Ascorbic acids, structure

Ascorbic acid (vitamin C) is one of the body s endogenous water-soluble antioxidants. Modifications on the ascorbic acid structure have led to some very interesting compounds, such as a novel series of 3-O-alkyl ascorbic-acid derivatives. They have been found to be inhibitors of lipid peroxidation (Nihro etal., 1991). This antioxidant activity is directly related to the lipophilicity of the alkyl chain, su esting that the lipid chain may anchor the antioxidant portion of the molecule in the membrane. 

The second route to an ascorbic acid analog consisted in oxidation by bromine to a 2-ketoacid with the same number of carbon atoms, enoliza-tion, and lactonization. The product was not crystallized, but the optical rotation of the sirup, [ ]d —20° (in water), was in fair agreement with that for the expected D-arabo-ascorbic acid. The sirup was strongly reducing and gave the absorption peak at 2450 A. characteristic of the ascorbic-acid structure. 

The growth and development of spectroscopic techniques in the years following the successful elucidation of the L-ascorbic acid structure have enabled that structure to be examined and understood more deeply. 

L-Ascorbic acid, better known as vitamin C, has the simplest chemical structure of all the vitamins (Figure 18.30). It is widely distributed in the animal and plant kingdoms, and only a few vertebrates—humans and other primates, guinea pigs, fruit-eating bats, certain birds, and some fish (rainbow trout, carp, and Coho salmon, for example)—are unable to synthesize it. In all these organisms, the inability to synthesize ascorbic acid stems from a lack of a liver enzyme, L-gulono-y-lactone oxidase. 

The isolation of ascorbic acid was first reported by Albert Szent-Gyorgyi (who called it hexuronie add) in 1928. The structure was determined by ITirst and Haworth in 1933, and, simultaneously, Reichstein reported its synthesis. Haworth and Szent-Gyorgyi, who together suggested that the name be changed to L-ascorbic acid to describe its antiscorbutic (antiscnrvy) activity, were awarded the Nobel Prize in 1937 for their studies of vitamin C. 

The reaction of iodate with triose reductone is not only a function of the concentration of the reagents, it is also dependent on the pH of the solution. In solutions of triose reductone more dilute than 10"3M, iodine is set free from iodate, if the pH of the solution is lower than about 3 (55). Dihydroxyfumaric and L-ascorbic acids (26), which also have free ene-diol structures, behave similarly. 

Vitamin C, or ascorbic acid, is surely the best known of all vitamins. It was the first vitamin to be discovered (1928), the first to be structurally characterized (1933), and the first to be synthesized in the laboratory (1933). Over 200 million pounds of vitamin C are now synthesized worldwide each year, more than the total amount of all other vitamins combined. In addition to its use as a vitamin supplement, vitamin C is used as a food preservative, a "flour improver" in bakeries, and. an animal food additive. 

Vitamin C. Figure 1 Structure of ascorbic acid, semidehydro ascorbic acid, and dehydroasorbic acid. 

DAG is an ascorbic acid derivative with the following structure ... 

Scurvy affects the structure of collagen. However, it is due to a deficiency of ascorbic acid (Chapter 45) and is not a genetic disease. Its major signs are bleeding... 

Colorimetric procedures used In steroid assays are often subject to drug Interference. In the determination of 17-Ketosterolds by the Zimmerman reaction, drugs with the 17-Keto basic structure such as ascorbic acid, morphine and reserplne will cause Increased values. In the determination of 17,21 -dlhydroxysterolds by the Porter-Sllber reaction the dlhydroxy-acetone chain Is the reactive unit. Drugs like meprobamate, chloral hydrate, chloropromazlne and potassium Iodide will Interfere with this reaction and cause elevated values. In the colorimetric determination of vanlllylmandellc acid (VMA) by a dlazo reaction, drugs like methocarbamol and methyl dopa cause... 

