Application of CE–ICP–MS and CE–ESI–MS in metalloproteomics: challenges,developments, and limitations

Application of capillary electrophoresis (CE) as a high-resolution separation technique in metalloproteomics research is critically reviewed. The focus is on the requirements and challenges involved in coupling CE to sensitive element and molecule-specific detection techniques such as inductively coupled plasma mass spectrometry (ICP–MS) or electrospray ionisation mass spectrometry (ESI–MS). The complementary application of both detection techniques to the structural and functional characterisation of metal-binding proteins and their structural metal-binding moieties is emphasised. Beneficial aspects and limitations of mass spectrometry hyphenated to CE are discussed, on the basis of the literature published in this field over the last decade. Recent metalloproteomics applications of CE are reviewed to demonstrate its potential and limitations in modern biochemical speciation analysis and to indicate future directions of this technique.     

Bulk properties and hydration numbers of components of water–salt,water–urea,and water–urea–salt systems

With an increase in the concentration of additives, the hydration numbers of compounds decrease. Thus, in a saturated 54.6% solution, urea loses approximately 3/4 of the initial amount of water, forming an aquacomplex of the composition (NH₂)₂CO?H₂O. In a supersaturated 44% solution, the sodium chloride aquacomplex is dehydrated by 2/3, and in a supersaturated 67% solution, sodium sulfate is dehydrated by 5/6. The density of these solutions is 1.354÷1.360 g/cm³ (44% NaCl) and 1.800÷1.849 g/cm³ (67% Na₂SO₄). In a saturated urea solution, NaNO₃, NaCl, and Na₂SO₄ complexes lose 53÷55% of hydration water. It is shown that the interactions in the binary water–urea system somewhat increase the hydration number of the salts (structural hydration). The hydration water density, a structurally important characteristic, increases in the series of solutions of urea, NaNO₃, NaCl, and Na₂SO₄. In the same series of additives, the excess volume of binary water–urea and water–salt systems becomes more negative.     

Four-membered ring cyclic ketene –O,O–, –O,S–, –O,N–, –S,S–, –S,N–, and –N,N–acetals and their corresponding cations: a computational study

A systematic computational study of four-membered cyclic ketene –O,O–, –O,S–, –O,N–, –S,N– and –N,N-acetals as well as their protonated analogs have been performed at the second order M?ller Plesset level with a polarized triple zeta basis set. The main purpose of this study was to make predictions about the nucleophilicity of these systems and the variations in nucleophilicity with the hetero atoms. Our calculations suggest that all six target molecules are good nucleophiles, and that the N,N analog is the strongest and the S,S analog the weakest nucleophile. Our results include molecular geometries, bond lengths, proton affinities, vibrational frequencies, and calculated charges.     

Synthesis and characterization of Sibunit-supported Pd–Ga,Pd–Zn,and Pd–Ag catalysts for liquid-phase acetylene hydrogenation

Pd/Sibunit and Pd–M/Sibunit (M = Ga, Zn, or Ag) catalysts have been synthesized, and their catalytic properties in liquid-phase acetylene hydrogenation have been investigated. Doping of the palladium catalyst with a metal M leads to the formation of the Pd₂Ga, PdZn, or Pd_0.46Ag_0.54 bimetallic compound. The bimetallic particles are much smaller (1.6–2.0 nm) than the monometallic palladium particles (4.0 nm). Doping with zinc raises the ethylene selectivity by 25% without affecting the activity of the catalyst. Specific features of the effect of each of the dopants on palladium are reported.     

