间二甲苯氨氧化法制备间苯二腈催化剂研究

对氨氧化法制备间苯二腈催化剂进行了研究. 在“微反-色谱”联用装置上完成催化剂的评比和筛选后,在内径30 m m 的石英管固定床反应器上印证并进行工艺条件实验. 考察了反应温度、氨比、空气比和空速对反应的转化率,摩尔收率和选择性的影响. 在所确定的工艺条件下使用m -509 号催化剂,转化率高达99.8% 、摩尔收率70.4% ,生成的间苯二腈为白色针状结晶,纯度高于98.5% . 在湖南南天实业股份有限公司的560 m m 工业流化床反应塔上进行了为期6 个月的工业性试验,摩尔收率达66.5% ,间苯二腈含量高于98% ,单腈含量低于0.25% ,性能优于现行工业催化剂.     

Application of Compound-Specific Isotope Analysis in Environmental Forensic and Strategic Management Avenue for Pesticide Residues

Unintended pesticide pollution in soil, crops, and adjacent environments has caused several issues for both pesticide users and consumers. For users, pesticides utilized should provide higher yield and lower persistence while considering both the environment and agricultural products. Most people are concerned that agricultural products expose humans to pesticides accumulating in vegetation. Thus, many countries have guidelines for assessing and managing pesticide pollution, for farming in diverse environments, as all life forms in soil are untargeted to these pesticides. The stable isotope approach has been a useful technique to find the source of organic matter in studies relating to aquatic ecology and environmental sciences since the 1980s. In this study, we discuss commonly used analytical methods using liquid and gas chromatography coupled with isotopic ratio mass spectrometry, as well as the advanced compound-specific isotope analysis (CSIA). CSIA applications are discussed for tracing organic pollutants and understanding chemical reactions (mechanisms) in natural environments. It shows great applicability for the issues on unintended pesticide pollution in several environments with the progress history of isotope application in agricultural and environmental studies. We also suggest future study directions based on the forensic applications of stable isotope analysis to trace pesticides in the environment and crops.     

茶叶中653种农药化学品残留GC-MS、GC-MS/MS与LC-MS/MS分析方法：国际AOAC方法评价预研究

选择了16个实验室,按AOAC方法评价指南对盲样进行了检测。对16个实验室的统计分析结果表明:剔除操作偏离方法的2个实验室的全部数据,剩余14个实验室GC-MS/SIM(GC-MS/MS):RSDr<8%的占100%;RSDR<16%的占57.5%,RSDR<25%的占92.5%;HorRat值小于1.0的占80.0%,HorRat值小于2.0的占97.5%。LC-MS/MS:RSDr<8%的占65.0%,RSDr<15%的占97.5%;RSDR<16%的占35.0%,RSDR<25%的占95.0%;HorRat值小于1.0的占92.5%,HorRat值小于2.0的占97.5%。建立的1 220条标准曲线中,有1 132个满足r2≥0.995的要求,占92.8%;检测目标农药离子3 600个,离子丰度符合EU要求的有3 443个,占95.6%。AOAC方法评价结果证明,该方法重现性和再现性良好,完全适用于茶叶中653农药残留的定性和定量分析。     

Determination of nicotinyl pesticide residues in vegetables by micellar electrokinetic capillary chromatography with quantum dot indirect laser-induced fluorescence

A new assay was developed by use of micellar electrokinetic capillary chromatography with indirect LIF fluorescence for the determination of thiamethoxam, acetamiprid, and imidacloprid residues in vegetables, in which the cadmium telluride quantum dots (QDs) synthesized in aqueous phase were used as fluorescent background substance and their excitation and emission wavelengths matched with LIF detector by engineering their size. The factors that affected the peak height and the resolution were optimized. The running buffer was composed of 4.4 μM cadmium telluride QDs as fluorescent background substance, 40 mM borate and 60 mM SDS, and its pH was adjusted to 8.0. The separation voltage was 25 kV. Under the optimum conditions, the detection limits were 0.05, 0.01, and 0.009 mg/kg; the linear dynamic ranges were 0.5-30, 0.1-30, and 0.1-30 mg/L; and the average recoveries of spiked samples were 72.0-101.2, 74.0-106.7, and 77.8-105.1% for thiamethoxam, acetamiprid, and imidacloprid, respectively. The assay can meet the requirement of maximum residue limits to these three pesticides in the regulations of European Union and Japan, and has been applied for determining their residues in vegetables.     

