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M Saran

Publications and source records attributed to M Saran.

At least 37 records · Page 2Linked to original sources

Calcium in lipid peroxidation: does calcium interact with superoxide?

Using a pulse radiolysis approach to generate and observe superoxide anions (O2-.) in the absence and presence of calcium, we have attempted to verify the recent hypothesis of Babizhayev (Arch. Biochem. Biophys. 266, 446-451, 1988) of a Ca2(+)-O2-. interaction during lipid peroxidation. We could not observe rapid scavenging of O2-. or complex formation with Ca2+ to account for an inhibitory effect of this cation on lipid peroxidation. Neither could we agree that the stimulatory effect is due to liberation of catalytic ferrous iron from weak complexes by Ca2+. Drawing on reports in the literature, we propose an alternate explanation for the apparent stimulation of lipid peroxidation by low Ca2+ concentrations. In our view, this is not a direct effect, but reflects independently initiated processes of lipid peroxidation and Ca2+ translocation, which interact subsequently in a synergistic manner. The reported inhibition at high Ca2+ concentrations is considered an artifact as it was observed at levels far in excess of those relevant to animal systems (but not necessarily in some plant compartments).

Acetates↗

Reaction of NO with O2-. implications for the action of endothelium-derived relaxing factor (EDRF).

Under physiological pH conditions (pH 7.2-7.4) the rate constant of the reaction NO + O2- yielding peroxonitrite (ONOO-) was determined as k = (3.7 +/- 1.1) x 10(7) M-1 s-1. The decay of peroxonitrite at this pH follows first order kinetics with a rate constant of 1.4 s 1. At alkaline pH peroxonitrite is practically stable. Possible consequences of these reactions for the biological lifetime of EDRF will be discussed.

Hydrogen-Ion Concentration↗

The mechanism of cytochrome C reduction by alkyl radicals. Evidence for multiple reaction pathways.

The reactions of the hydroxyalkyl radicals .CH2OH and (CH3)2.COH with oxidized cytochrome c are for more complex than previously reported. Analysis of the pulse-radiolytic data by kinetic modelling revealed that only about 40% of the alkyl radicals reduce the ferric iron chromophore. Altogether, four different reactions have to be considered for the disappearance of the alkyl radicals, only two of which affect the metal site. The data show that these radicals, similar to the much more reactive hydrated electrons and hydrogen atoms, are capable to react with biological macromolecules in diverse ways.

Cytochrome c Group↗

Oxygen radicals acting as chemical messengers: a hypothesis.

Based on a critical reappraisal of the reactions of radicals in a biological milieu, a hypothesis is proposed according to which superoxide anion radicals act as biological messengers rather than as mediators or precursors of cellular damage under oxidative stress conditions.

Animals↗

A critical reevaluation of some assay methods for superoxide dismutase activity.

We have compared the direct method of pulse radiolysis to the indirect methods of cytochrome c and nitroblue tetrazolium for assaying the superoxide dismutase activity of a compound. We have shown that with pulse radiolysis, where high concentrations of O2- are generated, the "turnover" rate constant, kcat, can be determined directly, while with the indirect methods, where relatively low steady state concentrations of O2- are formed, the value of kcat determined by these methods, can be orders of magnitude lower than that determined directly. The main reason for the lower values obtained with the indirect methods is due to the fast reoxidation of the reduced compound by molecular oxygen. Additional problems which arise with the use of indirect methods for determining superoxide dismutase catalytic activity are discussed.

Copper↗

Determination of sulfite radical (SO.3-) reaction rate constants by means of competition kinetics.

The sulfite radical anion (SO.3-) was found to react rapidly with the flavonoid quercetin (k = 2.5 x 10(8) dm3mol-1s-1) and the carotenoids crocin (k = 1.0 x 10(9) dm3mol-1s-1) and crocetin (k = 1.5 x 10(9) dm3mol-1s-1). The reactions can easily be monitored due to the strong absorptions of the substrates and, in the case of quercetin, the formation of a strongly absorbing transient species. Using these substances, we determined by means of competition kinetics rate constants of SO.3- reactions with nucleic acid components, polyunsaturated fatty acids, and glutathione.

Carotenoids↗

Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study.

