食品中邻苯二甲酸酯类化合物的分析方法研究进展

邻苯二甲酸酯是应用最广泛的增塑剂,具有生殖、发育毒性及致癌性,是近年来食品污染的一个重要来源。该类化合物种类多、同系物和同分异构体性质接近、在基体中含量范围宽,高效样品前处理、高选择性分离和高灵敏检测、降低本底干扰等技术是食品中邻苯二甲酸酯类化合物准确测定面临的挑战。本文综述了液液萃取、液液微萃取、固相萃取、固相微萃取、基质固相萃取等传统及新型的提取与净化技术在食品样品分析中的应用,比较分析了气相色谱、液相色谱、串联质谱、高分辨质谱以及酶联免疫、离子迁移谱等快速检测技术的特点,并展望了发展趋势。     

食品及环境样品中双酚类物质的前处理及检测方法研究进展

双酚类物质作为一种环境内分泌干扰物,广泛存在于食品包装材料及环境介质中,对生态环境造成污染,也对人体健康产生一定危害。双酚残留是目前重要的食品安全问题,检测食品和环境样品中的双酚类物质的含量对人体健康具有重要的意义。由于残留目标物浓度通常较低,且实际样品存在基质干扰,因此需经一定的样品前处理,并结合仪器分析方法,提高检测效率,增强分析灵敏度与可靠性。常用的前处理分析方法主要有液液萃取、微波辅助萃取、固相萃取、固相微萃取、基质分散固相萃取、QuEChERS等,常用仪器分析方法包括液相色谱法、气相色谱法、毛细管电泳法、酶联免疫吸附测定法、生物传感器法等。该文综述了食品及环境样品中双酚类物质的样品前处理及仪器分析方法,为双酚类化合物的残留监测提供了参考依据。     

复杂基体中痕量多环芳烃分析测定方法的研究进展

介绍了环境样品（水和土壤）以及植物油中痕量多环芳烃的分析检测方法。对样品的预处理过程和分析方法做了评价。采用一些新的预处理方法（包括液相色谱法、固相萃取法、超临界二氧化碳萃取法）,并结合色谱-质谱在线联用分析检测方法能够获得比较理想的分析结果。引用文献52篇。     

干果类食品的样品前处理与分析检测方法研究进展

坚果、果脯等干果类食品含有丰富的营养成分,深受国内外广大消费者的喜爱。但这些食品在果实生产、加工、储运时会使用农药或产生霉变等,造成干果中农药、重金属、霉菌毒素或添加剂等有害成分残留,甚至超过国家限量要求,带来严重的食品安全问题。因此,加强干果类食品的质量监督具有重要的经济和社会意义。但干果类食品基质复杂,有害物质种类多,结构和性质差异大,含量低,其分析检测需要快速高效的样品前处理技术和准确灵敏的分析检测方法。该文主要综述了近十年来干果类食品中有害物质的样品前处理及分析检测方法研究进展。其中样品前处理方法主要包括各种场辅助萃取法、相分离法和衍生化萃取方法等。场辅助萃取法主要是借助超声波和微波场等外场(协同)作用加快干果中有害物质的溶出速度,提高其萃取效率。相分离法,包括固相(微)萃取、分散固相萃取和液相(微)萃取法等,具有溶剂消耗少、分离富集效率高的优势,是干果样品分析中较常使用的前处理方法。该文还重点介绍了干果中各类有害成分分析检测技术,主要包括色谱、原子光谱、无机质谱、电化学分析等常规实验室方法,以及一些适用于现场分析的快速检测技术,并以此为基础,展望了干果类食品中有害物质分析检测技术的发展趋势。     

冷冻干燥技术在环境水样有机新污染物前处理中的应用进展

有机新污染物是一类在先进分析技术帮助下新鉴定的、现有法规未管制的、人为源的有机污染物。有机新污染物主要包括药品与个人护理、农药、全氟化合物、内分泌干扰物等,其会产生内分泌干扰效应、诱发抗性基因传播,还对人类和野生生物的生存与发展构成潜在威胁,因此检测环境样品中的有机新污染物浓度对生态环境和人体健康具有重大意义。由于环境样品中的有机新污染物浓度较低,为了达到检测仪器的检测要求,通常需要对环境样品进行前处理,包括样品的净化和浓缩。冷冻干燥技术是一种在真空干燥条件下通过升华方式去除水分的前处理技术,主要包括样品冷冻、初级干燥和再干燥3个阶段,常用于食品和药品行业。在药品行业中,冷冻干燥技术能维持药品的生物活性和化学活性,保持药品的物理化学特性。近年来,冷冻干燥技术逐步用于环境水样中有机新污染物的前处理。其主要的操作步骤包括水样预处理、冷冻干燥、洗脱、吹干、过滤、定容和上机检测。冷冻干燥技术具有操作简单、低成本、样品处理体积少、样品易保存和处理过程中样品损失少等优点,具有广泛应用于环境样品中有机新污染物监测的潜力。该文综述了环境样品中有机新污染物常见的种类,并重点介绍冷冻干燥技术的原理及其在环境样品前处理过程中的应用,提出了冷冻干燥技术在环境分析中的应用前景,为环境样品中有机新污染物的监测提供了参考。     

