全面二維氣相層析應用於空氣與生活複雜樣品之分析

簡易檢索 / 詳目顯示

回結果列表

研究生：	周裕傑 Yu-chieh Chou
論文名稱：	全面二維氣相層析應用於空氣與生活複雜樣品之分析 Application of vapor and liquid phase real samples by 2D-GC(GC×GC)
指導教授：	王家麟 Jia-lin Wang
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
畢業學年度：	100
語文別：	中文
論文頁數：	181
中文關鍵詞：	全面二維氣相層析
外文關鍵詞：	2D-GC (GC×GC)
相關次數：	點閱：7 下載：0
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

本次研究主要分為兩部分，第一部分為GC x GC – ECD，由於大氣中的鹵碳化合物濃度分布很廣(幾pptv至數百pptv)，因此必須透過濃縮方法提高有效濃度，以降低分析偵測極限，有鑑於此，本研究以自製前濃縮系統，內含自行填充吸附管以捕捉大氣中的鹵碳化合物，再以熱脫附方式注入全面二維層析系統分析；系統組裝採便利、易修繕、造價便宜、不需冷劑等優點的自製閥件型調制器(丁式切換器)，以脈衝( pulsed )方式將一維管柱( pre-column )沖堤物送入二維管柱( analytical column )作快速分離；資料以繪圖軟體( SurferR 8 )處理成三維結果；實驗由多種管柱搭配和最佳化調整後，成功以DB-5 x TG-1301組合能有效分離鹵碳化合物，此套系統的RSD值可低於0.94%，並以NOAA標準品定性定量各物種的實際濃度，而各物種的譜峰線性( R2 )也可達0.99以上，最後以此系統對大氣中的物種做連續監測，並可得良好效果；第二部分為GC x GC – FID，利用注射埠搭配雙火焰離子偵測器， DB-5 x DB-1701的管柱組合能成功對香水、精油、汽油、生質燃油和酒品作有效的分析，並藉由全面二維圖譜可發現，圖譜間的差異性相當明顯，可作為指紋圖譜資料庫的建立依據，若未來分析相同種類樣品時即可作為對照，以辨別樣品的來源和種類，若搭配定性功能極佳的質譜儀( GC x GC / ToF-MS )，也能針對特定物種進行定性探討。

This study consists of two objectives: one is to develop a GC x GC method with electron capture detection ( ECD ) to analyze trace levels ( ~pptv ) of atmospheric halocarbons, the other is to analyze complex liquid samples by GC x GC with flame ionization detection ( FID ).
To analyze atmospheric halocarbons a self-built pre-concentrator was employed for in-line enrichment before analyzed by GC x GC – ECD. To further lower the detection limits of chlorofluorocarbon ( CFC ) replacements, oxygen doping technique was adopted for electron capture detection. The GC x GC used a valve type modulator based on the Deans switch method. Analytes after eluting from the first column were cut into slices and sent to the second column for two-dimensional separation. A commercially available software, SuferR 8, was used to process the data into three-dimensional concentration contour plots. The column combination of DB-5 x TG-1301 was found to show the best separation results for halocarbons. The correlation coefficients ( R2 ) of 2D vs. 1D results were greater than 0.9920. The reproducibility ( RSD based on N = 30 ) was better than 0.94% for all target halocarbons. The method can be used in either online or offline mode. Flask samples can be analyzed when the system is operated in off-line mode, whereas continuous monitoring is possible when the system is operated in on-line mode.
As the second objective to analyze complex liquid samples, such as perfume, essential oil, wine, gasoline and biofuel, etc. the Deans switch GC x GC – FID method was tested. The column combination of DB-5 x DB-1 was found to show the optimal separation results. Rather than pursuing full separation as with the halocarbon analysis, the concept of “pattern recognition” of complex samples was adopted. A product series with minor composition variation can be distinguished based on pattern difference. This application is found particular useful where imitating products can be easily separated apart from their genuine counterparts. When compare the self-made GC x GC – FID method with the commercial GC x GC / ToF-MS method using the identical column combination, compound identification becomes possible, which further broadens the applicability of the proposed method.

