Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, Av. Prof. Lineu Prestes 748, 05508-000, São Paulo, SP, Brazil.
Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
Anal Chim Acta. 2017 Apr 29;964:24-44. doi: 10.1016/j.aca.2017.02.002. Epub 2017 Feb 7.
This review aims at presenting the state of the art concerning monolithic materials for on-line sample preparation emphasizing solid-phase extraction, matrix exchange, and analyte conversion. Emphasis was given to organic and silica-based, as well as hybrid monoliths reported in the literature mostly after 2010. The first part of this review presents materials and strategies for enrichment of inorganic species in environmental and biological samples using mostly ICP-MS detectors. In the second part we focus on organic analytes, discussing the role of surface area of the polymer monoliths and density of adsorption sites for specific interactions, including incorporation of nanoparticles, metal organic frameworks, as well as the preparation of hybrid organic-silica monoliths to increase the surface area. Incorporation of ionic liquids to increase the number of types of interaction mechanisms available for retention is also discussed. Monoliths affording molecular recognition properties achieved by including boronate moieties for cis-diol recognition, as well as antibodies and aptamers for specific molecular recognition are also reviewed. The largest number of applications of molecular recognition mechanisms was observed for molecularly imprinted polymer monoliths as a consequence of the simplicity of this approach when compared to the use of immunosorbents or aptamers. The final part examines the on-line applications of immobilized enzyme reactors used for protein digestion in proteomic analysis and for kinetic studies in drug discovery and clinical assays usually coupling the reactors to mass spectrometers.
本文旨在介绍在线样品制备用整体材料的最新研究进展，重点介绍固相萃取、基质交换和分析物转化方面的整体材料。重点介绍了 2010 年后文献中报道的有机和硅胶基以及杂化整体材料。本文的第一部分介绍了使用大多 ICP-MS 检测器在环境和生物样品中富集无机物种的材料和策略。在第二部分，我们重点讨论了有机分析物，讨论了聚合物整体材料的表面积和吸附位点密度对特定相互作用的作用，包括纳米粒子、金属有机骨架的掺入以及有机-硅胶杂化整体材料的制备，以增加表面积。还讨论了通过引入离子液体增加可用于保留的相互作用机制的类型的数量。本文还综述了通过包含硼酸酯部分实现顺二醇识别的分子识别特性以及用于特定分子识别的抗体和适体的整体材料。与使用免疫吸附剂或适体相比，分子印迹聚合物整体材料由于其方法简单，因此观察到分子识别机制的应用最多。最后一部分检查了用于蛋白质组分析中的蛋白质消化和药物发现和临床测定中的动力学研究的固定化酶反应器的在线应用，通常将反应器与质谱仪耦合。
