引言北大核心CSCD

灵敏、可靠地检测复杂样品中痕量、超痕量目标物对分析测量学提出了巨大挑战,目前市场上虽已有诸多智能化的现代分析检测仪器,但考虑到复杂的样品基底及目标组分的低含量,在进行仪器分析检测前,需进行有效的样品制备,以降低复杂样品基底的干扰,提高检测准确性,同时对目标组分进行富集,从而改善检测灵敏度。可以说,样品制备过程是整个分析过程中最为重要和耗时的步骤,影响着分析结果的准确性和可靠性。     

环境水样及固相样品中全氟化合物分析方法研究进展

全氟化合物(Perfluorinated compounds,PFCs)是一类持久性有机污染物,在环境中普遍检出,严重危害人体健康,已成为环境科学和毒理学研究的热点之一.PFCs含有较多同系物及同分异构体,且在环境中通常为痕量水平(ng/g或μg/L),迫切需要建立灵敏可靠的样品前处理和检测技术.国内外已针对环境样品基质中痕量PFCs的检测开展了大量研究,但有关复杂环境样品中PFCs前处理方法、分析方法、基质效应等方面的系统评述还相对较少.本文综述了环境样品(水、沉积物/污泥、土壤、植物)中PFCs的前处理方法、检测方法(尤其是同分异构体)及环境样品基质效应对其检测的影响,以期为相关研究提供参考.     

NEWS

纳米金材料( Au NPs)的广泛应用使其以多种渠道进入环境体系,从而对生物体的健康构成潜在威胁。因此,检测环境样品特别是水体环境中的微量纳米金对于环境监测和纳米粒子的生物安全性研究具有重要意义。然而在实际样品分析中,由于样品基质复杂,纳米粒子的浓度极低且存在易团聚等问题,在仪器分析之前必须辅以合适的样品前处理技术。目前用于纳米粒子分离富集的样品前处理技术较少,且存在操作繁琐、耗时长等问题。武汉大学化学与分子科学学院胡斌教授课题组近期提出了聚合物整体柱毛细管微萃取与等离子体质谱( ICP-MS)在线联用新方法,实现了环境水样中羧基功能基修饰Au NPs的测定,该方法具有灵敏度高、选择性好、样品通量大、试样消耗量少、操作简单、无需消解等特点。     

电感耦合等离子体质谱(ICP-MS)法与氢化物发生-原子吸收光谱(HG-AAS)法测定土壤中硒含量的对比研究

基于氢化物发生器与原子吸收光谱联用(HG-AAS),测定土壤样品中硒的含量,并与电感耦合等离子体质谱(ICP-MS)法测定值进行了对比。在两种仪器的最佳工作条件下,测定土壤硒的含量,实验结果表明:ICP-MS法和HG-AAS法对土壤硒含量测定的线性范围分别为0.85~100.00μg/L和0.08~16.00μg/L,检出限分别为0.25μg/L和0.02μg/L,精密度分别为1.3%和2.1%;用加标回收实验和测定国家标准土壤样品(GSS-7)对这两种方法的准确性进行了验证,ICP-MS法和HG-AAS法的加标回收率分别为96.7%~99.4%和94.9%~99.5%,GSS-7标准土样的结果均在标准值范围内,说明这两种测定土壤中硒含量的方法是准确可靠的。HG-AAS法测定线性范围窄,部分样品需要稀释,而且氢化物发生系统是手动进样,导致操作复杂,分析周期长;ICP-MS法仪器测定快速,但是仪器昂贵。     

