US2022348611A1PendingUtilityA1

Peptide pharmaceuticals

Assignee: MEDERIS DIABETES LLCPriority: Nov 20, 2012Filed: Sep 24, 2020Published: Nov 3, 2022
Est. expiryNov 20, 2032(~6.3 yrs left)· nominal 20-yr term from priority
Inventors:John J. Nestor
C07K 1/1077A61K 38/26A61K 38/07A61K 38/095A61K 38/08A61K 38/29C07K 7/06C09D 101/28A61K 38/00C07K 5/06078
66
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Claims

Abstract

Described herein are methods of syntheses and therapeutic uses of covalently modified peptides and/or proteins. The covalently modified peptides and/or proteins allow for improved pharmaceutical properties of peptide and protein-based therapeutics.

Claims

exact text as granted — not AI-modified
1 . A biologically active peptide product that binds to GLP-1 receptor (GLP1R) and/or glucagon receptor (GCGR) comprising a surfactant X covalently attached to a peptide, the peptide comprising a linker amino acid U and at least one other amino acid: 
       
         
           
           
               
               
           
         
         wherein X is 1-alkyl glycoside 
       
       
         
           
           
               
               
           
         
         
           wherein 
           A is a hydrophobic group which is a substituted or unsubstituted C 8 -C 30  alkyl group; and 
           B is a hydrophilic saccharide covalently attached to the peptide via a linker amino acid U. 
         
       
     
     
         2 . The peptide product of  claim 1 , wherein the peptide product is synthesized by reaction of a functionalized surfactant with the peptide. 
     
     
         3 . The peptide product of  claim 1 , wherein the 1-alkyl glycoside is an O-linked, S-linked, N-linked or C-linked alkyl glycoside. 
     
     
         4 . The peptide product of  claim 1 , wherein B is glucuronic acid. 
     
     
         5 . (canceled) 
     
     
         6 . (canceled) 
     
     
         7 . (canceled) 
     
     
         8 . The peptide product of  claim 1 , wherein the hydrophilic group in the surfactant X is attached to the peptide via an amide bond. 
     
     
         9 . The peptide product of  claim 1 , wherein the surfactant X comprises 1-eicosyl beta-D-glucuronic acid, 1-octadecyl beta-D-glucuronic acid, 1-hexadecyl beta-D-glucuronic acid, 1-tetradecylbeta D-glucuronic acid, 1-dodecyl beta D-glucuronic acid, 1-decyl beta-D-glucuronic acid, 1-octyl beta-D-glucuronic acid, 1-eicosyl beta-D-diglucuronic acid, 1-octadecyl beta-D-diglucuronic acid, 1-hexadecyl beta-D-diglucuronic acid, 1-tetradecyl beta-D-diglucuronic acid, 1-dodecyl beta-D-diglucuronic acid, 1-decyl beta-D-diglucuronic acid, 1-octyl beta-D-diglucuronic acid, 1-eicosyl beta-D-melibiouronic acid, 1-octadecyl beta-D-melibiouronic acid, 1-hexadecyl beta-D-melibiouronic acid, 1-tetradecyl beta-D-melibiouronic acid, 1-dodecyl beta-D-melibiouronic acid, 1-decyl beta-D-melibiouronic acid, 1-octyl beta-D-melibiouronic acid or functionalized 1-ecosyl beta-D-glucose, 1-octadecyl beta-D-glucose, 1-hexadecyl beta-D-glucose, 1-tetradecyl beta-D-glucose, 1-dodecyl beta-D-glucose, 1-decyl beta-D-glucose, 1-octyl beta-D-glucose, 1-eicosyl beta-D-maltoside, 1-octadecyl beta-D-maltoside, 1-hexadecyl beta-D-maltoside, 1-dodecyl beta-D-maltoside, 1-decyl beta-D-maltoside, 1-octyl beta-D-maltoside, 1-eicosyl beta-D-melibiose, 1-octadecyl beta-D-melibiose, 1-hexadecyl beta-D-melibiose, 1-tetradecyl beta-D-melibiose, 1-dodecyl beta-D-melibiose, 1-decyl beta-D-melibiose, or 1-octyl beta-D-melibiose. 
     
