Oxidation Of Bisulfite Research Articles

Chemical reactions of menadione with probes for superoxide: A cautionary note: [formula omitted], Lawrence J Berliner, A John Merola, Valerie P Wright, Thomas L Clanton. The Ohio State Univ, Pulm. and Crit. Care Med. and Biophysics, Columbus, OH

We have reexamined the formation and reactions of radicals formed from peroxynitrite (ONOO−)-mediated oxidation of glutathione (GSH),l-cysteine (Cys),N-acetyl-d,l-penicillamine (NAP), and sodium bisulfite (NaHSO3). Sulfur-centered and superoxide anion radicals were trapped using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and the radical adducts were analyzed by electron spin resonance (ESR) spectroscopy. The following sulfur-centered radicals were detected: glutathionyl radical (GS•) from GSH,l-cysteinyl radical (•Scys) froml-cysteine,N-acetyl-d,l-penicillamine thiyl radical (•Snap) from NAP, and sulfite anion radical[formula]from NaHSO3. Additionally the formation of the hydroxyl radical adduct of DMPO (DMPO/•OH) was observed. DMPO/•OH formation was totally inhibited by low-molecular-weight superoxide dismutase (SOD) mimics. This suggests that DMPO/•OH was formed from the decay of the superoxide radical adduct of DMPO. In the presence of SOD mimics, the DMPO-sulfur-centered adducts were more persistent, suggesting that[formula]is partially responsible for the instability of DMPO-thiyl adducts. Sulfur-centered radicals formed during oxidation of thiols and sulfite by peroxynitrite react with ammonium formate to form the carbon dioxide anion radical[formula]We conclude that sulfur-centered radicals produced from the oxidation of thiols and sulfite by peroxynitrite arise from a hydroxyl-radical-independent mechanism. Biological implications of peroxynitrite-mediated oxidation of thiols as well as the use of SOD mimics in biological spin-trapping are discussed.

Chemiluminescent Determination of Menadione Sodium Bisulfite

ABSTRACT A chemiluminescence (CL) system for menadione sodium bisulfite (MSB) combined with a flow-injection system is presented in this paper. It is based on CL produced by the oxidation of bisulfite liberated from MSB by Ce(IV). The system responds linearly to MSB concentration in the range of 0.01 ∼ 10 μg/mL with the detection limit (3τf) of 2 x 10−3 μg/mL. The relative standard deviation for 2 μg/mL MSB was 3.45% (n=10). The system has been applied successfully to the determination of MSB in injections.

Exploration of the Mechanism of the Oxidation of Sulfur Dioxide and Bisulfite by Hydrogen Peroxide in Water Clusters UsingAb InitioMethods

Mechanisms for the oxidation of sulfur dioxide and bisulfite by hydrogen peroxide in water droplets have been explored using ab initio electronic structure methods. The large barriers that are found for bimolecular reactions are considerably reduced upon the inclusion of explicit water molecules, which provide a proton shuttle mechanism to facilitate the reaction. Further solvation of these clusters, either by a continuum model or by explicit water molecules modeled classically, has little effect on the reaction energetics. The transition state for reaction of bisulfite and hydrogen peroxide effectively involves SO2 and OH-, thus leading to acid catalysis for this reaction, analogous to the oxygen exchange in bisulfite in aqueous solution. The possibility of direct formation of sulfur(VI) species in a single step is less likely on energetic grounds.

What are the reacting species in the oxidation of bisulfite by hydrogen peroxide in water clusters?

M. A. Vincent, I. H. Hillier and I. J. Palmer, Chem. Commun., 1997, 1725 DOI: 10.1039/A703949B

Uncatalyzed heterogeneous oxidation of calcium bisulfite

Wet limestone scrubbing is the most common flue gas desulfurization process for control of sulfur dioxide emissions from combustion of fossil fuels. Forced oxidation in the scrubber loop improves the dewatering properties of the sludge, leading to the formation of gypsum (CaSO 4·2H 2O). A literature analysis revealed that uncertainties on the mechanisms of the oxidation reaction and on the values of the kinetic parameters still remain. In the present work the oxidation rate was experimentally studied by contacting pure oxygen or mixtures of oxygen and nitrogen with a calcium bisulfite solution. The experiments were carried out in a well-mixed bubbling reactor varying temperature, oxygen partial pressure and sulfite concentration, in the absence of solid calcium sulfite and of catalytic species. It was shown that the rate of the process is controlled by reaction kinetics, and that the reaction rate is zero order in dissolved oxygen and 3 2- order in bisulfite ion.

