以環糊精修飾之聚甲基丙烯酸酯類整體成形管柱結合毛細管電層析-質譜儀測定酚酸化合物

本實驗首先利用甲基丙烯酸縮水甘油酯(glycidyl methacrylate, GMA)結構上之epoxy官能基，經化學反應鍵結環糊精(cyclodextrins, CDs)分子，形成CD-GMA單體，再結合二乙烯苯(divinylbenzene, DVB)交聯劑聚合產生新型cyclodextrin attached poly(glycidyl methacrylate-divinylbenzene)整體成形管柱，並應用於毛細管電層析搭配紫外光偵測器分離八種常見酚酸化合物(phenolic acids)。因酚酸化合物具高度親水性與結構相似性，導致其層析分離的困難，故本研究的重點在於，欲透過分析物與靜相上之環糊精形成主客錯合作用力且環糊精上之羥基可增加靜相之親水性，使酚酸達到基線分離。實驗中除了動相組成的最佳化(乙腈(acetonitrile, ACN)含量)外，將討論不同環糊精(α- or β-CD)修飾之α-CD-GMA及β-CD-GMA、不同CD取代數之β-CD-GMAn, (n=1,2)所製備之整體成形管柱及其長度變化對酚酸分離的影響。相較於文獻對於酚酸的分離結果，本研究於CEC-UV系統下之偵測極限並不理想，偵測極限(limit of detection, LOD)為0.95-14.74mg/L，最後為了更進一步的提升感度，將毛細管電層析串聯質譜儀，研究過程中藉由調整單體中比例變化以及動相中ACN含量的變化，最後使八種酚酸之LOD能降低至0.003-0.052 mg/L，並進一步應用於實際樣品葡萄酒的檢測上。

關鍵字

酚酸；毛細管電層析-質譜儀

並列摘要

In this study, CD-GMA monomer which was synthesized by glycidyl methacrylate (GMA) and cyclodextrins (CDs) via epoxy functional group of GMA was used to prepare poly(CD-GMAn-co-divinylbenzeze(DVB)) based monolith. This novel monolith was used as stationary phase for eight phenolic acids separation in CEC system. Previous reviews indicated these phenolic acids were not achieved baseline separation owing to their hydrophilic nature. Thus, in this study, we would like to improve thier separation by host-guest complex interaction between analytes and CD as well as increaced the hydrophilic property of stationary phase resulted from the hydroxyl groups on CD structure. In addition to optimize ACN level in the mobile phase, CD-GMA monomers’ types (α-CD-GMA or β-CD-GMA), degrees of substitution of GMA in β-CD structure (β-CD-GMAn, (n=1, 2)) and monolith length were discussed. As the poor limit of detection (LOD) (0.95-14.74mg/L) was obtained in this CEC-UV system, we use poly(β-CD-GMA2-DVB) monolith as the separation column of CEC-MS system and results indicated a great improvement in LOD (0.003-0.052 mg/L). Finally, this technique was applied in real sample, such as grape wine for phenolic acid analytes.

並列關鍵字

Phenolic acids ； Capillary electrochromatography-mass spectrometry

參考文獻

吳斯燻, 丁望賢。(2004) 利用毛細管電泳法計算主-客內包錯合物結合常數之探討 CHEMISTRY（THE CHINESE CHEM. SOC., TAIPEI) 62(4), 517-532

Alpert, A. J. (1990). Hydrophilic-interaction chromatography for the separation of peptides, nucleic acids and other polar compounds. Journal of Chromatography A, 499, 177-196.

Bartle, K. D., & Myers, P. (2001). “Capillary Electrochromatography”, Cambridge：Royal Society of Chemistry.

Bizzotto, C. S., Meinhart, A. D., Rybka, A. C. P., Sobrinho, M. R., Junior, S. B., Ballus, C. A., & Godoy, H. T. (2012). Quantification of phenolic compounds by capillary zone electrophoresis in extracts of four commercial types of mate herb before and after acid hydrolysis. Food Research International.

Bragg, W., & Shamsi, S. A. (2012). A novel positively charged achiral co-monomer for β-cyclodextrin monolithic stationary phase: Improved chiral separation of acidic compounds using capillary electrochromatography coupled to mass spectrometry. Journal of Chromatography A.

國際替代計量

以環糊精修飾之聚甲基丙烯酸酯類整體成形管柱結合毛細管電層析-質譜儀測定酚酸化合物

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