臺灣博碩士論文加值系統

本研究第一部份以固定比例混合兩種離子液體（[C4VIM][PF6]和[C9(VIM)2][PF6]2），模擬網版印刷碳電極塗覆製程方式，使用液滴塗覆法（drop coating）修飾在網版印刷碳電極（SPCE）表面，利用熱聚合的方式形成聚合型離子液體網版印刷碳電極（PIL-SPCE），此電極可藉由萃取來修飾上電子傳遞物質（mediator），Fe(CN)63- 形成FeCN-PIL-SPCE，修飾後電極對硫醇化合物具有電催化作用，可作為硫醇化合物的感測器；為了同時分析多種硫醇化合物，研究上進而結合高效能液相層析儀（High Performance Liquid Chromatography, HPLC），以實驗室自製離子液體管柱（SiImtBrCBS）在偵測電位、緩衝溶液濃度、流速、動相比例及pH值最佳化下成功分離偵測四種硫醇分子（Thioglycolic acid, 2-Mercaptoethanol, 3-Mercaptopropionic acid, Cysteamine）。由於硫醇分子對於pH值有較高的靈敏度，在高pH值時訊號較大但分離效果不佳，所以選擇pH 3的緩衝溶液作為動相進行分離，再使用補償系統提高電化學偵測時的pH值，對Thioglycolic acid (TGA)進行定量分析，偵測範圍為25-250ppm (R2=0.9936)，偵測極限為3.30ppm。此結果也可應用在定量燙髮劑中乙硫醇酸（TGA）的含量。
第二部份為應用上述電極研究的聚合型離子液體於固相萃取吸附劑上，以探討此類材料的萃取能力。實驗上將離子液體塗佈於silica gel表面作為固相萃取吸附劑，並比較添加Reduced graphene oxide (RGO)對萃取效率的影響，同時也改變離子液體組成比例成不同聚合型離子液體吸附劑，從混合[C4VIM][NTf2]及[C9(VIM)2][NTf2]2離子液體改為單純[C9(VIM)2][NTf2]2使其聚合更為完整。為比較不同吸附劑的吸附能力，以Naphthalene做突破曲線（Breakthrough curve）得到單純[C9(VIM)2][NTf2]2聚合形成的吸附劑(silica-C9)的吸附能力較佳。

In first part of the study, we simulated the manufacturing method of screen printed carbon electrode (SPCE) by using drop coating method to prepare the modified electrodes. Ionic liquids were coated onto a SPCE surface by mixing two ionic liquids in a fixed ratio ([C4VIM][PF6] : [C9(VIM)2][PF6]2 = 5 : 1). After coating, thermal polymerization was employed to form a hydrophobic polymerized ionic liquid membrane， PIL-SPCE. Then, the PIL-SPCE was used to extract an electrochemical mediator, ferricyanide (Fe(CN)63-) to form a FeCN-PIL-SPCE. This electrode was used as the working electrode to study the electrocatalytic oxidation of thiol compounds: Thioglycolic acid (TGA), Cysteamine, 2-Mercaptoethanol, and 3-Mercaptopropionic acid. The oxidation potentials of these thiols are much closed to each other and it needs to combine with HPLC for the determination of thiols mixture. The effects of various parameters, such as detection potential, flow rate, mobile phase concentration and pH, were studied in detail.
At high pH value, the sensitivity of oxidation is higher, but it has poor separation performance. In addition, column is not stable with high pH mobile phase. For these reasons, we used the pH 3 buffer as the mobile phase for better separation, then a high pH solution in the makeup system after the column to increase the pH value for electrochemistry detection. Under optimized conditions, the linear range for TGA is up to 250 ppm, correlation coefficient (R2) = 0.9936, with a detection limit of 3.30 ppm (S/N=3). The practical application of the proposed method was demonstrated by the determination of TGA concentration in a commercial hair-waving.
In the second part, we are interested in the extraction behavior of the polymerized ionic liquid employed in electrochemical study. Silica gel was coated with ionic liquid to form the SiO2-ILs sorbent. Sorbent added with some RGO was also examined to compare the effect of RGO in the sorbent. To find out a better sorbent material, we varied the composition of two ionic liquid monomer, [C4VIM][NTf2] and [C9(VIM)2][NTf2]2. In order to compare the adsorption capacity of different sorbents, breakthrough curves of naphthalene were examined and found out that polymerized ionic liquid with single monomer, [C9(VIM)2][NTf2]2, gave the best adsorption capacity.

