Synthesis of Triphenylamine Functional Dye for Highly Sensitive and Ultra-low Potential Photoelectrochemical Sensing of Glutathione†

doi:10.7503/cjcu20160003

Abstract

Abstract:

A triphenylamine functional dye(TCA) was synthesized and integrated with TiO₂ nanoparticles for the fabrication of photoelectrochemical(PEC) biosensors. The as-synthesized TCA with triphenylamine as an electron donor, thiophene as a π bridge and a carboxyl group as an electron acceptor possessed high molar absorption coefficient in visible light region, suitable excited state energy level and good excited state stability, as well as strong coordination ability with TiO₂ nanoparticles. Taking advantages of these merits, the TCA is bounded on TiO₂ nanoparticle and modified on the surface of fluorine doped tin oxide electrode(TCA-TiO₂/FTO). The obtained TCA-TiO₂/FTO electrode showed a photocurrent response at 0 V to a light excitation of 480 nm, which could be further enhanced through an oxidation process of biomolecules by the hole-injected TCA. Using gluthathione as a model analyte, a sensing strategy for sensitive PEC biosensing at an ultra-low potential and under irradiation of visible light was developed. Under optimal conditions, the PEC biosensor shows good linear relationships with GSH concentration in the ranges of 2 to 100 μmol/L and 0.1 to 2.4 mmol/L, with a detection limit of 1.0 μmol/L. This PEC biosensing platform offers an alternative method for monitoring biomolecules and provides a new strategy to design PEC biosensors with organic dyes.

Key words: Photoelectrochemical biosensor, Glutathione, Triphenylamine photoelectrochemical material, Ultra-low potential detection

CLC Number:

O657

TrendMD:

WU Shuo, XING Panpan, SONG Jie, ZHAO Yanqiu. Synthesis of Triphenylamine Functional Dye for Highly Sensitive and Ultra-low Potential Photoelectrochemical Sensing of Glutathione^†[J]. Chem. J. Chinese Universities, 2016, 37(4): 619.

Figures/Tables 8

Scheme 1 Synthetic routes of the TCA

Fig.1 UV-Vis absorption spectrum(a) and fluorescent emission spectrum(b) of TCA in CH2Cl2(A) and the cyclic voltammogram of TCA in CH2Cl2 containing 0.1 mol/L of tetrabutylammonium bromide as electrolyte and 0.05 mol/L of ferrocene as standard(B)

Fig.2 Photocurrent responses of the TiO2/FTO(a,c) and TCA-TiO2/FTO electrodes(b,d) before(a,b) and after(c,d) the addition of 2 mmol/L of GSH

Fig.3 Schematic diagram of the PEC sensor(A) and the energy level distribution diagram(B)

Fig.4 Influences of applied potential(A) and irradiation wavelength(B) on the photocurrent responses of TCA-TiO2/FTO to 1 mmol/L GSH

Fig.5 Photocurrent-time curves of different concentrations of GSH obtained at the TCA-TiO2/FTO electrode(A) and the corresponding calibration curve(B)^(A) Concentration of GSH/(μmol·L-1), a—o: 0, 2, 20, 40, 60, 80, 100, 400, 800, 1200, 1600, 2000, 2400, 2800, 3200. (B) Inset: amplified calibration curves of GSH in the concentration range of 0—100 μmol/L.

Fig.6 Photocurrent ratio of 1 mmol/L of GSH with and without 1 mmol/L of different interferents obtained at the TCA-TiO2/FTO^a. Met; b. Gly; c. Gin; d. His; e. Leu; f. Lys; g. Ala; h. Arg; i. Thr; j. Val; k. Glu; l. Trp; m. Tyr; n. Dop; o. GSH; p. HQ; q. AA.

Fig.7 Stability of TCA-TiO2/FTO electrode

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