Screening Method for the Determination at Parts Per Trillion Levels of Pesticide Residues in Vegetables Combining Solid‐Phase Microextraction and Gas Chromatography‐Tandem Mass Spectrometry

Abstract

A new analytical method is proposed for determining residues of 70 pesticides of different chemical families at parts per trillion levels in fresh vegetables. For that, only 4 g of the vegetable samples were quickly extracted with 10 ml of ethyl acetate. The method is based on a vanguard/rearguard strategy that reduces the average time required per sample when the method is applied to a high number of vegetable samples in a quality control laboratory. At the beginning, an aliquot of the extract is evaporated and re‐dissolved in a mixture water:acetone (9∶1 v/v). For screening purposes, the pesticides were extracted for only 10 min by direct immersion of a solid‐phase microextraction (SPME) fiber (65 µm polydimethylsiloxane‐divinylbenzene, PDMS‐DVB). The SPME device was automated and on‐line coupled to a gas chromatograph with an ion trap mass spectrometer (GC‐MS) operated in full scan mode for screening in less than 18 min those samples that potentially contain pesticides above 0.01 mg kg^?1 (cut off value). After that, only those potentially non‐negative samples were reanalyzed by a sensitive quantifying/confirming method that re‐extract by SPME the pesticides in 55 min of absorption and determine them by GC with tandem MS (MS/MS). The method has been validated following EU guidelines and compared with a conventional extraction method based on the use of higher amounts of organic solvents. The limits of detection (LOD), confirmation (LOC) and quantitation (LOQ) as well as the calibration curves obtained allowed the determination of the target pesticides at concentrations clearly below the maximum residue levels (MRL) stated by EU being possible the determination of parts per trillion of the pesticides in ecological (green) vegetables. The method has been applied to the analysis of real samples and the results compared with those obtained by a conventional extraction method accredited by ENAC (Spanish Accreditation Body). The proposed method was also evaluated participating in a proficiency test with adequate results (z‐score among±2).     

γ‐Irradiation Degradation of Methamidophos

The irradiation degradation of methamidophos in aqueous solutions by ⁶⁰Co‐γ rays was investigated. The effects of absorbed doses, saturated gas, and the additive of H₂O₂ on the degradation were also studied. The results showed that the oxidative radical, such as ·OH, played an important role in the irradiation degradation of methamidophos; while the reductive radicals, e^?_aq and ·H, had no contribution to the degradation. The degradation rate of methamidophos increased with the increase of the irradiation dosage. At certain irradiation dosage, methamidophos could be degraded completely. The degradation rate of methamidophos in the solution saturated with oxygen was higher than those saturated with other gases, which reached 100% when the absorbed dose was 8 kGy. H₂O₂ degraded methamidophos slowly when it was used alone, but could accelerate the degradation obviously when it was used with irradiation together.     

食用菌中19种农药的多残留分析

建立了食用菌中19种农药残留量的气相色谱分析方法.样品用乙腈提取,提取液浓缩后用弗罗里硅土柱净化,经HP-5石英毛细管柱分离后,采用GC-ECD同时测定19种农药残留量.六六六、DDT各4种异构体及同系物的质量浓度在0.01 ～1 mg/L范围内,其他11种农药在0.01 ～5 mg/L范围内,均有良好线性关系.相关系数r大于0.997,样品在3个添加水平时的回收率为80% ～115%,相对标准偏差为1.1% ～10%.检出限为0.43 ～2.9 μg/kg.方法简便、快速、净化效果较好,可同时满足进、出口食用菌中多种农药残留量的检测需要.     

四种农药人工抗原的合成与表征

设计并合成了四种农药的人工半抗原,其结构经~1H NMR表征.分别以牛血清蛋白和卵清蛋白为载体蛋白偶联得到对应的人工抗原,为建立四种农药的酶联免疫吸附分析方法奠定基础.     

气相色谱-离子阱质谱法测定蔬菜中9种有机磷农药的残留量

建立气相色谱-离子阱质谱法测定蔬菜中9种有机磷农药残留的方法.样品经乙酸乙酯提取、无水硫酸钠脱水、活性炭小柱净化,浓缩后通过气相色谱-离子阱质谱进行测定.9种有机磷农药的浓度在0.05～1.0μg/mL范围内与其对应的色谱峰面积具有良好的线性关系(r＞0.999).在3个不同添加浓度下的平均回收率为76.5%～101.2%,测定结果的相对标准偏差为3.9%～9.4%(n=7).该方法快速、准确、操作简便,能满足蔬菜中有机磷农药残留的检测要求.