纳米材料传感器在有机磷农药残留检测中的研究进展

doi:10.19894/j.issn.1000-0518.230293

摘要/Abstract

摘要：

有机磷农药（OPs）作为毒性大的农药之一，具有使用范围广、使用量大以及对人体健康危害大等显著特点。随着人们对健康生活的向往和不断追求，构建准确、灵敏、便捷和快速的OPs残留分析检测传感器显得尤为迫切和重要。由于纳米材料具有独特的光学、电化学和生物学等性质，基于纳米材料构建的OPs检测传感器具有灵敏、高效和经济等优点。本文综述了2015－2023年国内外基于稀土掺杂上转换纳米材料、金属纳米材料、金属氧化物纳米材料、碳纳米材料和量子点纳米材料检测OPs残留的传感器，为后续开发基于纳米材料的OPs多残留检测传感器提供思路和依据。

关键词: 纳米材料, 有机磷农药, 残留, 传感器

Abstract:

Organophosphorus pesticides （OPs）， as one of the most toxic pesticides， have the characteristics of wide use， large usage and great harm to human health. With people's longing and continuous pursuit of a healthy life， it is particularly urgent and important to build accurate， sensitive， convenient and fast OPs residual analysis and detection sensor. Because of the unique optical， electrochemical and biological properties of nanomaterials， OPs detection sensors based on nanomaterials have the advantages of sensitivity， high efficiency and economy. In this paper， the domestic and foreign sensors for detecting OPs residues based on rare earth doped upconversion nanomaterials， metal nanomaterials， metal oxide nanomaterials， carbon nanomaterials and quantum dot nanomaterials from 2015 to 2023 are reviewed， providing ideas and basis for the subsequent development of nanomaterial-based OPs multi residue detection sensors.

Key words: Nanomaterials, Organophosphorus pesticides, Residues, Sensors

中图分类号:

O652

彭孔浩, 白安琪, 孟颖, 殷慧, 宿欣瑶, 杨金玉, 李淑荣, 张凌燕, 罗利霞, 孟佩俊. 纳米材料传感器在有机磷农药残留检测中的研究进展[J]. 应用化学, 2024, 41(4): 472-483.

Kong-Hao PENG, An-Qi BAI, Ying MENG, Hui YIN, Xin-Yao SU, Jin-Yu YANG, Shu-Rong LI, Ling-Yan ZHANG, Li-Xia LUO, Pei-Jun MENG. Research Progress of Nanomaterial Sensors in the Detection of Organophosphorus Pesticide Residues[J]. Chinese Journal of Applied Chemistry, 2024, 41(4): 472-483.

