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.

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