Analysis of phenylurea and propanil herbicides by solid-phase microextraction and liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection

This study examines the application of solid-phase microextraction coupled with high performance liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection (SPME-HPLC-PIF-FD) for the determination of four phenylurea herbicides (monolinuron, diuron, linuron and neburon) and propanil in groundwater. Direct immersion (DI) SPME was applied using a 60 μm polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber for the extraction of the pesticides from groundwater samples. An AQUASIL C₁₈ column (150 mm × 4.6 mm i.d., 5 μm) was used for separation and determination in HPLC. The method was evaluated with respect to the limits of detection (LODs) and the limits of quantification (LOQs) according to IUPAC. The limits of detection varied between 0.019 μg L⁻¹ and 0.034 μg L⁻¹. Limits of quantification ranged between 0.051 μg L⁻¹ and 0.088 μg L⁻¹. These values meet the recommended limits for individual pesticides in groundwater (0.1 μg L⁻¹) established by the EU. Recoveries ranged between 86% and 105% and relative standard deviation values between 2% and 8%.     

Gas chromatographic analysis of phenylurea herbicides following catalytic hydrolysis on silica gel

Summary A method is described for the rapid catalytic hydrolysis of phenylurea herbicides on silica gel at elevated temperatures. After derivatisation of the anilines produced with heptafluorobutyric acid anhydride final analysis is done on a gas chromatograph equipped with an electroncapture detector. Detection limits are in the 1–5 picogram range. The method has successfully been applied to residue analysis of water samples at the 1 ppb level. The determination of free anilines present in water samples and the potential of various techniques to be used to discriminate between free anilines and parent herbicides are also discussed.     

Simultaneous HPLC determination of phenylurea herbicides and their corresponding anilines in water after on-line preconcentration

On-line preconcentration on a short C₁₈ column, prior to HPLC with UV and electrochemical detection, has been used for determination of some phenylurea herbicides and their possible degradation products, substituted anilines, in water samples. With electrochemical detection the detection limit at a signal-to-noise ratio of 3 was 5 ppt for 4-chloroaniline and 4-bromoaniline and 7 ppt for 3,4-dichloroaniline; with UV detection the detection limit was ca 300 ppt for all analytes.     

Amino functionalized magnetic covalent organic framework for magnetic solid-phase extraction of sulfonylurea herbicides in environmental samples from tobacco land

An amino-functionalized magnetic covalent organic framework composite TpBD-(NH₂)₂@Fe₃O₄ (Tp=Tp1,3,5-triformylphloroglucinol, BD-(NH₂)₂ is 3,3',4,4'-biphenyltetramine) was prepared by post-synthesis modification. Due to its abundant benzene rings and amino groups, large specific surface area and porous structure, the prepared TpBD-(NH₂)₂@Fe₃O₄ exhibits high extraction efficiency toward sulfonylurea herbicides. Based on this, a new method of magnetic solid-phase extraction with TpBD-(NH₂)₂@Fe₃O₄ as the sorbent combined with high-performance liquid chromatography and ultraviolet detection was developed for trace analysis of sulfonylurea herbicides in environmental water, soil and tobacco leaves samples from tobacco land. Under the optimized conditions, the limits of detection within 0.05–0.14 μg/L were achieved with a high enrichment factor of 217-260-fold, and the relative standard deviations were 4.9–7.5% (n = 7, c = 0.5 μg/L). The linear range was around three orders of magnitude with the square of correlation coefficient higher than 0.9936. The method was applied to analyze five sulfonylurea herbicides in the environmental water, soil, and tobacco leave samples collected from tobacco land. No sulfonylurea herbicides were detected in these samples. The recoveries of target sulfonylurea herbicides in spiked environmental water, soil, and tobacco leaf samples were found in the range of 90.7–104, 70.7–99.0, and 59.3–97.8%, respectively. The results illustrate that the established TpBD-(NH₂)₂@Fe₃O₄-magnetic solid-phase extraction- high-performance liquid chromatography–ultraviolet detection method is efficient for the analysis of trace sulfonylurea herbicides in environmental samples.     

基于混合固定相色谱柱的SPE-HPLC法检测环境水体中三嗪类除草剂

利用混合固定相色谱柱(Optimix SCX/C8)分析了8种三嗪类化合物,在0.01 mol/L乙酸钠缓冲溶液(pH4.2)-CH3CN(75：25,V/V)等度洗脱的流动相条件下,实现了利用液相色谱方法分离同分异构体敌草净和西草净,并对比了相同色谱条件下8种目标物在C8色谱柱上的分离效果;比较了PEP和C18固相萃...     

