잉어아과에 속하는 묵납자루와 각시붕어의 Carotenoid 색소성분의 비교

백승한(Seung-Han Baek),김수영(Soo-Young Kim),정계임(Kye-Im Geong),권문정(Moon-Jeong Kweon),최옥수(Ok-Soo Choi),김종현(Jong-Hyun Kim),김화선(Hwa-Seon Kim),하봉석(Bong-Seuk Ha) 한국식품영양과학회 1999 한국식품영양과학회지 Vol.28 No.6

어류의 carotenoids에 관한 비교 생화학적 연구의 일환으로서, 우리나라 특산의 담수산 어류인 자연산 묵납자루 및 각시붕어의 표피 carotenoids를 TLC, column chromatography 및 HPLC로 분리하고, NaBH₄에 의한 환원반응, I₂에 의한 이성화반응 및 UV-visible spectrophotometer로 동정하여 비교, 검토한 결과는 다음과 같다. 자연산 묵납자루 표피의 총 carotenoids 함량은 2.11㎎%였으며, carotenoids 조성은 zeaxanthin 42.6%, diatoxanthin 12.1% 및 lutein epoxide 12.1%로 주성분을 이루고 그 외 cynthiaxanthin 10.3%, zeaxanthin epoxide 8.3%, lutein 6.4% 및 α-cryptoxanthin 1.5%의 순으로 함유하였다. 자연산 각시붕어 표피의 총 carotenoids 함량은 산란기에 4.99㎎%, 산란후에 4.17㎎%로서 산란 후 총 carotenoids 함량이 감소하였다. Carotenoids 조성은 산란기에 zeaxanthin 46.7%, diatoxanthin 26.5% 및 lutein 12.3%로 주성분을 이루고, 그 외 zeaxanthin epoxide 6.2%, cynthiaxanthin 3.1%, α-cryptoxanthin 2.9% 및 canthaxanthin 0.7%의 순으로 함유하여 묵납자루와 유사하였으며, 산란후에는 diatoxanthin 30.5%, cynthiaxanthin 21.5% 및 zeaxanthin 16.8%로서 주성분을 이루고, 그 외 α-cryptoxanthin 14.0%, lutein 11.3% 및 canthaxanthin 3.4%의 순으로 함유하여, 산란후에는 산란기에 비하여 zeaxanthin의 함량비가 감소하고, α-cryptoxanthin과 cynthiaxanthin의 함량비가 증가하여 차이가 나타났다. 자연산 묵납자루와 각시붕어의 총 carotenoids 함량은 동일한 잉어 아과의 다른 어종에 비하여 함량이 높았으며, carotenoids 조성은 다른 잉어 아과의 어류와 유사함을 알 수 있었다. Differences in carotenoid composition in the integument of Korean bittering, Cheilognathus signifer and bride bittering, Rhodeus ukekii which are Korean native fresh water fish were compared. Total carotenoid contents in the integument of wild Korean bittering was 2.11㎎% and composed of 42.6% zeaxanthin, 12.1% diatoxanthin and 12.1% lutein epoxide which are predominant carotenoids and 10.3% cynthiaxanthin, 8.3% zeaxanthin epoxide, 6.4% lutein and 1.5% α-cryptoxanthin which are minor carotenoids. Total carotenoid contents in the integument of wild bride bittering was 4.99㎎% during a spawning period but after the spawning period it was decreased to 4.17㎎% and carotenoid composition of bride bittering during the spawning period was 46.7% zeaxanthin, 26.5% diatoxanthin and 12.3% lutein which are predominant carotenoids, and 6.2% zeaxanthin epoxide, 3.1% cynthiaxanthin, 2.9% α-cryptoxanthin and 0.7% canthaxanthin which are minor carotenoids. These results indicated that the carotenoid composition of bride bittering during spawning period was very similar to that of Korean bittering and carotenoid composition of bride bittering after the spawning period was 30.5% diatoxanthin, 21.5% cynthiaxanthin and 16.8% zeaxanthin which are predominant carotenoids and 14.0% α-cryptoxanthin, 11.3% lutein and 3.4% canthaxanthin which are minor carotenoids, indicating that after the spawning period, the content of zeaxanthin was decreased while that of α-cryptoxanthin and cynthiaxanthin was increased as compared to that of the spawning period. Total carotenoid contents in Korean bittering and bride bittering was relatively higher than that in other species of cyprinidae whereas composition of the carotenoid was similar.

