2,3-环氧羧酸-对-溴苯甲酰甲基酯的合成及其抗菌活性

环氧化合物,尤其是2,3-环氧羧酸类化合物既是一类重要的有机合成中间体,又是一类很有前途的生物活性物质,并广泛存在于自然界中,与生物体内的生理生化过程紧密相连。文献报导环氧化合物具有杀虫、杀螨、杀菌和生长调节的活性。Hendlin等从链霉菌的发酵液中分离到一种抗菌素(膦霉素),证明其为广谱的杀菌剂,其结构为2,3-环氧丙膦     

Critical review of the application of liquid chromatography/mass spectrometry to the determination of pesticide residues in biological samples

A critical review is made on the use of hyphenated liquid chromatography/mass spectrometry (LC–MS) for the identification and quantification of pesticides and their metabolites in human biosamples (whole blood, plasma, serum and urine). The first applications of LC–MS in this field began in the early 1990s. Since then, increasing interest has been shown in applying this powerful technique, with most applications dealing with the determination of a variety of chemically diverse metabolites in urine. The use of different LC–MS interfaces and mass spectral detection modes are discussed. Special attention is given to tandem mass spectrometry (MS/MS) due to its inherent advantages of increased sensitivity and selectivity, as well as its advantages for identification and confirmation of analytes in samples. Quantification can be severely affected by matrix effects, the most common being inhibition of the ionisation of analytes in the mass spectrometer, which leads to unacceptable errors if no correction is made. Different approaches can be employed to minimise this undesirable matrix effect, the preferred being the use of labelled internal standards (when available) in isotope dilution methods or the application of an efficient clean-up, performed off-line or automated on-line. Adequate criteria for confirming the identities of residues detected are required in order to avoid false positives. The criterion most commonly used with a triple quadrupole instrument is the monitoring of two MS/MS transitions together with the ion abundance ratio. TOF mass analysers are seldom used in pesticide residue analysis despite their improved resolution and mass accuracy characteristics, which makes them very suitable for confirmation purposes. The main reasons for the relative unpopularity of TOF MS in residue analysis are its limited sensitivity and its high acquisition cost. In this paper, we present a critical assessment on current techniques, trends and future developments, and give illustrative examples to point out the main characteristics of LC–MS for pesticide residue analysis in biological fluids.     

The status of pesticide pollution in Tanzania

The paper summarises the findings of recent studies carried out to assess the levels of pesticide residues in water, sediment, soil and some biota collected from different parts of Tanzania. Although the intention is to cover the whole country, so far the studies have focused on areas with known large-scale pesticide use (Southern Lake Victoria and its basin, TPC sugar Plantations in Kilimanjaro region, Dar es Salaam coast, Mahonda-Makoba basin in Zanzibar) and a former pesticide storage area at Vikuge Farm in Coast region). Analysis of the cleaned extracts in GC-ECD/NPD revealed the dominance of organochlorines in all samples. Generally, low levels of residues were found in areas associated with agricultural pesticide use but the levels in the former storage areas were substantially high. DDT and HCH were dominant in all the studied areas. In the former areas, levels of ∑DDT in water, sediments and soil were up to 2 μg L⁻¹, 700 μg kg⁻¹ and 500 μg kg⁻¹, respectively, while those of ∑HCH were up to 0.2 μg L⁻¹, 132 μg kg⁻¹ and 60 μg kg⁻¹, respectively. The levels in aquatic biota were much higher than those in the water most likely due to bioaccumulation. In the former storage area at Vikuge the levels of pesticides in the topsoil were alarmingly high. Their concentrations were up to 282,000 mg kg⁻¹ dry weight for ∑DDT and up to 63,000 mg kg⁻¹ for ∑HCH. A herbicide, pendimethalin [N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine], was also found at concentrations up to 41,000 mg kg⁻¹ dry weight. Thus the total pesticide content in the soil was almost 40%. Following these findings the area is now earmarked to be a demonstration site for a proposed GEF project ‘Bioremediation of POPs impacted soils in East Africa’.     

