Back to HOME

Carotenoid


DATA No : VCA0018 INFORMANT : Masayoshi Ito

NAME : (3R,3'S)-3,3'-Dihydroxy-b,b-carotene-4,4'-dione

COMMON NAME: meso-Astaxanthin/ (3R,3'S)-Astaxanthin
SYMBOL:
FORMULA: C40H52O4 MOL.WT (average) : 596.838


Download ChemDraw structure data
BIOLOGICAL ACTIVITY
Antioxidant activity (Ref. 0092/0093/0215)
Singlet oxygen quenching activity (Ref. 0088/0230/0441)
Immunomodulating action (Ref. 0213)
Chemoprevention of carcinogenesis (Ref. 0218/0219)
PHYSICAL AND CHEMICAL PROPERTIES
MELTING POINT:222-223degC (Ref. 0077)

BOILING POINT:

REFRACTIVE INDEX:

OPTICAL ROTATION:

DENSITY:

SOLUBILITY:
SPECTRAL DATA
UV SPECTRA:lmax (nm) (e): CHCl3 300 (17634), 490 (116386) (Ref. 0010/0077); hexane 294 (16946), 471 (126163) (Ref. 0077); benzene 485 (112876) (Ref. 0077); ethanol 250 (14002), 297 (15578), 471 (116570) (Ref. 0077)

IR SPECTRA:nmax(KBr)/cm-1: 3486m (OH), 1664s (conj. CO), 1607m, 1557s (C=C), 1399w, 1390m, 1366w (gem. Dimetyl), 1076s, 1039m (OH) and 969s (CH=CH, trans)
[Spectrum 0003] (Ref. 0010/0077)

NMR SPECTRA:1H-NMR d(500 MHz, CDCl3): 1.21 and 1.32 (each 6H, s, 1, 1'-gem-Me), 1.81 (2H, t, J 13, 2, 2'-Hax), 1.94 (6H, s, 5, 5'-Me), 1.98 and 2.00 (each 6H, s, 9, 9', 13, 13'-Me), 2.16 (2H, dd, J 6 and 13, 2, 2'-Heq), 3.67 (2H, d, J 2, 3, 3'-OH), 4.32 (2H, ddd, J 2, 6 and13, 3, 3'-H) and 6.20-6.70 (14H, m, olefinic-H) (Ref. 0068/0077)

MASS SPECTRA:m/z: 596 (M), (M-16), (M-16-16), (M-79), (M-92), (M-106), (M-92-16), (M-106-16), (M-154), (M-167), (M-207), (M-219), (M-233) (Ref. 0058/0077)

OTHER SPECTRA:CD data in EPA solution (25degC): no optical activity (Ref. 0421)
CHROMATOGRAM DATA
TLC (Kieselgel 60 Merck, CH2Cl2-acetone-formic acid 95:5:3) Rf = 0.3 --- (3S,3'S)-astaxanthin (Ref. 0010)
HPLC (column: Sumipax OA-2000 (10mm) 0.4times25 cm, eluent: hexane-CH2Cl2-EtOH 48:16:0.6, flow: 0.8 ml/min) tR = ca. 57 min (3R,3'R), ca. 60 min (meso), ca. 64 min (3S,3'S)
[Chromatogram 0004] (Ref. 0032/0069/0070/0210)
HPLC (column: LiChrosorb SI 60 (5 mm) 0.32times50 cm, eluent: hexane-ethyl acetate-acetonitrile 88:10:2, flow: 0.8 ml/min) tR = ca. 42 min (diacetate of all-E isomer)
[Chromatogram 0005] --- racemic astaxanthin (Ref. 0071)
HPLC (columun: TSK gel ODS-80Ts (Tosoh) 0.46times15 cm, eluent and flow: 1.0 ml/min, H2O-MeOH 5:95 for 5 min, follwed by 5 min-linear gradient MeOH-THF 7:3, and then MeOH-THF 7:3 for 5 min) b-carotene, echinenone, b-cryptoxanthin, 3-hydroxy-echinenone, cantaxanthin, 3'-hydroxy-echinenone, cis-adonixanthin, adonirubin, adonixanthin and astaxanthin were separated. tR = 6.30 min for astaxanthin (Ref. 0208).
Separation of (3S,3'S), (3S,3'R) and (3R,3'R) astaxanthin by HPLC on a Pirkle covalent L-leucine column (Ref. 1164).
SOURCE
Homarus gammarus (Lobster) (Ref. 0418)
Salmo salar, Oncorhynchus (salmon) (Ref. 0419)
Asterias rubens (starfish) (Ref. 0420)
Shrimps and lobsters (Ref. 0421)
Euphausia superba (antarctic krill) (Ref. 0422)
Asterina pectinifera, Asterias amurensis (starfish) (Ref. 0423)
Watasenia scintilans, Sepia modokai, Sepia officinales (cuttlefish) (Ref. 0424)
Octopus vulgaris, Octopus ocellatus, Octopus minor (octopus) (Ref. 0424)
CHEMICAL SYNTHESIS
The Wittig condensation of (R)-apoastaxanthinal (C25) with (S)-C15-phosphonium chloride in 1,2-epoxybutane provided meso-astaxanthin in 50-55% yield. (Ref. 0077)
METABOLISM

