US2002107389A1PendingUtilityA1

Conjugates of chemically defined non-polymeric valency platform molecules and biologically active molecules

Priority: Jul 15, 1992Filed: Dec 29, 2000Published: Aug 8, 2002
Est. expiryJul 15, 2012(expired)· nominal 20-yr term from priority
A61K 39/35A61K 47/54A61K 2039/6093A61K 39/0008
56
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Claims

Abstract

Chemically-defined, non-polymeric valency platform molecules and conjugates comprising chemically-defined valency platform molecules and biological or chemical molecules including polynucleotide duplexes of at least 20 base pairs that have significant binding activity for human lupus anti-dsDNA autoantibodies.

Claims

exact text as granted — not AI-modified
We claim:  
     
         1 . A conjugate comprising (a) biological or chemical molecules reacted with (b) a chemically-defined, non-polymeric valency platform molecule of the formula:  
       
         
           
             
               
                 
                   
                     
                       
                         G 
                         
                           [ 
                           1 
                           ] 
                         
                       
                        
                       
                         
                           { 
                           
                             T 
                             
                               [ 
                               1 
                               ] 
                             
                           
                           } 
                         
                         
                           n 
                            
                           
                             [ 
                             1 
                             ] 
                           
                         
                       
                     
                      
                     
                       
 
                     
                      
                     or 
                   
                 
                 
                   
                     Formula 
                      
                     
                         
                     
                      
                     1 
                   
                 
               
               
                 
                   
                     
                       G 
                       
                         [ 
                         2 
                         ] 
                       
                     
                      
                     
                       
                         { 
                         
                           
                             L 
                             
                               [ 
                               2 
                               ] 
                             
                           
                           - 
                           
                             J 
                             
                               [ 
                               2 
                               ] 
                             
                           
                           - 
                           
                             
                               
                                 Z 
                                 
                                   [ 
                                   2 
                                   ] 
                                 
                               
                                
                               
                                 ( 
                                 
                                   T 
                                   
                                     [ 
                                     2 
                                     ] 
                                   
                                 
                                 ) 
                               
                             
                             
                               p 
                                
                               
                                 [ 
                                 2 
                                 ] 
                               
                             
                           
                         
                         } 
                       
                       
                         n 
                          
                         
                           [ 
                           2 
                           ] 
                         
                       
                     
                   
                 
                 
                   
                     Formula 
                      
                     
                         
                     
                      
                     2 
                   
                 
               
             
           
           
           
               
           
         
       
       wherein 
 each of G [1]  and G [2] , if present, is independently a linear, branched or multiply-branched chain comprising 1-2000 chain atoms selected from the group C, N, O, Si, P and S;  
 each of the n [1]  moieties shown as T [1]  and each of the p [2] ×n [2]  moieties shown as T [2]  is independently chosen from the group NHR SUB  (amine), C(═O)NHNHR SUB  (hydrazide), NHNHR SUB  (hydrazine), C(═O)OH (carboxylic acid), C(═O)OR ESTER  (activated ester), C(═O)OC(═O)R B  (anhydride), C(═O)X (acid halide), S(═O) 2 X (sulfonyl halide), C(═NR SUB )OR SUB  (imidate ester), NCO (isocyanate), NCS (isothiocyanate), OC(═O)X (haloformate), C(═O)OC(═NR SUB )NHR SUB  (carbodiimide adduct), C(═O)H (aldehyde), C(═O)R B  (ketone), SH (sulfhydryl or thiol), OH (alcohol), C(═O)CH 2 X (haloacetyl), R ALK X (alkyl halide), S(═O) 2 OR ALK X (alkyl sulfonate), NR 1 R 2  wherein R 1 R 2  is —C(═O)CH═CHC(═O)— (maleimide), C(═O)CR B ═CR B   2  (α,β-unsaturated carbonyl), R ALK —Hg—X (alkyl mercurial), and S(═O)CR B ═CR B   2  (α,β-unsaturated sulfone);  
  wherein 
 each X is independently a halogen of atomic number greater than 16 and less than 54 or other good leaving group;  
 each R ALK  is independently a linear, branched, or cyclic alkyl (1-20C) group;  
 each R SUB  is independently H, linear, branched, or cyclic alkyl (1-20C), aryl (6-20C), or alkaryl (7-30C);  
 each R ESTER  is independently N-hydroxysuccinimidyl, p-nitrophenoxy, pentafluorophenoxy, or other activating group;  
 each R B  is independently a radical comprising 1-50 atoms selected from the group C, H, N, O, Si, P and S;  
 each of the n [2]  moieties shown as L [2] , if present, is independently chosen from the group O, NR SUB  and S;  
 each of the n [2]  moieties shown as J [2] , if present, is independently chosen from the group C(═O) and C(═S);  
 n [1] =1 to 32;  
 n [2] =1 to 32;  
 p [2] =1 to 8;  
 with the.proviso that the product n [2] ×p [2]  be greater than 1 and less than 33;  
 each of the n [2]  moieties shown as Z [2]  is independently a radical comprising 1-200 atoms selected from the group C, H, N, O, Si, P and S, containing attachment sites for at least p [2]  functional groups on alkyl, alkenyl, or aromatic carbon atoms.  
 
