電熱式揮發感應耦合電漿質譜（Eletrothermal vaporization inductively coupled plasma mass spectrometry，ETV-ICP-MS）是屬於乾進樣裝置，能有降低氧化物及氫氧化物所造成的光譜性干擾，相較於傳統氣動式霧化器而言，具有較高的傳輸效率，因此有較低偵測極限及較佳靈敏度。另外，具有樣品的需求量少（<50 μL）之優點，可避免因樣品本身量少而造成偵測上的限制。再搭配超音波泥漿自動取樣器裝置（Ultrasonic slurry sampling，USS），可直接對固體樣品進行偵測，省去樣品前處理的時間及降低在前處理過程中因導入汙染物或在消化過程中揮發損失等，造成定量上的不準確。
研究分為兩部分，第一部分是利用霧點萃取法結合電熱式揮發感應耦合電漿質譜儀於水樣中鉻、銅、鎘及鉛分析之應用。實驗中利用霧點萃取法（Cloud point extraction，CPE）作為前處理方法，來降低樣品中因含有高鹽類基質所造成的非光譜性干擾；再利用電熱式揮發樣品進樣系統及搭配動態反應管（Dynamic reaction cell，DRC），來降低在分析上面臨的光譜性干擾。霧點萃取法是在水樣中加入疏水性螯合劑與金屬離子生成錯合物，再加入界面活性劑進行萃取，可有效將基質作分離，且具有濃縮等優點。實驗中藉由微波來輔助霧點萃取，以提升萃取效率，縮短萃取時間。實驗結果中霧點萃取法之最適化為在pH值5條件下，添加0.5% m/v APDC和0.5% m/v Triton X-114，於60℃進行微波輔助萃取15分鐘。搭配ETV樣品需求量少的優點，可直接對萃取後的界面活性劑相進行分析，以減少對界面活性劑相稀釋。實驗中也針對影響分析物揮發訊號因素進行探討，包括修飾劑的添加、ETV的裂解溫度及揮發溫度等。
本研究中分析鉻時，因52Cr+嚴重受到40Ar12C+離子的光譜干擾，所以利用動態反應管來減輕干擾，選擇NH3作為反應氣體去除此干擾。最後選擇對標準參考樣品SLEW-3、SLRS-4、飲用水、自來水、澄清湖湖水和愛河河水樣品進行定量分析，並比對同位素稀釋法與基質匹配校正曲線法之定量結果，來驗證此方法的可行性。此方法對鉻、銅、鎘和鉛的偵測極限分別為0.004、0.002、0.001及0.001 μg L-1。
第二部分是以鈀奈米粒子（Palladium nanoparticles，Pd-NPs）作為電熱式揮發感應耦合電漿質譜法修飾劑進行探討，並應用於葉子與穀物樣品中砷、鋅、鎘、銻、汞及鉛之分析。Pd-NPs合成方法是選擇CMC（Carboxymethyl cellulose）作為保護劑及Ascorbic acid作為還原劑，實驗中將對Pd-NPs的尺寸與經升溫程式後於石墨平台（L’vov plateform）的分佈作分析，以及修飾劑的濃度、泥漿樣品的配製、儀器的操作條件與光譜干擾等影響離子強度的變因進行探討，由實驗結果發現，僅使用100 ng Pd-NPs作為修飾劑時即可有效提升分析物的訊號。經分析條件最適化後，選擇對標準參考樣品NIST SRM 1568a、NIST SRM 1573a、榕樹葉及市售米樣品進行分析，來驗證此方法的可行性。並使用標準添加法及同位素稀釋法來定量葉子與穀物樣品中微量元素的濃度，同時比較消化後的葉子與穀\\\物樣品以氣動式霧化器進行定量結果。此方法對於砷、鋅、鎘、銻、汞及鉛元素的方法偵測極限分別為3.8-7.2、0.3-0.7、0.9-1.5、0.1-0.3、0.7-1.5及0.7-1.1 μg kg-1。

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目錄
論文提要……………………………………………………………………………...….I
謝誌.................................................................................................................................III
目錄…………………………………………………………………………………….IV
圖表目錄………………………………………………………………………………VII