     
         10 . (canceled) 
     
     
         11 . The peptide product of  claim 1 , wherein the peptide product comprises a sequence selected from Formula 3-II: 
       
         
           
                 
                 
               
                     
                   Formula 3-II 
                 
                     
                   (SEQ. ID. NO. 303) 
                 
                     
                   aa 1 -aa 2 -aa 3 -aa 4 -aa 5 -aa 6 -aa 7 -aa 8 -aa 9 -aa 10 -aa 11 - 
                 
                     
                     
                 
                     
                   aa 12 -aa 13 -aa 14 -aa 15 -aa 16 -aa 17 -aa 18 -aa 19 -aa 20 -aa 21 - 
                 
                     
                     
                 
                     
                   aa 22 -aa 23 -aa 24 -aa 25 -aa 26 -aa 27 -aa 28 -aa 29 -aa 30 -aa 31 - 
                 
                     
                     
                 
                     
                   aa 32 -aa 33 -aa 34 -aa 35 -aa 36 -aa 37 -Z 
                 
             
                
                
                
                
                
                
                
                
                
               
            
           
         
         wherein:
 Z is OH, or —NH—R 3 , wherein R 3  is H or substituted or unsubstituted C 1 -C 12  alkyl, or a PEG chain of less than 10 Da; 
 aa 1  is His, N-Ac-His, pGlu-His, or N—R 3 -His; 
 aa 2  is Ser, Ala, Gly, Aib, Ac4c or Ac5c; 
 aa 3  is Gln, or Cit; 
 aa 4  is Gly, or D-Ala; 
 aa 5  is Thr, or Ser; 
 aa 6  is Phe, Trp, F2Phe, Me2Phe, or Nal2; 
 aa 7  is Thr, or Ser; 
 aa 8  is Ser, or Asp; 
 aa 9  is Asp, or Glu; 
 aa 10  is Tyr, Leu, Met, Nal2, Bip, or Bip2EtMeO; 
 aa 11  is Ser, Asn, or U; 
 aa 12  is Lys, Glu, Ser, Arg, or U; 
 aa 13  is absent or Tyr, Gln, Cit, or U; 
 aa 14  is absent or Leu, Met, Nle, or U; 
 aa 15  is absent or Asp, Glu, or U; 
 aa 16  is absent or Ser, Gly, Glu, Aib, Ac5c, Lys, Arg, or U; 
 aa 17  is absent or Arg, hArg, Gln, Glu, Cit, Aib, Ac4c, Ac5c, or U; 
 aa 18  is absent or Arg, hArg, Ala, Aib, Ac4c, Ac5c, or U; 
 aa 19  is absent or Ala, Val, Aib, Ac4c, Ac5c, or U; 
 aa 20  is absent or Gln, Lys, Arg, Cit, Glu, Aib, Ac4c, Ac5c, or U; 
 aa 21  is absent or Asp, Glu, Leu, Aib, Ac4c Ac5c, or U; 
 aa 22  is absent or Phe, Trp, Nal2, Aib, Ac4c, Ac5c, or U 
 aa 23  is absent or Val, Ile, Aib, Ac4c, Ac5c, or U; 
 aa 24  is absent or Gln, Ala, Glu, Cit, or U; 
 aa 25  is absent or Trp, Nal2, or U; 
 aa 26  is absent or Leu, or U; 
 aa 27  is absent or Met, Val, Nle, Lys, or U; 
 aa 28  is absent or Asn, Lys, or U; 
 aa 29  is absent or Thr, Gly, Aib, Ac4c, Ac5c, or U; 
 aa 30  is absent or Lys, Aib, Ac4c, Ac5c, or U; 
 aa 31  is absent or Arg, Aib, Ac4c, Ac5c, or U; 
 aa 32  is absent or Asn, Aib, Ac4c, Ac5c, or U; 
 aa 33  is absent or Arg, Aib, Ac4c, Ac5c, or U; 
 aa 34  is absent or Asn, Aib, Ac4c, Ac5c, or U; 
 aa 35  is absent or Asn, Aib, Ac4c, Ac5c, or U; 
 aa 36  is absent or Ile, Aib, Ac4c, Ac5C, or U; 
 aa 36  is absent or Ala, Aib, Ac4c, Ac5C, or U; 
 aa 37  absent or U; 
 U is a natural or unnatural amino acid comprising a functional group used for covalent attachment to the surfactant X; 
 
         wherein any two of aa 1 -aa 37  are optionally cyclized through their side chains to form a lactam linkage; and 
         provided that one, or at least one of aa 11 aa 37  is the linker amino acid U covalently attached to the surfactant X. 
       
     
     
         12 . A peptide product of  claim 1 , wherein the peptide product comprises a sequence selected from Formula 3-III-A: 
       
         
           
                 
                 
               
                     
                   Formula 3-III-A 
                 
                     
                   (SEQ. ID. NO. 304) 
                 
                     
                   aa 1 -aa 2 -aa 3 -aa 4 -aa 5 -aa 6 -aa 7 -aa 8 -aa 9 -aa 10 -aa 11 - 
                 
                     
                     
                 
                     
                   aa 12 -aa 13 -aa 14 -aa 15 -aa 16 -aa 17 -aa 18 -aa 19 -aa 20 -aa 21 - 
                 
                     
                     
                 
                     
                   aa 22 -aa 23 -aa 24 -aa 25 -aa 26 -aa 27 -aa 28 -aa 29 -Z 
                 
             
                
