Functional surfaces

Abstract

Articles having functional surfaces, for example antimicrobial functional surfaces, are prepared by methods comprising anodization. Organophosphorous compounds are deposited on a surface by methods comprising anodization, followed by attaching functional compounds, functional oligomers or functional polymers. Alternatively, functional organophosphorous compounds, functional oligomers or functional polymers are deposited on a surface by methods comprising anodization.

1 .- 28 . (canceled) 
     
     
         29 . A method for preparing an article having a functional surface, the method comprising:
 preparing a solution including an organophosphorous compound;   placing the article having a metal surface in the solution; and   depositing the organophosphorous compound on the metal surface via anodization,   wherein the organophosphorous compound comprises an organophosphonic acid, an organophosphinic acid, or an organophosphoric acid,   wherein the organophosphorous compound is modified by attaching one or more functional compounds, functional oligomers, or functional polymers to the organophosphorous layer to form a functional layer, and   wherein the one or more functional compounds, functional oligomers, or functional polymers comprise a quaternary ammonium salt, a pyridinium salt, or a phosphonium salt.   
     
     
         30 . The method of  claim 29 , wherein an organo group of the organophosphorous compound is a C 2 -C 12  hydrocarbyl group. 
     
     
         31 . The method of  claim 29 , wherein the metal surface comprises a surface comprising titanium, a titanium alloy, stainless steel, a cobalt chrome alloy, nickel, molybdenum, tantalum, zirconium, magnesium, or an alloy containing one or more of nickel, molybdenum, tantalum, zirconium, and magnesium. 
     
     
         32 . The method of  claim 29 , wherein the metal surface comprises a titanium surface. 
     
     
         33 . The method of  claim 29 , wherein an organo group of the organophosphorous compound is reacted with a diamine or an aminoalcohol to provide a distal amine which is subsequently quaternized to provide the functional layer comprising a quaternary ammonium compound. 
     
     
         34 . The method of  claim 29 , wherein the organophosphorous compound is an unsaturated organophosphorous monomer, and wherein the unsaturated organophosphorous monomer is reacted with an unsaturated functional monomer to form the functional layer comprising one or more of the functional oligomers or the functional polymers. 
     
     
         35 . The method of  claim 34 , wherein the unsaturated functional monomer is an antimicrobial monomer optionally comprising an ammonium salt, a pyridinium salt, or a phosphonium salt. 
     
     
         36 . The method of  claim 35 , wherein the antimicrobial monomer comprises a methacryloyloxydodecylpyridinium salt, diallyldimethylammonium chloride, a methacryloyloxyhexadecylpyridinium salt, a methacryloyloxydecyltriethylammonium salt, a 4-hexadecylmethacryloyloxyethylpyridinium salt, a methacryloyloxyethylhexadecylbipyridinium salt, a methacryloyloxydodecyltrimethylphosphonium salt, a methacryloyloxyoctadecyltriethylphosphonium salt, a 4-methacryloyloxyethyldodecylpyrldinium salt, a di(4-vinylbenzyl)hexadecylmethylammonium salt, a di(methacryloyloxyethyl)dodecylmethylammonium salt, or methacryloyloxyethyl(4-N-hexadecylpyridinylmethyl) succinate halide. 
     
     
         37 . The method of  claim 34 , wherein the unsaturated functional monomer comprises vinyl phosphonic acid, allyl phosphonic acid, 2-methyl allylphosphonic acid, 2-butenyl phosphonic acid, allyl phosphate, or ethyleneglycol methacrylatephosphate. 
     
     
         38 . The method of  claim 29 , wherein in the modifying step, atom transfer radial polymerization of an unsaturated functional monomer is utilized to attach one or more of the functional oligomers or the functional polymers to the organophosphorous layer to form the functional layer. 
     
     
         39 . The method of  claim 38 , wherein the unsaturated functional monomer comprises a methacryloyloxydodecylpyridinium salt, diallyldimethylammonium chloride, a methacryloyloxyhexadecylpyridinium salt, a methacryloyloxydecyltriethylammonium salt, a 4-hexadecylmethacryloyloxyethylpyridinium salt, a methacryloyloxyethylhexadecylbipyridinium salt, a methacryloyloxydodecyltrimethylphosphonium salt, a methacryloyloxyoctadecyltriethylphosphonium salt, a 4-methacryloyloxyethyldodecylpyrldinium salt, a di(4-vinylbenzyl)hexadecylmethylammonium salt, a di(methacryloyloxyethyl)dodecylmethylammonium salt, or methacryloyloxyethyl(4-N-hexadecylpyridinylmethyl) succinate halide. 
     
