Carotenoid DATA No : VCA0002 INFORMANT : Masayoshi Ito NAME : (3S,3'S)-3,3'-Dihydroxy-,-carotene-4,4'-dione COMMON NAME : Astaxanthin/ (3S,3'S)- Astaxanthin SYMBOL : FORMULA : C 40 H 52 O 4 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 ). Astaxanthin in cyst cells of Haematococcus pluvialis (green alga) functions as an antioxidant agent against oxidative stress (singlet oxygen, superoxide anion radical, hydrogen peroxide and peroxy radical) (Ref. 1140 ). Astaxanthin inhibited liver tumorigenesis in mouse (Ref. 1207 ). -Crustacyanin from Homarus gammarus (lobster) shell consists of five kinds of peptides; CRTC (A1, C1 and C2 peptides) and CRTA (A2 and A3 peptides) (Ref. 1273 ). -Crustacyanin is a heterodimer of one CRTA and one CRTC, and two molecules of astaxanthin are located between two peptides. -Crustacyanin is octamer of -
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
Carotenoid
DATA No : VCA0002 INFORMANT : Masayoshi Ito
NAME : (3S,3'S)-3,3'-Dihydroxy-,-carotene-4,4'-dione
COMMON NAME : Astaxanthin/ (3S,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). Astaxanthin in cyst cells of Haematococcus pluvialis (green alga) functions as an antioxidant agent against oxidative stress (singlet oxygen, superoxide anion radical, hydrogen peroxide and peroxy radical) (Ref. 1140). Astaxanthin inhibited liver tumorigenesis in mouse (Ref. 1207).
-Crustacyanin from Homarus gammarus (lobster) shell consists of five kinds of peptides; CRTC (A1, C1 and C2 peptides) and CRTA (A2 and A3 peptides) (Ref. 1273). -Crustacyanin is a heterodimer of one CRTA and one CRTC, and two molecules of astaxanthin are located between two peptides. -Crustacyanin is octamer of -crustacyanin (totally 16 peptides and 16 astaxanthin), and has a molecular weight of about 320 kDa. Absorption maximum of astaxanthin in organic solvent is ca. 480 nm, that of -crustacyanin is ca. 580 nm, and that of -crustacyanin is ca. 630 nm. Keto group is essential to bind peptide and spectral shift (Ref. 1275/1276). 3D-Structure of -crustacyanin (A1 and A2 dimer) is investigated (Ref. 1274).
CD data in CH2Cl2 solution: 224 (+12.8), 249 (-14.4), 280 (+12.5), 323 (-23.1), 384 (+6.7), 521 (-3.2) [Spectrum 0004] (Ref. 0064/0068/0078/0080) CD data in EPA solution (25 C): 240 (-20.0), 252 (0), 270 (+20.0), 284 (0), 314 (-34.0), 355 (0), 372 (+3.0) (Ref. 0421)
CHROMATOGRAM DATATLC (Kieselgel 60 Merck, CH2Cl2-acetone-formic acid 95:5:3) Rf = 0.3 (Ref. 0010) HPLC (column: Sumipax OA-2000 (10m) 0.4 25 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 m) 0.32 50 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] (Ref. 0071) HPLC (columun: TSK gel ODS-80Ts (Tosoh) 0.46 15 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) -carotene, echinenone, -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. 0422/0431/1256) Asterina pectinifera, Asterias amurensis (tarfish) (Ref. 0423) Watasenia scintilans, Sepia modokai, Sepia officinales (cuttlefish) (Ref. 0424) Octopus vulgaris, Octopus ocellatus, Octopus minor (octopus) (Ref. 0424) Adonis aestivalis (flower petals of higher plant) (Ref. 0433) Haematococcus pluvialis (green alga) (Ref. 1007) Agrobacterium aurantiacum, Alcaligenes sp. strain PC-1 (marine bacteria; present name Paracoccus sp. N81106 and MBIC03024, respectively) (Ref. 0068/0085) It has recently been shown that these marine bacteria belong to Paracoccus species according to their16S rDNA analysis, performed by T. Hamada of Marine Biotechnology Institute (DDBJ accession number: AB008114). Paracoccus marcusii (gram-negative bacterium, -3 subclass of the Proteobacteria) (Ref. 1012)