 
     
     
         2 . A conjugate according to  claim 1 , wherein the biological molecules comprise polynucleotide duplexes of at least about 20 base pairs each bound to the valency platform molecule, the duplexes each having a significant binding activity for human systemic lupus erythematosus anti-dsDNA autoantibodies.  
     
     
         3 . A conjugate according to  claim 1 , wherein the biological or chemical molecules are selected from the group consisting of carbohydrates, lipid, lipopolysaccharides, peptides, proteins, glycoproteins, single-stranded or double-stranded oligonucleotides, haptens, or chemical analogs thereof such as mimotopes, aptamers.  
     
     
         4 . A conjugate according to  claim 1 , wherein the biological or chemical molecules are analogs of immunogens wherein (a) the analog binds specifically to B cells to which the immunogen binds specifically and (b) the conjugate lacks a T cell epitope.  
     
     
         5 . The conjugate of  claim 1 , wherein the valency platform molecule is derivatized by a reagent selected from the group consisting of DABA, BAHA, BAHA ox , and AHAB.  
     
     
         6 . The conjugate of  claim 2 , wherein a linker molecule couples the duplexes to the valency platform molecule.  
     
     
         7 . The conjugate of  claim 6 , wherein the linker molecule is selected from the group consisting of HAD and HAD p S.  
     
     
         8 . The conjugate of  claim 2 , wherein the duplexes are substantially homogeneous in length.  
     
     
         9 . The conjugate of  claim 2 , wherein the duplexes are substantially homogeneous in nucleotide composition.  
     
     
         10 . The conjugate of  claim 2 , wherein the duplexes are 20 to 50 bp in length.  
     
     
         11 . The conjugate of  claim 2 , wherein the duplexes are bound to the valency platform molecule at or proximate one of their ends.  
     
     
         12 . The conjugate of  claim 2 , wherein the conjugate is a tolerogen for human systemic lupus erythematosus.  
     
     
         13 . A conjugate according to  claim 2 , wherein the polynucleotide duplexes have a B-DNA type helical structure and a significant binding activity for human systemic lupus erythematosus anti-dsDNA autoantibodies.  
     
     
         14 . A pharmaceutical composition for treating lupus comprising the conjugate of  claim 2  formulated with a pharmaceutically acceptable injectable vehicle.  
     
     
         15 . A method for treating an individual for lupus comprising administering a therapeutically effective amount of the composition  claim 14  to an individual in need of such treatment.  
     
     
         16 . A method for making the conjugate of  claim 2 , comprising: 
 (a) bonding a multiplicity of single-stranded polynucleotides of at least about 20 base pairs each on the valency platform molecule; and    (b) annealing complementary single-stranded polynucleotides to the single-stranded polynucleotides conjugated to the valency platform molecule to form said duplexes.    
     
     
         17 . A pharmaceutical composition for treating an antibody-mediated pathology comprising a therapeutically effective amount of the conjugate of  claim 2 , combined with a pharmaceutically acceptable carrier.  
     
     
         18 . A method of inducing specific B cell anergy to an immunogen in an individual comprising administering to the individual an effective amount of the conjugate of  claim 17 .  
     
     
         19 . A method of treating an individual for an antibody-mediated pathology in which undesired antibodies are produced in response to an immunogen comprising administering a therapeutically effective amount of the conjugate of  claim 17  to the individual.  
     
     
         20 . A method for making a conjugate according to  claim 2 , comprising 
 (a) covalently bonding the analog of the immunogen lacking T cell epitopes to the chemically-defined valency platform molecule to form a conjugate; and    (b) recovering the conjugate from the reaction mixture.    
     
