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研究生:利知耕
研究生(外文):Chich-Keng Li
論文名稱:以奈米材料混摻高分子之整體成形管柱微萃取食品中焦糖色素
論文名稱(外文):Solid-phase microextraction of caramel colors using nanomaterial-polymer monolithic column
指導教授:黃悉雅
指導教授(外文):Hsi-Ya Huang
學位類別:碩士
校院名稱:中原大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2015
畢業學年度:103
語文別:中文
論文頁數:79
中文關鍵詞:焦糖色素固相微萃取奈米材料
外文關鍵詞:Caramel Colorsnanomaterial-poiymerSPME
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本論文以奈米材料混摻高分子整體成形材料作為吸附劑,並應用於萃取焦糖色素,研究過程主要可分為兩大部分:第一部分為建立焦糖色素之偵測方法;第二部分探討未摻雜奈米材料或摻雜活性碳之高分子整體成形材料(AC-polymer)對焦糖色素之萃取效果。
實驗中分別以未混摻或混摻活性碳的高分子整體成形材料作為吸附劑對焦糖色素進行萃取,並以微胞電層析(micellar electrokinetic chromatography, MEKC) 方法檢測萃取效果。研究過程中比較純高分子及混摻活性碳高分子對焦糖色素的萃取效能,並探討活性碳高分子萃取管柱的最佳化條件。結果顯示含有1 mg帶電荷單體AMPS、50 wt% AC含量、萃取管柱長度5 cm、吸附溶劑1 mL ACN、脫附溶劑 1.5 mL 5 mM H3PO4為最佳化條件,得到焦糖色素於濃度為10 ppm之萃取回收率介於85.6% -96.1%,inter-day relative standard deviation (RSD)低於4.9% (n=3);intra-day回收率為84.5% -95.1%,RSD低於6.3% (n=3);不同合成批次之萃取管柱回收率為81.3% -96.1%,RSD低於7.1% (n=3)。由結果得知,AC-polymer SPME應用於焦糖色素之萃取具有良好效果與管柱再現性。最後我將利用此類萃取管柱對食品樣品中的醬油和可樂進行萃取並探討其效能。



In this study, a nanomaterial-polymer monolithic column was used as adsorbent for extraction of caramel colors. This dissertation is divided into two parts: first, a method was established to separate and detect caramel colors. Second part, the extraction efficiencies of the neat-polymer and activated carbon-polymer (AC-polymer) monolithic column of caramel colors were determined.
The neat-polymer and AC-polymer were used as adsorbent of caramel colors extraction, separation of caramel colors using micellar electrokinetic chromatography (MEKC) for determining the extraction efficiency. Considering the extraction efficiency between neat-polymer and AC-polymer of caramel colors, AC-polymer column and extraction condition were optimized. The optimized condition for AC-polymer monolithic column contained: 1 mg charge monomer AMPS, 50% (wt.%) AC, 5 cm of extraction column length, 1 mL ACN as loading solvent, 1.5 mL 5 mM H3PO4 as elution solvent. Based on the optimized results, when the concentration of caramel colors were 10 ppm, the recoveries and relative standard deviations (RSDs) for inter- and intra-day were in the ranged of 85.6-96.1% (< 4.9% RSDs) and 84.5-96.1% (< 6.3% RSDs) (n=3), respectively. The extraction recoveries for column-to-column were in the ranged of 81.3-96.1% (< 7.1 % RSDs) (n=3). Based on the above results, it suggests that AC-polymer monolithic column demonstrated a remarkable extraction efficiency and reproducibility as adsorbent in SPME of caramel colors. Finally, the AC-polymer was used to extract caramel colors in cola and soy sauce samples and determined the extraction efficiency.




