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 |
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 | : | 198-199 C (Ref. 0155) |
|
| BOILING POINT | : | |
|
| REFRACTIVE INDEX | : | |
|
| OPTICAL ROTATION | : | |
|
| DENSITY | : | |
|
| SOLUBILITY | : | |
| 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)
|
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)
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]
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 O
2, 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)
Semi-empirical molecular orbital calculations using AM1 Hamiltonian (MNDO-AM1 method) were performed in order to predict their stable structures (
Ref. 1337).
[0019]
| AUTHOR | : | Pfander,H. and Bartels,B. (1996) Carotenoids Volume 2: Synthesis Chapter 3: Carotenoid Synthesis Part III: Synthesis of Cyclic Carotenoids (Britton,G.,Liaaen-Jensen,S., and Pfander,H., eds), pp161-200, Birkhäuser Verlag,Basel,Boston,Berlin |
| TITLE | : | |
| JOURNAL | : | |
| VOL | : | PAGE : - () |
[0061]
| AUTHOR | : | Moss,G.P. |
| TITLE | : | Carbon-13 NMR spectra of carotenoids |
| JOURNAL | : | Pure Appl. Chem. |
| VOL | : | 2047 PAGE : 97 -102 (1976) |
[0155]
| AUTHOR | : | Acemoglu,M.,Uebelhart,P.,Rey,M., and Eugster,C.H. |
| TITLE | : | Synthese von enantiomerenreinen Violaxanthine und verwandten Verbindungen |
| JOURNAL | : | Helv. Chim. Acta |
| VOL | : | 71 PAGE : 931 -956 (1988) |
[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 |
| JOURNAL | : | Phytochemistry |
| VOL | : | 22 PAGE : 306 -306 (1983) |
[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 |
| JOURNAL | : | Biol Pharm Bull. |
| VOL | : | 18 PAGE : 227-233 (1995) |
[0409]
| AUTHOR | : | Goodwin T. W. (1980) The biochemistry of the carotenoids, Volume I, Plants, Chapman and Hall, London and New York |
| TITLE | : | |
| JOURNAL | : | |
| VOL | : | PAGE : - () |
[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) |
[0512]
| AUTHOR | : | Yamamoto,H.Y. |
| TITLE | : | Biochemistry of the Violaxanthin Cycle in Higher Plants |
| JOURNAL | : | Pure Appl. Chem. |
| VOL | : | 51 PAGE : 639 - (1979) |
[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)) |
| JOURNAL | : | Biochem. Syst. Ecol. |
| VOL | : | 23 PAGE : 747 -755 (1995) |
[1025]
| AUTHOR | : | Marin, E., Nussaume, L., Quesada, A., Gonneau, M., Sotta, B., Hugueney, P., Frey, A., and Marion-Poll, A. |
| 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 |
| JOURNAL | : | Embo J. |
| VOL | : | 15 PAGE : 2331-2342 (1996) |
[1026]
| AUTHOR | : | Bouvier, F., d'Harlingue, A., Hugueney, P., Marin, E., Marion-Poll, A., and Camara, B. |
| TITLE | : | Xanthophyll biosynthesis. Cloning, expression, functional reconstitution, and regulation of beta-cyclohexenyl carotenoid epoxidase from pepper (Capsicum annuum) PubMed ID:8910532 |
| JOURNAL | : | J Biol Chem. |
| VOL | : | 271 PAGE : 28861-28867 (1996) |
[1052]
| AUTHOR | : | Takaichi, S. and Shimada, K. |
| TITLE | : | Characterization of carotenoids in photosynthetic bacteria |
| JOURNAL | : | Methods Enzymol. |
| VOL | : | 213 PAGE : 374 -385 (1992) |
