US2020354480A1PendingUtilityA1

Water soluble nitric oxide-releasing polyglucosamines and uses thereof

Assignee: UNIV NORTH CAROLINA CHAPEL HILLPriority: Aug 17, 2012Filed: Jul 23, 2020Published: Nov 12, 2020
Est. expiryAug 17, 2032(~6.1 yrs left)· nominal 20-yr term from priority
C08B 37/003A61P 9/10A61P 43/00C08L 5/08A61P 37/06A61P 35/00A61P 9/00C08B 37/00A61P 15/00A61P 17/02A61P 7/02A61P 31/00A61P 29/00A61K 31/722A61P 1/04A61K 47/60A61K 31/7028A61P 15/10C07H 15/12A61P 25/04A61P 11/00
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Claims

Abstract

The presently disclosed subject matter provides nitric oxide-releasing polysaccharides and oligosaccharides, in particular, polyglucosamines, and their use in biomedical and pharmaceutical applications. More particularly, in some embodiments, the presently disclosed subject matter provides nitric oxide-releasing polysaccharides and oligosaccharides that release nitric oxide in a controlled and targeted manner, thereby prolonging the therapeutic effects of nitric oxide and improving the specificity of nitric oxide delivery to targeted cells and/or tissues.

Claims

exact text as granted — not AI-modified
That which is claimed is: 
     
         1 . A polyglucosamine comprising,
 at least one structural unit:   
       
         
           
           
               
               
           
         
         and optionally, at least one structural unit: 
       
       
         
           
           
               
               
           
         
         wherein,
 R 1 , R 2 , R 3  and R 4 , if present, are each independently selected from the group consisting of hydrogen, C 1-5  alkyl(C═O)— and C 1-5  alkyl; 
    in each instance, is a single or double bond, 
 wherein in each instance where it is a double bond, R 1 , R 2 , R 3  or R 4  attached to the double bond-O is absent; when R 1  is absent, R 5  is hydrogen, hydroxyl, C 1-5  alkyl or C 1-5  alkoxy; when R 3  is absent, R 6  is hydrogen, hydroxyl, C 1-5  alkyl or C 1-5  alkoxy; 
 wherein in each instance where it is a single bond, R 1 , R 2 , R 3  or R 4  attached to the double bond-O is present; when R 1  is present, R 5  is hydrogen; 
 
         when R 3  is present, R 6  is hydrogen;
 Q is —(CR c R d ) v —;
 wherein R c  and R d  are independently hydrogen or C 1-5  alkyl; and v is an integer from 2 to 6; 
 
 p is an integer from 1 to 10; 
 A is 
 
       
       
         
           
           
               
               
           
         
         
           
             wherein, L is S, O or N; and 
             G, in each instance, is independently, hydrogen, or is taken together with L to form a nitric oxide donor or is absent; 
           
           X is hydrogen, C 1-5  alkyl or is taken together with N to form a nitric oxide donor; 
           B is one hydrogen or —Y—Z, wherein Y is a spacer and Z is a polymer or a terminus; 
           D is NR a R b , wherein R a  and R b  are independently selected from the group consisting of hydrogen, formyl, C 1-5  alkyl(C═O)—, C 1-5  alkyl and C 1-5  alkyl ester; 
           or D is 
         
       
       
         
           
           
               
               
           
         
       
     
     
         2 . The polyglucosamine of  claim 1 , wherein at least one of said X and G is taken together with the atom on the polyglucosamine to which it is bound to form a nitric oxide donor. 
     
     
         3 . The polyglucosamine of  claim 1 , comprising the structural unit: 
       
         
           
           
               
               
           
         
         wherein, 
         m is an integer from 1 to 10,000. 
       
     
     
         4 . The polyglucosamine of  claim 1 , wherein said nitric oxide donor is taken together with the atom on the polyglucosamine to which it is bound is selected from the group consisting of a diazeniumdiolate, nitrosothiol, a nitrosamine, a hydroxyl nitrosamine, a hydroxyl amine, a hydroxyurea, and combination thereof. 
     
     
         5 . The polyglucosamine of  claim 4 , wherein said nitric oxide donor is diazeniumdiolate. 
     
     
         6 . The polyglucosamine of  claim 3 , wherein m is an integer from 1 to 50. 
     
     
         7 . The polyglucosamine of  claim 3 , wherein m is an integer from 1 to 10. 
     
     
         8 . The polyglucosamine of  claim 1 , comprising at least one structural unit: 
       
         
           
           
               
               
           
         
         wherein,
 D is —NR a R b , wherein R a  and R b  are independently selected from the group consisting of hydrogen, formyl, C 1-5  alkyl(C═O)—, C 1-5  alkyl and C 1-5  alkyl ester. 
 
       
     
     
         9 . The polyglucosamine of  claim 8 , wherein
   , in each instance, is a single bond   R 1 , R 2 , R 3  and R 4 , are each hydrogen, and   R 5  and R 6  are each hydrogen.   
     
