Fluorimetric determination of the fungicide benomyl after solvolysis

A simple spectrofluorimetric method for the determination of the fungicide benomyl in grapes is described. Benomyl is rapidly solvolysed in organic solvents to give the highly fluorescent metabolite carbendazim. Solvent effects on the spectral shape and their influence on analytical performance are studied. DMF was found to be the best solvent. The method is sensitive to 12 ng/ml benomyl, and has an RSD at the 0.5 g/ml level of 2.2%. The method is suitable for determining benomyl in spiked grapes, with recoveries in the range 97 to 104%.     

Carbendazim‐loaded electrospun poly(vinyl alcohol) fiber mats and release characteristics of carbendazim therefrom

Ultra‐fine poly(vinyl alcohol) (PVA) electrospun fiber mats containing carbendazim were successfully fabricated by electrospinning from the neat PVA solution containing carbendazim in various amounts based on the weight of PVA. The morphological appearance of both the neat and the carbendazim‐loaded electrospun PVA fibers were smooth and the incorporation of carbendazim in the neat PVA solution did not affect the morphology of the resulting fibers. The average diameters of the neat and the carbendazim‐loaded electrospun PVA fibers ranged between 155 and 160 nm. The chemical integrity of the as‐loaded carbendazim in the carbendazim‐loaded electrospun PVA fiber mats was intact as verified by the ¹H‐nuclear magnetic resonance spectroscopy. Thermal properties of the carbendazim‐loaded electrospun PVA fiber mats were analyzed by differential scanning calorimetry and thermogravimetric analysis. The release characteristics of the carbendazim‐loaded electrospun PVA mats were investigated by the total immersion method in distilled water at 30°C. The carbendazim‐loaded electrospun PVA mats exhibited greater amount of carbendazim released than the carbendazim‐loaded as‐cast films. Copyright © 2010 John Wiley & Sons, Ltd.     

Sulfonated poly(styrene‐divinylbenzene) modified with amines and the application for pipette‐tip solid‐phase extraction of carbendazim in apples

Sulfonated poly(styrene‐divinylbenzene) modified with five kinds of amine functional groups was applied to the determination of carbendazim in apple samples with a pipette‐tip solid‐phase extraction method. The structures of the polymers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Five different modifications of the solid‐phase extraction sorbent based on sulfonated poly(styrene‐divinylbenzene) were tested under static and pipette‐tip solid‐phase extraction conditions. The polymer modified with p‐methoxyaniline showed the best recognition capacity and adsorption amount for carbendazim. Under the optimum conditions, 3.00 mg of the adsorbent, 1.00 mL of ethyl acetate as washing solvent, and 1.00 mL of ammonia/acetonitrile (5:95, v/v) as elution solvent were used in the pretreatment procedure of apple samples. The calibration graphs of carbendazim in methanol were linear over 5.00–200.00 μg/mL, and the limits of detection and quantification were 0.01 and 0.03 μg/mL, respectively. The method recoveries of carbendazim were in the range of 91.31–98.13% with associated intraday relative standard deviations of 0.76–2.13% and interday relative standard deviations of 1.10–1.85%. Sulfonated poly(styrene‐divinylbenzene) modified with p‐methoxyaniline showed satisfactory results (recovery: 97.96%) and potential for the rapid purification of carbendazim in apple samples combined with the pipette‐tip solid‐phase extraction.     

高效液相色谱法测定香蕉中的多菌灵、噻菌灵、甲基硫菌灵

采用高效液相色谱法测定香蕉中的多菌灵、噻菌灵、甲基硫菌灵。样品经乙腈提取、硅胶柱净化后用HPLC法测定,外标法定量。对样品前处理和色谱分析条件进行了研究和优化。3种杀菌剂在确定的浓度范围内线性良好,相关系数r≥0．999。添加3个浓度水平标准品的回收率分别为：多菌灵80．5％～91．2％,噻菌灵81．2％～86．9％．68．9％～72．6％。该法对多菌灵、噻菌灵、甲基硫菌灵3种杀菌剂的检出限较低,分别为0．008,0．009,0．015mg／kg。该方法可满足香蕉中多菌灵、噻菌灵、甲基硫菌灵的残留限量检测要求。     

