Structural characterisation of tyrosine-nitrated peptides by ultraviolet and infrared matrix-assisted laser desorption/ionisation Fourier transform ion cyclotron resonance mass spectrometry

Nitration of tyrosine residues in proteins may occur in cells upon oxidative stress and inflammation processes mediated through generation of reactive nitroxyl from peroxynitrite. Tyrosine nitration from oxidative pathways may generate cytotoxic species that cause protein dysfunction and pathogenesis. A number of protein nitrations in vivo have been reported and some specific Tyrosine nitration sites have been recently identified using mass spectrometric methods. High-resolution Fourier transform ion cyclotron resonance mass spectrometry (MALDI) FT-ICR-MS) is shown here to be a highly efficient method in the determination of protein nitrations. Following the identification of nitration of the catalytic site Tyr-430 residue of bovine prostacyclin synthase, we synthesised several model peptides containing both unmodified tyrosine and 3-nitro-tyrosine residues, using solid-phase peptide synthesis (SPPS). The structures of the nitrotyrosine peptides were characterised both by ESI- and by matrix-assisted laser desorption/ionisation (MALDI)-FT-ICR-MS, using a standard ultraviolet (UV) nitrogen nitrogen laser and a 2.97 microm Nd-YAG infrared laser. Using UV-MALDI-MS, 3-nitrotyrosyl-peptides were found to undergo extensive photochemical fragmentation at the nitrophenyl group, which may hamper or prevent the unequivocal identification of Tyr-nitrations in cellular proteins. In contrast, infrared-MALDI-FT-ICR-MS did not produce fragmentation of molecular ions of Tyr-nitrated peptides.     

Investigations for Modification of Polyacrylamide-Bentonite by Phytic Acid and its Usability in Fe3+, Zn2+ and UO2 2+ Adsorption

Composite of polyacrylamide-bentonite (PAA-B) was prepared by direct polymerisation of PAA in a suspension of bentonite (B). Adsorption and thermodynamic features of phytic acid (Phy) adsorption onto B, PAA and PAA-B, and those of Fe³⁺, Zn²⁺, UO₂ ²⁺ adsorption onto PAA-B and its modification by Phy (PAA-B-Phy) have been investigated. The reusability, storagability, ion selectivity and recoverability of sorbed ions with 1 M HCl have also been considered.The chemical and physical structure of adsorbents has been characterised by means of FT-IR and XRD. All adsorption isotherms for Phy and the ions were L-type of the Giles classification except, the one which is S type for adsorption of Phy onto PAA. The maximum adsorption capacities for the ions adsorbed were in order of UO₂ ²⁺ > Fe³⁺ > Zn²⁺ for PAA-B and Zn²⁺ > Fe³⁺ > UO₂ ²⁺ for PAA-B-Phy. Langmuir equilibrium constants for the adsorption of ions onto PAA-B-Phy were significantly higher than those found for PAA-B; the magnitude of increase for UO₂ ²⁺ was about 100. The thermodynamic parameters indicated that adsorption reactions are spontaneous in terms of adsorption free enthalpy.The chemical structure of PAA-B-Phy was not changed at the end of the studies of reusability and storagability. The composite was selective for UO₂ ²⁺ of the ions of interest.The composite of PAA-B and its modification by Phy have been used for the first time in this investigation. It is proposed that the composites can be practically used in the investigations and applications of adsorption.     

Double-layer and pseudocapacitance types of electrochemical capacitors and their applications to the development of hybrid devices

The basis of the complementary use of electrochemical capacitors (so-called supercapacitors) in hybrid electric power generation by rechargeable batteries and fuel cells is explored. Electrochemical capacitors are of two types: one where the interfacial double-layer capacitance of high specific area carbon materials is the basis of electric charge storage (as ions and electrons); and the other where pseudocapacitance, associated with electrosorption and surface redox processes at high-area electrode materials, e.g. RuO₂, or at conducting polymers, provides the basis of charge storage. The former, double-layer, type of capacitance stores charge non-faradaically while the latter type, pseudocapacitance, stores charge indirectly through faradaic chemical processes but its electrical behaviour is like that of a capacitor. Two types of hybrid battery/capacitor system are recognized: one based on combination of an electrochemical capacitor cell with a rechargeable battery or a fuel cell in a load-leveling function, e.g. in an electric vehicle power train; and the other based on combination of a faradaic battery-type electrode coupled internally with a capacitative electrode in a two-electrode hybrid module (termed an asymmetric capacitor). Optimization of operation of such systems in terms of balancing of active masses, of power and charge densities, and choice of maximum but limited states-of-discharge, is treated.     

