餘甘子 (Phyllanthus emblica) 以對於治療和預防疾病的作用而聞名，並且是微量元素硒 (Selenium) 少見的來源。本研究旨在利用感應耦合電漿質譜儀結合高效液相層析技術，開發一套快速與可靠的硒物種分析方法應用於餘甘子。樣品前處理使用酵素 (蛋白酶 XIV) 水解以保留硒物種完整性，並透過微波的輔助可於 60℃、30 分鐘內完成萃取。高效液相層析–感應耦合電漿質譜連線分析系統使用 PRP-X100 陰離子交換管柱，動相為添加 2 % 甲醇之10 mM 檸檬酸銨緩衝溶液 (pH 5)，可於 20 分鐘內同時分離 SeMet、SeCys2、MeSeCys、Se(IV) 和 Se(VI)。五個硒物種的偵測極限介於 11.8–72.2 ng L-1 之間，並已透過驗證參考物質 SELM-1 進行方法確校。此物種分析方法已成功應用於六個不同地區的餘甘子樣品。結果顯示 SeMet 為餘甘子中主要硒物種，亦觀察到不同地區的差異，這些發現為餘甘子中硒物種分布提供了新的資訊。

Phyllanthus emblica (amla) is known for its therapeutic and preventive effects on diseases and is a rare source of the trace element selenium (Se). This study aimed to develop a rapid and reliable Se speciation analysis for P. emblica by coupling high performance liquid chromatographic separation technique with inductively coupled plasma–mass spectrometry. Sample preparation involved enzymatic (protease XIV) hydrolysis to preserve the integrity of Se species, which was accomplished within 30 minutes at 60°C with the assistance of microwaves. The developed high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) online analysis system utilized an anion-exchange column PRP-X100, and the mobile phase was 10 mM ammonium citrate buffer solution (pH 5) containing 2% MeOH. The system was able to simultaneously analyze SeMet, SeCys2, MeSeCys Se(IV) and Se(VI) within 20 mins. The detection limits for the five Se species ranged from 11.8 to 72.2 ng L-1, and the accuracy of the method was verified by analyzing the certified reference material (CRM) SELM-1. The speciation analysis method was successfully applied to P. emblica samples from six different regions. The results revealed that SeMet was the predominant species in P. emblica, and significant differences in the distribution of selenium species were observed among the different regions. These findings provide valuable insights into the distribution of Se species in P. emblica.

摘 要 I
ABSTRACT II
謝 誌 III
目 錄 V
圖目錄 VIII
表目錄 X
第一章 前言 1
1.1 餘甘子簡介 1
1.2 微量元素硒及其物種對於現代生物醫學的重要性 6
1.3 現行硒物種分析技術發展 11
1.4 研究目的及因應策略 12
第二章 儀器分析及原理 14
2.1 高效能液相層析儀 14
2.2 感應耦合電漿質譜儀 16
2.2.1 樣品導入系統 17
2.2.2 感應耦合電漿離子源 19
2.2.3 取樣界面 23
2.2.4 真空系統 25
2.2.5 離子透鏡 26
2.2.6 四極柱質量分析器 27
2.2.7 離子偵測器 29
第三章 實驗 32
3.1 儀器設備與裝置 32
3.2 試劑與材料 33
3.3 連線系統之建立 34
3.4 真實樣品製備 35
3.5 樣品前處理 36
第四章 結果與討論 37
4.1 層析分離條件最適化 38
4.1.1 動相 pH 值對於層析訊號之影響 38
4.1.2 動相濃度對於層析訊號之影響 42
4.1.3 甲醇濃度對於層析訊號之影響 43
4.2 萃取條件最適化 44
4.2.1 萃取方法對於分析物訊號之影響 44
4.2.2 酵素用量對於分析物訊號之影響 47
4.2.3 萃取溫度對於分析物訊號之影響 48
4.2.4 萃取時間對於分析物訊號之影響 49
4.3 連線分析系統效能評估 52
4.4 真實樣品分析 54
第五章 結論 61
第六章 未來展望 63
第七章 參考文獻 66
附錄、論文口試審查委員意見修正情形一覽 75

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