Effect of Superoxide Dismutase Mimics on Radical Adduct Formation during the Reaction between Peroxynitrite and Thiols—An ESR-Spin Trapping Study

We have reexamined the formation and reactions of radicals formed from peroxynitrite (ONOO−)-mediated oxidation of glutathione (GSH),l-cysteine (Cys),N-acetyl-d,l-penicillamine (NAP), and sodium bisulfite (NaHSO3). Sulfur-centered and superoxide anion radicals were trapped using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and the radical adducts were analyzed by electron spin resonance (ESR) spectroscopy. The following sulfur-centered radicals were detected: glutathionyl radical (GS•) from GSH,l-cysteinyl radical (•Scys) froml-cysteine,N-acetyl-d,l-penicillamine thiyl radical (•Snap) from NAP, and sulfite anion radical[formula]from NaHSO3. Additionally the formation of the hydroxyl radical adduct of DMPO (DMPO/•OH) was observed. DMPO/•OH formation was totally inhibited by low-molecular-weight superoxide dismutase (SOD) mimics. This suggests that DMPO/•OH was formed from the decay of the superoxide radical adduct of DMPO. In the presence of SOD mimics, the DMPO-sulfur-centered adducts were more persistent, suggesting that[formula]is partially responsible for the instability of DMPO-thiyl adducts. Sulfur-centered radicals formed during oxidation of thiols and sulfite by peroxynitrite react with ammonium formate to form the carbon dioxide anion radical[formula]We conclude that sulfur-centered radicals produced from the oxidation of thiols and sulfite by peroxynitrite arise from a hydroxyl-radical-independent mechanism. Biological implications of peroxynitrite-mediated oxidation of thiols as well as the use of SOD mimics in biological spin-trapping are discussed.

Kinetic Study of SO5- and HO2 Radicals Reactivity in Aqueous Phase Bisulfite Oxidation

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetic Study of SO5- and HO2 Radicals Reactivity in Aqueous Phase Bisulfite OxidationAleksandr N. Yermakov, Boris M. Zhitomirsky, Grigoriy A. Poskrebyshev, and Stanislav I. StoliarovCite this: J. Phys. Chem. 1995, 99, 10, 3120–3127Publication Date (Print):March 1, 1995Publication History Published online1 May 2002Published inissue 1 March 1995https://doi.org/10.1021/j100010a023RIGHTS & PERMISSIONSArticle Views177Altmetric-Citations14LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (789 KB) Get e-Alerts

Reaction Mechanism of the Iron(III)‐Catalyzed Autoxidation of Bisulfite in Aqueous Solution: Steady State Description for Benzene as Radical Scavenger

AbstractThe Fe(III)‐catalyzed oxidation of bisulfite in aqueous solution was studied at pH = 3 in the presence of benzene by monitoring the rise of hydrogen ion activity and phenol product concentration as a function of time, keeping [HS03−/[Fetot]>>l. After a brief initial period, during which product concentrations rose rapidly and Fe(III) was largely converted toward Fe(II), the reaction underwent a period of slower growth characterized by a quasistationary state and nearly constant [Fe(II)]/[Fe(III)] ratio until toward the end of the reaction, when most of the S(IV) was consumed, Fe(II) was reoxidized toward Fe(III). In two sets of experiments either the concentration of benzene or that of [Fe(III)]o was varied in ranges of 0.3–2.2 mmol dm−3 and 8.5–51 μmol dm−3, respectively, while keeping the other parameters constant ([HSO3−]o = 2 mmol dm−3). The data were analyzed by means of a steady state expression developed for the time period of nearly constant [Fe(II)]/[Fe(III)] ratio on the basis of a radical‐driven chain oxidation mechanism presented previously. The data display the behavior predicted by the steady state equation; this allowed the determination of ratios of rate coefficients for reaction pairs: SO4− reacting with HSO3− and benzene, k11/k12 = 0.31±0.04; S05− reacting with Fe2+ and HSO3−, k3/k10 = 54.1±1.7; HSO5− reacting with Fe2+ and HSO3−, k4/k16 = 2.2±0.2; and the branching ratio for the reaction of SO5− with HSO3− leading to (a) SO3− and (b) SO4− radicals, k10b/k10≤0.04. The experimental results largely support the proposed reaction mechanism.