目錄
摘要 I
Abstract II
目錄 III
圖目錄 VI
表格目錄 IX
第一章 緒論 1
1-1. 焦糖色素之介紹 1
1-1-1焦糖色素危害 2
1-1-2相關法規 3
1-2. 毛細管電泳簡介 4
1-2-1. 毛細管電泳原理 5
1-2-2. 電滲流(electroosmotic flow, EOF) 5
1-2-3. 毛細管電泳的應用 7
1-3. 萃取技術簡介 11
1-3-1液-液萃取技術簡介 11
1-3-2固相萃取技術簡介 12
1-4. 固相微萃取技術簡介 13
1-4-1. Fiber SPME 簡介 15
1-4-2. SBSE SPME 簡介 16
1-4-3. In-tube SPME 簡介 17
1-4-4. Syringe SPME 簡介 18
1-4-5. In-tip SPME 簡介 19
1-5. 奈米孔洞材料簡介 20
1-5-1. 活性碳簡介 20
1-6. 焦糖色素文獻回顧 23
1-6-1.焦糖色素檢測之文獻回顧 23
1-6-2. 焦糖色素萃取文獻回顧 27
1-7. 研究動機 29
第二章 實驗 30
2-1. 儀器設備及藥品 30
2-2.焦糖色素標準品 33
2-3. 固相微萃取管柱製備流程 35
2-3-1.管壁改質之前處理方法 35
2-3-2. 高分子整體成形管柱之製備 37
2-3-3. 萃取裝置介紹 39
2-3-4. 萃取流程 39
2-4.微胞電層析儀實驗條件 41
2-4-1.毛細管前處理條件 41
2-4-2.毛細管電泳儀偵測條件 42
第三章 結果與討論 43
3-1.建立焦糖色素之偵測方法 43
3-1-1.MEKC檢測焦糖色素 43
3-1-2.MEKC結合線上濃縮方式檢測低濃度焦糖色素 45
3-2.萃取管柱中吸附劑對焦糖色素之影響 47
3-2-1.帶電荷單體於高分子萃取管柱中對焦糖色素吸附之影響 47
3-2-2.混摻孔洞材料於高分子萃取管柱中對焦糖色素吸附之影響 50
3-2-3.萃取管柱長度對焦糖色素吸附之影響 53
3-2-4.活性碳含量對焦糖色素吸附之影響 55
3-3.探討活性碳-高分子萃取管柱的最佳化萃取流程 58
3-3-1.吸附溶劑種類的影響 58
3-3-2.脫附溶劑體積的影響 59
3-4.活性碳-高分子萃取管柱之鑑定 61
3-4-1.紅外線光譜儀之鑑定 61
3-4-2.拉曼光譜儀鑑定 62
3-4-3.掃描式電子顯微鏡之鑑定 63
3-4-4.氮氣等溫吸脫附表面測定儀 65
3-5.活性碳-高分子萃取焦糖色素之效能與壽命評估 66
3-5-1 .AC-polymer萃取效能評估 66
3-5-2.活性碳-高分子萃取管柱之耐用性測試 67
3-5-3. 不同奈米材料對焦糖色素的萃取效果 70
3-6.實際樣品 72
第四章 結論 74
參考文獻 76


