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Carotenoid

DATA No : VCA0014 INFORMANT : Masayoshi Ito
NAME : (3S,3'R)-3,3'-Dihydroxy-b,b-caroten-4-one
COMMON NAME: Adonixanthin/ 4-Ketozeaxanthin
SYMBOL:
FORMULA: C40H54O3 MOL.WT (average) : 582.855

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BIOLOGICAL ACTIVITY

PHYSICAL AND CHEMICAL PROPERTIES
MELTING POINT:(3R,3'R)-Isomer: 180-181degC; (3R,3'S)-isomer: 181.5-182.5degC; (3S,3'R)-isomer: 180-181degC (Ref. 0077>
BOILING POINT:
REFRACTIVE INDEX:
OPTICAL ROTATION:
DENSITY:
SOLUBILITY:
SPECTRAL DATA
UV SPECTRA:lmax (nm) (e): CHCl3 304 (16695), 480 (105444) (Ref. 0077); hexane 297 (18116), 459 (118149) (Ref. 0077); benzene 472 (116980) (Ref. 0077); ethanol 299 (16252), 465 (108660) (Ref. 0077)
IR SPECTRA:nmax/cm-1:3433s (OH), 1658s (conj. CO), 1557m, 1516m (conj. C=C), 1074m, 1038m (sek. OH), 964s (trans CH=CH) (Ref. 0077)
NMR SPECTRA:1H-NMR d(270 MHz, CDCl3): 1.075 (s, 1'-gem-Me), 1.213 (s, 1eq-Me), 1.322 (s, 1ax-Me), 1.48 (t, J 12, 2'ax-H), 1.738 (s, 5'-Me), 1.774 (m, 2'eq-H), 1.810 (t, J 13.5, 2ax-H), 1.948 (d, J 0.8, 5-Me), 1.974 (s, 9'-Me), ca. 1.983 (s, 13-, 13'-Me), 1.998 (s, 9-Me), 2.045 (dd, J 17.5, 10, 4'ax-H), 2.16 (dd, J 12.5, 5.5, 2eq-H), 2.39 (dd, J 17.5, 5, 4'eq-H), 3.704 (d, J 1.8, 3-OH), ca. 4.0 (br m, 3'ax-H), 4.33 (ddd, J 14, 6, 1.8, 3ax-H), ca. 6.13 (s, 7'-, 8'-H), 6.16 (d, J 11.5, 10'-H), 6.21 (d, J 16, 7-H), ca. 6.24-6.33 (m, 14-, 14'-, 10-H), 6.37 (d, J 15, 12'-H), 6.44 (d, J 16, 8-H), 6.45 (d, J 15, 12-H), ca. 6.65 (m, 11-, 11'-, 15-, 15'-H) (Ref. 0077)
13C-NMR d(100.6 MHz, CDCl3): 12.55 (9-Me), 12.76, 12.78, 12.85 (13-, 9'-13'-Me), 14.0 (5-Me), 21.62 (5'-Me), 26.14, 30.73 (1-gem-Me), 28.72 (1'ax-Me), 30.25 (1'eq-Me), 36.79 (C1), 37.11 (C1'), 42.54 (C4'), 45.38 (C2), 48.39 (C2'), 65.02 (C3'), 69.20 (C3), 123.11 (C7), 124.26 (C11), 125.26 (C11'), 125.75 (C7'), 126.23 (C5'), 126.72 (C5), 129.80, 130.94 (C15, C15'), 131.22 (C10'), 132.42 (C14'), 134.01 (C14), 134.29 (C9), 135.29 (C10), 135.94 (C9'), 136.07, 137.10 (C13, C13'), 137.42 (C12'), 137.71 (C6'), 138.42 (C8'), 139.86 (C12), 142.43 (C8), 162.27 (C6), 200.40 (C4) (Ref. 0077)
MASS SPECTRA:m/z (ion, intensity relative to base peak in %): 566 (M, 31), 564 (9), 548 (5), 474 (4), 412 (6), 203 (62), 159 (50), 145 (45), 119 (74), 105 (81), 91 (100), 69 (68), 55 (68), 41 (67) (Ref. 0077)
OTHER SPECTRA:CD data in EPA solution De: (3R,3'S)-isomer: 363 (-2.94), 307 (20.75), 290sh (11.38), 264 (-12.43) , 238 (10.43); (3R,3'R)-isomer: 369 (3.74), 307 (4.68), 293sh (2.66), 285sh (1.26) , 263 (-2.50), 246 (-0.63); (3S,3'R)-isomer: 366 (2.40), 307 (-18.95), 292sh (-11.64), 264 (11.12) , 238 (-9.85); (3S,3'S)-isomer: 371 (-3.83), 329 (-0.29), 307 (-4.87), 293sh (-2.95) , 283sh (-1.32), 264 (1.71), 243 (-0.21) (Ref. 0064/0077/0078)
CHROMATOGRAM DATA
HPLC (columun: TSK gel ODS-80Ts (Tosoh) 0.46times15 cm, eluent and flow: 1.0 ml/min, H2O-MeOH 5:95 for 5 min, then 5 min-linear gradient MeOH-THF 7:3) tR = 8.37 min
[Chromatogram 0012] (Ref. 0085)
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 = 8.32 min for adnixanthin (Ref. 0208)
SOURCE
Adonis annua (flower petals of higher plant) (Ref. 0412)
Pannulis japonicus (Spiny Lobster) (Ref. 0413)
Carassius auratus (Gold fish) as b-doradexanthin (Ref. 0412/0415)
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).
Brevundimonas sp. SD212 (bacterium) (Ref. 1343)
CHEMICAL SYNTHESIS
The Wittig condensation of the enantiomeric C25-apocarotenal with the enantiomeric C15-phosphonium salt by use of NaOMe as base provided (3R,3'R)-, (3R,3'S)-, (3S, 3'R)-, (3S, 3'S)-adnixanthin in ca. 45 % yield. (Ref. 0077)
METABOLISM

