In situ X‐ray data collection and structure phasing of protein crystals at Structural Biology Center 19‐ID

A prototype of a 96‐well plate scanner for in situ data collection has been developed at the Structural Biology Center (SBC) beamline 19‐ID, located at the Advanced Photon Source, USA. The applicability of this instrument for protein crystal diffraction screening and data collection at ambient temperature has been demonstrated. Several different protein crystals, including selenium‐labeled, were used for data collection and successful SAD phasing. Without the common procedure of crystal handling and subsequent cryo‐cooling for data collection at T = 100 K, crystals in a crystallization buffer show remarkably low mosaicity (<0.1°) until deterioration by radiation damage occurs. Data presented here show that cryo‐cooling can cause some unexpected structural changes. Based on the results of this study, the integration of the plate scanner into the 19‐ID end‐station with automated controls is being prepared. With improvement of hardware and software, in situ data collection will become available for the SBC user program including remote access.     

Can 2‐acylpyrroles form an intramolecular hydrogen bond?

The formation of intramolecular hydrogen bonding by certain N‐substituted 2‐acylpyrroles has been demonstrated by B3LYP/aug‐cc‐pVDZ calculations, the quantum theory of atoms in molecules, and the natural bond orbital method. Total electron energy densities H_BCP at the bond critical point of the H?O bond were applied to analyze the strength of these interactions. The relations between quantum theory of atoms in molecules, carbonyl stretching vibrational modes ν_{C = O}, and natural bond orbital parameters associated with the formation of the C–H?O interaction have been established. The short contacts were found experimentally in the crystal structure of a new 2‐acylpyrrole derivative 5‐chloro‐2‐oxopentyl‐1‐(5‐chloro‐2‐oxopentyl)pyrrolo‐2‐carboxylate. The influence of 2‐ and N‐substitution of 2‐acylpyrroles on C‐H?O interaction energy is discussed. It was found that the methylene group may act as a proton donor leading to a red‐shift or blue‐shift phenomenon of the ν_C–H stretching mode. Copyright © 2015 John Wiley & Sons, Ltd.     

Analytical quality solid-state composite reference electrode manufactured by injection moulding

An injection moulding method was used for fabricating solid-state reference electrodes (Ag/AgCl type) based on a polymer/inorganic salt composite. In this method, a silver/silver chloride wire was placed inside a mould into which the mixture of polymer and inorganic salt was injected. The obtained solid-state composite reference electrodes were extensively tested to study the influence of different parameters such as solution composition, the concentrations and mobility of ions and pH on the potential stability of the electrodes. These experiments revealed that the composite reference electrodes are insensitive to the matrix effect, have excellent potential readings stability and considerably reduced leakage of inorganic salt. The composite reference electrodes were compared favourably to high-quality commercial reference electrodes. It was concluded that the composite reference electrodes obtained by injection moulding are of analytical quality allowing for continuous, prolonged and intensive usage.     

Effects of serum proteins on corrosion behavior of ISO 5832–9 alloy modified by titania coatings

Stainless steel ISO 5832–9 type is often used to perform implants which operate in protein-containing physiological environments. The interaction between proteins and surface of the implant may affect its corrosive properties. The aim of this work was to study the effect of selected serum proteins (albumin and γ-globulins) on the corrosion of ISO 5832–9 alloy (trade name M30NW) which surface was modified by titania coatings. These coatings were obtained by sol–gel method and heated at temperatures of 400 and 800 °C. To evaluate the effect of the proteins, the corrosion tests were performed with and without the addition of proteins with concentration of 1 g L^?1 to the physiological saline solution (0.9 % NaCl, pH 7.4) at 37 °C. The tests were carried out within 7 days. The following electrochemical methods were used: open circuit potential, linear polarization resistance, and electrochemical impedance spectroscopy. In addition, surface analysis by optical microscopy and X-ray photoelectron spectroscopy (XPS) method was done at the end of weekly corrosion tests. The results of corrosion tests showed that M30NW alloy both uncoated and modified with titania coatings exhibits a very good corrosion resistance during weekly exposition to corrosion medium. The best corrosion resistance in 0.9 % NaCl solution is shown by alloy samples modified by titania coating annealed at 400 °C. The serum proteins have no significant effect onto corrosion of investigated biomedical steel. The XPS results confirmed the presence of proteins on the alloy surface after 7 days of immersion in protein-containing solutions.     

Platinum‐Promoted Ga/Al2O3 as Highly Active,Selective, and Stable Catalyst for the Dehydrogenation of Propane

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga³⁺ species are the active species and where Pt functions as a promoter.     

Ion recognition properties of new pyridine-2,6-dicarboxamide bearing propeller-like pendant residues: multi-spectroscopic approach

The synthesis and ion binding properties of new amide derived from propeller-like tris(2-pyridyl)amine and 2,6-pyridinedicarboxylic acid chloride were described. Amide binds divalent metal cations: copper(II), nickel(II), zinc(II), and lead(II) in acetonitrile. In acetonitrile:water mixture (9:1 v/v) amide interacts only with copper(II) and nickel(II) cations forming complexes of 1:1 stoichiometry. It was found that the introduction of bulky, nitrogen donor atom bearing pendant groups can influence coordination mode of pyridine-2,6-dicarboxamides. The probable model of ligand-ion interactions is proposed on the basis of 1H NMR and FT-IR spectroscopy.     

A novel catalytic adsorptive stripping voltammetric method for the determination of germanium ultratraces in the presence of chloranilic acid and the V(IV)·HEDTA complex

A novel, sensitive catalytic adsorptive stripping voltammetric procedure which can be used to determine trace amounts of germanium is described. The method is based on the interfacial accumulation of the complex formed by Ge(IV) and the product of the reduction of chloranilic acid on the hanging mercury drop electrode or the renewable silver amalgam film electrode, and its subsequent reduction from the adsorbed state followed by the catalytic action of the V(IV)·HEDTA complex. The presence of V(IV)·HEDTA greatly enhances the adsorptive stripping response of Ge. The reduction of the Ge(IV) in the presence of chloranilic acid and V(IV)·HEDTA was investigated in detail and the effects of pH, electrolyte composition, and instrumental parameters were studied. Under optimal conditions, the catalytic peak current of germanium exhibited good linearity for Ge(IV) concentrations in the range of 0.75–60 nM (for 60 s of accumulation at −0.1 V, r² = 0.995) and a low limit of detection (LOD = 0.085 nM). The procedure was successfully applied to determine Ge in water samples.

     

Model potentials in studies of atomic electron density distribution

In density functional theory (DFT ), a many-electron problem for the electron density in atoms may be reduced, according to the Kohn-Sham scheme, to a one-electron problem. In the present work, a variational model is proposed which leads, within some assumptions, to the set of equations describing the change of the electron density ρ and energy ϵ during the ionization process. It is shown that the one-electron density contributions are not necessarily spherically symmetric, but assume the symmetry which depends upon the symmetry of the positive field. A few nonspherically symmetric potentials are studied in the present article. The nonlinear differential equation for density r is formulated and solved for Coulombic, Fues-Kratzer, and Hartmann potentials. The solutions and some particular examples are presented. © 1996 John Wiley & Sons, Inc.