微量元素與人體的健康息息相關，而元素可以以不同氧化數及化合物所組成不同之物種型態，其對於生物體的毒性程度也有所差異，除了對於元素的總濃度進行測定外，對於其型態與含量分析結果也希望能更了解，以提供完整的樣品資訊。使用高效能液相層析(High Performance Liquid Chromatography，HPLC)結合感應耦合電漿質譜儀(Inductively Coupled Plasma Mass Spectroscopy，ICP-MS)進行偵測，因其具有高靈敏度、線性範圍廣以及同時進行多元素偵測等優點，搭配前者的物種分離，能夠以現有的標準品定量未知物種，並利用電噴灑質譜儀(Electrospray Ionization Mass Spectrometry，ESI-MS)對於物種的化合物結構進行分析，獲得定性及定量上的更完整資訊。
第一部分研究，使用陰離子交換樹脂 (Anion-exchange chromatography)作為管柱，以碳酸銨作為動相分離海洋藻類中含砷化合物，將含有砷醣(Arsenosuger)的海帶頭萃取液中添加入砷標準品，探討出最適化的液相層析條件，能在一支管柱將Arsenocholine、Arsenobetaine、OH-arsenoribose、As(III)、Dimethylarsinic acid、PO4-arsenoribose、Monomethylarsonic acid、SO3H-arsenoribose、As(V)、trialkylarsonioribosides 十種砷物種於19分鐘內分離，並且使用動態反應槽(Dynamic Reaction Cell)去除高鹽類樣品的氯離子在分析中所形成的ArCl+對於砷的光譜干擾，在最適化條件下，砷的偵測極限範圍介於0.006到0.018 ng mL-1 之間。
將此方法應用在分析BCR-279 ulva lactuca以及不同市售海洋藻類樣品，在真實樣品中的含砷未知物以液相層析連接電噴灑質譜儀系統 (HPLC-ESI-MS) 鑑定未知物，經過一次質譜和二次質譜的鑑定後，為OH-arsenoribose、PO4-arsenoribose
、SO3H-arsenoribose三種砷糖。
第二部分研究，以逆相層析法(Reverse phase chromatography)結合結合感應耦合電漿質譜儀對Cr(III)-EDTA與Cr(VI)進行分析。本篇層析系統利用含有Tetra-n-butylammonium phosphate (TBAP)做為離子對試劑以及Disodium ethylenediamine teraacetic acid (EDTA) 做為Cr(III)的螯合試劑，並幫助鉻的分離，在動相pH=6.9的環境下沖提C8管柱。為了減輕鉻在偵測時來自ArC的光譜干擾，選用NH3作為動態反應槽的反應氣體。在最適化條件下，本系統可以在2分鐘內分離鉻物種，鉻的偵測極限範圍為0.052與0.054 ng mL-1，鉻物種的波峰高度與波峰面積的在現性皆優於3.7 % (n=5)。選用NRCC SLRS-4 River Water作為標準參考樣品對於系統方法做確效，樣品選擇以商店所販售之酒類與藥局販售之營養補充即飲品。以簡單震盪處理樣品後即進入本系統中分析，其回收率介於89-98%之間，在樣品處理前加入標準品，確認物種不會因震盪而造成物種轉換，經計算後回收率介於92-98%之間，證實不會於震盪處理樣品時造成物種轉換。在實驗結果表示，酒類與營養補充即飲品內含有較多的有機鉻物種，其次為Cr(III)-EDTA與Cr(VI)。