图/表 6

参考文献 55

1	WEI L， ZHU N， LIU X， et al. Application of Hi-throat/Hi-volume SPE technique in assessing organophosphorus pesticides and their degradation products in surface water from Tai Lake， east China［J］. J Environ Manage， 2022， 305： 114346.
2	MEDITHI S， KASA Y D， AJUMEERA R， et al. Effect of organophosphorus pesticide exposure on the immune cell phenotypes among farm women and their children［J］. Arch Environ Occup Health， 2022， 77（9）： 702-710.
3	EDDLESTON M. Novel clinical toxicology and pharmacology of organophosphorus insecticide self-poisoning［J］. Annu Rev Pharmacol Toxicol， 2019， 59： 341-360.
4	ČADEŽ T， KOLIĆ D， ŠINKO G， et al. Assessment of four organophosphorus pesticides as inhibitors of human acetylcholinesterase and butyrylcholinesterase［J］. Sci Rep， 2021， 11（1）： 21486.
5	YU G， LI Y， JIAN T， et al. Clinical analysis of acute organophosphorus pesticide poisoning and successful cardiopulmonary resuscitation： a case series［J］. Front Public Health， 2022， 10： 866376.
6	SOBOLEV V E， SOKOLOVA M O， JENKINS R O， et al. Molecular mechanisms of acute organophosphate nephrotoxicity［J］. Int J Mol Sci， 2022， 23（16）： 8855.
7	TALAEE M， LORESTANI B， RAMEZANI M， et al. Microfunnel-filter-based emulsification microextraction followed by gas chromatography for simple determination of organophosphorus pesticides in environmental water samples［J］. J Sep Sci， 2019， 42（14）： 2418-2425.
8	YANG Y， LI Y， HUANG Z， et al. Trace detection of organophosphorus pesticides in vegetables via enrichment by magnetic zirconia and temperature-assisted ambient micro-fabricated glow discharge plasma desorption ionization mass spectrometry［J］. Analyst， 2021， 146（22）： 6944-6954.
9	刘平，王子怡，赵旭东，等. 通过式净化结合超高效液相色谱-串联质谱快速检测牛羊奶中有机磷农药残留［J］. 卫生研究， 2022， 51（3）： 483-489.
	LIU P， WANG Z Y， ZHAO X， et al. Determination of organophosphorus pesticide residues in milk of cows and sheep by ultra-high-performance liquid chromatography-tandem mass spectrometry combined with passing type purification method［J］. J Hygiene Res， 2022， 51（3）： 483-489.
10	LIU Z， XIA X， ZHOU G， et al. Acetylcholinesterase-catalyzed silver deposition for ultrasensitive electrochemical biosensing of organophosphorus pesticides［J］. Analyst， 2020， 145（6）： 2339-2344.
11	WU H L， WANG B Z， WANG Y， et al. Monoclonal antibody-based icELISA for the screening of diazinon in vegetable samples［J］. Anal Methods， 2021， 13（16）： 1911-1918.
12	BADAWY S M. Optimization of reaction time for detection of organophosphorus pesticides by enzymatic inhibition assay and mathematical modeling of enzyme inhibition［J］. J Environ Sci Health B， 2021， 56（2）： 142-149.
13	FAROKHZAD OC， LANGER R. Impact of nanotechnology on drug delivery［J］. ACS Nano， 2009， 3（1）： 16-20.
14	LI H H， ALI S， WEI W Y， et al. Rapid detection of organophosphorus in tea using NaY/GdF₄∶Yb，Er-based fluorescence sensor［J］. Microchem J， 2020， 159： 105462.
15	WANG P， LI H， HASSAN M M， et al. Fabricating an acetylcholinesterase modulated UCNPs-Cu²⁺ fluorescence biosensor for ultrasensitive detection of organophosphorus pesticides-diazinon in food［J］. J Agric Food Chem， 2019， 67（14）： 4071-4079.
16	MU X Q， WANG D， MENG L Y， et al. Glutathione-modified graphene quantum dots as fluorescent probes for detecting organophosphorus pesticide residues in radix angelica sinensis［J］. Spectrochim Acta A Mol Biomol Spectrosc， 2023， 286： 122021.
17	CHANG H W， CHEN C L， CHEN Y H， et al. Electrochemical organophosphorus pesticide detection using nanostructured gold-modified electrodes［J］. Sensors， 2022， 22（24）： 9938.
18	SONG D， JIANG X， LI Y， et al. Metal-organic frameworks-derived MnO₂/Mn₃O₄ microcuboids with hierarchically ordered nanosheets and Ti₃C₂ MXene/Au NPs composites for electrochemical pesticide detection［J］. J Hazard Mater， 2019， 373： 367-376.
19	PORTO L S， FERREIRA L F， PIO DOS SANTOS W T， et al. Determination of organophosphorus compounds in water and food samples using a non-enzymatic electrochemical sensor based on silver nanoparticles and carbon nanotubes nanocomposite coupled with batch injection analysis［J］. Talanta， 2022， 246： 123477.
20	程娇娇，彭微，孟颖，等. Yb³⁺/Er³⁺双掺杂的NaYF₄上转换纳米功能材料的制备与设计优化［J］.分析科学学报， 2022， 38（4）： 448-454.
	CHENG J J， PENG W， MENG Y， et al. Preparation and optimization of Yb³⁺/Er³⁺ double-doped NaYF₄ upconversion nanofunctional materials［J］. J Amal Sci， 2022， 38（4）： 448-454.
21	李明. NaYF₄∶Yb，Tm上转换发光纳米材料的合成及在手印显现中的应用研究［J］. 化学研究与应用， 2021， 33（9）： 1770-1775.
	LI M. Synthesis of NaYF₄∶Yb，‍Tm upconversion luminescent nanomaterials and their applications in fingerprint development［J］. Chem Res Appl， 2021， 33（9）： 1770-1775.
22	GE J， CHEN L， HUANG B， et al. Anchoring group-mediated radiolabeling of inorganic nanoparticles-a universal method for constructing nuclear medicine imaging nanoprobes［J］. ACS Appl Mater Interfaces， 2022， 14（7）： 8838-8846.
23	LIANG Z， WANG X， ZHU W， et al. Upconversion nanocrystals mediated lateral-flow nanoplatform for in vitro detection［J］. ACS Appl Mater Interfaces， 2017， 9（4）： 3497-3504.
24	ZOU R， CHANG Y， ZHANG T， et al. Up-converting nanoparticle-based immunochromatographic strip for multi-residue detection of three organophosphorus pesticides in food［J］. Front Chem， 2019， 7： 18.
25	LIU M， WEI J， WANG Y， et al. Dopamine-functionalized upconversion nanoparticles as fluorescent sensors for organophosphorus pesticide analysis［J］. Talanta， 2019， 195： 706-712.
26	RONG Y， LI H， OUYANG Q， et al. Rapid and sensitive detection of diazinon in food based on the FRET between rare-earth doped upconversion nanoparticles and graphene oxide［J］. Spectrochim Acta A Mol Biomol Spectrosc， 2020， 239： 118500.
27	向发椿. NaYF₄基上转换纳米材料的制备及在有机磷检测中的应用研究［D］. 成都：成都理工大学， 2021.
	XIANG F C. Preparation of based-NaYF₄ upconversion nanomaterials and application in the detection of organophosphorus‍［D］. Chengdu： Chengdu University of Technology， 2021.
