旋转玻碳电极上二茂铁的电化学阻抗行为及其与DNA的相互作用

应用旋转圆盘电极和电化学阻抗法研究了二茂铁在Tris-NaC l(pH=7.2)缓冲溶液中于旋转玻碳电极上的电化学阻抗行为及其与DNA的相互作用.结果表明,二茂铁于旋转电极的伏安曲线呈现明显的极限电流平阶,而其交流阻抗谱则出现两个电容弧.二茂铁与DNA的作用,若受扩散过程控制则其极限扩散电流随DNA浓度增大而减小,而在电化学控制过程中则表现为电化学反应电阻随DNA浓度增大而增大.根据旋转圆盘电极和电化学阻抗谱测试,表明由这两种方法数据拟合求得的二茂铁条件电位速率常数能够很好地相互吻合,但如存在DNA时,则其条件电位速率常数有一定程度的减小.

Electrochemical Impedance Spectrum of Ferrocene at a Rotating Disk Glassy Carbon Electrode and Its Interaction with DNA

The electrochemical impedance spectrum(EIS) of ferrocene(Fc) at a rotating glassy carbon(GC) electrode and its interaction with calf thymus DNA in Tris-NaCl buffer solution(pH=7.2) have been investigated by using electrochemical techniques such as rotating disk electrode(RDE),EIS and its data fitting.A plateau of the limiting current for the voltammetric curve and two capacitance arches obtained at the rotating GC electrode are exhibited.The interaction of Fc with DNA is represented by the decrease of limiting diffusion current and the increase of electrochemical reaction resistances with the increase of DNA concentration,respectively.On the other hand,based on the theoretical analysis and data fitting of RDE and EIS,values of the rate constant at the formal potential obtained by RDE are consistent with those by EIS on the rotating GC electrode.At the same time,the rate constant at the formal potential decreases in the presence of DNA.