Astaxanthin ester

Kobayashi, M. and Sakamoto, Y., Singlet oxygen quenching ability of astaxanthin esters from the green alga Haematococcus pluvialis, Biotechnol. Lett., 21, 265, 1999. 

Breithaupt DE. 2004. Identification and quantification of astaxanthin esters in shrimp (Pandalus borealis) and in a microalga (Haematococcus pluvialis) by liquid chromatography-mass spectrometry using negative ion atmospheric pressure chemical ionization. J Agric Food Chem 52 3870-3875. 

Takaichi S, Matsui K, Nakamura M, Muramatsu M and Hanada S. 2003. Fatty acids of astaxanthin esters in krill determined by mild mass spectrometry. Comp Biochem Physiol 136(2) 317-322. 

Astaxanthin free Astaxanthin ester Can tax an thin Echinenone /1-carotene Other carotene... 

Conversion of steryl esters and astaxanthin esters to their free... 

Conversion of Steryl Esters and Astaxanthin Esters to Their Free Forms... 

Lipase-catalyzed conversion of FAStEs to sterols in the presence of MeOH was applied to astaxanthin FA esters to free astaxanthin, because a screening test showed that commercial lipases did not hydrolyze astaxanthin FA esters. A mixture of astaxanthin and its mono- and diesters (5 80 15, by mol) was treated in the presence of 50wt% water with 5 mol EtOH for FAs in astaxanthin esters using P. aeruginosa lipase. After the reaction, the molar ratio of astaxanthin and its mono- and diesters was 89 10 1, showing that the lipase efficiently converts astaxanthin esters to free astaxanthin. The free form was also purified by n-hexane fractionation with 69% recovery of the initial content of astaxanthin in the mixture of its free and ester forms (Nagao et al., 2003). 

Weesepoel Y, Vincken J-P, Pop RM, Liu K, Gruppen H. Sodiation as a tool for enhancing the diagnostic value of MALDI-TOF/TOF-MS spectra of complex astaxanthin ester mixtures fromHaematococcuspluvialis. J Mass Spectrom. 2013 48 862-74. 

Yuan, J.P. and Chen, F. (2000) Purification of trans-astaxanthin from a high-yielding astaxanthin ester-producing strain of the microalga Haematococcuss pluvialis. Food Chem. 68, 443 48... 

Fig. 3. Commeicially important carotenoids P-caiotene (10), canthaxanthin [514-78-3] (11), astaxanthin [472-61-7] (12), P-apo-8 -caiotenal [1107-26-2] (13), P-apo-8 -caiotenoic acid ethyl ester [1109-11-1] (14), and citranaxanthin [3604-90-8] (15).

Grynbaum, M. D., Hentschel, R, Putzbach, K., Rehbein, J., Krucker, M., Nicholson, G., and Albert, K. 2005. Unambiguous detection of astaxanthin and astaxanthin fatty acid esters in krill (Euphausia superba... 

The success of the carotenoid extracts led to the commercialization of synthetic carotenoids, some with the same chemical structure as those in the plant extracts and others with modifications to improve their technological properties. The yellow beta-carotene was synthesized in 1950, followed by the orange beta-8-carotenal in 1962 and the red canthaxanthin in 1964. A number of others soon followed, methyl and ethyl esters of carotenoic acid, citraxanthin, zeaxanthin, astaxanthin, and recently lutein. 

Saponification is a purification procedure to remove unwanted lipids and chlorophylls. It has to be omitted when alkali-labile carotenoids (e.g., astaxanthin, fucoxanthin) or carotenoid esters are to be analyzed. To prevent the formation of artifacts produced by aldol condensation between acetone and carotenals, all traces of acetone have to be removed prior to saponification (41). 

Bowen, J. Soutar, C. Serwata, R.D. Lagocki, S. White, D.A. Davies, S.J. Young, A. J. 2002. Utilization of (3S, 3 S)-astaxanthin acyl esters in pigmentation of rainbow trout (Oncorhynchus mykiss). Aquacult. Nutr. 8 59-68. 

Physical Methods.—Separation and Assay. A range of isomers of astaxanthin (8) diacetate (9-cis, 13-cis, 15-cis, 9,9 -di-cis, 9,13-di-cw, 9,13 -di-cw, 13,13 -di-cw, 13,15-di-cw), prepared by thermal and iodine-catalysed isomerization of irans-(S) have been separated by h.p.l.c.126 A procedure has been developed for separation of bean leaf etioplast pigments, including carotenoids,127 by h.p.l.c. H.p.l.c. separations of esters of all-trans-, 9-cis-, 11-cw-, and 13-cw-retinol,128-130 and determinations of retinol in serum,131 retinol and 13-cw-retinoic acid,132 and the aromatic retinoid (195)133 in plasma have been described. A reversed-phase ion-pair... 

