MnO<sub>2</sub>/ZnO/GCE电化学传感器的构建及对蜂蜜中磺胺甲恶唑的检测

马永强; 张丝瑶; 遇世友; 王鑫; 黎晨晨

doi:10.13386/j.issn1002-0306.2022070271

MnO₂/ZnO/GCE电化学传感器的构建及对蜂蜜中磺胺甲恶唑的检测

doi: 10.13386/j.issn1002-0306.2022070271

哈尔滨商业大学食品工程学院，黑龙江哈尔滨 150028

基金项目: 黑龙江省普通本科高等学校青年创新人才培养计划（UNPYSCT-2018136）。

详细信息

作者简介:
马永强（1963−），男，硕士，教授，研究方向：食品化学，E-mail：qyma126@163.com

通讯作者:
遇世友（1984−），男，博士，讲师，研究方向：食品分析与检测，E-mail：davidyuhit@163.com

中图分类号: S896.1
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出版历程
- 收稿日期: 2022-07-21
- 网络出版日期: 2023-04-20
- 刊出日期: 2023-06-01

Construction of MnO₂/ZnO/GCE Electrochemical Sensor and the Detection of Sulfamethoxazole in Honey

College of Food Engineering, Harbin University of Commerce, Harbin 150028, China

摘要

摘要: 为快速检测蜂蜜中磺胺甲恶唑（sulfamethoxazole，SMZ）的残留，将水热法制备的氧化锌（ZnO）及共沉淀法制备的二氧化锰（MnO₂）材料复合于玻碳电极（GCE）上，构建了MnO₂/ZnO/GCE电化学传感器用于检测SMZ。采用扫描电镜（SEM）及红外光谱（FT-IR）对复合材料的形貌、结构进行表征。利用差分脉冲伏安法（DPV）对复合材料的比例、修饰量进行探究，从而对传感器的构建条件进行优化。并采用差分脉冲伏安法（DPV）及循环伏安法（CV）对缓冲溶液pH、扫描速率等检测条件进行考察。结果表明，当m(ZnO):m(MnO₂)质量比为1:0.6、MnO₂/ZnO复合材料修饰量为1.7×10⁻³ mg/mm²、缓冲溶液pH为8、扫描速率为30 mV/s时，该传感器对SMZ具有良好的检测效果。在0.3~100 μmol/L范围内，峰电流与SMZ浓度呈良好的线性关系，其线性方程为I_p=0.0843 c+4.5168（R²=0.9916），检测限为0.39 μmol/L，定量限为1.30 μmol/L。将传感器用于蜂蜜样品的检测，加标回收率为95.5%~102.6%，相对标准偏差（RSD）为0.68%~2.55%。表明该传感器能够实现对SMZ含量的准确检测，对于蜂蜜样品SMZ残留量的检测方面具有一定的应用价值。
- 氧化锌 /
- 二氧化锰 /
- 磺胺甲恶唑 /
- 蜂蜜 /
- 电化学检测
Abstract: In order to rapidly detect sulfamethoxazole (SMZ) residues in honey, zinc oxide (ZnO) prepared by hydrothermal method and manganese dioxide (MnO₂) prepared by co-precipitation method were compounded on glassy carbon electrode (GCE) to construct MnO₂/ZnO/GCE electrochemical sensor for the detection of SMZ. The morphology and structure of the composites were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Differential pulse voltammetry (DPV) was used to explore the ratio and modification amount of the composite material to optimize the construction conditions of the sensor. DPV and cyclic voltammetry (CV) were used to investigate the detection conditions such as buffer solution pH and scanning rate. The results showed that when the mass ratio of m(ZnO):m(MnO₂) was 1:0.6, the addition amount of MnO₂/ZnO composite was 1.7×10⁻³ mg/mm², the pH was 8 and the scanning rate was 30 mV/s, the sensor had a good detection effect on SMZ. In the range of 0.3~100 μmol/L, the peak current of SMZ had a good linear relationship with the concentration, the linear equation was I_p=0.0843c+4.5168 (R²=0.9916), the limit of detection was 0.39 μmol/L and the limit of quantification was 1.30 μmol/L. The sensor was applied to the determination of honey sample, with a recovery of 95.5%~102.6% and a relative standard deviation (RSD) of 0.68%~2.55%. It shows that the sensor can realize the accurate detection of SMZ content. It has certain application value for the detection of SMZ residues in honey samples.
- zinc oxide (ZnO) /
- manganese dioxide (MnO₂) /
- sulfamethoxazole /
- honey /
- electrochemical detection

