Determination of N-Methylpyrrolidine in Cefepime for Injection by Capillary Electrophoresis with Indirect UV Detection

N-Methylpyrrolidine in cefepime for injection was determined by capillary electrophoresis with indirect UV detection. Best results were achieved with background electrolyte consisting of 10 mM creatinine adjusted to pH 3.8 with formic acid and an applied voltage of 30 kV in a bare fused-silica capillary. Indirect UV detection was performed at a wavelength of 225 nm. The application of a small amount of inlet pressure during the separation assisted the attainment of a stable baseline. The optimized method was validated regarding selectivity, linearity, accuracy, precision, ruggedness, repeatability and detection limits. Careful control of capillary conditioning enabled migration time precision values of <0.2% RSD. The use of an internal standard enabled precision values of <1% RSD to be obtained for peak area ratios.     

Electrocatalytic reduction of ROOH by iron porphyrins

Electrocatalytic reduction of a series of chemical oxidants of different power (tert-butyl hydroperoxide, potassium peroxomonosulfate, peracetic acid, and m-chloroperbenzoic acid) at iron-porphyrin-modified graphite electrodes is studied in buffered aqueous solutions by rotating disk and ring-disk voltammetry. Both ferric and ferrous porphyrins are catalytically active. Turnover of ferric catalysts is slower than that of the ferrous analogues and involves competing catalytic reduction and disproportionation. The kinetic data are consistent with reactant binding being the rate-determining step in catalysis by Fe(III). In catalysis by Fe(II), the turnover is controlled by the first electron transfer. The covalently linked proximal imidazole ligand is found to be crucial for achieving the Fe(III) catalysis.     

Identification of peanut and hazelnut allergens by native two-dimensional gel electrophoresis

A procedure for the native two-dimensional electrophoresis of peanut and hazelnut proteins is described. Proteins were solubilised after acetone treatment using a combination of 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate (CHAPS) and tetramethylene sulphone. These extracts were analysed by a combination of isoelectric focusing in the presence of lactose in immobilized pH gradients followed by charge shift electrophoresis. Immunoblot analysis, using sera from nut allergic patients, allowed the identification of a peanut and hazelnut allergen with identical isoelectric point and apparent molecular mass. These proteins were recovered from duplicate gels using a mixture of formic acid, acetonitrile (ACN) and isopropanol. The molecular masses for both proteins, determined by matrix assisted laser desorption/ionisation-mass spectrometry (MALDI-MS), were 4826 Da.     

Functional analogues of the dioxygen reduction site in cytochrome oxidase: mechanistic aspects and possible effects of Cu(B)

Catalytic reduction of O(2) and H(2)O(2) by new synthetic analogues of the heme/Cu site in cytochrome c and ubiquinol oxidases has been studied in aqueous buffers. Among the synthetic porphyrins yet reported, those employed in this study most faithfully mimic the immediate coordination environment of the Fe/Cu core. Under physiologically relevant conditions, these biomimetic catalysts reproduce key aspects of the O(2) and H(2)O(2) chemistry of the enzyme. When deposited on an electrode surface, they catalyze the selective reduction of O(2) to H(2)O at potentials comparable to the midpoint potential of cytochrome c. The pH dependence of the half-wave potentials and other data are consistent with O-O bond activation at these centers proceeding via a slow generation of a formally ferric-hydroperoxo intermediate, followed by its rapid reduction to the level of water. This kinetics is analogous to that proposed for the O-O reduction step at the heme/Cu site. It minimizes the steady-state concentration of the catalytic intermediate whose decomposition would release free H(2)O(2). The maximum catalytic rate constants of O(2) reduction by the ferrous catalyst and of H(2)O(2) reduction by both ferric and ferrous catalysts are comparable to those reported for cytochrome oxidase. The oxidized catalyst also displays catalase activity. Comparison of the catalytic properties of the biomimetic complexes in the FeCu and Cu-free forms indicates that, in the regime of rapid electron flux, Cu does not significantly affect the turnover frequency or the stability of the catalysts, but it suppresses superoxide-releasing autoxidation of an O(2)-catalyst adduct. The distal Cu also accelerates O(2) binding and minimizes O-O bond homolysis in the reduction of H(2)O(2).     