GENETIC INFORMATION
Escherichia coli, which carries the Erwinia crtE, crtB, crtI, and crtY genes and the crtZ and crtW genes derived from Erwinia species or Agrobacterium aurantiacum, accumulates adonixanthin as one of intermediary metabolites in addition to astaxanthin of the final product (Ref. 0202).
NOTE

REFERENCES
[0064]
AUTHOR:Buchecker,R., and Noack,K. (1995) Carotenoids Volume 1B: Spectroscopy Chapter 3: Circular Dichroism (Britton,G.,Liaaen-Jensen,S., and Pfander,H., eds), pp63-116, Birkhäuser Verlag,Basel,Boston,Berlin
TITLE:
JOURNAL:
VOL: PAGE : - ()
[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]
[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
JOURNAL:Helv. Chim. Acta
VOL:64 PAGE : 1833 -136 (1981)
[TOP]
[0085]
AUTHOR:Yokoyama,A.,Adachi,K., and Shizuri,Y.
TITLE:New Carotenoid Glucosides, Astaxanthin Glucoside and Adonixanthin Glucoside, Isolation from the Astaxanthin-Producing Marine Bacterium Agrobacterium aurantiacum
JOURNAL:J. Nat. Prod.
VOL:58 PAGE : 1929 -1933 (1995)
[TOP]
[0202]
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
JOURNAL:J Bacteriol.
VOL:177 PAGE : 6575-6584 (1995)
[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]
[0412]
AUTHOR:Egger,K.
TITLE:Die Ketocarotinide In Adonis annua L.
JOURNAL:Phytochemistry
VOL:4 PAGE : 609 -618 (1965)
[TOP]
[0413]
AUTHOR:Matsuno,T.,Kusumoto,T.,Watanabe,T., and Ishihara,Y.
TITLE:Carotenoid pigments of spiny lobster
JOURNAL:Bull. Jap. Soc. Sci. Fish.
VOL:39 PAGE : 43 -50 (1973)
[TOP]
[0415]
AUTHOR:Matsuno,T.,Matsutaka,H., and Nagata,S.
TITLE:Metabolism of lutein and zeaxanthin to ketocarotenoids in goldfish, Carassius auratus
JOURNAL:Bull. Jap. Soc. Sci. Fish.
VOL:47 PAGE : 605 -611 (1981)
[TOP]
[1343]
AUTHOR:Yokoyama, A., Miki, W., Izumida, H., Shizuri, Y.
TITLE:New trihydroxy-keto-carotenoids isolated from an astaxanthin-producing marine bacterium
JOURNAL:Biosci. Biotech. Biochem.
VOL:60 PAGE : 200 -203 (1996)
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