臺灣博碩士論文加值系統

本實驗以不同乙醇濃度還原酒及花青素模式溶液，觀察乙醇濃度對花青素顏色及呈色安定性之影響，並探討可能之反應機制。
由實驗結果得知，不同乙醇濃度還原酒之酸鹼值，隨著乙醇濃度的增加而增加，並呈二次關係 (quadratic relation)。由於酸鹼值之變化，改變花青素之結構分佈，影響酒液顏色及呈色安定性。提高酒液中之乙醇濃度，將有助於減緩花青素之copigmentation及self-association，進而減緩花青素之聚合反應，降低沉澱量產生，並提高酒液之呈色安定性。
提高模式溶液之乙醇濃度，亦產生明顯的向紅效應 (bathochromic shift)。乙醇濃度越高，偏移越大。依粒徑及質譜分析結果推測，乙醇分子可能與花青素分子有交互作用，並產生花青素衍生物。當乙醇濃度改變時，此交互作用亦發生改變，導致光譜移動。粒徑分析結果亦支持花青素之self-association受乙醇濃度影響之說法，當提高模式溶液之乙醇濃度時，由於self-association作用力減弱，因此釋放出更多的游離flavylium cation及/或quinoidal base，改變花青素之結構分佈，影響花青素呈色。
不同乙醇濃度malvidin-3-glucoside模式溶液之降解反應為一次反應 (first-order reaction)，其降解速率隨著乙醇濃度及反應溫度的提高而增加。

Reconstituted wines and anthocyanin model solutions with different ethanol concentrations were used to investigate the effect of ethanol on the color phenomena of anthocyanin and then the possible mechanism was proposed.
Results show that the pH of reconstituted wines increased with increment of ethanol concentration following a quadratic relation. The equilibrium among different forms of anthocyanin was affected by the increase in pH value then the color and stability of wine. An increase in ethanol concentration in wine decreases the degrees of copigmentation, self-association, polymerization and precipitate formation then increased the color stability of wine.
The occurrence of bathochromic shift upon presence of ethanol increases with ethanol concentration. The results of particle size distribution and Mass spectra indicated that ethanol molecule could react with anthocyanin molecule and produced an anthocyanin adduct. This interaction changes with ethanol concentration and changes the spectra. The results of particle size distribution also proved that the self-association of anthocyanin was affected by ethanol concentration. The extent of self-association decreased with an elevated ethanol concentration in model solution and can be attributed to the increase in the contents of free flavylium cations and/or quinonoidal base that affects the equilibrium among different forms and color of anthocyanin.
The degradation of malvidin-3-glucoside follows apparent first order kinetics, and accelerates with the increase in ethanol concentration and temperature.

目 錄
頁次
中文摘要………………………………………………………………... I
英文摘要………………………………………………………………... II
目錄……………………………………………………………………... III
圖次……………………………………………………………………... VIII
表次……………………………………………………………………... XI

第一章 文獻整理……………………………………………………... 1
壹、釀酒原料……………………………………………………………. 1
(壹)、黑后葡萄………………………………………………………… 1
(貳)、紅肉李…………………………………………………………… 1
貳、花青素………………………………………………………………. 1
(壹)、花青素之結構…………………………………………………… 1
(貳)、花青素之穩定性………………………………………………… 7
(參)、花青素於水溶液系統之相關研究……………………………… 10
一、降解反應…………………………………………………………. 10
二、聚合反應…………………………………………………………. 10
三、copigmentation與self-association……………………..……. 11
(肆)、花青素於非水溶液系統之相關研究…………………………… 12
一、乙醇溶液中花青素之降解反應…………………………………. 12
二、乙醇溶液中花青素之聚合反應…………………………………. 12
三、乙醇溶液中花青素之copigmentation與self-association……. 13
參、參考文獻……………………………………………………………. 14