CHEMICAL SYNTHESIS
The Wittig condensation of C10-dialdehyde with 2 equiv. of C15-phosphonium salt and subsequent thermal isomerization afforded astaxanthin. Racemic astaxanthin --- C15-phosphonium salt was prepared starting from 6-oxo-isophorone. (Ref. 0011) (3S,3'S)-Astaxanthin --- C15-phosphonium salt was prepared starting from (4R,6R)-4-hydroxy-2,2,6-trimethylcyclohexanone. (Ref. 0010/0016) (3S,3'S)- and (3R,3'R)-Astaxanthin --- Enantiomeric chiral blocks of C15-phosphonium salts were synthesized via three different routes. (Ref. 0012/0016) (3S,3'S)- and (3R,3'R)-Astaxanthin --- C15-Phosphonium salts were prepared from enantiomeric 3-acetoxy-4-oxo--ionones obtained by separation of the corresponding diastereomeric camphanates and by microbial resolution. (Ref. 0015/0073) (3S,3'S)-7,8-Didehydro- and 7,8,7',8'-tetradehydro-astaxanthins were synthesized starting from (4'S)-(2E)-5-(4'-hydroxy-2',6',6'-trimethyl-3'-oxo-1'-cyclohexenyl)-3-methyl-2-penten-4-ynal. (Ref. 0016/0143) The Wittig reaction between 2 equiv. of the phenoxyacetylated (S)-C15-phosphonium bromide and C10-dialdehyde or C10-acetylenic dialdehyde gave (3S,3'S)-astaxanthin or (3S,3'S)-15,15'-didehydroastaxanthin. (3S,3'S)-15,15'-Didehydroastaxanthin was transformed into (3S,3'S)-astaxanthin by partial reduction and subsequent isomerization. (Ref. 0143)
METABOLISM
Rainbow trout and salmon: astaxanthin idoxanthin adonixanthin zeaxanthin zeaxanthin 5,6-epoxides (Ref. 0406/0407) Marine fish egg (Prognichthys aggo, Seriola quinqueradiata):astaxanthin idoxanthin ,-carotene-3,4,3'-triol zeaxanthin 3-hydroxy-,-caroten-3'-one ,-carotene-3,3'-dione 3-hydroxy-,-caroten-3'-dione tunaxanthin (Ref. 0408) Yellowtail (Seriola quinqueradiata): astaxanthin -carotene-triol zeaxanthin 3'-epilutein tunaxanthin (Ref. 0430/0435) astaxanthin 3-dehydroretinal retinal (Ref. 0216) Red sea bream (Pagrus major): astaxanthin -carotene-triol zeaxanthin 3'-epilutein tunaxanthin (Ref. 0432) astaxanthin idoxanthin 4-ketozeaxanthin (Ref. 0436) Tilapia (Tilapia nilotica): astaxanthin zeaxanthin 3,4-didehydroretinol (Ref. 0417/0216) Astaxanthin yield in various culture conditions of Haematococcus pluvialis (Chlorophyceae) (Ref. 1145) Astaxanthin and canthaxanthin are accumulated in lipoidal globules of Scenedesmus komarekii (Chlorophyceae, Chlorophyta) cultured under high light intensity and nitrogen limitaion (Ref. 1147).
GENETIC INFORMATION
Genes required for the biosynthesis of astaxanthin from -carotene were isolated from the marine bacteria, Agrobacterium aurantiacum and Alcaligenes sp. strain PC-1 (present name: Paracoccus sp. N81106 and MBIC03024, respectively) (Ref. 0202/1008), and the functions of the genes were determined (Ref. 0202/0205/1009). -Carotene is converted to astaxanthin by two dioxygenase enzymes CrtW (ketolase) and CrtZ (hydroxylase), which require O2, Fe2+, and 2-oxoglutarate (Ref. 1002). [Table 0002] The corresponding genes were also isolated from the green alga Haematococcus pluvialis (Ref. 0203/1010/1011).
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
AUTHOR :Widmer,E., Zell,R., Broger,E.A., Crameri,Y., Wagner,H.P., Dinkel,J., Schlageter,M., and Lukác,T.
TITLE :Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus 6-Oxo-isophoron. II. Ein neues Konzept für die Synthese von (3RS,3'RS)-Astaxanthin
AUTHOR :Zell,R., Widmer,E., Lukác,T., Leuenberger,H.G.W., Schönholzer,P., and Broger,E.A.