     
         40 . The method of  claim 29 , wherein the organophosphorous compound is covalently bonded to an oxide layer through phosphinate, phosphonate, or phosphate moieties. 
     
     
         41 . The method of  claim 29 , wherein the depositing step comprises:
 connecting the metal surface to a positive terminal of an electric power supply;   connecting a counter electrode placed in the solution to a negative electrode of the power supply; and   applying a voltage for a predetermined period.   
     
     
         42 . The method of  claim 41 , wherein the voltage ranges from about 1 to about 400 volts. 
     
     
         43 . The method of  claim 41 , wherein the predetermined period ranges from about 1 to about 60 seconds. 
     
     
         44 . The method of  claim 29 , wherein the article is a medical device. 
     
     
         45 . The method of  claim 29 , wherein the solution is partially aqueous. 
     
     
         46 . The method of  claim 45 , wherein the solution comprises an alcohol. 
     
     
         47 . An article having a functional surface, the article prepared by the method of  claim 29 . 
     
     
         48 . An article, comprising:
 a metal surface having a functional layer disposed thereon, wherein the functional layer comprises one or more functional compounds, functional oligomers, or functional polymers, wherein the one or more functional compounds, functional oligomers, or functional polymers comprise a quaternary ammonium salt, a pyridinium salt, or a phosphonium salt, and   an organophosphorous compound deposited on the metal surface, wherein one or more functional compounds, functional oligomers, or functional polymers are attached to the organophosphorous compound.   
     
     
         49 . The article of  claim 48 , wherein the organophosphorous compound comprises an organophosphonic acid, an organophosphinic acid, or an organophosphoric acid. 
     
     
         50 . The article of  claim 48 , wherein an organo group of the organophosphorous compound is a C 2 -C 12  hydrocarbyl group. 
     
     
         51 . The article of  claim 48 , wherein the metal surface comprises a surface comprising titanium, a titanium alloy, stainless steel, a cobalt chrome alloy, nickel, molybdenum, tantalum, zirconium, magnesium, or an alloy containing one or more of nickel, molybdenum, tantalum, zirconium, and magnesium. 
     
     
         52 . The article of  claim 48 , wherein the metal surface comprises a titanium surface. 
     
     
         53 . The article of  claim 48 , an organo group of the organophosphorous compound is reacted with a diamine or an aminoalcohol to provide a distal amine which is subsequently quaternized to provide the functional layer comprising the quaternary ammonium compound. 
     
     
         54 . The article of  claim 48 , wherein the organophosphorous compound is an unsaturated organophosphorous monomer, and wherein the unsaturated organophosphorous monomer is reacted with an unsaturated functional monomer to form the functional layer comprising one or more of the functional oligomers or the functional polymers. 
     
     
         55 . The article of  claim 54 , wherein the unsaturated functional monomer is an antimicrobial monomer optionally comprising an ammonium salt, a pyridinium salt, or a phosphonium salt. 
     
     
         56 . The article of  claim 55 , wherein the antimicrobial monomer comprises a methacryloyloxydodecylpyridinium salt, diallyldimethylammonium chloride, a methacryloyloxyhexadecylpyridinium salt, a methacryloyloxydecyltriethylammonium salt, a 4-hexadecylmethacryloyloxyethylpyridinium salt, a methacryloyloxyethylhexadecylbipyridinium salt, a methacryloyloxydodecyltrimethylphosphonium salt, a methacryloyloxyoctadecyltriethylphosphonium salt, a 4-methacryloyloxyethyldodecylpyrldinium salt, a di(4-vinylbenzyl)hexadecylmethylammonium salt, a di(methacryloyloxyethyl)dodecylmethylammonium salt, or methacryloyloxyethyl(4-N-hexadecylpyridinylmethyl) succinate halide. 
     
     
         57 . The article of  claim 48 , wherein the organophosphorous compound is covalently bonded to an oxide layer through phosphinate, phosphonate, or phosphate moieties. 
     
     
         58 . The article of  claim 48 , wherein the organophosphorous compound is deposited on the metal surface via anodization. 
     
     
         59 . The article of  claim 48 , wherein the article is a medical device.