以頂空固相微萃取法配合離子阱式氣相層析質譜儀偵測台灣酒類氣味物中的酯類化合物

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研究生：	林智立 Chih-Lih Lin
論文名稱：	以頂空固相微萃取法配合離子阱式氣相層析質譜儀偵測台灣酒類氣味物中的酯類化合物 Determination of esters in the flavor compounds of Taiwan’s wines by headspace solid-phase microextraction and gas chromatograph-ion trap mass spectrometer
指導教授：	黃賢達 Shang-Da Huang
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2004
畢業學年度：	92
語文別：	中文
論文頁數：	96
中文關鍵詞：	酒類、氣味、酯類化合物、固相微萃取法、氣相層析質譜儀
外文關鍵詞：	wines, flavor, esters, SPME, GC/MS
相關次數：	點閱：2 下載：0
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本論文是利用頂空固相微萃取法配合氣相層析離子阱式質譜儀 (HS-SPME—GC/ITMS) 分析酒類氣味中氣味分子的主要成分—酯類化合物 (esters)：ethyl acetate (EA)、isobutyl acetate (IBA)、ethyl butyrate (EB)、isoamyl acetate (IAA)、ethyl hexanoate (EHx)、hexyl acetate (HA)、benzyl acetate (BA)、ethyl octanoate (EO)、2-phenylethyl acetate (2PEA)。

固相微萃取法是具有快速方便、符合經濟效益、及兼顧環保等優點的一種前處理方法。本研究之內容即利用此方法將酒類氣味中的酯類化合物先進行前濃縮萃取的步驟，再以氣相層析質譜儀進行分離與定量。而研究重點在於影響頂空固相微萃取法之萃取效率的各項變因：固定靜相的種類、操作方式、萃取溫度與時間、脫附溫度與時間、離子強度、樣品攪拌程度、樣品體積、酒精濃度等。在求得最佳化條件之後，即以此方法實際應用在兩種台灣出產酒類—高粱酒與米酒進行真實樣品的分析。

本研究經實驗後得到結果如下：選擇以PDMS、厚度為100 □m的纖維作萃取，並以4-methyl-2-pentanol、ethyl heptanoate、2-octanol三種內標準品減低酒精濃度對萃取效率的影響。此方法除了ethyl octanoate僅具有一個級數的線性之外，其餘化合物皆具有兩個級數的良好線性，線性相關係數 (R2) 除了ethyl hexanoate為0.9917以外，其餘化合物皆大於0.998，顯示此方法具有良好的線性。精密度介於3.6%~10.2%之間。在真實樣品的測定上，兩種酒類所得到的回收率約在86 % ~ 132%之間，受基質影響並不嚴重，可適用於簡單的檢量線法。偵測極限介於13.65 □g/l ~ 6.60 mg/l之間。因此本研究成功地利用HS-SPME—GC/ITMS應用於酒類氣味中的酯類化合物分析。

A method for determining the flavor compounds – esters (ethyl acetate, isobutyl acetate, ethyl butyrate, isoamyl acetate, ethyl hexanoate, hexyl acetate, benzyl acetate, ethyl octanoate, 2-phenylethyl acetate) in wines by headspace solid-phase microextraction (HSSPME) combined with gas chromatography-ion trap mass spectrometry (GC/ITMS) was developed. Several parameters of extraction and desorption procedure such as types of fibers, extraction technique, extraction temperature, extraction time, desorption temperature, desorption time, stir rate, sample’s volume, salt concentration, ethanol content, were studied and optimized. The method shows good linearity in two orders for most of analysts. Good precisions (3.6% ~10.2%) are obtained using 4-methyl-2-pentanol, ethyl heptanoate, and 2-octanol as internal standards. Finally, the method was successful applied to analyze esters in two kinds of Taiwan’s wines – Rice Wine and Sorghum Wine.

目錄

壹．緒論...........................................1
  一．前言.........................................1
  二．酯類化合物...................................2
  三．前處理方法...................................5
  四．固相微萃取法.................................9
  五．酯類化合物的相關研究........................20
  六．離子阱式質譜儀..............................21
  七．研究目的....................................25
貳．實驗部份......................................26
  一．試藥........................................26
  二．實驗裝置....................................27
  三．儀器........................................28
  四．標準溶液....................................30
  五．真實樣品....................................34
  六．實驗步驟....................................35
參．結果與討論....................................38
  一．SPME最佳化之變因探討........................38
      1.纖維種類..................................38
      2.萃取方式..................................42
      3.脫附時間..................................44
      4.萃取時間..................................47
      5.樣品攪拌程度..............................50
      6.離子強度..................................53
      7.樣品體積..................................56
      8.脫附溫度..................................58
      9.萃取溫度..................................61
     10.酒精濃度..................................64
  二．校正曲線、精密度、方法偵測極限..............72
      1.校正曲線..................................72
      2.精密度....................................73
      3.方法偵測極限..............................73
      4.與文獻之比較..............................75
  三．真實樣品的定量..............................77
肆．結論..........................................91
伍．參考文獻......................................92
