                
                
                
                
                
                
               
            
           
         
         wherein: 
         Z is OH, or —NH—R 3  , wherein R 3  is H, or C 1 -C 12  substituted or unsubstituted alkyl, or a PEG chain of less than 10 Da; 
         aa 1  is His, N-Ac-His, pGlu-His, or N—R 3 -His; 
         aa 2  is Ser, Ala, Gly, Aib, Ac4c, or Ac5c; 
         aa 3  is Gln, or Cit; 
         aa 4  is Gly, or D-Ala; 
         aa 5  is Thr, or Ser; 
         aa 6  is Phe, Trp, F2Phe, Me2Phe, or Nal2; 
         aa 7  is Thr, or Ser; 
         aa 8  is Ser, or Asp; 
         aa 9  is Asp, or Glu; 
         aa 10  is Tyr, Leu, Met, Nal2, Bip, or Bip2EtMeO; 
         aa 11  is Ser, Asn, or U; 
         aa 12  is Lys, Glu, Ser, Arg, or U(X); 
         aa 13  is absent or Tyr, Gln, Cit, or U(X); 
         aa 14  is absent or Leu, Met, Nle, or U(X); 
         aa 15  is absent or Asp, Glu, or U(X); 
         aa 16  is absent or Ser, Gly, Glu, Aib, Ac5c, Lys, Arg, or U(X); 
         aa 17  is absent or Arg, hArg, Gln, Glu, Cit, Aib, Ac4c, Ac5c, or U(X); 
         aa 18  is absent or Arg, hArg, Ala, Aib, Ac4c, Ac5c, or U(X); 
         aa 19  is absent or Ala, Val, Aib, Ac4c, Ac5c, or U(X); 
         aa 20  is absent or Gln, Lys, Arg, Cit, Glu, Aib, Ac4c, Ac5c, or U(X); 
         aa 21  is absent or Asp, Glu, Leu, Aib, Ac4c, Ac5c, or U(X); 
         aa 22  is absent or Phe, Trp, Nal2, Aib, Ac4c, Ac5c, or U(X); 
         aa 23  is absent or Val, Ile, Aib, Ac4c, Ac5c, or U(X); 
         aa 24  is absent or Gln, Ala, Glu, Cit, or U(X); 
         aa 25  is absent or Trp, Nal2, or U(X); 
         aa 26  is absent or Leu, or U(X); 
         aa 27  is absent or Met, Val, Nle, Lys, or U(X); 
         aa 28  is absent or Asn, Lys, or U(X); 
         aa 29  is absent or Thr, Gly, Aib, Ac4c, Ac5c, or U(X); 
         wherein any two of aa 1 -aa 26  are optionally cyclized through their side chains to form a lactam linkage; and 
         provided that one, or at least one of aa 16 , aa 17 , aa 18 , aa 19 , aa 20 , aa 21 , aa 22 , aa 23 , aa 24 , aa 25 , aa 26 , aa 27 , aa 28  or aa 29  is the linker amino acid U covalently attached to the surfactant X. 
       
     
     
         13 . The peptide product of  claim 1 , wherein the peptide product comprises a sequence selected from has a structure of Formula 3-III-B: 
       
         
           
                 
                 
               
                     
                   Formula 3-III-B 
                 
                     
                   (SEQ. ID. NO. 305) 
                 
                     
                   His 1 -aa 2 -aa 3 -Gly 4 -Thr 5 -aa 6 -Thr 7 -Ser 8 -Asp 9 -aa 10 - 
                 
                     
                     
                 
                     
                   aa 11 -aa 12 -aa 13 -aa 14 -aa 15 -aa 16 -aa 17 -aa 18 -aa 19 -aa 20 - 
                 
                     
                     
                 
                     
                   aa 21 -aa 22 -aa 23 -Z 
                 
             
                
                
                
                
                
                
                
               
            
           
         