28	CHEN Y， XIANYU Y， JIANG X. Surface modification of gold nanoparticles with small molecules for biochemical analysis‍［J］. Acc Chem Res， 2017， 50（2）： 310-319.
29	RIAZ M， ALTAF M， FAISAL A， et al. Biogenic synthesis of AgNPs with Saussurea lappa C.B. clarke and studies on their biochemical properties［J］. J Nanosci Nanotechnol， 2018， 18（12）： 8392-8398.
30	YASEEN T， PU H， SUN D W. Rapid detection of multiple organophosphorus pesticides （triazophos and parathion-methyl） residues in peach by SERS based on core-shell bimetallic Au@Ag NPs［J］. Food Addit Contam Part A Chem Anal Control Expo Risk Assess， 2019， 36（5）： 762-778.
31	HOU L， ZHANG X， KONG M， et al. A competitive immunoassay for electrochemical impedimetric determination of chlorpyrifos using a nanogold-modified glassy carbon electrode based on enzymatic biocatalytic precipitation‍［J］. Mikrochim Acta， 2020， 187（4）： 204.
32	LIU D L， LI Y， SUN R， et al. Colorimetric detection of organophosphorus pesticides based on the broad-spectrum aptamer［J］. J Nanosci Nanotechnol， 2020， 20（4）： 2114-2121.
33	YANG H， SUN Z， QIN X， et al. Ultrasmall Au nanoparticles modified 2D metalloporphyrinic metal-organic framework nanosheets with high peroxidase-like activity for colorimetric detection of organophosphorus pesticides［J］. Food Chem， 2021， 376： 131906.
34	YANG F， LI J， DONG H， et al. A novel label-free electrochemiluminescence aptasensor using a tetrahedral DNA nanostructure as a scaffold for ultrasensitive detection of organophosphorus pesticides in a luminol-H₂O₂ system‍［J］. Analyst， 2022， 147（4）： 712-721.
35	YAN X， SONG Y， ZHU C， et al. MnO₂ nanosheet-carbon dots sensing platform for sensitive detection of organophosphorus pesticides［J］. Anal Chem， 2018， 90（4）： 2618-2624.
36	XIE Y， TU X， MA X， et al. A CuO-CeO₂ composite prepared by calcination of a bimetallic metal-organic framework for use in an enzyme-free electrochemical inhibition assay for malathion［J］. Mikrochim Acta， 2019， 186（8）： 567.
37	LIN Z， ZHANG S， HUANG Z， et al. Spectrophotometric detection of fenthion in foods after extraction by magnetic zirconia［J］. Appl Opt， 2020， 59（10）： 3043-3048.
38	QIN Y， WU Y， CHEN G， et al. Dissociable photoelectrode materials boost ultrasensitive photoelectrochemical detection of organophosphorus pesticides［J］. Anal Chim Acta， 2020， 1130： 100-106.
39	SUN Y， WEI J， ZOU J， et al. Electrochemical detection of methyl-paraoxon based on bifunctional cerium oxide nanozyme with catalytic activity and signal amplification effect［J］. J Pharm Anal， 2021， 11（5）： 653-660.
40	LV M， PU H， SUN D W. Preparation of Fe₃O₄@UiO-66（Zr）@Ag NPs core-shell-satellite structured SERS substrate for trace detection of organophosphorus pesticides residues［J］. Spectrochim Acta A Mol Biomol Spectrosc， 2023， 294： 122548.
41	YAO T， TIAN Z， ZHANG Y， et al. Phosphatase-like activity of porous nanorods of CeO₂ for the highly stabilized dephosphorylation under interferences［J］. ACS Appl Mater Interfaces， 2019， 11（1）： 195-201.
42	ZHAO H， LI B， LIU R， et al. Ultrasonic-assisted preparation of halloysite nanotubes/zirconia/carbon black nanocomposite for the highly sensitive determination of methyl parathion［J］. Mater Sci Eng C Mater Biol Appl， 2021， 123： 111982.
43	MOCCI F， DE VILLIERS ENGELBRECHT L， OLLA C， et al. Carbon nanodots from an in silico perspective［J］. Chem Rev， 2022， 122（16）： 13709-13799.
44	YU G， WU W， ZHAO Q， et al. Efficient immobilization of acetylcholinesterase onto amino functionalized carbon nanotubes for the fabrication of high sensitive organophosphorus pesticides biosensors［J］. Biosens Bioelectron， 2015， 68： 288-294.
45	CHU S， HUANG W， SHEN F， et al. Graphene oxide-based colorimetric detection of organophosphorus pesticides via a multi-enzyme cascade reaction［J］. Nanoscale， 2020， 12（10）： 5829-5833.
46	WEN L， WANG J， LIU Z， et al. A portable acetylcholinesterase-based electrochemical sensor for field detection of organophosphorus［J］. RSC Adv， 2023， 13（10）： 6389-6395.
47	程娇娇，彭微，靳敏，等. 量子点在卫生分析领域中的应用［J］. 化学通报， 2022， 85（3）： 341-350.
	CHENG J J， PENG W， JIN M，et al. Application of quantum dots in the field of health analysis［J］. Chemistry， 2022， 85（3）： 341-350.
48	MARTINS C S M， LAGROW A P， PRIOR J A V. Quantum dots for cancer-related miRNA monitoring［J］. ACS Sens， 2022， 7（5）： 1269-1299.
49	JIA M， JIA B， LIAO X， et al. A CdSe@CdS quantum dots based electrochemiluminescence aptasensor for sensitive detection of ochratoxin A［J］. Chemosphere， 2022， 287（Pt 1）： 131994.
50	LI X， ZHENG Z， LIU X， et al. Nanostructured photoelectrochemical biosensor for highly sensitive detection of organophosphorous pesticides［J］. Biosens Bioelectron， 2015， 64： 1-5.
51	HU T， XU J， YE Y， et al. Visual detection of mixed organophosphorous pesticide using QD-AChE aerogel based microfluidic arrays sensor［J］. Biosens Bioelectron， 2019， 136： 112-117.
52	KORRAM J， DEWANGAN L， KARBHAL I， et al. CdTe QD-based inhibition and reactivation assay of acetylcholinesterase for the detection of organophosphorus pesticides［J］. RSC Adv， 2020， 10（41）： 24190-24202.
53	YAN X， ZHANG Z， ZHANG R， et al. Rapid detection of dimethoate in soybean samples by microfluidic paper chips based on oil-soluble CdSe quantum dots［J］. Foods， 2021， 10（11）： 2810.
54	LIU F， LEI T， ZHANG Y， et al. A BCNO QDs-MnO₂ nanosheets based fluorescence “off-on-off” and colorimetric sensor with smartphone detector for the detection of organophosphorus pesticides［J］. Anal Chim Acta， 2021， 1184： 339026.
55	FAN M， GAN T， YIN G， et al. Molecularly imprinted polymer coated Mn-doped ZnS quantum dots embedded in a metal-organic framework as a probe for selective room temperature phosphorescence detection of chlorpyrifos［J］. RSC Adv， 2021， 11（45）： 27845-27854.

