Complex Kinetics in the Reaction of Taurine with Aqueous Bromine and Acidic Bromate : A Possible Cytoprotective Role against Hypobromous Acid

The most abundant aminoacid in the human body, 2-aminoethanesulphonic acid (H2NCH2CH2SO3H), is surprisingly stable and reacts exceedingly slowly even with the most powerful oxidizing agents like acidic bromate. Oxidation occurs only on the nitrogen centre to give the corresponding N-derivatives. No activity is observed at the sulphonic acid group and no cleavage of the C-S bond is observed. The stoichiometry of the oxidation of 2-aminoethanesulphonic acid by bromate is complex, yielding a mixture of monobromo- and dibromotaurines, oximes as well as the corresponding dimeric azo-compounds. In the presence of added bromide, the stoichiometry of the reaction is : 2BrO3- + 3H2NCH2CH2SO3H + 6H+ + 4Br- -> 3Br2NCH2CH2SO3H + 6H2O. Monobromotaurine is formedas an intermediate product before formation of the dibromotaurine. Aqueous bromine reacts quantitatively with 2-aminomethanesulphonic acid according to the stoichiometry : H2NCH2CH2SO3H + 2Br2 -> Br2NCH2CH2SO3H + 2Br- + 2H+. This reaction is strongly inhibited by acid due to the deactivation of the amino group to electrophilic attack by protonation. The formation of N-bromotaurines is suggested as a possible mechanism by which taurine can moderate the oxidative toxicity of bromine and hypobromous acid in the slightly basic physiological environments. South African Journal of Chemistry Vol.55 2002: 136-14

Low temperature synthesis of multiwalled carbon nanotubes and incorporation into an organic solar cell

Abstract: Metal nanoparticle (MNP) catalysts used for the synthesis of multiwalled carbon nanotubes (MWCNTs) consisted of single metals (Fe, Ni or Co) and bimetallic mixture (CoFe, NiFe or NiCo). MWCNTs were successfully synthesised at 200 _C in 10 min using liquefied petroleum gas as carbon source with non-equilibrium plasma enhanced chemical vapour deposition (PECVD) method. The nanostructures and the morphology of the MNPs and the MWCNTs film were characterised using relevant microscopic and spectroscopic methods. The synthesised MWCNTs were used as part of the electrode material in organic solar cell (OSC) set-up. Poly (3,4- ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) was used as an electron transporter and poly-3-hexyl thiophene (P3HT) as an electron donor. The performance of OSC devices was tested using standard electrical measurements and solar simulator operating at 100 mW/cm2. The measured power conversion efficiencies was found to be dependent on the metal catalyst used during synthesis. Among all the catalysts employed in this investigation, the best device performance was found from the synthesis of MWCNTs using Fe as a catalyst followed by Co and then Ni, respectively

Self-organization with traveling waves: A case for a convective torus

A traveling wave of BaSO4 in the chlorite-thiourea reaction has shown concentric precipitation patterns upon being triggered by the autocatalyst HOCl. The precipitation patterns show circular rings of alternate null and full precipitation regions. This self-organization appears to be the result of the formation of a convective torus. The formation of the convective torus can be described as a Benard-Marangoni instability with lateral heating

Electrochemistry-Coupled to Mass Spectrometry in Simulation of Metabolic Oxidation of Methimazole: Identification and Characterization of Metabolites

Methimazole (MMI), an antithyroid drug, is associated with idiosyncratic toxicity. Reactive metabolites resulting from bioactivation of the drug have been implicated in these adverse drug reactions. Mimicry of enzymatic oxidation of MMI was carried out by electrochemically oxidizing MMI using a coulometric flow-through cell equipped with a porous graphite working electrode. The cell was coupled on-line to electrospray ionization mass spectrometry (EC/ESI-MS). ESI spectra were acquired in both negative and positive modes. In acidic medium, ESI spectral analysis showed that the dimer was the main product, while in neutral and basic media, methimazole sulfenic acid, methimazole sulfinic acid and methimazole sulfonic acid were observed as the major electrochemical oxidation products. Oxidation of MMI and subsequent trapping with nucleophiles resulted in formation of adducts with N-acetylcysteine. Some of the electrochemically generated species observed in these experiments were similar to metabolites that have been observed from in vitro and in vivo studies. Trapping studies also showed that bioactivation of MMI proceeds predominantly through the S-oxide and not through formation of thiyl radicals. These results show that electrochemistry coupled to mass spectrometry can be used in mimicry of oxidative metabolism and subsequent high throughput screening of metabolites

