魚油對人類健康具重要性，常製成膳食補充劑，但市場上仍有摻偽現象。魚油容易因外在環境氧化裂解而導致標示不符。鯖魚分布廣、廣受人類喜愛，可製作為膳食補充劑。基質輔助雷射脫附游離-飛行時間質譜法具有樣品製備簡單、質譜分析過程快速的優點。本篇研究探討鯖魚油的不同萃取條件，使用溶劑萃取法、索式萃取法和微波輔助萃取法。微波輔助萃取鯖魚用乙醇做溶劑在微波功率時間 300 W/30 sec (14.3%) 時相對於傳統溶劑萃取 (10.3%) 和索式萃取 (3%) 有更高萃取率，取得油與極性萃取物。探討 MALDI-TOF MS 分析鯖魚油三酸甘油酯 (TAG) 時之最佳條件，使用不同基質、雷射強度、樣品基質比例和點樣次數，發現使用 2,5-dihydroxybenzoic acid 做基質、雷射強度比例 90%、樣品基質比例 (1/1, v/v) 和點樣三次時，可達到最佳的分析效果。使用 MALDI-TOF MS 分析鯖魚油之 TAG 將其質譜數據與線上資料庫 LIPID MAPS Online Tools 比對後，鑑別出鯖魚油中的 25 種 TAG 分子和推測出其中的脂肪酸組成，有 m/z 799.7 (C46:1, MPP1)、801.7 (C46:0, MPP)、813.6 (C48:8)、815.6 (C48:7, LM1D6/M1M1E5)、817.6 (C48:6, LP1E5/LLn3Ln3)、819.6 (C48:5, MME5)、825.7 (C48:2, MPL2/PP1P1)、827.7 (C48:1, PPP1/MPO1)、829.7 (C48:0, PPP)、839.6 (C50:9)、841.6 (C50:8, M1M1D6/LLn3E5)、843.6 (C50:7, LP1D6/M1P1E5)、845.7 (C50:6, MMD6/MP1E5)、849.7 (C50:4, ML2L2)、851.7 (C50:3, PPLn3/PP1L2)、853.7 (C50:2, PPL2/PP1O1)、867.6 (C52:9, LLn3D6/M1Ln3E5)、869.7 (C52:8, M1P1D6/MLn3E5)、875.7 (C52:5, PPE5/PL2Ln3)、877.7 (C52:4, PL2L2)、879.7 (C52:3, PO1L2)、889.6 (C54:12)、891.6 (C54:11, LE5D6/M1E5E5)、913.6 (C54:0)、915.6 (C56:13)。將其與鯡魚油和鱈魚肝油 之 TAG 對比，m/z 813.6、815.6、839.6、843.6、889.6、891.6 未存在於其中，m/z 799.7、825.7、827.7、829.7、845.7、849.7、853.7、869.7、875.7、877.7、879.7 為共同存在於鯡魚油和鱈魚肝油中。將其與大豆油、葵花油等植物油中共有的 TAG 對比具有顯著差異性。顯示測得之鯖魚油 TAG 分子對於鯖魚相關產品或研究做物種鑑定和鑑別在魚油或魚油飼料中加入較低價植物油的摻偽產品之潛力。同時，鯖魚油經 MALDI-TOF MS 分析後可測得其中的磷脂醯膽鹼 (PC)，分別是 m/z 803.6、805.6、831.7、833.7，分子組成依序為 PC(18:2/20:5)、PC(16:0/22:6)、PC(18:1/22:6)、PC(20:1/22:6)。