Design,synthesis, and characterization of fullerene–peptide–steroid covalent hybrids

The present study reports the synthesis, spectral characterization, self-assembly properties, and preliminary in vitro study of antioxidant capacity of two triple covalent hybrids consisting of fullerene C₆₀, peptide, and steroidal moiety. Previously synthesized fulleropyrrolidinic acid and pregnenolone were connected by peptide linker using a multistep DCC/DMAP and/or EDC/HOBT esterification/amidation procedure. The hybrids were characterized by comparative analysis of spectroscopic data obtained from FTIR, UV–vis, HRMS, and extensive NMR experiments (¹H, ¹³C, COSY, HSQC, and HMBC). The self-assembling properties and morphology of triads samples prepared by drop-drying method were examined by scanning electron microscopy (SEM). Preliminary in vitro antioxidant activity was studied by Ferrous ion Oxidation-Xylenol orange (FOX) method.     

Structural Properties of Water–PEG–LiOH,NaOH, and KOH Solutions,According to Viscometry and Densimetry Data

Russian Journal of Physical Chemistry A - The dynamic viscosity and density of water–PEG, water–PEG–LiOH, water–PEG–NaOH, and water–PEG–KOH systems are...     

Sputtered,electroless, and rolled palladium–ceramic membranes

Three techniques were used to produce palladium–ceramic (Pd–ceramic) composite membranes for hydrogen separation and production. They are sputtering, electroless deposition and rolling of thin Pd alloy films over ceramic porous tubes.After studying and developing the three coating techniques, an extensive testing and characterizing work was carried out on these thin film composite membranes. The results show that in the sputtered (0.5–5 μm) and electroless (2.5–20 μm) composite membranes, the thermal cycling of the hydrogenated metallic layer produces membrane failures. Such failures are characterized by crack formation and metal film peeling. This fact has been explained by an evaluation of the shear stresses at the metal–ceramic interface due to the differential elongation between the palladium (Pd) coating and the ceramic support under thermal cycling and hydrogen loading. The rolled membranes (50–70 μm), however, because of the particular coating solution, have shown a complete hydrogen selectivity and good chemical and physical stability in long-term tests.     

Polymer Waste Management–Biodegradation,Incineration, and Recycling

Abstract

Increasing volumes of synthetic polymers are manufactured for various applications. The disposal of the used materials is becoming a serious problem. Unlike natural polymers, most synthetic macromolecules cannot be assimilated by microorganisms. Although polymers represent slightly over 10% of total municipal waste, the problem of nonbiodegradability is highlighted by overflowing landfills, polluted marine waters, and unsightly litter. Existing government regulations in Europe and anticipated regulations in the United States will greatly limit the use of polymers in large volume applications (packaging, water treatment, paper and textile sizing, etc.) unless acceptable means of waste management are available. Total management of polymer wastes requires complementary combinations of biodegradation, incineration, and recycling. Biodegradation is the most desirable long-term future solution and requires intensive research and development before it becomes practical. On the other hand, incineration and recycling can become operational in a relatively short time for the improvement of the situation at present and in the near future.     

Spectra and dose with ANN of 252Cf, 241Am–Be, and 239Pu–Be

Artificial neural networks have been applied to unfold the neutron spectra and to calculate the effective dose, the ambient equivalent dose, and the personal dose equivalent for ²⁵²Cf, ²⁴¹Am–Be, and ²³⁹Pu–Be neutron sources. The count rates that these neutron sources produce in a Bonner Sphere Spectrometer with a ⁶LiI(Eu) were utilized as input in both artificial neural networks. Spectra and the ambient dose equivalent were also obtained with BUNKIUT code and the UTA4 response matrix. With both procedures spectra and ambient dose equivalent agrees in less than 10%. The Artificial neural network technology is an alternative procedure to unfold neutron spectra and to perform neutron dosimetry.     

