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博碩士論文 etd-0706101-144438 詳細資訊
Title page for etd-0706101-144438
論文名稱
Title
多頻道式TLC-on-chip結合電噴灑游離質譜法之開發
Multichannel TLC-on-chip and it's ES/MS interfaces
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
80
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2001-06-29
繳交日期
Date of Submission
2001-07-06
關鍵字
Keywords
線上分析、微片薄層層析、電噴灑游離質譜法、薄層層析法、微小化分析系統
ES/MS, TLC-on-chip, TLC, On-line analysis, u-TAS
統計
Statistics
本論文已被瀏覽 5660 次,被下載 6967
The thesis/dissertation has been browsed 5660 times, has been downloaded 6967 times.
中文摘要
將分析系統微小化(Miniaturized Total Analytical System, μ-TAS)是現代分析化學必然的發展趨勢。分析系統微小化後最主要的優點為樣品及分析試劑用量的大量減少。這不但可以減少對環境的污染與健康的傷害,也可節省分析成本及增加分析速度等。在分析上常用的各種層析法中,傳統薄層層析法(Thin-layer chromatography,TLC)具有構造簡單、成本低廉的優點,但是因需要使用大量樣品,且無法與其他光譜法直接連接以進行定性分析,因此也大大地限制了它的應用範圍。本研究即是將薄層層析微小化(亦即TLC-on-chip),主要做法是在微片上進行TLC,共開發出TLC-on-chip(I)與TLC-on-chip(II)兩種微片。研究中並發展了連接TLC-on-chip和質譜儀的兩種界面以進行物種的定性分析。此兩種界面分別是直接探針式微片ES/MS界面以及尖端式微片ES/MS界面。TLC-on-chip(I)連接直接探針式微片ES/MS界面是使用3 ×4 ㎝ 的鐵弗龍板作成的,以美工刀在上面刻劃出五條獨立且均填充有C18固定相的TLC的管道,每一管道在底部均有一動相容槽而且在離出口端約1公分處刻劃有一側管,側管連接到一ES溶液的容槽(以添加ES之電壓與溶劑)。出口端在填充管道的靜相物質時同時埋入二根光纖作為直接探針式電噴灑源(direct-emitter-probe, DEP)。電噴灑的產生是利用溶液在兩根光纖間的毛細現象而得到一穩定之電噴灑現象。而電噴灑所需要的高電壓則是以溶液導電方式導入二光纖的尖端出口。而TLC-on-chip(II)連接尖端式微片電噴灑游離界面是以刀將市售TLC矽膠片切割成有五條小的TLC分離管道的微片,每一管道的出口處切割成三角形尖端以作為電噴灑源。在出口端並放置有一毛細管,由一微量注射幫浦來推送及控制進行電噴灑時所需之輔助溶劑。樣品分離是利用溶液在TLC上的毛細現象而得到。研究中分別以西藥成分Clindamycin / Sildenafil以及有機金屬化合物Ferrocene / Biferrocenec之混合溶液做為樣品來測試兩種界面的效率。由所得到的結果顯示此兩種界面對於上述之兩種樣品的偵測均有很好的效果。本研究成功的證明了將TLC微小化以及使TLC進行線上分析(On-line analysis)是具體可行的分析方法。在研究中對於影響此兩種界面效率的相關因素,諸如微片上TLC管道的尺寸大小、噴灑口的型式、ES的流速控制、ES的施加位置以及尖端的處理方式等也有加以探討,並提出未來發展時一些值得注意的地方以供參考。
TLC技術很早就被普遍使用,而本研究所開發的TLC-on-chip結合電噴灑游離質譜法的微片界面則使它突破了舊有的禁錮,使其能應用在更多的用途上。相信這個技術未來仍有很大的成長空間。
Abstract
None
目次 Table of Contents
目 錄

摘 要 …………………………………………………………………………… I

目 錄 ……………………………………………………………………………III

圖目錄 ……………………………………………………………………………V

表目錄 ……………………………………………………………………………VII

第一章 緒論…………………………………………………………………………1
一、前言 ………………………………………………………………………1
二、簡介………………………………………………………………………3
(1) 薄層層析法之簡介 ………………………………………………3
1. 薄層層析法之發展………………………………………………3
2. 質譜法在薄層層析法上之應用…………………………………5
(2) 電噴灑游離質譜法之簡介…………………………………….…9
1. 電噴灑游離法之作用機制 …………………………………….9
2. 電噴灑游離質譜法之發展 ……………………………………12
(3) 微片電噴灑游離質譜法之發展…………………………………17

