US2005124547A1PendingUtilityA1

Tau-conotoxin peptides

48
Assignee: COGNETIX INCPriority: Feb 4, 1999Filed: Jul 16, 2003Published: Jun 9, 2005
Est. expiryFeb 4, 2019(expired)· nominal 20-yr term from priority
A61P 43/00A61P 25/06A61P 25/00A61K 38/00A61P 25/04A61P 29/00C07K 14/43504
48
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Claims

Abstract

The invention relates to relatively short peptides (termed τ-conotoxins herein), about 10-25 residues in length, which are naturally available in minute amounts in the venom of the cone snails or analogous to the naturally available peptides, and which preferably include two disulfide bonds.

Claims

exact text as granted — not AI-modified
1 . A substantially pure τ-conotoxin peptide selected from the group consisting of:  
       
         
           
                 
                 
                 
               
                     
                 
                   Phe-Cys-Cys-Xaa 1 -Val-Ile-Arg-Xaa 2 -Cys-Cys-Xaa 3 ; 
                   (SEQ ID NO: 2) 
                     
                 
                     
                 
                   Cys-Cys-Gln-Thr-Phe-Xaa 2 -Xaa 3 -Cys-Cys-Gln; 
                   (SEQ ID NO: 4) 
                 
                     
                 
                   Xaa 4 -Gly-Xaa 3 -Cys-Cys-Xaa 5 -Xaa 6 -Asn-Ile-Ala-Cys-Cys- 
                   (SEQ ID NO: 5) 
                 
                     
                 
                   Ile; 
                 
                     
                 
                   Gly-Cys-Cys-Ala-Arg-Leu-Thr-Cys-Cys-Val; 
                   (SEQ ID NO: 6) 
                 
                     
                 
                   Asn-Gly-Cys-Cys-Xaa 1 -Xaa 5 -Gln-Met-Arg-Cys-Cys-Thr; 
                   (SEQ ID NO: 7) 
                 
                     
                 
                   Asp-Xaa 3 -Asn-Ser-Cys-Cys-Gly-Xaa 5 -Asn-Xaa 1 -Gly-Cys- 
                   (SEQ ID NO: 8) 
                 
                     
                 
                   Cys-Xaa 1 -Xaa 3 ; 
                 
                     
                 
                   Xaa 4 -Gly-Xaa 3 -Cys-Cys-Xaa 5 -Xaa 6 -Asn-Ile-Arg-Cys-Cys- 
                   (SEQ ID NO: 9) 
                 
                     
                 
                   Val; 
                 
                     
                 
                   Xaa 6 -Cys-Cys-Xaa 6 -Asp-Gly-Xaa 3 -Cys-Cys-Thr-Ala-Ala- 
                   (SEQ ID NO: 10) 
                 
                     
                 
                   Xaa 1 -Leu-Thr; 
                 
                     
                 
                   Gly-Cys-Cys-Xaa 6 -Asp-Gly-Xaa 3 -Cys-Cys-Thr-Ala-Ala- 
                   (SEQ ID NO: 11) 
                 
                     
                 
                   Xaa 1 -Leu-Thr; 
                 
                     
                 
                   Asn-Gly-Cys-Cys-Arg-Ala-Gly-Asp-Cys-Cys-Ser-Arg-Phe- 
                   (SEQ ID NO: 12) 
                 
                     
                 
                   Xaa 6 -Ile-Xaa 5 -Xaa 6 -Asn-Asp-Phe; 
                 
                     
                 
                   Asn-Ala-Cys-Cys-Ile-Val-Arg-Gln-Cys-Cys; 
                   (SEQ ID NO: 13) 
                 
                     
                 
                   Asn-Gly-Cys-Cys-Arg-Ala-Gly-Asp-Cys-Cys-Ser; 
                   (SEQ ID NO: 14) 
                 
                     
                 
                   Cys-Cys-Xaa 1 -Arg-Arg-Leu-Ala-Cys-Cys-Ile-Ile; 
                   (SEQ ID NO: 15) 
                 
                     
                 
                   Cys-Cys-Xaa 1 -Asn-Xaa 5 -Xaa 1 -Cys-Cys-Phe-Ile; 
                   (SEQ ID NO: 16) 
                 
                     
                 
                   Gly-Cys-Cys-Ala-Met-Leu-Thr-Cys-Cys-Val; 
                   (SEQ ID NO: 17) 
                 
                     
                 
                   Leu-Cys-Cys-Val-Thr-Xaa 6 -Asp-Xaa 3 -Cys-Cys-Xaa 6 -Xaa 3 - 
                   (SEQ ID NO: 18) 
                 
