Process For Preparation Of Bioorganic Nylon Polymers And Their Use As Antibacterial Material

Abstract

The present invention relates to new biopolymer, i.e. bioorganic nylons incorporating peptidic blocks obtained by a process of polymerization of amino peptidic blocks. The process of the invention comprises the steps of mixing amino peptidic blocks with or without a diaminoalcane and reacting the mixture according to polycondensation with a diacyl chloride in homogeneous or heterogeneous media.

1 . A process for preparation of bioorganic nylon type polymers comprising the steps of
 i) preparing a basic solution containing at least one type of peptidic amino-building block selected from the group consisting of the following A, B, C, D and E blocks:         wherein AA is an amino-acid residue, PEPTIDE is a peptide residue corresponding to a chain of amino acid residues bound by peptidic bonds;      is the N terminus  of AA or PEPTIDE;      is the amino derivatized C terminus  of AA PEPTIDE;      is the free amino group of the side chain of AA or of an amino-acid residue of PEPTIDE;      is the C terminus  of AA or PEPTIDE;      is the protected N terminus of the AA or PEPTIDE; and
 ii) Initiating polymerization by contacting the solution of i) with a solution containing a diacyl G of the following formula (G): X(CO)—Y—(CO)X 
 wherein: 
   X is a halogen;   Y is (CH 2 ) q , C 6 H 4 , C 6 H 4 —W—C 6 H 4 , C 6 F 4 , C 6 F 4 —W—C 6 F 4 , or C 10 H 6 ;   W is a bond, SiO 2 [(CH 2 ) r CH 3 ] 2 , CH 2 , O or S,   with r comprised between 1 and 4; and
 q is comprised between 1 and 12. 
   
     
     
         2 . The process of  claim 1 , wherein solution of i) further contains a diamino building block F selected from the group consisting of diamino-alcane building block of general formula (F): H 2 N—Z—NH 2 ,
 wherein: 
 Z is (CH 2 ) p , C 6 H 4 , C 6 H 4 —W′—C 6 H 4 , C 6 F 4 , C 6 F 4 —W′—C 6 F 4 , or C 10 H 6 ; 
 W′ is a bond, CH 2 , O, S, or SiO 2 [(CH 2 ) s CH 3 ] 2    
 with s comprised between 1 and 4; and 
 p is comprised between 1 and 14. 
 
     
     
         3 . The process of  claim 1 , wherein the polymerization is achieved in homogeneous or heterogeneous phase. 
     
     
         4 . The process of  claim 1 , wherein the polymerization is achieved in homogeneous phase and the buildings blocks A to E are dissolved in a solvent which is also a solvent of the diacyl compound G. 
     
     
         5 . The process of  claim 1 , wherein the polymerization is achieved in heterogeneous phase and polymerization is initiated through interfacial polymerization. 
     
     
         6 . The process of  claim 1 , wherein the polymer is recovered and washed. 
     
     
         7 . The process of  claim 1 , wherein the basic solution of i) has a pH above 7. 
     
     
         8 . The process of  claim 1 , wherein the diacyl compound (G) is diacyl chloride 
     
     
         9 . The process of  claim 1 , wherein the molar concentration of peptidic-diamino building blocks [A+B+C+D+E] varies from 1 to 100% and the molar concentration of diaminoalcane building block [F] is comprised between 0 and 99%, the sum of both molar quantities being equal to 100% and corresponding to the molar quantity of diacyl compound [G] expressed as 100%. 
     
     
         10 . The process of  claim 1 , wherein the protected N-terminus of the AA or of the PEPTIDE is protected by a protecting group selected from the group consisting of Fmoc, Boc, Cbz, Dde, trityl, NVoc, Alloc and Troc. 
     
     
         11 . The process of  claim 1 , wherein the amino peptidic block comprises, within its peptidic chain or at any of its N terminus or C-terminus, a lysine or an amino acid residue having a side chain that contains the following structure: —(CH 2 ) m —NH 2  wherein m is comprised between 0 and 10. 
     