第二章 模式系統之建立……………………………………………... 18
壹、前言…………………………………………………………………. 18
貳、材料與方法…………………………………………………………. 19
(壹)、實驗架構………………………………………………………… 19
(貳)、實驗材料………………………………………………………… 20
(參)、實驗方法………………………………………………………… 20
參、結果與討論…………………………………………………………. 25
(壹)、發酵基酒之物化特性分析……………………………………… 25
一、發酵基酒之製備…………………………………………………. 25
二、基酒於發酵過程中之物化特性分析……………………………. 25
(貳)、還原酒之物化特性分析………………………………………… 33
一、果汁、新酒及還原酒之物化特性分析…………………………... 33
二、新酒及還原酒之HPLC圖譜分析………………………………. 34
三、新酒冷凝液之GC圖譜分析…………………………………….. 34
四、乙醇濃度對還原酒酸鹼值變化之影響…………………………. 40
五、乙醇濃度對還原酒Hunter’s L, a, b值變化之影響……………. 40
肆、結論…………………………………………………………………. 43
伍、參考文獻……………………………………………………………. 44

第三章 反應機制之探討……………………………………………... 45
壹、前言…………………………………………………………………. 45
貳、材料與方法…………………………………………………………. 46
(壹)、實驗架構………………………………………………………… 46
(貳)、實驗材料………………………………………………………… 46
(參)、實驗方法………………………………………………………… 47
參、結果與討論…………………………………………………………. 51
(壹)、花青素之分離、純化及鑑定…………………………………….. 51
一、黑后葡萄花青素之分離、純化及鑑定…………………………... 51
二、紅肉李花青素之分離、純化及鑑定……………………………... 51
(貳)、乙醇濃度對花青素模式溶液呈色變化之影響………………… 55
一、花青素模式溶液之光譜變化……………………………………. 55
二、不同乙醇濃度之花青素模式溶液與A530之相關性迴歸………. 55
三、花青素模式溶液之Hunter’s L, a, b值變化……………………. 60
四、花青素於不同pH水溶液中之光譜及Hunter’s L, a, b值變化... 60
(參)、乙醇濃度對Mv-3-glc模式溶液呈色變化之影響……………… 64
一、Mv-3-glc模式溶液之光譜變化…………………………………. 64
二、不同乙醇濃度之Mv-3-glc模式溶液與A530之相關性迴歸……. 64
三、Mv-3-glc模式溶液之Hunter’s L, a, b值變化…………………. 64
四、Mv-3-glc模式溶液之粒徑分析…………………………………. 65
(肆)、反應機制之證明………………………………………………… 70
一、乙醇濃度對酸鹼值之影響………………………………………. 70
二、氯化鈉對Mv-3-glc模式溶液光譜變化之影響…………………. 70
三、氯化鈉對Mv-3-glc模式溶液粒徑分佈之影響…………………. 71
四、Mv-3-glc模式溶液之質譜分析…………………………………. 72
肆、結論…………………………………………………………………. 77
伍、參考文獻……………………………………………………………. 78

第四章 花青素在乙醇溶液中呈色安定性之研究…………………... 80
壹、前言…………………………………………………………………. 80
貳、材料與方法…………………………………………………………. 81
(壹)、實驗架構………………………………………………………… 81
(貳)、實驗材料………………………………………………………… 81
(參)、實驗方法………………………………………………………… 82
參、結果與討論…………………………………………………………. 85
(壹)、真實系統之呈色安定性試驗…………………………………… 85
一、新酒與還原酒呈色安定性之比較………………………………. 85
二、葡萄還原酒之呈色安定性試驗…………………………………. 90
三、李子還原酒之呈色安定性試驗…………………………………. 95
(貳)、模式系統之呈色安定性試驗…………………………………… 101
一、高濃度花青素模式溶液 (500 mg anthocyanin/L)之呈色安定
性試驗…………………………………………………………...
101
二、低濃度花青素模式溶液 (50 mg anthocyanin/L)之呈色安定
性試驗…………………………………………………………...
106
(參)、花青素在乙醇溶液中降解反應動力學之研究………………… 112
一、Mv-3-glc模式溶液降解反應動力學之探討……………………. 112
(一)、反應溫度對Mv-3-glc模式溶液安定性之影響……………… 112
(二)、Mv-3-glc模式溶液降解反應級數之探討…………………… 112
肆、結論…………………………………………………………………. 119
伍、參考文獻……………………………………………………………. 120

