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To develope new type biosensors for protein detecting on the basis of non-metallic electrodes, we tried to synthesize COOH group containing pyrrole monomer(located on the 3 positioned carbon of pyrrole) and polymerize to high molecular weight film. Then we also synthesized ,-NH2 terminated polyelectrolyte and coupled with COOH containing polypyrrole film using DCC(N,N'-dicyclohexyl carbodiimide). Synthesized polymer composite film having negative charged polymeric chain showed repeated responses which were derived from electric oxidation/reduction signals. The introduction of polyelectrolyte to the polypyrrole surface was confirmed by quatrz crystal equipped with galvanostat, and by the CV(cyclic voltammogram) measurement of polypyrrole-polyelectrode film under the various galvanostat conditions. We could observe the mass change of the polymeric complex by ion transportation through the swelled/deswelled polymeric chains of polyelectrolyte according to the electric oxidation/reduction signals. These responses could be detected by the mass changes on quartz crystals inducing ion trapping in swelled/deswelled polymeric chains of polyelectrolyte which was bounded to polypyrrole film through covalent bonding. Therefore this system can be applied to simulate the selective protein adsorption and desorption on the surface of biomaterials in living body with very usefulness and stable controllability.