         wherein: 
         Z is OH, or —NH—R 3  , wherein R 3  is H or substituted or unsubstituted C 1 -C 12  alkyl; or a PEG chain of less than 10 Da;
 aa 2  is Ser, Ala, Gly, Aib, Ac4c, or Ac5c; 
 aa 3  is Gln, or Cit; 
 aa 6  is Phe, Trp, F2Phe, Me2Phe, MePhe, or Nal2; 
 aa 10  is Tyr, Leu, Met, Nal2, Bip, or Bip2EtMeO; 
 aa 11  is Ser, Asn, or U(X); 
 aa 12  is Lys, Glu, Ser, or U(X); 
 aa 13  is absent or Tyr, Gln, Cit, or U(X); 
 aa 14  is absent or Leu, Met, Nle, or U(X); 
 aa 15  is absent or Asp, Glu, or U(X); 
 aa 16  is absent or Ser, Gly, Glu, Aib, Ac4c, Ac5c, Lys, R, or U(X); 
 aa 17  is absent or Arg, hArg, Gln, Glu, Cit, Aib, Ac4c, Ac5c, or U(X); 
 aa 18  is absent or Arg, hArg, Ala, Aib, Ac4c, Ac5c, or U(X); 
 aa 19  is absent or Ala, Val, Aib, Ac4c, Ac5c, or U(X); 
 aa 20  is absent or Gln, Lys, Arg, Cit, Glu, Aib, Ac4c, Ac5c, or U(X); 
 aa 21  is absent or Asp, Glu, Leu, Aib, Ac4c, Ac5c, or U(X); 
 aa 22  is absent or Phe, Aib, Ac4c, Ac5c, or U(X) 
 aa 23  is absent or Val, Ile, Aib, Ac4c, Ac5c, or U(X); 
 
         wherein any two of aa 1 -aa 23  are optionally cyclized through their side chains to form a lactam linkage; and
 provided that one, or at least one of aa 16 , aa 17 , aa 18 , aa 19 , aa 20 , aa 21 , aa 22 , aa 23  or aa 24  is the natural or unnatural amino acid U covalently attached to the surfactant X. 
 
       
     
     
         14 . A peptide product of  claim 1 , wherein the surfactant X has the structure: 
       
         
           
           
               
               
           
         
         wherein:
 A is a substituted or unsubstituted C 1 -C 20  alkyl chain; 
 R 1b , R 1c , and R 1d  are each, independently at each occurrence, H, a protecting group, or a substituted or unsubstituted C 1 -C 30  alkyl group; 
 W 1  is independently, at each occurrence, —CH 2 —, —CH 2 —O—, —(C═O), —(C═O)—O—, —(C═O)—NH—, —(C═S)—, —(C═S)—NH—, or —CH 2 —S—; 
 W 2  is —O— or —S—; 
 R 2  is a bond to U, C 2 -C 4 -alkene, C 2 -C 4 -alkyne, or —(CH 2 ) m -maleimide; and 
 m is 1-10. 
 
       
     
     
         15 . The peptide product of  claim 1 , wherein the surfactant X has the structure: 
       
         
           
           
               
               
           
         
       
     
     
         16 . The peptide product of  claim 1 , wherein the surfactant X has the structure: 
       
         
           
           
               
               
           
         
       
     
     
         17 . The peptide product of  claim 1 , wherein the surfactant X has the structure: 
       
         
           
           
               
               
           
         
         wherein:
 A is a substituted or unsubstituted C 8 -C 20  alkyl group; 
 R 1b , R 1c , and R 1d  are each, independently at each occurrence, H, a protecting group, or a substituted or unsubstituted C 1 -C 30  alkyl group; 
 W 1  is —(C═O)—NH—; 
 W 2  is —O—; 
 R 2  is a bond to U. 
 
       
     
     
         18 . The peptide product of  claim 1 , wherein X has the structure: 
       
         
           
           
               
               
           
         
         wherein:
 A is a substituted or unsubstituted C 8 -C 30  alkyl group; 
 R 1b , R 1c , and R 1d  are H; 
 W 1  is —(C═O)—NH—; 
 W 2  is —O—; and 
 R 2  is a bond to U. 
 
       
     
     
         19 . The peptide product of  claim 1 , wherein A is a substituted or unsubstituted C 8 -C 20  alkyl group. 
     
     
         20 - 37 . (canceled) 
     
     
         38 . A pharmaceutical composition comprising a therapeutically effective amount of a peptide product of  claim 1 , or pharmaceutically acceptable salt thereof, and at least one pharmaceutically acceptable carrier or excipient. 
     
     
         39 . (canceled) 
     
     
         40 . A method of inducing weigh loss comprising administering to a subject in need thereof a therapeutically effective amount of the peptide product of  claim 1 . 
     
     
         41 . A method of preparing the peptide product of  claim 1  wherein the peptide that binds to GLP-1 receptor (GLP1R) and/or glucagon receptor (GCGR) is synthesized using solid phase synthesis followed by acid-based deprotection and cleavage from a resin and purification by high performance liquid chromatography, wherein the surfactant X of  claim 1  is covalently attached to the peptide to form the peptide product. 
     
     
         42 - 47 . (canceled) 
     
     
         48 . A method of treating metabolic syndrome, comprising administering to a subject in need thereof a therapeutically effective amount of the peptide product of  claim 1 . 
     
     
         49 . The method of  claim 48 , wherein the therapeutically effective amount is from about 0.1 mg/kg/day to about 100.0 mg/kg/day, or from about 0.01 mg/kg/day to about 1 mg/kg/day or from about 0.1 mg/kg/day to about 50 mg/kg/day.

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