칼납자루의 사료 Carotenoids 대사와 체색개선에 미치는 영향

김현영(Hyun-Young Kim),백승한(Seung-Han Baek),김수영(Soo-Young Kim),정계임(Kye-Im Geong),권문정(Moon-Jeong Kweon),김종현(Jong-Hyun Kim),하봉석(Bong-Seuk Ha) 한국식품영양과학회 1999 한국식품영양과학회지 Vol.28 No.5

어류의 carotenoid에 관한 비교 생화학적 연구의 일환으로서 잉어아과에 속하는 칼납자루 표피의 carotenoid 조성을 분석 비교하고, 칼납자루에 대한 사료 carotenoid의 체내 대사와 체색 개선에 미치는 영향을 검토하기 위하여, lutein, cynthiaxanthin 및 astaxanthin을 각각 첨가한 사료로써 4주간 사육한 결과는 다음과 같다. 칼납자루 표피의 carotenoids의 조성비는 자연산에는 zeaxanthin 47.2%, lutein epoxide 11.4%, diatoxanthin 11.0%, lutein 9.7% 및 zeaxanthin epoxide 8.3%가, 2주간 순치후에는 α-cynptoxanthin 29.9%, zeaxanthin 19.3%, lutein epoxide 13.1%, diatoxanthin 12.0% 및 zeaxanthin epoxide 8.8%가 주성분으로 함유하여 칼납자루에는 zeaxanthin, diatoxanthin, lutein epoxide 및 zeaxanthin epoxide의 대사가 활발하다는 것을 알 수 있었다. 칼납자루 표피의 총 carotenoids 함량은 자연산 1.72㎎%, 2주간 순치후 2.08㎎%로 나타났고, 사육 시험 2주후에는 control구 2.10㎎%에 비하여 lutein 첨가구 2.23㎎%, cynthiaxanthin 첨가구 2.36㎎% 및 astaxanthin 첨가구 2.49㎎%로 carotenoid 첨가구에서 모두 높게 나타났으며, 사육 시험 4주후에는 control구 1.76㎎%, lutein 첨가구 1.95㎎%, cynthiaxanthin 첨가구 1.74㎎% 및 astaxanthin 첨가구 1.72㎎%로 감소하여, carotenoids는 신속하게 축적, 그리고 대사된다는 것을 알 수 있었다. 칼납자루 표피에서의 carotenoids 축적률은 astaxanthin 첨가구가 가장 높게 나타나서 체색 선명화 효과가 컸으며, cynthiaxanthin, lutein 첨가구의 순으로 나타났다. 사육 시험후, 각 carotenoid 첨가구의 총 carotenoids 함량과 조성의 변화에 의한 칼납자루 표피에서의 carotenoids 대사 경로는 lutein이 α-doradexanthin(4-ketolutein)과 β-doradexanthin(4-ketozeaxanthin)을 경유하여 astaxanthin으로 변화하는 산화적 대사과정이 있고, 또한, zeaxanthin을 경유하여 zeaxanthin epoxide로 변화되는 산화적 대사과정이 존재한다. cynthiaxanthin은 diatoxanthin과 zeaxanthin으로 변화하는 환원적 대사과정를 경유하여 zeaxanthin epoxide로 변화하는 산화적 대사과정이 있고, 또한, diatoxanthin, zeaxanthin 및 β-doradexanthin을 경유하여 astaxanthin으로 변화하는 산화적 대사과정이 존재한다. 그리고 astaxanthin은 β-doradexanthin과 zeaxanthin으로 변화하는 환원적 대사과정을 경유한 후 zeaxanthin epoxide로 변화하는 산화적 대사과정이 존재한다. 일반적으로 담수어에는 산화적 대사가 주된 대사이나 환원적 대사도 함께 존재함을 알 수 있었다. Effects of dietary carotenoids were investigated on metabolism of the carotenoids, and body pigmentation in oily bittering, Acheilognathus koreensis. Two weeks later after depletion, oily bitterings were fed the diets supplemented with either lutein, cynthiaxanthin and astaxathin for 4 weeks. Carotenoids distributed to and metabolized in integument were analyed. The carotenoid isolated from the integument of wild oily bittering, composed of 47.2% zeaxanthin, 