                     
                 
                   Xaa 3 ; 
                 
                   and 
                 
                     
                 
                   Val-Cys-Cys-Arg-Xaa 1 -Val-Gln-Asp-Cys-Cys-Ser; 
                   (SEQ ID NO: 19) 
                 
                     
                 
             
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
         wherein Xaa 1  is Pro or hydroxy-Pro; Xaa 2  is Tyr, mono-halo-Tyr, di-halo-Tyr, O-sulpho-Tyr, O-phospho-Tyr or nitro-Tyr; Xaa 3  is Trp or halo-Trp; Xaa 4  is Gln or pyro-Glu; Xaa 5  is Lys, N-methyl-Lys, N,N-dimethyl-Lys or N,n,N-trimethyl-Lys, Xaa 6  is Glu or gamma-carboxy-Glu (Gla);  
         and the C-terminus contains a carboxyl or amide group.  
       
     
     
         2 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein Xaa 6  is Glu.  
     
     
         3 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein Xaa 5  is Lys.  
     
     
         4 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein Xaa 4  is Gln.  
     
     
         5 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein Xaa 2  is mono-iodo-Tyr.  
     
     
         6 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein Xaa 2  is di-iodo-Tyr.  
     
     
         7 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:2, wherein Xaa 1  is Pro, Xaa 2  is Tyr and Xaa 3  is Trp.  
     
     
         8 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:4, wherein Xaa 2  is Tyr and Xaa 3  is Trp.  
     
     
         9 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:5, wherein wherein Xaa 3  is Trp, Xaa 4  is Gln, Xaa 5  is Lys and Xaa 6  is Glu.  
     
     
         10 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO: 6.  
     
     
         11 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:7, wherein Xaa 1  is Pro and Xaa 5  is Lys.  
     
     
         12 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:8, wherein Xaa 1  is Pro, Xaa 3  is Trp and Xaa 5  is Lys.  
     
     
         13 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:9, wherein Xaa 3  is Trp, Xaa 4  is Gln, Xaa 5  is Lys and Xaa 6  is Glu.  
     
     
         14 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:10, wherein Xaa 1  is Pro, Xaa 3  is Trp and Xaa 6  is Glu.  
     
     
         15 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:11, wherein Xaa 1  is Pro, Xaa 3  is Trp and Xaa 6  is Glu.  
     
     
         16 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:12, wherein Xaa 5  is Lys and Xaa 6  is Glu.  
     
     
         17 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:13.  
     
     
         18 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:14.  
     
     
         19 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:15, wherein Xaa 1  is Pro.  
     
     
         20 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:16, wherein Xaa 1  is Pro and Xaa 5  is Lys.  
     
     
         21 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:17.  
     
     
         22 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:18, wherein Xaa 3  is Trp and Xaa 6  is Glu.  
     
     
         23 . The substantially pure τ-conotoxin peptide of  claim 1 , wherein said peptide has the sequence set forth in SEQ ID NO:19, wherein Xaa 1  is Pro.  
     
