Chemical functionalization of surfaces

• US 5,582,955 A
• Filed: 06/26/1995
• Issued: 12/10/1996
• Est. Priority Date: 06/23/1994
• Status: Expired due to Fees

• Current Assignee: University of Oregon
• Original Assignee: University of Oregon
• Inventors: Keana, John F. W., Wybourne, Martin N., Yan, Mingdi, Cai, Sui X.
• Primary Examiner(s): CHAPMAN, MARK A
• Application Number:
  US08/495,005
• Time in Patent Office: 533 Days
• Field of Search: 430/296, 430/942, 568/941, 427/581
• US Class Current: 430/296
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08F 8/34 Introducing sulfur atoms or sulfur-containing groups
• CPC Class Codes: Y10S 430/143 Electron beam

Abstract

Methods for covalently modifying surfaces of various substrates are disclosed, along with various substrates having surfaces modified by such methods. Candidate surfaces include various polymeric, siliceous, metallic, allotrophic forms of carbon, and semiconductor surfaces. The surfaces are exposed to a reagent, having molecules each comprising a nitrenogenic group and a functionalizing group, in the presence of energized charged particles such as electrons and ions, photons, or heat, which transform the nitrenogenic reagent to a nitrene intermediate. The nitrene covalently reacts with any of various chemical groups present on the substrate surface, thereby effecting nitrene addition of the functionalizing groups to the substrate surface. The functionalizing groups can then participate in downstream chemistry whereby any of a large variety of functional groups, including biological molecules, can be covalently bonded to the surface, thereby dramatically altering the chemical behavior of the surface. Such functionalizations of the surface can be done in a single reactive step or in multiple reactive steps.

Claims

1. A functionalizing reagent comprising molecules having a first end and a second end covalently connected together via a spacer group, the first end comprising a perfluorophenyl azide (PFPA) group and the second end comprising an N-hydroxysuccinimide (NHS) group, and the spacer group comprising (a) a carboxyl group or an organic amido group, and (b) an alkyl group of one to six carbon atoms, or an aryl group, or a heterocyclic group.

12. A method for producing a functionalized surface on a substrate, comprising the steps:

(a) providing a non-fluid substrate having a surface comprising surface molecules having chemical moieties each capable of undergoing an addition reaction with a nitrene;

(b) providing a first functionalizing reagent comprising molecules as recited in claim 1;

(c) applying the first functionalizing reagent to the substrate surface; and

(d) either subsequent to or simultaneously with step (c), exposing the surface to a reaction-energy source so as to convert the --N₃ groups, on the molecules as set forth in step (b), to nitrenes that undergo addition reactions with the chemical moieties on the surface molecules, thereby covalently bonding molecules of the first functionalizing reagent to the surface molecules.

2. A functionalizing reagent comprising molecules having the structure:

##STR22## wherein X is a spacer group comprising (a) a carboxyl group or an organic amido group, and (b) an alkyl group of one to six carbon atoms, or an aryl group, or a heterocyclic group.

3. A functionalizing reagent as recited in claim 2 wherein x comprises a structure selected from a group consisting of --(R)_n --C(O)NH--(R)_n --C(O)O--, --(R)_n --C(O)O--(R)_n --C(O)O--, --C(O)NH--(R)_n --C(O)O--, --C(O)O--(R)_n --C(O)O--, --(R)_n --NH--(R)_n --C(O)O--, --C(O)NH--(R)_n --C(O)NH--, --(R)_n --C(O)NH--(R)_n --C(O)NH--, --(R)_n --C(O)O--(R)_n --C(O)NH--, and --C(O)O--(R)_n --C(O)NH--, wherein R is an alkyl group of one to six carbon atoms, or an aryl group, or a heterocyclic group, and n is 0 or 1.

4. A functionalizing reagent as recited in claim 3 wherein the spacer further comprises an --S--S-- group.

5. A functionalizing reagent comprising molecules having the structure:

##STR23## wherein X is a spacer comprising (a) a moiety selected from a group consisting of organic esters, organic amides, organic acid halides, and organic anhydrides, and (b) an alkyl group having one to six carbon atoms, or an aryl group, or a heterocyclic group.

6. A functionalizing reagent as recited in claim 5 wherein the spacer further comprises an --S--S-- group.

7. A functionalizing reagent comprising molecules having the structure:

##STR24## wherein X is a spacer group comprising (a) a carboxyl group or an organic amido group, and (b) an alkyl group of one to six carbon atoms, or an aryl group, or a heterocyclic group; and

R is selected from a group consisting of -N-hydroxysuccinimides, pyrenes, substituted pyrenes, aliphatic amines, aliphatic hydroxyls, aliphatic hydroxylamines, C₆ to C₂₀ alkyls, aminocholestanes, hexyldimethylsilyls, glucosamines, polyethylenimines, polylysines, polyamines, polyhydroxyls, surfactants, enzymes, lectins, antibodies, polypeptides, biotins, and biotin derivatives.

8. A functionalizing reagent comprising molecules having the structure:

##STR25## wherein n is 1 to 6.

9. A functionalizing reagent comprising molecules having the structure:

##STR26## wherein n is independently 1 to 6.

10. A functionalizing reagent comprising molecules having the structure:

##STR27## wherein X is --C(O)--NH-- or --NH--C(O)--, and n is independently 1 to 6.

11. A functionalizing reagent comprising molecules having the structure:

##STR28## wherein n is independently 1 to 6.

13. A method as recited in step 12 including the steps, after step (d), of

providing a second functionalizing reagent comprising molecules capable of undergoing a reaction with the first functionalizing reagent resulting in covalent attachment of the second functionalizing reagent to the first functionalizing reagent;

and

reacting the second functionalizing reagent with the product of step (d) to covalently attach molecules of the second functionalizing reagent to molecules of the first functionalizing reagent.