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研究生：	鄭元凱 Yuan-Kai Cheng
論文名稱：	阿達瑪轉換/氣相層析質譜術對揮發性氣體偵測法的開發與研究 Applications of Hadamard transform-gas chromatography/mass spectrometry (HT-GC/MS) to volatile organic compounds (VOCs)
指導教授：	林震煌 Lin, Cheng-Huang
學位類別：	碩士 Master
系所名稱：	化學系 Department of Chemistry
論文出版年：	2011
畢業學年度：	99
語文別：	中文
論文頁數：	100
中文關鍵詞：	阿達瑪轉換、呼出氣體、六甲基二矽氧烷、氣相層析質譜術
英文關鍵詞：	Hadamard Transfer, Exhaled breath, HMDSO, GC/MS
論文種類：	學術論文
相關次數：	點閱：182 下載：8
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本研究利用阿達瑪轉換/氣相層析質譜術 (HT-GC/MS) 成功偵測到人體呼出氣體內及晶圓廠中無塵室內的揮發性有機氣體。將編碼的層析圖譜阿達瑪轉換後與大多數 GC/MS 系統單次進樣比較，可使得訊號與雜訊比值 (signal-to-noise ratio) 大幅提升。在第一個飲酒者的呼出氣體情況下，使用傳統單次進樣得到的小離子強度 (相當於 ~0.1 ng 乙醇)約等於或低於偵測極限。在第二個吸菸者的呼出氣體情況下，使用傳統單次進樣只得到微弱離子訊號 (相當於 ~0.7 pg 甲苯) 的偵測邊緣。在這兩個實驗中，當加入阿達瑪轉換技術時，便能讓 S/N 比分別得到 8.0 及 7.9 倍的提升，雖然利用此技術偵測出的呼出氣體成分有待確認，但卻不需要任何前處理的步驟。另外在無塵室內環境空氣情況下，利用更高進樣次數的阿達瑪矩陣 255、1023、2047 分析 HMDSO，其提升的 S/N 比分別得到 7.4、15.1、20.1 倍，與理論值(8.0、16.0、22.6 倍) 皆相當地接近。在未經過前處理的 HMDSO 樣品，其單次進樣 (4 uL) 的濃度偵測極限在 20 ppbv。然而在使用了阿達瑪 2047 次的轉換後，其偵測濃度可達 1 ppbv (S/N = 3)。與此相比，當加入吸附/脫附系統時，其 HMDSO 濃度偵測極限可改善至 0.03 ppbv。實驗結果發現，此技術大幅改善了 S/N 比，並也提高了偵測靈敏度。

The Hadamard transform-gas chromatography/mass spectrometry (HT-GC/MS) technique was successfully employed for detecting of volatile organic compounds from the exhaled breath of humans and a clean room of a wafer factory. Compared to the single injection used in most GC/MS systems, the signal-to-noise (S/N) ratios were substantially improved after inverse Hadamard transformation of the encoded chromatogram. In the first case of breath from a drinker, using a conventional single injection, a small ion peak (corresponding to ~ 0.1 ng of ethanol), the intensity of which was approximately equal to or less than the limit of detection. Furthermore, in the second case of breath from a smoker, using conventional injection, a weak ion peak (corresponding to ~0.7 pg of toluene) was marginally detected. When the HT technique was applied, the signal-to-noise (S/N) ratio were improved to 8.0- and 7.9-fold, respectively. In both cases, the HT technique permitted specific components in exhaled breath to be determined, without the need for any extraction procedures. In the other case of airborne air from a clean room, when Hadamard matrices of 255, 1023 and 2047 were used, the S/N ratios of the signals for HMDSO were substantially improved to 7.4-, 15.1- and 20.1-fold, respectively. Those improvements are in good agreement with those obtained by theory (8.0-, 16.0- and 22.6-fold, respectively). Without any pretreatment, the limit of detection of HMDSO was 20 ppbv by means of a single injection (injection volume, 4 µL). However, this can be improved to 1 ppbv (S/N = 3) when a 2047 order of Hadamard matrix was applied. In contrast to this, when an absorption/desorption system was used, the limit of detection of HMDSO can be further improved to 0.03 ppbv. However, the HT technique led to an improvement in the S/N ratio, with the peak corresponding to the limit of detection.

