质谱法在食品样本农药残留分析中的应用进展

质谱法(Mass spectrometry,MS)是当前农药残留分析中的主导检测技术。对气相色谱-质谱法(GC-MS)、气相色谱-串联质谱法(GC-MS/MS)、液相色谱-串联质谱法(LC-MS/MS)和飞行时间质谱法(time-of-flight mass spectrometry,TOF-MS)在食品样本农药残留分析中的应用进行了综述,重点对质谱技术在国内外多残留分析方法研究中的应用进展进行了总结和归纳,简要比较了质谱分析时常用的几种样品前处理技术的优缺点及其适用性,展望了质谱法在农药残留分析研究领域的发展前景。     

自动固相微萃取与气相色谱-质谱联用在农药残留分析中的应用

介绍了自动固相微萃取与气相色谱-质谱联用技术的特点以及这项技术在水果、蔬菜、土壤、水体等样品中农药残留分析中的应用和发展.     

苹果锈果类病毒山东栖霞分离物的分子鉴定及序列分析

本研究以采自山东省栖霞市的两个苹果样品为试验材料,利用二维电泳、斑点杂交、RT PCR等分子生物学技术对样品中的苹果锈果类病毒(ASSVd)带毒情况进行了检测。结果表明：两个样品均携带ASSVd。对两个样品中的ASSVd进行克隆测序,并利用生物学软件DNAMAN对所得序列进行分析,结果表明：与世界上首次报道的ASSVd序列(X17696)相比,本研究所得到的ASSVd序列变异较小,相对比较保守。     

浊点萃取法在农药残留分析中的应用

浊点萃取法是近年来发展较快的一种环境友好型液液萃取技术,与传统的提取方法(如液液分配、固相萃取、索氏提取等)相比,具有高效、低毒、操作简单等优点,目前已成功应用于金属离子、蛋白质、环境样品的前处理和分离、纯化。概述了浊点萃取法的机理和分类(温度诱导的浊点萃取法、凝聚萃取法和混合胶束介质萃取法),总结了近年来该方法在农药残留分析领域环境样品前处理中的应用及其优缺点。     

超高效液相色谱-串联质谱法分析水及3种生物基质中矮壮素和野麦枯残留

建立了超高效液相色谱-串联质谱 (UPLC-MS/MS) 测定环境样品水基质以及人的血液、尿液和肝脏3种生物样品中矮壮素和野麦枯残留的方法。空白水、空白血、空白尿及空白肝脏样品中加入矮壮素和野麦枯标准溶液,经pH = 8的氨水稀释后,涡旋离心,上清液过混合型弱阳离子交换柱 (WCX) 进行富集提取后,采用UPLC-MS/MS检测。质谱检测采用正离子扫描,多反应离子监测模式 (MRM)。定性和定量均以矮壮素和野麦枯母离子和子离子进行分析。结果表明:试验期间矮壮素和野麦枯标准品在不同条件下的降解率为2.4%~11.9%,稳定性好。在0.010、0.10、0.25、0.50和1.0 mg/kg 5个添加水平下,矮壮素和野麦枯在空白水、空白血、空白尿及空白肝脏样品中的回收率在71%~104%之间,相对标准偏差在1.1%~19%之间,定量限均为0.01 mg/kg,检出限均为0.005 mg/kg。该方法灵敏度高,分析速度快,操作简便。     

MALDI-TOF-MS鉴定水稻细菌性叶鞘褐腐病菌的方法研究

利用基质辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS)技术对3株水稻细菌性叶鞘褐腐病菌（Pseudomonas fuscovaginae）标准菌株进行蛋白质指纹图谱分析,将不同培养基、不同培养时间和不同样品处理方法等条件下所收集到的质谱峰进行比较,筛选出最佳实验方法,收集20张参考图谱与水稻常见病原细菌质谱峰进行比较,建立该病菌的蛋白质指纹图谱。结果显示用金氏 B 培养基分离纯化后经提取处理法进行 MALDI-TOF-MS 分析为最佳的实验方法。该方法对检测与鉴定水稻细菌性叶鞘褐腐病菌具有较高的灵敏度和重复性,且分析过程简单快速,有一定的应用价值。     

