基于共价有机框架修饰电极的维生素A和C的选择性检测★

doi:10.6023/A23040170

摘要/Abstract

电极界面的设计与调控, 对于实现复杂样品中待测物质的准确分析具有重要意义. 用1,3,5-三(4-氨苯基)苯(TAPB)分别与对苯二甲醛(PDA)和溴取代对苯二甲醛(BrPDA)缩聚, 在液/液界面上制备了两种亲疏水性不同的共价有机框架(COF)膜, 并将其转移到氧化铟锡玻璃(ITO)电极上, 研究了疏水性的维生素A (VA)和亲水性的维生素C (VC)在两种COF修饰电极上的电化学响应. 结果显示, TAPB-BrPDA COF/ITO电极表面较为疏水, 在排阻VC的同时可对VA进行选择性的电化学检测, 线性范围为5~100 μmol/L, 检出限为1.32 μmol/L. 而TAPB-PDA COF/ITO电极则恰好相反, 可排阻VA而对VC有较好的选择性, 电化学检测的线性范围为5~200 μmol/L, 检出限为1.35 μmol/L. 因此, 两种电极可用于维生素复合片中VA和VC的定量测定, 回收率分别达到104%和101%.

关键词: 共价有机框架, 电化学分析, 维生素, 结构调控, 选择性

The engineering and regulation of electrode interfaces are of great significance for accurate analysis of specific analyte in complex samples. Covalent organic frameworks (COF), as a class of crystalline polymers formed precisely and periodically by building blocks, have provoked exponential interest due to their pre-designable and adjustable pore sizes, hydrophobicity, geometry and so on. Therefore, varying the structures of monomers is able to modulate the molecular permeability of COF and achieve selective detection of different analytes. In this work, the polycondensation reaction between the amine monomer, namely 1,3,5-tris(4-aminophenyl) benzene (TAPB), and two different aldehyde monomers, namely terephthalaldehyde (PDA) and 2,5-dibromoterephthalaldehyde (BrPDA), at the liquid/liquid interface was conducted to prepare continuous and uniform imine-linked covalent organic framework (COF) membranes. The membranes were subsequently transferred onto the surface of indium tin oxide (ITO) glass electrodes and then the electrochemical responses of hydrophobic vitamin A (VA) and hydrophilic vitamin C (VC) at two COF modified electrodes were investigated. Due to the existing of Br groups on the pore walls of TAPB-BrPDA COF, it is hydrophobic with a contact angle of 122°, while the TAPB-PDA COF membrane is hydrophilic with a contact angle of 73°. The electrochemical responses of two COF modified electrodes towards hydrophobic VA and hydrophilic VC were studied in 1 mol/L NaCl solution. The results of cyclic voltammetry revealed that TAPB-BrPDA COF could prohibit effectively the permeability of VC whereas allow that of VA, eventually achieving the selective electrochemical detection of the latter with a detection linear range of 5~100 μmol/L and a limit of detection at 1.32 μmol/L. In contrast, TAPB-PDA COF/ITO electrode can reject the access of VA whereas permit that of VC, thus showing good electrochemical selectivity toward VC and yielding a linear detection range of 5~200 μmol/L and a limit of detection at 1.35 μmol/L. Finally, two electrodes were successfully used for the quantitative determination of VA and VC in multivitamin tablets with recoveries of 104% and 101%, respectively. This work constitutes a step in the surface engineering of electrodes by COF to realize pre-designed composition and functions and thus excellent selectivity towards specific molecules.

Key words: covalent organic framework, electrochemical analysis, vitamin, structure control, selectivity

引用此文

杨蓉婕, 周璘, 苏彬. 基于共价有机框架修饰电极的维生素A和C的选择性检测^★[J]. 化学学报, 2023, 81(8): 920-927.

Rongjie Yang, Lin Zhou, Bin Su. Selective Detection of Vitamins A and C based on Covalent Organic Framework Modified Electrodes^★[J]. Acta Chimica Sinica, 2023, 81(8): 920-927.