摘要	I
Abstract	II
謝誌	IV
目錄	VII
圖目錄	XII
表目錄	XVIII
一、層析技術發展	1
1-1層析技術的發展	1
1-2 全面二維層析基本架構	6
1-2.1 管柱組合	6
1-2.2 調制器( modulator )	9
1-2.3 偵測器	16
1-3 研究目的和方法	17
二、全面二維層析系統之實驗運作和基本原理	19
2-1 調制器	19
2-2 偵測器	22
2-2.1電子捕捉偵測器( electron capture detector, ECD )	22
2-2.2火焰離子偵測器( flame ionization detector, FID )	23
2-2.3質譜儀( mass spectrometer, MS )	24
2-3 數據處理	26
2-3.1 數據處理	26
2-3.2 圖譜繪製	27
2-3.3. 3D繪圖	28
2-3.4 體積積分	28
2-4 設備與材料	29
2-4.1 GC x GC – ECD	29
2-4.1.1 前濃縮系統	29
2-4.1.2 全面二維層析系統	30
2-4.1.3 管柱	30
2-4.2 GC x GC – FID	30
2-4.2.1 全面二維層析系統	30
2-4.2.2 管柱	31
三、鹵碳化合物之應用	32
3-1 大氣中的鹵碳化合物	32
3-1.1 氟氯碳化物之發展	32
3-1.2 氫氟氯碳化合物和氫氟碳化合物之發展	40
3-1.3 鹵碳化合物之量測	46
3-2 .GC X GC – ECD系統	49
3-2.1 前濃縮系統	50
3-2.2 多重床捕捉吸附管( multi-bed trapping tube )	53
3-2.3 綴氧裝置( oxygen doping device )	54
3-2.4 全面二維ECD層析儀-管柱系統	56
3-2.5 全面二維ECD層析儀-調制器(自製)	58
3-3 結果與討論	59
3-3.1 管柱組合	59
3-3.2 載流氣體和輔助氣體	62
3-3.3 調制脈衝和調制週期	66
3-3.4 譜峰定性	70
3-3.5 綴氧系統	71
3-3.6 檢量線和相對標準偏差	72
3-3.7 實際量測	76
3-3.7.1 周界空氣連續監測	76
3-3.7.2 廠區實測	79
四、生活中複雜液態樣品之應用	82
4-1 全面二維層析技術之應用	82
4-1.1 石油化學	82
4-1.2 生質燃油	86
4-1.3 芳香類使用品	87
4-1.4 其他	90
4-2 GC X GC – FID系統	92
4-2.1 注射埠	92
4-2.2全面二維FID層析儀-管柱系統	92
4-2.3全面二維FID層析儀-調制器(商業化)	94
4-2.4 液態樣品之說明與製備	95
4-2.4.1 香水	95
4-2.4.2 精油	96
4-2.4.3 汽油	97
4-2.4.4 生質燃料存餘液	97
4-2.4.5 酒品	98
4-2.4.6 自行製備之標準品	100
4-3 結果與討論	104
4-3.1 管柱選擇	104
4-3.2 最佳化參數	108
4-3.3 注射埠之分流/不分流	109
4-3.4 定溫測試	111
4-3.5 群落分布	112
4-3.6 實際量測	114
4-3.6.1 香水	115
4-3.6.2 精油	115
4-3.6.3 汽油和生質燃料存餘液	121
4-3.6.4 酒品	125
五、結論	133
附錄一	134
附錄二	142
附錄三	143
附錄四	147
附錄五	148
六、參考文獻	152

                                

