US2008058270A1PendingUtilityA1

Apolipoprotein A-I agonists and their use to treat dyslipidemic disorders

Assignee: DASSEUX JEAN-LOUISPriority: Sep 29, 1997Filed: Feb 9, 2007Published: Mar 6, 2008
Est. expirySep 29, 2017(expired)· nominal 20-yr term from priority
A61P 43/00A61P 9/00A61P 9/10A61P 3/06A61P 3/04A61P 31/04A61P 3/00A61K 38/10A61K 38/16C07K 14/775A61K 38/00
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Claims

Abstract

The present invention provides peptides and peptide analogues that mimic the structural and pharmacological properties of human ApoA-I. The peptides and peptide analogues are useful to treat a variety of disorders associated with dyslipidemia.

Claims

exact text as granted — not AI-modified
1 . An ApoA-I agonist comprising: 
 (i) a 14 to 22-residue peptide or peptide analogue which forms an amphipathic α-helix in the presence of lipids and which comprises the structural formula (I):      Z 1 -X 1 —X 2 —X 3 —X 4 —X 5 —X 6 —X 7 —X 8 —X 9 —X 10 —X 11 —X 12 —X 13 —X 14 —X 15 —X 16 —X 17 —X 18      X 1  is Pro (P), Ala (A), Gly (G), Asn (N), Gln (Q) or D-Pro (p);    X 2  is an aliphatic amino acid;    X 3  is Leu (L);    X 4  is an acidic amino acid;    X 5  is Leu (L) or Phe (F);    X 6  is Leu (L) or Phe (F);    X 7  is a basic amino acid;    X 8  is an acidic amino acid;    X 9  is Leu (L) or Trp (W);    X 10  is Leu (L) or Trp (W);    X 11  is an acidic amino acid or Asn (N);    X 12  is an acidic amino acid;    X 13  is Leu (L), Trp (W) or Phe (F);    X 14  is a basic amino acid or Leu (L);    X 15  is Gln (Q) or Asn (N);    X 16  is a basic amino acid;    X 17  is Leu (L);    X 18  is a basic amino acid;    Z 1  is H 2 N— or RC(O)NH—;    Z 2  is —C(O)NRR, —C(O)OR or —C(O)OH or a salt thereof;    each R is independently —H, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkenyl, (C 1 -C 6 ) alkynyl, (C 5 -C 20 ) aryl, (C 6 -C 26 ) alkaryl, 5-20 membered heteroaryl or 6-26 membered alkheteroaryl or a 1 to 4-residue peptide or peptide analogue;    each “—” between residues X n  independently designates an amide linkage, a substituted amide linkage, an isostere of an amide or an amide mimetic; or    (ii) a deleted from of structural formula (I) in which at least one and up to eight of residues X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17  and X 18  are deleted; or    (iii) an altered form of structural formula (I) in which at least one of residues X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17  or X 18  is conservatively substituted with another residue.    
     
     
         2 . The ApoA-I agonist of  claim 1  which exhibits at least about 38% LCAT-activation activity as compared with human ApoA-I.  
     
     
         3 . The ApoA-I agonist of  claim 1  which is the altered form of structural formula (I).  
     
     
         4 . The ApoA-I agonist of  claim 3  in which the hydrophobic residues are fixed according to structural formula (I) and at least one non-fixed residue is conservatively substituted with another residue.  
     
     
         5 . The ApoA-I agonist of  claim 4  in which: 
 X 1  is Pro (P), D-Pro (p), Gly (G), Asn (N) or Ala (A);    X 2  is Ala (A), Leu (L) or Val (V);    X 3  is Leu (L);    X 5  is Leu (L) or Phe (F);    X 6  is Leu (L) or Phe (F);    X 9  is Leu (L) or Trp (W);    X 10  is Leu (L) or Trp (W);    X 13  is Leu (L), Trp (W) or Phe (F);    X 17  is Leu (L); and    at least one of X 4 , X 7 , X 8 , X 11 , X 12 , X 14 , X 15 , X 16  and X 18  is conservatively substituted with another residue.    
     
