[基于功能材料的固相微萃取技术在法医学中的应用]

[Applications of functional materials-based solid phase microextraction technique in forensic science].

作者信息

Xie Wei-Ya, Zhu Xiao-Han, Mei Hong-Cheng, Guo Hong-Ling, Li Ya-Jun, Huang Yang, Qin Hao, Zhu Jun, Hu Can

机构信息

People's Public Security University of China, Beijing 100038, China.

Institute of Forensic Science, Ministry of Public Security, Beijing 100038, China.

出版信息

Se Pu. 2023 Apr;41(4):302-311. doi: 10.3724/SP.J.1123.2022.06018.

Abstract

Sample extraction is a crucial step in forensic analysis, especially when dealing with trace and ultra-trace levels of target analytes present in various complex matrices (e. g., soil, biological samples, and fire debris). Conventional sample preparation techniques include Soxhlet extraction and liquid-liquid extraction. However, these techniques are tedious, time-consuming, labor-intensive and require large amounts of solvents, which poses a threat to the environment and health of researchers. Moreover, sample loss and secondary pollution can easily occur during the preparation procedure. Conversely, the solid phase microextraction (SPME) technique either requires a small amount of solvent or no solvent at all. Its small and portable size, simple and fast operation, easy-to-realize automation, and other characteristics thus make it a widely used sample pretreatment technique. More attention was given to the preparation of SPME coatings by using various functional materials, as commercialized SPME devices used in early studies were expensive, fragile, and lacked selectivity. Examples of those functional materials include metal-organic frameworks, covalent organic frameworks, carbon-based materials, molecularly imprinted polymers, ionic liquids, and conducting polymers, all widely used in environmental monitoring, food analysis, and drug detection. However, these SPME coating materials have relatively few applications in forensics. Given the high potential of SPME technology for the in situ and efficient extraction of samples from crime scenes, this study briefly introduces functional coating materials and summarizes the applications of SPME coating materials for the analysis of explosives, ignitable liquids, illicit drugs, poisons, paints, and human odors. Compared to commercial coatings, functional material-based SPME coatings exhibit higher selectivity, sensitivity, and stability. These advantages are mainly achieved through the following approaches: First, the selectivity can be improved by increasing the , hydrogen bonds, and hydrophilic/hydrophobic interactions between the materials and analytes. Second, the sensitivity can be improved by using porous materials or by increasing their porosity. Third, thermal, chemical, and mechanical stability can be improved by using robust materials or fixing the chemical bonding between the coating and substrate. In addition, composite materials with multiple advantages are gradually replacing the single materials. In terms of the substrate, the silica support was gradually replaced by the metal support. This study also outlines the existing shortcomings in forensic science analysis of functional material-based SPME techniques. First, the application of functional material-based SPME techniques in forensic science remains limited. On one hand, the analytes are narrow in scope. As far as explosive analysis is concerned, functional material-based SPME coatings are mainly applied to nitrobenzene explosives, while other categories, such as nitroamine and peroxides, are rarely or never involved. Research and development of coatings is insufficient and the application of COFs in forensic science has not yet been reported. Second, functional material-based SPME coatings have not been commercialized as they don't yet have inter-laboratory validation tests or established official standard analytical methods. Therefore, some suggestions are proposed for the future development of forensic science analyses of functional material-based SPME coatings. First, research and development of functional material-based SPME coatings, especially fiber coatings with broad-spectrum applicability and high sensitivity, or outstanding selectivity for some compounds, is still an important direction for SPME future research. Second, a theoretical calculation of the binding energy between the analyte and coating was introduced to guide the design of functional coatings and improve the screening efficiency of new coatings. Third, we expand its application in forensic science by expanding the number of analytes. Fourth, we focused on the promotion of functional material-based SPME coatings in conventional laboratories and established performance evaluation protocols for the commercialization of functional material-based SPME coatings. This study is expected to serve as a reference for peers engaged in related research.

摘要

样品提取是法医分析中的关键步骤,尤其是在处理存在于各种复杂基质(如土壤、生物样品和火灾残骸)中的痕量和超痕量目标分析物时。传统的样品制备技术包括索氏提取和液液萃取。然而,这些技术繁琐、耗时、劳动强度大且需要大量溶剂,这对环境和研究人员的健康构成威胁。此外,在制备过程中容易发生样品损失和二次污染。相反,固相微萃取(SPME)技术要么需要少量溶剂,要么根本不需要溶剂。其体积小、便于携带、操作简单快速、易于实现自动化等特点,使其成为一种广泛应用的样品预处理技术。由于早期研究中使用的商业化SPME装置昂贵、易碎且缺乏选择性,因此人们更加关注使用各种功能材料制备SPME涂层。这些功能材料包括金属有机框架、共价有机框架、碳基材料、分子印迹聚合物、离子液体和导电聚合物,它们在环境监测、食品分析和药物检测中都有广泛应用。然而,这些SPME涂层材料在法医领域的应用相对较少。鉴于SPME技术在从犯罪现场原位高效提取样品方面具有很高的潜力,本研究简要介绍了功能涂层材料,并总结了SPME涂层材料在分析爆炸物、可燃液体、非法药物、毒物、涂料和人体气味方面的应用。与商业涂层相比,基于功能材料的SPME涂层具有更高的选择性、灵敏度和稳定性。这些优势主要通过以下途径实现:第一,通过增加材料与分析物之间的 、氢键以及亲水/疏水相互作用来提高选择性。第二,通过使用多孔材料或增加其孔隙率来提高灵敏度。第三,通过使用坚固的材料或固定涂层与基底之间的化学键来提高热稳定性、化学稳定性和机械稳定性。此外,具有多种优势的复合材料正逐渐取代单一材料。在基底方面,二氧化硅载体逐渐被金属载体所取代。本研究还概述了基于功能材料的SPME技术在法医学分析中存在的不足之处。第一,基于功能材料的SPME技术在法医学中的应用仍然有限。一方面,分析物的范围较窄。就爆炸物分析而言,基于功能材料的SPME涂层主要应用于硝基苯类炸药,而其他类别,如硝基胺和过氧化物,很少或从未涉及。涂层的研发不足,共价有机框架在法医学中的应用尚未见报道。第二,基于功能材料的SPME涂层尚未商业化,因为它们尚未进行实验室间验证测试或建立官方标准分析方法。因此,针对基于功能材料的SPME涂层在法医学分析的未来发展提出了一些建议。第一,研发基于功能材料的SPME涂层,特别是具有广谱适用性和高灵敏度或对某些化合物具有出色选择性的纤维涂层,仍然是SPME未来研究的一个重要方向。第二,引入分析物与涂层之间结合能的理论计算,以指导功能涂层的设计并提高新涂层的筛选效率。第三,通过扩大分析物的数量来扩大其在法医学中的应用。第四,我们专注于在传统实验室中推广基于功能材料的SPME涂层,并建立基于功能材料的SPME涂层商业化的性能评估方案。本研究有望为从事相关研究的同行提供参考。

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