GENETIC INFORMATION

NOTE
Almost the same stereochemical composition in astaxanthin, its monoester and its diester in krill are found: 62-71% (3R,3'R)-, 11-14% (3R,3'S; meso)- and 17-26% (3S,3'S)-astaxanthin (Ref. 0422). Those in Euphausia, Thysanoessa, Calanus, Acanthephyra and Cancer (Crustaceans) are also reported (Ref. 1257).
Semi-empirical molecular orbital calculations using AM1 Hamiltonian (MNDO-AM1 method) were performed in order to predict their stable structures (Ref. 1337).
REFERENCES
[0010]
AUTHOR:Widmer,E., Zell,R., Lukác,T., Casadei,M.,S chönholzer,P., and Broger,E.A.
TITLE:Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus Oxo-isophoron. I. Modifizierung der Kienzle-Mayer-Synthese von (3S,3'S)-Astaxanthin
JOURNAL:Helv. Chim. Acta
VOL:64 PAGE : 2405 -2418 (1981)
[TOP]

[0032]
AUTHOR:Matsuno,T.
TITLE:Structure and Characterization of Carotenoids from Various Habitats and Natural Sources
JOURNAL:Methods Enzymol.
VOL:213 PAGE : 22 -31 (1992)
[TOP]

[0058]
AUTHOR:Bjfrnland,T. and Aguilar-Martinez,M.
TITLE:Carotenoids in red algae
JOURNAL:Phytochemistry
VOL:15 PAGE : 291 -296 (1976)
[TOP]

[0068]
AUTHOR:Yokoyama, A., Izumida, H., and Miki, W.
TITLE:Production of Astaxanthin and 4-Ketozeaxanthin by the Marine Bacterium, Agrobacterium aurantiacum
JOURNAL:Biosci. Biotechnol. Biochem.
VOL:58 PAGE : 1842 -1844 (1994)
[TOP]

[0069]
AUTHOR:Pfander,H., and Riesen,R. (1995) Carotenoids Volume 1A: Isolation and Analysis Chapter 6: Chromatography: Part IV High-Performance Liquid Chromatography (Britton,G.,Liaaen-Jensen,S., and Pfander,H., eds), pp145-190, Birkhäuser Verlag,Basel,Boston,Berlin
TITLE:
JOURNAL:
VOL: PAGE : - ()
[TOP]

[0070]
AUTHOR:Maoka,T.,Komori,T., and Matsuno,T.
TITLE:Direct diastereomeric resolution of carotenoids I. 3-Hydroxy-4-oxo-b-end group
JOURNAL:J. Chromatogr.
VOL:318 PAGE : 122 -124 (1985)
[TOP]

