Retinyl

Fig. 1. Vitamin A and derivatives retinol (1), retinyl acetate [127-47-9] (2), retinyl palmitate [79-81-2] (3), and retinyl propionate [7069-42-3] (4).

Property Retinol Retinyl acetate Retinyl palmitate Retinyl propionate o p-carotene... 

Spectroscopic methods such as uv and fluorescence have rehed on the polyene chromophore of vitamin A as a basis for analysis. Indirectly, the classical Carr-Price colorimetric test also exploits this feature and measures the amount of a transient blue complex at 620 nm which is formed when vitamin A is dehydrated in the presence of Lewis acids. For uv measurements of retinol, retinyl acetate, and retinyl palmitate, analysis is done at 325 nm. More sensitive measurements can be obtained by fluorescence. Excitation is done at 325 nm and emission at 470 nm. Although useful, all of these methods suffer from the fact that the method is not specific and any compound which has spectral characteristics similar to vitamin A will assay like the vitamin... 

Retinyl acetate [127-47-9] M 328.5, m 57". Separated from retinol by column chromatography, then crystd from MeOH. See Kofler and Rubin [Vitamins and Hormones (NY) 18 315 1960] for review of purification methods. Stored in the dark, under N2 or Ar, at 0°. See Vitamin A acetate p. 574 in Chapter 6. 

Retinal (Vitamin A aldehyde). Retinoic acid (Vitamin A acid), Retinyl acetate, Retinyl palmitate see entries in Chapter 4. 

Retinoids are needed for cellular differentiation and skin growth. Some retinoids even exert a prophylactic effect on preneoplastic and malignant skin lesions. Fenretlnide (54) is somewhat more selective and less toxic than retinyl acetate (vitamin A acetate) for this purpose. It is synthesized by reaction of all trans-retinoic acid (53), via its acid chloride, with g-aminophe-nol to give ester 54 (13). 

Figure 10.9 Cliromatogi ams of foitified coconut oil obtained by using (a) normal-phase HPLC and (b) GPC/noimal-phase HPLC. Peak identification is as follows 1 (a,b), DL-a-toco-pheryl acetate, 2 (b), 2,6-di-tert-butyl-4-methylphenol 2 (a) and 3 (b), retinyl acetate 3 (a) and 4 (b), tocol 4 (a) and 5 (b), ergocalciferol. Reprinted from Analytical Chemistry, 60, J. M. Brown-Thomas et al., Determination of fat-soluble vitamins in oil matrices by multidimensional liigh-peiformance liquid cliromatography , pp. 1929-1933, copyright 1988, with permission from the American Chemical Society.

Retinyl Palmitate Topical 0.5-5% Emulsions Cosmetic agents ... 

Vitamin A describes a group of substances (retinol, retinyl esters, and retinal) with defined biological... 

C2()H2yCl 39668-34-3) see Betacarotene retinyl phenyl sulfone (C26H ,402S 39668-37-6) see Betacarotene retroprogesterone... 

Cosmetic Ingredient Review (1987) Final report on the safety assessment of retinyl palmitate and retinol. J Am Coll Toxicol 6 279-320... 

The a-tocopherol, P-carotene (ATBC) Cancer Prevention study was a randomised-controlled trial that tested the effects of daily doses of either 50 mg (50 lU) vitamin E (all-racemic a-tocopherol acetate), or 20 mg of P-carotene, or both with that of a placebo, in a population of more than 29,000 male smokers for 5-8 years. No reduction in lung cancer or major coronary events was observed with any of the treatments. What was more startling was the unexpected increases in risk of death from lung cancer and ischemic heart disease with P-carotene supplementation (ATBC Cancer Prevention Study Group, 1994). Increases in the risk of both lung cancer and cardiovascular disease mortality were also observed in the P-carotene and Retinol Efficacy Trial (CARET), which tested the effects of combined treatment with 30 mg/d P-carotene and retinyl pahnitate (25,000 lU/d) in 18,000 men and women with a history of cigarette smoking or occupational exposure to asbestos (Hennekens et al, 1996). 

VAN DEN BERG H and VAN VLIET T (1998) Effects of simultaneous, single oral doses of 3-carotene, with lutein or lycopene on the (3-carotene and retinyl ester responses in the triacylglycerol-rich lipoprotein fractions in men. Am J Clin Nutr 68(1) 82-89. 

VAN VLIET T, SCHREURS w H and VAN DEN BERG H (1995) Intestinal beta-carotene absorption and cleavage in men response to beta-carotene and retinyl esters in the triglyceride-rich lipoprotein fi action after a single oral dose of beta-carotene. Am J Clin Nutr 62(1) 110-16. 

In intestinal cells, carotenoids can be incorporated into CMs as intact molecules or metabolized into mainly retinol (or vitamin A), but also in retinoic acid and apoc-arotenals (see below for carotenoid cleavage reactions). These polar metabolites are directly secreted into the blood stream via the portal vein (Figure 3.2.2). Within intestinal cells, retinol can be also esterified into retinyl esters. 

Both intact carotenoids and their apolar metabolites (retinyl esters) are secreted into the lymphatic system associated with CMs. In the blood circulation, CM particles undergo lipolysis, catalyzed by a lipoprotein lipase, resulting in the formation of CM remnants that are quickly taken up by the liver. In the liver, the remnant-associated carotenoid can be either (1) metabolized into vitamin A and other metabolites, (2) stored, (3) secreted with the bile, or (4) repackaged and released with VLDL particles. In the bloodstream, VLDLs are transformed to LDLs, and then HDLs by delipidation and the carotenoids associated with the lipoprotein particles are finally distributed to extrahepatic tissues (Figure 3.2.2). Time-course studies focusing on carotenoid appearances in different lipoprotein fractions after ingestion showed that CM carotenoid levels peak early (4 to 8 hr) whereas LDL and HDL carotenoid levels reach peaks later (16 to 24 hr). 

Borel, P. et al.. Chylomicron (3-carotene and retinyl palmitate responses are dramatically diminished when men ingest (3-carotene with medinm-chain rather than long-chain triglycerides, J. Nutr, 128, 1861, 1998. 

Sharpless, K.E. et al., Valne assignment of retinol, retinyl palmitate, tocopherol, and carotenoid concentrations in standard reference material 2383 (baby food composite), J. AOAC Int., 82, 288, 1999. 

Retinol and retinyl Liver Common eider No Increased Wayland et al. 

Mossman, B.T., Craighead, J.E. and MaePherson, B.V. (1980). Asbestos-induced epithelial changes in organ cultures of hamster trachea inhibition by retinyl methvi ether. Science 207, 311-313. 

Tanumihardjo, S. A., H. C. Furr, O. Amedee-Manesme, and J. A. Olson. 1990. Retinyl ester (vitamin A ester) and carotenoid composition in human liver. Int. J. Vitam. Nutr. Res. 60 307-313. 

Vitamin A deficiency affects more than 100 million children around the world (Miller and others 2002) and thus remains an important public health problem in many countries. Vitamin A is essential for vision, reproduction, growth, immune function, and general health of humans (van Lieshout and others 2001). The major sources of vitamin A in the human diet are retinyl esters (preformed vitamin A) found in foods of animal origin and provitamin A carotenoids from fruits and vegetables. Unfortunately, foods containing preformed vitamin A (meat, milk, eggs, etc.) are frequently too expensive for some economically deprived developing countries, and therefore dietary carotenoids are the main source of vitamin A in these countries. 

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