高效液相色谱-质谱联用仪检测苹果中的丁硫克百威和克百威的残留量

本文研究了克百威,丁硫克百威在苹果上的残留量,建立了使用液质联用仪同时检测的方法。样品经甲醇(缓冲液)提取,二氯甲烷液分配净化,液相色谱-质谱/质谱联用仪检测。该方法操作简单、快速、灵敏度高。     

MALDI-TOF质谱技术鉴定植物病原体研究进展

基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)技术具有快速和高通量特点,适合分析微量蛋白质、多肽、多糖和核酸,该技术已在生命科学领域广泛应用。本文综述了 MALDI-TOF MS 技术原理以及近年来在植物病原真菌和细菌鉴定方面的研究进展。MALDI-TOF MS 作为一种简便和快捷的检测技术,必将在植物病原菌鉴定领域发挥更大的作用。     

"胃袋式"大体积直接进样分析大米中多种有机磷农药残留

初步研究了"胃袋式"大体积直接进样和质谱选择离子监测技术相结合检测大米中多种有机磷农药残留的方法。考察了无前处理进样时大米基质对14种农药信噪比的影响,结合质谱的选择离子监测技术,建立了其中9种有机磷农药的检测方法。其中7种农药的最低定量限(LOQ)为4.0~10.0 μg/kg,样品添加回收率范围在67%~106%之间,RSD大部分小于20%(n=6)。     

基于功能磁性材料和固相微萃取净化富集一体化的茶饮料中三唑类农药残留分析

构建了固相微萃取(SPME)富集与功能磁性材料净化相结合的一体化协同提取技术,并应用于茶饮料中三唑类杀菌剂的残留分析。以磁性材料四氧化三铁-N-丙基乙二胺 (Fe₃O₄-PSA)为净化吸附剂,采用SPME萃取针富集样品溶液中的目标农药后直接进气相色谱-质谱联用仪 (GC-MS)进样口解吸附、分析,无需其他样品转移等操作,方法简便、灵敏。本研究系统优化了SPME条件 (如萃取时间、萃取温度、氯化钠用量及pH值),并采用正交试验设计,探明了磁性材料用量与SPME条件的交互影响,以确定最佳试验条件。对优化的分析方法进行方法确证,结果表明:在0.002～0.2 mg/L范围内,19种三唑类农药在茶饮料中均表现出很好的线性关系,相关系数 (r)均大于0.99,检出限 (LOD)在0.00012~0.0089 mg/L之间,定量限 (LOQ)均为0.002 mg/L。采用基质匹配标准溶液校正时,回收率在71%～98%之间,RSD不高于16% (n=3)。此方法较常规法简单、操作便捷、可靠,且环境友好,适用于茶饮料中三唑类农药残留的分析。     

QuEChERS方法在农药多残留检测中的应用研究进展

QuEChERS方法作为一种农药多残留前处理方法,由于具有快速、简单、廉价、有效、可靠、安全的特点而成为了研究的热点。随着气相色谱(GC)、液相色谱(LC)及气相色谱-质谱(GC-MS)和液相色谱-质谱(LC-MS)联用仪器的不断研发改进,其高效的分离能力和定性鉴定能力结合QuEChERS前处理方法,可在短时间内实现对几十种甚至上百种复杂化合物的分离、定性及定量。重点综述了近年来QuEChERS方法在农药多残留检测前处理方面的应用,详细评述了在样品处理、提取、净化及提取液浓缩等方面对QuEChERS方法进行优化改进的研究进展。     

Trace analysis of polar agrochemicals using mass spectrometry techniques

The analysis of polar compounds by mass spectrometry has traditionally required prior conversion to a volatile derivative. The advent of Fast Atom Bombardment (FAB) allows the direct analysis of such compounds and offers the prospect of quantitative analysis without sample pretreatment. An application of quantitative FAB is described which demonstrates the techniques involved and their practical limitations. The method is both fast and highly specific. The problem of matrix effects is readily overcome by the use of a suitable internal standard, and in the work described, an amino acid has been used as the internal standard. The problem of background interference is less easily solved, and a number of approaches have been tried. Two additional new mass spectrometry techniques for the trace analysis of polar compounds are discussed.     

