铈离子与焦磷酸根离子配位聚合物网络用于草甘膦快速荧光检测

张强; 王冬伟; 蒋建功; 刘雪科; 刘东晖; 周志强

doi:10.16801/j.issn.1008-7303.2022.0045

铈离子与焦磷酸根离子配位聚合物网络用于草甘膦快速荧光检测

doi: 10.16801/j.issn.1008-7303.2022.0045

张强^1,,
王冬伟^{1, 2},
蒋建功¹,
刘雪科¹,
刘东晖^1, ,,
周志强¹

1.
中国农业大学理学院，北京 100193
2.
农业农村部农药检定所，北京 100125

基金项目: 中国农业大学2115人才培育发展支持计划.

详细信息

作者简介:
张强，421176474@qq.com

通讯作者:
刘东晖，liudh@cau.edu.cn

中图分类号: O657.39；TQ457
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- 文章访问数: 371
- HTML全文浏览量: 139
- PDF下载量: 31
- 被引次数: 0
出版历程
- 收稿日期: 2022-02-11
- 录用日期: 2022-03-23
- 网络出版日期: 2022-05-09
- 刊出日期: 2022-10-10

Cerium ion (Ce³⁺) and pyrophosphate ion coordination polymer networks for the rapid fluorometric detection of glyphosate

1.
College of Science, China Agricultural University, Beijing 100193, China
2.
Institute of the Control of Agrochemicals, Ministry of Agriculture and Rural Affairs, Beijing 100125, China

Funds: the 2115 Talent Development Program of China Agricultural University.

摘要

摘要: 本文基于铈离子与焦磷酸根离子 (Ce-PPi) 配位聚合物网络 (coordination polymer networks，CPNs) 开发出一种草甘膦快速检测方法。通过铈离子 (Ce³⁺) 与焦磷酸根离子 (PPi) 之间的配位作用，自组装合成出Ce-PPi CPNs，并对其结构和性质进行了表征。草甘膦可以减弱PPi与Ce³⁺之间的配体场效应，导致Ce-PPi CPNs的荧光减弱。基于这一原理，通过优化条件，实现了草甘膦的定量检测，R²为0.9972，检出限为0.014 μmol/L。该方法检测灵敏度较高，且对草甘膦具有优异的选择性，可应用于自来水与苹果样品中草甘膦的检测，方法定量限为0.05 mg/kg，回收率在77%~87%之间，为草甘膦的快速、现场和实时实际样品检测提供了新的选择。
- 铈离子 /
- 焦磷酸盐 /
- 配位聚合物网络 /
- 草甘膦 /
- 荧光检测
Abstract: A rapid fluorometric method was established to detect glyphosate by using cerium ion and pyrophosphate ion (Ce-PPi) coordination polymer networks (CPNs). Based on coordination of cerium ion (Ce³⁺) and pyrophosphate ion (PPi), fluorescent Ce-PPi CPNs were synthesized by simple self-assemble process, and the structure and properties were characterized. Upon introducing glyphosate, the ligand field effect of PPi with Ce³⁺ was weakened resulting in a decrease in fluorescence of Ce-PPi CPNs. Based on this principle, the quantitative detection of glyphosate was achieved by optimizing the conditions, with R² of 0.9972 and the detection limit of 0.014 μmol/L. The established method based on Ce-PPi CPNs possessed outstanding sensitivity and exclusive selectivity for rapid detction of glyphosate, and could be used for the detection of glyphosate in tap water and apple samples. The limit of quantitation (LOQ) was 0.05 mg/kg and the recoveries were between 77% and 87%. The method provided a potential choice for the rapid, on-site and real-time, detection of glyphosate.
- cerium ion /
- pyrophosphate /
- coordination polymer networks /
- glyphosate /
- fluorescence detection

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图 1 Ce³⁺与Ce-PPi CPNs能级和能量转移过程示意图^[27]

Figure 1. Schematic diagram of energy levels and energy transfer process of Ce³⁺ and Ce-PPi CPNs^[27]

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图 2 Ce-PPi CPNs用于草甘膦荧光检测示意图

Figure 2. Principle of the fluorometric glyphosate assay based on Ce-PPi CPNs

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图 3 Ce- PPi CPNs的SEM谱图

Figure 3. SEM image of Ce-PPi CPNs

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图 4 Ce- PPi CPNs SEM (A)、EDS (B)和 (C)(磷：红色，铈：绿色)谱图

Figure 4. (A) SEM image of Ce-PPi CPNs; EDS mapping images of (B) P in red and (C) Ce in green

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图 5 Ce-PPi CPNs的XPS谱图

Figure 5. XPS image of Ce-PPi CPNs

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图 6 Ce-PPi CPNs的激发和发射光谱

Figure 6. The excitation and emission spectra of Ce-PPi CPNs

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图 7 不同物质的紫外-吸收光谱 (浓度均为1 mmol/L)