三、研究目標 ………………………………………………………………22

第二章 實 驗 ……………………………………………………………………24
一、 TLC-on-chip 結合 ES/MS 界面之設計 ……………………………24
二、 儀器裝置………………………………………………………………31
三、 藥品與試劑……………………………………………………………33

第三章、結果與討論 ………………………………………………………………37
一、 實驗結果 …………………………………………………………………37
(1)TLC-on-chip(I)結合直接探針式ES/MS界面……………………37
(2)TLC-on-chip(II)結合尖端式ES/MS界面…………………………46
二、討論…………………………………………………………………………55
(1)影響TLC-on-chip結合 ES/MS界面之分析品質之因素的探討……55
(2)TLC-on-chip結合 ES/MS界面之未來發展…………………………71

第四章 結論…………………………………………………………………………73

附錄 參考資料………………………………………………………………………74


圖目錄


圖一、電噴灑游離法的作用機制……………………………………………………10
圖二、TLC-on-chip(I)及直接探針式電噴灑游離界面之構造示意圖…………25
圖三、直接探針式電噴灑游離界面的光籤尖端進行電噴灑時之顯微照相………27
圖四、TLC-on-chip(II)及尖端式電噴灑游離界面之構造示意圖……………29
圖五、尖端式電噴灑游離界面之尖端進行電噴灑時之顯微照相…………………30
圖六、以直接電噴灑探針分析Clindamycin與Sildenafil所得到的質譜圖……34
圖七、以直接電噴灑探針分析Ferrocene與Biferrocene所得到的質譜圖……36
圖八、Clindamycin與Sildenafil之結構…………………………………………38
圖九、以TLC-on-chip(I)結合直接探針式電噴灑游離界面進行空白樣品分析所得之背景質譜圖……………………………………………………………40
圖十、TLC-on-chip(I)上只有Clindamycin時以直接探針式電噴灑游離界面進行分析所得到的質譜層析圖…………………………………………………42
圖十一、TLC-on-chip(I)上只有Sildenafil時以直接探針式電噴灑游離界面進行分析所得到的質譜層析圖………………………………………………43
圖十二、TLC-on-chip(I)上有Clindamycin與Sildenafil混合樣品時以直接探針式電噴灑游離界面進行分析所得到的質譜層析圖……………………44
圖十三、TLC-on-chip(I)上有Clindamycin與Sildenafil混合樣品時以直接探針式電噴灑游離界面進行分析所得到的質譜圖…………………………45
圖十四、Ferrocene與Biferrocene之結構………………………………………47
圖十五、以TLC-on-chip(II)結合尖端式電噴灑游離界面進行空白樣品分析所得之背景質譜圖………………………………………………………………49
圖十六、TLC-on-chip(II)上只有Ferrocene時以尖端式電噴灑游離界面進行分析所得到的質譜層析圖……………………………………………………50
圖十七、TLC-on-chip(II)上只有Biferrocene時以尖端式電噴灑游離界面進行分析所得到的質譜層析圖…………………………………………………51
圖十八、TLC-on-chip(II)上有Ferrocene與Biferrocene混合樣品時以尖端式電噴灑游離界面進行分析所得到的質譜層析圖…………………………53
圖十九、TLC-on-chip(II)上有Ferrocene與Biferrocene混合樣品時以尖端式電噴灑游離界面進行分析所得到的質譜圖………………………………54
圖二十、直接探針式電噴灑游離界面之噴灑口的設計……………………………56
圖二十一、電噴灑品質不佳時所得到的質譜層析圖………………………………60
圖二十二、電噴灑品質良好時所得到的質譜層析圖………………………………61
圖二十三、樣品量過大(Overloading)時所得到的質譜層析圖。TLC分離效果差………………………………………………………………………………63
圖二十四、樣品量仍然過量時所得到的質譜層析圖。TLC分離效果雖有改善仍不理想……………………………………………………………………………64
圖二十五、樣品量適中時所得到的質譜層析圖。TLC可得到理想的分離效果…65
圖二十六、尖端式電噴灑游離界面之噴灑口位置上薄層的型式…………………67
圖二十七、尖端式電噴灑游離界面之高電壓位置之選擇…………………………68
圖二十八、尖端式電噴灑游離界面之補充ES溶液的毛細管位置之選擇………70

表目錄

表一、 TLC-on-chip(I)結合直接探針式微片電噴灑游離質譜界面之實驗條件……………………………………………………………39
表二、 TLC-on-chip(II)結合尖端式微片電噴灑游離質譜界面之實驗條件……………………………………………………………………48
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