Permeation layer attachment chemistry and method

Abstract

Electronically addressable microchips having covalently bound permeation layers and methods of making such covalently bonded permeation layers to microchips are provided. The covalent bonding is derived from combining the use of electrodes with silane derivatives. Such chemistry provides the ability to apply an electronic bias to the electrodes of the microchip while preventing permeation layer delaminating from the electrode surface. Methods for covalently attaching the permeation layer to the microchips are also described.

1 . A method of covalently attaching a permeation layer having reactive moieties to an electrode of an electronically addressable microchip comprising: 
 contacting the surface of the electrode with a linker molecule by vapor deposition wherein the linker molecule comprises a first reactive moiety that is capable of reacting with the electrode surface to form a covalent bond with the electrode, and a second reactive moiety that is capable of reacting with monomers to form the permeation layer;    reacting the first moiety of the linker molecule with the electrode surface to form a covalent bond between the linker molecule and the electrode surface;    synthesizing the permeation layer by reacting the linker molecule with monomers under conditions where polymerization is conducted between the monomers and the second reactive moiety of the linker;    wherein the resulting covalent attachment between the electrode and the linker and the permeation layer material is stable at a current density of at least 0.10 nA/μm 2 .    
     
     
         2 . The method of  claim 1 , wherein the electrode is a metal/silicide electrode selected from the group consisting of platinum silicide, tungsten silicide, titanium silicide, and gold silicide.  
     
     
         3 . The method of  claim 1 , wherein the electrode is a metal/metal electrode selected from the group consisting of platinum/titanium and gold /titanium.  
     
     
         4 . The method of  claim 1 , wherein the electrode is an organic electrode selected from the group consisting of poly(phenylene vinylene), polythiophene, and polyaniline.  
     
     
         5 . The method of  claim 1 , wherein the linker has the formula  
       
         
           
           
               
               
           
         
       
       wherein 
 X is selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, allyl, vinyl, acetyl, amine, substituted amine, epoxy and thiol;  
 SPACER is selected from the group consisting of alkyl, aryl, mono- or polyalkoxy, ethyleneglycol, polyethyleneglycol, mono- or polyalkylamine, mono- or polyamide, thioether derivatives, and mono- or polydisulfides;  
 A and B are selected from the group consisting of Oxygen-R, Cl, Br, X-SPACER moiety, and any combination thereof, wherein R is selected from the group consisting of H, alkyl, methyl, ethyl, propyl, isopropyl, and branched or linear alkyl of 4 to 10 carbon atoms; and  
 C is a hydrolyzable moiety selected from the group consisting of Oxygen-R, Cl, and Br, wherein R is selected from the group consisting of H, branched alkyl, methyl, ethyl, propyl, isopropyl, and branched or linear alkyl. of 4 to 10 carbon atoms.  
 
     
     
         6 . The method of  claim 5 , wherein the linker is selected from the group consisting of  
         H 2 NCH 2 CH 2 CH 2 Si(OCH 3 ) 3,    H 2 NCH 2 CH 2 NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3,    H 2 NCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3,    CH 2 ═C(CH 3 )COOCH 2 CH 2 CH 2 Si(OCH 3 ) 3,  and  CH 2 ═CHCONHCH 2 CH 2 CH 2 Si(OC 2 Hs) 3 .  
     
     
         7 . The method of  claim 6 , wherein the linker is H 2 NCH 2 CH 2 CH 2 Si(OCH 3 ) 3 .  
     
     
         8 . The method of  claim 6 , wherein the linker is H 2 NCH 2 CH 2 NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 .  
     
     
         9 . The method of  claim 6 , wherein the linker is CH 2 ═C(CH 3 )COOCH 2 CH 2 CH 2 Si(OCH 3 ) 3 .  
     
     
         10 . The method of  claim 5 , wherein the linker is an acrylate linker selected from the group consisting of  
         CH 2 ═CHCOOCH 2 CH 2 CH 2 Si(OCH 3 ) 3,    CH 2 ═CHCOOCH 2 CH 2 CH 2 SiCl 3,    CH 2 ═CHCOOCH 2 CH 2 CH 2 Si(CH 3 )(OCH 3 ) 2,    CH 2 ═CHCOOCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OCH 3 ),  CH 2 ═CHCOOCH 2 CH 2 CH 2 Si(CH 3 )Cl 2,  and  CH 2 ═CHCOOCH 2 CH(OH)CH 2 NHCH 2 CH 2 CH 2 Si(OC2H 5 ) 3.    
     