第五章 其他因子對花青素在乙醇溶液中呈色安定性之影響……... 121
壹、前言…………………………………………………………………. 121
貳、材料與方法…………………………………………………………. 121
(壹)、實驗架構………………………………………………………… 121
(貳)、實驗材料………………………………………………………… 122
(參)、實驗方法………………………………………………………… 122
參、結果與討論…………………………………………………………. 126
(壹)、溶劑效應………………………………………………………… 126
一、水分活性對花青素呈色安定性之影響…………………………. 126
二、其他溶劑對花青素呈色安定性之影響…………………………. 131
(貳)、其他化合物對花青素呈色安定性之影響……………………… 135
一、醣類對花青素模式溶液呈色安定性之影響……………………. 135
(一)、乙醇溶液中焦糖化反應之探討……………………………… 135
(二)、葡萄糖對花青素模式溶液呈色安定性之影響……………… 137
(三)、果糖對花青素模式溶液呈色安定性之影響………………… 137
二、維生素C對花青素模式溶液呈色安定性之影響………………. 140
三、二氧化硫對花青素模式溶液脫色反應之探討…………………. 140
肆、結論…………………………………………………………………. 143
伍、參考文獻……………………………………………………………. 144

附錄一：符號索引………………………………………………………. 145




圖 次
頁次
圖1-1. 花青素之結構……………………………………………….. 3
圖1-2. 酸性水溶液中花青素分子結構之轉變…………………..… 4
圖1-3. 花青素結構之平衡分佈曲線……………………………….. 5
圖1-4. 5, 7, 4’-trihydroxyflavylium cation之共振結構………….... 6
圖2-1. 葡萄酒及李子酒發酵過程之酒精度變化………………….. 28
圖2-2. 葡萄酒及李子酒發酵過程之總花青素變化……………….. 29
圖2-3. 葡萄酒及李子酒發酵過程之揮發性酸變化……………….. 30
圖2-4. 葡萄酒及李子酒發酵過程之可滴定酸變化……………….. 31
圖2-5. 葡萄酒及李子酒發酵過程之酸鹼值變化………………….. 32
圖2-6. 葡萄新酒及還原酒之HPLC圖譜………………………….. 37
圖2-7. 李子新酒及還原酒之HPLC圖譜………………………….. 38
圖2-8. 葡萄新酒冷凝液之GC圖譜………………………………... 39
圖2-9. 乙醇濃度對還原酒酸鹼值變化之影響…………………….. 41
圖2-10. 乙醇濃度對還原酒Hunter’s L, a, b值變化之影響……….. 42
圖3-1. 黑后葡萄花青素之HPLC圖譜…………………………….. 53
圖3-2. 紅肉李花青素之HPLC圖譜……………………………….. 54
圖3-3. 葡萄花青素模式溶液之光譜變化………………………….. 57
圖3-4. 李子花青素模式溶液之光譜變化………………………….. 58
圖3-5. 不同乙醇濃度之花青素模式溶液與A530之相關性迴歸….. 59
圖3-6. 葡萄及李子花青素模式溶液之Hunter’s L, a, b值變化….. 62
圖3-7. 葡萄花青素於不同pH水溶液中之光譜及Hunter’s L, a, b值變化………………………………………………………..
63
圖3-8. Mv-3-glc模式溶液之光譜變化…………………………….. 66
圖3-9. 不同乙醇濃度之Mv-3-glc模式溶液與A530之相關性迴歸.. 67
圖3-10. Mv-3-glc模式溶液之Hunter’s L, a, b值變化…………….. 68
圖3-11. Mv-3-glc模式溶液之粒徑分佈變化……………………….. 69