圖目錄
圖1-1 焦糖色素4-MeI及THI結構 3
圖1-2 毛細管電泳裝置圖 4
圖1-3電雙層示意圖 6
圖1-4電滲流與分析物遷移方向示意圖(a)施加電壓前(b)施加電壓後 6
圖1-5 CZE分離原理示意圖 7
圖1-6微胞示意圖 8
圖1-7 MEKC分離原理示意圖 8
圖1-8高pH值時油滴移動方向 9
圖1-9低pH值時油滴在外加正電壓下分離的移動方向 10
圖1-10低pH值時油滴在外加負電壓下分離的移動方向 10
圖1-11 LLE方法之示意圖 11
圖1-12 SPE示意圖 12
圖1-13 SPME方法之分類及裝置圖 14
圖1-14 Fiber SPME示意圖 15
圖1-15 (a) SBSE示意圖(b) HS-SBSE (c) DI-SBSE 16
圖1-16 In-tube SPME流程示意圖(a)吸附(b)脫附 17
圖1-17 PMME使用裝置示意圖 18
圖1-18 In-tip SPME流程示意圖 19
圖1-19活性碳表面之含氧官能基與電子 20
圖1-20碳的同素異形體 21
圖1-21活性碳孔徑分布圖 21
圖1-22 Wang團隊在2012年以LC-MS上分離四種焦糖色素層析圖 23
圖1-23 Schee團隊在2013年以LC-MS分離三種焦糖色素層析圖 24
圖2-1 玻璃管壁改質前處理流程圖 35
圖2-2 玻璃管管壁改質示意圖(a)改質前(b)改質後 36
圖2-3 高分子整體成形管柱製備流程 38
圖2-4 萃取裝置示意圖 39
圖2-5 萃取流程示意圖 39
圖3-1 以不同SDS濃度分離三種焦糖色素標準品之電泳圖 44
圖3-2 利用線上濃縮微胞電層析方式檢測低濃度焦糖色素 46
圖3-3 AMPS之結構 47
圖3-4焦糖色素樣品經高分子材料loading後溶液之電泳圖 48
圖3-5 帶電荷單體AMPS含量對焦糖色素之吸附效果 49
圖3-6 AC之表面結構 50
圖3-7 polymer or AC-polymer 對焦糖色素吸附及脫附之電泳圖 51
圖3-8 polymer與AC-polymer對焦糖色素萃取之回收率 52
圖3-9不同長度萃取管柱對焦糖色素萃取之回收率 53
圖3-10 不同長度萃取管柱對萃取效果影響之電泳圖 54
圖3-11 不同AC含量的高分子萃取管柱對焦糖色素萃取效果之電泳圖 56
圖3-12不同AC含量之高分子萃取管柱對焦糖色素萃取之回收率 57
圖3-13不同吸附溶劑對AC-polymer吸附焦糖色素之吸附效果 58
圖3-14不同脫附溶劑體積對5 cm AC-polymer萃取焦糖色素之影響 59
圖3-15不同脫附溶劑體積對AC-polymer萃取焦糖色素之層析圖 60
圖3-16 (a)AC-polymer (b)neat-poly (c)AC 之IR鑑定圖譜 61
圖3-17 (a)AC-polymer (b) AC (c) neat-poly 之Raman鑑定圖譜 62
圖3-18 (a)(b) neat-polmer (c)(d) 50% AC-polymer (8 mg)管柱之SEM圖 63
圖3-19 (a) 50% AC-polymer管柱之SEM-EDS圖 64
圖3-19 (b) neat-polymer管柱之SEM-EDS圖 64
圖3-20 AC-polymer 、AC 、neat-poly 之氮氣等溫吸附圖 65
圖3-21 AC-polymer 重複萃取焦糖色素之結果 67
圖3-22 AC-polymer 重複萃取焦糖色素之層析圖 68
圖3-23 (a)(b) 未進行萃取 (c)(d) 萃取30次後管柱之SEM圖 69
圖3-24不同奈米材料萃取管柱對焦糖色素萃取之回收率 71
圖3-25 AC-polymer對可樂樣品之萃取 72
圖3-26 AC-polymer對紹興酒樣品之萃取 73

表格目錄

表1-1焦糖色素之食品添加物使用範圍及限量暨規格標準 3
表1-2活性碳的性質及分類 22
表1-3檢測焦糖色素之文獻 (2000 - 2014年) 25
表1-3(續)檢測焦糖色素之文獻 (2000 - 2014年) 26
表1-4以SPE方法對焦糖色素萃取之文獻 28
表2-1儀器設備名稱及廠牌 30
表2-1(續)儀器設備名稱及廠牌 31
表2-2製備高分子所需試藥 31
表2-3常用試藥之名稱 32
表2-4焦糖色素標準品 33
表2-5 Poly(BMA-EDMA)高分子聚合溶液比例 37
表2-6 焦糖色素之萃取最佳化條件 40
表3-1 一般偵測方法與線上濃縮偵測方法之LOD與放大倍率 45
表3-2不同AMPS含量的高分子萃取管柱萃取焦糖色素之吸附率 49
表3-3 polymer與AC-polymer對焦糖色素萃取之回收率 52
表3-4 不同AC含量的高分子萃取管柱之背壓a 55
表3-5 不同AC含量的高分子萃取管柱萃取焦糖色素之回收率 57
表3-6 50% AC-polymer 之元素分布比例 64
表3-7 不同萃取管柱之表面積 65
表3-8 AC-polymer對焦糖色素萃取之再現性 66
表3-9 不同奈米材料的高分子萃取管柱萃取焦糖色素之回收率 70
表3-10 實際樣品中焦糖色素之回含量 73
表4-1 本實驗與文獻比較 75

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