a bio - adhesive supramacromolecular complex of the general formula : wherein r 1 is independently selected from the group consisting of an alkane unsubstituted or substituted with alkoxy groups ; r 2 is independently selected from the group consisting of c1 - 6 alkyl ; r 3 and r 4 are independently selected from the group consisting of optionally substituted aliphatic or aromatic alkyl ; r 5 is independently selected from the group consisting of h or c1 - 6 alkyl ; w is a hydrogen - bond accepting functional group - containing entity ; y is a carboxylic acid ester or amide linkage ; r is an independently selected peptide linking group ; t 1 , t 2 , t 3 and t 4 are independently selected polymer residues ; and m 1 , m 2 , m 3 , n 1 and n 2 are integers selected from at least 25 ; and wherein p has a molecular weight of about 1 × 10 3 to 1 × 10 7 and q has a molecular weight of about 1 × 10 3 to 1 × 10 7 . the complex provides controlled nitric oxide release over a longer period of time than prior art compounds in the locally delivery systems . novel compositions , methods of preparation , apparatus including layer - by - layer assemblies coating , electrospinning and ultrasonic atomization , skin coverings containing and medical use of the complexes are described .