圖3-12. 乙醇濃度對酸鹼值之影響………………………………….. 73
圖3-13. 氯化鈉對Mv-3-glc模式溶液光譜變化之影響…………….. 74
圖3-14. 氯化鈉對Mv-3-glc模式溶液粒徑分佈之影響…………….. 75
圖3-15. Mv-3-glc模式溶液之質譜分析…………………………….. 76
圖4-1. 葡萄新酒與還原酒呈色變化之比較……………………….. 87
圖4-2. 葡萄新酒與還原酒光譜變化之比較……………………….. 88
圖4-3. 葡萄新酒與還原酒酸鹼值變化之比較…………………….. 89
圖4-4. 葡萄還原酒之呈色變化…………………………………….. 92
圖4-5. 葡萄還原酒之光譜變化…………………………………….. 93
圖4-6. 葡萄還原酒之酸鹼值變化………………………………….. 94
圖4-7. 李子還原酒之呈色變化…………………………………….. 97
圖4-8. 李子還原酒之光譜變化…………………………………….. 98
圖4-9. 李子還原酒之酸鹼值變化………………………………….. 99
圖4-10. 李子還原酒之濁度變化…………………………………….. 100
圖4-11. 高濃度葡萄花青素模式溶液 (500 mg anthocyanin/L)之呈色變化……………………………………………………..
103
圖4-12. 高濃度葡萄花青素模式溶液 (500 mg anthocyanin/L)之酸鹼值變化…………………………………………………..
104
圖4-13. 高濃度葡萄花青素模式溶液 (500 mg anthocyanin/L)之濁度變化……………………………………………………..
105
圖4-14. 低濃度葡萄花青素模式溶液 (50 mg anthocyanin/L)之呈色變化………………………………………………………..
108
圖4-15. 低濃度葡萄花青素模式溶液 (50 mg anthocyanin/L)之酸鹼值變化……………………………………………………..
109
圖4-16. 低濃度李子花青素模式溶液 (50 mg anthocyanin/L)之呈色變化………………………………………………………..
110
圖4-17. 低濃度李子花青素模式溶液 (50 mg anthocyanin/L)之酸鹼值變化……………………………………………………..
111
圖4-18. 反應溫度對Mv-3-glc模式溶液安定性之影響…………….. 115
圖4-19. 不同乙醇濃度Mv-3-glc模式溶液之一次降解反應動力學.. 116
圖4-20. 不同乙醇濃度Mv-3-glc模式溶液之Arrhenius線性迴歸… 117
圖5-1. 不同濃度乙醇溶液之水分活性變化……………………….. 128
圖5-2. 不同水分活性甘油模式溶液之光譜變化………………….. 129
圖5-3. 不同水分活性模式溶液之呈色變化……………………….. 130
圖5-4. 不同溶劑模式溶液之光譜變化…………………………….. 132
圖5-5. 不同溶劑模式溶液之Hunter’s L, a, b值變化…………….. 133
圖5-6. 不同溶劑模式溶液之呈色變化…………………………….. 134
圖5-7. 不同乙醇濃度模式溶液之A294及A420變化……………….. 136
圖5-8. 不同乙醇濃度之葡萄糖/花青素模式溶液之呈色變化……. 138
圖5-9. 不同乙醇濃度之果糖/花青素模式溶液之呈色變化………. 139
圖5-10. 不同乙醇濃度維生素C/花青素模式溶液之呈色變化…….. 141
圖5-11. 二氧化硫對花青素模式溶液脫色變化之影響…………….. 142



表 次
頁次
表2-1. 葡萄汁、新酒及還原酒之物化特性分析…………………… 35
表2-2. 李子汁、新酒及還原酒之物化特性分析…………………… 36
表4-1. 乙醇濃度對Mv-3-glc模式溶液降解反應速率常數 (k)、半衰期 (T1/2)及活化能 (Ea)之影響…………………………..
118