The effect of various types of inhibitors with respect to structure and solubility on the formation of N-Nitrosodiethanolamine was studied in a prototype oil in water anionic emulsion, Nitrosation resulted from the action of nitrite on diethanolamine at pH 5.2-5.A, Among the water soluble inhibitors incorporated into the aqueous phase, sodium bisulfite and ascorbic acid were effective. Potassium sorbate was much less so. The oil soluble inhibitors were incorporated into the oil phase of the emulsion. 

Garcia-Viguera, C. and Bridle, R, Influence of structure on colour stability of anthocyanins and flavylium salts with ascorbic acid, Food Chem., 64, 21, 1999. 

Antioxidant capacities of common individual curcuminoids were determined in vitro by phosphomolybdenum and linoleic acid peroxidation methods. Antioxidant capacities expressed as ascorbic acid equivalents (pmol/g) were 3099 for curcumin, 2833 for demethoxycurcumin, and 2677 for bisdemethoxycurcumin at concentrations of 50 ppm. The same order of antioxidant activity (curcumin > demethoxycurcumin > bisdemethoxycurcumin) was observed when compared with BHT (buty-lated hydroxyl toluene) in linoleic peroxidation tests. The antioxidant activity of curcumin in the presence of ethyl linoleate was demonstrated and six reaction products were identified and structurally characterized. The mechanism proposed for this activity consisted of an oxidative coupling reaction at the 3 position of the curcumin with the lipid and a subsequent intramolecular Diels-Alder reaction. ... 

The presence of o-qulnone surface waves seems, at the present time, to be coincidental to activation particularly In the case of ascorbic acid oxidation. On the other hand. Its presence may serve as a criterion of cleanliness and activation. Thus, the surface waves at 0.250 and 0.190 are Indicators or signatures for active GCE electrodes and should be used as diagnostic for a clean GCE surface as Is the hydrogen fine structure for platinum (31). It Is unfortunate that the o-qulnone peaks do not appear to be proportional to the surface area as Is the platinum fine structure. 

Many compounds of biomedical interest, both of endogenous and exogenous origin, are heterocyclic in structure. Many of these compounds are electroactive at potentials useful for LCEC analysis. Methods for the determination of both ascorbic acid and uric acid were developed in the early days of LCEC. The important enzyme... 

Figure 12.4 Molecular structures of L-ascorbic acid and D-glucose.

It should be remembered that some of the established antioxidants have other metabolic roles apart from free-radical scavenging. The finding of reduced antioxidant defences in diabetes, for example, may not be prima fascie evidence of increased oxidative stress, since alternative explanations may operate. For example, this may reflect a response to reduced free-radical activity as su ested by the results of a previous study (Collier et al., 1988). In the case of ascorbate, an alternative explanation has been proposed by Davis etal. (1983), who demonstrated competitive inhibition of ascorbate uptake by glucose into human lymphocytes. This view is supported by the similar molecular structure of glucose and ascorbic acid (see Fig. 12.4) and by a report of an inverse relationship between glycaemic control and ascorbate concentrations in experimental diabetes in rats. Other investigators, however, have not demonstrated this relationship (Som etal., 1981 Sinclair etal., 1991). 

Since many essential nutrients (e.g., monosaccharides, amino acids, and vitamins) are water-soluble, they have low oil/water partition coefficients, which would suggest poor absorption from the GIT. However, to ensure adequate uptake of these materials from food, the intestine has developed specialized absorption mechanisms that depend on membrane participation and require the compound to have a specific chemical structure. Since these processes are discussed in Chapter 4, we will not dwell on them here. This carrier transport mechanism is illustrated in Fig. 9C. Absorption by a specialized carrier mechanism (from the rat intestine) has been shown to exist for several agents used in cancer chemotherapy (5-fluorouracil and 5-bromouracil) [37,38], which may be considered false nutrients in that their chemical structures are very similar to essential nutrients for which the intestine has a specialized transport mechanism. It would be instructive to examine some studies concerned with riboflavin and ascorbic acid absorption in humans, as these illustrate how one may treat urine data to explore the mechanism of absorption. If a compound is... 

Vitamin C or L-ascorbic acid, the antiscorbutic vitamin, has been shown by degradative1 and synthetic methods1 to have the structure I. 

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