Review of the QuEChERS method for the analysis of organic pollutants: Persistent organic pollutants,polycyclic aromatic hydrocarbons,and pharmaceuticals

In multi-residue pesticide analysis, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method has replaced less efficient traditional extraction methods due to its many advantages. In addition to pesticide analysis, this method has been widely used for the detection and analysis of pharmaceuticals, polycyclic aromatic hydrocarbons (PAHs), and several persistent organic pollutants (POPs), including dioxins, polychlorinated biphenyls, perfluoroalkyl substances, and brominated flame retardants in food, biological, and environmental matrices. The analysis of PAHs and POPs is challenging due to the properties of the target compounds and their low concentrations in complex matrices. This review summarizes previously reported the QuEChERS extraction approaches to the analysis of a wide range of analytes. The QuEChERS approaches, which include dispersive solid phase extraction (d-SPE), have generally been combined with either gas chromatography–mass spectrometry (GC–MS) or liquid chromatography–mass spectrometry (LC–MS) analysis. Further on, in recent years, GC and LC-tandem mass spectrometry has been utilized with the QuEChERS extraction due to its high selectivity, sensitivity, and specificity. This enables the extraction methods for target analytes to be modified through the selection of different extraction solvents, salt formulations, and buffers for salting-out partitioning and the selection of different d-SPE and SPE sorbents for the clean-up process. The most significant advantage of this method is that concentration steps are not required. This review aims to provide an up-to-date overview of information regarding the modification of extraction techniques based on target compounds and sample matrices.     

植物油中真菌毒素检测技术的研究进展

真菌毒素是由丝状真菌或霉菌产生的结构多样的小分子次级代谢产物，常见于粮油中，具有致畸性、肝毒性、肾毒性、致癌性、出血性、免疫抑制及破坏生殖系统等毒性。真菌毒素在基体中存在浓度低、种类多、极性范围广、同族类化合物结构类似、性质接近，定性信息缺乏。植物油是易受真菌毒素污染的食品之一，并且含有大量的油脂、脂肪酸和色素，可能增加基质效应，降低灵敏度，并损坏仪器。因此，建立高效样品前处理方法及高灵敏度、高通量、多种真菌毒素检测技术成为植物油基体中真菌毒素准确测定面临的巨大挑战。该文综述了溶剂提取（LLE）、固相萃取（SPE）、凝胶渗透色谱（GPC）、动态共价化学肼（DCHC）、QuEChERS方法在油中真菌毒素前处理中的应用，分析了气相色谱、液相色谱、液相色谱-串联质谱及免疫传感器等检测技术的特点，并对植物油中真菌毒素污染检测的发展应用进行了展望。     

食品中有机磷酸酯阻燃剂检测技术的研究进展

有机磷酸酯(OPEs)是阻燃剂和塑化剂的主要原料,通常以添加形式存在于各种材料中,在生产和使用过程中伴随磨损和挥发易释放到环境中,现已成为新兴污染物。因为该类化合物的神经毒性、致癌性、破坏内分泌系统以及生殖系统等毒性,食品样品中OPEs的检测成为近年来关注的热点。该文重点围绕食品基质中OPEs检测存在的含量低、本底干扰严重、缺乏灵敏可靠分析方法等问题,对OPEs类化合物的性质、样品前处理、检测技术、质量控制等进行了全面评述。首先总结了30余种常见OPEs类化合物的类型、官能团、极性、沸点等理化性质,对可能的前处理和检测技术进行了理论分析;其次梳理了加速溶剂萃取(ASE)、基质固相分散萃取(MSPD)、微波辅助萃取(MAE)、超声辅助萃取(UAE)、QuEChERS、固相萃取(SPE)、凝胶渗透色谱(GPC)、分散固相萃取(d-SPE)等前处理方法在食品中OPEs化合物分析中的特点,其中UAE和QuEChERS结合多步净化能够有效降低高脂类食品的基质效应,具有良好应用前景;此外比较了气相色谱和液相色谱在分离和检测方面的优缺点,比较已有文献的检出限、回收率等数据;概括了标准品和内标物来源、过程污染与基质效应的产生原因和预防措施;最后对高分辨质谱筛查和鉴别OPEs未知代谢物,以及相关分析方法趋势进行了展望。     

