差分脉冲伏安法对果蔬中亚硝酸盐和抗坏血酸的同时测定

陈林林; 宋佳琪; 王玲; 杨茜瑶; 郑凤鸣; 张佳欣; 张娜

doi:10.13386/j.issn1002-0306.2022040260

差分脉冲伏安法对果蔬中亚硝酸盐和抗坏血酸的同时测定

doi: 10.13386/j.issn1002-0306.2022040260

哈尔滨商业大学食品工程学院，黑龙江哈尔滨 150028

基金项目: 国家自然科学基金项目（21573055）；黑龙江省“百千万”工程科技重大专项（SC2021ZX04B0019）；哈尔滨商业大学博士科研启动项目（12DL010）；国家级大学生创新创业训练计划项目（202110240019）。

详细信息

作者简介:
陈林林（1979−），女，博士，副教授，研究方向：食品科学，E-mail：chenlinl2013@126.com

通讯作者:
陈林林（1979−），女，博士，副教授，研究方向：食品科学，E-mail：chenlinl2013@126.com

中图分类号: TS207
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- 被引次数: 0
出版历程
- 收稿日期: 2022-04-24
- 网络出版日期: 2023-01-12
- 刊出日期: 2023-03-01

Simultaneous Determination of Nitrite and Ascorbic Acid in Fruits and Vegetables by Differential Pulse Voltammetry

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

摘要

摘要: 采用对苯二酚（Hydroquinone，HQ）催化甲烷氧化菌素（Methanobactin，Mb）还原氯金酸合成纳米金（Gold Nanoparticles，AuNPs），利用电沉积法将Mb@AuNPs修饰到裸金电极表面，制备Mb@AuNPs/Au电极。采用差分脉冲伏安法对亚硝酸盐和抗坏血酸进行同时测定并对条件进行优化，结果表明：电极组装条件为电沉积扫速100 mV/s、扫描圈数为40圈；检测体系为浓度0.20 mol/L pH6.5的磷酸盐缓冲溶液，在2~5600 μmol/L和1~6000 μmol/L的线性范围内，Mb@AuNPs/Au对亚硝酸盐和抗坏血酸同时检测的氧化峰电流与浓度呈良好的线性关系（R²>0.9928），检出限分别为0.31和0.57 μmol/L。实际样品中亚硝酸盐和抗坏血酸的加标回收率范围分别为92.59%~109.26%、90.01%~103.51%，表明该方法具有良好的重现性和稳定性，可用于果蔬中亚硝酸盐和抗坏血酸的同时测定。
- 亚硝酸盐 /
- 抗坏血酸 /
- 差分脉冲伏安 /
- 修饰电极
Abstract: Hydroquinone (HQ) was used to catalyze Methanobactin (Mb) to reduce chlorauric acid to prepare Gold Nanoparticles (AuNPs). Mb@AuNPs was modified onto the surface of a bare gold electrode via electrodeposition to prepare the Mb@AuNPs/Au electrode. Subsequently, differential pulse voltammetry was conducted for the simultaneous determination of nitrite and ascorbic acid concentrations as well as condition optimization. For the electrode assembly, electrodeposition was performed with a 0.20 mol/L and pH6.5 PBS at a 100 mV/s scan rate for 40 cycles. In the linear range of 2~5600 μmol/L and 1~6000 μmol/L, the oxidation peak current of both nitrite and ascorbic acid detected by Mb@AuNPs/Au showed a good linear relationship with the concentration (R²>0.9928), and the limit of detection (LOD) was 0.31 and 0.57 μmol/L, respectively. The recovery rates of standard addition for the actual samples were 92.59%~109.26%, 90.01%~103.51%. The method has good reproducibility and stability and can be used for simultaneous determination of nitrite and ascorbic acid in fruits and vegetables.
- nitrite /
- ascorbic acid /
- differential pulse voltammetry /
- modified electrode

HTML全文

图 1 AA和NO₂⁻在修饰电极上的电化学行为示意图

Figure 1. Electrochemical behavior of AA and NO₂⁻ at the modified electrode

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图 2 HQ催化Mb还原HAuCl₄合成纳米金紫外光谱

Figure 2. Ultraviolet spectra of gold nanoparticles synthesized by reduction of HAuCl₄with Mb catalyzed by HQ

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图 3 Mb@AuNPs修饰电极CV图

Figure 3. Cyclic voltammetry of Mb@AuNPs modified electrode

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图 4 Mb@AuNPs修饰电极EIS图

Figure 4. Electrochemical impedance spectrum of Mb@AuNPs modified electrode

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图 5 AA和NO₂⁻在Mb@AuNPs修饰电极上的电化学行为

Figure 5. Electrochemical behavior of AA and NO₂⁻ on Mb@AuNPs modified electrode

注：不同字母表示差异性显著（P<0.05），图6、图8、图10~图12、表3同。

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图 6 不同扫描速度对Mb@AuNPs/Au电化学性能的影响

Figure 6. Effect of different scanning speed on the electrochemical performance of Mb@AuNPs/Au

