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Carotenoid


DATA No : VCA0060 INFORMANT : Masayoshi Ito

NAME : (3S,5R,6S,3'S,5'R,6'S)-5,6:5',6'-Diepoxy-5,6,5',6'-tetrahydro-b,b-carotene-3,3'-diol

COMMON NAME: Violaxanthin
SYMBOL:
FORMULA: C40H56O4 MOL.WT (average) : 600.870


Download ChemDraw structure data
BIOLOGICAL ACTIVITY
Inhibitotory effect on Epstein-Barr virus activation (anti-tumor promotion) (Ref. 0217)
Singlet oxygen quenching activity (Ref. 0441)
Fucoxanthin-chlorophyll a/c-protein assembly (FCPA) with energy transfer activity from fucoxanthin to chlorophyll a and from chlorophyll c to chlorophyll a isolated from Dictyota dichotoma (brown alga); 10 fucoxanthin, 1 violaxanthin, no b-carotene, 3 chlorophyll c, 13 chlorophyll a and a 54 kDa protein to form a 4.8 S complex (Ref. 1115).
PHYSICAL AND CHEMICAL PROPERTIES
MELTING POINT:198-199degC (Ref. 0155)

BOILING POINT:

REFRACTIVE INDEX:

OPTICAL ROTATION:

DENSITY:

SOLUBILITY:
SPECTRAL DATA
UV SPECTRA:lmax (nm) (e): EPA 265.5 (37500), 414.5 (102600), 437 (152500), 467 (150000) (Ref. 0155); methanol 326, 415, 436, 466, %III/II=89.9
[Spectrum 1112] (Ref. 1052)

IR SPECTRA:

NMR SPECTRA:1H-NMR d(400 MHz, CDCl3): 0.98 (s, 16-Me), 1.16 (s, 17-Me), 1.19 (s, 18-Me), 1.25 (dd, J 12.5, 11, 2ax-H), 1.63 (dd, J 14.5, 8.8, 4ax-H), 1.63 (ddd, J 12.5, 3.5, 1.8, 2eq-H), 1.93 (s, 19-Me), 1.97 (s, 20-Me), 2.39 (ddd, J 14.3, 5, 1.8, 4eq-H), 3.92 (m, 3-H), 5.88 (d, J 15.5, 7-H), 6.20 (d, J 11, 10-H), 6.27 (m, 14-H), 6.30 (d, J 15.5, 8-H), 6.37 (d, J 15, 12-H), 6.61 (dd, J 15, 11, 11-H), 6.64 (m, 15-H) (Ref. 0155)
13C-NMR d(CDCl3, 25.16 MHz): 35.49 (1), 47.93 (2), 63.19 (3), 41.86 (4), 67.19 (5), 70.55 (6), 125.51 (7), 137.52 (8), 134.86 (9), 132.70 (10), 125.45 (11), 138.62 (12), 138.62 (13), 133.56 (14), 130.94 (15), 25.45 (16), 29.76 (17), 20.39 (18), 13.07 (19), 12.86 (20) (Ref. 0061/0156) 15-cis form (Ref. 0156)

MASS SPECTRA:CI-MS m/z: 601 (57, M+1), 583 (36, M+1-H2O), 565 (22, M-2H2O), 510 (35), 509 (M+1-toluene), 491 (30), 232 (15), 211 (27), 181 (100), 165 (21), 121 (20) (Ref. 0155)
FD-MS m/z: 600 (100%) (Ref. 1053)

OTHER SPECTRA:CD in EPA: De 212.5 (-6.2), 217.8 (0), 230 (+9.8), 240 (0), 264.5 (-27.9), 292 (0), 325 (5), 347 (0) (Ref. 0155); figure (Ref. 1235)
CHROMATOGRAM DATA