摘要 i
Abstract iii
總目錄 v
圖目錄 ix
表目錄 xii
第一章 緒論 1
1.1研究動機 1
1.1.1第一部份：聚合型離子液體電極結合高效能液相層析於化妝品中硫化物之分析 1
1.1.2第二部份：離子液體結合石墨烯的複合材料於固相萃取的研究 2
1.2離子液體 3
1.3離子液體的應用 4
1.4離子液體修飾電極 5
1.5網版印刷電極（Screen Printed Electrode, SPE） 7
1.6電化學方法簡介 7
1.6.1循環伏安法（Cyclic Voltammetry, CV） 8
1.6.2安培法（Amperometry） 8
1.7固相萃取法（Solid phase extraction） 10
1.8離子液體應用於固相萃取 12
1.9突破曲線（Breakthrough curve） 13
1.10石墨烯 15
第二章 實驗設備、藥品及方法 17
2.1儀器設備 17
2.2實驗藥品 17
2.2.1有機溶劑 17
2.2.2離子液體前驅物 18
2.2.3緩衝溶液 18
2.2.4分析物 18
2.2.5其他藥品 19
2.3離子液體的合成 19
2.3.1合成[C4VIM][Br]離子液體 19
2.3.2合成非水溶性[C4VIM][PF6]/[NTf2]2離子液體 19
2.3.3合成[C9(VIM)2][Br]2離子液體 20
2.3.4合成非水溶性[C9(VIM)2][PF6]2/[NTf2]2離子液體 20
2.4製備兩性離子液體靜相管柱：SiImtBrCBS靜相製備 21
2.5管柱充填（Surry Packing） 23
2.6藥品配置 24
2.6.1磷酸鹽緩衝溶液 ( Phosphate Buffer Solution, PBS ) 24
2.6.2電子傳遞物質（Mediator）水溶液 24
2.7網版印刷碳電極修飾 24
2.7.1網版印刷碳電極前處理 24
2.7.2聚合型離子液體塗覆之網版印刷碳電極 25
2.7.3 PIL-SPCE萃取修飾上電子傳遞物質（Mediator） 25
2.8固相萃取 26
2.8.1吸附劑製備 26
2.8.1.1 silica-PIL及silica-C9吸附劑 26
2.8.1.2 silica-PIL-RGO及silica-C9-RGO吸附劑 26
2.8.1.3 Ionic liquids ball 26
2.8.2固相萃取步驟 27
2.8.3突破曲線(Breakthrough curve)的測定 27
第三章 聚合型離子液體電極結合高效能液相層析於化妝品中硫化物之分析 28
3.1離子液體的鑑定 28
3.2離子液體靜相於液相層析之探討 28
3.3 Fe(CN)63-反應機制的探討 29
3.4 FeCN-PIL-SPCE偵測TGA 31
3.5電催化機制的探討 31
3.6 TGA反應機制的探討 32
3.7偵測其他硫醇分子 32
3.8流動注射分析系統（FIA）之電位及離子強度探討 33
3.9高效能液相層析分離硫醇分子參數探討 34
3.9.1動相pH值 34
3.9.2動相組成 34
3.9.3流速 35
3.10補償系統 35
3.11偵測TGA之濃度線性及偵測極限 36
3.12真實樣品 36
第四章 離子液體結合石墨烯的複合材料於固相萃取的研究 38
4.1吸附劑的製備 38
4.2比較不同吸附劑之萃取 38
4.3不同吸附劑之突破曲線（Breakthrough curve） 40
第五章 總結 41
第六章 參考資料 70

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