Research Progress on Detection Methods of Phthalates Plasticizers in Food

doi:10.19586/j.2095-2341.2022.0076

Current Biotechnology ›› 2023, Vol. 13 ›› Issue (1): 11-21.DOI: 10.19586/j.2095-2341.2022.0076

• Special Forum on Food Safety Detection • Previous Articles Next Articles

Research Progress on Detection Methods of Phthalates Plasticizers in Food

Teng WANG(), Yifei YU(), Rui WANG(), Xin WANG, Yunyi LI, Yang CHEN, Nan CHENG()

Beijing Laboratory for Food Quality and Safety，College of Food Science and Nutritional Engineering，China Agricultural University，Beijing 100083，China

Received:2022-05-15 Accepted:2022-08-05 Online:2023-01-25 Published:2023-02-07
Contact: Nan CHENG

食品中邻苯二甲酸酯类塑化剂检测方法研究进展

王腾(), 余逸飞(), 王睿(), 王鑫, 李昀怡, 陈洋, 程楠()

中国农业大学食品科学与营养工程学院，食品质量与安全北京实验室，北京 100083

通讯作者: 程楠
作者简介:王腾1601420251@qq.com
余逸飞 E-mial: hbyuyifei@163.com
王睿 E-mail: 2083104633@qq.com
E-mail: chengnanFSNE@cau.edu.cn第一联系人：（王腾、余逸飞和王睿并列第一作者）
基金资助:
中国农业大学2115人才工程项目

Abstract

Abstract:

Plasticizers， as a processing aid， which can increase the plasticity of polymers， have been widely used in chemical， pharmaceutical， daily necessities， food packaging and other fields. Phthalates are the most used plasticizers， which are found to migrate into food during production and distribution， causing irreversible damage to the human body. This article reviewed the principles， advantages and disadvantages and applicability of pretreatment methods and traditional detection methods for the detection of phthalates plasticizers in food. Then， according to the different types of output signals， the principles， characteristics， and applications of several phthalate rapid detection methods were reviewed， and their development directions were prospected. Finally， the disadvantages of several rapid detection methods were summarized and compared， with a view to provide reference for the research of plasticizer detection methods， and provide ideas for the development of new rapid detection methods.

Key words: plasticizer, phthalate, detection method, rapid detection

摘要：

塑化剂作为一种加工助剂，可增加聚合物的可塑性，目前已被广泛应用于化工、医药、日用品和食品包装等各领域。邻苯二甲酸酯是最常用的一种塑化剂，其可在生产、流通等过程中迁移到食品内部，对人体造成不可逆伤害。总结了食品中邻苯二甲酸酯类塑化剂检测的前处理方法及传统检测方法的原理、优缺点及适用性，并按照输出信号种类不同分类，综述了几种邻苯二甲酸酯快速检测方法的原理、特点和应用，总结和比较了几种快速检测方法的优缺点，并对其发展方向进行展望，以期为塑化剂检测方法的研究和开发新型快速的检测方法提供参考思路。

关键词: 塑化剂, 邻苯二甲酸酯, 检测方法, 快速检测

CLC Number:

TS207.3

Teng WANG, Yifei YU, Rui WANG, Xin WANG, Yunyi LI, Yang CHEN, Nan CHENG. Research Progress on Detection Methods of Phthalates Plasticizers in Food[J]. Current Biotechnology, 2023, 13(1): 11-21.

王腾, 余逸飞, 王睿, 王鑫, 李昀怡, 陈洋, 程楠. 食品中邻苯二甲酸酯类塑化剂检测方法研究进展[J]. 生物技术进展, 2023, 13(1): 11-21.

Figures/Tables 8

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中文名称	英文简称	CAS号	最大残留限量/(mg·kg^-1)
邻苯二甲酸二(2-乙基己基)酯	DEHP	117-81-7	1.5
邻苯二甲酸二异壬酯	DINP	28553-12-0	9.0
邻苯二甲酸二正丁酯	DBP	84-74-2	0.3

中文名称	英文简称	CAS号	最大残留限量/(mg·kg^-1)
邻苯二甲酸二(2-乙基己基)酯	DEHP	117-81-7	1.5
邻苯二甲酸二异壬酯	DINP	28553-12-0	9.0
邻苯二甲酸二正丁酯	DBP	84-74-2	0.3

