Functionalization of substrate surfaces with silane mixtures

• US 6,258,454 B1
• Filed: 09/01/1998
• Issued: 07/10/2001
• Est. Priority Date: 09/01/1998
• Status: Expired due to Fees

• Current Assignee: Agilent Technologies, Inc.
• Original Assignee: Agilent Technologies, Inc.
• Inventors: Dellinger, Douglas J., Hotz, Charles Z., Lefkowitz, Steven M., Fulcrand, Geraldine
• Primary Examiner(s): Nakarani, D. S.
• Application Number:
  US09/145,015
• Time in Patent Office: 1,043 Days
• Field of Search: 106/287.13, 106/287.14, 106/287.15, 106/287.16, 427/387, 427/399, 427/400, 428/333, 428/429, 428/447, 428/451
• US Class Current: 428/333
• CPC Class Codes: B05D 1/185 applying monomolecular layers B05D1/204 takes precedence
• CPC Class Codes: B32B 17/10688 Adjustment of the adherence to the glass layers
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: G01N 33/54353 with ligand attached to the carrier via a chemical coupling agent coatings G01N33/54393
• CPC Class Codes: Y10T 428/261 In terms of molecular thickness or light wave length
• CPC Class Codes: Y10T 428/31612 As silicone, silane or siloxane
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31667 Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Abstract

Low surface energy functionalized surfaces on solid supports are provided by treating a solid support having hydrophilic moieties on its surface with a derivatizing composition containing a mixture of silanes. A first silane provides the desired reduction in surface energy, while the second silane enables functionalization with molecular moieties of interest, such as small molecules, initial monomers to be used in the solid phase synthesis of oligomers, or intact oligomers. Molecular moieties of interest may be attached through cleavable sites. Derivatizing compositions for carrying out the surface functionalization process are provided as well.

Claims

1. A substrate having a functionalized surface, comprising:

a solid support having a plurality of surface hydrophilic, nucleophilic groups, a first fraction of which are covalently bound to an —

Si—

R¹ moiety and a second fraction of which are covalently bound to an —

Si—

(L)_n—

R² moiety, wherein R¹ is a chemically inert moiety that lowers the surface energy of the solid support and is selected from the group consisting of C₁₀ to C₁₈ alkyl and benzyl optionally substituted with 1 to 5 halogen atoms, n is 0 or 1, L is a linking group, R² is a functional group enabling covalent binding of a molecular moiety or a modifiable group that can be converted to such a functional group, and the solid support is comprised of a material selected from the group consisting of polystyrene, agarose, dextran, cellulosic polymers, polyacrylamides, and glass.

4. The process of claim 1, wherein the reactive hydrophilic moieties are selected from the group consisting of hydroxyl, carboxyl, thiol, amino, and combinations thereof.

6. The process of claim 1, wherein the R^L are selected from the group consisting of halogen and alkoxy.

7. The process of claim 6, wherein the R^L are selected from the group consisting of chloro and lower alkoxy.

8. The process of claim 3, wherein R¹ is C₁₀ to C₁₈ alkyl.

9.The process of claim 1, wherein n is 1.

12. The process of claim 1, wherein R² is —

CH═

CH₂.

13. The process of claim 1, wherein, in the first silane, R^x and R^y are lower alkyl.

14. The process of claim 1, wherein, in the second silane, R^x and R^y are lower alkyl.

2. A substrate having a functionalized surface, comprising:

a solid support having a plurality of surface hydrophilic, nucleophilic groups, a first fraction of which are covalently bound to an —

Si—

R¹ moiety and a second fraction of which are covalently bound to an —

Si(R^xR^y)—

L—

R² moiety, wherein R^x and R^y are independently selected from the group consisting of halogen, lower alkoxy and lower alkyl, R¹ is C₁₀ to C18 alkyl, L is C₁-C₂₄ alkylene, and R² is —

CH═

CH₂.