     
         10 . The polyglucosamine of  claim 9 , comprising at least one structural unit: 
       
         
           
           
               
               
           
         
       
     
     
         11 . The polyglucosamine of  claim 10 , wherein B is hydrogen. 
     
     
         12 . The polyglucosamine of  claim 11 , wherein B is —Y—Z. 
     
     
         13 . The polyglucosamine of  claim 12 , wherein B is —Y—Z, wherein Z has the structure: 
       
         
           
           
               
               
           
         
       
       wherein j, in each instance, is an integer from 1 to 100. 
     
     
         14 . The polyglucosamine of  claim 12 , wherein Y has the structure: 
       
         
           
           
               
               
           
         
         wherein, 
         R p , R q , R s  and R t , in each instance, are independently, hydrogen or hydroxyl; and 
         k is an integer from 1 to 20. 
       
     
     
         15 . The polyglucosamine of  claim 1 , comprising the structural unit: 
       
         
           
           
               
               
           
         
         wherein, 
         D is 
       
       
         
           
           
               
               
           
         
       
     
     
         16 . The polyglucosamine of  claim 15 , wherein
   , in each instance, is a single bond, and   R 1 , R 2 , R 3  and R 4 , are each hydrogen.   
     
     
         17 . The polyglucosamine of  claim 1 , wherein
 B is —Y—Z, wherein Z has the structure:   
       
         
           
           
               
               
           
         
       
       wherein j, in each instance, is an integer from 1 to 100. 
     
     
         18 . The polyglucosamine of  claim 17 , wherein j is an integer from 1 to 50. 
     
     
         19 . The polyglucosamine of  claim 17 , wherein j is an integer from 1 to 15. 
     
     
         20 . The polyglucosamine of  claim 1 , wherein
 A is   
       
         
           
           
               
               
           
         
         
           wherein G is hydrogen, or is taken together with N to form a nitric oxide donor or is absent; and 
         
         B is hydrogen. 
       
     
     
         21 . The polyglucosamine of  claim 1 , comprising the structural unit: 
       
         
           
           
               
               
           
         
         wherein, 
         m is an integer from 1 to 1,000, and 
         n is an integer from 1 to 1,000. 
       
     
     
         22 . The polyglucosamine of  claim 21 , wherein m and n are each independently selected from an integer of 1 to 50. 
     
     
         23 . The polyglucosamine of  claim 21 , comprising the structural unit: 
       
         
           
           
               
               
           
         
       
     
     
         24 . The polyglucosamine of  claim 20 , wherein
 X is hydrogen or is taken together with N to form a diazeniumdiolate; and   A is   
       
         
           
           
               
               
           
         
         
           wherein G is hydrogen or is taken together with N to form a diazeniumdiolate. 
         
       
     
     
         25 . The polyglucosamine of  claim 21 , wherein
 B is —Y—Z, wherein Z has the structure:   
       
         
           
           
               
               
           
         
       
       wherein j, in each instance, is an integer from 1 to 100. 
     
     
         26 . The polyglucosamine of  claim 22 , wherein Y has the structure: 
       
         
           
           
               
               
           
         
         wherein, 
         R p , R q , R s  and R t , in each instance, are independently, hydrogen or hydroxyl; and 
         k is an integer from 1 to 20. 
       
     
     
         27 . The polyglucosamine of  claim 1 , wherein A is N. 
     
     
         28 . The polyglucosamine of  claim 1 , wherein A is S. 
     
     
         29 . The polyglucosamine of  claim 1 , wherein
 R c  and R d  are independently hydrogen or methyl; and   v is 2.   
     
     
         30 . A method of delivering nitric oxide to a subject, comprising:
 administering an effective amount of said polyglucosamine of  claim 1  to said subject.   
     
     
         31 . A method of treating a disease state, comprising:
 administering an effective amount of said polyglucosamine of  claim 1  to a subject in need thereof, wherein said disease state is selected from the group consisting of a cancer, a cardiovascular disease, a microbial infection; platelet aggregation and platelet adhesion caused by the exposure of blood to a medical device; pathological conditions resulting from abnormal cell proliferation; transplantation rejections, autoimmune diseases, inflammation, vascular diseases; scar tissue; wound contraction, restenosis, pain, fever, gastrointestinal disorders, respiratory disorders, sexual dysfunctions, and sexually transmitted diseases.   
     
     
         32 . The method of  claim 31 , wherein said disease state is cystic fibrosis. 
     
     
         33 . A pharmaceutical formulation comprising:
 iii. said polyglucosamine of  claim 1 ; and   iv. a pharmaceutically acceptable carrier.   
     
     
         34 . The pharmaceutical formulation of  claim 33 , wherein said polyglucosamine is water-soluble. 
     
     
         35 . The polyglucosamine of  claim 1 , wherein said polyglucosamine is water soluble.

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