第一章 霧點萃取法結合電熱式揮發感應耦合電漿質譜儀於水樣中鉻、銅、鎘及鉛分析之應用
壹、 前言…………………………………………..…………………………………….1
一、 研究背景………………………………………………….……………….….1
二、 霧點萃取法（Cloud point extraction）簡介………………….…………..……2
三、 微波輔助萃取（Microwave-assisted extraction）簡介………..............………4
四、 電熱式揮發（Electrothermal vaporization）樣品輸入系統簡介…………..…4
五、 動態反應管（Dynamic reaction cell）簡介……………………………….….8
六、 鉻、銅、鎘和鉛之各論……………………………………………………….11
七、 同位素稀釋法（Isotope dilution）…………………………..………………..12
貳、 實驗部分…………………………………………..……………………………...13
一、 儀器裝置及操作條件…………….…………..……………..………………13
二、 試劑藥品及溶液的配製……………….…………………………...….……16
&#21442;、實驗過程……………………………………………………………………...……18
一、 霧點萃取條件之最適化…………………………………………………….18
二、 ETV之最適化…………………………………………………………….…24
三、 DRC系統之最適化………………………………………………….………25
四、 光譜(同質量)干擾………………………………………………………...…27
五、 校正曲線……………………………………………………….……………27
六、 樣品製備與分析…………………………………………………………….28
肆、結果與討論……………………………………………………………...…………28
一、 霧點萃取條件之最適化…………...………………………………………..28
二、 ETV之最適化………………………………..………………………..……38
三、 DRC系統之最適化……………………………...………………………….41
四、 光譜(同質量)干擾………………………………………...………………...47
五、 校正曲線…………………………………………………………...………..47
六、 真實樣品分析…………………………………………………...………..…53
伍、 結論………………………………………………………………………….…….63
陸、參考資料…………………………………………………………………………..64

第二章 以鈀奈米粒子為電熱式揮發感應耦合電漿質譜法修飾劑之研究
壹、 前言………….……………………………………………………………………69
一、 研究背景…………………………………….………………………………69
二、 砷、鋅、鎘、銻、汞及鉛之個論……………………………………….………71
壹、 實驗部分…………………………………………………………….……………72
一、 儀器裝置及操作條件………………………………………….……………72
二、 試劑藥品及溶液的配製…………………………………………………….76
貳、 實驗過程………………………………………………………………………….78
一、 Pd-NPs之探討……………………………………………………………….78
二、 Pd-NPs濃度對分析訊號的影響…………………………….…………....…82
三、 泥漿樣品濃度對分析物訊號的影響………………..………………………84
四、 酸濃度對分析物訊號的影響………..………………………………………84
五、 界面活性劑對分析物訊號的影響……..……………………………………84
六、 裂解溫度及揮發溫度的選擇..………………………………………………85
七、 光譜(同質量)干擾 …………………………………….....…………………85
八、 校正曲線………………………………………………………..……………85
九、 泥漿樣品製備與分析………………………………………………………..87
肆、結果與討論………………………………………………………………………..90
一、 Pd-NPs之探討……………………………..………………...………………90
二、 Pd-NPs濃度對分析訊號的影響………………………………..……...……93
三、 泥漿樣品濃度對分析物訊號的影響……………………..…………………93
四、 酸濃度對分析物訊號的影響……………………………………………..…99
五、 界面活性劑對分析物訊號的影響……………………………………..……99
六、 裂解溫度及揮發溫度的選擇……………………..…………………..…..…99
七、 光譜(同質量)干擾 …………………………………………….…..…..……99
八、 校正曲線……………………………………………………………………105
九、 樣品分析……………………………………………………………………105
伍、結論………………………………………………………………………………115
陸、參考文獻…………………………………………………………………………116

第一章 霧點萃取法結合電熱式揮發感應耦合電漿質譜儀於水樣中鉻、銅、鎘及鉛分析之應用
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第二章 以鈀奈米粒子為電熱式揮發感應耦合電漿質譜法修飾劑之研究
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2. Bhat, A. R.; Wu, H. F., Synthesis, characterization and application of modified Pd nanoparticles as preconcentration probes for selective enrichment/analysis of proteins via hydrophobic interactions from real-world samples using nanoparticleliquid-liquid microextraction coupled to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Rapid Commun. Mass Spectrom. 2010, 24, 3547-3552.

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