Han Tingting, Chen Sini, Song Tao, Han Dongxue, Niu Li
Center for Advanced Analytical Science, Guangzhou Key Laboratory of Sensing Materials & Devices, Guangdong Engineering Technology Research Center for Photoelectric Sensing Materials & Devices, Key Laboratory of Optoelectronic Materials and Sensors in Guangdong Provincial Universities, School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, P.R. China.
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, P.R. China.
ACS Meas Sci Au. 2025 Mar 13;5(2):216-225. doi: 10.1021/acsmeasuresciau.4c00093. eCollection 2025 Apr 16.
Here, we propose new single-frequency effective capacitance and membrane resistance readout principle for solid-contact ion-selective electrodes (SCISEs). Conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with polystyrenesulfonate (PSS), , PEDOT(PSS), as solid contact and valinomycin-based membrane were prepared for K-SCISEs. At high frequencies, the membrane resistance of K-SCISEs corresponding to impedance absolute value was recorded constantly as KCl aqueous solution diluted with water. The membrane resistance increases as the electrolyte concentration decreases. Under identical dilution steps, the linear slope of the logarithmic membrane resistance log log for K-SCISEs with the spin-coated membrane is larger than that of the electrode covered with the drop-cast membrane. As the K-SCISE resistance with the spin-coated membrane was reduced to hundreds of Ω, the log of K-SCISEs is linearly proportional to log in the range of -1 to -3.4, providing a possibility of utilizing membrane resistance as a calibration-free analytical signal for SCISEs. The effective capacitance of K-SCISEs with the spin-coated membrane was performed in 0.1 M KCl applied with single frequency ranging from 1 MHz and decreases by a factor of 10 to 10 mHz. The obtained of K-SCISEs with the spin-coated membrane is linearly proportional to login the range of 1 MHz to 10 Hz with a slope of -0.97, while at a low frequency ranging from 1 Hz to 10 mHz, the linear slope of log log is suppressed, where Warburg diffusion takes effect. Furthermore, the membrane resistance is independent of applied high frequencies, and the effective capacitance is independent of the excitation amplitude.
在此,我们提出了用于固体接触离子选择性电极(SCISEs)的新型单频有效电容和膜电阻读出原理。制备了掺杂聚苯乙烯磺酸盐(PSS)的导电聚合物聚(3,4 - 乙撑二氧噻吩)(PEDOT),即PEDOT(PSS)作为固体接触,并制备了基于缬氨霉素的膜用于钾固体接触离子选择性电极(K - SCISEs)。在高频下,随着用水稀释KCl水溶液,对应于阻抗绝对值的K - SCISEs的膜电阻被持续记录。膜电阻随着电解质浓度降低而增加。在相同的稀释步骤下,旋涂膜的K - SCISEs的对数膜电阻log log的线性斜率大于滴铸膜覆盖的电极的线性斜率。当旋涂膜的K - SCISE电阻降低到数百Ω时,K - SCISEs的log在 - 1至 - 3.4范围内与log呈线性比例关系,这为将膜电阻用作SCISEs的无校准分析信号提供了可能性。对旋涂膜的K - SCISEs的有效电容在0.1 M KCl中施加1 MHz至10 mHz的单频进行测量。旋涂膜的K - SCISEs获得的在1 MHz至10 Hz范围内与log呈线性比例关系,斜率为 - 0.97,而在1 Hz至10 mHz的低频范围内,log log的线性斜率受到抑制,此时瓦尔堡扩散起作用。此外,膜电阻与施加的高频无关,有效电容与激励幅度无关。