     
         24 . A method for inducing analgesia in an individual which comprises administering an effective amount of a substantially pure τ-conotoxin peptide having the generic formula I: Xaa 1 -Xaa 2 -Xaa 3 -Xaa 4 -Cys-Cys-Xaa 5 -Xaa 6 -Xaa 7 -Xaa 8 -Xaa 9 -Cys-Cys-Xaa 10 -Xaa 11 -Xaa 12 -Xaa 13 -Xaa 14 -Xaa 15 -Xaa 16 -Xaa 17 -Xaa 18 -Xaa 19  (SEQ ID NO:1), wherein Xaa 1  is des-Xaa 1 , Asp, Glu or γ-carboxy-Glu (Gla); Xaa 2  is des-Xaa 2 , Gln, Asn, Glu, Trp (D or L), neo-Trp, halo-Trp or any unnatural aromatic amino acid; Xaa 3  is des-Xaa 3 , Gly, Ala, Asn or Gln; Xaa 4  is des-Xaa 4 ,Val, Leu (D or L), Ile, Ala, Gly, Glu, Gla, Asp, Ser, Thr, Phe, Trp (D or L), neo-Trp, halo-Trp (D or L) or any unnatural aromatic amino acid; Xaa 5  is Pro, hydroxy-Pro, Gln, Asn, Glu, Gla, Ala, Gly, Lys, Arg, Ile, Val, homoarginine, ornithine, N-methyl-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys or any unnatural basic amino acid; Xaa 6  is Val, Phe, Thr, Ser, Glu, Gla, Asp, Asn, Gln, Ala, Gly, Ile, Leu (D or L), Met, Pro, hydroxy-Pro, Arg, homoarginine, ornithine, Lys, N-methyl-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, any unnatural basic amino acid or any unnatural aromatic amino acid; Xaa 7  is any Val, Ile, Asn, Leu (D or L), Gln, Gly, Ala, Phe, Glu, Gla, Arg, ornithine, homoarginine, Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, any unnatural basic amino acid or any unnatural aromatic amino acid; Xaa 8  is Ile, Leu (D or L), Met, Thr, Ser, Pro, hydroxy-Pro, Gln, Asp, Glu, Gla, Asn, Arg, homoarginine, ornithine, Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, Tyr, nor-Tyr, mono-halo-Tyr, di-halo-Tyr, O-sulpho-Tyr, O-phospho-Tyr, nitro-Tyr, any unnatural basic amino acid, any unnatural aromatic amino acid or any unnatural hydroxy containing amino acid; Xaa 9  is des-Xaa 9 , Ala, Gly, Asp, Glu, Gla, Trp (D or L) neo-Trp, halo-Trp (D or L), Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, Arg, homoarginine, ornithine, Tyr, nor-Tyr, mono-halo-Tyr, di-halo-Tyr, O-sulpho-Tyr, O-phospho-Tyr, nitro-Tyr or any unnatural basic amino acid; Xaa 10  is des-Xaa 10 , Ile, Leu (D or L), Val, Glu, Gla, Asp, Thr, Ser, Pro, hydroxy-Pro, Trp (D or L), neo-Trp, halo-Trp (D or L), Phe, any unnatural aromatic amino acid or any unnatural hydroxy containing amino acid; Xaa 11  is des-Xaa 11 , Gln, Asn, Leu (D or L), Ile, Val, Ala, Gly, Trp (D or L), neo-Trp, halo-Trp (D or L)′, Arg, homoarginine, ornithine, Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, any unnatural basic amino acid or any unnatural aromatic amino acid; Xaa 12  is des-Xaa 12 , Ala, Gly, Phe, Trp (D or L), neo-Trp, halo-Trp (D or L) or any unnatural aromatic amino acid; Xaa 13  is des-Xaa 13 , Glu, Gla, Asp, Phe or any unnatural aromatic amino acid; Xaa 14  is des-Xaa 14 , Ile, Val or Leu (D or L); Xaa 15  is des-Xaa 15 , Thr, Ser, Arg, homoarginine, ornithine, Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys or any unnatural basic amino acid; Xaa 16  is des-Xaa 16 , Glu, Gla or Asp; Xaa 17  is des-Xaa 17 , Asn or Gln; Xaa 18  is des-Xaa 18 , Asp, Glu or Gla; Xaa 19  is des-Xaa 19 , Phe or any unnatural aromatic amino acid; and the C-terminus contains a free carboxyl group or an amide group.  
     
     
         25 . A method for inducing analgesia in an individual which comprises administering an effective amount of the τ-conotoxin peptide of  claim 1 .  
     
     
         26 . The method of  claim 24 , wherein the substantially pure τ-conotoxin peptide is modified to contain an O-glycan, an S-glycan or an N-glycan.  
     
     
         27 . The method of  claim 25 , wherein the substantially pure τ-conotoxin peptide is modified to contain an O-glycan, an S-glycan or an N-glycan.  
     
