Using direct electrochemistry to probe rate limiting events during nitrate reductase turnover

Protein film voltammetry of NarGH catalysing nitrate reduction under steady state conditions provides information on events occurring within the enzyme during the catalytic cycle. In this discussion we have focused on exploring the ability of two simple catalytic schemes to reproduce the voltammetric response of NarGH; electron transfer to the enzyme's active site being described either by interfacial electron exchange (Scheme 1) or intramolecular electron delivery via the operation of an electron relay centre (Scheme 2). When the two electron reduced, catalytically competent active site of the enzyme is generated from the oxidised form in 'rapid', non-rate limiting steps of the catalytic cycle, the voltammetric behaviour of NarGH cannot be reproduced. Rather under all the conditions investigated, one electron reduction of the active site from a semi-reduced to a fully-reduced state is found to be crucial to progression through the enzyme's catalytic cycle. The catalytically relevant semi- and fully-reduced oxidation states of the NarGH active site are most likely to correspond to the Mo(V) and Mo(IV) states of the Mo(MGD)2 centre, respectively, although it is not possible to rule out the possibility that they correspond to molybdopterin based oxidation states as observed in other enzymes. We suggest that the rate of either conformational rearrangement within the semi-reduced active site or intramolecular electron delivery to the active site constitutes a defining feature in the catalytic cycle of NarGH and results in the napp approximately 1 appearance of the catalytic waveform.     

Mössbauer study of the corrosion of mild steel due to prolonged immersion in deionized water

The corrosion of mild steel as a result of 3 years of immersion in deionized water, using Mössbauer results, indicates that -FeOOH, -FeOOH and Fe₃O₄ are formed as corrosion products. This study shows that purified water will produce -FeOOH only when the exposure time is long. It is proposed that ferrihydrite, which is formed as an intermediate corrosion product, is converted to -FeOOH, which in turn is converted to -FeOOH and Fe₃O₄.     

Kinetics of thermal decomposition of metal acetates

The acetates of magnesium, nickel, copper, manganese, sodium and barium were subjected to thermal decomposition by means of thermogravimetric techniques (TG) under a constant flow of nitrogen. The decompositions occurred in steps and the kinetics of every set of reactions was determined by the Coats and Redfern method. These results were analysed to establish the decomposition kinetics and hence to calculate activation energies. The activation energies were also determined by applying the Horowitz-Hugh method, which yielded similar results.

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Zusammenfassung Mittels TG in konstantem Stickstoffstrom wurde die thermische Zersetzung von Magnesium-, Nickel-, Kupfer-, Mangan-, Natrium- und Bariumazetat untersucht. Es erfolgte eine schrittweise Zersetzung, die Kinetik für jede der Reaktionen wurde mit Hilfe der Methode von Coats und Redfern bestimmt. Diese Ergebnisse wurden genutzt, um die Kinetik der Zersetzung und anschlie\end die Aktivierungsenergien festzustellen. Ähnliche Werte für die Aktivierungsenergien erhielt man auch mit Hilfe der Methode von Horowitz Hugh.

     

Correlation between work hardening and stress relaxation in polycrystalline nickel

Stress-relaxation rates at a constant strain in A-grade nickel polycrystals has been reported to depend in a peculiar manner on the initial stress levelσ ₀ at which relaxation is allowed to start. For large grains (D>75μm),s varies withσ ₀ linearly over the entire stress strain curve. For small grains (D<75μm),s-σ ₀ curve undergoes a change in its slope at a critical value of plastic strainɛ, which decreases as grain size increases. The observation referred to are found to correlate well with the work-hardening behaviour of the nickel polycrystals.     

A Digital Image Confidentiality Scheme Based on Pseudo-Quantum Chaos and Lucas Sequence

Several secure image encryption systems have been researched and formed by chaotic mechanisms in current decades. This work recommends an innovative quantum color image encryption method focused on the Lucas series-based substitution box to enhance the competence of encryption. The suggested encryption technique has more excellent key space and significant confidentiality. The chaotic system, along with the substitution box, exhibits additional complicated dynamical behavior, sufficient arbitrariness, and uncertainty than all others focused on just chaotic models. Theoretical and simulation assessments show that the offered image encryption performs admirably, its traditional equivalents in terms by efficiency in terms of statistical analysis.     

Simultaneous determination of nitrite and nitrate by normal phase ion-pair liquid chromatography

Normal phase ion-pair high performance liquid chromatography has been used for simultaneous separation of nitrite and nitrate using tetraethylammonium (TEA)(+) as ion-pairing reagent. The concentration effect of (TEA)(+), buffer salt and pH of the eluent on separation is investigated. The UV detector response at various wavelengths has been optimized. The performance of the proposed method is compared with ion chromatography for quantification of the anions in potable water, wastewater and in food samples, such as spinach and lettuce.     

Resonances and O-curves in Hamiltonian systems

We investigate the problem of the existence of trajectories asymptotic to elliptic equilibria of Hamiltonian systems in the presence of resonances.      

Slow Motion and Metastability for a Nonlocal Evolution Equation

In this paper we consider a nonlocal evolution equation in one dimension, which describes the dynamics of a ferromagnetic system in the mean field approximation. In the presence of a small magnetic field, it admits two stationary and homogeneous solutions, representing the stable and metastable phases of the physical system. We prove the existence of an invariant, one dimensional manifold connecting the stable and metastable phases. This is the unstable manifold of a distinguished, spatially nonhomogeneous, stationary solution, called the critical droplet.^{(4, 10)} We show that the points on the manifold are droplets longer or shorter than the critical one, and that their motion is very slow in agreement with the theory of metastable patterns. We also obtain a new proof of the existence of the critical droplet, which is supplied with a local uniqueness result.     

Surface roughness and hydrodynamic boundary slip of a newtonian fluid in a completely wetting system

The influence of surface roughness on the boundary condition for the flow of a Newtonian fluid near a hard wall has been investigated by measurement of the hydrodynamic drainage force. The degree of slip is found to increase with surface roughness. This leads to the conclusion that in most practical situations boundary slip takes place, leading to a reduction of the drainage force.     

Absolute branching fraction measurements of exclusive D+ semileptonic decays

Using data collected at the psi(3770) resonance with the CLEO-c detector at the Cornell e+e- storage ring, we present improved measurements of the absolute branching fractions of D+decays to K0e+ve, pi0e+ve, K*0e+ve, and p0e+ve, and the first observation and absolute branching fraction measurement of D+ --> omega e+ve. We also report the most precise tests to date of isospin invariance in semileptonic D0 and D+ decays.