Recent applications of chromatography for analysis of contaminants in cannabis products: a review

In the last few years, the cultivation of cannabis has been increasing due to greater use in foods, recreational use, creams, oils, and other applications. Thus, analysis of contaminants (e.g. pesticides and mycotoxins) in cannabis products is necessary to ensure consumer safety. This review is focused on the analytical procedures, based on chromatographic techniques, used for the determination of contaminants in cannabis and related products, developed from 2015 to 2020. QuEChERS (acronym of quick, easy, cheap, effective, rugged and safe) was mainly used for the extraction of pesticides and other contaminants from cannabis because its versatility and capacity to extract a wide range of substances, and therefore, increasing the scope of the analysis. The most employed technique to determine pesticides and mycotoxins in cannabis products was liquid chromatography (LC) coupled to mass spectrometry (MS), although gas chromatography (GC) coupled to MS was also employed for the analysis of non-polar compounds, using triple quadrupole (QqQ) as mass analyzer. Nevertheless, new advances in cannabis analysis are also discussed, introducing techniques such as high-resolution mass spectrometry (HRMS), which allows for performing both targeted and untargeted (unknown and suspect) analyses. © 2021 Society of Chemical Industry.     

Stability of the tranquilizer drug propionylpromazine hydrochloride in formulated products

An analytical method to evaluate propionylpromazine hydrochloride (PPZHCl) in tranquilizer formulations was developed using high-performance liquid chromatography (HPLC). During analysis of aged quality-control samples, a previously unreported chromatographic response was observed at a shorter retention time than PPZHCl. Further investigation of formulations stored in trap tap devices at temperatures ranging from 5 to 40 degrees C during field trials at four different locations confirmed the degradation of the active ingredient. Further investigation using HPLC/tandem mass spectrometry revealed two to five degradates, with the major degradates being oxidation products of the active ingredient, PPZHCl. As PPZHCl formulations must be stable when stored at 5 to 40 degrees C for 6 to 12 months, reformulation with the anti-oxidant ascorbic acid was utilized to achieve the required PPZHCl stability.     

环戊噁草酮在稻田中的残留及消解动态

建立了超高效液相色谱-串联质谱测定糙米、谷壳、稻秆、土壤和稻田水中环戊草酮残留的分析方法,结合田间试验研究了环戊草酮在稻田中的残留及消解动态。结果表明:在0.01～1 mg/L范围内,环戊草酮的质量浓度与相应的峰面积间呈良好的线性关系。在0.02、0.05和0.5 mg/kg添加水平下,环戊草酮在糙米、谷壳、稻秆、土壤和稻田水样品中的平均回收率在75%～95%之间,相对标准偏差在1.5%～9.5%之间,检出限 (LOD) 为0.01 ng,在糙米、谷壳、稻秆、土壤和稻田水中的最低检出浓度 (LOQ) 为0.02 mg/kg。浙江、山东和湖南3地2年的田间试验表明:环戊草酮在稻秆和土壤中的半衰期分别为4.2～9.0 d和7.0～11.6 d,其消解规律符合一级反应动力学方程。分别以有效成分含量375(低剂量) 和562.5 g/hm2(高剂量)2个剂量施用90 g/L环戊草酮悬浮剂1次,于收获成熟期采样检测发现,环戊草酮在糙米中的最终残留量均小于0.02 mg/kg,该研究结果可为制定环戊草酮在糙米中的最大残留限量值 (MRL) 提供数据支撑。     

Determination of chlormequat residues in cotton seed by gas chromatography

A simple and sensitive method to determine chlormequat (chlorocholine chloride) residues in plant tissue has been devised. The technique is based on an in-vitro multi-step reaction where chlormequat is initially N-demethylated with potassium pentafluorothiophenolate followed by a further reaction with excess reagent to produce a pentafluorothiophenyl derivative. Electron capture detection and mass spectrometry were used for quantitative determination and identification. The method was applied to the analysis of cotton seed harvested from cotton plants treated with various concentrations of chlormequat.     