     
         12 . The process of  claim 1 , wherein the PEPTIDE corresponds to the homo- or hetero-oligomer according to the following motif: 
       
         
           
           
               
               
           
         
         wherein:
 n is comprised between 2 and 25; 
 R is the side chain of an amino-acid selected from the group consisting of natural aminoacids side chains, non-natural aminoacids side chains, and modified aminoacids side chains; 
 R′ is H or a C3-C6 alkyl linked to R thus forming a R-R′ ring; and 
 d and e being such that d+e=0 to 10. 
 
       
     
     
         13 . The process of  claim 1 , wherein the amino-building block is labelled with a probe. 
     
     
         14 . A bioorganic nylon type polymer obtainable by a process according to  claim 1 . 
     
     
         15 . A bioorganic nylon type polymer comprising or consisting of at least one group of repeated unit, said group being selected from:
 a) group a, wherein group a is selected from the group consisting of repeated units of formula A1 and A2   
       
         
           
           
               
               
           
         
         b) group b, wherein group b is selected from the group consisting of repeated units of formula B1 to B8: 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         c) group c, wherein group c is selected from the group consisting of repeated units of formula C1 and C2: 
       
       
         
           
           
               
               
           
         
         d) group d, wherein group d is selected from the group consisting of repeated units of formula D1 and D2: 
       
       
         
           
           
               
               
           
         
         e) group e, wherein group e is selected from the group consisting of repeated units of formula E1 and E2: 
       
       
         
           
           
               
               
           
         
         wherein each AA is an amino-acid residue; 
         PEPTIDE is a peptide residue corresponding to a chain of amino acid residues bound by peptidic bonds; 
         Y is (CH 2 ) q , C 6 H 4 , C 6 H 4 —W—C 6 H 4 , C 6 F 4 , C 6 F 4 —W—C 6 F 4 , or C 10 H 6 ; 
         Z is (CH 2 ) p , C 6 H 4 , C 6 H 4 —W′—C 6 H 4 , C 6 F 4 , C 6 F 4 —W′—C 6 F 4 , or C 10 H 6 ; 
         PG(Nter) denotes the protected N terminus  of the AA or PEPTIDE; 
         and (Cter) denotes the C terminus  of AA PEPTIDE. 
       
     
     
         16 . The bioorganic nylon type polymer of  claim 15 , consisting of at least one group repeated units selected from group a, group c, group d, and/or group e. 
     
     
         17 . The bioorganic nylon type polymer of  claim 16 , wherein it is of the following formula (IA), (IC), (ID) or (IE): 
       
         
           
           
               
               
           
         
         wherein each AA is an amino-acid residue; 
         PEPTIDE is a peptide residue corresponding to a chain of amino acid residues bound by peptidic bonds; 
         Y is (CH 2 ) q , C 6 H 4 , C 6 H 4 —W—C 6 H 4 , C 6 F 4 , C 6 F 4 —W—C 6 F 4 , or C 10 H 6 ; 
         Z is (CH 2 ) p , C 6 H 4 , C 6 H 4 —W′—C 6 H 4 , C 6 F 4 , C 6 F 4 —W′—C 6 F 4 , or C 10 H 6 ; 
         PG(Nter) denotes the protected N terminus  of the AA or PEPTIDE; 
         (Cter) denotes the C terminus  of AA or PEPTIDE; m and m′ are independently selected from positive real numbers, for instance integers selected from 0 and 2000, 
         m and m′ may not be simultaneously 0, and 
         t is a positive integer from 1 to 2000. 
       
     
     
         18 . An antibacterial material comprising the bioorganic nylon type polymer of  claim 14 . 
     
     
         19 . A fabric comprising a bioorganic nylon type polymer of  claim 14 . 
     
     
         20 . An antibacterial material comprising the bioorganic nylon type polymer of  claim 17 .