Kinetics and mechanism of the oxidation of bisulfite by peroxymonosulfate

The oxidation of bisulfite ion is of importance in flue gas desulfurization processes and in the conversion of gaseous SO[sub 2] into acid rain in water droplets in the atmosphere. The oxidation of bisulfite ion by peroxymonosulfate ion, HSO[sub 5][sup [minus]], to form sulfate ion has been studied in the pH region 3.8-7.9. The reaction HSO[sub 5][sup [minus]] + HSO[sub 3][sup [minus]] [yields] 2SO[sub 4][sup 2[minus]] + 2H[sup +] was found to obey the rate law -d[HSO[sub 5][sup [minus]]]/dt = [l brace]k[sub a][alpha][sub H[sup +]] + k[sub b][alpha][sub H[sup +]][sup [minus]1] + k[sub c][r brace][l brace]HSO[sub 5][sup [minus]][HSO[sub 3][sup [minus]]], where [alpha][sub H[sup +]] is the activity of hydrogen ion. At 25[degrees]C and ionic strength 0.0050 M the rate constants k[sub a], k[sub b], and k[sub c] have the values 1.27 [times] 10[sup 7], 6.4 [times] 10[sup [minus]5], and 55 M[sup [minus]1] S[sup [minus]1], with the activity of hydrogen ion taken to be dimensionless. For the reaction path corresponding to the k[sub a] term, 90% of the reaction yields the intermediate pyrosulfate ion, S[sub 2]O[sub 7][sup 2[minus]], which then hydrolyzes with about a 1-min lifetime to sulfate and hydrogen ions. Similarly the k[sub c] path forms mostly S[sub 2]O[sub 7][supmore » 2[minus]] as an intermediate. The k[sub b] path appears to all go directly to sulfate ion. Possible mechanisms for the various reaction paths are discussed. 25 refs., 4 figs., 3 tabs.« less

Corrosion Mechanisms for Zinc Exposed to the Atmosphere

Physical and chemical information on zinc corrosion layer formation, evolution, morphology, and chemical makeup is organized and presented, together with information on minerals containing zinc and other crystalline structures that might be expected to be present. The chemical reactions involved in the formation of these constituents during the corrosion process are then surveyed. The pH of the aqueous surface film is found to be crucial to the corrosion process, since it controls the dissolution of the passive oxyhydroxide surface. (The outdoor pH is largely a function of atmospheric and and is low in fogs and some rains, near neutral in dew, and generally lower in winter than in summer; indoors, the surface acidity is controlled by the composition of deposited particles.) The transition from traditional winter maxima in outdoor zinc corrosion to the more recent summer and fall maxima is explained as the juxtaposition of annually‐varying rates of bisulfite oxidation by and of atmospheric concentrations. Indoors, most of the surface degradation can be attributed to adsorbed sulfate aerosol particles; the indoor corrosion rates can be constrained to negligible levels by maintaining moderate relative humidities. Zinc is the only one of the common industrial metals for which a product containing carbonate is abundant, but sulfates and chlorides appear as well. In each case, the predominant forms are the slightly soluble hydroxide mixed salts. While full quantitative analyses of atmospheric zinc corrosion are not yet possible, it is clear that the process can only be understood in the context of the anionic surface chemistry of zinc.

Amperometric flow injection technique for determination of hydrogen peroxide and sulfur(IV) in atmospheric liquid water

A sensitive, selective and fast method for the determination of hydrogen peroxide and sulfur(IV) present in atmospheric liquid phase is described and discussed. The flow injection system used contains a specially designed electrochemical micro-cell. The necessary selectivity is achieved using an alkaline carrier flow for the oxidative determination of H2O2 and an acidic one for the bisulfite oxidation, and employing differential measurements before and after addition of catalase or sulfite oxidase, respectively. Samples of 200 μl volume can be injected at a rate of 30 per hour and the electroactive species be determined in the range from millimolar level down to the detection limit of 2 · 10−8mol/l. The S(IV) present as hydroxymethanesulfonate or in form of other carbonyl adducts is determined after a previous alkalinization of the sample to liberate the sulfite. The method has been tested with rain, snow, fog and cryo-sampled atmospheric water vapor. The time resolution is adequate to follow precipitation events.

Peroxidase-catalyzed oxidation of (bi)sulfite: reaction of free radical metabolites of (bi)sulfite with (+/-)-7,8-dihydroxy-7, 8-dihydroxy[a]pyrene.

