臺灣博碩士論文加值系統

花青素為自然界植物中色彩鮮豔的色素之一，維生素 C 是果汁中普遍存在的營養成分，但花青素在維生素C存在下，容易產生無色化合物而失去原有色澤，使其原本鮮豔的紅色褪色。為維持花青素顏色的穩定，本研究以洛神葵為材料，於高濃度的維生素C (500 ppm)下，分別就 pH 2與pH 3模擬系統中，探討添加不同的酚類物質(阿魏酸、沒食子酸、兒茶素、漂木酸、咖啡酸)，以形成花青素-酚類複合物達到共色作用之最適條件( pH值、濃度)。分析項目包括共色測定(增色效應、波長偏移及共色量)，顏色品質（色澤密度、花青素裂解指數及L a b值）、花青素型態（共色花青素百分比copigmented ACN %、單體花青素monomeric ACN %及聚合體花青素polymeric ACN %）、花青素與維生素C保留率，以及抗氧化能力（DPPH清除百分比、FRAP還原力）。另外則選取上述共色條件之酚酸，分別就維生素C、二氧化硫及溫度探討形成共色後，對花青素複合物穩定性之影響。期望花青素經由與這些酚類物質的共色作用，可延緩花青素受維生素C破壞褪色的情形，有助於提升花青素與維生素C共存時之穩定性。
結果顯示，上述五種酚酸之添加，皆可使洛神花青素產生共色作用，包含了最大吸光值增加的增色效應(hyperchromic effect)，及最大吸收波長右移之波長偏移(bathochromic shift)二大現象。在波長偏移方面，以阿魏酸的波長右移最大，其次為漂木酸；在增色效應方面，以兒茶素 與咖啡酸效果最強，所有樣品與控制組比較，隨著酚酸莫耳濃度比例的增加，最大吸光值及共色強度增加的情形愈明顯，以pH 3者增色的效果較pH 2好，波長位移則pH 3與pH 2結果相似。隨著添加酚類化合物莫耳比例的增加，可降低花青素裂解指數( DI值)，提升a值與色澤密度，以漂木酸者效果最明顯。在花青素型態方面，添加酚酸後會使花青素單體下降，聚合體及共色花青素百分比上升。進一步分析花青素保留率發現，與酚酸共色可使花青素對溫度、維生素C及二氧化硫的穩定性有增加的趨勢，在抗氧化力方面也有相似的情形。
綜合上述顯示，與酚類化合物共色不僅減緩花青素與維生素C共存
時顏色的褪色，對於抗氧化力也有明顯的提升。

Anthocyanins are one of the bright pigments in nature; vitamin C is a common nutritional composition in juices. Howerever, when anthocyanin and vitamin C coexist, it usually leads to the formation of colorless product and degradation of anthocyanin. In order to keep the color stability of anthocyanin, Roselle was targeted in this research. The objective was aimed to study the optimum condition (pH and molar ratio) for the copigment formation through five kinds of phenolic compounds (ferulic acid, gallic acid, catechin, chlorogenic acid, and caffeic acid) addition in two model systems (pH 2 and pH 3) with 500 ppm vitamin C. A model system was used to investigate the change of color quality, patterns of anthocyanin, retention percentage of anthocyanin and vitamin C, and antioxidant capacity. In addition, the heating treatments, vitamin C and SO2 stability of the copigment, were investigated. It is anticipated that the copigmentation between anthocyanin and phenolic compounds may delay the anthocyanin degradation and improve its stability when coexisted with vitamin C.
Result showed that all the phenolic compounds favor the copigment formation, in both hyperchromic effect and bathochromic shift. Ferulic acid showed the greatest effect on bathochromic shift, followed by chlorogenic


acid. Catechin and caffeic acid are strongest on hyperchromic effect. Both hyperchromic effect and bathochromic shift increased with increasing molar ratio of phenolic compounds present. As in copigmentation effect at different pH values; in hyperchromic effect, the result of pH 3 was better than that of pH 2; in the bathochromic shift, no significant difference was detected between pH 2 and pH 3. The higher the ratio of phenolic compounds, the lower DI value and monomeric anthocyanin appeared. Color density, Hunter a value, polymeric and copigmented anthocyanin also increased with higher contents of phenolic compounds. Further analysis revealed that copigmentation between anthocyanin and phenolic compounds may increase the anthocyanin stability against heat and sulfide, which leads to a better antioxidant capacity. In conclusion, the copigmentation may significantly decrease the anthocyanin degration by vitamin C and increase the antioxidant capacity of the system.

