Functionalization of substrate surfaces with silane mixtures

• US 6,444,268 B2
• Filed: 07/02/2001
• Issued: 09/03/2002
• Est. Priority Date: 09/01/1998
• Status: Expired due to Term

• Current Assignee: Agilent Technologies, Inc.
• Original Assignee: Agilent Technologies, Inc.
• Inventors: Hotz, Charles Z., Dellinger, Douglas J., Lefkowitz, Steven M., Fulcrand, Geraldine
• Primary Examiner(s): CAMERON, ERMA C
• Application Number:
  US09/897,340
• Publication Number:
  US 20010051221A1
• Time in Patent Office: 428 Days
• Field of Search: 427/337, 427/407.2, 427/412.1
• US Class Current: 427/337
• 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 process for synthesizing an oligomer array on a substrate surface, comprising:

(a) functionalizing a substrate surface by 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 groups which leave the silanes during the coupling, 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, 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 is capable of being converted to such a functional group; and

(b) synthesizing a plurality of substrate-bound oligomers at each R² by sequentially coupling monomers thereto, wherein array features are created by the separation of individual coupling reactions as the oligomers are synthesized so as to form an oligomer array on the functionalized surface provided in (a);

wherein the substrate comprises a polymeric material, silica, glass, or ceramic.

2. The process of claim 1, wherein the monomers are amino acids and the oligomers are oligopeptides.

3. The process of claim 1, wherein the monomers are nucleotides and the oligomers are oligonucleotides.

4. The process of claim 1, wherein the monomers are protected and a deprotection step is carried out after each sequential coupling.

5. The process of claim 1, wherein prior to (b) a linking group is coupled to each R², and the monomers are sequentially coupled to a free terminus of the linking group.

6. The process of claim 5, wherein the linking group contains a site capable of being cleaved.

7. The process of claim 6, wherein the cleavable site is chemically cleavable.

9. A process according to claim 1 wherein the substrate comprises agarose, dextran, cellulosic polymers, or polyacrylamides.

10. A process according to claim 1 wherein the substrate comprises silica or glass.

8. A process for preparing an oligomer array, comprising:

(a) functionalizing a substrate surface by 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 groups which leave the silanes during the coupling, 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, 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 is capable of being converted to such a functional group; and

(b) binding a plurality of oligomers to the functionalized substrate by coupling an oligomer to each R²;

wherein the substrate comprises a polymeric material, silica, glass, or ceramic.

11. A process according to claim 8 wherein the substrate comprises silica or glass.

12. A process for synthesizing an oligomer array on a substrate surface, comprising:

(a) functionalizing a substrate surface by 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 groups which leave the silanes during the coupling, 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 space 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 is capable of being convened to such a functional group; and

(b) synthesizing a plurality of substrate-bound oligomers at each R² by sequentially coupling monomers thereto, wherein array features are created by the separation of individual coupling reactions as the oligomers are synthesized so as to form an oligomer array on the functionalized surface provided in (a);

wherein the substrate has reactive hydrophilic moieities selected from any one or more of hydroxyl groups, carboxyl groups, thiol groups, and substituted or unsubstituted amino groups.

13. A process for preparing an oligomer array, comprising:

(a) functionalizing a substrate surface by contacting a substrate having reactive hydropbilic 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 groups which leave the silanes during the coupling, 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, 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 is capable of being converted to such a functional group; and

(b) binding a plurality of oligomers to the functionalized substrate by coupling an oligomer to each R²;

wherein the substrate has reactive hydrophilic moieities selected from any one or more of hydroxyl groups, carboxyl groups, thiol groups, and substituted or unsubstitited amino groups.