Isomerization carotenoids

In the stomach, carotenoids are exposed to acid environments. This can lead to carotenoid isomerization, which can change carotenoid antioxidant properties, solubility, and absorption. In humans, (3-carotene absorption is reduced when the pH of the gastric fluids is below 4.5 (Tang and others 1995). Vitamin E consumption seems to reduce carotenoid absorption in animals, presumably because vitamin E and carotenoids compete for absorption (Furr and Clark 1997). Dietary sterols, such as those in sterol-supplemented functional foods, are also known to decrease carotenoid absorption. 

Boskovic, M.A. 1979. Fate of lycopene in dehydrated tomato products carotenoid isomerization in food system. J. Food Sci. 44 84-86. 

While only two geometrical isomers exist in simple unsaturated molecules, a number of cis-trans isomers can exist in polyenes (e.g. carotenoids ). Normally, the alI-/ra/w-isomer is preponderant in carotenoids. Isomerization of the all-ftms-carotenoids by acid- or iodine-catalysis yield the so-called neo-carotenoids. The neo-carotenoids are believed to possess one c/s-ethylenic bond in the central position of the conjugated chain9. The neo-carotenoids exhibit not only a weaker long wavelength band 470 nyx) than the all... 

Carotenoid isomerization can occur in the acidic gastric milieu. Lycopene present in fruits and vegetables occurs almost exclusively as the aW-trans isomer, but is converted to cis isomers, which seem to be more bioavailable. Plasma and tissue profiles show that cis isomers make up more than 50% of the total lycopene present. On the other hand, studies show that no trans/cis isomerization of /3-carotene occurs in the stomach. In fact, evidence has been found for transfer of a significant portion of both /3- and a-carotene to the fat phase of the meal in the stomach, which would increase bioavailability of these carotenoids for absorption. No studies are available relating isomerization to bioavailability of other carotenoids. 

PApo-8 -carotenal. The specifications of this colorant. (38) were discussed earlier. P-Apo-8 -carotenal has provitamin activity with 1 g of the colorant equal to 1,200,000 lU of vitamin A. Like all crystalline carotenoids, it slowly decomposes ia air through oxidatioa of its coajugated double boads and thus must be stored ia sealed coataiaers uader an atmosphere of iaert gas, preferably under refrigeration. Also like other carotenoids P-apo-8 -carotenal readily isomerizes to a mixture of its cis and trans stereoisomers when its solutions are heated to about 60°C or exposed to ultraviolet... 

Carotenoids have two general characteristics of importance to the food iadustry they are not pH sensitive ia the normal 2—7 range found ia foods, and they are not affected by vitamin C, making them especially important for beverages. They are more expensive than synthetic food dyes and have a limited color range. In their natural environment they are quite stable, but they become more labile when heated or when they are ia solution. Under those conditions, there is a tendency for the trans-double bonds to isomerize to the cis-stmcture with a subsequent loss of color iatensity. The results of controlled tolerance and toxicity tests, usiag pure carotenoids, iadicate that they are perfecdy safe as food colors (132). 

CLOUGH j M and pattenden g (1983) Stereochemical assignment of prolycopene and other poly-c isomeric carotenoids in fruits of the tangerine tomato Lycopersicon esculentum var, Tangella J Chem Soc Perkin Trans, 1, 30121-18. 

The effects of temperature on carotenoid content can be considered from three perspectives (1) evaluation of stability or retention of carotenoids, (2) study of the chemical changes (isomerization, oxidation, epoxy-furanoid rearrangement), and (3) their effects on the nutritional value and other carotenoid actions in humans. The first two topics are discussed in the following sections. The third is presented in Section 3.2.4.1 of Section 3.2. 

Among thermal processes, canning caused the largest trans-to-cis isomerization of provitamin A carotenoids, increasing the total cis isomers by 39% for sweet potatoes, 33% for carrots, 19% for collards, 18% for tomatoes, and 10% for peaches 13-di-P-carotene was the isomer formed in highest amonnts. ... 

Losses of 45 to 48% in the P-carotene contents and formation of cis isomers were also verified by pasteurization of carrot juice at 110 and 120°C for 30 sec. No significant effects on trans-to-cis isomerization of a- and P-carotene isomers were observed after acidification and heating of carrot juice at 105°C for 25 sec. In addition, an increase of only 3% in the cis isomers of provitamin A carotenoids was observed after orange juice pasteurization. " ... 

Aside from isomerization, transformation of the 5,6-epoxy to the 5,8-furanoid group is a common alteration during heating treatments of carotenoids. Violaxanthin was found to be the major carotenoid in mangoes however, in commercially processed mango juice, violaxanthin was not detected while auroxanthin, not present in the... 

In dark conditions, the spontaneous isomerization of carotenoids occurs in solution the rate is dependent on temperature, solvent, and carotenoid structure. In the case of P-carotene, 13-di-P-carotene was formed approximately three times faster than the 9-cis- isomer at room temperature and at 150°C. ... 

Scotter, M.J., Characterization of the coloured thermal degradation products of bixin from annatto and a revised mechanism for their formation, Food Chem., 53, 111, 1995. Zechmeister, L., Cis-trans isomerization and stereochemistry of carotenoids and diphenylpolyenes, Chem. Rev., 34, 267, 1944. 

Desaturation and Isomerization to Coeored Carotenoids Biosynthesis of Lycopene... 

The carotenoid isomerase (CRTISO) was the first isomerase associated with the desaturation steps and named at a time when Z-ISO was unknown to exist ise.ws.ieo.iei (and reviewed in references ). In vitro analysis of substrate conversion " and transcript profiling in planta associated CRTISO with the desaturation steps. Isaacson demonstrated that CRTISO is specific for the 7,9 or 7,9- cis bond configuration and is not involved in the isomerization of the l5-l5-cis double bond to the trans conformation. As recently shown, Z-ISO is required for isomerization of the 15-15 cis double bond of phytoene produced in dark-grown tissues as well as in stressed photosynthetic tissues. Therefore, desaturation of phytoene to lycopene involves a two-step desaturation by PDS, followed l5-cis isomerization by Z-ISO, and then each pair of double bonds introduced by ZDS is followed by CRT-ISO-mediated isomerization of the resulting conjugated double bond pair. 

Clough, J.M. and Pattenden, G., Stereochemical assignment of prolycopene and other poly-z-isomeric carotenoids in the fruits of the tangarine tomato Lycopersicum esculentum var. Tangella, J. Chem. Soc. Perkin Trans. I, 3011, 1983. 

When the aim is isolation for identification by direct probe insertion mass spectrometry (MS), plastic materials, filter papers, and blenders should be avoided to prevent contamination during extraction and chromatography. It is also very important to avoid the cis-trans isomerization of carotenoids in solution, which is accelerated by heat, light, acids, and active surfaces. Therefore, a pure carotenoid or even a crude extract should never be stored in solution it should be kept completely dry in an inert atmosphere at low temperature. 

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