5. The process of claim 2, wherein the reactive hydrophilic moieties are hydroxyl groups.

3. A process for functionalizing the surface of a substrate, comprising:

contacting a substrate having reactive hydrophilc moieties on the surface there with a derivatizing composition comprising a first silane R¹—

Si(R^LR^xR^y) and a second silane R²—

(L)_n—

Si(R^LR^xR^y) under reaction conditions effective to couple the silanes to the substrate surface and provide —

Si—

R¹ groups and —

Si—

(L)_n—

R² groups thereon, wherein the R^L, moieties, which may be the same or different, are leaving groups, the R^x and R^y are independently lower alkyl or leaving groups, R¹ is a chemically inert moiety that upon binding to the substrate surface lowers the surface energy thereof and is selected from the group consisting of C₁₀ to C₁₈ alkyl and benzyl optionally substituted with 1 to 5 halogen atoms, n is 0 or 1, L is a linking group, and R² is a functional group enabling covalent binding of a molecular moiety or a modifiable group that may be converted to such a functional group.

9. the process of claim 9, wherein L is a C₁-C₂₄ hydrocarbylene linking group substituted with 0 to 6 substituents selected from the group consisting of lower alkyl, hydroxyl, halogen and amino, optionally containing 1 to 6—

O—

, —

S—

, —

NR—

, —

CONH—

, —

(CO)—

or —

COO—

linkages wherein R is hydrogen or lower alkyl.

10. The process of claim 10, wherein L is C₁-C₂₄ alkylene.

11. The process of claim 11, wherein L is C₁₀-C₁₈ alkylene.

15. A process for functionalizing the surface of a substrate, comprising:

contacting a substrate having reactive hydrophilic moieties on the surface thereof with a derivatizing composition comprising a first silane R¹—

Si(R^LR^xR^y) and a second silane R²—

L—

Si(R^LR^xR^y) under reaction conditions effective to couple the silanes to the substrate surface and provide —

Si—

L—

R¹ groups and —

Si—

L—

R² groups thereon, wherein the R^L moieties are independently selected from the group consisting of halogen and lower alkoxy, R^x and R^y are independently selected from the group consisting of halogen, lower alkoxy and lower alkyl, R¹ is C₁₀ to C₁₈ alkyl, L is C₁-C₂₄ alkylene, and R² is —

CH═

CH₂.

16. The process of claim 16, further comprising converting R² to a hydroxyl group by boration and oxidation.

17. A process for functionalizing the surface of a substrate, comprising:

contacting a substrate having reactive hydrophilic moieties on the surface thereof with a derivatizing composition comprising a first silane R¹—

Si(R^LR^xR^y) and a second silane R²—

(L)_n—

Si(R^LR^xR^y) under reaction conditions effective to couple the silanes to the substrate surface and provide —

Si—

R¹ groups and —

Si—

(L)_n—

R² groups thereon, wherein the R^L, moieties, which may be the same or different, are leaving groups, the R^x and R^y are independently lower alkyl or leaving groups, R¹ is a C₁₀ to C₁₈ chemically inert moiety that upon binding to the substrate surface lowers the surface energy thereof, n is 0 or 1, L is a linking group, and R² is a functional group enabling covalent binding of a molecular moiety or a modifiable group that may be converted to such a functional group.

18. A derivatizing composition for functionalizing the surface of a substrate, comprising:

a first silane R¹—

Si(R^LR^xR^y) and a second silane R²—

(L)_n—

Si(R^LR^xR^y), wherein the R^L are independently leaving groups, the R^x and R^y may be the same or different and are either lower alkyl or leaving groups, R¹ is a chemically inert moiety that upon binding to a substrate surface lowers the surface energy thereof and is selected from the group consisting of C₁₀ to C₁₈, alkyl and benzyl optionally substituted with 1 to 5 halogen atoms, n is 0 or 1, L is a linking group, and R² is a functional group enabling covalent binding of a molecular moiety or a modifiable group that can be converted to such a functional group.

19. A derivatizing composition for functionalizing the surface of a substrate, comprising a first silane R¹—

Si(R^LR^xR^y) and a second silane R²—

L—

Si(R^LR^xR^y), wherein the R^L moieties are independently selected from the group consisting of halogen and lower alkoxy, R^x and R^y are independently selected from the group consisting of halogen, lower alkoxy and lower alkyl, R¹ is C₁₀ to C₁₈ alkyl, L is C₁-C₂₄ alkylene, and R² is —

CH═

CH₂.