检测物质	前处理方法	检测方法	检出限	回收率/%	相对标准偏差/%	参考文献
水	固相萃取-分散液-液微萃取	GC-MS	0.000 5~0.001 μg·L^-1	90.6~108.3	5.3~7.5	[18]
瓶装水	在线管内固相微萃取技术	HPLC	0.052~0.100 ng·mL^-1	84.6~111.6	≤4.3	[20]
白酒	全自动涡流辅助液-液微萃取	GC-MS	0.003~0.006 μg·L^-1	85.7~96.1	≤3.1	[21]
牛奶	酸碱诱导共晶溶剂-涡旋辅助液-液微萃取	HPLC	1.06~4.55 ng·mL^-1	93.9~107.0	1.63~4.44	[22]
婴儿食品	QuEChERS	GC-MS	LOQ=0.03~1.11 μg·kg^-1	70~120	≤19	[23]
高粱	QuEChERS	GC-MS	0.4~0.8 g·kg^-1	82.0~120.2	1.2~7.6	[24]
CiCi饮料梨汁	以ZIF-8@GO为吸附剂的搅拌棒吸附萃取	GC-MS	0.15~0.60 g·L^-1 0.75~2.20 g·kg^-1	72~100	<11	[27]
白酒矿泉水	4,4′-二氨基对三联苯三嗪(PDT)涂层搅拌棒吸附萃取	HPLC	0.04~0.27 μg·L^-1	85.4~117.0	4.5~9.4	[28]
水	固相微萃取	GC-FID	0.32~3.13 μg·L^-1	82~119	7.5~15.6	[29]
麦芽饮料	磁性固相萃取	GC-MS	13~30 ng·L^-1	94.2~104.3	<7.6	[31]
食品接触材料	超分子溶剂液液微萃取技术	UPLC-MS	0.1~1.0 μg·L^-1	84.4~117.5	2.1~18.7	[32]
酒	前吸附技术	UPLC-MS	0.003~0.050 mg·kg^-1	75.4~118.2	4.0~11.2	[33]
香精	—	近红外光谱法	—	—	—	[34]
饮料	—	快速漫反射紫外光谱法	0.007 9 mg·L^-1	99~105	1.0~5.0	[35]

检测物质	前处理方法	检测方法	检出限	回收率/%	相对标准偏差/%	参考文献
水	固相萃取-分散液-液微萃取	GC-MS	0.000 5~0.001 μg·L^-1	90.6~108.3	5.3~7.5	[18]
瓶装水	在线管内固相微萃取技术	HPLC	0.052~0.100 ng·mL^-1	84.6~111.6	≤4.3	[20]
白酒	全自动涡流辅助液-液微萃取	GC-MS	0.003~0.006 μg·L^-1	85.7~96.1	≤3.1	[21]
牛奶	酸碱诱导共晶溶剂-涡旋辅助液-液微萃取	HPLC	1.06~4.55 ng·mL^-1	93.9~107.0	1.63~4.44	[22]
婴儿食品	QuEChERS	GC-MS	LOQ=0.03~1.11 μg·kg^-1	70~120	≤19	[23]
高粱	QuEChERS	GC-MS	0.4~0.8 g·kg^-1	82.0~120.2	1.2~7.6	[24]
CiCi饮料梨汁	以ZIF-8@GO为吸附剂的搅拌棒吸附萃取	GC-MS	0.15~0.60 g·L^-1 0.75~2.20 g·kg^-1	72~100	<11	[27]
白酒矿泉水	4,4′-二氨基对三联苯三嗪(PDT)涂层搅拌棒吸附萃取	HPLC	0.04~0.27 μg·L^-1	85.4~117.0	4.5~9.4	[28]
水	固相微萃取	GC-FID	0.32~3.13 μg·L^-1	82~119	7.5~15.6	[29]
麦芽饮料	磁性固相萃取	GC-MS	13~30 ng·L^-1	94.2~104.3	<7.6	[31]
食品接触材料	超分子溶剂液液微萃取技术	UPLC-MS	0.1~1.0 μg·L^-1	84.4~117.5	2.1~18.7	[32]
酒	前吸附技术	UPLC-MS	0.003~0.050 mg·kg^-1	75.4~118.2	4.0~11.2	[33]
香精	—	近红外光谱法	—	—	—	[34]
饮料	—	快速漫反射紫外光谱法	0.007 9 mg·L^-1	99~105	1.0~5.0	[35]

