“一锅法”制备聚(苯乙烯-丙烯酸)共聚物改性的硅基固定相及其在混合模式液相色谱中的应用  

One-pot synthesis of a poly(styrene-acrylic acid)copolymer-modified silica stationary phase and its applications in mixed-mode liquid chromatography

作　　者：王晓庆 崔健 顾一鸣[2] 王硕 周谨[2] 王树东[2] WANG Xiaoqing;CUI Jian;GU Yiming;WANG Shuo;ZHOU Jin;WANG Shudong(University of Science and Technology of China,Hefei 230026,China;Dalian National Laboratory for Clean Energy,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China)

机构地区：[1]中国科学技术大学,安徽合肥230026 [2]中国科学院大连化学物理研究所,大连清洁能源国家实验室,辽宁大连116023

出　　处：《色谱》2023年第7期562-571,共10页Chinese Journal of Chromatography

摘　　要：聚合物作为一种来源广泛、功能基团丰富、生物相容性良好的修饰配体,被广泛用作硅基色谱固定相。本工作以苯乙烯和丙烯酸为聚合单体,乙烯基三甲氧基硅烷为硅烷偶联剂,通过自由基聚合反应一锅法制备了聚(苯乙烯-丙烯酸)共聚物改性的硅基固定相(SiO_(2)@P(St-b-AA))。傅里叶红外光谱、热重分析、扫描电镜、N_(2)吸附-脱附、Zeta电势分析等表征手段证明了该固定相已成功合成,且保持了良好的介孔球形结构。在固定相性能评价中,分别采用疏水性分析物、极性分析物和离子型化合物作为探针,对固定相的分离性能和保留机理进行了考察。其中,由于苯环提供的疏水和π-π相互作用,烷基苯和多环芳香烃在固定相上的保留随着流动相中甲醇含量的增加而减弱;由于羧酸基团可以为固定相与核苷碱基等极性溶质之间提供亲水相互作用,随着流动相中乙腈含量的增加,极性分析物的保留逐渐增强;与自制的C18和Amide固定相相比,SiO_(2)@P(St-b-AA)固定相在反相和亲水模式下均表现出良好的分离性能。此外,通过探究流动相pH对离子型化合物保留的影响,证明了该固定相还具有弱阳离子交换能力。多种分离模式表明SiO_(2)@P(St-b-AA)固定相可提供多种相互作用,并在不同极性组分分析物的分离中具有良好的应用前景。通过考察制备方法的重复性,证明了该方法具有良好的制备批次稳定性,简便的“一锅法”为新型聚合物改性硅基固定相的发展提供了一种新思路。As modified ligands with a wide range of sources,abundant functional groups,and good biocompatibility,polymers have been widely used in the development of silica-based chromatographic stationary phases.In this study,a poly(styrene-acrylic acid)copolymer-modified silica stationary phase(SiO_(2)@P(St-b-AA))was prepared via one-pot free-radical polymerization.In this stationary phase,styrene and acrylic acid were used as functional repeating units for polymerization and vinyltrimethoxylsilane(VTMS)was used as a silane coupling agent to link the copolymer and silica.Various characterization methods,such as Fourier transform infrared(FT-IR)spectroscopy,thermogravimetric analysis(TGA),scanning electron microscopy(SEM),N_(2) adsorption-desorption analysis,and Zeta potential analysis,confirmed the successful preparation of the SiO_(2)@P(St-b-AA)stationary phase,which had a well-maintained uniform spherical and mesoporous structure.The retention mechanisms and separation performance of the SiO_(2)@P(St-b-AA)stationary phase in multiple separation modes were then evaluated.Hydrophobic and hydrophilic analytes as well as ionic compounds were selected as probes for different separation modes,and changes in the retention of the analytes under various chromatographic conditions,including different methanol or acetonitrile contents and buffer pH values,were investigated.In reversed-phase liquid chromatography(RPLC)mode,the retention factors of alkyl benzenes and polycyclic aromatic hydrocarbons(PAHs)on the stationary phase decreased with increasing methanol content in the mobile phase.This finding could be attributed to the hydrophobic andπ-πinteractions between the benzene ring and analytes.The retention changes of alkyl benzenes and PAHs revealed that the SiO_(2)@P(St-b-AA)stationary phase,similar to the C18 stationary phase,exhibited a typical reversed-phase retention behavior.In hydrophilic interaction liquid chromatography(HILIC)mode,carboxylic acid groups,which could provide hydrophilic interactions between the stationa

关 键 词：聚合物改性固定相 一锅法 混合模式液相色谱 

分 类 号：O658[理学—分析化学]