Figure 7. UV-Vis absorption spectra of different substances (the concentration of all substances was 1 mmol/L)

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图 8 Ce³⁺浓度(A)、PPi添加量(B)、 PPi与Ce³⁺结合时间 (C)以及草甘膦与 Ce³⁺作用时间(D)对Ce-PPi CPNs相对荧光强度的影响

Figure 8. Effects of the concentration of Ce³⁺(A) , the addition amount of PPi (B) , the combination time between PPi with Ce³⁺(C) and reaction time of glyphosate and Ce³⁺ (D) on relative fluorescence intensities of Ce-PPi CPNs

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图 9 Ce-PPi CPNs在不同浓度草甘膦存在下的荧光光谱

Figure 9. Fluorescence spectra of Ce-PPi with various concentration of glyphosate

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图 10 草甘膦和潜在干扰物质存在时的相对荧光强度

1~23分别代表：1-草甘膦、2-Na⁺、3-Ca²⁺、4-Zn²⁺、5-抗坏血酸、6-葡萄糖、7-甘氨酸、8-毒死蜱、9-灭多威、10-莠去津、11-异丙甲草胺、12-戊唑醇、13-嘧菌酯、14-马拉硫磷、15-杀螟硫磷、16-草铵膦、17-辛硫磷、18-乙酰甲胺磷、19-H₂PO₄⁻、20-HPO₄²⁻、21-PO₄³⁻、22-百草枯、23-PBS缓冲液(pH=7.4) (所有物质浓度均为5 μmol/L)

Figure 10. The relative fluorescence intensity change rate of glyphosate and potential interfering substances towards detection

1-23 was 1-glyphosate, 2-Na⁺, 3-Ca²⁺, 4-Zn²⁺, 5-ascorbic acid, 6-glucose, 7-glycine, 8-chlorpyrifos, 9-methomyl, 10-atrazine, 11-metolachlor, 12-tebuconazole, 13-azoxystrobin, 14-malathion, 15-fenitrothion, 16-glufosinate ammonium, 17-phoxim, 18-acephate, 19-H₂PO₄⁻, 20-HPO₄²⁻, 21-PO₄³⁻, 22-paraquat, 23-PBS buffer (pH=7.4) , respectively (5 μmol/L for all substances)

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表 1 Ce-PPi CPNs和NIST数据库中被测元素的结合能

Table 1. Binding energies of tested elements in Ce-PPi and NIST database

元素 Element	结合能 Binding energy
元素 Element	Ce-PPi/eV	NIST/eV
铈 Cerium (3d_3/2)	904.4	904.0 (CePO₄)^*
铈 Cerium (3d_5/2)	885.5	885.4 (CePO₄)
氧 Oxygen	531.3	531.0 (CePO₄)
磷 Phosphorus	133.8	133.3 (NaP₂O₇)
注：^NIST 结合能括号内的内容为元素所属的具体物质。Note: ^The content in the NIST binding energy brackets is the specific substance to which the element belongs.

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表 2 不同草甘膦检测方法的检出限和检测时间对比

Table 2. Comparison of limit of detection (LOD) and detection time of glyphosate by different analytical methods

分析方法　 Analytical method	检出限 LOD/ (μg/L)	检测时间 Detection time/ min	参考文献 Reference
荧光法 Fluorescence	5	7	[29]
免疫测定法 Immunoassay	4.06 × 10⁵	30	[30]
比色法 Colorimetry	100	50	[31]
电化学法 Electrochem SENSE	10	5	[32]
化学发光法 Chemiluminescence	46	10	[33]
液相色谱-质谱联用 LC-MS/MS	0.23	15	[34]
Ce-PPi CPNs荧光传感器 Fluorescent sensor based on Ce-PPi CPNs	2.37 (0.014 μmol/L)	5	本工作 This work

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表 3 自来水和苹果样品中草甘膦的添加回收率和相对标准偏差(n=5)

Table 3. Recoveries and relative standard deviations (RSD) of glyphosate in tap water and apple samples(n=5)

样品种类 Sample	线性方程及决定系数 Linear equation and determination coefficient (0.05~1 mg/L (mg/kg))	添加水平 Spiked level	平均回收率 Average recovery/%	相对标准偏差 RSD/%	定量限 The limit of quantitation, LOQ
自来水 Tap water	F= −5331.582 log c + 7311.298 R²=0.9955	0.05 mg/L	80	8.7	0.05 mg/L
		0.5 mg/L	84	6.4
		1 mg/L	87	6.8
苹果 Apple	F= −5072.112 logc + 7899.375 R²=0.9980	0.05 mg/kg	77	8.8	0.05 mg/kg
		0.5 mg/kg	80	8.0
		1 mg/kg	86	6.1

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