摘要………………………………………………………………………Ⅰ
Abstract…………………………………………………………………Ⅱ
目錄………………………………………………………………………Ⅳ
圖目錄……………………………………………………………………Ⅵ
表目錄……………………………………………………………………Ⅶ

第一章    緒論
1-1 研究目的……………………………………………………………1
1-2 揮發性有機物簡介…………………………………………………1
1-2-1 呼氣中揮發性有機物……………………………………………3
1-2-2 呼氣檢測之特性…………………………………………………3
1-2-3 呼氣採樣方法……………………………………………………7
1-2-4 飲酒對呼氣之影響………………………………………………9
1-2-5 抽菸對呼氣之影響………………………………………………11
1-3 環境中微量氣態汙染物簡介………………………………………12
1-3-1 AMCs 對晶圓廠機台之影響……………………………………13
1-3-2 有機矽化合物……………………………………………………14
1-3-3 無塵室內的採樣與分析…………………………………………18

第二章    研究方法及原理
2-1 阿達瑪矩陣原理……………………………………………………20
2-1-1 矩陣起源…………………………………………………………21
2-1-2 阿達瑪轉換法……………………………………………………22
2-1-3 LabVIEW操作程式………………………………………………29
2-1-4 阿達瑪轉換提高S/N值的理論值………………………………31
2-2 阿達瑪矩陣轉換在其他方面的應用………………………………34
2-2-1 在分析化學上的應用……………………………………………34
2-2-2在其它方面上的應用……………………………………………37

第三章    研究儀器和藥品
3-1 實驗儀器……………………………………………………………39
3-1-1 氣相層析質譜法…………………………………………………39
3-1-2 氣相層析儀………………………………………………………39
3-1-3 界面………………………………………………………………42
3-1-4 質譜儀……………………………………………………………42
3-1-5 資料處理…………………………………………………………46
3-1-6 質譜儀校正………………………………………………………47
3-1-7 儀器及週邊設備列表……………………………………………48
3-2 實驗藥品列表………………………………………………………50

第四章    研究過程和結果討論
4-1 阿達瑪進樣系統……………………………………………………51
4-1-1 阿達瑪進樣器……………………………………………………51
4-1-2 標準品配製………………………………………………………54
4-1-3 標準品進樣………………………………………………………56
4-1-4 真實樣品採樣……………………………………………………57
4-1-5 Tenax-GR 吸附管脫附進樣……………………………………58
4-1-6 呼出氣體樣品進樣………………………………………………59
4-1-7 系統清潔方法……………………………………………………60
4-2 數據紀錄之時間校正………………………………………………61
4-3 阿達瑪進樣條件最佳化……………………………………………63
4-3-1 汽化管體積對波峰的影響………………………………………63
4-3-2 進樣體積的測量…………………………………………………66
4-3-3 阿達瑪進樣轉換結果與理論值比較……………………………70
4-3-1 進樣器穩定度與阿達瑪轉換再現性……………………………73
4-4 分析物特定離子質荷比分析………………………………………74
4-5 阿達瑪轉換在真實樣品上的應用…………………………………76
4-5-1 飲酒者的呼出氣體研究…………………………………………76
4-5-2 抽菸者的呼出氣體研究…………………………………………81
4-5-3半導體廠中無塵室內 HMDSO 氣體的研究………………………85

第五章    結論
5-1 阿達瑪轉換進樣方面………………………………………………92
5-2 真實樣品分析方面…………………………………………………92
5-3 未來展望……………………………………………………………93
論文發表…………………………………………………………………94
參考資料…………………………………………………………………95
                                

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