填充吸附剂微萃取技术及其在微小体积样品萃取应用中的研究进展

微萃取技术是分析化学领域发展迅速,且已经得到广泛应用的样品前处理技术。填充吸附剂微萃取(MEPS)是一种微量固相萃取技术,使用微量的吸附剂填充于微量注射器,通过反复抽推方式使样品多次流经吸附剂以完成样品吸附萃取过程,萃取后的样品可直接用于色谱分析。典型的MEPS萃取设备包括MEPS注射器和MEPS吸附床(BIN)。MEPS优化的主要因素为MEPS处理过程的参数,包括样品流速、样品量与样品萃取循环次数,吸附剂及淋洗、洗脱溶剂的种类和体积,还需要考虑样品基质对MEPS性能的影响和样品残留和重复使用问题。MEPS中最重要的部分是吸附剂,主要有商品化的MEPS吸附剂,包括硅基的Silica、C18、C8等,碳材料的Hypercarb和聚苯乙烯聚合物类的SDVB、HDVB吸附剂等。研究用的吸附剂包括分子印迹材料、限进分子印迹材料、碳基材料、导电聚合物类材料、改性硅基材料及共价-有机骨架材料等。MEPS结合多种分析仪器已经成功应用于从不同基质中提取单一或多种分析物,所涵盖基质包括生物样品(尿液、唾液、血浆或血液)、河流水体或生活污水以及几种食品和饮料。MEPS处理复杂生物基质样品时,通常需要稀释样品、除蛋白质等预处理。MEPS具有需要样品体积小、操作快速等特点,在生物基质样品分析中有望得到更广泛的使用。在环境样品中,该技术可与现场便携仪器联用,未来将有望在现场进行快速检测,并于易分解样品等方面发挥作用。     

电感耦合等离子体质谱(ICP-MS)联用技术的应用及展望

总结了ICP-MS联用技术在国内外检测领域的最新应用,并就"分离器与ICP-MS"、"进样系统与ICP-MS"、"ICP-MS与其它仪器物理联用"等联用技术进行了分类、拓展和总结。ICP-MS联用技术的发展重点将倾向于提高分析精密度、复杂基体元素超痕量分析、同位素比值及形态研究领域,相关联用技术的国家标准或行业标准出台已迫在眉睫。     

食品中黄曲霉毒素检测的样品前处理技术研究进展

黄曲霉毒素主要存在于发霉的粮食、豆类、坚果及与其相关的食品中,有极强的毒性和致癌性,因此建立食品中黄曲霉毒素的检测方法对于保障食品安全,保护人们身体健康具有重要的意义。目前食品中黄曲霉毒素的检测以色谱和质谱等仪器分析方法为主。由于食物样品基质复杂,而黄曲霉毒素浓度很低,在仪器分析前需采取适当的样品前处理技术对目标物进行富集和纯化。本文对近年来食品中黄曲霉毒素检测的样品前处理方法进行了综述。     

六溴环十二烷的样品前处理和检测方法研究进展北大核心CSCD

作为一种常见的溴代阻燃剂,六溴环十二烷(HBCDs)因具备持久性、长距离迁移性、生物蓄积性和高毒性,于2013年被列入《斯德哥尔摩公约》。因此,环境样品中HBCDs污染水平的准确分析和严格控制对完善环境监管长效机制至关重要。然而,实际样品中HBCDs的定性定量分析正面临着基质复杂、目标物含量低等问题。尤其,HBCDs在高温环境及特定有机溶剂中易降解,会产生异构体,提高了分析难度。该综述简述了HBCDs的理化性质、毒性危害和标准限制,重点围绕不同基质中HBCDs的样品前处理和仪器检测两方面进行了总结。论文内容引用2000~2022年的70余篇源于科学引文索引(SCI)与中文核心期刊中的相关论文。总结归纳了固体和液体样品中HBCDs分析的前处理技术,包括索式提取、超声辅助萃取、加速溶剂萃取、超临界流体萃取、液液萃取、分散液液微萃取、固相萃取、分散固相萃取和固相微萃取等,介绍了气相色谱、液相色谱和色谱-质谱联用技术等仪器检测方法在HBCDs分析中的应用。通过综述近期相关研究,侧面表明HBCDs的分析方法研究发展迅速,但也面临一些挑战,如样品前处理步骤繁琐、耗时长、样品量和有机溶剂用量大等问题。最后,对新型样品前处理技术在HBCDs分析中的应用进行了展望。     

超高效液相色谱-串联质谱法测定水华样品中微囊藻毒素及其基质效应的消除

超高效液相色谱-串联质谱法(UPLC-MS/MS)由于其快速、简便的特点,目前广泛应用于水中微囊藻毒素的测定。由于蓝藻水华样品基质比较复杂,UPLC-MS/MS在复杂基质的分析过程中容易发生基质效应问题,严重影响其定量分析结果的准确性。通过稀释样品、优化梯度洗脱程序、减少进样量等方法有效地降低或消除了基质干扰及基质效应问题。7种目标物在各自线性范围内线性关系良好,相关系数(r2)≥0.99;检出限和定量限分别为0.064~0.103μg/L和0.213~0.343μg/L。通过稀释样品、减少进样量等措施,成功测定了水华爆发时实际样品中的微囊藻毒素,并有效降低了基质效应的干扰。该法为微囊藻毒素的准确测定提供一定的参考,对保障饮用水源地的安全具有十分重要的意义。     