解密草甘膦

草甘膦作为全球第一大农药单剂,在2017年市场需求量超过80万吨。中国作为第一大草甘膦出口国在2017年的总产量超过50万吨,其中约80%用于出口。从草甘膦结构和性质、毒性、合成、使用量以及污染的治理方面进行介绍,其目的是唤醒公众重视环境保护,帮助大众树立环境保护从身边做起的意识。     

拓展浓度加和模型预测三种三嗪类除草剂混合物的时间依赖毒性

浓度加和(CA)模型是评估与预测化学混合物毒性效应的常用模型之一,已广泛应用于药物组合与农药混配等多个混合物体系. 然而,CA不能用于包含不同时间具有不同效应组分的混合物体系,需要拓展. 以具有不同时间依赖毒性特征的三种三嗪类除草剂即嗪草酮(MET)、西草净(SIM)和环嗪酮(HEX)为混合物组分,以直接均分射线法(EquRay)构建它们的二元混合物,以青海弧菌Q67为受试生物,在6个不同时间(即0.25,2,4,8,12和16 h)下测定各混合物组分及其二元混合物暴露于Q67时的发光抑制毒性,分析与归纳抑制毒性随时间的变化规律. 结果表明,三种除草剂对发光菌Q67的发光抑制毒性具有不同的时间变化规律：MET的毒性随时间延长有明显增大的趋势,SIM的毒性在不同时间没有显著性变化,而HEX随着时间的延长毒性开始有所增加,而后变化很小;二元混合物毒性的时间变化规律与混合物组分有关,MET与HEX的二元混合物体系的毒性随暴露时间的延长而逐步增加,MET-SIM体系开始有所下降而后缓慢增加,而SIM-HEX体系的毒性在不同时间差异不明显;应用拓展后的CA模型分析所有二元混合物在不同时间点的毒性变化,表明都是加和的,没有协同或拮抗作用.     

气相色谱-质谱法测定茶叶中29种酸性除草剂的残留量

建立了茶叶中29种酸性除草剂残留量的气相色谱-质谱测定与确证方法。采用乙腈超声振荡提取试样中29种酸性除草剂,石墨化炭黑固相萃取柱净化,三甲基硅烷化重氮甲烷衍生化,再经弗罗里硅土固相萃取柱净化,用气相色谱-质谱法选择离子监测方式测定,外标法定量,根据离子丰度比确证。在加标水平为0.01,0.05,0.1 mg/kg时,29种目标物的加标回收率为57.1%～120.4%,相对标准偏差(RSD)为4.3%～20.9%;方法的检出限在0.002～0.005 mg/kg之间。该方法准确、灵敏、快速,可满足国际上对茶叶中29种酸性除草剂残留的检测需要。     

具有药物活性的离子液体

离子液体阴阳离子的可设计性使其具有可控溶解性、独特表面活性、高热稳定性、增强的生物利用率和生物活性,这些特点使离子液体在消除同质多晶现象、改变药物传输模式及可包含传统药物组分等方面具有优势,成为当前离子液体研究领域的热点之一。本文对离子液体在医药领域的应用做了全面的阐述,主要介绍了近十年来离子液体在活性药物组分、抗菌剂及除草剂方面的成果,探讨了当前存在的问题及研究方向,并对其应用做了展望。     

毛细管电泳-激光诱导荧光法测定草甘膦、草胺膦及氨甲基膦酸

建立了一种快速、有效的毛细管电泳分离-激光诱导荧光检测有机磷除草剂草甘膦、草胺膦和草甘膦的代谢物氨甲基膦酸的方法。将荧光衍生试剂5-(4, 6-二氯三嗪基)氨基荧光素(DTAF)成功用于衍生上述3种化合物。最佳衍生条件: DTAF的浓度为1.0 μmol/L,以50 mmol/L硼酸(pH 9.5)作为缓冲溶液,在30 ℃下反应40 min。以pH 9.5的30 mmol/L硼酸缓冲溶液(含15 mmol/L Brij-35)作为电泳背景电解质,3种衍生物得到基线分离。在优化的条件下,草甘膦、草胺膦、氨甲基膦酸的检出限分别为3.21、6.14和1.99 ng/kg。将该方法应用于环境水样和土壤中除草剂及代谢物的测定,回收率为91.3%～106.0%。该方法准确、灵敏,可满足环境样品中有机磷农药及其代谢物残留的检测要求。