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图 7 不同扫描速度对Mb@AuNPs/Au影响的EIS图

Figure 7. Electrochemical impedance spectrum of the effects on Mb@AuNPs/Au with different scanning speed

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图 8 不同电沉积圈数对Mb@AuNPs/Au电化学性能的影响

Figure 8. Effects of different deposition cycles on the electrochemical performance of Mb@AuNPs/Au

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图 9 不同电沉积圈数对Mb@AuNPs/Au影响的EIS图

Figure 9. Electrochemical impedance spectrum of the effects on Mb@AuNPs/Au with different deposition cycles

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图 10 不同缓冲溶液对NO₂⁻和AA电化学行为影响的DPV图

Figure 10. DPV of the effects on the electrochemical behavior of NO₂⁻ and AA with different buffer solutions

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图 11 不同PBS缓冲溶液pH对NO₂⁻和AA电化学行为影响的DPV图

Figure 11. DPV of the effects on the electrochemical behavior of NO₂⁻ and AA with different pH of PBS buffer solution

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图 12 不同PBS缓冲溶液浓度对NO₂⁻和AA电化学行为影响的DPV图

Figure 12. DPV of the effects on the electrochemical behavior of NO₂⁻ and AA with different PBS buffer solution concentration

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图 13 Mb@AuNPs/Au同时检测NO₂⁻和AA标准曲线

Figure 13. Standard curves for simultaneous detection of NO₂⁻ and AA with Mb@AuNPs/Au

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表 1 几种修饰电极同时检测NO₂⁻和AA的比较

Table 1. Comparison of some modified electrodes in the determination of NO₂⁻ and AA

修饰电极	线性范围（μmol/L）		检出限（μmol/L）		参考文献
修饰电极	AA	NO₂⁻	AA	NO₂⁻	参考文献
N-LC/CoS₂⁻MoS₂	9.9~4800	0.5~5160	3.00	0.20	[38]
Poly-NALM/GC	10.0~1000	1.0~500	0.97	0.75	[29]
Carbon hybrid electrode	6.0~1500	6.0~1500	5.00	3.00	[34]
Fe（III）TPyP-Ba/GCE	5.0~330	1.0~250	0.90	0.50	[39]
Mb@AuNPs/Au	2.0~5600	1.0~6000	0.57± 0.017	0.31± 0.002	本法

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表 2 同时测定时AA和NO₂⁻的回收率

Table 2. Recovery rate of AA and NO₂⁻ in simultaneous determination

样品	AA初始量（mg/100 mL）	NO₂⁻初始量（mg/L）	加标量（mg/L）	AA测定量（mg/100 mL）	NO₂⁻测定量（mg/L）	AA回收率（%）	NO₂⁻回收率（%）	AA RSD （%）	NO₂⁻ RSD （%）
菠菜	0.47	0.72	1	1.48	1.78	102.84	109.26	1.87	2.03
			5	5.44	5.73	93.60	102.15	2.64	2.89
			10	10.46	10.69	102.84	96.75	2.64	2.12
大白菜	0.32	0.61	1	1.30	10.58	93.75	95.08	1.83	2.33
			5	5.33	5.60	103.13	98.90	2.80	1.99
			10	10.31	10.31	99.03	99.02	1.39	1.87
西红柿	0.19	0.41	1	1.18	1.38	94.74	93.49	2.16	2.07
			5	5.20	5.19	99.99	101.76	2.91	1.54
			10	10.20	10.20	103.51	103.51	1.89	1.63
水晶梨	0.4	未检出	1	1.36	0.98	90.01	98.00	2.45	2.23
			5	5.37	5.09	94.89	101.80	1.72	1.43
			10	10.39	9.99	97.50	99.90	1.70	2.74
苹果	0.51	0.39	1	1.48	1.38	94.12	97.44	2.12	2.21
			5	5.50	5.37	98.03	94.87	1.81	1.98
			10	10.49	10.39	96.08	99.99	1.99	2.01
橘子	1.48	0.27	1	2.49	1.26	100.68	96.30	1.23	1.81
			5	6.46	5.25	98.65	92.59	1.51	1.02
			10	11.48	10.27	99.99	100.00	2.44	1.07

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表 3 果蔬中NO₂⁻和AA贮存期间测定的回收率

Table 3. Recovery rate of NO₂⁻ and AA in fruits and vegetables during storage

样品	不同贮存时间 NO₂⁻含量（mg/L）				不同贮存时间 NO₂⁻测定回收率（%）			不同贮存时间 AA含量（mg/100 mL）				不同贮存时间 AA测定回收率（%）
样品	0 d	3 d	6 d	9 d	3 d	6 d	9 d	0 d	3 d	6 d	9 d	3 d	6 d	9 d
大白菜	0.61^c	0.62^c	0.71^b	0.75^a	95.17	91.55	92.00	0.32^a	0.31^a	0.31^a	0.27^b	90.32	93.54	92.60
苹果	0.39^c	0.39^c	0.44^b	0.47^a	94.89	93.18	91.50	0.51^a	0.51^a	0.47^b	0.44^c	94.12	95.74	90.91

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