離子液體應用於超臨界流體層析及高效能液相層析分離之靜相開發

王玉君(Yu-Chun Wang)

指導教授 ： 魏國佐

國立中正大學/理學院/化學暨生物化學系/碩士(2012年)

摘要

本實驗室先前開發的兩性離子液體管柱 ZWIMS 在SFC下成功的分離酸、中、鹼性化合物，且分離效果皆優於商業管柱。為了進一步探討兩性離子液體管柱的效能，本研究以 ZWIMS 化學結構為參考，設計出兩種新離子液體靜相 ZWIMBrS 及 C9(Im)2ZWIMS ，並選用酸性、中性、鹼性等三種化合物測試其分離效能。結果顯示此兩靜相皆可順利將大多數分析物分離完全，其線性相關係數皆大於 0.9676 及 0.9913 ，理論板數最高分別達到 17,280 及 7,090 (plate/m) ，同日間的再現性分別小於 0.34 % (N=5) 及 1.26 % (N=10) ，異日間的再現性分別小於 3.48 % (N=5) 及 7.28 % (N=10) ；不同合成批次的管柱再現性則分別小於 22.91 % (N=2) 及 13.51 % (N=2) ，管柱再現性較差最主要是不同批次合成的靜相覆蓋量不同。本研究並且以線性溶解度能量關係式 (Linear solvation energy relationship, LSER) 為輔助，探討不同靜相結構之作用力，對於各類分析物分離的影響性。由LSER 模型比對分離效果，得知含芳香環類分析物可選用靜相e (n-π/π-π電子作用力) 值較大之管柱，酸性分析物本身可提供氫鍵，故可選用a (氫鍵接受能力) 值較顯著之管柱，鹼性分析物則可參考b (氫鍵提供能力) 值較明顯的管柱。
本研究並檢視這些兩性離子液體靜相應用在親水相液相層析 (Hydrophilic interaction liquid chromatography, HILIC) 及富水相液相層析 (Per-aqueous liquid chromatography, PALC) 分離的可行性。在 HILIC&PALC 的測試上，選用了核苷與鹼基 (Nucleobases and bases) 和三聚氰胺衍生物 (Melamines) 兩種分析物，結果顯示它們皆可在 HILIC 模式下成功得被分離開來。 ZWIMBrS 及 C9(Im)2ZWIMS 的線性相關係數皆大於0.9982及0.9962，同日間的再現性分別小於 2.61 % (N=4) 及 0.36 % (N=8) ，異日間的再現性則分別小於7.67 % (N=4) 及 4.48 % (N=8) 。

關鍵字

離子液體 ； 靜相

並列摘要

A zwitterionic liquid stationary phase ZWIMS was successfully synthesized and shown to have higher separation efficiency than the commercial column in our previous work. Based on ZWIMS structure to explore more about zwitterionic liquid stationary phase, we further designed two novel zwitterionic liquid stationary phases, ZWIMBrS and C9(Im)2ZWIMS. The linear solvation energy relationship (LSER) model was used to characterize these two stationary phases. In addition, the separation performance of these two stationary phase on hydrophilic interaction liquid chromatography (HILIC), per-aqueous liquid chromatography (PALC), and supercritical fluid chromatography (SFC) were investigated.
The new columns successfully separated polar and hydrophilic compounds of nucleobases and bases and melamines with HILIC mode. The linear correlation coefficients of ZWIMBrS and C9(Im)2ZWIMS were greater than 0.9982 and 0.9962 and the reproducibility of interday analysis were less than 2.61% (N=4) and 0.36% (N=8), respectively, whereas the reproducibility of intraday were less than 7.67% (N=4) and 4.48% (N=8), respectively. We also correlated the separation results with the LSER. The coefficients of LSER indicate that a larger value of e (n-π/π-π electrons interaction) is favor to separate the aromatic analytes, a larger value of a (hydrogen bond acceptor ability) is favor to separate the acidic compounds, and a larger value of b (hydrogen bond donor ability) is favor to separate the basic compounds.
In the SFC, acidic, neutral and basic compounds were chosen to test the performance of these stationary phases. Most of the analytes were completely separated by ZWIMBrS and C9(Im)2ZWIMS with the linear correlation coefficients of greater than 0.9676 and 0.9913. The number of theoretical plates are 17,280 and 7,090 (plate/m), the reproducibility of interday analysis are less than 0.34% (N=5) and 1.26% (N=10), the reproducibility of intraday analysis are less than 3.48% (N=5) and 7.28% (N=10), respectively for ZWIMBrS and C9(Im)2ZWIMS. The column reproducibility of two different batches are less than 22.91% and 13.51%, respectively for ZWIMBrS and C9(Im)2ZWIMS. The poor batch-to-batch performance is due to the different modifier coverage.

並列關鍵字

ionic liquid ； stationary phase

參考文獻

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