毛細管電泳技術(Capillary electrophoresis, CE) 具有分離效率高、樣品與溶劑用量少等優點，而感應偶合電漿質譜儀(Inductively coupled plasma mass spectrometry, ICP-MS)具有低偵測極限、寬廣的線性範圍以及快速多元素分析和同位素分析能力等特性之高靈敏度的元素選擇偵測器。本研究係藉由一商業化的毛細管電泳/感應偶合電漿質譜儀的介面(CEI-100)將這兩種分析技術結合，以此作為下列四個研究計畫之化合物與元素物種分析的測定系統。
本研究的第一部份為CE-ICPMS應用於核

Capillary electrophoresis (CE) is in comparison with other chromatographic techniques, CE has several advantages such as high resolving power, small sample volume requirement, minimal buffer consumption and high sample throughtput. As a detection technique, inductively coupled plasma mass spectrometry (ICPMS) provides the advantages of low detection limit, multielement detection, and element- and isotope-specific detection capabilities. Therefore, the use of CE as a high resolution separation technique with ICP-MS as a sensitive element specific detector is of growing interest for analytical research. Four studies in our research are described below, respectively.
A preliminary study of a modified microconcentric nebulizer (CEI-100, CETAC) as the sample introduction device of capillary electrophoresis inductively coupled plasma mass spectrometry (CE-ICP-MS) for the determination of monophosphate nucleotides is described. The monophosphate nucleotides studied include adenosine 5’-monophosphate (AMP), guanosine 5’-monophosphate (GMP), uridine 5’-monophosphate (UMP) and inosine 5’-monophosphate (IMP). The species studied were well separated using a 70 cm length × 75 μm id fused silica capillary while the applied voltage was set at -22 kV and a 20 mmol/L ammonium citrate/citric acid buffer (pH 4.0) containing 0.1% m/v cationic polymer (hexadimethrine bromide, Polybrene) was used as the electrophoretic buffer. The electroosmotic flow was reversed by flushing the fused silica capillary with 0.2% m/v Polybrene to accelerate separation. The detection limit of various species studied was in the range of 0.036~0.054 μg P/mL, which corresponded to the absolute detection limit of 1.1~1.6 pg P based on the injection volume of 30 nl. We determined the concentrations of nucleotides in two IG-enriched monosodium glutamates purchased from the local market. The recovery was in the range of 100~112% for various species, and the concentrations of IMP and GMP in these samples were in the range of 0.15–0.18% m/m.
Capillary electrophoresis dynamic reaction cellTM inductively coupled plasma mass spectrometry (CE-DRC-ICP-MS) for the determination of sulfur-containing amino acids is described. The sulfur-containing amino acids studied include L-cysteine, L-cystine, DL-homocystine and L-methionine. The species studied were well separated using a 70 cm length × 75 μm i.d. fused silica capillary while the applied voltage was set at +22 kV and a 10 mmol/L disodium tetraborate buffer (pH 9.8) containing 0.1 mmol/L EDTA and 0.5 mmol/L Triton X-100 was used as the electrophoretic buffer. The sulfur-selective electropherogram was determined at m/z 48 as 32S16O+ by using its reaction with O2 in the reaction cell. The method avoided the effect of polyatomic isobaric interferences at m/z 32 caused by 16O16O+ and 14N18O+ on 32S+ by detecting 32S+ as the oxide ion 32S16O+ at m/z 48, which is less interfered. The detection limit of various species studied was in the range of 0.047~0.058 μg S/mL, which corresponded to the absolute detection limit of 1.3~1.6 pg S based on the injection volume of 27 nl. We determined the concentrations of selected sulfur-containing amino acids in urine and nutritive complement samples. The recovery was in the range of 92~128% for various species.
Capillary electrophoresis-dynamic reaction cell inductively coupled plasma mass spectrometry (CE-DRC-ICP-MS) for the speciation of iron (III/II), vanadium (V/IV) and chromium (VI/III) is described. Two different CE migration modes were employed for separating the six metal ions using pre-capillary complexation. One is counter-electroosmotic mode in which iron (III/II) and vanadium (V/IV) ions were well separated using a 60 cm × 75 μm i.d. fused silica capillary. The voltage was set at +22 kV and a 15 mmol/L tris(hydroxymethyl)aminomethane (Tris) buffer (pH 8.75) containing 0.5 mmol/L ethylenediaminetetraacetic acid (EDTA) and 0.5 mmol/L ortho-phenanthroline (phen) was used as the electrophoretic buffer. The other is co-electroosmotic mode in which chromium (VI/III) ions were well separated while the applied voltage was set at −22 kV and a 10 mmol/L ammonium citrate buffer (pH 7.7) containing 0.5 mmol/L diethylenetriaminepentaacetic acid (DTPA) and 0.01% polybrene was used as the electrophoretic buffer. The mass spectra were measured at m/z 51, 52 and 56 for V, Cr and Fe, respectively. The interfering polyatomic ions of 35Cl16O+, 40Ar12C+ and 40Ar16O+ on 51V+, 52Cr+ and 56Fe+ determination were reduced in intensity significantly by using NH3 as the reaction cell gas in the DRC. The detection limits were in the range of 0.1~0.5, 0.4~1.3 and 1.2~1.7 μg/L for V, Cr and Fe, respectively. Applications of the method for the speciation of V, Cr and Fe in wastewater were demonstrated. The recoveries were in the range of 92~120% for various species.
A capillary electrophoresis-inductively coupled plasma-mass spectrometric (CE-ICPMS) method for the speciation of six arsenic compounds, namely arsenite [As(III)], arsenate [As(V)], monomethyl arsonic acid, dimethylarsinic acid, arsenobetaine and arsenocholine is described. The separation has been achieved on a 70 cm length × 75 μm ID fused-silica capillary. The electrophoretic buffer used was 15 mmol/L Tris (pH 9.0) containing 15 mmol/L sodium dodecyl sulfate (SDS), while the applied voltage was set at +22 kV. The arsenic species in biological tissues were extracted into 80% v/v methanol-water mixture, put in a closed centrifuge tube and kept in a water bath, using microwaves at 80℃ for 3 min. The extraction efficiencies of individual arsenic species added to the sample at 0.5 mg As/g level were between 96% and 107%, except for As(III), for which it was 89% and 77% for oyster and fish samples, respectively. The detection limits of the species studied were in the range 0.3~0.5 μg As/L. The procedure has been applied for the speciation analysis of two reference materials, namely dogfish muscle tissue (NRCC DORM-2) and oyster tissue (NIST SRM 1566a), and two real-world samples.

