Macromolecular arrays on polymeric brushes & methods for preparing the same

Abstract

Polymeric brush substrates and methods for their preparation are provided. Methods are also provided for preparing macromolecular arrays on such polymeric brush substrates. Using polymeric brush substrates allows control over functional site density as well as wettability and porosity of the substrate. These polymeric brushes are useful in solid-phase synthesis of arrays of peptides, polynucleotides or small organic molecules.

1 - 8 . (canceled)  
     
     
         9 . A method for affixing functional sites to a surface of a solid substrate, the method comprising: 
 (a) providing a substrate to which one or more free radical initiators are covalently attached, wherein each free radical initiator has a radical generation site distal to the substrate; and    (b) contacting the substrate with a mixture of linking monomers and diluent monomers under conditions that promote free radical polymerization from the radical generation sites of the initiators to produce a brush polymer comprising functional sites, wherein the density of the functional sites is determined by the ratio of functional monomers to diluent monomers.    
     
     
         10 . The method of  claim 9 , wherein the linking monomers comprise a vinyl group.  
     
     
         11 . The method of  claim 9 , wherein the linking monomers comprise at least two different linking monomers.  
     
     
         12 . The method of  claim 9 , wherein the initiator is an azo type initiator.  
     
     
         13 . The method of  claim 9 , wherein the functional sites are selected from the group consisting of amino, hydroxyl, carboxyl or sulfydryl.  
     
     
         14 . The method of  claim 9 , wherein the ratio of linking monomers to diluent monomers is from about 1:2 to about 1:200.  
     
     
         15 . The method of  claim 9 , wherein the ratio of linking monomers to diluent monomers is from about 1:2 to about 1:2000.  
     
     
         16 . The method of  claim 9 , wherein the monomers independently have the structure:  
       
         
           
           
               
               
           
         
         wherein R1 is hydrogen or lower alkyl; and  
         R2 and R3 are independently hydrogen, alkyl, alkoxy, hydroxyalkyl, polyalkylene oxide, or —Y-Z, wherein Y is linear or branched lower alkyl, aryl, alkylaryl, or polyalkylene oxide, and Z is hydrogen, hydroxyl, alkoxy, carboxy, amino, hydrazino, sulfydryl, or R, where R is hydrogen, hydroxy, lower alkoxy or aryloxy.  
       
     
     
         17 . The method of  claim 9 , wherein the substrate comprises glass or silica.  
     
     
         18 . A substrate capable of supporting macromolecular array synthesis, the substrate comprising polymer brushes formed by free radical polymerization, wherein said polymer brushes comprise hydroxyl, amino, or carboxyl, groups or a combination thereof.  
     
     
         19 . The substrate of  claim 18 , wherein the density of the polymer brushes is 0.1 to 1000 pmoles of individual polymer chains per cm2 of substrate surface area.  
     
     
         20 . The substrate of  claim 18 , further comprising an array of macromolecules attached to polymeric brushes on the substrate.  
     
     
         21 . The substrate of  claim 20 , wherein the macromolecules comprise polynucleotides.