[0071]
AUTHOR:Englert,G., and Vecchi,M.
TITLE:trans/cis Isomerization of Astaxanthin Diacetate/Isolation by HPLC and Identification by 1H-NMR Spectroscopy of Three Mono-cis- and Six Di-cis-Isomers
JOURNAL:Helv. Chim. Acta
VOL:63 PAGE : 1711 -1718 (1980)
[TOP]

[0077]
AUTHOR:Bernhard,K.,Englert,G.,Mayer,H.,Müller,R.K.,Rüttimann,A.,Vecchi,M.,Widmer,E., and Zell,R.
TITLE:Synthese von optisch aktiven, natürlichen Carotenoiden und strukturell verwandten Naturprodukten IX. Synthese von (3R)-Hydroxyechinenon, (3R,3'R)- und (3R,3'S)-Adnixanthin, (3R)-Adonirubin, deren optischen Antipoden und verwandten Verbindungen
JOURNAL:Helv. Chim. Acta
VOL:64 PAGE : 2469 -2484 (1981)
[TOP]

[0088]
AUTHOR:Di Mascio, P., Kaiser, S., and Sies, H.
TITLE:Lycopene as the most efficient biological carotenoid singlet oxygen quencher PubMed ID:2802626
JOURNAL:Arch Biochem Biophys.
VOL:274 PAGE : 532-538 (1989)
[TOP]

[0092]
AUTHOR:Lim, B. P., Nagao, A., Terao, J., Tanaka, K., Suzuki, T., and Takama, K.
TITLE:Antioxidant activity of xanthophylls on peroxyl radical-mediated phospholipid peroxidation PubMed ID:1627620
JOURNAL:Biochim Biophys Acta.
VOL:1126 PAGE : 178-184 (1992)
[TOP]

[0093]
AUTHOR:Terao, J.
TITLE:Antioxidant activity of beta-carotene-related carotenoids in solution PubMed ID:2779372
JOURNAL:Lipids.
VOL:24 PAGE : 659-661 (1989)
[TOP]

[0208]
AUTHOR:Yokoyama, A., and Miki, W.
TITLE:Composition and Presumed Biosynthetic Pathway of Carotenoids in the Astaxanthin-Producing Bacterium Agrobacterium aurantiacum
JOURNAL:FEMS Microbiol. Lett.
VOL:128 PAGE : 139 -144 (1995)
[TOP]

[0213]
AUTHOR:Jyonouchi, H., Zhang, L., and Tomita, Y.
TITLE:Studies of immunomodulating actions of carotenoids. II. Astaxanthin enhances in vitro antibody production to T-dependent antigens without facilitating polyclonal B-cell activation PubMed ID:8346076
JOURNAL:Nutr Cancer.
VOL:19 PAGE : 269-280 (1993)
[TOP]

[0215]
AUTHOR:Miki,W.
TITLE:Biological Functions and Activities of Animal Carotenoids
JOURNAL:Pure Appl. Chem.
VOL:63 PAGE : 141 -146 (1991)
[TOP]

[0218]
AUTHOR:Tanaka, T., Morishita, Y., Suzui, M., Kojima, T., Okumura, A., and Mori, H.
TITLE:Chemoprevention of mouse urinary bladder carcinogenesis by the naturally occurring carotenoid astaxanthin PubMed ID:8293542
JOURNAL:Carcinogenesis.
VOL:15 PAGE : 15-19 (1994)
[TOP]

[0219]
AUTHOR:Tanaka, T., Makita, H., Ohnishi, M., Mori, H., Satoh, K., and Hara, A.
TITLE:Chemoprevention of rat oral carcinogenesis by naturally occurring xanthophylls, astaxanthin and canthaxanthin PubMed ID:7664280
JOURNAL:Cancer Res.
VOL:55 PAGE : 4059-4064 (1995)
[TOP]

[0230]
AUTHOR:Shimidzu,N.,Goto,M., and Miki,W.
TITLE:Carotenooids as Singlet Oxygen Quenchers in Marine Organisms.
JOURNAL:Fisheries Sci.
VOL:62 PAGE : 134 -137 (1996)
[TOP]

