Carotene bixin

Carotenoids are also present in animal products such as eggs, lobsters, greyflsh, and various types of hsh. In higher plants, they occur in photosynthetic tissues and choloroplasts where their color is masked by that of the more predominant green chlorophyll. The best known are P-carotene and lycopene but others are also used as food colorants a-carotene, y-carotene, bixin, norbixin, capsanthin, lycopene, and P-apo-8 -carotenal, the ethyl ester of P-apo-8-carotenic acid. These are Upid-soluble compounds, but the chemical industry manufactures water-dispersible preparations by formulating coUoid suspensions by emulsifying the carotenoids or by dispersing them in appropriate colloids. ... 

Coloring of food can be accomplished by synthetic or natural dyes. The laws pertaining to food colorings are different from country to country. However, natural products (- dyes, natural) are normally accepted. Examples are cochineal, chlorophyll, carotenes, bixin and betanin as well as - caramel color. 

Annatto is a colored pigment that is extracted from the Central and South American plant Bixa orellana. The color comes from the resinous outer covering of the seeds of the plant, which is composed of the carotenoid pigments bixin and norbixin and their esters. The central portion of those molecules is the same as that of the molecule beta-carotene, and the yellow-orange color of annatto comes from the same physical chemistry origins as the orange color of beta-carotene. 

Legally, carotenoids are divided between two E numbers. El60 covers the carotenoid hydrocarbons P-carotene, lycopene and paprika as well as the apo-carotenoids, e.g. bixin. E161 covers the xanthophylls and the carotenoids lutein, astaxanthin and canthaxanthin. 

Both bixin and nor-bixin produce orange solutions. Bixin produces an orange solution in oily media while nor-bixin produces an orange aqueous solution. Obviously, bixin is the product of choice for high fat systems while nor-bixin is used in aqueous systems. Nor-bixin is one of the two water-soluble carotenes. 

ANNATTO FOOD COLORS. These colors are natural carotenoid colorants derived from the seed of the tropical annatto tree (Bixa nrellana). The surface of the seeds contains a highly colored resin, consisting primarily of the carotenoid bixin. The bixin is extracted from the seed by a special process to produce a pure, soluble colorant. Bixin, one of the relatively few naturally occurring cts compounds, has a chemical structure similar to the nucleus of carotene with a free and esterified carboxyl group as end groups. Its formula is CM LoCL. (See Fig. I). 

Lutein Capsanthin Capsorubin Bixin Canthaxanthin (3-apo-8 -carotenal ((3,e-carotene-3,3 -diol)... 

Many studies have been conducted on the volatile thermal degradation products of carotenoids. Several authors have reported the formation of toluene and xylene as TDP of bixin and capsanthin (18) and B-carotene (10, 11, 18-25), as well as canthaxanthin (26). 

Several examples of this possible relationship are found in nature. One of the best known is the formation of retinin and vitamin A from P-carotene (Figure 6-19). Another obvious relationship is that of lycopene and bixin (Figure 6-20). Bixin is a food... 

Figure 6-20 Relationship Between Lycopene and Bixin. Source From E.C. Grob, The Biogenesis of Carotenes and Carotenoids, in Carotenes and Carotenoids, K. Lang, ed., 1963, Steinkopff Verlag.

Annatto is classified as El 60(b). It is extracted from the seeds of the tree Bixa orellana which grows in America, India and East Africa. The extract is a mixture of two pigments, bixin and nor-bixin. Bixin is oil soluble, whereas nor-bixin is water soluble (it is one of the two water soluble carotenes - the other is crocin), and both of the pigments are diapo-carotenoids. Annatto has long been used as a food colouring and also has some uses as a food flavouring. 

Margarine is colored with carotenoids, and synthetic p-carotene is by far the most widely used. Carotene dissolves very slowly in oil. Therefore, the compound is pulverized to a particle size of 2-5 pm and the microcrystals are suspended in oil to retard oxidation (228). Natural extracts containing carotenoids, for example, annatto (bixin), carrot oil, and red palm oil also have been used. Annatto, which is used in butter, is somewhat sensitive to light and may have an orange or slightly pink hue, particularly when the aqueous phase is acid (4). Mixtures of annatto and turmeric extracts result in a more typical color than annatto alone (229). Many margarine manufacturers purchase blends of colors and vitamins customized for their specific products. 