Discovering metabolites of post-harvest fungicides in citrus with liquid chromatography/time-of-flight mass spectrometry and ion trap tandem mass spectrometry

In this study, we benefit from the combination of liquid chromatography (LC)/time-of-flight (TOF) MS accurate mass measurements to generate elemental compositions of ions and LC/ion trap multiple MS (MSn) providing complementary structural information, which is useful for the elucidation of unknown organic compounds at trace levels in complex food extracts. We have applied this approach to investigate different citrus fruits extracts, and we have identified two post-harvest fungicides (imazalil and prochloraz), the main degradation product of imazalil ([M + H]+, m/z 257) and a non-previously reported prochloraz degradation product ([M + H]+, m/z 282). The database-mediated identification of the parent compounds was based on the generated elemental composition obtained from accurate mass measurements and additional qualitative information from the high resolution chlorine isotopic clusters of both the protonated molecules (imazalil, [M + H]+ 297.0556, <0.1 ppm error, 2-Cl; prochloraz, [M + H]+ 376.0381, 1.9 ppm error, 3-Cl) and their characteristic fragments ions (imazalil: m/z 255 and 159; prochloraz: m/z 308 and 266). The correlation between the structural information provided by ion trap MS/MS fragmentation pathways of the parent species and the TOF accurate mass elemental composition data of the degradation products were the key to elucidate the structures of the degradation products of both post-harvest fungicides. Finally, where standards were not available (prochloraz), further confirmation was obtained by synthesizing the proposed degradation product by acid hydrolysis of the parent standard and confirmation by LC/TOF-MS.     

Gas and liquid chromatography and enzyme linked immuno sorbent assay in pesticide monitoring of surface water from the western mediterranean (Comunidad Valenciana,Spain)

Summary A monitoring programme based on gas chromatography (NPD, ECD) using MSD for confirmatory purposes and coupled-column liquid chromatography was applied to the analysis of pesticide residues in surface water from a predominantly agricultural area of Spain (Comunidad Valenciana). Samples analysed by means of enzyme-linked immunosorbent assay gave similar results to those obtained by GC (MSD) for the determination of total triazines. The test employed had the advantages of a simple test procedure, short analysis time and high confirmatory value. Nevertheless, the multiresidue character, accuracy and unequivocal identification of individual pesticide residues of GC (MSD) make this technique the most appropriate for environmental monitoring programmes. In this monitoring programme about 200 samples were analysed between 1993–1994. 27 different pesticides were detected in 91 of these samples. The pesticides more frequently detected were dimethoate, methidathion, endosulfan A and B, endosulfan sulphate and pirimicarb. The highest concentrations found were 39.9 g L^–1 of dimethoate, 10.6 of pirimicarb and 10.6 of methidathion.     

Microwave‐assisted extraction and high‐throughput monolithic‐polymer‐based micro‐solid‐phase extraction of organophosphorus,triazole, and organochlorine residues in apple

A high‐throughput micro‐solid‐phase extraction device based on a 96‐well plate was constructed and applied to the determination of pesticide residues in various apple samples. Butyl methacrylate and ethylene glycol dimethacrylate were copolymerized as a monolithic polymer and placed in the cylindrically shaped stainless‐steel meshes of 96‐micro‐solid‐phase extraction device and used as an extracting unit. Before the micro‐solid‐phase extraction, microwave‐assisted extraction was employed to facilitate the transfer of the pesticide residues from the apple matrix to liquid media. Then, 1 mL of the aquatic samples was transferred into the 96‐well plate and the 96‐micro‐solid‐phase extraction device was applied for the extraction of the selected pesticides. Influential parameters, such as sorbent‐to‐sorbent reproducibility, microwave‐assisted extraction time, ionic strength and micro‐solid‐phase extraction time, were optimized. The limits of quantitation were below 120 μg/kg, which are lower than the maximum residue limits. The developed method was successfully implemented for the extraction and determination of the selected pesticides from 20 different apple samples gathered from local markets. Phosalone was identified and quantified at the concentration level of 147 (±16.4) μg/kg in one of the samples.     