第1章 毛細管電泳 - 1 -
1.1前言 - 1 -
1.2分離原理[1,4-5] - 1 -
1.2.1電滲流 - 4 -
1.2.2電泳 - 6 -
1.2.3物種的淨流速 - 6 -
1.3樣品注入的方法 - 7 -
1.3.1電壓注入法(Electrokinetic injection) - 10 -
1.3.2流體注入法(Hydrodynamic injection) - 10 -
1.4 偵測方法 - 11 -
1.4.1光譜吸收/放射偵測系統[8] - 11 -
1.4.2電化學偵測法(Electrochemical detection, EC)[32] - 13 -
1.4.3化學冷光測定法(Chemiluminescence detection) - 16 -
1.4.4質譜偵測法(Mass spectrometric detection) - 19 -
1.5與液相層析法的比較 - 21 -
1.6參考文獻 - 26 -
第2章 動態反應槽感應偶合電漿質譜儀 - 29 -
2.1前言 - 29 -
2.2原理 - 30 -
2.2.1 樣品引入系統 - 30 -
2.2.2 離子化過程(Ionization) - 36 -
2.2.3 介面 - 37 -
2.2.4 四極柱式質量分析器 - 37 -
2.3 ICP-MS的干擾 - 40 -
2.3.1光譜性干擾(Spectral interference) - 40 -
2.3.2 非光譜性干擾(Nonspectral interference) - 41 -
2.4 質量重疊干擾的去除 - 44 -
2.5碰撞室/動態反應槽 - 45 -
2.5.1 前言 - 45 -
2.5.2 離子-分子反應化學（理論背景） - 46 -
2.5.3 離子-分子反應化學（實際的分析考量）[5] - 49 -
2.5.4質量選擇的離子化學(Mass selected ion chemistry) - 49 -
2.5.5 應用 - 53 -
2.6參考文獻 - 60 -
第3章 毛細管電泳連接感應偶合電漿質譜儀的介面 - 63 -
3.1 前言 - 63 -
3.2 介面的設計與發展 - 65 -
3.3 CEI-100的介紹 - 75 -
3.4 CE-ICP-MS的偵測極限 - 77 -
3.5 CE-ICP-MS的應用 - 77 -
3.6參考文獻 - 80 -
第4章 毛細管電泳結合感應偶合電漿質譜儀於核

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