     
         6 . The ApoA-I agonist of  claim 3  in which the hydrophilic residues are fixed according to structural formula (I) and at least one non-fixed residue is conservatively substituted with another residue.  
     
     
         7 . The ApoA-I agonist of  claim 6  in which: 
 X 4  is Asp (D) or Glu (E);    X 7  is Arg (R), Lys (K) or Orn;    X 8  is Asp (D) or Glu (E);    X 11  is Asn (N) or Glu (E);    X 12  is Glu (E);    X 14  is Lys (K), Arg (R) or Orn;    X 15  is Gln (Q) or Asn (N);    X 16  is Lys (K), Arg (R) or Orn;    X 18  is Asn (N) or Gln (Q); and    at least one of X 1 , X 2 , X 3 , X 5 , X 6 , X 9 , X 10 , X 13  and X 17  is conservatively substituted with another residue.    
     
     
         8 . The ApoA-I agonist of  claim 6  in which X 3  is Leu (L), X 6  is Phe (F), X 9  is Leu (L) or Trp (W), X 10  is Leu (L) or Trp (W) and at least one of X 1 , X 2 , X 5 , X 13  and X 17  is conservatively substituted with another residue.  
     
     
         9 . The ApoA-I agonist of  claim 5  or  7  in which the substituting residue is classified within the same sub-category as the substituted residue.  
     
     
         10 . The ApoA-I agonist of  claim 1  which is the deleted form of structural formula (I).  
     
     
         11 . The ApoA-I agonist of  claim 10  in which one helical turn of the peptide or peptide analogue is deleted.  
     
     
         12 . The ApoA-I agonist of  claim 1  which is an 18-residue peptide or peptide analogue of structural formula (I).  
     
     
         13 . The ApoA-I agonist of  claim 12  in which: 
 the “—” between residues designates —C(O)NH—;    Z 1  is H 2 N—; and    Z 2  is —C(O)OH or a salt thereof.    
     
     
         14 . The ApoA-I agonist of  claim 13 , in which: 
 X 1  is Pro (P), Ala (A), Gly (G), Asn (N) or D-Pro (p);    X 2  is Ala (A), Val (V) or Leu (L);    X 3  is Leu (L);    X 4  is Asp (D) or Glu (E);    X 5  is Leu (L) or Phe (F);    X 6  is Leu (L) or Phe (F);    X 7  is Arg (R), Lys (K) or Orn;    X 8  is Asp (D) or Glu (E);    X 9  is Leu (L) or Trp (W);    X 10  is Leu (L) or Trp (W);    X 11  is Glu (E) or Asn (N);    X 12  is Glu (E);    X 13  is Leu (L), Trp (W) or Phe (F);    X 14  is Arg (R), Lys (K) or Orn;    X 15  is Gln (Q) or Asn (N);    X 16  is Arg (R), Lys (K) or Orn;    X 17  is Leu (L); and    X 18  is Arg (R), Lys (K) or Orn.    
     
     
         15 . The ApoA-I agonist of  claim 1  which is selected from the group consisting of:  
       
         
           
                 
                 
                 
                 
               
                     
                     
                 
                     
                   peptide 191 
                     
                     
                 
                     
                   PVLDLLRELLEELKQKLK*; 
                   (SEQ ID NO:191) 
                 
                     
                     
                 
                     
                   peptide 192 
                 
                     
                   PVLDLFKELLEELKQKLK*; 
                   (SEQ ID NO:192) 
                 
                     
                     
                 
                     
                   peptide 193 
                 
                     
                   PVLDLFRELLEELKQKLK*; 
                   (SEQ ID NO:193) 
                 
                     
                     
                 
                     
                   peptide 194 
                 
                     
                   PVLELFRELLEELKQKLK*; 
                   (SEQ ID NO:194) 
                 
                     
                     