The peroxidase-catalyzed metabolism of (bi)sulfite (hydrated sulfur dioxide) in the presence of (+/-)-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene (BP-7,8-diol) was examined. Both horseradish peroxidase and prostaglandin peroxidase catalyze the one-electron oxidation of (bi)sulfite. This results in the formation of a sulfur trioxide radical anion which then reacts with molecular oxygen to form a peroxyl radical. This (bi)sulfite-derived peroxyl radical then reacts with BP-7,8-diol to form BP-7,8-diol-9,10-epoxides, the ultimate carcinogenic form of benzo[a]pyrene (BP). Addition of (bi)sulfite to incubations containing BP-7,8-diol and an active peroxidase resulted in significantly increased levels of BP diol-epoxide formation. This result may, in part, explain the reported co-carcinogenic effect of sulfur dioxide on BP-induced tumors in the respiratory tracts of rats and hamsters. The sulfur trioxide radical anion also reacts directly with BP-7,8-diol to form a sulfonate adduct. This reaction was particularly significant under conditions where molecular oxygen was depleted from the incubations. While the significance of this particular adduct is not known, its formation suggests that the sulfur trioxide radical anion generated during the peroxidase-catalyzed oxidation of (bi)sulfite could react with a wide assortment of compounds to form sulfonate adducts.

Spin-trapping of sulfite radical anion, [formula omitted], by a water-soluble, nitroso-aromatic spin-trap

Sulfite radical anion, SO 3 • , which is generated either by non-enzymatic reaction of hydrogen peroxide (H 2O 2−) with sulfite (SO 3 2−) or by the oxidation of bisulfite (HSO 3 2−) with Ce 4+ ion, can be trapped with a water-soluble, nitroso-aromatic spin-trap, sodium 3,5-dibromo-4-nitrosobenzenesulfonate (DBNBS, 1), yielding an ESR spectrum with coupling constants [a N (1) = 12.9 G̃, a H (2)=0.8 G] and a g-value of 2.0063. The SO 3 − radical adduct (spin adduct) was observed even in the presence of the very low concentration of H 2O 2 (1.21 × 10 −2 μmol).

Incompatibility of cisplatin and Reglan Injectable

The stability of cisplatin ( cis-diamminedichloroplatinum (II)) in solutions containing Reglan Injectable, comprised of metoclopramide, sodium metabisulfite and sodium chloride, was examined. Loss of cisplatin was monitored by measuring the increasing chloride ion concentrations with a chloride ion-specific electrode. Cisplatin was stable in solution with metoclopramide alone, but degraded very rapidly in solution with metabisulfite. At concentrations similar to those which might be expected in clinical situations (cisplatin = 0.2 mg/ml, metabisulfite = 0.148 mg/ml, metoclopramide = 0.5 mg/ml) there was total loss of cisplatin within 30 min at room temperature. The results indicate that cisplatin reacts with species formed in the oxidation of bisulfite. Therefore, cisplatin should not be admixed with Reglan Injectable solution or any solution containing bisulfite or chemically related antioxidants.

High Efficiency Annular Denuder for Formaldehyde Monitoring

Abstract A practical and correct methodology for evaluating CH2O in air without sampling artifact formation is presented. Formaldehyde is collected on an annular denuder coated with bisulfite-triethanolamine. The sorbent layer is extracted with water and the solution analyzed by the chromotropic acid (CTA) procedure. Sorption efficiency and loading capacity have been investigated along with storage stability. Results of laboratory validation studies have indicated that a small annular denuder was able to sample about 300 μg CH2O without an appreciable decrease in the initial collection efficiency (99% at 2.5 1 min−1). Tests on storage stability before and after exposure have also demonstrated that both oxidation of bisulfite and release of CH2O did not occur for time periods as long as 1 month.

The formation of sulfur trioxide radical anion during the prostaglandin hydroperoxidase-catalyzed oxidation of bisulfite (hydrated sulfur dioxide).

The mechanism of prostaglandin synthase-dependent (bi)sulfite (hydrated sulfur dioxide) oxidation was investigated using an enzyme preparation derived from ram seminal vesicles. The horseradish peroxidase-catalyzed oxidation of (bi)sulfite was used as a model system. Incubation of (bi)sulfite with prostaglandin synthase and arachidonic acid, 15-hydroperoxyarachidonic acid, or H2O2 results in the formation of the reactive sulfur trioxide anion radical (SO3(-)). The horseradish peroxidase/H2O2 system also oxidizes (bi)sulfite to SO3(-). This free radical reacts with oxygen resulting in oxygen consumption by these incubations. The free radical was detected with the indirect electron spin resonance technique of spin trapping. The SO3(-) radical adduct formed by the reaction of SO3(-) with the spin trap, 5,5-dimethyl-1-pyrroline-N-oxide, gives a nitroxide free radical with a nearly unique electron spin resonance spectrum (aH = 16.0 G and aN = 14.7 G). Using the spin-trapping technique, the SO3(-) could be detected even in incubations of guinea pig lung microsomes. When arachidonic acid-derived prostaglandin G2 was the source of hydroperoxide, formation of SO3(-) could be inhibited by indomethacin. When 15-hydroperoxyarachidonic acid or hydrogen peroxide was used to drive the enzymatic oxidation of (bi)sulfite, indomethacin had no effect. This hydroperoxidase activity was not nearly as heat-labile as the cyclo-oxygenase reaction which forms prostaglandin G2. Finally, the peroxidatic oxidation of (bi)sulfite may occur in vivo in competition with the mitochondrial sulfite oxidase, which oxidizes (bi)sulfite to sulfate without the formation of free radicals.