荧光方法	基底	检测限	线性范围	预处理方式	应用	参考文献
荧光纳米传感器	hPEI-Cu NCs	0.4 mg·kg^-1	1~7 mg·kg^-1	—	白酒中DEHP质量分数检测	[36]
荧光信号变化值法	SNA	1.008 μg·L^-1	0~100 μg·L^-1	过滤混合水样	液体环境DEHP的快速检测	[37]
荧光光谱法	ZnS∶Mn QDs	0.27 μmol·L^-1	5.0~50 μmol·L^-1	8 000 r·min^-1离心30 min	液体环境DBP的快速检测	[38]
荧光传感器法	多孔晶体带	1 μg·L^-1	—	在60 ℃下加热2 h	商用聚氯乙烯产品释放的邻苯二甲酸盐检测	[39]

Research Progress on Detection Methods of Phthalates Plasticizers in Food

食品中邻苯二甲酸酯类塑化剂检测方法研究进展

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检测方法	检测限	线性范围	预处理方式	应用	参考文献
hPEI-Cu NCs	0.144 mg·L^-1	—	—	检测食品中DEHP的质量分数	[40]
DMP胶体金试纸条	0.4 μg·mL^-1	—	—	快速检测食品中DMP	[41]
dc-ELISA	0.39 ng·mL^-1	0.56~100 0 ng·mL^-1	4 ℃、3 000 r·min^-1离心10 min	快速检测液体环境MEHP	[42]
dc-ELISA	0.004 2 ng·mL^-1	10^-3~10³ ng·mL^-1	—	测定婴幼儿用品中DEHP	[43]
BA-ELISA	0.007 4 μg·L^-1	0.021~12.948 μg·L^-1	—	快速检测饮料中DEHP	[44]
ic-ELISA	1.98 μg·L^-1	—	—	快速检测白酒、牛奶、食用油中DBP	[45]

方法名称	基底	检测限	线性范围	预处理方式	应用	参考文献
非标记型SERS法	AuNS@AgNCs	10^-9 mol·L^-1	—	离心沉淀	检测液体中BBP	[48]
非标记型SERS法	Au@Ag@IP6	10^-8 mol·L^-1	10^-4~10^-5 mol·L^-1	仅需要简单预处理	检测能量饮料试剂样品中痕迹量DEHP	[49]
非标记型SERS法	β环糊精功能化的Ag@Fe₃O₄@Ag	1 μg·L^-1	1~1 000 μg·L^-1	无需预处理	检测白酒中的BBP	[50]
非标记型SERS法	UCNPs、AuNPs复合物	0.008 7 ng·L^-1（荧光信号）、0.010 8 ng·L^-1（拉曼光谱信号）	10^-3~100 ng·mL^-1（荧光）信号、10^-2~100 ng·mL^-1（拉曼光谱信号）	无需预处理	检测塑料包装中PAE的迁移	[51]
标记型SERS法	标记型检测方式	10^-8mol·L^-1	0.008~182 nmol·L^-1	无需预处理	检测自来水、瓶装水、碳酸饮料中DEHP	[52]

传感器	检测限	线性范围	响应信号	响应时间	应用	参考文献
适配体-Au	0.103 pg·mL^-1	7.629~2×10⁶ pg·mL^-1	阻抗	30 min	检测自来水中的DEHP	[54]
Au@Fe₃O₄@RGO-MIP	0.304 9 nmol·L^-1	0.01~0.1 μmol·L^-1	电流	6 min	检测水中DBP	[55]
AuSs/NCs/SPCE	2.3×10^-2 pg·mL^-1	0.5~10⁶ pg·mL^-1	电流	2 h	检测塑料产品迁移到水中的DEHP	[56]
E-MIP	9 μmol·L^-1	—	电流	5 min	检测淡水中的DOP	[57]

快速检测方法	不足
荧光法	需要专业仪器进行检测，实验操作要求较高；需要通过过滤等前处理方式消除悬浊物对荧光信号的干扰，操作繁琐
胶体金比色法	不借助专业检测仪器，比色法仅能够实现半定量检测；适配体识别相偶联的胶体金和化学显色的比色法均在溶液体系内反应，对实验操作要求较高
酶联免疫法	抗体和酶的成本较高、不易保存
表面增强拉曼光谱法	专业仪器进行检测，实验操作要求较高
电化学法	难以长期保存，使用寿命较短

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