                 
                     
                   peptide 195 
                 
                     
                   PVLELFKELLEELKQKLK*; 
                   (SEQ ID NO:195) 
                 
                     
                     
                 
                     
                   peptide 196 
                 
                     
                   PVLDLFRELLEELKNKLK*; 
                   (SEQ ID NO:196) 
                 
                     
                     
                 
                     
                   peptide 197 
                 
                     
                   PLLDLFRELLEELKQKLK*; 
                   (SEQ ID NO:197) 
                 
                     
                     
                 
                     
                   peptide 198 
                 
                     
                   GVLDLFRELLEELKQKLK*; 
                   (SEQ ID NO:198) 
                 
                     
                     
                 
                     
                   peptide 199 
                 
                     
                   PVLDLFRELWEELKQKLK*; 
                   (SEQ ID NO:199) 
                 
                     
                     
                 
                     
                   peptide 200 
                 
                     
                   NVLDLFRELLEELKQKLK*; 
                   (SEQ ID NO:200) 
                 
                     
                     
                 
                     
                   peptide 201 
                 
                     
                   PLLDLFKELLEELKQKLK*; 
                   (SEQ ID NO:201) 
                 
                     
                     
                 
                     
                   peptide 202 
                 
                     
                   PALELFKDLLEELRQKLR*; 
                   (SEQ ID NO:202) 
                 
                     
                     
                 
                     
                   peptide 203 
                 
                     
                   AVLDLFRELLEELKQKLK*; 
                   (SEQ ID NO:203) 
                 
                     
                     
                 
                     
                   peptide 204 
                 
                     
                   PVLDFFRELLEELKQKLK*; 
                   (SEQ ID NO:204) 
                 
                     
                     
                 
                     
                   peptide 205 
                 
                     
                   PVLDLFREWLEELKQKLK*; 
                   (SEQ ID NO:205) 
                 
                     
                     
                 
                     
                   peptide 206 
                 
                     
                   PLLELLKELLEELKQKLK*; 
                   (SEQ ID NO:206) 
                 
                     
                     
                 
                     
                   peptide 207 
                 
                     
                   PVLELLKELLEELKQKLK*; 
                   (SEQ ID NO:207) 
                 
                     
                     
                 
                     
                   peptide 208 
                 
                     
                   PALELFKDLLEELRQRLK*; 
                   (SEQ ID NO:208) 
                 
                     
                     
                 
                     
                   peptide 209 
                 
                     
                   PVLDLFRELLNELLQKLK; 
                   (SEQ ID NO:209) 
                 
                     
                     
                 
                     
                   peptide 210 
                 
                     
                   PVLDLFRELLEELKQKLK; 
                   (SEQ ID NO:210) 
                 
                     
                     
                 
                     
                   peptide 211 
                 
                     
                   PVLDLFRELLEELOQOLO*; 
                   (SEQ ID NO:211) 
                 
                     
                     
                 
                     
                   peptide 212 
                 
                     
                   PVLDLFOELLEELOQOLK*; 
                   (SEQ ID NO:212) 
                 
                     
                     
                 
                     
                   peptide 213 
                 
                     
                   PALELFKDLLEEFRQRLK*; 
                   (SEQ ID NO:213) 
                 
                     
                     
                 
                     
                   peptide 214 
                 
                     
                   pVLDLFRELLEELKQKLK*; 
                   (SEQ ID NO:214) 
                 
                     
                     
                 
                     
                   peptide 215 
                 
                     
                   PVLDLFRELLEEWKQKLK*; 
                   (SEQ ID NO:215) 
                 
                     
                     
                 
                     
                   peptide 229 
                 
                     
                   PVLELFERLLEDLQKKLK; 
                   (SEQ ID NO:229) 
                 
                     
                     
                 
                     
                   peptide 230 
                 
                     
                   PVLDLFRELLEKLEQKLK; 
                   (SEQ ID NO:230) 
                 
                     
                     
                 
                     
                   peptide 231 
                 
                     
                   PLLELFKELLEELKQKLK*; 
                   (SEQ ID NO:231) 
                 
                     
                     
                 
             
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
         in either the N- and/or C-terminal blocked or unblocked forms.  
       