11.4% lutein epoxide, 11.0% diatoxanthin, 9.7% lutein and 8.3% zeaxanthin epoxide. Meanwhile, two weeks later after depletion, the carotenoid composed of 29.9% α-crytoxanthin, 19.3% zeaxanthin, 13.2% lutein epoxide, 12.0% diatoxanthin and 8.8% zeaxanthin epoxide. These indicated that zeaxanthin, diatoxanthin. lutein epoxide and zeaxanthin epoxide were actively metabolized in oily bittering. compared to that of other fresh water fish. Total carotenoid content in the integument of wild oily bittering and oily bittering depleted for two weeks was found to be 1.72㎎% and 2.08㎎%, respectively. Two weeks later after treatment of experimental diet, total carotenoids content was increased to 2.23㎎% in lutein. 2.36㎎% in cynthiaxanthin and 2.49㎎% in astaxanthin supplemented group. which were relatively higher than 2.10㎎% in control group. Meanwhile, 4 weeks later, total carotenoids content was decreased to 1.76㎎% in control, 1.95㎎% in lutein. 1.74㎎% in cynthiaxanthin and 1.72㎎% in astaxanthin supplemented groups. These result indicate that dietary carotenoids were rapidly accumulated and then metabolized to certain metabolites shortly after feeding. Body pigmentation effects of the carotenoids due to accumulation of carotenoids in the integument of oily bittering was the most effectively shown in the astaxanthin supplemented group, followed by cynthiaxanthin and lutein supplemented groups. In the integument of oily bittering, dietary carotenoids were presumably biotransformed via either oxidative or reductive pathways as presumed the variation of total carotenoid content and carotenoid composition in all experimental groups. The lutein was oxidized either to astaxanthin via α-doradexanthin and β-doradexanthin, or to zeaxanthin epoxide via zeaxanthin by oxidative pathway. Cynthiaxanthin was converted either to diatoxanthin and zeaxanthin by reductive pathway and then to zeaxanthin epoxide by oxidative pathway, or it was converted to astaxanthin via diatoxanthin. zeaxanthin and β-doradexanthin by oxidative pathway. Astaxanthin was converted to β-doradexanthin and zeaxanthin by reductive pathway and then to zeaxanthin epoxide by oxidative pathway. These results suggest that, oxidative pathway of carotenoids was major metabolic pathway along with reductive pathway in fresh water fish.