[1]Št’avova, J.; Stahl, D. C.; Seames, W. S.; Kubatova, A.
Journal of Chromatography A. 2012, 1224, 79–88.
[2]Fujitsu Quality Laboratory
http://jp.fujitsu.com/group/fql/en/
[3]Wang, C. H.; Chiang, S. W.; Wang, J. L. Journal of
Chromatography A. 2010, 1217, 353–358.
[4]Wang, C. H.; Chang, C. C.; Wang, J. L. Journal of Chromatography A. 2005, 1087, 150–157.
[5]Bedini, F. Thermo Electron Corporation- GC x GC: A new dimension in chromatography.
[6]Adahchour, M.; Beens, J.; Vreuls, R. J. J.; Batenburg, A. M.; Brinkman, U. A. T. Journal of Chromatography A. 2004, 1054, 47–55.
[7]Tranchida, P. Q.; Purcaro, G.; Visco, A.; Conte, L.; Dugo, P.; Dawes, P.; Mondello, L. Journal of Chromatography A. 2011, 1218, 3140–3145.
[8]Beens, J.; Brinkman, U. A. T. trends in analytical chemistry. 2000, 19, 260-275.
[9]Marriott, P. J.; Kinghorn, R. M. Anal. Chem. 1997, 69, 2582-2588.
[10]Beens, J.; Adahchour, M.; Vreuls, R. J. J.; Altena, K. V.; Brinkman, U. A. T. Journal of Chromatography A. 2001, 2001, 127–132.
[11]Harynuk, J.; Gorecki, T. Journal of Chromatography A. 2003, 1016, 53–63.
[12]Pursch, M.; Eckerle, P.; Biel, J.; Streck, R.; Cortes, H.; Sun, K.; Winniford,B. Journal of Chromatography A. 2003, 1019, 43–51.
[13]Bruckner, C. A.; Prazen, B. J.; Synovec, R. E. Anal. Chem. 1998, 70, 2796-2804.
[14]Seeley, J. V.; Kramp, F.; Hicks, C. J. Anal. Chem. 2000, 72, 4346-4352.
[15]Seeley, J. V.; Micyus, N. J.; Bandurski, S. V.; Seeley, S. K.; McCurry, J. D. Anal. Chem.2007, 79, 1840-1847.
[16]http://www.perkinelmer.com/Catalog/Category/ID/Electron
[17]http://www.chemistry.adelaide.edu.au/external/soc-rel/content/fid.htm
[18]http://hiq.linde-gas.com/international/web/lg/spg/
like35lgspg.nsf/docbyalias/appl_mass
[19]Ozone Layer Protection – Science
http://www.epa.gov/ozone/science/ods/classone.html
[20]Molina, M. J.; Rowland, F. S. Nature. 1974, 249, 810-812.
[21]Farman, J. C.; Gardiner, B. C.; Shanklin, J. D. Nature. 1985, 315, 207-210.
[22]Zurer, P. S. Chem. Eng. News. 1988, 66, 16-25.
[23]Loyola, D.; Erbertseder, T.; Balis, D.; Lambert, J. C.; Spurr, R.; Roozendael, V. M.; Valks, P.; Zimmer, W.; Meyer-Arnek, J.; Lerot, C. Operational Monitoring of the Antarctic Ozone Hole: Transition from GOME and
SCIAMACHY to GOME-2.
[24]http://www.theozonehole.comaustralianskincancer.htm
[25]UNEP Ozone Secretariat. (2006), http://ozone.unep.org/
[26]Wuebbles, D. J. Journal of Geophysical Research. 1983, 88, 1433-1443.
[27]Hayman, G. D.; Jenkin, M. E.; Murrells, T. P.; Johnson, C.E. Atmospheric Environment. 1994, 28, 421-437.
[28]Radiatively Active Global Gas measurements by the Advanced Global