Key words：anthocyanin, copigmentation, vitamin C, antioxidant capacity

目錄
頁次
中文摘要…………………………………………………………………..…Ι
英文摘要…………………………………………………………………… Ⅲ
目錄………………………………………………………………………….Ⅴ
圖索引……………………………………………………………………….Ⅷ
表索引……………………………………………………………………….Ⅹ
第一章 前言………………………………………………………………….1
第二章 文獻回顧………………………………………………………...…3
2.1 花青素介紹………………………………………………………3 2.2 花青素基本結構與特性………………………………………………3
2.3 醯化花青素……………………………………………………………... 6
2.4 口比喃花青素…………………………………………………………....6
2.5 影響花青素穩定因子…………………………………………………………8
2.5.1 溫度…………………………………………………………….…....8
2.5.2 pH值…………………………………………………………..……9
2.5.3 糖類………………………………………………………………… 9
2.5.4 氧氣與線……………………………………………………...…..11
2.5.5 維生素C……………………………………………………………14
2.5.6 金屬離子…………………………………………………………...15
2.6 共色作用介紹…………………………………………………………..15
2.6-1 共色作用的種類與機制…………………………………………...15
2.6-2 參與共色反應的物質與共呈色的特性……………………...……18
2.6-3 穩定花青素顏色與共色作用的相關例子…………...……………19
2.7 多酚類化合物介紹……………………………………………………..19
2.8 花青素等酚類相關之生理活性研究變化………………….……….…20
2.8.1 抗氧化能力之評估…………………………………………………………20
2.8.2 抗發炎之相關研究………………………………………………….…21
2.8.3 預防心血管疾病之相關研究………………………………………21
第三章 材料與方法………………………………………………………...23
3.1 試驗材料………………………………………………………………23
3.2 化學試藥………………………………………………………………23
3.3 試驗儀器………………………………………………………………24
3.4試驗設計……………………………………………………………….24
3.4.1 洛神花青素在高維生素C下形成共色之最適條件探討…………24
3.4.2 形成共色複合物後在洛神花青素模擬系統中對花青素顏色品質、
聚合型態及抗氧化力響…………………………………………………...25
3.4.3.共色複合物在不同時間、維生素C、溫度以及二氧化硫濃度
下穩定性探討………………………………………….…………25
3.5 試驗方法………………………………………………………………30
3.5.1 洛神葵花青素粉末之製備…………………………………….…30
3.5.2 共色(copigmentation)測定……………………………………….30
3.5.3.共色強度(copigment intensity)的測定……………………………30
3.6顏色品質測定……………………………………………………….…30
3.6.1色澤密度（color density）…………………………………………30
3.6.2花青素裂解指數測定（degradation Index，簡稱DI）…………31
3.6.3 L a b值的測定…………………………………………………….31
3.7 花青素型態測定………………………………………………………31
3.8高效能液相層析儀分析維生素C殘存率……………………………31
3.9高效能液相層析儀分析花青素殘存率……………………………….32
3.10抗氧化能力分析………………………………………...……………32
3.10.1 DPPH清除百分比測定………………………………………….33
3.10.2 FRAP還原力測定…………………………………………….…33
3.11 活化能測定…………………………………………………………..33
3.12 統計分析…………………………………………………………..…34
第四章 結果與討論……………………………………………………….35
4.1 花青素在高維生素C下與酚類化合物形成共色作用之探討………35
4.1.1 形成共色之最適pH值…………………………………………...36
4.1.2 形成共色之最適莫耳比…………………………………………..38
4.1.3 不同種類酚類化合物形成共色之比較…………………………..40
4.2共色對顏色品質的影響…………………………………………….…42
4.3共色對花青素顏色品質相關性分析……………………………….....44
4.4共色對花青素形態的影響…………………………………………….45
4.5 共色對抗氧化力的影響………………………………………………47
4.5.1還原力…………………………………………………………..…48
4.5.2 DPPH自由基清除能力…………………………………………...51
4. 6共色對抗氧化力相關性分析…………………………………………52
4.7 花青素與不同酚類化合物共色作用之主成分分析…………………53
4.8 新色素複合物的發現…………………………………………………53
4.9 共色對花青素穩定性影響……………………………………………54
4.9.1 最大吸收波長與最大吸光值…………………………………….54
4.9.2共色作用對顏色品質穩定性的影響……………………………..55
4.9.3對花青素殘存率的影響…………………………………………..56
4.10 共色作用對維生素C殘存率的影響……………………………….58
4.11 熱穩定性試驗………………………………………………………..59
4.11.1耐熱性試驗………………………………………………………59
4.11.2花青素降解熱動力學……………………………………………60
4.12. 與漂木酸共色複合物在不同維生素C濃度下穩定性…………….61
4.12.1 顏色品質的穩定性………………………………………………...62
4.12.1.1 外觀顏色的變化…………………………………………...….62
4.12.1.2 吸光值的變化……………………………………………...….63
4.12.1.3 褐變指數(DI值)的變化……………………………………….64
4.12.1.4花青素殘存率的影響……………………………………….…64
4.13對不同二氧化硫濃度的穩定性…………………………………...…64
4.13共色對花青素穩定性分析…………………………………………...65
第五章 結論……………………………………………………………...106
第六章 參考文獻…………………………………………………………108

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