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5628
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NC093FJU00255002
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輔仁大學
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食品營養學系
舊
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學
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491446091
研
究 林婉清
生
(中)
研
究 Wan Ching, Lin
生
(英)
論
文
以液態層析法測定蝦穀中的類胡蘿蔔素
名
稱
(中)
論
文
Determination of Carotenoids in Shrimp Shells by Liquid Chromatography
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(英)
其
他
題
名
指
導
陳炳輝 陳烱堂
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(中)
指
導
Bing Huei, Chen John Tung, Chien
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(英)
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93
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關
鍵
字
蝦紅素 液態層析 氣相層析 超臨界流體 蝦穀 類胡蘿蔔素
(中)
關
鍵 Astaxanthin HPLC GC SC-CO2 Shrimp shells Carotenoids
字
(英)
蝦殼色素成分主要為蝦紅素及其異構物與酯類衍生物，蝦紅素具有很強的
抗氧化活性，並可能具有預防慢性病例如癌症的效果。傳統萃取類胡蘿蔔
素的方法以溶劑為主，但溶劑會造成環境污染與安全等問題，因此超臨界
流體萃取技術己逐漸取代有機溶劑的使用。本研究目的為發展適當的高效
率液相層析法(HPLC)分析劍蝦殼中的類胡蘿蔔素，配合使用 photodiodearray 偵檢器和化學反應鑑定，並比較超臨界二氧化碳與溶劑萃取蝦殼中類
胡蘿蔔素萃出率的影響。蝦紅素酯類的定性和定量則使用氣相層析配合火
焰離子偵檢器進行分析。 結果顯示，使用 Cosmosil 5C18-AR-II 管柱，配合
(A)甲醇/二氯甲烷/氰甲烷(90:5:5, v/v/v)和(B)水(100 %)的梯度動相系統，起
始比例為 8 % B，92 % A，9.5 分鐘為 4 % B，26 分鐘則為 1 % B，35 分鐘
為 0 % B，維持 25 分鐘，於 61 分鐘回到起始比例，流速為 2 mL/min，偵
測波長 480 nm，可於 60 分鐘內分離出全反式蝦紅素、二種蝦紅素異構
物、五種蝦紅素單酯類和十一種蝦紅素雙酯類。同時評估樣品溶劑二氯甲
摘 烷、甲醇/二氯甲烷(75:25, v/v)以及甲醇/二氯甲烷(50:50, v/v)對劍蝦殼類胡
蘿蔔素之分離效果，結果以甲醇/二氯甲烷(50:50, v/v)最佳。評估氫氧化鉀
與氫氧化鈉進行皂化對蝦紅素及其酯類之影響，結果以 0.05 M 氫氧化鈉
的皂化效果最好。根據滯留時間、吸收光譜與 Q-ratio 值，可暫時鑑定出劍
要 蝦殼中含有(3S,3´S)-trans-astaxanthin、(3S,3´S)-9-cis-astaxanthin、(3S,3´S)-13(中) cis-astaxanthin、(3S,3´S)-trans-astaxanthin monoester、(3S,3´S)-9 or 9´-cisastaxanthin monoester、(3S,3´S)-13 or 13´-cis-astaxanthin monoester、(3S,3´S)trans-astaxanthin diester、(3S,3´S)-9 or 9´-cis- astaxanthin diester、(3S,3´S)- 13 or
13´-cis-astaxanthin diester 等 19 種色素，其中蝦紅素及其異構佔全部色素
13.20 %，蝦紅素單酯類佔 29.42 %，而蝦紅素雙酯類則佔 57.38 %。 以氣相
層析配合火焰離子偵測器，起始溫度為 150℃，維持 1 分鐘，以每分鐘升
溫 3℃，升至 180℃，再以每分鐘升溫 1℃，上升至 215℃，最後以每分鐘
5℃升溫至 240℃，維持 10 分鐘，可分離和鑑定出劍蝦殼之蝦紅素雙酯類
中含有 12 種脂肪酸，其中以 C16:0 與 C18:1 含量最多；而蝦紅素單酯類則
含有 10 種脂肪酸，其中以 C20:0 含量為最多。 使用超臨界二氧化碳萃取
劍蝦殼中的類胡蘿蔔素，以 45℃和 400 bar 萃取(3S,3´S)-trans-astaxanthin、
蝦紅素單酯類與蝦紅素雙酯類之萃出量為最高，而(3S,3´S)-9-cis-astaxanthin
與(3S,3´S)-13-cis-astaxanthin 之萃出量，則以 75℃和 400 bar 為最佳。添加
10 %乙醇修飾劑會較未添加萃出更多的蝦紅素及其異構物與蝦紅素單酯
類。使用溶劑可萃出較高量的(3S,3´S)-trans-astaxanthin、蝦紅素單酯類與蝦
紅素雙酯類，而超臨界二氧化碳則可萃取較高量的 (3S,3´S)-9-cis-astaxanthin
和(3S,3´S)-13-cis-astaxanthin。
摘 The major pigments in shrimp shells are composed of astaxanthin and its cis isomers
要 as well as esters. Astaxanthin has been reported to possess strong antioxidant
(英) activity and may prevent chronic diseases such as cancer. The traditional method for
extraction of carotenoids is often carried out by using solvent, but solvent extraction
method can create environmental pollution and safety problems. Thus, supercritical
fluid extraction was used more often instead of solvent extraction in recent years.
