Use of Polymeric Indicator for Electrochemical DNA Sensors:  Poly(4-vinylpyridine) Derivative Bearing [Os(5,6-dimethyl-1,10-phenanthroline)₂Cl]²⁺

A poly(4-vinylpyridine) (PVP) derivative bearing redox-active osmium complexes, PVP-[Os(5,6-dmphen)(2)Cl](2+) (5,6-dmphen = 5,6-dimethyl-1,10-phenanthroline), was employed as a hybridization indicator for electrochemical DNA sensors. PVP-[Os(5,6-dmphen)(2)Cl](2+) exhibited approximately 1000 times higher sensitivity than the corresponding monomeric analogue, [Os(5,6-dmphen)(3)](2+), in DNA determination due to polymeric effects. The detection limit of the present sensor was approximately 0.5 amol. Another merit of the polymeric indicator is that the redox potential was found to be +360 mV (vs Ag/AgCl), which is significantly lower than that reported for the monomeric analogue (+672 mV). The polymeric indicator was applicable to the discrimination of single- and double-base-mismatched DNAs from fully matched target DNA. The polymeric indicator can be removed from the electrode surface by rinsing the electrode in a high-temperature buffer for 6 min, and thus, the polymeric indicator-based DNA sensor can be used repeatedly.