基于智能手机的纸微流控电化学农药检测芯片的研究

纸质微流控装置的出现为低成本化学分析提供了一种简单而实用的平台.本研究开发了一种基于浓差电池原理的新型电化学检测纸质芯片,通过智能手机的辅助实现了农药的检测.检测芯片由色谱纸喷蜡打印制作而成.加入样品与芯片上的预加试剂反应5 min,然后将丝网印刷的电极层置于芯片上,利用模具的重力作用使电极层与纸芯片的两极紧密接触,再通过智能手机的USB读取装置获取芯片的电位,并由电位-农药浓度关系得到检测结果.使用此芯片实现了农药敌百虫(三氯磷酸酯)的快速、简便、可自供电的电化学定量检测,检出限为0.89 μ mol/L.     

Colorimetric technique for the detection of carbofuran and its application in various environmental samples

A large variety of pesticides have been used in the agriculture area to raise the quality, extend and yield storage life of crops. The nonstop uses of these pesticides have resulted in pollution of the environment and also caused risk to human health. For the rapid detection of selective CBFpesticide, we developed a simple and sensitive colorimetric detection method based on azo-coupling reaction. After a simple pre-treatment of carbofuran (2, 2-dimethyl-2, 3-dihydro-7-benzofuranyl N-methyl carbamate) (CBF) (1000 ​μg ​mL⁻¹) with a diazotized solution, the resulting is rapidly undergoing azo-coupling reaction with p-aminoantipyrine (1% alcoholic) with a dramatic color change only in few minutes. Finally, we successfully applied the concentrations of CBF pesticide on vegetable, fruit, soil, and water samples in the presence of natural interferences using UV–Vis spectrophotometer and FTIR with limits of detection at 0.004μgmL⁻¹. CBF had recoveries in the range of 93–98%, with relative standard deviation values less than 2% and good linearity was achieved with r ​≥ ​0.98. The inhibition rate was linear with CBF concentration in the range of 1μgmL⁻¹ to 10μgmL⁻¹. The proposed method applies to analyze CBF pesticide in real samples. FTIR technique was used to consider and gain structural information about the existing intermolecular interactions for vegetable samples.     

Monoclonal Antibodies Useful in Sensitive Immunoassays for Aldicarb in Either Laboratory or the Field

Although polyclonal antisera have been used for immunodiagnostic measurement of aldicarb, both as components of commercial kits and as stand-alone products, no monoclonal antibody (MAb) reactive to this carbamate pesticide has yet been described. We have generated two MAbs with specificity to aldicarb, which function in our prototypic field immunoassays to identify this chemical in water samples. Further exploitation of these inherently stable immunoreagents should be valuable for point-of-need testing for the presence of aldicarb.     

A high-throughput approach for the determination of pesticide residues in cucumber samples using solid-phase microextraction on 96-well plate

A high-throughput solid-phase microextraction (SPME) on 96-well plate together with gas chromatography–mass spectrometry (GC–MS) was developed for the determination of some selected pesticides in cucumber samples. Pieces with the length of 1.0 cm of silicon tubing were precisely prepared and then coated on the end part of stainless steel wires. The prepared fibers were positioned in a home-made polytetrafluoroethylene (PTFE)-based constructed ninety-six holes block to have the possibility of simultaneous immersion of the SPME fibers into the center of individual wells. Pesticides such as diazinon, penconazol, tebuconazol, bitertanol, malathion, phosalone and chlorpyrifos-methyl were selected for their highly application in cucumber field. The performances of the SPME fibers, such as intra and inter-fibers reproducibility, were evaluated and the results showed a good similarity in extraction yields. A volume of 1 mL of the aquatic supernatant of the cucumber samples was transferred into the 96-well plate and the array of SPME fibers was applied for the extraction of the selected pesticides. The important parameters influencing the whole extraction process including, organic solvent percent, salt addition, dilution factor, stirring rate and extraction time were optimized. The inter- and intra-day RSD% were found to be less than 15.4%. Limits of detection (LOD) and limits of quantification (LOQ) were below 60 and 180 μg kg⁻¹, respectively. The coefficient of determination was satisfactory (r² > 0.99) for all the studied analytes. The developed method was successfully applied to the monitoring of several samples gathered from local markets.