School of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi 214122, China.
Anal Methods. 2021 Feb 7;13(5):685-694. doi: 10.1039/d0ay01901a. Epub 2021 Jan 21.
Electrochemical determination of histamine (HA) is quite challenging owing to the high oxidation potential and electrode fouling from HA oxide polyhistamine, which leads to poor sensitivity and unrepeatable measurement. In the present work, a simple, sensitive and repeatable electrochemical measurement of HA was developed based on a Nafion and multi-walled carbon nanotube (MWCNTs) composite membrane modified glassy carbon electrode (GCE). Compared with the bare GCE, the Nafion and MWCNT composite membrane modified electrode significantly enhanced the oxidation peak current and reduced the peak potential to 1.12 V (vs. SCE). Moreover, the characterization of the modified electrode by XPS and EIS showed that polyhistamine scarcely deposited on the composite membrane of the modified GCE, which made it possible to realize repeatable electrochemical measurement of HA. The electrochemical oxidation behavior of HA on the modified electrode was studied by differential pulse voltammetry (DPV). The oxidation peak current has linear and natural log-linear relationships with HA concentration in the range of 20-200 μmol L and 0.5-10 μmol L, respectively. The detection limit was 0.39 μmol L (S/N = 3). The modified electrode could be used to determine 100 μmol L HA ten times repeatedly; the peak currents in consecutive runs were all above 95% of the initial response. This method was also successfully applied to the determination of HA in fish samples and recoveries ranged from 98.2 to 101.2%.
电化学测定组氨酸（HA）具有挑战性，因为 HA 的氧化电位高，并且 HA 的氧化物聚组氨酸会导致电极污垢，从而导致灵敏度差和测量不可重复。在本工作中，基于 Nafion 和多壁碳纳米管（MWCNTs）复合膜修饰的玻碳电极（GCE）开发了一种简单、灵敏和可重复的 HA 电化学测定方法。与裸 GCE 相比，Nafion 和 MWCNT 复合膜修饰电极显著增强了氧化峰电流，将峰电位降低至 1.12 V（相对于 SCE）。此外，通过 XPS 和 EIS 对修饰电极的表征表明，聚组氨酸几乎不会沉积在修饰 GCE 的复合膜上，这使得能够实现 HA 的可重复电化学测量。通过差分脉冲伏安法（DPV）研究了 HA 在修饰电极上的电化学氧化行为。氧化峰电流与 HA 浓度在 20-200 μmol L 和 0.5-10 μmol L 范围内分别呈线性和自然对数线性关系。检测限为 0.39 μmol L（S/N = 3）。修饰电极可用于连续 10 次测定 100 μmol L 的 HA，连续运行的峰电流均高于初始响应的 95%。该方法还成功应用于鱼样中 HA 的测定，回收率在 98.2%至 101.2%之间。
