臺灣博碩士論文加值系統

研究第一部份使用陰離子交換層析法（Anion exchange chromatography）結合感應耦合電漿質譜儀分析酒類樣品中砷與硒物種之含量。研究中利用PRP-X100陰離子交換管柱，動相A 為10 mM (NH4)2CO3和1% (v/v)甲醇（MeOH）(pH 8.0)，動相B為70 mM (NH4)2CO3和1% (v/v)甲醇（MeOH）(pH 8.0)，以梯度沖堤方式在11分鐘內同時分離As(Ⅲ)、DMA、MMA、As(Ⅴ)、Se(Ⅳ)和Se(Ⅵ)等六個物種，但由於78Se 和80Se的偵測上會有38Ar40Ar+及40Ar40Ar+所造成的同質量干擾，因此藉由動態反應槽（Dynamic Reaction Cell，DRC）系統，使用CH4作為反應氣體，將分析物及干擾物離子的質量或電荷改變以減輕干擾，以獲得準確之定量結果。砷物種偵測極限為0.005-0.01 ng mL-1之間，硒物種偵測極限為0.02-0.03 ng mL-1之間，各物種波峰高度和波峰面積之再現性RSD小於4.5% (n=5)，所得校正曲線相關係數（r2）優於0.9993。將所建立的最適化系統應用於市售酒類樣品分析，其添加回收率（spike recovery）為94-106%，進一步證實本研究之可行性和準確性。
研究第二部分使用離子對逆相層析法（Ion pair reversed phase chromatography）結合感應耦合電漿質譜儀於食物中碲物種分析之應用，在此使用C8逆相層析管柱，以等位沖堤方式分離Te(Ⅳ)和Te(Ⅵ)，動相為10 mM Ammonium citrate和2% (v/v) MeOH (pH 6.5)，可快速並有效率的分離目標分析物，並於2分鐘內達到完全分離，Te(Ⅳ)和Te(Ⅵ)偵測極限分別為0.051和0.039 ng mL-1，碲物種波峰高度和波峰面積之再現性RSD優於5.7% (n=5)，分析物所得校正曲線相關係數皆在0.9994以上。最後利用微波輔助萃取（Microwave assisted extraction）方式萃取香菇中的碲物種，以在動相溶液當中加入蛋白酶（Protease type XIV）作為萃取試劑，以提高碲的萃取效率，於70℃下萃取30分鐘，樣品萃取效率介於91-98%，本研究定量時有基質壓抑問題，因此改使用標準添加法，以準確定量真實樣品中碲物種之濃度。

In the first parts, a method based on anion-exchange chromatography with ICP-MS for simultaneous determination of arsenic and selenium species in wines was developed. The separation was performed on a PRP-X100 anion exchange column using gradient elution program which contains 10 mM (NH4)2CO3 and 1% (v/v) MeOH at pH 8.0 as mobile phase A and 70 mM (NH4)2CO3 and 1% (v/v) MeOH at pH 8.0 as the second one. Simultaneous separation of four arsenic (As(Ⅲ), DMA, MMA and As(Ⅴ)) and two selenium species (Se(Ⅳ) and Se(Ⅵ)) was attained within 11 minutes. The potentially interfering 38Ar40Ar+ and 38Ar40Ar+ at the selenium mass m/z 78 and 80 were reduced by dynamic reaction cell system using CH4 as reaction cell gas. The limits of detection of the species were in the range of 0.005-0.01 ng mL-1 for arsenic and 0.02-0.03 ng mL-1 for selenium, respectively. The reproducibility of peak height and peak area were less than 4.5% form 5 replicate injections, and the linear coefficients of the calibration curves were better than 0.9993. The optimum system was applied to commercially wine samples. The spike recoveries were in the range of 94–106% to demonstrate the feasibility and the accuracy of the proposed method.
In the second parts, a method based on ion-pair reversed-phase chromatography with ICP-MS for simultaneous determination of tellurium species in food. The separation of Te(Ⅳ) and Te(Ⅵ)was performed on an ion-pair reversed-phase column C-8 by using isocratic elution with 10 mM Ammonium citrate and 2% (v/v) MeOH at pH 6.5 as mobile phase. This method was rapid and efficient to separate the target analysts. The limit of detection for tellurite and tellurate were 0.051 and 0.039 ng mL-1. The reproducibility of peak height and peak area were less than 5.7% form 5 replicate injections. The separation of tellurium species was attained within 2 minutes, and the linear coefficients of the calibration curves were better than 0.9994. Tellurium species was extracted from mushroom by microwave assisted extraction, which adding protease type XIV in the mobile phase as the extracted reagent to enhance the extraction efficiency. The extraction efficiency of tellurium species in the range of 91-98% under heating at 70℃ for 30 minutes. In our study, the standard addition method was used to accurately quantify the concentration of tellurium species in real samples due to the matrix effect.

論文審定書 i
謝誌 ii
摘要 iii
Abstract iv
目錄 vi
圖目錄 viii
表目錄 x

第一章 液相層析結合感應耦合電漿質譜儀於酒類樣品中砷與硒物種分析之應用
壹、 前言 1
貳、 動態反應槽原理 5
參、 實驗部分 7
一、 儀器裝置與設備 7
二、 試藥與溶液的配製 7
肆、 實驗過程 13
一、 液相層析分離條件探討 13
二、 DRC-ICP-MS系統最適化探討 13
三、 再現性 15
四、 校正曲線及偵測極限 15
五、 樣品製備 16
伍、 結果與討論 17
一、 液相層析條件之分離條件最適化 17
二、 DRC-ICP-MS系統最適化探討 28
三、 再現性、檢量線與偵測極限 31
四、 真實樣品的分析應用 39
陸、 結論 47
柒、 參考文獻 48
第二章 液相層析結合感應耦合電漿質譜儀於食物中碲物種分析之應用
壹、 前言 52
貳、 實驗部分 55
一、 儀器裝置與設備 55
二、 試藥與溶液的配製 58
參、 實驗過程 61
一、 液相層析分離條件探討 61
二、 再現性 61
三、 校正曲線及偵測極限 61
四、 樣品製備 61
肆、 結果與討論 65
一、 液相層析分離條件探討 65
二、 重複性、檢量線與偵測極限 68
三、 樣品中碲物種總量與萃取效率探討 72
四、 真實樣品分析 80
伍、 結論 85
陸、 參考文獻 86

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