.

5. The device of claim 1 where the substrate is a metal substrate, further comprising a non-photoactive component associated with at least a portion of the surface not occupied by the at least one carbohydrate monomer or carbohydrate polymer, producing a mixed monolayer on the surface.

6. The device of claim 5 where the carbohydrate polymer comprises a glycosaminoglycan and the non-photoactive component comprises a functional group that interacts with the glycosaminoglycan.

7. The device of claim 5 where the substrate is gold and the non-photoactive component is selected from carbohydrate-derivatized thiols and carbohydrate-derivatized disulfides.

8. The device of claim 1 where the substrate is a gold-plated quartz crystal microbalance and the perhalophenylazide comprises a sulfur-bearing perhalophenylazide.

9. The device of claim 8, further comprising a protein operatively associated with at least a portion of the gold-plated quartz crystal that is not occupied by the at least one carbohydrate monomer or carbohydrate polymer.

10. The device of claim 8, further comprising a polymeric material covalently bonded to the gold-plated quartz crystal using a thiol-perhalophenylazide or a disulfide-perhalophenylazide where the polymeric material is between the gold-plated quartz crystal and the at least one carbohydrate monomer or carbohydrate polymer.

11. The device of claim 1, where the substrate is a silica-based substrate having a proteophobic polymeric material covalently bonded using a perhalophenylazide to the surface of the substrate to produce a polymer-coated substrate, and the at least one carbohydrate monomer or carbohydrate polymer is covalently bonded to at least a portion of the polymer-coated substrate in a pre-determined pattern.

12. The device of claim 11, further comprising:

a plurality of carbohydrate monomers, carbohydrate polymers, or a combination thereof; and

an additional component in combination with the plurality of carbohydrate monomers, carbohydrate polymers, or a combination thereof, where the additional component is selected from biomolecules and compounds comprising a functional group.

13. A nanocomposite, comprising:

a substrate comprising a clay or a mineral;

an ammonium alkyl compound coupled to at least a portion of a surface of the substrate; and

a polymer covalently bonded to at least a portion of the surface of the substrate using an ammonium-functionalized perhalophenylazide.

14. A method for functionalizing a substrate, comprising:

providing a substrate having at least one surface, wherein the substrate is a nanoparticle or a gold-plated quartz crystal;

functionalizing a least a portion of the substrate surface with a perhalophenylazide to provide a perhalophenylazide-functionalized nanoparticle;

applying at least one monomer or polymer to the perhalophenylazide-functionalized substrate; and

exposing the monomer or polymer to a reaction energy source to covalently bond the monomer or polymer to the substrate to produce a monomer- or polymer-functionalized substrate.

15. The method of claim 14 where the substrate is a magnetic nanoparticle and the perhalophenylazide comprises a phosphate-perhalophenylazide, further comprising:

exposing the monomer- or polymer-functionalized magnetic nanoparticle to at least one specific ligand in a solution, wherein the nanoparticle binds the at least one specific ligand to produce a ligand-nanoparticle complex; and

magnetically separating the ligand-nanoparticle complex from the solution.

16. The method of claim 15 where the at least one monomer or polymer is a carbohydrate, the carbohydrate selected to associate with at least one specific ligand in a solution, and wherein the at least one specific ligand is a toxin or a pathogen.

17. The method of claim 14 where the at least one monomer or polymer is a first polymeric material, further comprising:

functionalizing at least one carbohydrate with a second perhalophenylazide to provide a perhalophenylazide-functionalized carbohydrate;

applying the perhalophenylazide-functionalized carbohydrate to at least a portion of the polymer-coated substrate; and

exposing the perhalophenylazide-functionalized carbohydrate to a reaction energy source to covalently bond the carbohydrate to the polymer-coated substrate, producing a carbohydrate-derivatized, polymer-coated substrate.

18. The method of claim 14 where the substrate is a gold-plated quartz crystal and the at least one monomer or polymer is a carbohydrate selected to interact with one or more specific proteins, thereby producing a carbohydrate-coated, gold-plated quartz crystal, and further comprising utilizing the carbohydrate-coated, gold-plated quartz crystal as a component of a quartz crystal microbalance for studying carbohydrate-protein interactions.

19. A method for attaching a carbohydrate to a substrate surface, comprising:

providing a substrate having at least one surface;

functionalizing a least a portion of the substrate surface with a first perhalophenylazide to provide a perhalophenylazide-functionalized surface;

applying a first polymeric material to the perhalophenylazide-functionalized surface of the substrate;

exposing the first polymeric material to a reaction energy source to covalently bond a layer of the polymeric material to the substrate to produce a polymer-coated substrate;

functionalizing at least one carbohydrate with a second perhalophenylazide to provide a perhalophenylazide-functionalized carbohydrate;

applying the perhalophenylazide-functionalized carbohydrate to at least a portion of the polymer-coated substrate in a predetermined pattern;

exposing the perhalophenylazide-functionalized carbohydrate to a reaction energy source to covalently bond the carbohydrate to the polymer-coated substrate, producing a carbohydrate-derivatized, polymer-coated substrate; and

using the carbohydrate-derivatized, polymer-coated substrate for screening a solution of ligands and detecting ligands that interact with the at least one carbohydrate.

20. A method for functionalizing graphene, comprising:

providing graphite;

combining the graphite with a solution comprising a perhalophenylazide in a solvent to produce a mixture;

heating the mixture;

removing unreacted graphite from the mixture to produce a supernatant comprising perhalophenylazide-functionalized graphene; and

isolating the perhalophenylazide-functionalized graphene from the supernatant.

21. The method of claim 20, further comprising:

before combining the graphite with the solution comprising a perhalophenylazide in a solvent, reacting the graphite with a mixture of concentrated sulfuric acid and nitric acid in a 3;

1 ratio to produce intercalated graphite;

filtering, washing, and drying the intercalated graphite; and

heating the intercalated graphite to 1000°

C. for one minute in a mixture of 3% hydrogen in argon.

22. The method of claim 20 further comprising:

exposing the perhalophenylazide-functionalized graphene to aminopropyltriethyl silane to produce an amino-perhalophenylazide-functionalized graphene;

reacting an antibody with periodic acid to produce an antibody comprising at least one aldehyde group; and

combining the antibody comprising the at least one aldehyde group with the amino-PHPA-functionalized graphene.

23. The method of claim 20 further comprising:

before combining the graphite with the solution comprising the perhalophenylazide in a solvent, reacting the graphite with potassium metal to produce potassium-intercalated graphite; and

reacting the potassium-intercalated graphite with a tetraalkylammonium salt to produce expanded graphite

24. A method for immobilizing graphene on a silicon wafer, comprising:

providing a silicon wafer;

coating the silicon wafer with perfluorophenylazide-silane to produce a functionalized wafer;

pressing graphite onto the functionalized wafer;

exposing the graphite and functionalized wafer to heat or ultraviolet irradiation; and

removing the graphite to produce a graphene-perfluorphenylazide-silicon wafer.