Laser–Induced Fluorescence Detection of Carbamates Traces in Water

The absorption and fluorescence spectra of carbaryl (CB), carbofuran (CF) and carbendazim (MBC) have been studied. Fluorescence lifetime and fluorescence quantum yields are also reported as well as the influence of pH, solvent and presence of humic acids on fluorescence. The limit of detection (LD) of the three compounds has been measured by direct analysis by laser-induced fluorescence (LIF) using a pulsed YAG laser with an Optical Parametric Oscillator (OPO) as excitation source and an Intensified Charged Coupled Device (ICCD) camera for the fluorescence detection. Instrumental LD found for CB, for MBC and for CF are respectively 4, 50 and 1000 ng L⁻¹. In tap water, the LD obtained is 800 ng L⁻¹ for MBC and 20,000 ng L⁻¹ for CF. For CB, the use of a time shift between excitation and emission allows to reach a LD of 20 ng L⁻¹ in tap water.     

桑叶中多菌灵的紫外光谱分析

用甲醇作溶剂，在室温下对试样进行提取，在盐酸溶液─—氯仿中净化，用０．３ｍｏｌ／ＬＨＣｌ作参比和吸光度差值法建立了桑叶中多菌灵的紫外光谱测定方法，方法回收率在９０％～９６％之间，浓度在０～２０ｍｇ／Ｌ范围内呈线性关系。     

Rapid determination of carbendazim in complex matrices by electrospray ionization mass spectrometry with syringe filter needle

The determination of pesticide residues is an indispensable task in controlling food safety and environment protection. Carbendazim is one of the extensive uses of pesticides in the agricultural industry. In this study, a simple method utilizing syringe filter has been applied as electrospray ionization emitter for mass spectrometric identification and quantification of carbendazim in complex matrices including soil, natural water, and fruit juice samples, which contain many insoluble materials. With online syringe filter of the complex samples, most of insoluble materials such as soil were excluded in spray ionization process due to the filter effect, and analytes were subsequently sprayed out from syringe needle for mass spectrometric detection. The pore sizes of filters and diameters of syringe needles also were investigated. The analytical performances, including the linear range (1–200 ng·mL⁻¹), limit of detection (0.2–0.6 ng·mL⁻¹, S/N > 3), limit of quantitation (3.5–8.6 ng·mL⁻¹, S/N > 10), reproducibility (6.4%–12.5%, n = 6), and recoveries (72.1%–91.0%, n = 6) were well acceptable for direct analysis of raw samples. Matrix effect for detection of carbendazim in soil samples also was experimentally investigated. This study demonstrated that syringe filter needle coupled with electrospray ionization mass spectrometry is a simple, efficient, and sensitive method for detection of pesticide residues in water, soil, and fruit juice for risk assessment.     

Analysis of the dissipation kinetics of thiophanate‐methyl and its metabolite carbendazim in apple leaves using a modified QuEChERS–UPLC–MS/MS method

As one of the main fungicides for the apple leaf disease control, thiophanate‐methyl (TM) mainly exerts its fungicidal activity in the form of its metabolite carbendazim (MBC), whose dissipation kinetics is very distinct from that of its parent but has been paid little attention. The aim of this work was to investigate the dissipation kinetics of TM and its active metabolite MBC in apple leaves using a modified QuEChERS–UPLC–MS/MS method. The results showed that TM and MBC could be quickly extracted by this modified QuEChERS procedure with recoveries of 81.7–96.5%. The method linearity was in the range of 0.01–50.0 mg kg^?1 with the quantification limit of 0.01 mg kg^?1. Then this method was applied to the analysis of fungicide dissipation kinetics in apple leaves. The results showed that the dissipation kinetics of TM for the test in 3 months can be described by a first‐order kinetics model with a DT₅₀ (dissipation half‐life) range of 5.23–6.03 days and the kinetics for MBC can be described by a first‐order absorption–dissipation model with the T_max (time needed to reach peak concentration) range of 4.78–7.09 days. These models can scientifically describe the behavior of TM and MBC in apple leaves, which provides necessary data for scientific application.     

基于太赫兹时域光谱的橙子和多菌灵成分的定量研究

利用太赫兹时域光谱技术对橙子和多菌灵混合样品进行检测,获得混合样品的太赫兹(THz)时域波形;对其进行傅里叶变换,采用菲涅尔公式计算折射率和吸收谱,最后以各样品的吸收谱为研究对象,利用多元线性回归技术进行定量分析研究,获得多菌灵和橙子组分含量。研究结果表明:多菌灵和橙子组分含量的相对误差均小于7%;太赫兹时域光谱技术能够用于水果与农药混合物的定量分析研究,同时,本实验也为该技术应用于农产品农药鉴别检测提供了借鉴。