     
         21 . A chemically-defined, non-polymeric valency platform molecule of the formula:  
       
         
           
             
               
                 
                   
                     
                       
                         G 
                         
                           [ 
                           6 
                           ] 
                         
                       
                        
                       
                         
                           { 
                           
                             O 
                             - 
                             
                               C 
                                
                               
                                 ( 
                                 
                                   = 
                                   0 
                                 
                                 ) 
                               
                             
                             - 
                             
                               NR 
                               SUB 
                             
                             - 
                             
                               
                                 
                                   Q 
                                   
                                     [ 
                                     6 
                                     ] 
                                   
                                 
                                  
                                 
                                   ( 
                                   
                                     T 
                                     
                                       [ 
                                       6 
                                       ] 
                                     
                                   
                                   ) 
                                 
                               
                               
                                 p 
                                  
                                 
                                   [ 
                                   6 
                                   ] 
                                 
                               
                             
                           
                           } 
                         
                         
                           n 
                            
                           
                             [ 
                             6 
                             ] 
                           
                         
                       
                     
                      
                     
                       
 
                     
                      
                     or 
                   
                 
                 
                   
                     Formula 
                      
                     
                         
                     
                      
                     6 
                   
                 
               
               
                 
                   
                     
                       G 
                       
                         [ 
                         7 
                         ] 
                       
                     
                      
                     
                       
                         { 
                         
                           O 
                           - 
                           
                             C 
                              
                             
                               ( 
                               
                                 = 
                                 0 
                               
                               ) 
                             
                           
                           - 
                           
                             
                               N 
                                
                               
                                 ( 
                                 
                                   
                                     
                                       Q 
                                       
                                         [ 
                                         7 
                                         ] 
                                       
                                     
                                      
                                     
                                       ( 
                                       
                                         T 
                                         
                                           [ 
                                           7 
                                           ] 
                                         
                                       
                                       ) 
                                     
                                   
                                   
                                     
                                       
                                         p 
                                          
                                         
                                           [ 
                                           7 
                                           ] 
                                         
                                       
                                       / 
                                       2 
                                     
                                      
                                     
                                         
                                     
                                   
                                 
                                 ) 
                               
                             
                             2 
                           
                         
                         } 
                       
                       
                         n 
                          
                         
                           [ 
                           7 
                           ] 
                         
                       
                     
                   
                 
                 
                   
                     Formula 
                      
                     
                         
                     
                      
                     7 
                   
                 
               
             
           
           
           
               
           
         
       
       wherein 
 each of G [6]  and G [7] , if present, is independently a linear, branched or multiply-branched chain comprising 1-2000 chain atoms selected from the group C, N, O, Si, P and S;  
 each of the n [6] ×p [6]  moieties shown as T [6]  and each of the n [7] ×p [7]  moieties shown as T [7]  is independently chosen from the group NHR SUB  (amine), C(═O)NHNHR SUB  (hydrazide), NHNHR SUB  (hydrazine), C(═O)OH (carboxylic acid), C(═O)OR ESTER  (activated ester), C(═O)OC(═O),R B  (anhydride), C(═O)X (acid halide), S(═O) 2 X (sulfonyl halide), C(═NR SUB )OR SUB  (imidate ester), NCO (isocyanate), NCS (isothiocyanate), OC(═O)X (haloformate), C(═O)OC(═NR SUB )NHR SUB  (carbodiimide adduct), C(═O)H (aldehyde), C(═O)R B  (ketone), SH (sulfhydryl or thiol), OH (alcohol), C(═O)CH 2 X (haloacetyl), R ALK X (alkyl halide), S(═O) 2 OR ALK X (alkyl sulfonate), NR 1 R 2  wherein R 1 R 2  is —C(═O)CH═CHC(═O)— (maleimide), C(═O)CR B ═CR B   2  (α,β-unsaturated carbonyl), R ALK —Hg—X (alkyl mercurial), and S(═O)CR B ═CR B   2  (α,β-unsaturated sulfone);  
  wherein 
 each X is independently a halogen of atomic number greater than 16 and less than 54 or other good leaving group;  
 each R ALK  is independently a linear, branched, or cyclic alkyl (1-20C) group;  
 each R SUB  is independently H, linear, branched, or cyclic alkyl (1-20C), aryl (1-20C), or alkaryl (1-30C);  
 each R ESTER  is independently N-hydroxysuccinimidyl, p-nitrophenoxy, pentafluorophenoxy, or other activating group;  
 each R B  is independently a radical comprising 1-50 atoms selected from the group C, H, N, O, Si, P and S;  
 n [6] =1 to 32;  
 p [6] =1 to 8;  
 with the proviso that the product n [6] ×p [6]  be greater than 1 and less than 33;  
 n [7] =1 to 32;  
 p [7] =2, 4, 6 or 8;  
 with the proviso that the product n [7] ×p [7]  be greater than 1 and less than 33;  
 each of the n [6]  moieties shown as Q [6]  and each of the 2×n [7]  moieties shown as Q [7]  is independently a radical comprising 1-100 atoms selected from the group C, H, N, O, Si, P and S, containing attachment sites for at least p [6]  (for Q [6] ) or p [7] /2 (for Q [7] , where p [7] /2 is an integer) functional groups on alkyl, alkenyl, or aromatic carbon atoms.

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