Nanomaterials matrix	Sensor type	Advantage	Disadvantage	The development trend
Rare earth doped upconversion nanomaterial	Fluorescence sensor	High sensitivity， good stability， simple sample pretreatment， real-time monitoring， with visualization	Need specific band light source irradiation excitation， detection scene is limited； The anti-interference ability of some fluorescence sensors needs to be enhanced	The nucleic acid aptamer， antigen and antibody with strong specificity were used to improve the specificity and anti-interference ability and realize the simultaneous detection of multiple residual targets
Metallic nanomaterial	Surface enhanced raman scattering sensor， colorimetric sensor， electrochemical sensor	High sensitivity， good stability， simple sample preparation， the sensitive electrochemical sensor is efficient， rapid detection	The anti-interference ability of some sensors needs to be enhanced， and the related sensors using the principle of enzyme inhibition can only detect the total amount of organophosphorus pesticides， and cannot achieve accurate detection of single residue	Using the characteristics of its own materials and other materials to construct a composite sensor， further improve the detection sensitivity， repeatability and anti-interference ability of the sensor
Metal oxide nanomaterial	Electrochemical sensor， surface enhanced raman scattering sensor， spectrophotometer sensor	Wide detection linear range， high sensitivity， high efficiency， low cost， can be used in the field of rapid detection， metal oxide properties， can be used in a variety of sensors	The anti-interference ability needs to be strengthened， the related sensors using the principle of enzyme inhibition cannot realize the simultaneous detection of multiple residues， and the repeatability needs to be improved	The composite sensor is constructed by using the characteristics of its own material and other materials， and the unique properties of the matrix material are fully utilized to optimize the performance of the sensor
Carbon nanomaterials	Electrochemical sensor， colorimetric sensors	High sensitivity， strong stability， portable， can realize the field rapid detection.	The related sensor based on the principle of enzyme inhibition can not realize the simultaneous detection of multiple residues， and the repeatability needs to be improved	The stability and modifiability of the material combined with other materials are utilized to further improve the sensor's specificity and multi-residue detection capability
Quantum dot nanomaterials	Photoelectric chemical sensor， Fluorescence sensor	High sensitivity， good stability， strong anti-interference ability	Some quantum dot composites are potentially toxic； Some sensors have poor specificity	Low-toxic or non-toxic quantum dots are used to build sensors and composite with other materials to improve sensor detection performance

