膜修饰液/液界面上亚叶酸离子的转移

doi:10.7503/cjcu20170413

摘要/Abstract

摘要：

采用复合介孔膜修饰水/1,6-二氯己烷(W/DCH)界面得到阵列介观W/DCH界面, 利用循环伏安法、差分脉冲伏安法以及计时电量法考察了亚叶酸离子在该阵列介观W/DCH界面上的转移过程. 结果表明, 亚叶酸离子在膜修饰W/DCH界面上转移的电化学响应与复合介孔膜内表面活性剂十六烷基三甲基溴化铵密切相关. 循环伏安结果表明, 亚叶酸离子由膜内水相向油相转移的峰电流与扫描速率的平方根呈线性关系, 根据Randles-Sevčik方程, 计算得到亚叶酸离子在复合介孔膜内水相中的扩散系数为2.036×10^-8 cm²/s. 利用计时电量法测得亚叶酸离子在该界面上转移反应的标准速率常数为2.72×10^-3 cm/s.

关键词: 亚叶酸钙, 液/液界面, 离子转移, 膜, 电化学

Abstract:

The ion transfer of leucovorin ion across the water/1,6-dichlorohexane(W/DCH) interface modified by hybrid mesoporous silica membrane(HMSM) was studied by employing cyclic voltammetry(CV), differential pulse voltammetry(DPV) and chronocoulometry. It was found that the electrochemical behaviors of ion transfer of leucovorin ion across such a membrane-modified W/DCH interface are closely related with the ionic surfactant cetyltrimethylammonium bromide(CTAB), which was self-assembled within the silica nanochannels of the HMSM. According the linear relationship between the peak current of CV corresponding to the ion transfer of leucovorin ion from water to DCH and the square root of scan rate, as well as the equation of Randles-Sevčik, the diffusion coefficient of leucovorin ion in water was calculated to be about 2.036×10^-8 cm²/s. In addition, the standard reaction rate constant of the ion transfer of leucovorin ion at such a membrane-modified W/DCH interface was estimated to be about 2.72×10^-3 cm/s via chronocoulometry. This work is expected to help understanding the transport processes of leucovorin across biomembrane in bioscience and provide an elctrochemical method to detect calcium leucovorin.

Key words: Calcium leucovorin, Liquid/liquid interface, Ion transfer, Membrane, Electrochemistry

中图分类号:

O647

TrendMD:

张烨桦, 姜涛, 刘书峰, 于雅倩, 陈勇. 膜修饰液/液界面上亚叶酸离子的转移. 高等学校化学学报, 2018, 39(4): 764.

ZHANG Yehua, JIANG Tao, LIU Shufeng, YU Yaqian, CHEN Yong. Ion Transfer of Leucovorin Ion Across the Membrane-modified Liquid/Liquid Interface^†. Chem. J. Chinese Universities, 2018, 39(4): 764.

图/表 9

Scheme 1 Schematic representation of the electrochemical cell

Scheme 2 Schematic diagram of the electrochemical cellRE1 and RE2 are the reference electrodes; CE1 and CE2 are the counterelectrodes.

Fig.1 CVs obtained at the W/DCH interface modified by HMSM-CTAB in the absence of calcium leucovorin(a) and in the presence of 0.8 mmol/L calcium leucovorin(b) at a scan rate of 20 mV/s

Fig.2 CVs obtained at the W/DCH interface modified by HMSM-CTAB in the absence of calcium leucovorin(dash line) and in the presence of 2 mmol/L calcium leucovorin(solid line) at different scan ratesFrom inner CVs to outer CVs, the scan rates are 20, 40, 60, 80 and 100 mV/s, respectively. Inset: the corresponding plot of peak current for calcium leucovorin from W to DCH against the square root of scan rate.

Fig.3 CVs obtained at the W/DCH interface modified by HMSM(A) and HMSM-CTAB(B) at a scan rate of 20 mV/sFrom inner CVs to outer CVs, the concentrations of calcium leucovorin are 0, 0.8, 1.2, 1.6, 2.0 and 2.4 mmol/L, respectively. Insets: the corresponding plots of peak current for the transfer of leucovorin ion from W to DCH vs. the concentration of calcium leucovorin in aqueous solution.

Fig.4 DPVs collected at the W/DCH interface modified by HMSM(A) and HMSM-CTAB(B) for different concentrations of calcium leucovorinFrom top to bottom, the concentrations of calcium leucovorin are 0, 0.8, 1.2, 1.6, 2.0, and 2.4 mmol/L, respectively.Insets: the corresponding plots of peak current for calcium leucovorin from W to DCH vs. the concentration of calcium leucovorin in aqueous solution.

Fig.5 Plots of Q vs. t1/2 and their asymptotesStep potential: (A) 0.70-0.46 V; (B) 0.70-0.47 V; (C) 0.70-0.48 V; (D) 0.70-0.49 V;(E) 0.70-0.50 V; (F) 0.70-0.51 V.

Fig.6 Plot of kf vs. E

Fig.7 Plot of lnkf vs. (E-Eθ')

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