     
     
         16 . A multimeric ApoA-I agonist which exhibits at least about 38% LCAT activation activity as compared with human ApoA-I and which has the structural formula (II):  
         HH LL m -HH   n LL m -HH  (II)  or a pharmaceutically acceptable salt thereof, wherein: 
 each m is independently an integer from 0 to 1;  
 n is an integer from 0 to 10;  
 each “HH” is independently a peptide or peptide analogue according to  claim 1;   
 each I“LL” is independently a bifunctional linker; and  
 each “-” independently designates a covalent linkage.  
   
     
     
         17 . A multimeric ApoA-I agonist which exhibits at least about 38% LCAT activation activity as compared with human ApoA-I and which has the structural formula (III):  
         X—N ya —X (ya-1)   N yb —X (yb-1) ) p   (III)  
       or a pharmaceutically acceptable salt thereof, wherein: 
 each X is independently HH LL m -HH   n LL m -HH;  
 each HH is independently a core peptide of structure (I) or an analogue or mutated, truncated, internally deleted or extended form thereof as described herein;  
 each LL is independently a bifunctional linker;  
 each m is independently an integer from 0 to 1;  
 each n is independently an integer from 0 to 8;  
 N ya  and N yb  are each independently a multifunctional linking moiety where y a  and y b  represent the number of functional groups on N ya  and N yb , respectively;  
 each y a  or y b  is independently an integer from 3 to 8;  
 p is an integer from 0 to 7; and  
 each “-” independently designates a covalent bond.  
 
     
     
         18 . A multimeric ApoA-I agonist which exhibits at least about 38% LCAT activation activity as compared with human ApoA-I and which has the structural formula (IV) or (V):  
       
         
           
           
               
               
           
         
         or a pharmaceutically acceptable salt thereof, wherein: 
 each X is independently HH LL m -HH   n LL m -HH;  
 each HH is independently a peptide or peptide analogue according to  claim 1;   
 each LL is independently a bifunctional linker;  
 each n is independently an integer from 0 to 1;  
 each m is independently an integer from 0 to 8;  
 R 1  is —OR or —NRR; and  
 each R is independently —H, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkenyl, (C 1 -C 6 ) alkynyl; (C 5 -C 20 ) aryl (C 6 -C 26 ) alkaryl, 5-20 membered heteroaryl or 6-26 membered alkheteroaryl.  
 
       
     
     
         19 . The multimeric ApoA-I agonist of  claim 16 ,  17  or  18  in which the bifunctional linker is cleavable.  
     
     
         20 . The ApoA-I multimeric agonist of  claim 16 ,  17  or  18  in which n is 0.  
     
     
         21 . The multimeric ApoA-I agonist of  claim 20  in which m is 0.  
     
     
         22 . The multimeric ApoA-I agonist of  claim 16 ,  17  or  18  in which each HH is independently a peptide according to  claim 13 .  
     
     
         23 . The multimeric ApoA-I agonist of  claim 16 ,  17  or  18  in which each HH is independently a peptide according to  claim 14 .  
     
     
         24 . The multimeric ApoA-I agonist of  claim 16 ,  17  or  18  in which each HH is independently a peptide according to  claim 15 .  
     
     
         25 . An ApoA-I agonist-lipid complex comprising an ApoA-I agonist and a lipid, wherein the ApoA-I agonist is a peptide or peptide analogue according to  claim 1 , a multimeric ApoA-I agonist according to  claim 16 , a multimeric ApoA-I agonist according to  claim 17 , or a multimeric ApoA-I agonist according to  claim 18 .  
     
     
         26 . The ApoA-I agonist-lipid complex of  claim 25  in which the ApoA-I agonist is a peptide according to  claim 12 .  
     