Nanomaterials matrix	Sensor type	Advantage	Disadvantage	The development trend
Rare earth doped upconversion nanomaterial	Fluorescence sensor	High sensitivity， good stability， simple sample pretreatment， real-time monitoring， with visualization	Need specific band light source irradiation excitation， detection scene is limited； The anti-interference ability of some fluorescence sensors needs to be enhanced	The nucleic acid aptamer， antigen and antibody with strong specificity were used to improve the specificity and anti-interference ability and realize the simultaneous detection of multiple residual targets
Metallic nanomaterial	Surface enhanced raman scattering sensor， colorimetric sensor， electrochemical sensor	High sensitivity， good stability， simple sample preparation， the sensitive electrochemical sensor is efficient， rapid detection	The anti-interference ability of some sensors needs to be enhanced， and the related sensors using the principle of enzyme inhibition can only detect the total amount of organophosphorus pesticides， and cannot achieve accurate detection of single residue	Using the characteristics of its own materials and other materials to construct a composite sensor， further improve the detection sensitivity， repeatability and anti-interference ability of the sensor
Metal oxide nanomaterial	Electrochemical sensor， surface enhanced raman scattering sensor， spectrophotometer sensor	Wide detection linear range， high sensitivity， high efficiency， low cost， can be used in the field of rapid detection， metal oxide properties， can be used in a variety of sensors	The anti-interference ability needs to be strengthened， the related sensors using the principle of enzyme inhibition cannot realize the simultaneous detection of multiple residues， and the repeatability needs to be improved	The composite sensor is constructed by using the characteristics of its own material and other materials， and the unique properties of the matrix material are fully utilized to optimize the performance of the sensor
Carbon nanomaterials	Electrochemical sensor， colorimetric sensors	High sensitivity， strong stability， portable， can realize the field rapid detection.	The related sensor based on the principle of enzyme inhibition can not realize the simultaneous detection of multiple residues， and the repeatability needs to be improved	The stability and modifiability of the material combined with other materials are utilized to further improve the sensor's specificity and multi-residue detection capability
Quantum dot nanomaterials	Photoelectric chemical sensor， Fluorescence sensor	High sensitivity， good stability， strong anti-interference ability	Some quantum dot composites are potentially toxic； Some sensors have poor specificity	Low-toxic or non-toxic quantum dots are used to build sensors and composite with other materials to improve sensor detection performance

