唑啉草酯的水解及光解特性

欧将; 刘开林; 滕玉婷; 曾利红; 张贵群; 聂春林; 欧晓明

doi:10.16801/j.issn.1008-7303.2022.0020

唑啉草酯的水解及光解特性

doi: 10.16801/j.issn.1008-7303.2022.0020

欧将^{1, 2,},
刘开林³,
滕玉婷³,
曾利红^{1, 2},
张贵群^{1, 2},
聂春林^{1, 2},
欧晓明^{1, 2, ,}

1.
湖南化工研究院国家农药创制工程技术研究中心/湖南省农用化学品重点实验室，长沙 410014
2.
湖南化研院检测技术有限公司，长沙 410014
3.
湖南农业大学植物保护学院，长沙 410128

基金项目: 湖南省自然科学基金项目(2019JJ50270).

详细信息

作者简介:
欧将，bestjiang@foxmail.com

通讯作者:
欧晓明，xmouhn@163.com.

中图分类号: O657.63；TQ457.2
计量
- 文章访问数: 75
- HTML全文浏览量: 55
- 被引次数: 0
出版历程
- 收稿日期: 2021-08-16
- 录用日期: 2021-12-17
- 网络出版日期: 2022-03-01

Hydrolysis and photolysis characteristics of pinoxaden

OU Jiang^{1, 2
,},
LIU Kailin³,
TENG Yuting³,
ZENG Lihong^{1, 2},
ZHANG Guiqun^{1, 2},
NIE Chunlin^{1, 2},
OU Xiaoming^{1, 2
, ,}

1.
National Engineering Research Center for Agrochemicals/Hunan Province Key Laboratory for Agrochemicals, Hunan Research Institute of Chemical Industry, Changsha 410014, China
2.
Hunan Research Institute of Chemical Industry Testing Technology Co., Ltd., Changsha 410014, China
3.
College of Plant Protection, Hunan Agricultural University, Changsha 410128, China

Funds: the Natural Science Foundation of Hunan Province (2019JJ50270)

摘要

摘要: 在实验室条件下，采用高效液相色谱和高效液相色谱-串联质谱研究了唑啉草酯在不同条件下的水解和光解特性。结果表明：在pH值分别为4.0、7.0和9.0的缓冲溶液中，25 ℃时唑啉草酯的半衰期分别为347、40.8和1.08 h，50 ℃时则分别为57.8、11.6和0.498 h，均为易水解；唑啉草酯在碱性条件下易水解，酸性条件下水解较慢；其水解速率随温度升高而升高，温度效应系数为2.18~6.00。在模拟太阳光氙灯辐射下，唑啉草酯在缓冲溶液中的光解速率随其pH值的升高而加快，在pH值为8.0时最短，为10.0 h；唑啉草酯在自然水体中的光解速率依次为池塘水>稻田水>河水>纯水，4种条件下的半衰期分别为5.17、7.79、8.56和38.5 h。唑啉草酯水解的主要产物是 M2 (8-(2,6-二乙基-4-甲基苯基)-9-羟基-1,2,4,5-四氢吡唑[1,2-d][1,4,5]噁二氮杂卓-7-酮)，其降解机理主要是酯水解反应， M2 在光照条件下进一步降解，表明光解为唑啉草酯降解的一个重要途径。研究结果可为唑啉草酯在水体中的环境行为及其环境安全性评价提供参考。
- 唑啉草酯 /
- 水解 /
- 光解 /
- 半衰期
Abstract: The hydrolytic and photolytic characteristics of pinoxaden under different conditions were investigated by high performance liquid chromatography (HPLC) and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in laboratory conditions. The results showed that in the buffer solutions of pH 4.0, 7.0 and 9.0, the hydrolysis half-lives of pinoxaden were 347, 40.8 and 1.08 h at 25 ℃, and were 57.8, 11.6 and 0.498 h at 50 ℃, respectively, which classified it as easily hydrolysis type. The hydrolysis of pinoxaden was rapid under alkaline conditions, but slowly under acidic conditions. The hydrolytic rate of pinoxaden increased with the increase of temperature, and the temperature effect coefficients ranged from 2.18 to 6.00. Under the irradiation of xenon simulated sunlight, the photo-degradation half-lives of pinoxaden in the buffer solutions were decreased with the increase of pH value, and the shortest was 10.0 h at pH of 8.0. The photolytic rates of pinoxaden in different natural water showed the following sequence: pond water > paddy water > river water > pure water, and the half-lives were 5.17, 7.79, 8.56 and 38.5 h, respectively. The main hydrolysis product of pinoxaden was M2 (8-(2,6-diethyl-4-methyl-phenyl)-9-hydroxy-1,2,4,5-tetrahydro-pyrazolo[1,2-d][1,4,5]oxadiazepin-7-one), and the main degradation mechanism was the hydrolyzation of the ester group. M2 was further degraded under light conditions, indicating that photolysis was an important degradation way of pinoxaden. The results provided a scientific reference for the environmental behavior and safety assessment of pinoxaden in water environment.
- pinoxaden /
- hydrolysis /
- photolysis /
- half-life