     
         11 . The method of  claim 5 , wherein the linker is a methacrylate linker selected from the group consisting of  
         CH 2 ═C(CH 3 )COOCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ,  CH 2 ═C(CH 3 )COOCH 2 CH 2 CH 2 SiCl 3,    CH 2 ═C(CH 3 )COOCH 2 CH 2 CH 2 Si(CH 3 )(OCH 3 ) 2,    CH 2 ═C(CH 3 )COOCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OCH 3 ),  CH 2 ═C(CH 3 )COOCH 2 CH 2 CH 2 Si(CH 3 )Cl 2,  and  CH 2 ═C(CH 3 )COOCH 2 CH(OH)CH 2 NHCH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3.    
     
     
         12 . The method of  claim 5 , wherein the linker is an acrylamide linker selected from the group consisting of  
         CH 2 ═CHCONHCH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3,    CH 2 ═CHCONHCH 2 CH 2 CH 2 SiCl 3,    CH 2 ═CHCONHCH 2 CH 2 CH 2 Si(CH 3 )(OCH 3 ) 2,    CH 2 ═CHCONHCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OCH 3 ),  CH 2 ═CHCONRCH 2 CH 2 CH 2 Si(CH 3 )C1 2,    CH 2 ═CHCONHCH 2 CH(OH)CH 2 NHCH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3 , and  CH 2 ═CHCONHCH 2 CH 2 CONHCH 2 CH 2 CONHCH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3.    
     
     
         13 . The method of  claim 5 , wherein the linker is a methacrylamide linker selected from the group consisting of  
         CH 2 ═C(CH 3 )CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ,  CH 2 ═C(CH 3 )CONHCH 2 CH 2 CH 2 SiCl 3,    CH 2 ═C(CH 3 )CONHCH 2 CH 2 CH 2 Si(CH 3 )(OCH 3 ) 2,    CH 2 ═C(CH 3 )CONHCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OCH 3 ),  CH 2 ═C(CH 3 )CONHCH 2 CH 2 CH 2 Si(CH 3 )Cl 2,  and  CH 2 ═C(CH 3 )CONHCH 2 CH(OH)CH 2 NHCH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3.    
     
     
         14 . The method of  claim 5 , wherein the linker is an allyl derivative linker selected from the group consisting of  
         CH 2 ═CHCH 2 NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3,    CH 2 ═CHCH 2 SiH(OCH 3 ) 2,    CH 2 ═CHCH 2 Si(CH 3 ) 2 Cl,  CH 2 ═CHCH 2 SiHCl 2,  and  CH 2 ═CHCH 2 Si(OCH 3 ) 3.    
     
     
         15 . The method of  claim 5 , wherein the linker is an amino derivative linker selected from the group consisting of  
         H 2 NCH 2 CH 2 NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3,    H 2 NCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ,  H 2 NCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , and  H 2 NCH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3.    
     
     
         16 . The method of  claim 5 , wherein the linker is an epoxy derivative linker selected from the group consisting of  
       
         
           
           
               
               
           
         
       
     
     
         17 . The method according to  claim 1 , wherein the permeation layer is a hydrogel comprising a material selected from the group consisting of agarose, glyoxylagarose, acrylamide, methacrylamide, polyacrylamide, and other synthetic polymers.  
     
     
         18 . The method of  claim 17 , wherein the hydrogel comprises glyoxylagarose.  
     
     
         19 . The method of  claim 17 , wherein the hydrogel comprises polyacrylamide.  
     
     
         20 . The method of  claim 1 , wherein the step of reacting the linker molecule with monomers is a Schiff base reduction or polymerization.  
     
     
         21 . The method of  claim 1 , wherein the second reactive moiety of the linker comprises an amine group.  
     
     
         22 . The method of  claim 1 , wherein steps (b) and (c) occur at different times.  
     
     
         23 . The method of  claim 1 , wherein the step of reacting the first moiety of the linker molecule with the electrode surface comprises heat curing of the linker molecule and the electrode surface.  
     
     
         24 . The method of  claim 1 , wherein the resulting covalent attachment between the electrode and the linker and the permeation layer material is stable at a current density of at least 0.14 nA/μm 2 .  
     
     
         25 . The method of  claim 1 , wherein the resulting covalent attachment between the electrode and the linker and the permeation layer material is stable at a current density of at least 0.2 nA/μm 2 .  
     
     
         26 . The method of  claim 1 , wherein the resulting covalent attachment between the electrode and the linker and the permeation layer material is stable at a current density of at least 0.4 nA/μm 2 .  
     
     
         27 . The method of  claim 1 , wherein the step of reacting the linker molecule with monomers is a free radical polymerization reaction.  
     
     
         28 . The method of  claim 1 , wherein the polymerization is conducted in a solution phase reaction.  
     
     
         29 . The method of  claim 1 , wherein the polymerization is conducted between the monomers, and between the monomers and the second reactive moiety of the linker.