Confirmation and quantification of pesticide residues by mass spectrometry

The sensitivity and specificity of mass spectrometry makes this an attractive technique for the confirmation and quantification of trace levels of pesticide residues. Two applications of mass spectrometry are outlined, that of combined headspace gas chromatography (g.c.)/mass spectrometry (m.s.), for the analysis of volatile fumigants such as ethylene dibromide (EDB) in imported fruits and multi-residue halogenated compounds in bran products, and that of quantitative g.c./m.s. for the determination of a range of organochlorine pesticide residues. The approach to setting-up a capillary g.c. multiple ion monitoring programme is described, with emphasis on quantitative aspects, and in particular the use of stable isotope internal standards. This is illustrated with an example of the quantification of organochlorine pesticide residues in eggs.     

Comparison of efficacy, absorption and translocation of three glyphosate formulations on velvetleaf (Abutilon theophrasti)

Growth analysis, absorption and translocation studies were conducted to compare a 1-aminomethanamide dihydrogen tetraoxosulfate (GLY-A) formulation of glyphosate with two isopropylamine (GLY-IPA-1, GLY-IPA-2) formulations of glyphosate on velvetleaf. The two isopropylamine formulations differed by the presence of a surfactant in the formulation, GLY-IPA-1 containing surfactant whereas GLY-IPA-2 did not. Four- to six-leaf velvetleaf was treated with GLY-A and GLY-IPA-1 and GLY-IPA-2 (0, 50, 67, 89, 119, 158, 280, 420, 560 and 840 g AE ha(-1)) with and without ammonium sulfate (AMS; 20 g L(-1)). GLY-A and GLY-IPA-2 included a non-ionic surfactant (2.5 mL L(-1)) in the spray solution at all herbicide concentrations. No additional surfactant was added to GLY-IPA-1. The IC50 value for GLY-A was 88 g AE ha(-1) compared with 346 and 376 g AE ha(-1) for GLY-IPA-1 and GLY-IPA-2 respectively in the absence of AMS. When AMS (20 g L(-1)) was added to the spray solution, the estimated IC50 values were 143, 76 and 60 g AE ha(-1) for GLY-IPA-1, GLY-IPA-2 and GLY-A respectively. Absorption of 14C-glyphosate into the third leaf of five- to six-leaf velvetleaf was three- to sixfold greater 72 h after treatment (HAT) when applied as GLY-A compared with GLY-IPA-1 and GLY-IPA-2 respectively in the absence of AMS. AMS (20 g L(-1)) increased absorption of 14C-glyphosate in all glyphosate formulations two- to threefold, but differences among the formulations remained. Approximately three- and sixfold more 14C-glyphosate applied as GLY-A had translocated out of the treated leaf compared with GLY-IPA-1 and GLY-IPA-2 respectively by 72 HAT. Adding AMS (20 g L(-1)) increased translocation of 14C-glyphosate out of the treated leaf approximately 2.5-fold for all three formulations. The increased efficacy of GLY-A versus GLY-IPA-1 and GLY-IPA-2 on velvetleaf is due to the greater rate of absorption and subsequent translocation of glyphosate out of the treated leaf. AMS increased the efficacy of all three formulations by increasing absorption and translocation of glyphosate in the plant.     

气相色谱-串联质谱法测定虾体中18种多氯联苯

建立了基于气相色谱-串联质谱法测定虾体不同组织（虾肉、虾头、虾壳、虾黄）中7种环境指示类和12种类二英类多氯联苯（PCBs）的定性定量分析方法。样品经V（二氯甲烷）:V（正己烷）=1:1混合溶液匀浆提取,加入浓硫酸磺化,采用弗罗里硅土柱净化。气相色谱部分采用HP-5柱,经程序升温对18种PCBs分离,进入串联四极杆质谱后,以EI+离子源多反应监测模式（MRM）进行定性定量分析。结果表明:在50、400和1 000 ng/kg 3个添加水平下,18种PCBs在虾肉、虾头、虾壳和虾黄4种样品中的平均回收率在72%~109%之间,相对标准偏差均小于10%,18种PCBs的检出限在0.10~10 ng/kg之间。本方法具有较好精密度和准确度,前处理方法简单快速,可用于虾体中18种PCBs测定。对南京某养殖场的实际样品进行检测,只有部分PCBs检出。