分子印迹电化学传感器对食用油中塑化剂邻苯二甲酸二异壬酯的快速检测

doi:10.16085/j.issn.1000-6613.2023-0194

化工进展 ›› 2023, Vol. 42 ›› Issue (12): 6469-6477.DOI: 10.16085/j.issn.1000-6613.2023-0194

• 材料科学与技术 • 上一篇

分子印迹电化学传感器对食用油中塑化剂邻苯二甲酸二异壬酯的快速检测

黄世慧¹(), 潘相玉¹, 张榴萍², 周丽绘¹, 王斯峥², 罗世龙², 张颖霞², 胡军¹()

^1.华东理工大学化学与分子工程学院，上海 200237
^2.中储粮镇江粮油质量检测中心有限公司，江苏镇江 212000

收稿日期:2023-02-14 修回日期:2023-03-24 出版日期:2023-12-25 发布日期:2024-01-08
通讯作者: 胡军
作者简介:黄世慧（1997—），女，硕士研究生，研究方向为分子分离与检测。E-mail：Y30200327@mail.ecust.edu.cn。
基金资助:
国家自然科学基金(22278126);上海市质量监督检验技术研究院国家市场监管重点实验室开放课题(MDPDMT-2022-01)

Rapid and specific detection of plasticizer of diisononyl phthalate in edible oil by molecularly imprinted electrochemical sensors

HUANG Shihui¹(), PAN Xiangyu¹, ZHANG Liuping², ZHOU Lihui¹, WANG Sizheng², LUO Shilong², ZHANG Yingxia², HU Jun¹()

^1.School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China
^2.Zhenjiang Grain and Oil Quality Testing Center Co. , Ltd. , Zhenjiang 212000, Jiangsu, China

Received:2023-02-14 Revised:2023-03-24 Online:2023-12-25 Published:2024-01-08
Contact: HU Jun

摘要/Abstract

摘要：

邻苯二甲酸酯类塑化剂（PAEs）是塑料制品加工中常用的添加剂，食用油、乳制品等食品行业大量使用塑料包装材料，存在塑化剂泄漏风险。本文以邻苯二甲酸二异壬酯（DINP）为典型的塑化剂目标分子，通过量化计算筛选分子印迹聚合物（MIP）单体；采用一锅法自由基聚合得到含DINP的分子印迹聚合物（DINP-MIP），其对DINP的吸附等温线符合Langmuir模型，饱和吸附容量为8.61mg/g，是非印迹聚合物（NIP）的2倍以上。将该分子印迹聚合物修饰丝网印刷电极（SPE），获得了可快速检测塑化剂的分子印迹电化学传感器（DINP-MIP/SPE）。在DINP浓度为0.05×10^-6～0.7×10^-6mol/L范围内，检测电流差与浓度具有优异的线性规律，DINP检出限可达0.117mg/kg。在实际食用油检测中，空白加标回收率为104.9%～106.6%，标准偏差RSD为4%～6%，表明分子印迹电化学传感器在塑化剂快速检测中具有优异的实用价值。

关键词: 分子印迹聚合物, 邻苯二甲酸二异壬酯, 聚合物, 电化学传感器, 电化学分析, 安全

Abstract:

Phthalate plasticizers (PAEs) are wildly used in the plastic production, which may bring a risk of leakage in the food industries as packaging materials. Herein, to detect residual plasticizers in food such as edible oil, a specific electrochemical sensor was developed by the molecular imprinted polymer (MIP) approach. One of the PAE molecules of diisononyl phthalate (DINP) was selected as the target molecule and the MIP was optimized and obtained by a one-pot radical polymerization. The DINP adsorption isotherms conformed to the Langmuir model, and the saturated adsorption capacity was calculated as high as 8.61mg/g, more than twice that of non-imprinted polymer (NIP). The DINP-MIP was modified on the surface of a screen-printed electrode to obtain a DINP-MIP/SPE electrochemical sensor. In the detection range of 0.05×10^-6—0.7×10^-6mol/L, the standard working curve of simulated oil had excellent linearity, and the limitation of detection (LOD) of DINP could reach 0.117mg/kg. In the detection of edible oil, the blank spiked recoveries were 104.9%—106.6%, indicating its promising practical applications in the rapid detection of plasticizers.

Key words: molecularly imprinted polymer, diisononyl phthalate, polymers, electrochemical sensor, chemical analysis, safety

中图分类号:

TH15

黄世慧, 潘相玉, 张榴萍, 周丽绘, 王斯峥, 罗世龙, 张颖霞, 胡军. 分子印迹电化学传感器对食用油中塑化剂邻苯二甲酸二异壬酯的快速检测[J]. 化工进展, 2023, 42(12): 6469-6477.

HUANG Shihui, PAN Xiangyu, ZHANG Liuping, ZHOU Lihui, WANG Sizheng, LUO Shilong, ZHANG Yingxia, HU Jun. Rapid and specific detection of plasticizer of diisononyl phthalate in edible oil by molecularly imprinted electrochemical sensors[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6469-6477.

图/表 9

图1 DINP分子分别与5种不功能单体的结合能氢—白色；碳—灰色；氧—红色；氮—蓝色

图2 DINP-MIP合成过程及性质表征图

图3 DINP-MIP的电镜图

表1 不同摩尔比的印迹聚合物DINP-MIP和非印迹聚合物NIP的孔性质参数

样品	比表面积/m²·g^-1	总孔容积/cm³·g^-1	介孔容积/cm³·g^-1	孔径/nm	饱和吸附量/mg·g^-1
(1∶4∶30) DINP-MIP	330.50	0.566	0.042	3.85	0.49
(1∶3∶30) DINP-MIP	378.23	0.597	0.046	3.82	0.55
(1∶3∶20) DINP-MIP	294.40	0.457	0.041	3.80	0.46
(1∶4∶20) DINP-MIP	247.33	0.431	0.036	4.00	0.44
NIP	238.40	0.400	0.041	3.85	—

图4 DINP-MIP和NIP对DINP的吸附等温线

图5 在5mmol/L K3[Fe(CN)6]溶液中，不同电极的电化学相关性能

图6 MIP和NIP对各类塑化剂的电化学响应对比图

图7 不同DINP添加浓度的DINP-MIP修饰电极对实际油样品的CV响应曲线

表2 食用油中DINP的空白加标回收率

样品	添加量 /μmol·L^-1	平均回收量 /μmol·L^-1	平均回收率/%	相对标准偏差RSD/%
1	0.10	0.108	108.7	4.04
2	0.30	0.353	106.6	6.29
3	0.50	0.525	104.9	5.03

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分子印迹电化学传感器对食用油中塑化剂邻苯二甲酸二异壬酯的快速检测

Rapid and specific detection of plasticizer of diisononyl phthalate in edible oil by molecularly imprinted electrochemical sensors

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