Partial cyanide inhibition of bisulfite oxidation in rodent hepatic mitochondria.

Partial cyanide inhibition of bisulfite oxidation in rodent hepatic mitochondria.

Catalysis by cationic polyelectrolytes and micelles in bisulfite oxidation

AbstractThe oxidation of sodium bisulfite in the presence of cationic polyelectrolytes or micelles has been studied. The formation of cationic‐bisulfite complexes is indicated, and a kinetic analysis suggests the validity of the enzyme kinetics applied to determine the kinetic parameters. Distinct differences in the activity of cationics depend on the configuration of the cationics in solution; micelle‐forming cationics are more effective than nonmicellar polycationics, except in the case of poly(diallyldimethylammonium chloride), (PDADM). The oxidation rate is strongly affected by the presence of monomer in the system, especially where nonmicellar polycationics are involved.

A model for the reversible washout of sulfur dioxide, ammonia and carbon dioxide from a polluted atmosphere and the production of sulfates in raindrops

A model has been developed to describe the washout of trace atmospheric gases and the production of acids in rain. The model is applied to washout of sulfur dioxide, carbon dioxide and ammonia and incorporates reversible mass transfer of the trace gases, ionic equilibria of the compounds in solution and catalyzed oxidation of the dissolved sulfur species to sulfates. The significance of ammonia and carbon dioxide on the raindrops' capacity for sulfur and on sulfate production based solely on bisulfite oxidation are explored in detail. The influence of raindrop size, rainfall intensity, cloud-base height, the presence of oxidation catalyzing compounds in the atmosphere and the initial composition of the raindrops as they enter the polluted atmospheric layer on the detailed chemical composition of rain at ground level and the time scale for gaseous sulfur dioxide removal are evaluated. Illustrative model simulations demonstrate that when simultaneous mass transfer of SO 2 and NH 3 are involved, the effective driving force for the transport of both gases can be reduced. This results in much longer relaxation times for the absorption process, and may shift conditions to a point where mass-transfer is the rate controlling step in the SO 2 oxidation process. Carbon dioxide was found to have little effect on the concentration transients or the approach to equilibrium composition of raindrops as they fall through the mixed layer. Ammonia, however, considerably increases rain's capacity for sulfur and may cause the chemical composition of even small droplets (light rainfalls) to be mass-transfer rate limited in extremum conditions. In addition, the effect of a background non-volatile base (such as NaOH) on the transient composition of rain was found to be quite different than the effect of a volatile base, (NH 3) g. The presence of a non-volatile base in the atmosphere may be causitive to occurrence of a bimodal pH distribution in raindrop size spectra.

Bisulfite Degrades Aflatoxin: Effect of Citric Acid and Methanol and Possible Mechanism of Degradation

Citric acid retarded degradation of aflatoxins B1 and G1 by bisulfite. Replacement of potassium acid phthalate-NaOH with citric acid-NaOH in the mixture of buffer (50 ml, 0.035 M)-methanol (0.65 ml)−0.8g of K2SO3, pH 5.5, at 25 C resulted in a decrease from 9.76 × 10−3h− to 2.47 × 10−3h− and from 1.19 × 10−2h− to 4.32 × 10−3h− in rate of degradation of aflatoxin B1 and G1, respectively. Methanol also retarded degradation of aflatoxin by bisulfite. Increasing the methanol concentration from 1.3 to 10.0% (v/v) in 50 ml of 0.035M KHP-NaOH buffer, pH 5.5, plus 0.40g of K2SO3, resulted in a decrease in rate constants from 4.26 × 10−3h− to 2.16 × 10−3h− for aflatoxin B1 and from 5.54 × 10−3h− to 2.98 × 10−3h− for aflatoxin G1, Presence of citric acid and various concentrations of methanol also reduced rates at which free bisulfite concentrations changed. From these observations, known effects of methanol and probable effects of citric acid on bisulfite oxidation, we suggest that degradation of aflatoxin by bisulfite is dependent on bisulfite oxidation. 14C-labelled aflatoxin B1 was treated with K2SO3 at pH 5.5 and allowed to react for 96 h. Most of the degradation product(s) were in the water soluble phase, indicating that a structural modification of aflatoxin occurred.