A bio-adhesive supramacromolecular complex of the general formula: wherein R1 is independently selected from the group consisting of an alkane unsubstituted or substituted with alkoxy groups； R2 is independently selected from the group consisting of C1-6 alkyl； R3 and R4 are independently selected from the group consisting of optionally substituted aliphatic or aromatic alkyl； R5 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； T1, T2, T3 and T4 are independently selected polymer residues； and m1, m2, m3, n1 and n2 are integers selected from at least 25； and wherein P has a molecular weight of about 1×103 to 1×107 and Q has a molecular weight of about 1×103 to 1×107. 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.