Linoleic acid peroxyl radicals (LOO.) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using the technique of pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N2O/O2-saturated solutions leads to a mixture of peroxyl radical isomers, whereas reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N2O-saturated solution produces 13-LOO. radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with the two flavonols, kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO.). The same aroxyl radicals were generated by .OH and N3. with rate constants exceeding 10(9) dm3 mol-1 s-1. Applying a reaction scheme that includes competing generation and decay reactions of both LOO. and ArO. radicals, we derived individual rate constants for LOO. reactions with the phenols (greater than 10(7) dm3 mol-1 s-1), with the aroxyl radicals to form covalent adducts (greater than 10(8) dm3 mol-1 s-1), as well as for their bimilecular decay (3.0 X 10(8) dm3 mol-1 s-1). These results demonstrate the high reactivity of both fatty acid peroxyl radicals and the flavone antioxidants in aqueous solution.

Antioxidants↗

The reaction of sulfite radical anion with nucleic acid components.

The sulfite radical anion (SO3.-) is the first intermediate in the autoxidation of sulfite to sulfate. Using competition kinetics, its reactivities with the nucleic acid bases and the corresponding nucleosides were investigated. The second order rate constants were found to be rather low, k less than or equal to 1 x 10(6) dm3mol-1s-1 at pH 7. As a competitor, the carotenoid crocin was used, which was found to be bleached very efficiently by SO3.- (k = 1.0 x 10(9) dm3mol-1 s-1).

Carotenoids↗

Radical scavenging by flavonoid antioxidants.

Aroxyl radicals of fifteen structurally distinct flavonoids were generated by attack of azide radicals (N3.) on the parent compounds dissolved in aqueous solution at pH 11.5. Generation rate constants were all found to be very high (2.4-8.8 x 10(9) dm3mol-1 s-1), whereas the decay rates differed considerably, ranging from 10(5) to 10(8) dm3mol-1 s-1. In most cases the spectral characteristics of the transient aroxyl radicals relate to structural features of the parent compounds and according to spectral similarities they can be classed in three distinct groups (with only two exceptions). Although the data do not conclusively prove that the biological function of flavonoids might be the scavenging of radicals, the very high rate constants of formation and the relative stability of some of the aroxyl radicals, are in support of such a hypothesis.

Antioxidants↗

The kinetics of the reaction of ferritin with superoxide.

Using pulse radiolysis and competition kinetics with cytochrome c, the reaction of superoxide with horse spleen ferritin was investigated. The second-order rate constant is estimated to be 2 +/- 1 x 10(6) dm3 mol-1 s-1.

Cytochrome c Group↗

Pulmonary tuberculosis among contacts of patients with tuberculosis in an urban Indian population.

The study was conducted among 1810 contacts of 50 index "cases"/"suspects" of pulmonary tuberculosis including 312 household and 1498 neighbourhood contacts in the Jhansi city of Uttar Pradesh. The overall prevalence of radiologically active and bacteriologically confirmed tuberculosis was 2.9% and 1.1%. The prevalence rates of radiologically active and bacteriologically confirmed disease, although comparatively high in both the contact groups, were significantly higher in household (5.4% and 2.6%) than in neighbourhood contacts (2.3% and 0.8%). Significant differences in distribution of secondary cases among clusters were observed. Although higher prevalence rates were found in contacts of sputum positive source than in contacts of sputum negative source in both the contact groups, the statistical difference was observed to be insignificant. Case yield among contact symptomatics was 80.0% (30.8% cases and 49.2% suspects).

Adolescent↗

The value of the small bowel enema to the general surgeon.

Lesions of the small bowel are notoriously difficult to diagnose, many only coming to light at laparotomy. At this hospital the small bowel enema has been used for radiology of the small bowel for many years. The procedure is uncomfortable for the patient, as intubation of the proximal small bowel is essential, and for the radiologist it can be very time-consuming. A review of patients referred by the general surgeons over the past 5 years has demonstrated the value of the technique. It has proved to be accurate in over 90 per cent of cases with only 2 per cent false negative and 1 per cent false positive results. The most common diagnosis has been Crohn's disease which can be very accurately assessed. Other lesions diagnosed include lymphoma, involvement by metastases, benign stricture and adhesions. A normal results has prevented an unnecessary laparotomy in several patients. It is concluded that this technique is the most satisfactory method for radiology of the small bowel and it should be much more widely available.

Adolescent↗

Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons.

The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (.OH) and hydrated electrons (eaq-), while superoxide anions (O2-) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation.

Carotenoids↗

Formation of ethylene from methionine. Reactivity of radiolytically produced oxygen radicals and effect of substrate activation.

Ethylene was determined by gas chromatography after reaction of radiolytically produced OH and O2- radicals with methionine, methionine + pyridoxal phosphate and S-adenosyl-methionine (SAM). Both oxygen radicals, alone or in combination, liberate ethylene from methionine and methionine/pyridoxal phosphate. From SAM ethylene was primarily produced by the combined attack of OH nad H2O2 or O2-.

Chromatography, Gas↗