Selective Detection of Vitamins A and C based on Covalent Organic Framework Modified Electrodes★

doi:10.6023/A23040170

Abstract

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

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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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Fig. & Tab. 6

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

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

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)

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)

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

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

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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^★