Convective Instabilities Derived from Dissipation of Chemical Energy

Oxidation reactions of a series of organosulfur compounds by chlorite are excitable, autocatalytic, and exothermic and generate a lateral instability upon being triggered by the autocatalyst. This article reports on the convective instabilities derived from the reaction of chlorite and thiourea in a Hele-Shaw cell. Reagent concentrations used for the development of convective instabilities delivered a temperature jump at the wave front of 2.1 K. The reaction zone was 2 mm and due to normal cooling after the wave front, this induced a spike rather than the standard well-studied front propagation. Localized spatiotemporal patterns develop around the wave front. This exothermic autocatalytic reaction has solutal and thermal contributions to density changes that act in opposite directions due to the existence of a positive isothermal density change in the reaction. The competition between these effects generates thermal plumes. The fascinating feature of this system is the coexistence of plumes and fingering in the same solution as the front propagates through the Hele-Shaw cell. Wave velocities of descending and ascending fronts are oscillatory. Fingers and plumes are generated in alternating frequency as the front propagates. This generates hot and cold spots within the Hele-Shaw cell, and subsequently spatiotemporal inhomogeneities. The small ΔT at the wave front generated thermocapillary convection which competed effectively with thermogravitational forces at low Eötvös numbers. A simplified reaction-diffusion-convection model was derived for the system. Plume formation is heavily dependent on boundary effects from the cell dimensions. This article reports of self-organization derived from the dissipation of chemical energy. The unique aspect of this article is as follows: generally, addition of convection to reaction-diffusion mechanisms destroys most coherence and self-organization. It is not so, as reported in this article. The delicate balance between thermogravitational, thermocapillary diffusion effects can deliver remarkable self-organization in ungelled environments

Lyapunov Exponents and the Belousov-Zhabotinsky Oscillator: An Interactive Computational Approach

The Belousov-Zhabotinsky (BZ) chemical oscillator is the most studied oscillator. It has been modelled on the basis of single-step mechanisms which have been continuously refined since the seminal manuscript by Field, Koros and Noyes in 1972. This manuscript reports on a unique way of modelling the global dynamics of the oscillator by assuming that the BZ oscillator has shown chaotic behaviour. The unique mathematical definition of chaos is very stringent, and, in this manuscript, we attempt to trace this unique exotic behaviour by the use of ‘onto’ maps of the interval onto itself which are known to exhaustively show a universal sequence of states that has all the hallmarks of chaotic behaviour. A series of one-humped maps of the interval display, through iterations and subsequent symbolic dynamics, a universal sequence of steps that commence with period-doubling, culminating in chaotic behaviour at some accumulation point of an appropriate bifurcation parameter. We put this theory to the test for the BZ oscillator in this manuscript by selecting a unique continuous map of the interval. This was then decomposed by an iterative treatment. Metric entropy and subsequent arbiter of chaotic behaviour was determined by evaluation of Lyapunov exponents which were then compared to observed BZ oscillator states. Our proposed map satisfactorily modelled the global dynamics of the BZ oscillator; predicted period-doubling, and a regime after a critical bifurcation parameter, where chaotic sequences were dense. We also produce, in the Addendum, an iterative MatLab procedure that any reader can utilize to reveal the type of states and behaviour reported here

Electrochemical versus Enzymatic in Vitro Oxidations of 6-propyl-2-thiouracil: Identification, Detection, and Characterization of Metabolites

