New boron-containing anion active functional copolymers are synthesized by complex-radical copolymerization of 4-vinylphenyl boronic acid and maleic or citraconic anhydrides with 2,2'-azobisisobutyronitrile as an initiator in DMF at 70 degreesC under nitrogen atmosphere. Macrobranched derivatives of these copolymers are synthesized by the partial grafting with alpha-hydroxy,omega-methoxy-poly(ethylene oxide) and incorporation with poly(ethylene imine). Effect of H-bonding on the formation of self-assembled supramolecular macrocomplexes with higher crystallinity and thermal stability was observed and confirmed by FTIR, and H-1(C-13 DEPT-135( NMR spectroscopy, X-ray diffraction, DSC and TGA analyses of monomer, homopolymer, copolymer and grafted copolymer systems. Observed water solubility, biocompatibility and high density of acid groups in macromolecules allow these anion active B-containing copolymer systems for the developing new generation of effective antitumor agents, polymeric carriers for enzymes, gene delivery and boron neutron capture therapy. (C) 2004 Published by Elsevier Ltd.