Atmospheric Gases Experiment (AGAGE) and Affiliated Networks, 2010.
[29]http://zh.wikipedia.org/zh-tw/京都議定書
[30]中華民國行政院環境保護署-環境檢驗所
http://www.niea.gov.tw/analysis/method/ListMethod.asp?methodtype=AIR
[31]Advanced Global Atmospheric Gases Experiment
http://agage.eas.gatech.edu/
[32]Grimsrud, E. P.; Miller, D. A. Analytical Chemistry. 1978, 50, 1141-1145.
[33]Miller, D. A.; Grimsrud, E. P. Analytical Chemistry. 1979, 51, 851-859.
[34]O’Doherty, S.J.; Nickless, G.; Bassford, M.; Pajot, M.; Simmonds, P. Journal of Chromatography A. 1999, 832, 253–258.
[35]劉文治, 以二維氣相層析監測空氣中氟氯碳化物及氫氟氯碳化物,中央大學化學研究所碩士論文 (2008).
[36]蘇源昌, 自動氣相層析質譜儀於分析揮發性有機化合物之硬體研究與實測應用, 中央大學化學研究所碩士論文 (2011).
[37]鄧明凱, 全面二維層析技術分析空氣中之氟氯碳化物, 中央大學化學研究所碩士論文 (2010).
[38]廖偉呈, 全面二維層析技術分析揮發性有機化合物, 中央大學化學研究所碩士論文 (2009).
[39]Van Geem, K. M.; Pyl, S. P.; Reyniers, M. F.; Vercammen, J.; Beens, J.; Marin, G. B. Journal of Chromatography A. 2010, 1217, 6623–6633.
[40]Avila, B. M. F.; Pereira, R.; Gomes, A. O.; Azevedo, D. A. Journal of Chromatography A. 2011, 1218, 3208–3216.
[41]Machado, M. E.; Caramao, E. B.; Zini, C. A. Journal of Chromatography A. 2011, 1218, 3200–3207.
[42]Dutriez, T.; Courtiade, M.; Thiebaut, D.; Dulot, H.; Hennion, M. C. Fuel. 2010, 89, 2338–2345.
[43]Dutriez, T.; Courtiade, M.; Thiebaut, D.; Dulot, H.; Bertoncini, F.; Vial, J.; Hennion, M. C. Journal of Chromatography A. 2009, 1216, 2905–2912.
[44]Omais, B.; Courtiade, M.; Charon, N.; Thiebaut, D.; Quignard, A.; Hennion, M. C. Journal of Chromatography A. 2011, 1218, 3233–3240.
[45]Vendeuvre, C.; Ruiz-Guerrero, R.; Bertoncini, F.; Duval, L.; Thiebaut, D.; Hennion, M. C. Journal of Chromatography A. 2005, 1086, 21–28.
[46]Semard, G.; Gouin, C.; Bourdet, J.; Bord, N.; Livadaris, V. Journal of Chromatography A. 2011, 1218, 3146–3152.
[47]Micyus, N. J.; McCurry, J. D.; Seeley, J. V. Journal of Chromatography A. 2005, 1086, 115–121.
[48]Fraga, C. G.; Prazen, B. J.; Synovec, R. E. Anal. Chem. 2000, 72, 4154-4162.
[49]Adam, F.; Bertoncini, F.; Coupard, V.; Charon, N.; Thiebaut, D.; Espinat, D.; Hennion, M. C. Journal of Chromatography A. 2008, 1186, 236–244.
[50]Pyl, S. P.; Schietekat, C. M.; Van Geem, K. M.; Reyniers, M.; Vercammen, J.; Beens, J.; Marin, G. B. Journal of Chromatography A. 2011, 1218, 3217–3223.
[51]Manzano, P.; Arnaiz, E.; Diego, J. C.; Toribio, L.; Garcia-Viguera, C.; Bernal, J. L.; Bernal, J. Journal of Chromatography A. 2011, 1218, 4952–4959.
[52]Tran, T. C.; Marriott, P. J. Atmospheric Environment. 2008, 42, 7360–7372.
[53]Vial, J.; Nocairi, H.; Sassiat, P.; Mallipatu, S.; Cognon, G.; Thiebaut, D.; Teillet, B.; Rutledge, D. N. Journal of Chromatography A. 2009, 1216, 2866–2872.