HTML全文

图 1 MnO₂/ZnO/GCE对SMZ的检测示意图

Figure 1. The detection schematic diagram of SMZ by MnO₂/ZnO/GCE

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图 2 ZnO（a）和MnO₂/ZnO（b）的扫描电镜图

Figure 2. SEM images of ZnO (a) and MnO₂/ZnO (b)

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图 3 MnO₂、ZnO和MnO₂/ZnO的红外光谱图

Figure 3. FT-IR spectra of MnO₂, ZnO and MnO₂/ZnO

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图 4 GCE、ZnO/GCE及MnO₂/ZnO/GCE的Nyquist图

Figure 4. Nyquist plots of GCE, ZnO/GCE and MnO₂/ZnO/GCE

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图 5 SMZ的氧化机理示意图

Figure 5. Schematic diagram of oxidation mechanism of SMZ

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图 6 SMZ在不同电极上的DPV图

Figure 6. DPV curves of different elctrodes with SMZ

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图 7 ZnO和MnO₂比例对电极检测SMZ的影响

Figure 7. Effects of the ratio of ZnO to MnO₂ on the electrode detection of SMZ

注：不同小写字母表示差异显著（P<0.05）；图8~图9同。

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图 8 复合材料修饰量对检测SMZ的影响

Figure 8. Effects of composite material modification on the detection of SMZ

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图 9 pH对检测SMZ的影响

Figure 9. Effects of pH on the detection of SMZ

注：b-1为电流；b-2为电位。

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图 10 扫描速率对检测SMZ的影响

Figure 10. Effects of scanning rate on the detection of SMZ

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图 11 不同浓度下SMZ的DPV曲线及标准曲线

Figure 11. DPV curves and standard curves of SMZ at different concentrations

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图 12 干扰物对MnO₂/ZnO/GCE检测SMZ的影响

Figure 12. Effects of interference on SMZ detection by MnO₂/ZnO/GCE

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表 1 不同修饰电极检测磺胺甲恶唑的性能对比（n=3）

Table 1. Comparison of the performance of different chemically modified electrodes for detecting SMZ (n=3)

修饰电极	线性范围（μmol/L）	检测限（μmol/L）	参考文献
GR-ZnO/GCE	1~220	0.4	[23]
MWCNT/GCE	50~1000	10	[42]
TYR-AuNPs-SPCEs	20~200	22.6±2.1	[43]
GC/rGO-AgNP	1~10	0.6	[44]
MnO₂/ZnO/GCE	0.3~100	0.39	本文

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表 2 磺胺甲恶唑的加标回收率及相对标准偏差

Table 2. Spiked recoveries and RSD of SMZ

检测物	加标量（μmol/L）	测得量（μmol/L）	回收率（%）	相对标准偏差（%）
	5	4.90	98.1	0.85
SMZ	10	9.53	95.3	2.48
	15	14.33	95.5	2.72

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表 3 实际样品中不同浓度磺胺甲恶唑的加标回收率及相对标准偏差

Table 3. Spiked recoveries and RSD of real sample on different concentration of SMZ

样品	加标量（μmol/L）	测得量（μmol/L）	回收率（%）	相对标准偏差（%）
市售蜂蜜	2	1.93	96.5	0.79
	5	4.89	97.8	0.82
	10	9.55	95.5	2.22
散装蜂蜜	2	1.97	98.5	2.55
	5	5.13	102.6	1.03
	10	10.13	101.3	0.68

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