In the first study, speciation of arsenic in seaweeds was carried out using ion chromatography (IC) for separation and inductively coupled mass spectrometry (ICP-MS) for detection. The arsenic species studied were arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobeta-
ine (AsB), arsenocholine (AsC), OH-arsenoribose (OH-AsR), PO4-arsenoribose (PO4- AsR) , SO3H-arsenoribose (SO3H - AsR), and trialkylarsonioribosides (Trialkyl-AsR). Chromatographic separation of all the species was achieved in <19 min in gradient elution mode using (NH4)2CO3 at pH 8.7. Since there was not standard of arsenosugar, in the experiment used extraction of Laminaria japonica Areschoug spiked [As(III)], [As(V)], MMA, DMA, AsB, AsC. The outlet of the IC column was directly connected to the nebulizer of ICP-MS for the determination of arsenic. The speciation of arsenic has been carried out in several seaweed samples. A microwave-assisted extraction method was used for the extraction of arsenic species from seaweed samples. With a mixture of mobile phase A and methanol as extractant, the extraction efficiency was >73%, and the recoveries from spiked samples were in the range of 93−109%. The unknown compounds detected in different seaweeds were identified by coupling IC directly with electrospray ionization−mass spectrometry (ESI-MS). Four arsenosugars and tetramethylarsonium ion (TMA) were identified in different seaweeds. A fat-
soluble arsenolipid compound was identified in the extract of certified reference material BCR-279 Ulva lactuca when 1% HNO3 was used as the extractant.
Second study, A HPLC separation procedure has been developed for the specia-
tion of Cr(III), Cr(VI) in wine and diabetic supplement drinks samples. The species were separated on a reversed phase column (C8) in gradient elution mode. The mobile phase consisting of EDTA and TBAP in methanol at pH 6.9, yielded well resolved chromatograms of all the species within 2 min. The analyses were carried out using dynamic reaction cell inductively coupled plasma-mass spectrometer (DRC-ICP-MS). The DRC conditions have also been optimized to obtained interference free measure-
ments of 52Cr+ and 53Cr+, which were otherwise interfered by: 35Cl16O1H+, 35Cl17O+, 40Ar12C+ on 52Cr+; and 37Cl16O+, 40Ar13C+, 40Ar12C1H+ on 53Cr+. The detection limits of the procedure were 0.052 ng 52Cr ml-1 and 0.054 ng 53Cr ml-1. The accuracy of the method has been validated by comparing the sum of the concentrations obtained for individual species with total concentration of the elements in NRCC SLRS-4 River Water. The method has also been applied on several real samples, included environmental water, wine and supplement drinks, in which case the comparison total chromium concentration. Supplement drinks has been made with total concentrations determined after complete dissolution of the samples. The species were separated by HPLC-DRC-ICP-MS in appropriate dilute.

目錄
論文審定書 i
謝誌 ii
摘要 iii
Abstract v
目錄 vii
圖目錄 ix
表目錄 xi
縮寫表 xiii

第一章 液相層析結合感應耦合電漿質譜儀於海洋藻類樣品中砷物種分析之應用
壹、前言 1
貳、動態反應槽(Dynamic Reaction Cell，DRC) 6
參、實驗部分 8
一、儀器裝置 8
二、試藥與溶液配製 9
肆、實驗過程 12
一、液相層析條件最適化探討 12
二、DRC-ICP-MS 系統最適化探討 12
三、再現性 14
四、校正曲線與偵測極限的估計 14
五、萃取條件 15
六、真實樣品分析 15
伍、結果與討論 18
一、液相層析條件最適化探討 18
二、DRC-ICP-MS 系統最適化探討 24
三、再現性 36
四、校正曲線與偵測極限的估計 36
五、真實樣品分析 36
陸、結論 58
柒、參考文獻 59
第二章 液相層析結合感應耦合電漿質譜儀對於鉻物種分析之應用
壹、前言 63
貳、實驗部分 66
一、儀器裝置 66
二、藥品與溶液之配製 66
參、實驗流程 68
一、液相層析條件最適化探討 68
二、DRC-ICP-MS系統最適化探討 68
三、再現性 70
四、校正曲線與偵測極限的估計 70
五、真實樣品分析 70
肆、結果與討論 73
一、液相層析最適化探討 73
二、DRC-ICP-MS系統最適化條件 75
三、再現性 87
四、校正曲線與偵測極限的估計 87
伍、結論 107
陸、參考文獻 108

第一章 液相層析結合感應耦合電漿質譜儀於海洋藻類樣品中砷物種分析之應用
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第二章 液相層析結合感應耦合電漿質譜儀對於鉻物種分析之應用
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