[1]	裴佳欢, 齐小花, 邹明强, 金涌, 汪德颖, 罗云敬. 表面增强拉曼光谱在动物源性食品兽药残留检测的研究进展[J]. 应用化学, 2024, 41(4): 459-471.
[2]	尹娜, 王樱蕙, 张洪杰. 稀土纳米材料在脑肿瘤成像和治疗中的研究进展[J]. 应用化学, 2024, 41(3): 309-327.
[3]	周学敏, 吕姝臻, 张国芳, 崔竹梅, 毕赛. 基于上转换信标探针构建信号放大近红外激发荧光生物传感器用于microRNA检测[J]. 应用化学, 2024, 41(1): 137-146.
[4]	姚春莹, 朱晓艳, 刘艳玲. 三维葡萄糖电化学传感器与胶原水凝胶集成实时监测细胞代谢[J]. 应用化学, 2024, 41(1): 156-163.
[5]	卢剑天, 邹金辉, 赵博霖, 张玉微. 无机纳米酶在分析传感领域的应用研究进展[J]. 应用化学, 2024, 41(1): 60-86.
[6]	谭翠盈, 丁威超, 马婷婷, 肖瑶, 刘健. 超亲水/超疏气电解水催化剂的研究进展[J]. 应用化学, 2023, 40(8): 1109-1125.
[7]	李慧慧, 姚开胜, 赵亚南, 范李娜, 田钰琳, 卢伟伟. 离子液体调控合成Pt-Pd双金属纳米材料及其催化氨硼烷水解释氢[J]. 应用化学, 2023, 40(4): 597-609.
[8]	姜士鹏, 周禹希, 孟沛然, 谢炎轩, 宋祉怡, 赵洹影, 孙越. 基于无金属可见光诱导原子转移自由基聚合方法制备人血清白蛋白超微印迹传感器及其性能[J]. 应用化学, 2023, 40(2): 299-308.
[9]	柳小虎, 赖小娟, 曹红燕, 王婷婷, 党志强. 起泡剂/稳泡剂/SiO₂复合泡沫缓速酸液体系协同增效性能[J]. 应用化学, 2023, 40(1): 91-99.
[10]	王文栋, 李在均. 钌-石墨烯量子点人工酶合成及用于胡萝卜中辛硫磷的光度检测[J]. 应用化学, 2022, 39(8): 1285-1293.
[11]	李东东, 秦丽, 唐录华, 高文惠. 碱性橙Ⅱ印迹传感器的制备及其应用[J]. 应用化学, 2022, 39(7): 1052-1064.
[12]	邵姗, 张剑, 邓凯强, 杨杰, 杨绍明. 镍钴双金属-卟啉有机框架复合纳米材料构建的无酶传感器检测多巴胺[J]. 应用化学, 2022, 39(7): 1098-1107.
[13]	王涛, 刘厦, 刘宝林, 高志贤. 基于适配体和抗体的生物传感器在雌二醇检测中的应用[J]. 应用化学, 2022, 39(3): 374-390.
[14]	杜慧, 姚晨阳, 彭皓, 姜波, 李顺祥, 姚俊烈, 郑方, 杨方, 吴爱国. 过渡金属掺杂磁性纳米粒子在生物医学领域中的研究进展[J]. 应用化学, 2022, 39(3): 391-406.
[15]	秦丽, 尤晓亭, 唐录华, 李建文, 张寅, 高文惠, 韩俊华. 基于纳米材料修饰的碱性嫩黄O印迹传感器的制备及其应用[J]. 应用化学, 2022, 39(12): 1880-1890.