Distributions of carotenoids can be characteristic for various groups of photosynthetic organisms. Fucoxan-thin is characteristic of diatoms (BaciUariophyceae) and peridinin is found in many dinoflagellates (Dinophyceae Fig. 2.23). In contrast, diatoxanthin and diadinoxanthin occur in many phytoplanktonic classes due to their xanthophyll cycle role (Fig. 2.25).Although it is a less specific marker compound, (3-carotene is abundant in cyanobacteria. Photosynthetic bacteria produce acyclic and aromatic carotenoids (e.g. lycopene and okenone, respectively Fig. 2.23). Astaxanthin and its esters are major constituents of marine zooplankton (Fig. 2.23). 

Sporopollenin, the polymeric material forming the protective coatings of spores and pollens, may contain carotenoid and/or carotenoid ester structures such as astaxanthin dipalmitate. However, the major part of sporopollenin is synthesized from unbranched aliphatic chains, probably derived from fatty acids. Polyhydroxy-benzene units similar to lignin precursors (see Section 2.5.1) have also been identified. Sporopollenin is found in the pollen grains of angiosperms and gymnosperms,... 

The HPLC methods proposed by Aas et al. (1987) can be used to distinguish between astaxanthin stereoisomers in a fish flesh. These methods can separate the stereoisomers after transformation to their respective dicam-phenate esters. However, to avoid coelution between 7,8-didehydro- and 7,8,7, 8 -tetradihydro-astaxanthin and (3S,3 S)-cA isomers of astaxanthin, the astaxanthin fraction should be purified by TLC on alkaline plates (Bjomland et al., 1989). A Pirckle covalent L-leucine column is preferable, especially for routine analyses, since the separation is achieved in 18 minutes (Turujman, 1993). In addition, this method is able to separate the cis and tram isomers. 

Pacific Ocean was reported lipid made up 55% of the slick, and 80% of the total lipid was wax esters. The red color of the slick was caused by the carotenoid pigment, astaxanthin, also a constituent of the zooplankton (Lee and Williams, 1974). The same compounds are the principal constituents of a solid waxy material that accumulates during cold winters on the shores of Bute Inlet, a British Columbia fjord. 

The pioneering synthetic work quickly led to the synthesis of carotenoids on an industrial scale. The industrial production of p,p-carotene (3) began in 1954, only four years after its first synthesis on a laboratory scale. This extremely rapid development was made possible by the enthusiasm and perseverance of Isler and his colleagues at Roche in Basel. Since then, commercial synthesis of carotenoids has continuously advanced and today the two major industrial producers Roche and BASF produce six different carotenoids, namely p,p-carotene (3), canthaxanthin (380), optically inactive astaxanthin (403) and the apocarotenoids 8 -apo-p-caroten-8 -al (482), 8-apo-p-caroten-8 -oic acid (486) ethyl ester, and citranaxanthin (466). The total annual sale is now in the region of US 300 million, and the commercially produced carotenoids are used mainly as food and feed additives. 

Apo-8 -carotenic acid, ethyl ester 3-Apo-8 -carotenic acid, methyl ester Astaxanthin Barley (Hordeum distichon) extract Beet powder... 

NMR assignments for (35,3 S)-astaxanthin (28) have been confirmed by Yb (dpm)3-induced shifts (69). Data for the 15-m isomer agreed with those previously obtained for 15-m-P,P-carotene (68, 135). Recently the NMR signals of azafrin (6) methyl ester and of... 

Astaxanthin is present in crab and lobster shells and lobsters, the red astaxanthin is released from and, in combination with proteins, provides three a green carotenoid-protein complex. Astaxanthin blue hues (a-, 3- and y-crustacyanin) and one usually occurs in lobster shell as an ester, e. g., diyellow pigment. During the cooking of crabs palmitic ester. 

Six main carotenoids are produced industrially by chemical synthesis (3-carotene, canthaxanthin, astaxanthin, p-apo-8 -carotenal, p-apo-8 -carotenoic ethyl ester, and citranaxanthin. The pigment is usually presented in microcrystalline form for its use in fatty foods, or microencapsulated as a hydrophilic colloid for use in aqueous media. 

In contrast, most carotenoids are considerably stable to the action of alkalis, enabling saponihcation as a routine procedure to eliminate fatty matter and chlorophylls, or for hydrolysis of the esters of xanthophylls with fatty acids. Certain carotenoids are, however, alkali-sensitive, notably astaxanthin and in general the carotenoids containing 3-hydroxy-4-oxo-(3 end groups. When analyzing samples containing such carotenoids, contact with alkalis should be avoided. 

Excepting the carotenoids obtained at industrial scale, and thus commercially available ( -carotene, canthaxanthin, astaxanthin, (3-apo-8 -carotenal, (3-apo-8 -caro-tenoic ethyl ester and, citranaxanthin), carotenoid standards must be obtained either by total or partial synthesis, or from natural sources in which their presence is confirmed using the extraction and separation techniques described above. Table 6.2 (presence and distribution of the most common carotenoids in foods) can be used to choose the natural source from which carotenoid pigment standards can be obtained. 

Carotenoids occur free or as esters of fatty acids or as complexes with proteins and carbohydrates for example, in paprika, capsanthin is esterified with lauric acid. In live lobster, astaxanthin is complexed with protein the astaxanthin-protein complex is blue-gray, the color of live lobster, but on heating, the complex is broken and the freed astaxanthin imparts its red color to the cooked lobster. 

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