Fish oil is used as a dietary supplement for human health, but it has often been adulterated on the market for years. Fish oil is easily degraded by the environmental factors, leading to mislabel or insecurity. Mackerel is widely distributed and its oil has been made into dietary supplements. Matrix-assisted laser desorption-time-of-flight mass spectrometry (MALDI-TOF MS) has the advantage of easy sample preparation and rapid mass spectrometry analysis. This study explores the optimum extraction conditions for mackerel oil using Bligh and Dyer, soxhlet extraction and microwave-assisted extraction. It was found that the use of microwave-assisted extraction of mackerel oil at a microwave power of 300 W for 30 sec (14.3%) has a higher extraction rate than solvent extraction (10.3%) and soxhlet extraction (3%). To explore conditions for the analysis of triacylglycerides (TAG) of mackerel oil by MALDI-TOF MS, using different matrix, laser intensity, sample to matrix ratio and deposited times. The optimum conditions are 2,5-dihydroxybenzoic acid as matrix and laser energy 90%, the sample to matrix ratio (1/1, v/v) and deposited three times, according to peak abundance and profile clarity in the spectrum. MALDI-TOF MS analysis on TAG is matched with the online database LIPID MAPS Online Tools to identify TAG in mackerel oil. The main TAG molecules and the assigned fatty acid compositions in mackerel oil are identified as 25 TAGs: m/z 799.7 (C46:1, MPP1), 801.7 (C46:0, MPP), 813.6 (C48:8), 815.6 (C48:7, LM1D6/M1M1E5), 817.6 (C48:6, LP1E5/LLn3Ln3), 819.6 (C48:5, MME5), 825.7 (C48:2, MPL2/PP1P1), 827.7 (C48:1, PPP1/MPO1), 829.7 (C48:0, PPP), 839.6 (C50:9), 841.6 (C50:8, M1M1D6/LLn3E5), 843.6 (C50:7, LP1D6/M1P1E5), 845.7 (C50:6, MMD6/MP1E5), 849.7 (C50:4, ML2L2), 851.7 (C50:3, PPLn3/PP1L2), 853.7 (C50:2, PPL2/PP1O1), 867.6 (C52:9, LLn3D6/M1Ln3E5), 869.7 (C52:8, M1P1D6/MLn3E5), 875.7 (C52:5, PPE5/PL2Ln3), 877.7 (C52:4, PL2L2), 879.7 (C52:3, PO1L2), 889.6 (C54:12), 891.6 (C54:11, LE5D6/M1E5E5), 913.6 (C54:0), 915.6 (C56:13).When comparing with the TAG of menhaden and cod liver oils, m/z 813.6, 815.6, 839.6, 843.6, 889.6, 891.6 are unique for mackerel oil, and m/z 799.7, 825.7, 827.7, 829.7, 845.7, 849.7, 853.7, 869.7, 875.7, 877.7, 879.7 are co-present in menhaden and cod liver oils. The TAG shared in vegetable oils of soybean oil and sunflower oil are apparently different from that of the mackerel oil . The TAG molecule of mackerel oil have potential power of discrimination for species identification and determination of adulterated products with lower priced vegetable oils in fish oil or fish oil feed. At the same time, the phosphatidylcholine (PC) of mackerel oil was analyzed by MALDI-TOF MS, which were m/z 803.6, 805.6, 831.7, 833.7, and the molecular composition was PC (18:2/20:5), PC (16:0/22:6), PC (18:1/22:6), PC (20:1/22:6).

目錄
第一章、前言 1
第二章、文獻回顧 2
第一節、魚油 2
1.1 簡介 2
1.2 魚油氧化性導致補充劑標示不符之影響、 2
1.3 魚油的摻假 3
1.4 魚油萃取方法 4
第二節、TAG 分析 6
2.1 食用油 TAG 種類分析 6
2.2 魚油的 TAG 種類分析 7
第三節、MALDI-TOF-MS 9
3.1 簡介 9
3.2 基質選擇和基質與分析物比例的影響 9
3.3 加成物 (adduct) 的影響 9
3.4 應用性 10
3.5 在食品油脂分析上的應用 10
第三章、實驗架構 13
第一節、魚油萃取 13
第二節、探討鯖魚油 TAG 的 MALDI-TOF-MS 之分析條件與鑑定 14
第四章、材料方法 15
第一節、實驗材料 15
第二節、實驗方法 17
2.1 鯖魚取肉前處理 17
2.2 萃油 17
2.3 油脂氧化程度測試 18
2.4 探討鯖魚油之 MALDI-TOF-MS 最適分析條件 19
2.5 MALDI-TOF-MS 之鯖魚油 TAG 種類分析鑑定 20
第五章、結果與討論 22
第一節、探討鯖魚油之不同萃取方式 22
1.1 溶劑萃取法和索式萃取法 22
1.2 微波輔助萃取法 22
第二節、探討鯖魚油之 MALDI-TOF-MS 分析條件 24
2.1 雷射強度與基質種類選擇 24
2.2 樣品基質比例選擇 25
第三節、MALDI-TOF-MS 之鯖魚油 TAG 定性分析 26
3.1 基質 (DHB) 的 MALDI-TOF-MS 訊號 26
3.2 Triolein 標準品 26
3.3 TAG 分子定性分析 26
第四節、MALDI-TOF-MS 之鯖魚油磷脂醯膽鹼 30
第六章、結論 32
第七章、參考文獻 33
表 38
圖 48
附錄 60

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