6-Propylthiouracil, PTU, is a well-known antithyroid drug that has been the mainstay of treatment of Graves’ disease. It is, however, also associated with liver toxicity and idiosyncratic toxicity. These toxicities are generally associated with metabolites derived from its bioactivation. In this manuscript, bioactivation of PTU was studied via two separate techniques: electrochemical oxidation and through the use of human liver microsomes. The aim of this work was to compare the bioactivation products of these two techniques. The electrochemical technique was studied online with a mass spectrometer, EC/ESI/MS. The microsomal oxidations were studied in tandem with liquid chromatography. The EC/ESI/MS technique was devoid of the normal reducing biological matrix prevalent in microsomal incubations. The predominant product at 400 mV was the dimeric PTU species with negligible formation of other metabolites. At higher potentials, complete desulfurization of PTU was observed with formation of sulfate. No sulfonic acid was observed, suggesting that the cleavage of the C–S bond was effected at the sulfinic acid stage, releasing a highly reducing sulfur species which is known to give rise to genotoxicity. The microsomal oxidations, surprisingly, showed formation of the unstable sulfenic acid, the S-oxide. Further incubation showed both the sulfinic and sulfonic acids. None of the systems showed any adducts with nucleophiles such as glutathione, showing that none of the reactive metabolites were stable enough to be adducted to nucleophiles in both the biological matrix and the electrochemical oxidizing environment

Oxyhalogen-Sulfur Chemistry: Kinetics and Mechanism of Oxidation of N-acetylthiourea by Aqueous Bromate and Acidified Bromate

The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess bromate conditions. The reaction displays an induction period before formation of bromine. The stoichiometry of the reaction was determined to be 4:3: 4BrO 3 – +3(CH 3 CO)NH(NH 2 )C=S+3H 2 O®4Br – +3(CH 3 CO)NH(NH 2 )C=O+3SO 4 2– +6H + (A) with a complete desulfurization of ACTU to its urea analogue. In excess bromate conditions the stoichiometry was 8:5: 8BrO 3 – + 5(CH 3 CO)NH(NH 2 )C=S + H 2 O ® 4Br 2 + 5(CH 3 CO)NH(NH 2 )C=O + 5SO 4 2+ + 2H + (B). Bromine is derived from an extraneous reaction in which bromide from stoichiometry (A) reacts with excess acidic bromate. The oxidation of ACTU by aqueous bromine gave stoichiometry (C): 4Br 2 (aq)+(CH 3 CO)NH(NH 2 )C=S+5H 2 O®8Br – +CH 3 CO)NH(NH 2 )C=O+SO 4 2– + 10 H + .Reaction (C) is much faster than reactions (A) and (B), with a lower limit bimolecular rate constant of 2.1 ×10 5 M –1 s –1 such that appearance of bromine signals complete consumption of ACTU. We were unable to trap any intermediate sulfur oxo-acids of ACTU on its oxidation pathway to N-acetylurea. As opposed to other substituted thioureas, none of its intermediates were stable enough to be isolated and detected

Reactivity Measurement in Estimation of Benzoquinone and Benzoquinone Derivatives’ Allergenicity

Benzoquinone (BQ) and benzoquinone derivatives (BQD) are used in the production of dyes and cosmetics. While BQ, an extreme skin sensitizer, is an electrophile known to covalently modify proteins via Michael Addition (MA) reaction whilst halogen substituted BQD undergo nucleophilic vinylic substitution (SNV) mechanism onto amine and thiol moieties on proteins, the allergenic effects of adding substituents on BQ have not been reported. The effects of inserting substituents on the BQ ring has not been studied in animal assays. However, mandated reduction/elimination of animals used in cosmetics testing in Europe has led to an increased need for alternatives for the prediction of skin sensitization potential. Electron withdrawing and electron donating substituents on BQ were assessed for effects on BQ reactivity toward nitrobenzene thiol (NBT). The NBT binding studies demonstrated that addition of EWG to BQ as exemplified by the chlorine substituted BQDs increased reactivity while addition of EDG as in the methyl substituted BQDs reduced reactivity. BQ and BQD skin allerginicity was evaluated in the murine local lymph node assay (LLNA). BQD with electron withdrawing groups had the highest chemical potency followed by unsubstituted BQ and the least potent were the BQD with electron donating groups. The BQD results demonstrate the impact of inductive effects on both BQ reactivity and allergenicity, and suggest the potential utility of chemical reactivity data for electrophilic allergen identification and potency ranking