[0418]
AUTHOR:Rønneberg,H.,Renstrom,B.,Aareskjold,K.,Liaaen-Jensen,S.,Veechi,M.,Leuenberger,F.J.,Müller,R.K., and Mayer,H.
TITLE:Natural occurrence of enatiomeric and meso-astaxanthin 1. Ex Lobster Eggs (Homarus gammarus)
JOURNAL:Helv. Chim. Acta
VOL:63 PAGE : 711 -715 (1980)
[TOP]

[0419]
AUTHOR:Schiedt,K.,Leuenberger,F.J., and Vecchi,M.
TITLE:Natural Occurrences of enantiomeric and meso-astaxanthin 5, Ex Wild salmon (Salmo salar and Oncorynchus)
JOURNAL:Helv. Chim. Acta
VOL:64 PAGE : 449 -457 (1981)
[TOP]

[0420]
AUTHOR:Bernhard,K.,Englert,G.,Meister,W.Vecchi,M.,Renstrom,B., and Liaaen-Jensen,S.
TITLE:Carotenoids of the carotenoprotein asteriarubin. Optical purity of asterinic acid
JOURNAL:Helv. Chim. Acta
VOL:65 PAGE : 2224 -2229 (1982)
[TOP]

[0421]
AUTHOR:Matsuno,T.,Maoka,T.,Katsuyama, M.,Ookubo,M.,Katagiri,K., and Jimura,H.
TITLE:The occurence of enantiomeric and meso-astaxanthin in aquatic animals
JOURNAL:Bull. Jap. Soc. Sci. Fish.
VOL:50 PAGE : 1589 -1592 (1984)
[TOP]

[0422]
AUTHOR:Maoka,T.,Katsuyama,M.,Kaneko,N., and Matsuno,T.
TITLE:Stereochemical investigation of the carotenoids in the antarctic krill Euphausia superba
JOURNAL:Bull. Jap. Soc. Sci. Fish.
VOL:51 PAGE : 1671 -1673 (1985)
[TOP]

[0423]
AUTHOR:Maoka,T.,Tsushima,M., and Matsuno,T.
TITLE:New acetylenic carotenoids from the starfishes Asterina pectinifera and Asterias amurensis
JOURNAL:Comp. Biochem. Physiol.
VOL:93 PAGE : 829 -834 (1989)
[TOP]

[0424]
AUTHOR:Maoka,T.,Yokoi,S., and Matsuno,T.
TITLE:Comparative biochemical studies of carotenoids in nine species of cephalopoda
JOURNAL:Comp. Biochem. Physiol.
VOL:92 PAGE : 247 -250 (1989)
[TOP]

[0441]
AUTHOR:Hirayama, O., Nakamura, K., Hamada, S., and Kobayasi, Y.
TITLE:Singlet oxygen quenching ability of naturally occurring carotenoids PubMed ID:8152349
JOURNAL:Lipids.
VOL:29 PAGE : 149-150 (1994)
[TOP]

[1164]
AUTHOR:Turujman, S.A.
TITLE:Rapid direct resolution of the stereoisomers of all-trans astaxanthin on a Pirkle covalent L-leucine column
JOURNAL:J. Chromatogr.
VOL:631 PAGE : 197 -199 (1993)
[TOP]

[1257]
AUTHOR:Foss, P., Renstrøn, B., Liaaen-Jensen, S.
TITLE:Natural occurrence of enantiomeric and meso astasanthin: 7. Crustaceans including zooplankton
JOURNAL:Comp. Biochem. Physiol. B
VOL:86 PAGE : 313 -314 (1987)
[TOP]

[1337]
AUTHOR:Hashimoto, H., Yoda, T., Kobayashi, T., Young, A.J.
TITLE:Molecular structures of carotenoids as predicted by MNDO-AM1 molecular orbital calculations
JOURNAL:J. Mol. Struct.
VOL:604 PAGE : 125 -146 (2002)
[TOP]

Last updated June 19, 2007. Copyright © 1989-2007 Japanese Conference on the Biochemistry of Lipids (JCBL). All rights reserved.