The objectives of this study were to develop an HPLC method for analysis of
carotenoids in shrimp shells (Parapenaeopsis hardwickii). Identification of
carotenoids was carried out by using a photodidode-array detector for spectrum
analysis and chemical reaction, and compares the extraction efficiency of
carotenoids by supercritical carbon dioxide and solvents. Astaxanthin esters were
analyzed by using GC-FID. Results showed that most appropriate HPLC method
was accomplished by employing a Cosmosil 5C18-AR-II column and a mobile
phase of methanol-dichloromethane-acetonitrile (90:5:5, v/v/v) (A) and water
(100%) (B) with the following gradient elution: 92 % A and 8 % B in the beginning,
decreased to 4 % B in 9.5 min, 1 % B in 26 min, 0 % B in 35 min, maintained for
25 min, and returned to 92 % A and 8 % B in 61 min. All-trans astaxanthin and its
two cis isomers, as well as five astaxanthin monoesters and eleven diesters were
resolved within 60 min with flow rate at 2 mL/min and detection at 480 nm. By
comparing the effect of sample solvents, dichloromethane (100 %), methanoldichloromethane (75:25, v/v) and methanol-dichloromethane (50:50, v/v), on the
separation efficiency of carotenoids in shrimp shells, methanol-dichloromethane
(50:50, v/v) showed the best result. Using 0.05 M NaOH for saponification was
shown to result in better efficiency than KOH. Spear shrimp shell was found to
contain 19 carotenoids, including (3S, 3´S)-trans-astaxanthin, (3S, 3´S)-9-cisastaxanthin, (3S, 3´S)-13-cis- astaxanthin, (3S, 3´S)-trans-astaxanthin monoester,
(3S,3´S)-9 or 9´-cis-astaxanthin monoester, (3S, 3´S)-13 or 13´-cis-astaxanthin
monoester, (3S,3´S)-trans-astaxanthin diester, (3S, 3´S)-9 or 9´-cis- astaxanthin
diester, (3S, 3´S)- 13 or 13´-cis-astaxanthin diester. The cis isomers of astaxanthin
were tentatively identified based on retention time, absorption spectra, and Q-ratios.
The shrimp shell was composed of astaxanthin and its cis isomers (13.20 %),
astaxanthin monoester (29.42 %) and diester (57.38 %). Based on the analysis of
GC-FID, the temperature programming condition was isothermal for 1 min at
150℃, increased to 180℃at a rate of 3℃/min, 215℃at a rate of 1℃/min, 240℃ at
a rate of 5℃/min and maintained for 10 min. Astaxanthin diesters were found to
contain 12 fatty acids, of which palmitic acid and stearic acid constituted a large
portion, whereas astaxanthin monoesters were found to contain 10 fatty acids, with
arachidonic acid dominated. The SC-CO2 extraction of carotenoids from shrimp
shell, resulted in a higher yield of (3S, 3´S)-trans-astaxanthin, astaxanthin
monoesters and diesters under the condition of 45℃ and 400 bar. The highest yield
of (3S, 3´S)-9-cis-astaxanthin and (3S, 3´S)-13-cis-astaxanthin was shown when
extracted at 75℃ and 400 bar. SC-CO2 extraction in combination with 10 %
cosolvent ethanol could result in a higher yield of astaxanthin, and its cis isomers as
well as astaxanthin monoester than without cosolvent ethanol. However, solvent
extraction could generate higher content of (3S, 3´S)-trans-astaxanthin, astaxanthin
monoester and diester, while SC-CO2 extraction could produce greater level of (3S,
3´S)-9-cis-astaxanthin and (3S, 3´S)-13-cis-astaxanthin.