The syntheses of methyl bixin (24) and other natural carotenoids were mentioned above. A biogenetically inspired synthesis of e-carotene used the titanium tetrachloride complex of lycopene (16). Dehydrolycopene was also isolated. Two more syntheses of ) -carotene (2) have been reported which use intermediates in the synthesis of vitamin A (see Scheme 2). Although ll-cis-j5-carotene was produced it is rapidly isomerised to the all-frons form. The cross-conjugated system (72) has a previously unknown chromophore. Another example of this system, but with an additional 4 -oxo-group, was synthesised by Surmatis et al. in a study of the synthesis of keto carotenoids. They prepared echinenone (73) and the two protected 3,3 -dioxo-j8-carotene compounds (74) and (75). Treatment of the ketal with sulphuric acid gave mainly 3,3 -dioxo- -carotene (76) while hydrochloric acid gave 3,3 -dioxo-c-carotene (77). Under both conditions the enol ether gave the latter product. 

Minguez-Mosquera, M.I., Homero-Mendez, D., and Gandul-Rojas, B. 1995a. Detection of bixin, lycopene, canthaxanthin, and 3-apo-8 -carotenal in products derived from red pepper. JAOAC Int. 78, 491-496. 

Bixin, a bolaamphiphile with one methylester and one carboxylate end group, appears in the waxy cover of seed granules of the South American and African tree Bixa orellana. This lively colored coating of the seed proteins may protect them against attack by microorganisms. Why is an unsymmetrical bolaamphiphile needed, if the protective role can presumably also be played by P-carotene Why is a cw-double bond introduced at one end ... 

The carotenoid activity during oxidation is strongly influenced by the oxygen pressure (PO2) of the experimental conditions. Kiokias and Oreopoulou have shown that certain natural carotenoid mixtures (paprika, bixin and tomato, and palm-oil preparations) inhibited the azo-initiated oxidation of sunflower oil-in-water emulsions (operated rapidly under low pOj) in terms of both primary and secondary oxidation products. However, other studies " concluded that carotenoids not only did not inhibit aerial lipid autoxidation (high PO2) but even exerted a prooxidant character, a phenomenon also observed at high carotenoid concentrations that could be due mainly to a more increased formation of carotene-peroxyl radicals, promoting the propagation of autoxidation. 

A sensitive HPLC multimethod was developed by BreithaupT for the determination of the carotenoid food additives (CFA) norbixin, bixin, capsanthin, lutein, canthaxanthin, b-apo-80-carotenal, b-apo-80-carotenoic acid ethyl ester, b-carotene, and lycopene in processed food using an RP C30 column. For unequivocal identification, the mass spectra of all analytes were recorded using LC-(APcl) MS. For extraction, a manual process as well as accelerated solvent extraction (ASE) was applied. Important ASE parameters were optimized. ASE was used for the first time to extract CEA from various food matrices. Average recoveries for all analytes ranged from 88.7% to 103.3% (manual extraction) and from 91.0% to 99.6% (ASE), with the exception of norbixin using ASE (67.4%). Limits of quantitation (LOQ) ranged from 0.53 to 0.79 mg/L. The presented ASE method can be used to monitor both, forbidden application of CFA or the compliance of food with legal limits. 

In natural materials, the concentration of C. is usually in the order of 0.02-0.1% of the dry mass. The C. content of the eye ring of the pheasant Narcissus majalis is extremely high, being 16%, or about times that in carrots. An estimated ICf metric tonnes of C. are produced per year by living organisms, the most abundant being fucoxanthin, lutein, violaxan-thin and neoxanthin, followed by p-carotene, zeaxanthin, lycopene, capsanthin and bixin. More than 90 % of the C. in a plant is found in the leaves, usually as a mixture of 20 0% carotenes (containing more than 70 % p-carotene) and 60-80 % xanthophylls like lutein, violaxanthin, cryptoxanthin and zeaxanthin. 

A TLC method for analysis of bixin, lycopene, canthaxanthin, and P-apo-8 -carotenal was recently presented (104) for rapid screening of food color adulteration. Another method that was quickly supplanted by HPLC was that of liquid-gel partition chromatography, using stationary phases such as Sephadex LH-20 or hydroxyalkoxypropyl Sephadex (50). This method, which is capable of resolving retinyl esters, retinol, retinal, and retinoic acid, was applied to studying vitamin A metabolism, but it is slower and gives less resolution than HPLC on sturdy silica stationary phases. 

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