Reinvestigation of the paracetamol–caffeine,aspirin–caffeine,and paracetamol–aspirin phase equilibria diagrams

Many drug candidates are poorly soluble. The formation of solid dispersion can improve their solubility, consequently their bioavailability. For this purpose, the use of eutectic mixtures is well known in the pharmaceutical field. At the eutectic composition, both components are in reduced particle size and well dispersed. In this work, we focus on the combination of paracetamol, aspirin, and caffeine, which is highly effective for the treatment of migraine headache pain. We have reinvestigated the paracetamol–caffeine, aspirin–caffeine, and paracetamol–aspirin phase equilibria diagrams taking into account the polymorphism of caffeine, paracetamol, and aspirin. The three phase diagrams are determined using X-ray diffraction and the differential scanning calorimetry from the binary mixtures. It is concluded that the paracetamol–caffeine and aspirin–caffeine systems are similar and exhibit two invariants, one eutectic and one metatectic. The paracetamol–aspirin phase diagram reveals the formation of one eutectic. The composition of the three eutectics formed is confirmed by the related Tamman’s triangles. No compound formation is found in the three systems.     

Donor–acceptor perylenediimide–ferrocene conjugates: synthesis,photophysical, and electrochemical properties

Donor–acceptor, perylenediimide–ferrocene conjugates have been synthesized by Suzuki, and Sonogashira coupling reactions. The photophysical and electrochemical properties of these conjugates are discussed. It has been shown that fluorescence as well as the electron affinity of the perylenediimide can be tuned by attaching the appropriate ferrocenyl derivatives.     

Reactivity of the Ge–H,Sn–H,P–H,and Se–H Bonds in Radical Abstraction Reactions

The experimental data for the liquid- and gas-phase reactions of atoms and radicals with organoelement compounds R _{n – 1}E–H

Qualitative metabolism assessment and toxicological detection of xylazine, a veterinary tranquilizer and drug of abuse, in rat and human urine using GC–MS, LC–MS n , and LC–HR-MS n

Xylazine is used in veterinary medicine for sedation, anesthesia, and analgesia. It has also been reported to be misused as a horse doping agent, a drug of abuse, a drug for attempted sexual assault, and as source of accidental or intended poisonings. So far, no data concerning human metabolism have been described. Such data are necessary for the development of toxicological detection methods for monitoring drug abuse, as in most cases the metabolites are the analytical targets. Therefore, the metabolism of xylazine was investigated in rat and human urine after several sample workup procedures. The metabolites were identified using gas chromatography (GC)–mass spectrometry (MS) and liquid chromatography (LC) coupled with linear ion trap high-resolution multistage MS (MS ⁿ ). Xylazine was N-dealkylated and S-dealkylated, oxidized, and/or hydroxylated to 12 phase I metabolites. The phenolic metabolites were partly excreted as glucuronides or sulfates. All phase I and phase II metabolites identified in rat urine were also detected in human urine. In rat urine after a low dose as well as in human urine after an overdose, mainly the hydroxy metabolites were detected using the authors’ standard urine screening approaches by GC–MS and LC–MS ⁿ . Thus, it should be possible to monitor application of xylazine assuming similar toxicokinetics in humans.

Synthesis,characterization and electrocatalytic activity for ethanol oxidation of carbon supported Pt,Pt–Rh,Pt–SnO2 and Pt–Rh–SnO2 nanoclusters

Nanoclusters of Pt, Pt–Rh, Pt–SnO₂ and Pt–Rh–SnO₂ were successfully synthesized by polyol method and deposited on high-area carbon. HRTEM and XRD analysis revealed two phases in the ternary Pt–Rh–SnO₂/C catalyst: solid solution of Rh in Pt and SnO₂. The activity of Pt–Rh–SnO₂/C for ethanol oxidation was found to be much higher than Pt/C and Pt–Rh/C and also superior to Pt–SnO₂/C. Quasi steady-state measurements at various temperatures (30–60 °C), ethanol concentrations (0.01–1 M) and H₂SO₄ concentrations (0.02–0.5 M) showed that Pt–Rh–SnO₂/C is about 20 times more active than Pt/C in the potential range of interest for the fuel cell application.     

Electrodeposition,properties, and composition of rhenium–nickel alloys

The process of deposition of the Re–Ni alloy, its current efficiency, and the alloy composition are studied as a function of the current density and the solution temperature. The hydrogen content in the deposits, their surface morphology, internal structure, and properties as the cathodic material for HER are examined. It is assumed that besides the high rhenium content, the high catalytic activity of nickel–rhenium alloys is associated with the high degree of their structural disordering.     