固相微萃取在水样污染物检测中的应用

固相微萃取是一种具有高灵敏度、回收率和重复性等优点的前处理技术,广泛应用于水中痕量污染物的处理,本文从固相微萃取装置、基本原理及其在水样污染物检测的中应用展开介绍,并以固相微萃取作为主题检索词,利用ISI Web of Knowledge中Web of Science引文数据库,对1998年到2012年间的相关文献进行计量分析。结果表明,固相微萃取主要应用于水样前处理,杀虫剂是主要的富集对象,气相、液相色谱以及质谱是常使用的检测器。     

Hair Analysis as Method for Determination of Level of Drugs and Pharmaceutical in Human Body: Review of Chromatographic Procedures

Abstract

Interest in hair analysis as an alternativ or complementary approach to urinalysis for drug abuse detection has grown in recent years. Hair analysis can be particularly advantageous for drugs and their enantiomers.

More than hundred pharmaceuticals, drugs of abuse agents are reported to be detectable in human and animal hair. This article reviews the aalysis of drugs and drug metabolites by chromatographic procedures, incuding the pretreatment steps, and the xtraction methods. Tihe eneral tendency in the last years, to highly sophisticated techiques gas chromatography–mass spectrometry (GC–MS–NCI), high pressure liquid chromatography–mass spectrometry (HPLC–MS), gas chromatography–mass spectrometry–mass spectrometry (GC–MS–MS) well illustrates this constant fight for sensitivity.     

A review of analytical methods for the determination of aminoglycoside and macrolide residues in food matrices

The development of antibiotic resistance in bacteria has been attributed to the overuse of antimicrobials in human medicine. Another route by which humans are exposed to antibiotics is through the animal foods we eat. In modern agricultural practice, veterinary drugs are being used on a large scale, administered for treating infection or prophylactically to prevent infection. Hence, there is pressure on analytical scientists to detect and confirm the presence of antimicrobials in foods of animal origin.The aminoglycosides and macrolides are two families of antibiotics, each with important applications in veterinary medicine. These antibiotics are widely used in the treatment of bacterial disease, e.g., aminoglycosides for mastitis and macrolides for enteric infections. They have also been used as feed additives for growth promotion. As a result, legislation has been laid down by the European commission in which member states must meet strict criteria for monitoring residues (including antimicrobials). Testing for low levels of aminoglycosides and macrolides in foods is a priority and hence the development of fast, reliable, sensitive methods for their extraction and subsequent analysis is of great interest.This paper reviews analytical methods for both extracting and determining these classes of antibiotics in various food matrices focusing in particular on the last 10 years. Extraction and clean-up methods such as deproteinisation, and solid-phase extraction are described. Various screening methods are also covered including thin layer chromatography (TLC), enzyme immunoassay, capillary electrophoresis (CE) and microbiological assays. Finally, liquid chromatography (LC) methods are discussed which are combined with mass spectrometry (MS) when sensitivity requirements are stringent.     

Comprehensive analysis of polycyclic aromatic hydrocarbons in wastewater using stir bar sorptive extraction and gas chromatography coupled to tandem mass spectrometry

The objective of this study was the optimization and comparison of two extraction methods for the determination of polycyclic aromatic hydrocarbons (PAHs) in wastewater (WW). A distribution study of the target compounds between the aqueous phase and the suspended particulate matter (SPM) has been performed in order to establish whether the analysis of both phases is necessary. In this sense, the feasibility of stir bar sorptive extraction (SBSE) and solid-phase extraction (SPE) for the determination of 24 PAHs in WW samples has been evaluated. The results demonstrated the suitability of SBSE to perform a comprehensive analysis of liquid samples containing high amounts of SPM, such as in the determination of PAHs in WWs. A gas chromatography triple quadrupole mass spectrometry (GC-QqQ-MS/MS) method has been also optimized for the separation and detection of the target compounds, avoiding the co-elution of some groups of isomers, such as benzo[b], [j] and [k] fluoranthenes and indene[1,2,3-cd]pyrene/dibenz[a,h]anthracene. For that purpose, a specific capillary column developed for PAH determination was used. The SBSE procedure was validated and adequate parameters (such as recovery, linearity, precision, limits of detection and quantification) were obtained. Finally, the validated method was applied to the analysis of real samples collected from an experimental WW treatment plant, detecting some PAHs at concentrations in the range 0.007-0.022 μg L(-1).     