表目錄

Table 1 本研究中各分析物之物理性質.......................4
Table 2 吹氣捕捉法與固相微萃取法的比較...................6
Table 3 固相萃取法與固相微萃取法的比較...................8
Table 4 各標準品之定量離子一覽表........................29
Table 5 工作標準溶液中各標準品濃度表....................30
Table 6 校正曲線、精密度、方法偵測極限、真實樣品測試之標準品儲存溶液中各標準品濃度表................................31
Table 7 校正曲線、精密度、方法偵測極限、真實樣品測試之內標準品儲存溶液中各內標準品濃度表............................31
Table 8 校正曲線建立時，工作溶液所使用之溶劑中所含內標準品濃度表....................................................32
Table 9 建立各標準品校正曲線之各點濃度表................32
Table 10 本實用使用之SPME纖維之調態溫度與時間表.........35
Table 11 目前已商業化之固相微萃取纖維之種類、厚度、適用範圍表......................................................39
Table 12 各標準品所對應之內標準品一覽表.................69
Table 13 各標準品之線性範圍與線性相關係數表.............72
Table 14 各標準品之相對標準偏差值表.....................73
Table 15 各標準品在標準溶液、米酒、高粱酒中之偵測極限表.74
Table 16 參考文獻[7]與本研究之實驗結果比較..............75
Table 17 米酒與高粱酒之氣味中所含待測物之定量表.........78
Table 18 各標準品之回收率表.............................79

圖目錄

Fig.1 本研究中所偵測之酯類化合物結構式...................3
Fig.2 Pawliszyn實驗室最初設計之固相微萃取裝置...........11
Fig.3 商業化之手動式固相微萃取裝置圖....................12
Fig.4固相微萃取之操作流程圖.............................14
Fig.5靜止水層之概念圖...................................16
Fig.6 離子阱的基本構造..................................22
Fig.7 離子在阱中之安定圖................................23
Fig.8 離子在阱中的運動軌跡圖............................24
Fig.9 固相微萃取裝置圖..................................36
Fig.10 纖維種類與萃取效率關係圖.........................41
Fig.11 萃取方式與萃取效率關係圖.........................43
Fig.12 脫附時間與萃取效率關係圖.........................45
Fig.13 萃取時間與萃取效率關係圖.........................48
Fig.14 樣品攪拌程度與萃取關係圖.........................51
Fig.15 NaCl添加克數與萃取效果關係圖.....................54
Fig.16 樣品液氣相比與萃取效率圖.........................57
Fig.17 脫附溫度與萃取效率圖.............................59
Fig.18 萃取溫度與萃取效率圖.............................62
Fig.19 酒精濃度與萃取效率圖（NaCl未飽和）...............65
Fig.20 酒精濃度與萃取效率圖（NaCl已飽和）...............67
Fig.21 酒精濃度與各標準品之相對波峰面積關係圖...........70
Fig.22 各標準品以Table 9中濃度2的濃度，內標準品以Table 8的濃度配製而成的標準溶液，經最佳化條件萃取之後所得氣相層析圖......................................................77
Fig.23 標準品與兩種真實樣品經最佳化條件萃取之後所得到之層析圖比對..................................................81
Fig.24 Ethyl acetate在真實樣品中與標準溶液中之質譜圖比較......................................................82
Fig.25 Isobutyl acetate在真實樣品中與標準溶液中之質譜圖比較......................................................83
Fig.26 Ethyl butyrate在真實樣品中與標準溶液中之質譜圖比較......................................................84
Fig.27 Isoamyl acetate在真實樣品中與標準溶液中之質譜圖比較......................................................85
Fig.28 Ethyl hexanoate在真實樣品中與標準溶液中之質譜圖比較......................................................86
Fig.29 Ethyl octanoate在真實樣品中與標準溶液中之質譜圖比較......................................................87
Fig.30 2-Phenylethyl acetate在真實樣品中與標準溶液中之質譜圖比較....................................................88
Fig. 31 在標準品層析圖中（Fig. 23），compound 9與compound 10之間的訊號，其質譜圖經過資料庫比對之後得到的結果........89
Fig. 32 在標準品層析圖中（Fig. 23），compound 10與compound 11之間的訊號，其質譜圖經過資料庫比對之後得到的結果......90

                                

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