脱氢枞酸酯键合硅胶色谱固定相的制备及应用  

Preparation and Application of Dehydroabietic Acid Glycidyl Methacrylate Ester-bonded Silica Stationary Phase

作　　者：曾磊 唐小松 史伯安 雷福厚 ZENG Lei;TANG Xiao-song;SHI Bo-an;LEI Fu-hou(Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products,Guangxi Key Laboratory of Chemistry and Engineering of Forest Products,Key Laboratory of Chemistry and Engineering of Forest Products of State Ethnic Affairs Commission,School of Chemistry and Chemical Engineering,Guangxi Minzu University,Nanning 530006,China;School of Chemical and Environmental Engineering,Hubei Minzu University,Enshi 445000,China)

机构地区：[1]广西民族大学化学化工学院,林产化学与工程国家民委重点实验室,广西林产化学与工程重点实验室,广西林产化学与工程协同创新中心,广西南宁530006 [2]湖北民族大学化学与环境工程学院,湖北恩施445000

出　　处：《分析测试学报》2023年第5期541-549,共9页Journal of Instrumental Analysis

基　　金：国家自然科学基金资助项目(32060325)。

摘　　要：将天然可再生资源脱氢枞酸与甲基丙烯酸缩水甘油酯反应制得脱氢枞酸酯(DAGME),并将其通过“巯-烯”点击反应接枝到巯基功能化硅胶表面,制备得到一种疏水型脱氢枞酸酯键合硅胶色谱固定相(SilDAGME)。利用傅里叶变换红外光谱(FT-IR)、热失重分析(TGA)和元素分析(EA)对固定相进行表征,结果表明Sil-DAGME固定相成功制备。以烷基苯、Tanaka测试混合物、多环芳烃、酚类化合物和黄酮类化合物作为分离对象对Sil-DAGME的分离性能及保留机制进行评价。研究发现Sil-DAGME除疏水作用保留机制外,还具有氢键和π-π相互作用。基于多种保留机制的协同作用,Sil-DAGME对上述分析物均表现出良好的分离性能。此外,Sil-DAGME不仅具有良好的重现性(RSD为0.050%~0.19%,n=10)、稳定性(RSD为0.25%~1.0%,n=7)和可重复制备性(RSD为0.78%~2.1%,n=3),还对红豆杉树皮粗提物表现出良好的分离效果。将脱氢枞酸用于制备新型的色谱填料不仅为紫杉醇的分离和检测提供了一种新途径,也为以天然产物松香作为功能配体设计和制备新型固定相提供了参考。A dehydroabietic acid glycidyl methacrylate ester(DAGME)-bonded silica stationary phase(Sil-DAGME)was fabricated in this paper.The DAGME was firstly prepared using dehy⁃droabietic acid and glycidyl methacrylate via a ring-opening addition reaction,and then grafted onto the surface of a thiol-functionalized spherical silica by click reaction to obtain the Sil-DAGME.The successful immobilization of DAGME on the silica was confirmed through series of characterizations including Fourier-transform infrared spectroscopy(FT-IR),thermal gravimetric analysis(TGA)and elemental analysis(EA).The chromatographic performance and retention mechanisms of Sil-DAGME were validated using a variety of compounds including alkylbenzenes,Tanaka standard test mixtures,polycyclic aromatic hydrocarbons,phenols and flavonoids.Meanwhile,the Sil-DAG⁃ME exhibits multiple interactions,including hydrophobic,π-πand hydrogen bonding interaction between the stationary phase and the analytes during the separation process due to the co-existing of benzene ring,carbonyl group,hydroxyl group and hydrophobic rigid tricyclic hydrophenanthrene skeleton in the DAGME on the silica surface.Based on synergistic action of multiple retention mech⁃anisms,the probe molecules metioned above achieved ideal resolution and flexible selectivity in sep⁃aration.In addition,the Sil-DAGME not only exhibited good stability,repeatability and reproduc⁃ibility with the run-to-run relative standard deviations(RSDs)of 0.050%-0.19%(n=10),the dayto-day RSDs of 0.25%-1.0%(n=7),and the column-to-column RSDs of 0.78%-2.1%(n=3)for the retention time,but also showed an excellent separation ability for Yew tree bark extract.In short,the application of dehydroabietic acid in chromatographic separation materials not only provid⁃ed a new approach for the separation and detection of paclitaxel,but also presented a reference for the design stationary phase using natural product rosin as functional ligand.

关 键 词：脱氢枞酸 键合固定相 保留机制 紫杉醇 

分 类 号：O657.7[理学—分析化学]