Electrochemical attachment of phosphonic acids to metallic substrates and antimicrobial medical devices containing same

Abstract

A method of preparing a modified-metal surface. The method includes preparing a solution of a phosphorous-based acid in a solvent; immersing a strip of the metal work piece into the solution of the phosphorous-based acid; immersing a strip of a reference metal into the solution of the phosphorous-based acid; supplying a voltage for a duration of time to prepare a phosphorous acid-modified metal work piece; removing the phosphorous acid-modified metal work piece; cleaning and drying the phosphorous acid-modified metal work piece; applying a chitosan solution to the surface in order to attach chitosan/modified chitosan to the phosphorous acid based modified surface; prepare the modified-metal surface; and cleaning and drying the modified-metal surface.

We claim: 
     
         1 . A method of preparing a functional surface comprising a metal, polymer, biopolymer, or ceramic material, the method comprising:
 preparing a solution of a phosphorous-based acid in a solvent;   immersing at least a portion of a work piece into the solution of the phosphorous-based acid, wherein the workpiece comprises a metal, polymer, biopolymer, or ceramic material;   immersing at least a portion of a reference metal into the solution of the phosphorous-based acid;   supplying a voltage for a duration of time to prepare a phosphorous acid-modified work piece;   removing the phosphorous acid-modified work piece; and   further modifying the phosphorous acid-terminated work piece with a chitosan solution to prepare a functional surface.   
     
     
         2 . The method according to  claim 1 , wherein the phosphorous-based acid is a phosphonic acid, a phosphoric acid, a phosphinic acid, or mixtures thereof 
     
     
         3 . The method according to  claim 2 , wherein the phosphonic acid is 11-phosphono-1-undecanol. 
     
     
         4 . The method according to  claim 1 , wherein the solvent is selected from the group consisting of n-butanol, isopropanol, ethanol, methanol, formic acid, acetic acid, tetrahydrofuran (THF), demethylformamide (DMF), dimethyl sulfoxide (DMSO), and ionic liquids. 
     
     
         5 . The method of  claim 1 , wherein the chitosan solution comprises an oligo-chitosan modified with a quaternary phosphonium salt. 
     
     
         6 . The method according to  claim 1 , wherein the workpiece comprises a metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Al, and alloys thereof. 
     
     
         7 . The method according to  claim 1 , wherein the workpiece comprises stainless steel. 
     
     
         8 . An article comprising a work piece having a modified surface, wherein the surface comprises a polymer, biopolymer, or ceramic material, and wherein the modified surface comprises a chitosan modified with a quaternary ammonium salt. 
     
     
         9 . The article according to  claim 8 , wherein the chitosan is connected to a surface of the work piece via a phosphorous-based acid linker. 
     
     
         10 . The article according to  claim 9 , wherein the phosphorous-based acid is a phosphonic acid, a phosphoric acid, a phosphinic acid, or mixtures thereof 
     
     
         11 . The article according to  claim 10 , wherein the phosphonic acid is 11-phosphono-1-undecanol. 
     
     
         12 . The article according to  claim 8 , wherein the article has an antibacterial effect. 
     
     
         13 . The article according to  claim 8 , wherein the article has an antifungal and/or antiviral effect. 
     
     
         14 . An article prepared according to the method of  claim 1 . 
     
     
         15 . The article according to  claim 14 , wherein the chitosan is connected to a surface of the work piece via a phosphorous-based acid linker. 
     
     
         16 . The article according to  claim 14 , wherein the article has an antibacterial effect. 
     
     
         17 . The article according to  claim 14 , wherein the article has an antifungal or antiviral effect. 
     
     
         18 . A method of preparing a functional metal surface, the method comprising:
 preparing a solution of a phosphorous-based acid in a solvent;   immersing at least a portion of a metal work piece into the solution of the phosphorous-based acid;   immersing at least a portion of a reference metal into the solution of the phosphorous-based acid;   supplying a voltage for a duration of time to prepare a phosphorous acid-modified metal work piece;   removing the phosphorous acid-modified metal work piece; and   further modifying the phosphorous acid-terminated work piece with a polysaccharide solution to prepare a functional metal surface.   
     
     
         19 . The method according to  claim 18 , wherein the phosphorous-based acid is a phosphonic acid, a phosphoric acid, a phosphinic acid, or mixtures thereof 
     
     
         20 . The method according to  claim 18 , wherein the solvent is selected from the group consisting of n-butanol, isopropanol, ethanol, methanol, formic acid, acetic acid, tetrahydrofuran (THF), demethylformamide (DMF), dimethyl sulfoxide (DMSO), and ionic liquids.