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图/表 6

图1. (a)通过液/液界面聚合法制备COF膜并将其转移到ITO电极表面及(b) BrPDA、PDA、TAPB、TAPB-BrPDA COF和TAPB-PDA COF的结构

Figure 1. (a) Synthesis of COF membrane through liquid/liquid interfacial polymerization and then transfer of the membrane onto ITO electrode and (b) structures of BrPDA, PDA, TAPB, TAPB-BrPDA COF and TAPB-PDA COF

图2. TAPB-BrPDA COF膜(a, b, c, d)和TAPB-PDA COF膜(e, f, g, h)的表征 (a, e) COF的X射线衍射(XRD)图谱, 黑线为实际测量图谱, 红线为用Material Studio软件模拟出的AA堆积的图谱. (b, f)在77 K下测量的氮气吸附-脱附等温曲线以及计算出的Brunauer-Emmett-Teller比表面积(SBET). (c, g)孔径分布图. (d, h)接触角测量图像

Figure 2. Characterization of TAPB-BrPDA COF membrane (a, b, c, d) and TAPB-PDA COF membrane (e, f, g, h) (a, e) X-Ray diffraction (XRD) patterns of COF. Black curves represent the experimental patterns, while red curves represent the AA stacking pattern simulated by Material Studio software. (b, f) Nitrogen sorption isotherms measured at 77 K and the calculated Brunauer-Emmett-Teller surface area (SBET). (c, g) Pore size distribution profiles. (d, h) Images of contact angle measurement

图3. TAPB-BrPDA COF/ITO电极(a)和TAPB-PDA COF/ITO电极(b)分别在含有100 μmol/L VC(黑线)或100 μmol/L VA(蓝线)的1 mol/L NaCl溶液中的循环伏安响应(电位扫描速度为100 mV?s－1)

Figure 3. CVs of TAPB-BrPDA COF/ITO (a) and TAPB-PDA COF/ITO electrode (b) obtained in 1 mol/L NaCl solution containing 100 μmol/L VC (black curve) or 100 μmol/L VA (blue curve), respectively (scan rate was 100 mV?s－1)

图4. TAPB-BrPDA COF/ITO电极(a)和TAPB-PDA COF/ITO电极(c)在不同浓度的VA (a)或VC (c)溶液中的SWV响应(电解质溶液为1 mol/L NaCl)及(b, d)SWV曲线中的氧化峰电流与VA (b)或VC (d)浓度的线性关系(n=3)

Figure 4. SWV responses of TAPB-BrPDA COF/ITO electrode (a) and TAPB-PDA COF/ITO electrode (c) obtained in solutions containing different concentrations of VA (a) or VC (c) (The electrolyte solution was 1 mol/L NaCl) and (b, d) linear relationship between the oxidation peak currents in SWV curves and the concentrations of VA (b) or VC (d) (n=3)

图5. (a)向样品中加入50 μmol/L VA前(黑线)和后(红线), TAPB-BrPDA COF/ITO电极在溶液中的SWV响应、(b)向稀释了10倍的样品中添加不同浓度的VA, 用TAPB-BrPDA COF/ITO电极测得的SWV曲线叠加图、(c)图(b)中的SWV曲线的氧化峰电流与添加的VA浓度的线性关系(n=3)及(d)将样品用1 mol/L NaCl溶液稀释50倍后, 用TAPB-PDA COF/ITO电极测定VC(黑线和红线分别代表向稀释后的样品中加入200 μmol/L VC前和加入后的SWV响应)

Figure 5. (a) SWV responses of TAPB-BrPDA COF/ITO electrode obtained in sample before (black curve) and after (red curve) the addition of 50 μmol/L VA, (b) the superimposed SWV curves of TAPB-BrPDA COF/ITO electrode obtained in the solution with the addition of different concentrations of VA after diluting the sample 10 times, (c) linear dependence of the oxidation peak currents of SWV curves in Figure (b) on the added VA concentrations (n=3) and (d) TAPB-PDA COF/ITO electrode was used to detect VC in the solution after diluting the sample 50 times with 1 mol/L NaCl solution (The black and red curves represent SWV responses obtained before and after the addition of 200 μmol/L VC, respectively)

分析物	数据来源	含量	回收率/%	R.S.D./%
VA	标示值	52.4 μmol/L	104	7.1
VA	本工作	54.5 μmol/L	104	7.1
VC	标示值	2.84 mmol/L	101	7.6
VC	本工作	2.88 mmol/L	101	7.6

表1. 电化学检测维生素复合片中的VA和VC

Table 1. Electrochemical detection of VA and VC in a multivitamin tablet

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