[1053]
| AUTHOR | : | Takaichi, S. |
| TITLE | : | Usefulness of field desorption mass spectrometry in determining molecular masses of carotenoids, natural carotenoid derivatives and their chemical derivatives |
| JOURNAL | : | Org. Mass Spectrom. |
| VOL | : | 28 PAGE : 785 -788 (1993) |
[1081]
| AUTHOR | : | Grung, M., Metzger, P., and Liaaen-Jensen, S. |
| TITLE | : | Primary and secondary carotenoids in two races of the green alga Botryococcus braunii |
| JOURNAL | : | Biochem. System. Ecol. |
| VOL | : | 17 PAGE : 263 -269 (1989) |
[1115]
| AUTHOR | : | Katoh, T., Mimuro, M., and Takaichi, S. |
| TITLE | : | Light-harvesting particles isolated from a brown alga, Dictyota dichotoma. A supramolecular assembly of fucoxanthin-chlorophyll-protein compleses |
| JOURNAL | : | Biochim. Biophys. Acta |
| VOL | : | 976 PAGE : 233 -240 (1989) |
[1141]
| AUTHOR | : | Rockholm, D. C., and Yamamoto, H. Y. |
| TITLE | : | Violaxanthin de-epoxidase PubMed ID:8742341 |
| JOURNAL | : | Plant Physiol. |
| VOL | : | 110 PAGE : 697-703 (1996) |
[1142]
| AUTHOR | : | Bugos, R. C., and Yamamoto, H. Y. |
| TITLE | : | Molecular cloning of violaxanthin de-epoxidase from romaine lettuce and expression in Escherichia coli PubMed ID:8692813 |
| JOURNAL | : | Proc Natl Acad Sci U S A. |
| VOL | : | 93 PAGE : 6320-6325 (1996) |
[1143]
| AUTHOR | : | Grotz, B., Molnár, P, Stransky, H., and Hager, A. |
| TITLE | : | Substrate specificity and functional aspects of violaxanthin-de-epoxidase, an enzyme of the xanthophyll cycle |
| JOURNAL | : | J. Plant Physiol. |
| VOL | : | 154 PAGE : 437 -446 (1999) |
[1144]
| AUTHOR | : | Yamamoto, H. Y., and Higashi, R. M. |
| TITLE | : | Violaxanthin de-epoxidase. Lipid composition and substrate specificity PubMed ID:102251 |
| JOURNAL | : | Arch Biochem Biophys. |
| VOL | : | 190 PAGE : 514-522 (1978) |
[1157]
| AUTHOR | : | Schwartz, S. H., Tan, B. C., Gage, D. A., Zeevaart, J. A., and McCarty, D. R. |
| TITLE | : | Specific oxidative cleavage of carotenoids by VP14 of maize PubMed ID:9188535 |
| JOURNAL | : | Science. |
| VOL | : | 276 PAGE : 1872-1874 (1997) |
[1159]
| AUTHOR | : | Schwartz, S. H., Qin, X., and Zeevaart, J. A. |
| TITLE | : | Characterization of a novel carotenoid cleavage dioxygenase from plants PubMed ID:11316814 |
| JOURNAL | : | J Biol Chem. |
| VOL | : | 276 PAGE : 25208-25211 (2001) |
[1235]
| AUTHOR | : | Matsuno, T., Tsushima, M., and Maoka, T. |
| TITLE | : | Salmoxanthin, deepoxysalmoxanthin, and 7,8-didehydrodeepoxysalmoxanthin from the Salmon Oncorhynchus keta PubMed ID:11325236 |
| JOURNAL | : | J Nat Prod. |
| VOL | : | 64 PAGE : 507-510 (2001) |
[1268]
| AUTHOR | : | Hieber, A. D., Bugos, R. C., and Yamamoto, H. Y. |
| TITLE | : | Plant lipocalins: violaxanthin de-epoxidase and zeaxanthin epoxidase PubMed ID:11058750 |
| JOURNAL | : | Biochim Biophys Acta. |
| VOL | : | 1482 PAGE : 84-91 (2000) |
[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) |
Last updated June 19, 2007. Copyright © 1989-2007 Japanese Conference on the Biochemistry of Lipids (JCBL). All rights reserved.
