Uncatalyzed reactions in the classical Belousov-Zhabotinsky system. I. Reactions of bromomalonic acid with acidic bromate and with HOBr

The uncatalyzed reactions of bromomalonic acid (BrMA) with acidic bromate and with hypobromous acid were studied in 1 M sulfuric acid, a usual medium for the oscillatory Belousov-Zhabotinsky (BZ) reaction, by following the rate of the carbon dioxide evolution associated with these reactions. In addition, the decarboxylation rate of dibromomalonic acid (Br2MA) was also measured to determine the first-order rate constant of its decomposition (4.65 x 10(-5) s(-1) in 1 M H2SO4). The dependence of that rate constant on the hydrogen ion concentration suggests a carbocation formation. A slow oligomerization of BrMA observed in sulfuric acid solutions is also rationalized as a carbocationic process. The initial rate of the BrMA-BrO3- reaction is a bilinear function of the BrMA and BrO3- concentrations with a second-order rate constant of 3.8 x 10(-4) M(-1) s(-1). When a great excess of BrO3- is applied, then BrMA is oxidized mostly to CO2. A reaction scheme compatible with the experimental finding is also given. On the other hand, when less BrO3- and more organic substrate - BrMA or malonic acid (MA)--is applied, then addition reactions of various carbocations with the enol form of the organic substrates should be taken into account in later stages of the reaction. It was discovered that HOBr, which brominates BrMA to Br2MA when BrMA is in excess, can also oxidize BrMA when HOBr is in excess. As Br2MA does not react with HOBr, it is assumed that the acyl hypobromite, formed in the first step of the HOBr and BrMA reaction, can react with an additional HOBr to give oxidation products. It was found that the initial rate of the reaction can be described by the following experimental rate law: k(BHOB)[BrMA]0[HOBr]0(2), where k(BHOB) = 5 M(-2) s(-1). A reaction scheme for the oxidation of BrMA by HOBr is given for conditions where HOBr is in excess. Model calculations illustrate qualitatively that the suggested reaction schemes are able to mimic the experiments. (More quantitative simulations are prevented by kinetic data missing for the various carbocation intermediates.) Finally, the effects of these newly observed reactions on oscillatory BZ systems are discussed briefly.     

Characterization of polypyrrole-silver nanocomposites prepared in the presence of different dopants

Conducting polypyrrole (PPy) powder synthesized by using FeCl3 x 6 H2O and/or Fe(NO3)3 oxidants was impregnated in silver salt solutions. The stability and decomposition of the material was followed by thermogravimetric measurements. The total silver content was determined by atom absorption spectroscopy (ICP-AAS). The heat and electric conductivities of the composites were measured and correlated with the silver content. The incorporated silver was speciated and measured by X-ray diffraction (XRD). The spectra proved that the chemical state of the silver incorporated into the composite depends on the anion used in the polymerization process. In the case of the polymerization in a nitrate ion containing solution, the impregnation leads exclusively to the formation of metallic silver. The size distribution of the AgCl and Ag nanoparticles, determined from transmission electron microscopy (TEM) pictures in the different composites, proves the formation of a rather uniform species below 10 and 7 nm, respectively. The observations can be correlated with the different interactions in the PPy-chloride/nitrate-silver systems. The redox type interaction based conclusions can be considered as a guide during the preparation of other metal-conducting polymer composites.     

Femtosecond pulsed laser deposition of diamond-like carbon films: The effect of double laser pulses

The bonding structure of carbon films prepared by pulsed laser deposition is determined by the plasma properties especially the change of the kinetic energy. Using double laser pulses the ablation process and the characteristics of the generated plasma can be controlled by the setting of the delay between the pulses. In our experiments, amorphous carbon films have been deposited in vacuum onto Si substrates by double pulses from a Ti:sapphire laser (180 fs, λ = 800 nm, at 1 kHz) and a KrF laser system (500 fs, λ = 248 nm, at 5 Hz). The intensities have been varied in the range of 3.4 × 10¹² to 2 × 10¹³ W/cm². The morphology and the main properties of the thin layers were investigated as a function of the time delay between the two ablating pulses (0-116.8 ps) and as a function of the irradiated area on the target surface. Atomic force microscopy, spectroscopic ellipsometry and Raman-spectroscopy were used to characterize the films. It was demonstrated that the change of the delay and the spot size results in the modification of the thickness distribution of the layers, and the carbon sp²/sp³ bonding ratio.     

Compaction of poly(dimethylsiloxane) (PDMS) due to proton beam irradiation

This work is about the detailed investigation of the changes of the surface topography, the degree of compaction/shrinkage and its relation to the irradiation fluence and the structure spacing in poly(dimethylsiloxane) (PDMS) patterned with 2 MeV proton microbeam. The irradiated periodic structures consisted of parallel lines with different widths and spacing. To achieve different degrees of compaction, each structure was irradiated with more different fluences. At the irradiated areas the surface topography, the adhesion, the wettability and the rigidity of the surface also changes due to the chemical/structural change of the basic poly(dimethylsiloxane) polymer. The surface topography, the phase modification of the surface, and the connection between them was revealed with using an atomic force microscope (AFM).     

Ultrashort laser pulse bioeffects and safety.

Recent studies of retinal damage due to ultrashort laser pulses have shown that less energy is required for retinal damage for pulses shorter than 1 ns than that for longer pulses. It has also been shown that more energy is required for near-infrared (NIR) wavelengths than in the visible because the light focuses behind the retina, requiring more energy to produce a damaging fluence on the retina. We review the progress made in determining the trends in retinal damage from laser pulses of 1 ns to 100 fs in the visible and NIR wavelength regimes. We have determined the most likely damage mechanism(s) operative in this pulse width regime.     

A small Dowker space in ZFC

We construct a hereditarily normal topological space whose product with the unit interval is not normal. The space is -relatively discrete and has cardinality of the continuum .

     

ChemInform Abstract: B2N2O4: Prediction of a Magnetic Ground State for a Light Main‐Group Molecule.

DFT and coupled‐cluster calculations show that the B₂N₂O₄ molecule has a triplet ground state and therefore is paramagnetic.     

An infinite mapping layer for deep water waves

In order to accurately and efficiently model the propagation of surface gravity waves in infinitely deep domains, we introduce an infinite mapping layer which transforms the unbounded physical domain into a bounded computational domain by means of a mapping function. The method was implemented in the framework of the finite element method, where it can be straightforwardly combined with a perfectly matched layer to model unbounded domains in horizontal direction. Finally, the application of the method is demonstrated by a simple 3D example. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Syntheses of new conformationally constrained S‐[2‐[(1‐iminoethyl)amino] ethyl]homocysteine derivatives as potential nitric oxide synthase inhibitors

The efficient syntheses of two new types of conformationally constrained S‐[2‐[(1‐iminoethyl)amino]ethyl]homocysteine derivatives, 1‐amino‐3‐[2[(1‐iminoethyl)amino]ethylthio]cyclobutane carboxylic Acid ( 5 ) and (4S)‐4‐[[2‐[(1‐Iminoethyl)amino]ethyl]thio]‐L‐proline ( 6 ), are reported. These molecules represent the first attempts to probe conformational constraint near the α‐amino acid moiety of known homocysteine‐based inhibitors of nitric oxide synthase. Targets 5 and 6 were evaluated as potential inhibitors of the three human isoforms of nitric oxide synthase. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:77–83, 2002; DOI 10.1002/hc.1109