SOURCE
Botryococcus braunii (Green alage) (Ref. 1081)
Higher plants (Ref. 0409)
Prasinophytes (algae) (Ref. 0513)
CHEMICAL SYNTHESIS
The optically active 3-hydroxy-5,6-epoxy-C15-aldehyde was reacted with the acetylenic C10-diphosphonate to give the 15,15'-didehydro-violaxanthin which, after hydrogenation and iomerization, gave all-E violaxanthin. (Ref. 0019/0155)
METABOLISM
zeaxanthin -> antheraxanthin -> violaxanthin (xanthophyll-cycle) in plant (Ref. 0512).
Xanthophyll cycle is catalyzed by violaxanthin de-epoxidase, which is present in lumen of chloroplast in plant leaves, and whose pH optimum is pH 5.2 and requires ascorbate. pI is 5.4 (Ref. 1141).
All-trans violaxanthin is the substrate of violaxanthin de-epoxidase, but cis forms are not (Ref. 1143/1144).
9-Cis epoxy-carotenoids (9'-cis neoxanthin and 9-cis violaxanthin) are cleaved to xanthoxin, which is a precursor of abscisic acid (plant hormone), by nine-cis epoxy-carotenoid dioxygenase (NCED) or neoxanthin cleavage enzyme (NCE) of maize and tomato (Ref. 1157/1159). Similar enzyme, carotenoid cleavage dioxygenase (CCD), cleaves carotenoids symmetrically to produce a C14 dialdehyde and two C13 products (Ref. 1159).
[Table 1030]
GENETIC INFORMATION
The zeaxanthin epoxidase gene, which was isolated from higher plants, Nicotiana plumbaginifolia and Capsicum annuum (red pepper), encoded an enzyme catalyzing the conversion of zeaxanthin to violaxanthin by way of antheraxanthin under the presence of O2, ferredoxin, and NADPH-ferredoxin redactase (Ref. 1025/1026).
A gene of violaxanthin de-epoxidase, which catalyzes the conversion of violaxanthin to zeaxanthin by way of antheraxanthin (xanthophyll cycle), is cloned from romaine lettuce and expressed in Escherichia coli (Ref. 1142).
Review of characteristics of zeaxanthin epoxidase and violaxanthin de-epoxidase (Ref. 1268)
NOTE
Semi-empirical molecular orbital calculations using AM1 Hamiltonian (MNDO-AM1 method) were performed in order to predict their stable structures (Ref. 1337).
REFERENCES
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[0155]
AUTHOR:Acemoglu,M.,Uebelhart,P.,Rey,M., and Eugster,C.H.
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[TOP]

[0156]
AUTHOR:Radics,L.,Molnár,P., and Szabolcs,J.
TITLE:13C NMR evidence for the central nono-cis stereochemistry of a naturally occurring violaxanthin isomer
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[TOP]

[0217]
AUTHOR:Tsushima, M., Maoka, T., Katsuyama, M., Kozuka, M., Matsuno, T., Tokuda, H., Nishino, H., and Iwashima, A.
TITLE:Inhibitory effect of natural carotenoids on Epstein-Barr virus activation activity of a tumor promoter in Raji cells. A screening study for anti-tumor promoters PubMed ID:7742789
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[0409]
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[0441]
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VOL:29 PAGE : 149-150 (1994)
[TOP]

[0512]
AUTHOR:Yamamoto,H.Y.
TITLE:Biochemistry of the Violaxanthin Cycle in Higher Plants
JOURNAL:Pure Appl. Chem.
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[0513]
AUTHOR:Egeland,E.S., Eikrem,W., Throndsen,J., Wilhelm,C., Zapata,M., Liaaen-Jensen,S.
TITLE:Algal carotenoids 61: Carotenoids from Prasinophyceae 6: Carotenpids from Further Prasinophytes (Erratum 24: 179-180 (1996))
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TITLE:Molecular identification of zeaxanthin epoxidase of Nicotiana plumbaginifolia, a gene involved in abscisic acid biosynthesis and corresponding to the ABA locus of Arabidopsis thaliana PubMed ID:8665840
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[1026]
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TITLE:Xanthophyll biosynthesis. Cloning, expression, functional reconstitution, and regulation of beta-cyclohexenyl carotenoid epoxidase from pepper (Capsicum annuum) PubMed ID:8910532
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[1052]
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[1053]
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[1081]
AUTHOR:Grung, M., Metzger, P., and Liaaen-Jensen, S.
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[1115]
AUTHOR:Katoh, T., Mimuro, M., and Takaichi, S.
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[1141]
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[1142]
AUTHOR:Bugos, R. C., and Yamamoto, H. Y.
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[1143]
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[1157]
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[1235]
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[1268]
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[1337]
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