An Infrared Spectroscopic Study on the Hofmann-diam-type 1,12-Diaminododecanemetal(II) Tetracyanonickelate(II)-aromatic Guest Clathrates: M(H2N(CH2)12NH2)Ni(CN)4ċG(M=Co, Ni or Cd; G = Benzene, Naphthalene, Anthracene, Phenanthrene or Biphenyl)

Three Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)₄G (M = Co, Ni or Cd; G = benzene, naphthalene, anthracene, phenanthrene or biphenyl) have been prepared in powder form. The 1,12-diaminododecane molecules in the host lattice permit the inclusion of bulky guest molecules. The spectral features suggest that these compounds are similar in structure to the other Hofmann-diam-type clathrates.     

Under pressure: predicting pressurized metered dose inhaler interactions using the atomic force microscope

Drug particulate interactions in pressurized metered dose inhalers (pMDI) may lead to a decrease in aerosolization efficiency and subsequent efficacy in patient treatment. The interactions between salbutamol sulfate (commonly used in Ventolin pMDIs) and a series of pMDI canister materials were investigated using the atomic force microscope (AFM) colloid probe technique. Approximately 4000 individual force-distance curves were determined for a drug probe and three surfaces (10 x 10 mum areas) in situ, in a model propellant. The area under each force-distance curve was integrated to obtain separation energy values. Median separation energy values followed the rank order borosilicate glass > aluminum > PTFE, suggesting PTFE to be the most suitable canister coating.     

Comparative EIS study of a paste electrode containing zinc powder in neutral and near neutral solutions

The corrosion and passivation of Zn powder particles dispersed in a paste electrode immersed in 0.5 M Na₂SO₄ and 5×10^–3 M Na₂HPO₄ solutions were studied mainly by electrochemical impedance spectroscopy. The role played by diffusion in the mechanism of anodic oxidation of zinc powder particles has been shown. It was demonstrated that the anodic reactionof Zn powder in neutral or near neutral media involves at least two adsorbed intermediates. By simulating the porous structure of the electrode, some information about porous nature of zinc electrode could be extracted. Electronic Publication     

Direct determination of manganese in vitamin-mineral tablets using solid sampling electrothermal atomic absorption spectrometry

Manganese in vitamin-minerals tablets was determined by solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS) using three different calibration methods, namely calibration against aqueous standards, standard addition with aqueous standards on solid samples and calibration against solid certified standards. Samples were only finely ground and introduced directly into the furnace by means of solid autosampler system without any dissolving process. Effects of different calibration techniques, temperatures and heating rates of atomization and pyrolysis steps on the accuracy and precision of the analyte elements were investigated. After optimization of the experimental parameters, there is good agreement (at 95% confidence level) between the results obtained by solid sampling and those obtained by acid digestion of samples.     

Uniformization of Riemann surfaces revisited

Annals of Global Analysis and Geometry - We give an elementary and self-contained proof of the uniformization theorem for noncompact simply connected Riemann surfaces.     

On the strong almost convergence of double sequences

In this paper, necessary and sufficient conditions that the real doubly infinite matrixA sums every strongly almost convergent double sequence, leaving the limit invariant, have been determined.     

SOOT combustion. co and k catalysts supported on different supports

The catalytic combustion of particulate material was studied on cobalt catalysts promoted with potassium using different supports for its preparation. Silica, aluminium oxides and hydroxides, zirconium oxide and hydroxide were used as supports. The catalytic activity for combustion depends on the type of support used, the higher activity corresponding to the supported catalyst on zirconium oxide. TPR studies indicate that the interaction metal/support allows to explain the higher activity of the CoK/SiO₂ catalyst with respect to the CoK/Al₂O₃ but the high activity found in CoK/ZrO₂is not explained by this interaction. In all cases the Co and K improved the performance of the catalysts.