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。     

Matrix effects demystified: Strategies for resolving challenges in analytical separations of complex samples

Matrix effects can significantly impede the accuracy, sensitivity, and reliability of separation techniques presenting a formidable challenge to the analytical process. It is crucial to address matrix effects to achieve accurate and precise measurements in complex matrices. The multifaceted nature of matrix effects which can be influenced by factors such as target analyte, sample preparation protocol, composition, and choice of instrument necessitates a pragmatic approach when analyzing complex matrices. This review aims to highlight common challenges associated with matrix effects throughout the entire analytical process with emphasis on gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, and sample preparation techniques. These techniques are susceptible to matrix effects that could lead to ion suppression/enhancement or impact the analyte signal at various stages of the analytical workflow. The assessment, quantification, and mitigation of matrix effects are necessary in developing any analytical method. Strategies can be implemented to reduce or eliminate the matrix effect by changing the type of ionization, improving extraction and clean-up methods, optimization of chromatography conditions, and corrective calibration methods. While development of an effective strategy to completely mitigate matrix effects remains elusive, an integrated approach that combines sample preparation, analytical extraction, and effective instrumental analysis remains the most promising avenue for identifying and resolving matrix effects.     

Acid interferences in atomic spectrometry: analyte signal effects and subsequent reduction

When considering elemental analysis by atomic spectrometry techniques (e.g. flame atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry), the sample is normally introduced as a solution. In many instances an acid is present in that solution, as a result of previous sample preparation steps, analyte stabilization procedures, etc. Therefore, acids are among the most common matrices involved in spectroscopic analysis. The effect of the acid on the different stages taking place during the whole analytical process has been reviewed. Attention has been paid to the three techniques mentioned above. The results summarized here reveal the crucial role that acids play in atomic spectrometry, being one of the most important sources of interferences suffered by these techniques. In the last part of this bibliographic survey, the methods found for correction of the acid effect are mentioned and briefly described.     

Use of a novel array detector for the direct analysis of solid samples by laser ablation inductively coupled plasma sector-field mass spectrometry

The use of laser ablation (LA) as a sample-introduction method for inductively coupled plasma mass spectrometry (ICP-MS) creates a powerful tool for trace elemental analysis. With this type of instrument, high analyte spatial resolution is possible in three dimensions with ng/g limits of detection and minimal sample consumption. Here, simultaneous detection is used to eliminate the correlated noise that plagues the ablation process. This benefit allows analyses to be performed with single laser pulses, resulting in improved depth resolution, even less sample consumption, and improved measurement precision. The new instrument includes an LA sample-introduction system coupled to an ICP ionization source and a Mattauch-Herzog mass spectrograph (MHMS) fitted with a novel array detector. With this instrument, absolute limits of detection are in the tens to hundreds of fg regime and isotope-ratio precision is better than 0.02% RSD with a one-hour integration period. Finally, depth-profile analysis has been performed with a depth resolution of 5 nm per ablation event.     

Time-resolved measurements of individual ion cloud signals to investigate space-charge effects in plasma mass spectrometry

A new approach to directly monitor space charge induced effects due to high concentrations of efficiently ionized elements in inductively coupled plasma mass spectrometry (ICP-MS) is described. The broadening of ion clouds produced from individual, monodisperse drops of sample is measured by using time-resolved ICP-MS. The extent of broadening due to high concentrations of Pb in the sample is related inversely to the analyte mass. For the lightest analyte investigated, Li⁺, the relative width of the time-resolved analyte peak increases and then shows a dip in the center as the Pb concentration is increased to 500 and then 1500 µg/mL. The initial results of experiments that investigated chemical matrix effects as a function of concomitant species concentration, analyte mass, and sampling location in ICP-MS are consistent with space-charge effects.     

