内置式薄层色谱-表面增强拉曼光谱联用基底的制备及在有机反应检测中的应用  

Preparation of TLC-SERS Hyphenated Substrate and Application in Monitoring Organic Reactions

作　　者：卢贝贝 张晨杰[1] 徐敏敏[1] 姚建林[1] LU Beibei;ZHANG Chenjie;XU Minmin;YAO Jianlin(College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou 215123,China)

机构地区：[1]苏州大学材料与化学化工学部,苏州215123

出　　处：《高等学校化学学报》2025年第4期8-14,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22172109,21773166);江苏省高等学校自然科学研究项目(批准号:21KJA150009)资助。

摘　　要：表面增强拉曼光谱(SERS)因其灵敏度高、特异性强和可无损原位检测等优点,已发展成为一种功能强大的分析技术,但通常混合体系的SERS快速检测仍然存在巨大的技术挑战.本文采用液-液两相界面自组装法制备了大面积和高均匀性的Au@SiO_(2)单层膜SERS基底,结合薄层色谱(TLC),构建了新型TLC-SERS联用技术,将TLC的快速分离和SERS的高灵敏检测有机结合,克服了混合体系检测中分离叠加光谱和出现假阴性结果的困难.系统研究了内置Au@SiO_(2)单层膜SERS基底的稳定性和均匀性,解决了以往TLC-SERS联用技术中分离斑点二次扩散和硅胶背景干扰等问题.通过新型TLC-SERS联用技术,实现了模型反应苯硼酸和3-溴吡啶的Suzuki偶联反应过程的监测,以及分离鉴定无标准样品的未知烯烃加成反应产物.结果表明,通过SERS对TLC分离后的斑点所含物质进行结构分析,对分离后出现斑点重叠而难以区分的样品进行成像技术分析,获得相对应物种的信息.该新型联用技术可为解决众多难以分离鉴定的有机化学反应混合产物的难题提供新思路.Surface-enhanced Raman spectroscopy(SERS)has become a powerful analytical technique due to its high sensitivity,strong specificity,and non-destructive in situ detection.However,there are still great challenges for rapid detection with SERS in mixed systems.Herein,a large-area Au@SiO_(2)monolayer film with highly homogeneous was prepared by the liquid-liquid interface self-assembly method,and was transferred to the plate as SERS substrate.By combining the SERS with thin layer chromatography(TLC)techniques,a novel TLC-SERS hyphenated technology was constructed to overcome the difficulty of detection in mixed systems and allowed to realize the rapid separation and high-sensitivity detection.Studies on the stability and uniformity of the built-in Au@SiO_(2)SERS substrates were performed.It demonstrated that the problems of secondary diffusion of separation spots and interference of silica gel background in the previous TLC-SERS hyphenated technology were dissolved successfully.The new TLC-SERS hyphenated technology was explored to monitor the Suzuki coupling reaction process of phenylboronic acid and 3-bromopyridine.The overlap of different species on the hyphenated plate and the by-product were recognized according.Furthermore,it was successfully used to separate and identify the selective 1,2-dialkylation reaction products without standard samples.The result revealed that SERS played the important role in characterizing the structure of the spots separated by TLC and distinguishing the corresponding information for overlapping spots.The present hyphenated technology based on the novel combined substrate can be developed as a promising tool for solving the problems of separation on mixtures and fast monitoring the organic chemical reactions.

关 键 词：薄层色谱 表面增强拉曼光谱 联用技术 Au@SiO_(2) 有机反应 

分 类 号：O657[理学—分析化学]