Oxidation-reduction polymer including transition metal complex, and electrochemical biosensor using same

Abstract

The present disclosure relates to an oxidation-reduction polymer including a transition metal complex, which has a unique structure, and so can be prepared in a simpler step compared to a conventional method, and can increase the immobilization rate of the transition metal complex and facilitates the introduction of a functional group or a linker, a method for preparing the same and an electrochemical biosensor comprising the oxidation-reduction polymer.

1 . An oxidation-reduction polymer for an electron transport medium of an electrochemical biosensor, having any one structure of the following Chemical Formulas 1 to 4: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein, 
         M is a transition metal selected from the group consisting of Os, Rh, Ru, Ir, Fe and Co; 
         L 1  and L 2  are combined with each other to form a bidentate ligand selected from the following Chemical Formulas 5 to 7; 
         L 3  and L 4  are combined with each other to form a bidentate ligand selected from the following Chemical Formulas 5 to 7; 
         L 5  and L 6  are each combined with each other to form a bidentate ligand selected from the following Chemical Formulas 5 to 7; 
       
       
         
           
           
               
               
           
         
         the R 1 , R 2  and R′ 1  are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alcohol group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylhalogen group having 1 to 20 carbon atoms, a substituted or unsubstituted thiol group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl azide group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl azide group having 7 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 40 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen, 
         the R 3  to R 20  are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alcohol group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylhalogen group having 1 to 20 carbon atoms, a substituted or unsubstituted thiol group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl azide group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl azide group having 7 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylamino group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 40 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen; 
         the Ad is selected from the group consisting of a primary and secondary amine group, an ammonium group, a halogen group, an epoxy group, an azide group, an acrylate group, an alkenyl group, an alkynyl group, a thiol group, isocyanate, an alcohol group, and a silane group; 
         the X is a counter ion; 
         the a is an integer of 1 to 15; 
         the b is an integer of 1 to 15; 
         the c is an integer of 1 to 15; 
         the m is an integer of 10 to 600; 
         the n is an integer of 10 to 600; and 
         the o is an integer of 0 to 600. 
       
     
     
         2 . The oxidation-reduction polymer for an electron transport medium according to  claim 1 , wherein the compound of Chemical Formula 1 has a structure represented by the following Chemical Formula 8 or 9. 
       
         
           
           
               
               
           
         
       
     
     
         3 . A method for preparing an oxidation-reduction polymer as set forth in  claim 1 , the method comprising the steps of:
 (i) functionalizing polyvinylpyridine or polyimidazole to produce a polyvinylpyridine precursor or a polyimidazole precursor;   (ii) functionalizing the transition metal complex; and   (iii) reacting the polyvinylpyridine precursor or polyimidazole precursor produced in step (i) and the functionalized transition metal complex produced in step (ii) by a click reaction to prepare the oxidation-reduction polymer as set forth in  claim 1 .   
     
     
         4 . The preparation method according to  claim 3 , wherein the click reaction of step (iii) is azide-alkyne Huisgen cycloaddition or thiol-ene reaction. 
     
     
         5 . A composition for an electrochemical biosensor comprising:
 an enzyme capable of subjecting a liquid biological sample to an oxidation-reduction reaction; and   the oxidation-reduction polymer as set forth in  claim 1 .   
     
     
         6 . The composition according to  claim 5 , wherein the enzyme comprises:
 at least one oxidoreductase selected from the group consisting of dehydrogenase, oxidase, and esterase; or   at least one oxidoreductase selected from the group consisting of dehydrogenase, oxidase, and esterase, and at least one cofactor selected from the group consisting of flavin adenine dinucleotide (FAD), nicotinamide adenine dinucleotide (NAD), and pyrroloquinoline quinone (PQQ).   
     
     
         7 . The composition according to  claim 5 , wherein the enzyme is at least one selected from the group consisting of flavin adenine dinucleotide-glucose dehydrogenase (FAD-GDH) and nicotinamide adenine dinucleotide-glucose dehydrogenase. 
     
     
         8 . The composition according to  claim 5 , further comprising one or more additives selected from the group consisting of surfactants, water-soluble polymers, and thickeners, and a crosslinking agent. 
     
     
         9 . An electrochemical biosensor comprising the oxidation-reduction polymer according to  claim 1 . 
     
     
         10 . The electrochemical biosensor according to  claim 9 , further comprising a sensing layer, a diffusion layer, a protection layer, two or more electrodes, an insulator and a substrate, comprising the oxidation-reduction polymer as set forth in  claim 1 . 
     
     
         11 . The electrochemical biosensor according to  claim 10 , wherein the electrode is a 2-electrode consisting of an working electrode and a counter electrode, or a 3-electrode consisting of an working electrode, a counter electrode and a reference electrode. 
     
     
         12 . The electrochemical biosensor according to  claim 9 , wherein the biological sample is blood.