     
         28 . A method for inducing analgesia in an individual which comprises administering an effective amount of a pharmaceutical composition comprising a τ-conotoxin peptide or a pharmaceutically acceptable salt thereof and a pharmaceutically acceptable carrier, said τ-conotoxin peptide having the generic formula I: Xaa 1 -Xaa 2 -Xaa 3 -Xaa 4 -Cys-Cys-Xaa 5 -Xaa 6 -Xaa 7 -Xaa 8 -Xaa 9 -Cys-Cys-Xaa 10 -Xaa 11 -Xaa 12 -Xaa 13 -Xaa 14 -Xaa 15 -Xaa 16 -Xaa 17 -Xaa 18 -Xaa 19  (SEQ ID NO:1), wherein Xaa 1  is des-Xaa 1 , Asp, Glu or γ-carboxy-Glu (Gla); 
 Xaa 2  is des-Xaa 2 , Gln, Asn, Glu, Trp (D or L), neo-Trp, halo-Trp or any unnatural aromatic amino acid; Xaa 3  is des-Xaa 3 , Gly, Ala, Asn or Gln; Xaa 4  is des-Xaa 4 ,Val, Leu (D or L), Ile, Ala, Gly, Glu, Gla, Asp, Ser, Thr, Phe, Trp (D or L), neo-Trp, halo-Trp (D or L) or any unnatural aromatic amino acid; Xaa 5  is Pro, hydroxy-Pro, Gln, Asn, Glu, Gla, Ala, Gly, Lys, Arg, Ile, Val, homoarginine, ornithine, N-methyl-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys or any unnatural basic amino acid; Xaa 6  is Val, Phe, Thr, Ser, Glu, Gla, Asp, Asn, Gln, Ala, Gly, Ile, Leu (D or L), Met, Pro, hydroxy-Pro, Arg, homoarginine, ornithine, Lys, N-methyl-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, any unnatural basic amino acid or any unnatural aromatic amino acid; Xaa 7  is any Val, Ile, Asn, Leu (D or L), Gln, Gly, Ala, Phe, Glu, Gla, Arg, ornithine, homoarginine, Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, any unnatural basic amino acidorany unnatural aromatic amino acid; Xaa 8  is Ile, Leu (D or L), Met, Thr, Ser, Pro, hydroxy-Pro, Gln, Asp, Glu, Gla, Asn, Arg., homoarginine, ornithine, Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, Tyr, nor-Tyr, mono-halo-Tyr, di-halo-Tyr, O-sulpho-Tyr, O-phospho-Tyr, nitro-Tyr, any unnatural basic amino acid, any unnatural aromatic amino acid or any unnatural hydroxy containing amino acid; Xaa 9  is des-Xaa 9 , Ala, Gly, Asp, Glu, Gla, Trp (D or L) neo-Trp, halo-Trp (D or L), Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, Arg, homoarginine, ornithine, Tyr, nor-Tyr, mono-halo-Tyr, di-halo-Tyr, O-sulpho-Tyr, O-phospho-Tyr, nitro-Tyr or any unnatural basic amino acid; Xaa 10  is des-Xaa 10 , Ile, Leu (D or L), Val, Glu, Gla, Asp, Thr, Ser, Pro, hydroxy-Pro, Trp (D or L), neo-Trp, halo-Trp (D or L), Phe, any unnatural aromatic amino acid or any unnatural hydroxy containing amino acid; Xaa 11  is des-Xaa 11 , Gln, Asn, Leu (D or L), Ile, Val, Ala, Gly, Trp (D or L), neo-Trp, halo-Trp (D or L), Arg, homoarginine, ornithine, Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys, any unnatural basic amino acid or any unnatural aromatic amino acid; Xaa 12  is des-Xaa 12 , Ala, Gly, Phe, Trp (D or L), neo-Trp, halo-Trp (D or L) or any unnatural aromatic amino acid; Xaa 13  is des-Xaa 13 , Glu, Gla, Asp, Phe or any unnatural aromatic amino acid; Xaa 14  is des-Xaa 14 , Ile, Val or Leu (D or L); Xaa 15  is des-Xaa 15 , Thr, Ser, Arg, homoarginine, ornithine, Lys, N-methy-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys or any unnatural basic amino acid; Xaa 16  is des-Xaa 16 , Glu, Gla or Asp; Xaa 17  is des-Xaa 17 , Asn or Gln; Xaa 18  is des-Xaa 18 , Asp, Glu or Gla; Xaa 19  is des-Xaa 19 , Phe or any unnatural aromatic amino acid; and the C-terminus contains a free carboxyl group or an amide group.    
     
     
         29 . The method of  claim 28 , wherein the pharmaceutical composition is modified to contain an O-glycan, an S-glycan or an N-glycan.  
     
     
         30 . A method for inducing analgesia in an individual which comprises administering an effective amount of a pharmaceutical composition comprising a τ-conotoxin peptide or a pharmaceutically acceptable salt thereof and a pharmaceutically acceptable carrier, said τ-conotoxin peptide selected from the group consisting of:  
       
         
           
                 
                 
                 
               
                     
                 
                   Phe-Cys-Cys-Xaa 1 -Val-Ile-Arg-Xaa 2 -Cys-Cys-Xaa 3 ; 
                   (SEQ ID NO: 2) 
                     
                 
                     
                 
                   Phe-Cys-Cys-Xaa 1 -Phe-Ile-Arg-Xaa 2 -Cys-Cys-Xaa 3 ; 
                   (SEQ ID NO: 3) 
                 
                     
                 
