Studies of Electrochemical Polymerization of Thionine Using a Wavelength-interrogated Surface Plasmon Resonance Sensor†

doi:10.7503/cjcu20160681

Abstract

Abstract:

The electrochemical polymerization of thionine on gold layer was investigated by using a wavelength-interrogated surface plasmon resonance(SPR) sensor that operates at a fixed angle of incidence. The experimental results show that the resonant wavelength of SPR sensor linearly increases with increasing the number of voltammetry scanning cycles and the total redshift of resonance wavelength is 96.6 nm after 100 scanning cycles. The findings indicate that the film growth rate in every scanning cycle is constant and the poly(thionine) film formed after 100 cycles is ca. 71 nm thick based on the best fit of simulation results to the measured data. The poly(thionine) film in acidic buffer solution exhibits high electrochemical activity and its electrochemical reaction is diffusion-controlled. The resonant wavelength of SPR sensor reversibly changes in a voltammetry scanning cycle, indicating the complete reversibility of electrochemical oxidation-reduction reactions for the poly(thionine) film. Compared with the reduced poly(thionine) film, the oxidization of poly(thionine) film leads to a redshift of resonant wavelength, giving a sign that the refractive index of oxidized poly(thionine) film is higher than that of the reduced one.

Key words: Surface plasmon resonance(SPR), Electrochemical polymerization, Poly(thionine), Wavelength interrogation, Kinetic analysis

CLC Number:

O657

TrendMD:

GONG Xiaoqing, WAN Xiumei, LU Danfeng, GAO Ran, CHENG Jin, QI Zhimei. Studies of Electrochemical Polymerization of Thionine Using a Wavelength-interrogated Surface Plasmon Resonance Sensor^†[J]. Chem. J. Chinese Universities, 2017, 38(4): 567.

Figures/Tables 9

Fig.1 Schematic diagram of wavelength-interrogated SPR sensor for in situ analysis of electrochemical process

Fig.2 Cyclic voltammograms during the electropolymerization of thionine on gold electrode with the PBS containing 0.05 mmol/L thionine(A) and SPR spectra recorded before the first voltammogram cycle and after the 100th voltammogram cycle(B)Inset in (A): cyclic voltammograms measured in the range of -0.3—0.9 V under the same conditions above.

Fig.3 SPR spectra at the scan potential of 1.0 V during the growth of poly(thionine) film on gold electrode(A) and resonant wavelengths(λR) as a function of cyclic numbers(B)

Fig.4 SPR spectra calculated at various thickness of poly(thionine) film based on Fresnel equation(A) and linear dependences of λR with thickness of poly(thionine) film(B)

Fig.5 Cyclic voltammogram curves and the resonant wavelengths versus the scan potentials at the first cycle(A), second cycle(B) and fiftieth cycle(C) during the thionine electropolymerization process

Fig.6 Cyclic voltammogram curves at various potential scan rates for the poly(thionine) film coated on the gold electrode(A) and linear dependences of the reduction and oxidation peak currents on the square root of the scan rate(B)

Fig.7 Cyclic voltammograms at the scan rate of 50 mV/s and the corresponding SPR resonance wavelengths versus the scan potentials for the poly(thionine) film coated on the gold electrode(A) and the SPR spectra recorded at the scan potential of 1.0 V with different scan rates(B)

Fig.8 Cyclic voltammograms of the poly(thionine) in PBS at different pH values(A) and the cathodic peak potentials and the corresponding resonant wavelengths versus pH values(B)

Fig.9 Raman spectra for thionine(a) and poly(thionine)(b) films coated on the gold electrodes

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