Analytical predictions of shapes of laminar diffusion flames in microgravity and earth gravity

Flame shape is an important observed characteristic of flames that can be used to scale flame properties such as heat release rates and radiation. Flame shape is affected by fuel type, oxygen levels in the oxidiser, inverse burning and gravity. The objective of this study is to understand the effect of high oxygen concentrations, inverse burning, and gravity on the predictions of flame shapes. Flame shapes are obtained from recent analytical models and compared with experimental data for a number of inverse and normal ethane flame configurations with varying oxygen concentrations in the oxidiser and under earth gravity and microgravity conditions. The Roper flame shape model was extended to predict the complete flame shapes of laminar gas jet normal and inverse diffusion flames on round burners. The Spalding model was extended to inverse diffusion flames. The results show that the extended Roper model results in reasonable predictions for all microgravity and earth gravity flames except for enhanced oxygen normal diffusion flames under earth gravity conditions. The results also show trends towards cooler flames in microgravity that are in line with past experimental observations. Some key characteristics of the predicted flame shapes and parameters needed to describe the flame shape using the extended Roper model are discussed.     

Modeled quenching limits of spherical hydrogen diffusion flames

Hydrogen–air diffusion flames were modeled with an emphasis on kinetic extinction. The flames were one-dimensional spherical laminar diffusion flames supported by adiabatic porous burners of various diameters. Behavior of normal (H₂ flowing into quiescent air) and inverse (air flowing into quiescent H₂) configurations were considered using detailed H₂/O₂ chemistry and transport properties with updated light component diffusivities. For the same heat release rate, inverse flames were found to be smaller and 290 K hotter than normal flames. The weakest normal flame that could be achieved before quenching has an overall heat release rate of 0.25 W, compared to 1.4 W for the weakest inverse flame. There is extensive leakage of the ambient reactant for both normal and inverse flames near extinction, which results in a premixed flame regime for diffusion flames except for the smallest burners with radii on the order of 1 μm. At high flow rates H + OH(+M) → H₂O(+M) contributes nearly 50% of the net heat release. However at flow rates approaching quenching limits, H + O₂(+M) → HO₂(+M) is the elementary reaction with the largest heat release rate.     

Unwanted combustion enhancement by C6F12O fire suppressant

Several agents are under consideration to replace CF₃Br for use in suppressing fires in aircraft cargo bays. In a Federal Aviation Administration (FAA) performance test simulating the explosion of an aerosol can, however, the replacements, when added at sub-inerting concentrations, have all been found to create higher pressure rise than with no agent, hence failing the test. Thermodynamic equilibrium calculations as well as perfectly-stirred reactor (PSR) simulations with detailed reaction kinetics, are performed for one of these agents, C₆F₁₂O (Novec 1230), to understand the reasons for the unexpected enhanced combustion rather than suppression. The high pressure rise with added agent is shown to depend on the amount of agent, and can only occur if a large fraction of the available oxidizer in the chamber is consumed, corresponding to stoichiometric proportions of fuel, oxygen, and agent. A kinetic model for the reaction of C₆F₁₂O in hydrocarbon–air flames has been developed. Stirred-reactor simulations predict that at higher agent loadings, the inhibition effectiveness of C₆F₁₂O is relatively insensitive to the overall stoichiometry, and the marginal inhibitory effect of the agent is greatly reduced, so that the mixture remains flammable over a wide range of conditions corresponding to those of the FAA test. The present findings are consistent with and support the earlier analyses for C₂HF₅ and CF₃Br, which were also evaluated in the FAA test.