保健食品中非法添加物检测的前处理及分析方法研究进展

保健食品作为一种特定的食品种类,能调节人体的机能,适用于特定人群食用.但是在保健食品中添加化学药物和非法添加物的现象也层出不穷,因此迫切需要建立多指标的有效检测方法,为保健食品的质量安全提供技术保障.高效的前处理方法和高灵敏的分析方法为检测非法添加物提供了有效的技术手段.综述了近三年来溶剂萃取和固相萃取样品前处理方法,以及高效液相色谱、实时直接分析质谱、表面增强拉曼光谱及色谱-质谱串联技术等分析方法在微量及痕量非法添加物检测中的应用,为进一步研究建立高效简便的前处理方法和检测新方法、新技术提供理论参考.     

样品预处理与实时直接分析质谱的联用技术及应用

近年来,与实时直接分析质谱(DART-MS)相结合的样品预处理技术发展迅速,使得对复杂生物、环境、法医学、食品、个体小生物以及单细胞样品中的分析物进行直接分析成为可能。然而固体基质内部分析物检测困难、痕量分析物检测性能不佳已成为限制DART-MS进一步发展的关键问题。针对这些问题,多年来,研究人员在不同领域对样品预处理与质谱联用进行了多种尝试。该文以固相萃取(SPE)、分散固相萃取(DSPE)、搅拌棒吸附萃取(SBSE)、固相微萃取(SPME)、机械化学提取(MCE)和微波提取(MAE)等样品预处理技术为例,对不同研究领域中样品预处理技术与DART-MS联用的研究成果进行了综述,并对未来的发展趋势进行了展望。希望该综述能为开发与DART-MS联用的新型样品处理技术提供参考和帮助。     

Determination of polycyclic aromatic hydrocarbons in water by solid-phase microextraction and liquid chromatography.

This study describes the determination of polycyclic aromatic hydrocarbons (PAHs) in water using high-performance liquid chromatography (HPLC) coupled with fluorescence detection (FLD). Because individual PAHs are generally present in water only at trace levels, a sensitive and accurate determination technique is essential. The separation and detection of five PAHs were run completely within 25 min by the HPLC/FLD system with an analytical C18 column, a fluorescence detection, and acetonitrile-water gradient elution. Calibration graphs were linear with very good correlation coefficients (r > 0.9998), and the detection limits were in the range of 2-6 ng/l for five PAHs. Solid phase microextraction (SPME) was performed for sample pretreatment prior to HPLC-FLD determination, and the governing parameters were investigated. Compared to conventional methods, SPME has high recovery, saves considerable time, and reduces solvents waste. The extraction efficiencies of five PAHs were above 88% and the extraction times were 35 min in one pretreatment procedure. One particular discovery is that 1.5 M sodium monochloroactate (ClCH2COONa) can improve the extraction yield of PAH compounds more than other inorganic salts. The SPME-HPLC-FLD technique provides a relatively simple, convenient, practical procedure, which was here successfully applied to determine five PAHs in water from authentic water samples.     

固相萃取吸附材料在植物激素样品前处理中的应用新进展

植物激素在植物生长过程中具有重要作用,调节植物生长、发育及抗逆的各个过程。植物激素超微精准定量分析一直是植物生理学研究的瓶颈问题。植物激素的准确、高效检测目前大多是基于液相色谱-串联质谱联用技术。样品前处理是植物激素色谱-质谱分析中必不可少的一个步骤,直接影响后续检测方法的灵敏度和准确性。在植物激素各种前处理方法中,固相萃取(SPE)技术应用非常广泛。在萃取小柱基础上发展了多种新形式(分散固相萃取、磁性固相萃取、固相微萃取等,称之为SPE相关方法)。在上述SPE相关方法中,吸附材料的选择均是关键因素,决定了样品前处理过程的目标物提取、净化和富集效果。碳基材料(包括碳纳米管、石墨烯、碳氮化合物等)和有机骨架材料(包括金属有机骨架、共价有机材料)拥有结构可设计、比表面积大、稳定性良好等特性,非常适合作为吸附材料。分子印迹聚合物和超分子化合物依靠主-客体特异性分子识别作用,能显著提高样品前处理方法的选择性。本文重点针对植物激素样品前处理中的SPE技术,综述了近5年来上述几类功能化吸附材料的最新应用进展,并对其发展趋势进行展望。     

