微孔有机网络材料的合成方法及其在样品前处理中的应用进展

Advances in synthesis methods and applications of microporous organic networks for sample preparation

样品前处理是色谱分析中必不可少的环节。固相萃取是一类应用广泛的前处理方法,吸附剂的优劣直接影响萃取过程对目标化合物的吸附和富集效率,并影响前处理及后续分析方法的灵敏度和选择性。因此吸附剂的选择和开发成为一个研究热点。微孔有机网络(microporous organic networks,MONs)是由芳香炔烃和芳香卤化物通过Sonogashira反应合成的一类新型共价有机材料,具有结构可修饰、比表面积大、孔隙率高、合成简单等优点。本文概述了MONs的合成和功能化修饰方法,着重介绍了该材料在样品前处理领域的应用新进展,并对其发展趋势进行了展望。在合成方法方面,MONs材料的制备从回流合成法、溶剂热合成法发展到室温合成法,合成条件趋向于更温和、更高效。在材料功能化修饰方面,引入大分子物质以及氨基、羟基、羧基等活性基团,能增加MONs材料的选择性和作用位点;将MONs与Fe_(3)O_(4)、SiO_(2)、MOFs结合,形成核壳结构MONs,在此基础上进行煅烧和刻蚀,可形成多孔碳结构或空心多层材料。上述功能化修饰的MONs及其复合材料和目标物之间存在多重作用机制(氢键、疏水、静电、π-π相互作用等),因此能实现各类化合物的高效萃取。将MONs作为吸附剂材料应用于固相萃取、固相微萃取、分散固相萃取、磁性固相萃取等多种前处理方法,结合色谱、色谱-质谱联用等技术,获得了较好的吸附效果和较高的灵敏度,展现了MONs材料在样品前处理领域的应用潜力。

Sample pretreatment is an essential step in chromatographic analysis.Solid phase extraction(SPE)is a widely used sample pretreatment method.In SPE,the quality of the adsorbent directly affects the adsorption and enrichment efficiency of the target compounds as well as the sensitivity and selectivity of the pretreatment and subsequent analysis.Therefore,the selection and development of adsorbents has become a research hotspot.Microporous organic networks(MONs)are a novel type of covalent organic materials that are synthesized by the Sonogashira reaction of aromatic alkynes and aromatic halides.These networks have the advantages of modifiable structures,large specific surface areas,high porosity,and simple synthesis methods.This paper reviews the synthesis and functional modification methods of MONs,with an emphasis on their applications in sample pretreatment.Future development trends are also prospected.In terms of synthesis,the preparation methods for MON-based materials have progressed from reflux and solvothermal synthesis to room-temperature synthesis,the conditions of which tend to be milder and more efficient.In terms of functional modification,the introduction of macromolecules and active groups(including amino,hydroxyl,and carboxylic groups)can increase the selectivity and active sites of MON-based materials.The combination of MONs with Fe_(3)O_(4),SiO_(2),and metal organic frameworks yields core-shell-structured MONs.Furtherly,they can be calcined and etched to form porous carbon structures or hollow multilayer materials.Functionalized MONs and their composite materials have multiple interaction mechanisms(e.g.,hydrogen bonding,hydrophobic,electrostatic,andπ-πinteractions)with various target compounds,thereby realizing their efficient extraction.MONs can be used as adsorbent materials in SPE,Solid phase microextraction,dispersed solid phase extraction,magnetic solid phase extraction,and other pretreatment methods.When combined with chromatography and chromatography-mass spectrometry,MONs achieve good adsorption effects and high sensitivity,demonstrating the application potential of these materials in sample pretreatment.