TITLE :Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus 6-Oxo-isophoron. III. Ein neues Konzept für die Synthese der enantiomeren Astaxanthine
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--end group
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
AUTHOR :Becher,E.,Albrecht,R.,Bernhard,K.,Leuenberger,H.G.W.,Mayer,H.,Müller,R.K.,Schüep,W., and Wagner,H.P.
TITLE :Synthese von Astaxanthin aus -Jonon. I. Erschliessung der enantiomeren C15-Wittig salze durch chemische und mikrobiologishe Racematspaltung von ( )-3-Acetoxy-4-oxo--jonon
JOURNAL
: Helv. Chim. Acta
VOL : 64 PAGE : 2419 -2435 (1981)[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]
[0078]
AUTHOR : Noack,K.
TITLE :Temperaturabhängiger Circulardichroismus von (3S,3'R)- und (3S,3'S)-Adnixanthin
TITLE :New Carotenoid Glucosides, Astaxanthin Glucoside and Adonixanthin Glucoside, Isolation from the Astaxanthin-Producing Marine Bacterium Agrobacterium aurantiacum
TITLE :Antioxidant activity of beta-carotene-related carotenoids in solution PubMed ID:2779372
JOURNAL : Lipids.VOL : 24 PAGE : 659-661 (1989)
[TOP]
[0143]
AUTHOR : Bernhard,K., Kienzle,F., Mayer,H., and Müller, R.K.
TITLE :Synthesis of optically active natural carotenoids and structurally related compounds. VIII. Synthesis of (3S,3'S)-7,8,7',8'-tetradehydroastaxanthin and (3S,3'S)-7,8-didehydroastaxanthin (asterinic acid)
AUTHOR :Misawa, N., Satomi, Y., Kondo, K., Yokoyama, A., Kajiwara, S., Saito, T., Ohtani, T., and Miki, W.
TITLE :Structure and functional analysis of a marine bacterial carotenoid biosynthesis gene cluster and astaxanthin biosynthetic pathway proposed at the gene level PubMed ID:7592436
AUTHOR :Kajiwara, S., Kakizono, T., Saito, T., Kondo, K., Ohtani, T., Nishio, N., Nagai, S., and Misawa, N.
TITLE :Isolation and functional identification of a novel cDNA for astaxanthin biosynthesis from Haematococcus pluvialis, and astaxanthin synthesis in Escherichia coli PubMed ID:7579184
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
TITLE :Carotenoid and vitanin A, and metabplism of carotenoids, -carotene, canthaxanthin, astaxanthin, zeaxanthin, lutein and tunaxanthin in tilapia Tilapia nilotica
AUTHOR :Miki,W.,Yamaguchi,K.,Konosu,S.,Takane,T.,Satake,M.,Fujita,T.,Kuwabara,H.,Shimeno,S., and Takeda,M.
TITLE : Origin of tunaxaqnthin in the integument pf yellowtail (Seriola quinqueradiata) JOURNAL
: Comp. Biochem, Physiol.
VOL : 80 PAGE : 195 -201 (1985)[TOP]
[0436]
AUTHOR : Miki,W.,Yamaguchi,K.,Konosu,S., and Watanabe,T. TITLE : Metabolism of dietary carotenoids in eggs of red sea bream JOURNAL : Comp. Biochem. Physiol. VOL : 77 PAGE : 665 -668 (1984)
[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]
[1002]
AUTHOR : Misawa, N., and Shimada, H.
TITLE :Metabolic engineering for the production of carotenoids in non-carotenogenic bacteria and yeasts PubMed ID:9519479
AUTHOR : Fraser, P. D., Shimada, H., and Misawa, N.
TITLE :Enzymic confirmation of reactions involved in routes to astaxanthin formation, elucidated using a direct substrate in vitro assay PubMed ID:9523693
TITLE :Cloning and expression in Escherichia coli of the gene encoding beta-C-4-oxygenase, that converts beta-carotene to the ketocarotenoid canthaxanthin in Haematococcus pluvialis PubMed ID:7750556
Nishino, H., Tokuda , H., Satomi, Y., Masuda, M., Bu, P., Onozuka, M., Yamaguchi, S., Okuda, Y., Takayasu, J., Tsurata, J., Okada, M., Ichiishi, E., Murakoshi, M., Kato, T., Misawa, N., Narisawa, T., Takasuka, N., and Yano, M.