新型样品前处理材料在环境污染物分析检测中的研究进展

针对复杂样品的分析和痕量目标物的检测,样品前处理是必不可少的,高效的样品前处理技术不仅可以去除或减小样品基质干扰而且能够实现分析物的富集,提高分析检测的准确性和灵敏度。近年来,固相萃取、磁分散固相萃取、枪头固相萃取、搅拌棒萃取、固相微萃取等高效的样品前处理技术已在环境污染物分析检测中获得广泛关注,萃取效率主要取决于萃取材料,所以新型的高效萃取材料一直是样品前处理研究领域的重要发展方向。该文总结和讨论了近年来新型样品前处理材料在环境污染物分析检测中的研究进展,主要聚焦在石墨烯、氧化石墨烯、碳纳米管、无机气凝胶、有机气凝胶、三嗪基功能材料、三嗪基聚合物、分子印迹聚合物、共价有机框架材料、金属有机框架材料以及它们的功能化萃取材料等。这些材料已经被应用于环境样品中不同类别污染物的萃取富集,如重金属离子、多环芳烃、塑化剂、烷烃、苯酚、氯酚、氯苯、多溴联苯醚、全氟磺酸、全氟羧酸、雌激素、药物残留、农药残留等。这些样品前处理材料具有高的表面积、大量的吸附位点,并涉及多种萃取机理如π-π、静电、疏水、亲水、氢键、卤键等相互作用。基于这些萃取材料的多种样品前处理技术与各类检测方法如色谱、质谱、原子吸收光谱、荧光光谱、离子迁移谱等相结合,已广泛应用于环境污染物的高灵敏分析检测。最后,该文总结了样品前处理发展中存在的问题,并展望了其未来在环境分析中的发展趋势。     

Modern state of high-performance liquid chromatography of polycyclic aromatic hydrocarbons

The review is devoted to the recent studies in the field of high-performance liquid chromatography (HPLC) of polycyclic aromatic hydrocarbons (PAHs). The existing certified techniques, developments of synthesis of new sorbents for separating PAH isomers, and study of the retention mechanism are discussed. It also considers the modern methods of extraction and concentration of PAHs, mainly from environmental objects, which are compatible with subsequent identification by HPLC, as well as the necessity of analytical control of contamination of the environment, food sources, and food supplies with PAHs.     

氮川三乙酸的样品前处理和检测方法研究进展

氮川三乙酸(NTA)及其盐是一类广泛用于工业生产的配合剂.由于NTA及其盐的大量使用和排放,导致其在生活用品、食品和环境水体中均有检出.然而,NTA及其盐具备较强的毒性和致癌作用,涉及NTA及其盐的使用和排放必须进行监测和限制.实际环境样品中NTA的含量低、共存基质复杂,导致其分析和监测存在困难.NTA的灵敏分析必须经...     

Bioanalytical chromatographic methods for the determination of catechol-O-methyltransferase inhibitors in rodents and human samples: A review

In the past years, it has been recognised that the levodopa therapy may be improved with therapeutic regimens including a catechol-O-methyltransferase (COMT) inhibitor. At the present time, tolcapone and entacapone are the only two COMT inhibitors available in the market. However, further COMT inhibitors are under development for Parkinson's disease, namely nebicapone and opicapone (formerly known as BIA 9-1067). In addition, the nitecapone, another well-known COMT inhibitor, is also in preclinical development but for neuropathic pain. Since the 1990s different liquid chromatography methods have been developed and validated to quantify tolcapone, entacapone, nitecapone, nebicapone and some metabolites in biological samples, particularly in plasma samples obtained from rodent and human species. These bioanalytical methods have been primarily used to support pharmacokinetic assays with such COMT inhibitors in non-clinical and clinical studies. As these inhibitors present hydrophobic groups in their chemical structures, reversed-phase liquid chromatography has been used as the major approach for the determination of such compounds, especially high-performance liquid chromatography coupled to ultraviolet detection (HPLC-UV), electrochemical detection (HPLC-ECD) and mass spectrometry detection (HPLC–MS). Regarding the sample preparation, the traditional liquid–liquid extraction (LLE) and solid-phase extraction (SPE) were also the most widely used procedures for extraction of the analytes of interest prior to the analysis of samples. Thus, this review aimed to gather, for the first time, sufficient background information about the bioanalytical chromatographic methods which have been already developed and applied for the determination of tolcapone, entacapone, nitecapone, nebicapone and their metabolites. Moreover, some pharmacokinetic aspects of the COMT inhibitors with interest from a bioanalytical perspective were also addressed.