論
文
目
次
第一章 緒言……………………………………………………………..1 第二
章 文獻回顧………………………………………………………..3 一、類胡
蘿蔔素的分類…………………………………………3 二、蝦紅素的特性與
應用………………………………………3 三、蝦紅素的生理活
性………………………………………....9 (一)抗氧化
性………………………………………………...9 (二)光保護
劑…………………………………………….....13 (三)預防眼睛之疾
病……………………………………….13 (四)預防皮膚
癌…………………………………………….15 (五)蝦紅素與心臟之健
康………………………………….15 (六)蝦紅素與細胞之健
康………………………………….16 (七)預防癌
症……………………………………………….18 (八)預防發
炎……………………………………………….18 (九)蝦紅素對肝臟與解毒的
功能………………………….19 (十)免疫反
應……………………………………………….19 (十一)蝦紅素和神經退化疾
病…………………………….20 四、超臨界流體技
術…………………………………………..20 (一)超臨界流體的定義與性
質…………………………….20 (二)超臨界二氧化碳流體之特
性………………………….23 (三)修飾劑的效
應………………………………………….26 五、蝦殼中類胡蘿蔔素之萃
取………………………………..28 (一)油萃取
法……………………………………………….28 (二)Carotenoprotein 的萃
取………………………………..28 (三)有機溶劑萃取
法……………………………………….30 (四)超臨界流體萃
取………………………………….........30 六、類胡蘿蔔素之分
離………………………………………..30 (一)薄層色層分析
法……………………………………….30 (二)管柱色層分析
法……………………………………….33 (三)高效能液相層析
法…………………………………….33 (四)氣相層析
法…………………………………………….36 七、類胡蘿蔔素之定
性………………………………………..36 (一)蝦紅素及異構物的鑑
定………………………………...36 (二)蝦紅素酯類的鑑
定……………………………………...40 1.皂化反
應……………………………………………….40 2.還原反
應……………………………………………….43 3.乙醯化反
應…………………………………………….43 八、類胡蘿蔔素之定
量………………………………………..43 第三章 材料與方
法……………………………………………………45 一、研究架
構……………………………………………..........45 二、試驗材
料……………………………………………..........45 (一)原
料………………………………………………...........45 (二)化學藥
品…………………………………………...........45 (三)儀器設
備…………………………………………...........48 三、實驗方法與結果分
析………………………………..........51 (一)類胡蘿蔔素分析方法之評估與改
良…………………...51 1.管柱種類之評
估……………………………………….51 2.溶劑系統的發
展……………………………………….51 (二)溶劑與超臨界萃取對蝦殼中類
胡蘿蔔素萃出率之比
較…………………………………………………............52 1.以溶劑萃取蝦殼
之類胡蘿蔔素……………………….53 2.以超臨界二氧化碳萃取蝦殼之類胡
蘿蔔素………….53 (三)萃取回收率之測
定……………………………………...53 (四)波峰純度之測
定………………………………………...56 (五)蝦紅素及其異構物之鑑
定……………………………...56 1.以光照進行蝦紅素的異構化作
用…………………….56 2.蝦紅素之鑑定方
法…………………………………….56 3.蝦紅素異構物的鑑
定………………………………….57 (六)蝦紅素酯類之鑑
定……………………………………...57 1.皂化反
應……………………………………………….57 2.蝦紅素單酯類與雙酯類之
分離……………………….58 3.甲基酯化作
用………………………………………….58 4.GC-FID 分析脂肪酸之條
件…………………………...59 5.脂肪酸之鑑
定………………………………………….59 6.脂肪酸含量的測
定…………………………………….59 (七)標準曲線製
作…………………………………………...60 1.標準溶液配
置………………………………………….60 2.標準曲線繪
製………………………………………….60 (八)蝦紅素及其異構物與衍生物
的定量…………………...60 (九)結果分
析………………………………………………...61 第四章 結果與討
論……………………………………………............62 一、HPLC 分析蝦殼中
類胡蘿蔔素方法之評估與改良……...62 (一)管柱種類之評
估…………………………………...........62 (二)動相系統之發
展…………………………………...........65 1.動相等比系
統…………………………………………68 (1)甲醇與二氯甲烷之動相系
統……………………….68 (2)甲醇與異丙醇之動相系
統………………………….70 (3)甲醇與水之動相系
統……………………………….70 (4)甲醇、二氯甲烷、氰甲烷與水之動相
系統……….70 2.動相梯度系統…………………………………………70 (三)
樣品溶劑之評估…………………………………...........72 (四)蝦殼波峰成分
之鑑定…………………………………...75 二、蝦殼中脂肪酸種類之鑑定與
含量分析…………………..95 三、以溶劑和超臨界二氧化碳萃取蝦殼中類
胡蘿蔔素之萃出率比
較………………………………………………………..99 (一)分析方法精密
度檢定…………………………………...99 (二)濃度對積分面積校正曲線的
製作…………………….100 (三)偵測極限和定量極
限………………………………….100 (四)回收
率………………………………………………….102 (五)超臨界流體萃取對
蝦紅素及其異構物與衍生物萃出率之影
響…………………………………………………….104 (六)溶劑與超臨界萃
取對蝦紅素及其異構物與衍生物萃出率之影
響…………………………………………………..113 (七)劍蝦殼的色素含
量…………………………………….116 第五章 結
論…………………………………………………………..118 參考文
獻………………………………………………………………120
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