chapter 1
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chapter 2
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6.Hermosín-Gutiérrez I. 2003. Influence of ethanol content on the extent of copigmentation in a Cencibel young red wine. J Agric Food Chem. 51:4079-4083.
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chapter 3
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5.Gao Y, Cahoon GA. 1995. High performance liquid chromatographic analysis of anthocyanins in the red seedless table grape reliance. Am J Enol Vitic. 46:339-345.
6.Goiffon JP, Mouly PP, Gaydou EM. 1999. Anthocyanic pigment determination in red fruit juices, concentrated juices and syrups using liquid chromatography. Anal Chim Acta. 382:39-50.
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9.Hermosín-Gutiérrez I. 2003. Influence of ethanol content on the extent of copigmentation in a Cencibel young red wine. J Agric Food Chem. 51:4079-4083.
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12.Ribereau-Gayon P, Pontallier P, Glories Y. 1983. Some interpretations of colour changes in young red wines during their conservation anthocyanins, tannins. J Sci Food Agric. 34:506-516.
13.Romero C, Bakker J. 2000a. Effect of storage temperature and pyruvate on kinetics of anthocyanin degradation, vitisin A derivative formation, and color characteristics of model solutions. J Agric Food Chem. 48:2135-2141.
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16.Shen SC, Wu JSB. 2004. Maillard browning in ethanolic solution. J Food Sci. 69:273-279.
17.Shen SC, Tseng KC, Wu JSB. 2006. Studies in kinetics and semi-products of Maillard browning in ethanolic solution. Food Chem. Accepted.
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chapter 4
1.Baranowski ES, Nagel CW. 1983. Kinetics of malvidin-3-glucoside condensation in wine model systems. J Food Sci. 48:419-421,429.
2.Calvi JP, Francis FJ. 1978. Stability of concord grape (V. labursca) anthocyanins in model systems. J Food Sci. 43:1448-1456.
3.Cemeroğlu B, Velioğlu S, Işik S. 1994. Degradation kinetics of anthocyanins in sour cherry juice and concentrate. J Food Sci. 59:1216-1217.
4.Daravingas G, Cain RF. 1968. Thermal degradation of black raspberry anthocyanin pigments in model systems. J Food Sci. 33:138-142.
5.Debicki-Pospišil J, Lovrić T, Trinajstić N, Sabljić A. 1983. Anthocyanin degradation in the presence of furfural and 5-hydroxymethylfurfural. J Food Sci. 48:411-416.
6.Hermosín-Gutiérrez I. 2003. Influence of ethanol content on the extent of copigmentation in a Cencibel young red wine. J Agric Food Chem. 51:4079-4083.
7.Jackman RL, Yada RY, Tung MA, Speers RA. 1987. Anthocyanins as food colorants- A review. J Food Biochem. 11:201-247.
8.Kirca A, Cemeroğlu B. 2003. Degradation kinetics of anthocyanins in blood orange juice and concentrate. Food Chem. 81:583-587.
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10.Maccarone E, Maccarone A, Rapisarda P. 1987. Technical note: Color stabilization of orange fruit juice by tannic acid. Int J Food Sci Technol. 22:153-160.
11.Markakis P, Livingstone GE, Fellers CR. 1957. Quantitative aspects of strawberry pigment degradation. Food Res. 22:117-130.
12.Teh LS, Francis FJ. 1988. Stability of anthocyanins from zebrina pendula and ipomoea tricolor in model beverage. J Food Sci. 53:1580-1581.
13.Tinsley IJ, Bockian AH. 1960. Some effects of sugars on the breakdown of pelargonidin-3-glucoside in model systems at 90 oC. Food Res. 25:161-165.

chapter 5
1.Bronnum-Hansen K, Flink JM. 1985. Anthocyanin colorants from elderberry. III. Storage stability of the freeze dried product. J Food Tech. 20:725-733.
2.Eichner K, Karel M. 1972. The influence of water activity on the sugar-amino browning reaction in model systems under various conditions. J Agric Food Chem. 20:218-223.
3.Garzon GA, Wrolstad RE. 2001. The stability of pelargonidin-based anthocyanins at varying water activity. Food Chem. 75:185-196.
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5.Toribio JL, Lozano JE. 1984. Nonenzymeatic browning in apple juice concentrate during storage. J Food Sci. 49:889-892.