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研究生: 楊勝凱
Yang, Sheng-Kai
論文名稱: 電噴灑游離質譜法對難溶性有機金屬「茜素-媒染劑」的分析與研究
Study of the chemical structures of insoluble organometallic compound “alizarin-mordant” based on electrospray/mass spectrometry
指導教授: 林震煌
Lin, Cheng-Huang
口試委員: 丁望賢 呂家榮
口試日期: 2021/06/11
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2021
畢業學年度: 109
語文別: 中文
論文頁數: 57
中文關鍵詞: 二階段-竹筆尖電噴灑游離茜素媒染
英文關鍵詞: two-step bamboo nib-electrospray, alizarin, mordant
DOI URL: http://doi.org/10.6345/NTNU202100522
論文種類: 學術論文
相關次數: 點閱:62下載:0
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  • 茜素在媒染過程中,經常使用醋酸鋁或明礬作為媒染劑。媒染劑中的金屬離子可以和茜素在布料纖維上形成不可溶的有機金屬錯合物,達到固色的目的。不過這些有機金屬錯合物的結構式,至今仍無法以質譜儀來進行測量。
    本實驗利用二階段-竹筆尖/電噴灑游離質譜法(two-step bamboo nib-electrospray/mass spectrometry) 成功測量到茜素與醋酸鋁反應時,形成「茜素-鋁離子」有機金屬錯合物之前的中間產物,包括[C14H7O4Al(OH)(CH3OH)]2+, (m/z=314)及[C14H7O4Al(CH3OH)2]2+, (m/z=329)。此反應一旦形成有機金屬錯合物,其沉澱物為紅色。該紅色沉澱物可使用基質輔助雷射脫附/飛行時間型質譜儀加以測量,並以CHCA (alpha-cyano-4-hydroxycinnamic acid)作為基質。實驗結果發現在負電模式時,質譜圖上有一明顯的訊號在m/z=502,符合兩個茜素分子與醋酸鋁中的鋁離子錯合的荷質比。此外在測量茜素與明礬(鉀鋁礬)溶液的訊號時,還發現了兩個含有鉀離子的訊號,分別是[C14H7O4K(CH3OH)3], (m/z=373)及[C14H7O4K(OH)(CH3OH)3], (m/z=390)。
    本論文闡述二階段-竹筆尖/電噴灑游離質譜法的原理及應用。對於測量「茜素-媒染劑」的中間產物的實驗條件,包括電噴灑時的正或負電模式、進樣流速、溫度等條件均有詳細探討。對於今後測量反應快速的錯合反應,提供了一種新的質譜分析方法。

    It is common that use aluminium acetate or alum as a mordant dye during the dyeing process. The metal ions in the mordant reacts with the alizarin, forming insoluble organometallic precipitate and attaching it firmly to the fabric. However, the structural formulas of these insoluble organometallic precipitate cannot be measured by mass spectrometers.
    The research is successfully detected the intermediate products of alizarin-aluminum ion that alizarin reacts with aluminum acetate by using two-step bamboo nib-electrospray/mass spectrometry. The intermediate products include [C14H7O4Al(OH)(CH3OH)]2+, (m/z=314) and [C14H7O4Al(CH3OH)2]2+, (m/z=329). The precipitate that alizarin reacts with aluminum acetate is red, when the reaction forms an insoluble organometallic complex. The red precipitate can be measured by using matrix-assisted laser desorption/time-of-flight mass spectrometer with CHCA (alpha-cyano-4-hydroxycinnamic acid) as the matrix. The results found that in the negative mode, there is an obvious signal on the mass spectrum at m/z=502, which is consistent with the mass-to-charge ratio of the complex of two alizarin molecules with aluminum ions. In addition, when detecting the signal of alizarin and alum solution, two signals containing potassium ions were also found. One is [C14H7O4K(CH3OH)3], (m/z=373), and the other is [C14H7O4K(OH)(CH3OH)3], (m/z=390).
    This research describes the principle and application of the two-step bamboo nib-electrospray/mass spectrometry. The experimental conditions for measuring the intermediate product of “alizarin-mordant”, including the positive or negative mode of electrospray, the injection flow rate, temperature and other conditions are discussed in detail. It provides a new method of mass spectrometry for measuring the rapid reaction of complex reactions in the future.

    第一章 緒論 1 1-1 研究目的 1 1-2 分析物簡介 3 1-2-1 茜素 (Alizarin) 3 1-2-2 明礬 (Alum) 4 1-2-3 乙酸鋁 (Aluminium acetate) 4 第二章 分析原理及方法 5 2-1 電噴灑游離質譜法 (ESI/MS)的發展與原理 5 2-1-1 電噴灑游離質譜的發展歷程 5 2-1-2 電噴灑游離質譜的原理與機制 10 2-2 竹筆尖電噴灑游離質譜 13 2-2-1 竹筆尖電噴灑游離簡介 13 2-2-2 竹筆尖電噴灑之竹筆尖頭製作 14 2-3 竹筆尖電噴灑游離質譜之使用 16 第三章 實驗儀器與藥品 18 3-1 實驗藥品 18 3-2 儀器與周邊設備 20 第四章 研究過程與結果討論 22 4-1 茜根成分確認 22 4-1-1 樣品配製 22 4-1-2 實驗條件 23 4-1-3 實驗結果 23 4-2 茜素與含有不同金屬離子的媒染劑反應 25 4-2-1 樣品配製 25 4-2-2 實驗結果 26 4-3 茜素與金屬離子錯合物參考文獻 28 4-4 以MALDI-TOF進行確認明礬與醋酸鋁錯合物 30 4-4-1 樣品配製 30 4-4-2 實驗條件 31 4-4-3 實驗結果 31 4-5 茜素與醋酸鋁錯合物質譜分析 33 4-5-1 樣品配製 33 4-5-2 實驗條件 33 4-5-3 實驗結果 34 4-6 茜素與明礬錯合物質譜分析 37 4-6-1 樣品配製 37 4-6-2 實驗條件 37 4-6-3 實驗結果 38 第五章 結論 41 附錄 43 參考資料 52

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