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1 唑啉草酯和M2结构式

1. The structural formula of pinoxaden and M2

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图 1 水解条件下唑啉草酯和M2随时间变化曲线(pH 7.0，25 ℃)

Figure 1. The variation curve of pinoxaden and M2 with time under hydrolysis conditions (pH 7.0, 25 ℃)

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图 2 唑啉草酯降解为M2的反应

Figure 2. Reaction of the degradation of pinoxaden to M2

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图 3 光解条件下唑啉草酯和M2随时间变化曲线(pH 7.0，25 ℃)

Figure 3. The variation curve of pinoxaden and M2 with time under photolysis conditions (pH 7.0, 25 ℃)

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表 1 供试水样的理化性质

Table 1. Physical and chemical properties of tested water samples

水体　　　 Water sample	pH值 pH value	电导率 Conductivity/ (μS/cm)	溶解氧 Dissolved oxygen/ (mg/L)
纯水 Pure water	6.260	4.60	9.18
河水 River water	6.844	271	12.64
池塘水 Pond water	8.003	250	13.77
稻田水 Paddy water	7.393	176	13.10

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表 2 唑啉草酯水解试验取样时间表

Table 2. Sampling time for hydrolysis test of pinoxaden

pH	温度 Temperature/ ℃	取样时间 Sampling time
4.0	25	0、3、7、11、15、19、23、30、42、51 d
4.0	50	0、1、2、3、4、5、6、7、8 d
7.0	25	0、8、22、29、37、45、49、54、81、 95、120、169、190、210 h
7.0	50	0、4、8、18、21、24、28、32、42 h
9.0	25	0、0.5、0.75、1、1.25、1.5、1.75、2、3、4 h
9.0	50	0、10、20、25、30、40、50、60、90、120 min

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表 3 唑啉草酯在不同pH值和不同温度条件下的水解动力学参数

Table 3. Hydrolytic kinetics parameters of pinoxaden under different pH value and temperatures

pH	温度 t/℃	动力学方程 Kinetic equation	决定系数 R²	半衰期 t_1/2/h	活化能 E_a/(kJ/mol)	温度效应系数 Q
4.0	25	C_t = 10.12e^−0.002t	0.9802	347	57.3	6.00
4.0	50	C_t = 11.84e^−0.012t	0.9264	57.8	57.3	6.00
7.0	25	C_t = 9.53e^−0.017t	0.9959	40.8	40.4	3.53
7.0	50	C_t = 9.47e^−0.06t	0.9902	11.6	40.4	3.53
9.0	25	C_t = 9.07e^−0.64t	0.9843	1.08	24.9	2.18
9.0	50	C_t = 12.35e^−1.392t	0.9652	0.498	24.9	2.18

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表 4 唑啉草酯在不同缓冲溶液中的光解动力学参数

Table 4. Photolysis kinetics parameters of pinoxaden in different buffer solutions

pH	动力学方程 Kinetic equation	决定系数 R²	半衰期 t_1/2/h
3.0	C_t = 10.21e^−0.011t	0.9422	63.0
4.0	C_t = 10.04e^−0.011t	0.9617	63.0
5.0	C_t = 10.33e^−0.014t	0.9582	49.5
6.0	C_t = 10.44e^−0.013t	0.9594	53.3
7.0	C_t = 10.18e^−0.028t	0.9939	24.8
8.0	C_t = 9.54e^−0.069t	0.9925	10.0

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表 5 唑啉草酯在自然水体中的光解动力学参数

Table 5. Photolysis kinetics parameters of pinoxaden in natural water

水体　　 Water sample	动力学方程 Kinetic equation	决定系数 R²	半衰期 t_1/2/h
纯水 Pure water	C_t = 10.72e^−0.018t	0.9872	38.5
河水 River water	C_t = 10.43e^−0.081t	0.9782	8.56
池塘水 Pond water	C_t = 11.85e^−0.134t	0.9828	5.17
稻田水 Paddy water	C_t = 11.54e^−0.089t	0.9636	7.79

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