[54]Wu, J.; Lu, X.; Tang, W.; Kong, H.; Zhou, S.; Xu, G. Journal of Chromatography A. 2004, 1034, 199–205.
[55]Godoy, L. A. F.; Hantao, L. W.; Pedroso, M. P.; Poppi, R. J.; Augusto, F. Analytica Chimica Acta. 2011, 699, 120–125.
[56]Shellie, R.; Mondello, L.; Marriott, P.; Dugo, G.; Journal of Chromatography A. 2002, 970, 225–234.
[57]Ratel, J.; Engel, E. Journal of Chromatography A. 2009, 1216, 7889–7898.
[58]Pena-Abaurrea, M.; Covaci, A.; Ramos, L. Journal of Chromatography A. 2011, 1218, 6995–7002.
[59]Weldegergis, B. T.; Villiers, A.; McNeish, C.; Seethapathy, S.; Mostafa, A.; Gorecki, T.; Crouch, A. M. Food Chemistry. 2011, 129, 188–199.
[60]Perestrelo, R.; Petronilho, S.; Camara, J. S.; Rocha, S. M. Journal of Chromatography A. 2010, 1217, 3441–3445.
[61]Cardeal, Z. L.; Marriott, P. J. Food Chemistry. 2009, 112, 747–755.
[62]Welke, J. E.; Manfroi, V.; Zanus, M.; Lazarotto, M.; Zini, C. A. Journal of Chromatography A. 2012, 1226, 124–139.
[63]Robinson, A. L.; Boss, P. K.; Heymann, H.; Solomon, P. S.; Trengove, R. D. Journal of Chromatography A. 2011, 1218, 504–517.
[64]Zhu, S.; Lu, X.; Ji, K.; Guo, K.; Li, Y.; Wu, C.; Xu, G. Analytica Chimica Acta. 2007, 597, 340–348
[65]Ieda, T.; Ochiai, N.; Miyawaki, T.; Ohura, T.; Horii, Y. Journal of Chromatography A. 2011, 1218, 3224–3232.
[66]Hashimoto, S.; Takazawa, Y.; Fushimi, A.; Tanabe, K.; Shibata, Y.; Ieda, T.; Ochiai, N.; Kanda, H.; Ohura, T.; Tao, Q.; Reichenbach, S. E. Journal of Chromatography A. 2011, 1218, 3799–3810.
[67]Silva, I.; Rocha, S. M.; Coimbra, M. A.; Marriott, P. J. Journal of Chromatography A. 2010, 1217, 5511–5521.
[68]Kallio, M.; Jussila, M.; Rissanen, T.; Anttila, P.; Hartonen, K.; Reissell, A.; Vreuls, R.; Adahchour, M.; Hyotylainen, T. Journal of Chromatography A. 2006, 1125, 234–243.
[69]Mieth, M.; Schubert, J. K.; Groger, T.; Sabel, B.; Kischkel, S.; Fuchs, P.; Hein, D.; Zimmermann, R.; Miekisch, W. Anal. Chem. 2010, 82, 2541–2551.
[70]Harju, M.; Danielsson, C.; Haglund, P. Journal of Chromatography A. 2003, 1019, 111–126.
[71]Silva, J. M.; Zini, C. A.; Caramao, E. B. Journal of Chromatography A. 2011, 1218, 3116–3172.
[72]Kristenson, E. M.; Korytar, P.; Danielsson, C.; Kallio, M.; Brandt, M.; Makela, J.; Vreuls, R. J. J.; Beens, J.; Brinkman, U. A. Th. Journal of Chromatography A. 2003, 1019, 65–77.
[73]Welthagen, W.; Schnelle-Kreis, J.; Zimmermann, R. Journal of Chromatography A. 2003, 1019, 233–249.
[74]Chen, S.; Shi, L.; Shan, Z.; Hu, Q. Food Chemistry. 2007, 104, 1315–1319.
[75]Schoenmakers, P. J.; Oomen, J. L. M. M.; Blomberg, J.; Genuit, W.; Velzen, G. V. Journal of Chromatography A. 2000, 892, 29–46.

簡易檢索 / 詳目顯示

相關論文