Electrodeposition,Structure, and Properties of Iron–Tungsten Alloys

The electrodeposition, structure, and properties of Fe–W alloys are studied. Working current densitiesirange from 1 to 5 A dm^–2at 50°C. The W content (45 wt %) barely depends oni. The current efficiency is about 40%. Alloys obtained at ibelow 2 A dm^–2are crystalline oversaturated solid solutions of W in Fe and are magnetic. Higher current densities yield amorphous nonmagnetic alloys of the same composition. Either alloy has a very high resistivity (nearly 300 ohm cm) and, after a treatment at 500–600°C, transforms into a more equilibrium binary system comprising a saturated solid solution and an intermetallic compound.     

Solvothermal preparation,and characterization,of Cu–Ag nanoparticles

Cu–Ag nanoparticles have been successfully synthesized by one-pot solvothermal treatment of a mixture of AgNO₃ and Cu(OAc)₂·H₂O in ethylene glycol solution at 180 °C for 10 h. The samples were characterized by UV–visible absorption, X-ray diffraction (XRD), and extended X-ray absorption fine structure (EXAFS) spectroscopy, transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). The results showed that Cu–Ag nanoparticles and a small amount of phase-separated Cu–Ag alloy nanoparticles with an average diameter of 100 ± 30 nm were synthesized by the solvothermal treatment procedure. The mechanism of formation is discussed.     

Contracted polarization functions for the atoms Ca, Ga–Kr, Sr, and In–Xe

 Contracted Gaussian-type function sets are proposed for polarization functions of the atoms Ga–Kr and In–Xe. We also report polarization functions for Ca and Sr. A segmented contraction scheme is used for its compactness and computational efficiency. The contraction coefficients and orbital exponents are fully optimized to minimize the deviation from accurate atomic natural orbitals. The present polarization functions yield more than 99% of atomic correlation energies predicted by accurate natural orbitals of the same size. Received: 23 February 2001 / Accepted: 19 April 2001 / Published online: 13 June 2001     

Synthesis,spectroscopic, luminescent and electrochemical studies of new Ru–Ni–Ru and Pd–Ni–Pd trinuclear complexes with an azolo-linked tetraaza macrocycle

Ru–Ni–Ru and Pd–Ni–Pd trinuclear complexes containing azolo [thiazolo (L¹) and triazolo (L²)] linked 6,8,15,17-tetramethyldibenzo-5,9,14,18-tetraazacyclotetradecene nickel(II) diacetate as a bridging ligand were synthesised and characterized by elemental analysis, conductance and i.r., u.v.–vis., ¹H-n.m.r. spectra and FAB-mass data. The luminescent and electrochemical properties of the complexes were also studied.     

Thermochemistry of Pd–In,Pd–Sn and Pd–Zn alloy systems

The standard enthalpy of formation of several Pd–M alloys (M = In, Sn and Zn) has been measured using a high temperature direct drop calorimeter. The reliability of the calorimetric results has been determined and supported by using different analytical techniques: light optical microscopy, scanning electron microscopy equipped with electron probe microanalysis (EPMA with EDS detector) and X-ray powder diffraction analysis. The values of Δ_fH (kJ/mol atoms) for the following phases were obtained for the formation in the solid state at 300 K: PdIn (49 at.%In): ?69.0 ± 1.0; Pd₂In₃ ?57.0 ± 1.0; Pd₃In₇: ?43.0 ± 1.0; PdSn₂: ?50.0 ± 1.0; Pd₂Zn₉ (77 at.%Zn): ?33.7 ± 1.0; Pd₂Zn₉ (78 at.%Zn): ?34.0 ± 1.0; Pd₂Zn₉ (80 at.%Zn): ?35.0 ± 1.0. The results show exothermic values which increase from the Pd–Zn to the Pd–Sn and Pd–In systems; the data obtained have been discussed in comparison with those available in literature.