臺灣博碩士論文加值系統

超音波泥漿取樣法（Ultrasonic Slurry Sampling，USS）是一種將固體樣品導入電熱式揮發器（Electrothermal Vaporizer，ETV）的方法，已廣泛且成功地使用在感應耦合電漿質譜儀（ICP-MS）上。相較於傳統固體樣品需經強酸消化再進行分析，泥漿取樣法的直接取樣分析有簡化樣品前處理的繁雜過程，避免於樣品前處理過程中導入污染物及降低易揮發物種在消化時之損失等優點；再配合 ETV 樣品輸入裝置，其相較於傳統氣動式霧化器而言，有靈敏度較佳、偵測極限較低、所需樣品量少及可直接固體進樣等優點。此外，由於在 ICP-MS 中常會因光譜干擾而造成定量上準確性不佳，因此，可配合動態反應室（Dynamic Reaction Cell，DRC）來減輕在定量時光譜干擾所造成的影響。

本研究是以電熱式揮發感應耦合電漿質譜儀（ETV-ICP-MS）偵測藥錠及中草藥中之微量元素。研究分為兩個部分：第一部分為使用泥漿取樣法結合電熱式揮發感應耦合電漿質譜儀（USS-ETV-ICP-MS）同時偵測藥錠中鉻、鉬、鈀、鎘、鉑及鉛的含量，並配合動態反應室（DRC）的使用，以降低因基質或輸送氣體所造成的光譜干擾。在研究中，對於修飾劑、DRC 條件、泥漿樣品的配製及儀器設定的條件等因素進行探討。實驗結果發現，以 1% m/v Ammonium pyrrolidine dithiocarbamate（APDC）及 0.025% m/v 8-Hydroxyquinoline （8-HQ）當作修飾劑時可以有效提升分析物的訊號；在泥漿樣品的配製中，則是選擇 1% m/v 的濃度，以避免因稀釋倍數太大而造成定量上的誤差，或因稀釋倍數太小而使樣品無法完全揮發；在儀器設定上，使用裂解溫度 300℃ 及揮發溫度 2400℃ 時可得最佳的訊號。在 DRC 系統中，使用 NH3 做反應氣體，可有效地降低 ArC+ 及 ClO+ 對 Cr 產生的多原子干擾，經過最適化的條件探討後，期望將 Cr 受到的光譜干擾降到最低以達到較準確的定量結果。最後，分析方法最適化後，將對三種市售的高血壓藥錠進行定量，其分析結果與藥錠微波消化後測得的值來做比較，發現並沒有太大差異，且定量結果其 RSD 值除了 Pt 為 14 - 25% 外，其餘皆介於 1.2% - 4.7%。藉此來驗證此分析方法之可行性。此方法對鉻、鉬、鈀、鎘、鉑及鉛的方法偵測極限分別為 0.5、0.9、0.3、0.3、0.1 及 0.3 ng g-1。

第二部分則是使用 USS-ETV-ICP-MS 對中草藥中有毒重金屬元素砷、鎘、汞及鉛的分析。在實驗中使用 1% m/v 8-HQ 當作修飾劑；泥漿樣品的配製中，則是選擇 0.5% m/v 的濃度；ETV 的設定選擇裂解溫度 180℃ 及揮發溫度 1900℃。在各分析條件最適化後，將此系統應用於三種中草藥的定量分析。為了驗證分析方法的可行性，首先選擇與中草藥有類似基質的標準參考樣品（Standard Reference Material）— SRM 1573a（蕃茄葉)及 SRM 1547 (桃葉)進行分析，其定量結果與標準參考值（Certified value）相吻合，且三種中草藥的定量結果與中草藥微波消化後以氣動式霧化器進樣及本實驗室同學使用氫化物生成進樣系統結合 ICP-MS 所測得的值結果相近，可證明 USS-ETV-ICP-MS 於分析中草藥中砷、鎘、汞及鉛的實用性。其定量結果的 RSD 值介於 1.0% - 4.4% 之間。此方法對砷、鎘、汞及鉛的方法偵測極限分別為 0.3、0.6、0.2 及 0.6 ng g-1。

論文提要............................................................................... I
謝誌....................................................................................... IV
目錄........................................................................................V
圖表目錄.............................................................................VIII

第一章 泥漿取樣法結合電熱式揮發感應耦合電漿質譜儀於藥錠中鉻、鉬、鈀、鎘、鉑及鉛等元素之分析應用
壹、前言................................................................................1
一、研究背景........................................................................1
二、超音波泥漿取樣法結合電熱式揮發樣品輸入系統簡介..8
三、動態反應室系統簡介..................................................11
貳、實驗部分......................................................................12
一、儀器裝置及操作條件..................................................12
二、試劑藥品及溶液的配製..............................................19
三、藥錠泥漿樣品的製備與消化......................................22
參、結果與討論................................................................. 25
一、修飾劑的選擇..............................................................25
二、界面活性劑對分析物訊號的影響..............................32
三、酸對分析物訊號的影響..............................................32
四、稀釋倍數的探討..........................................................35
五、裂解溫度（Pyrolysis Temperature）及揮發溫度（Vaporization Temperature）的選擇...........................37
六、DRC系統之最佳化.....................................................40
七、光譜（同質量）干擾..................................................51
八、校正曲線..................................................................... 54
九、樣品定量分析..............................................................58
肆、結論..............................................................................61
伍、參考文獻......................................................................62

第二章 泥漿取樣法結合電熱式揮發感應耦合電漿質譜儀於中草藥中砷、鎘、汞及鉛等元素之分析應用
壹、前言.............................................................................68
一、研究背景.....................................................................68
二、砷、鎘、汞及鉛之個論.............................................73
貳、實驗部分.....................................................................75
一、儀器裝置及操作條件.................................................75
二、試劑藥品及溶液的配製.............................................78
三、中草藥泥漿樣品的製備與消化.................................81
參、結果與討論.................................................................83
一、修飾劑的選擇.............................................................83
二、界面活性劑對分析物訊號的影響.............................87
三、酸與鹼及氧化試劑對分析物訊號的影響.................90
四、稀釋倍數的探討.........................................................94
五、裂解溫度（Pyrolysis Temperature）及揮發溫度（Vaporization Temperature）的選擇 .........................94
六、光譜（同質量）干擾.................................................97
七、校正曲線..................................................................100
八、樣品定量分析..........................................................102
肆、結論..........................................................................107
伍、參考文獻..................................................................108

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