                   Cys-Cys-Gln-Thr-Phe-Xaa 2 -Xaa 3 -Cys-Cys-Gln; 
                   (SEQ ID NO: 4) 
                 
                     
                 
                   Xaa 4 -Gly-Xaa 3 -Cys-Cys-Xaa 5 -Xaa 6 -Asn-Ile-Ala-Cys-Cys- 
                   (SEQ ID NO: 5) 
                 
                     
                 
                   Ile; 
                 
                     
                 
                   Gly-Cys-Cys-Ala-Arg-Leu-Thr-Cys-Cys-Val; 
                   (SEQ ID NO: 6) 
                 
                     
                 
                   Asn-Gly-Cys-Cys-Xaa 1 -Xaa 5 -Gln-Met-Arg-Cys-Cys-Thr; 
                   (SEQ ID NO: 7) 
                 
                     
                 
                   Asp-Xaa 3 -Asn-Ser-Cys-Cys-Gly-Xaa 5 -Asn-Xaa 1 -Gly-Cys- 
                   (SEQ ID NO: 8) 
                 
                     
                 
                   Cys-Xaa 1 -Xaa 3 ; 
                 
                     
                 
                   Xaa 4 -Gly-Xaa 3 -Cys-Cys-Xaa 5 -Xaa 6 -Asn-Ile-Arg-Cys-Cys- 
                   (SEQ ID NO: 9) 
                 
                     
                 
                   Val; 
                 
                     
                 
                   Xaa 6 -Cys-Cys-Xaa 6 -Asp-Gly-Xaa 3 -Cys-Cys-Thr-Ala-Ala- 
                   (SEQ ID NO: 10) 
                 
                     
                 
                   Xaa 1 -Leu-Thr; 
                 
                     
                 
                   Gly-Cys-Cys-Xaa 6 -Asp-Gly-Xaa 3 -Cys-Cys-Thr-Ala-Ala- 
                   (SEQ ID NO: 11) 
                 
                     
                 
                   Xaa 1 -Leu-Thr; 
                 
                     
                 
                   Asn-Gly-Cys-Cys-Arg-Ala-Gly-Asp-Cys-Cys-Ser-Arg-Phe- 
                   (SEQ ID NO: 12) 
                 
                     
                 
                   Xaa 6 -Ile-Xaa 5 -Xaa 6 -Asn-Asp-Phe; 
                 
                     
                 
                   Asn-Ala-Cys-Cys-Ile-Val-Arg-Gln-Cys-Cys; 
                   (SEQ ID NO: 13) 
                 
                     
                 
                   Asn-Gly-Cys-Cys-Arg-Ala-Gly-Asp-Cys-Cys-Ser; 
                   (SEQ ID NO: 14) 
                 
                     
                 
                   Cys-Cys-Xaa 1 -Arg-Arg-Leu-Ala-Cys-Cys-Ile-Ile; 
                   (SEQ ID NO: 15) 
                 
                     
                 
                   Cys-Cys-Xaa 1 -Asn-Xaa 5 -Xaa 1 -Cys-Cys-Phe-Ile; 
                   (SEQ ID NO: 16) 
                 
                     
                 
                   Gly-Cys-Cys-Ala-Met-Leu-Thr-Cys-Cys-Val; 
                   (SEQ ID NO: 17) 
                 
                     
                 
                   Leu-Cys-Cys-Val-Thr-Xaa 6 -Asp-Xaa 3 -Cys-Cys-Xaa 6 -Xaa 3 - 
                   (SEQ ID NO: 18) 
                 
                     
                 
                   Xaa 3 ; 
                 
                   and 
                 
                     
                 
                   Val-Cys-Cys-Arg-Xaa 1 -Val-Gln-Asp-Cys-Cys-Ser; 
                   (SEQ ID NO: 19) 
                 
                     
                 
             
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
       wherein Xaa 1  is Pro or hydroxy-Pro; Xaa 2  is Tyr, mono-halo-Tyr, di-halo-Tyr, O-sulpho-Tyr, O-phospho-Tyr or nitro-Tyr; Xaa 3  is Trp or halo-Trp; Xaa 4  is Gln or pyro-Glu; Xaa 5  is Lys, N-methyl-Lys, N,N-dimethyl-Lys or N,n,N-trimethyl-Lys, Xaa 6  is Glu or gamma-carboxy-Glu (Gla); and the C-terminus contains a carboxyl or amide group.  
     
     
         31 . The method of  claim 30 , wherein the pharmaceutical composition is modified to contain an O-glycan, an S-glycan or an N-glycan.

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