구굴무치과에 속하는 동사리와 얼룩동사리의 Carotenoid 색소성분의 비교

김명선(Moung-Sun Kim),백승한(Seung-Han Baek),김현영(Hyun-Young Kim),김수영(Soo-Young Kim),정계임(Kye-Im Geong),권문정(Moon-Jeong Kweon),하봉석(Bong-Seuk Ha) 한국식품영양과학회 1998 한국식품영양과학회지 Vol.27 No.5

어류의 carotenoid에 관한 비교 생화학적 연구의 일환으로서, 우리나라 특산의 담수어인 구굴무치과의 동사리와 얼룩동사리의 표피 carotenoid를 TLC, column chromatography 및 HPLC로 분리하고 NaBH₄에 의한 환원반응, I₂에 의한 이성화반응 및 uv-visible spectrophotometer로 비교하고 IR, ¹H-NMIR 및 mass spectrum을 측정하여 carotenoid를 동정한 결과는 다음과 같다. 동사리 표피의 총 carotenoids 함량은 4윌산에 3.01㎎%, 9월산에 3.67㎎%로서 산란기에 가까워질수록 높게 나타났고, carotenoid 조성은 4월산에 β-carotene(25.6%), lutein(18.5%), zeaxanthin(12.0%)이 주성분을 이루고, 그 외 isocryptoxanthin, diatoxanthin, tunaxanthin, cynthiaxanthin, canthaxanthin 및 α-cryptoxanthin을 소량 성분으로 함유하였으며, 9월산에는 β-carotene(16.5%), zeaxanthin(13.7%) cynthiaxanthin(13.6%)이 주성분을 이루며, 그 외 lutein, isocryptoxanthin, tunaxanthin, α-cryptoxanthin, diatoxanthin 및 canthaxanthin을 소량 성분으로 함유하여, 산란기에 가까워질수록 cynthiaxanthin과 α-cryptoxanthin의 조성이 증가하는 것을 볼 수 있었다. 얼룩동사리 표피의 총 carotenoids 함량은 4월산에 2.00㎎%, 9월산에 2.84㎎%로서 산란기에 가까워질수록 높게 나타났고, carotenoid 조성은 4월산과 9월산 모두에서 β-carotene(24.9%, 27.5%), zeaxanthin(14.4%, 20.9%), lutein(l2.6%, 11.4%)이 주성분을 이루고, 그 외 cynthiaxanthin, tunaxanthin, diatoxanthin, isocryptoxanthin, α-cryptoxanthin 및 canthaxanthin을 소량 성분으로 함유하여, 산란기에 가까워질수록 zeaxanthin의 조성이 증가하는 것을 볼 수 있었으며, 동사리와 비교하여 서로 다르게 나타났다. 이러한 결과는 같은 구굴무치과이면서도 서식 환경 및 표피 색체의 차이에 기인하는 것으로 보아진다. 그리고 동사리와 얼룩동사리는 다른 담수어에서는 드물게 볼 수 있는 cynthiaxanthin과 diatoxanthin의 함량이 높게 함유하며 해산어 특유의 tunaxanthin도 함유하여 매우 특이하였다. This study was performed as a part of comparative biochemical studies of carotenoid pigment for the fresh water fish. Carotenoids in integument of Korean dark sleeper, Odontobutis platycephala, and dark sleeper, Odontobutis odontobutis interrupta, which are all the Korean native fresh water fish, were separated by thin layer chromatography. column chromatography and HPLC. The separated carotenoid were then reduced and isomerized by NaBH₄ and I₂ respectively to investigate UV-Vis spectrophotometeric patterns and characterized by IR, ¹H-NMR and Mass spectrum. The content of total carotenoids in the integument of Korean dark sleeper was 3.01㎎% in April, but it was increased to 3.74㎎% in September at the near of spawning period. The carotenoid isolated in April consisted of β-carotene(25.6%), lutein(18.5%) and zeaxanthin(12.0%) as major carotenoids and also contained isocryptoxanthin, diatoxanthin, tunaxanthin, cynthiaxanthin, canthaxanthin and α-cryptoxanthin as minor carotenoids. Similarly, in September the carotenoid consisted of β-carotene(16.5%), zeaxanthin(13.7%) and cynthiaxanthin(13.6%) as major carotenoids and also contained lutein, isocryptoxanthin, tunaxanthin, α-cryptoxanthin, diatoxanthin and canthaxanthin as minor carotenoids. At the near of spawning period, the content of cynthiaxanthin and α-cryptoxanthin were increased. The content of total carotenoids in the integument of dark sleeper was 2.00㎎% in April but it was increased to 2.84㎎% in September at the near of spawning period. The carotenoid isolated in April and September consisted of β-carotene(24.9%, 27.5%), zeaxanthin(14.4%, 20.9%) and lutein(l2.6%, 11.4%) as major carotenoids and also contained cynthiaxanthin, tunaxanthin, diatoxanthin, isocryptoxanthin, α-cryptoxanthin and canthaxanthin as minor carotenoids. At the near of spawning period, the content of zeaxanthin was increased, indicating that the carotenoid composition were dependent upon their living conditions and their integument colors. Both Korean dark sleeper and dark sleeper contained high amount of cynthiaxanthin and diatoxanthin which are found as rare carotenoids in the other of fresh water fish. It is interest that they also contained tunaxanthin which is a specific carotenoid in marine fishes.