     
         27 . The ApoA-I agonist-lipid complex of  claim 25  in which the ApoA-I agonist is a peptide according to  claim 13 .  
     
     
         28 . The ApoA-I agonist-lipid complex of  claim 25  in which the ApoA-I agonist is a peptide according to  claim 14 .  
     
     
         29 . The ApoA-I agonist-lipid complex of  claim 25  in which the ApoA-I agonist is a peptide according to  claim 15 .  
     
     
         30 . The ApoA-I agonist-lipid complex of  claim 25  in which the lipid is sphingomyelin.  
     
     
         31 . The ApoA-I agonist-lipid complex of  claim 25  which is in the form of a lyophilized powder.  
     
     
         32 . The ApoA-I agonist-lipid complex of  claim 25  which is in the form of a solution.  
     
     
         33 . A pharmaceutical composition comprising an ApoA-I agonist and a pharmaceutically acceptable carrier, excipient or diluent, wherein the ApoA-I agonist is a peptide or peptide analogue according to  claim 1 , a multimeric ApoA-I agonist according to  claim 16 , a multimeric ApoA-I agonist according to  claim 17 , or a multimeric ApoA-I agonist according to  claim 18 .  
     
     
         34 . The pharmaceutical composition of  claim 33  in which the ApoA-I agonist is a peptide according to  claim 12 .  
     
     
         35 . The pharmaceutical composition of  claim 33  in which the ApoA-I agonist is a peptide according to  claim 13 .  
     
     
         36 . The pharmaceutical composition of  claim 33  in which the ApoA-I agonist is a peptide according to  claim 14 .  
     
     
         37 . The pharmaceutical composition of  claim 33  in which the ApoA-I agonist is a peptide according to  claim 15 .  
     
     
         38 . The pharmaceutical composition of  claim 33 ,  34 ,  35 ,  36  or  37 , in which the ApoA-I agonist is in the form of an ApoA-I agonist-lipid complex, said complex comprising the ApoA-I agonist and a lipid.  
     
     
         39 . The pharmaceutical composition of  claim 38  in which the ApoA-I agonist-lipid complex is in the form of a lyophilized powder.  
     
     
         40 . A method of treating a subject suffering from a disorder associated with dyslipidemia, said method comprising the step of administering to the subject an effective amount of the ApoA-I agonist of  claim 1 .  
     
     
         41 . The method of  claim 40  in which the ApoA-I agonist is in the form of a pharmaceutical composition, said composition comprising the ApoA-I agonist and a pharmaceutically acceptable carrier, excipient or diluent.  
     
     
         42 . The method of  claim 40  in which the ApoA-I agonist is in the form of an ApoA-I agonist-lipid complex, said complex comprising the ApoA-I agonist and a lipid.  
     
     
         43 . The method of  claim 40  in which the disorder associated with dyslipidemia is hypercholesterolemia.  
     
     
         44 . The method of  claim 40  in which the disorder associated with dyslipidemia is cardiovascular disease.  
     
     
         45 . The method of  claim 40  in which the disorder associated with dyslipidemia is atherosclerosis.  
     
     
         46 . The method of  claim 40  in which the disorder associated with dyslipidemia is restenosis.  
     
     
         47 . The method of  claim 40 , in which the disorder associated with dyslipidemia is HDL or ApoA-I deficiency.  
     
     
         48 . The method of  claim 40 , in which the disorder associated with dyslipidemia is hypertriglyceridemia.  
     
     
         49 . The method of  claim 40 , in which the disorder associated with dyslipidemia is metabolic syndrome.  
     
     
         50 . A method of treating a subject suffering from septic shock, said method comprising the step of administering to the subject an effective amount of the ApoA-I agonist of  claim 1 .  
     
     
         51 . The method of  claim 40  or  50  in which said subject is a human.  
     
     
         52 . The method of  claim 40  or  50  in which about 0.5 mg/kg to about 100 mg/kg ApoA-I agonist is administered to said subject.

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