Application of a microwave-based desolvation system for multi-elemental analysis of wine by inductively coupled plasma based techniques

Elemental wine analysis is often required from a nutritional, toxicological, origin and authenticity point of view. Inductively coupled plasma based techniques are usually employed for this analysis because of their multi-elemental capabilities and good limits of detection. However, the accurate analysis of wine samples strongly depends on their matrix composition (i.e. salts, ethanol, organic acids) since they lead to both spectral and non-spectral interferences. To mitigate ethanol (up to 10% w/w) related matrix effects in inductively coupled plasma atomic emission spectrometry (ICP-AES), a microwave-based desolvation system (MWDS) can be successfully employed. This finding suggests that the MWDS could be employed for elemental wine analysis. The goal of this work is to evaluate the applicability of the MWDS for elemental wine analysis in ICP-AES and inductively coupled plasma mass spectrometry (ICP-MS). For the sake of comparison a conventional sample introduction system (i.e. pneumatic nebulizer attached to a spray chamber) was employed. Matrix effects, precision, accuracy and analysis throughput have been selected as comparison criteria. For ICP-AES measurements, wine samples can be directly analyzed without any sample treatment (i.e. sample dilution or digestion) using pure aqueous standards although internal standardization (IS) (i.e. Sc) is required. The behaviour of the MWDS operating with organic solutions in ICP-MS has been characterized for the first time. In this technique the MWDS has shown its efficiency to mitigate ethanol related matrix effects up to concentrations of 1% (w/w). Therefore, wine samples must be diluted to reduce the ethanol concentration up to this value. The results obtained have shown that the MWDS is a powerful device for the elemental analysis of wine samples in both ICP-AES and ICP-MS. In general, the MWDS has some attractive advantages for elemental wine analysis when compared to a conventional sample introduction system such as: (i) higher detection capabilities; (ii) lower ethanol matrix effects; and (iii) lower spectral interferences (i.e. ArC(+)) in ICP-MS.     

Sample preparation with solid phase microextraction and exhaustive extraction approaches: Comparison for challenging cases

In chemical analysis, sample preparation is frequently considered the bottleneck of the entire analytical method. The success of the final method strongly depends on understanding the entire process of analysis of a particular type of analyte in a sample, namely: the physicochemical properties of the analytes (solubility, volatility, polarity etc.), the environmental conditions, and the matrix components of the sample. Various sample preparation strategies have been developed based on exhaustive or non-exhaustive extraction of analytes from matrices. Undoubtedly, amongst all sample preparation approaches, liquid extraction, including liquid–liquid (LLE) and solid phase extraction (SPE), are the most well-known, widely used, and commonly accepted methods by many international organizations and accredited laboratories. Both methods are well documented and there are many well defined procedures, which make them, at first sight, the methods of choice. However, many challenging tasks, such as complex matrix applications, on-site and in vivo applications, and determination of matrix-bound and free concentrations of analytes, are not easily attainable with these classical approaches for sample preparation.     

电感耦合等离子体质谱技术在法庭科学中的研究和应用进展

电感耦合等离子体质谱法(inductively coupled plasma-mass spectrometry,ICP-MS)具有灵敏度高、干扰少、选择性好、适合进行超痕量多元素同时分析和同位素比值的测定等优点,在法庭科学中得到了广泛应用.综合归纳了ICP-MS技术在重金属及有害元素投(中)毒案件、食品药品环境分析、交通肇事及涉枪等案(事)件中重金属及微量元素分析中的应用.介绍了不同检材的样品前处理方法以及如何减少基体干扰,并且综述了优化ICP-MS仪器参数和碰撞反应池技术以消除质谱干扰,展望了ICP-MS在法庭科学中的应用.     

替代模板分子印迹技术在样品前处理中的应用

分子印迹聚合物具有抗恶劣环境、选择性高、稳定性好等特点,广泛应用于复杂样品的前处理。采用结构类似物作为替代模板分子,可以解决分子印迹聚合物制备时目标物溶解性差的问题,替代模板分子印迹聚合物不仅对目标分析物具有选择性识别能力,还可以避免模板泄露对痕量分析造成的影响。本文综述了替代模板分子印迹技术在样品前处理中的应用进展,包括替代模板分子印迹技术在固相萃取、固相微萃取、色谱固定相、基质固相分散萃取中的应用,最后对替代模板分子印迹技术在未来的样品前处理中的研究进行了展望。