Size versus volume extensivity of a new class of density matrix functionals

Despite being size-extensive, the "second-generation" 1-matrix functionals for the electron-electron repulsion energy V(ee) yield vanishing correlation energy for the homogeneous electron gas. This failure is directly related to the idempotency condition imposed upon an auxiliary matrix that enters the expression for V(ee). In particular, the recently proposed Kollmar-Hess functional is not volume-extensive and thus is incapable of properly describing any delocalized system at its thermodynamic limit.     

Influence of rhodium additive on hydrogen electrosorption in palladium-rich Pd�CRh alloys

Hydrogen electrosorption into Pd-rich (>80?at.% Pd in the bulk) Pd?CRh alloys has been studied in acidic solutions (0.5?M H₂SO₄) using cyclic voltammetry and chronoamperometry. The influence of temperature (in the range between 283 and 328?K), electrode potential and alloy bulk composition on hydrogen electrosorption properties of Pd?CRh alloys is presented. It has been found that the additive of Rh to Pd?CRh alloys increases the maximum hydrogen solubility (for Rh bulk content below 10?at.%), decreases the potential of absorbed hydrogen oxidation peak and decreases the potential of the ???????? phase transition. Increasing temperature decreases the potential of absorbed hydrogen oxidation peak, the maximum hydrogen solubility, and the potential of the ???????? phase transition. The amounts of electrosorbed hydrogen for ??- and ??-phase boundaries, i.e., ??_max and ??_min, have been determined from the integration of the initial parts of current?Ctime responses in hydrogen absorption and desorption processes. The H/M ratio corresponding to ??_max increases with increasing Rh content, while for ??_min a maximum of H/M ratio is observed for the alloys containing ca. 95% Rh.     

The lattice generated by <Emphasis Type="Italic">τ</Emphasis>-quasicontinuous functions

The lattices generated by the families of quasicontinuous and τ-quasicontinuous functions are described.     

Thermodynamic property values of selected polycyclic aromatic hydrocarbons measured by differential scanning calorimetry

In this study, the use of differential scanning calorimetry (DSC) is demonstrated as a powerful technique that can provide accurate thermodynamic property values of environmental contaminants such as polycyclic aromatic hydrocarbons (PAHs). In total, 47 high purity PAH certified reference materials were selected and analysed by DSC. Their onset melting temperature, enthalpy of fusion and eutectic purity were calculated from the obtained melting endotherms. In addition, the entropy of fusion, which was calculated from the onset melting temperature and enthalpy of fusion, is presented. All measurements were evaluated in a metrologically rigorous manner, including measurement uncertainties.     

The Intensity of Heat Exchange between Rock and Flowing Gas in Terms of Gas-Geodynamic Phenomena

Gas-induced geodynamic phenomena can occur during underground mining operations if the porous structure of the rock is filled with gas at high pressure. In such cases, the original compact rock structure disintegrates into grains of small dimensions, which are then transported along the mine working space. Such geodynamic events, particularly outbursts of gas and rock, pose a danger both to the life of miners and to the functioning of the mine infrastructure. These incidents are rare in copper ore mining, but they have recently begun to occur, and have not yet been fully investigated. To ensure the safety of mining operations, it is necessary to determine parameters of the rock–gas system for which the energy of the gas will be smaller than the work required to disintegrate and transport the rock. Such a comparison is referred to as an energy balance and serves as a starting point for all engineering analyses. During mining operations, the equilibrium of the rock–gas system is disturbed, and the rapid destruction of the rock is initiated together with sudden decompression of the gas contained in its porous structure. The disintegrated rock is then transported along the mine working space in a stream of released gas. Estimation of the energy of the gas requires investigation of the type of thermodynamic transformation involved in the process. In this case, adiabatic transformation would mean that the gas, cooled in the course of decompression, remains at a temperature significantly lower than that of the surrounding rocks throughout the process. However, if we assume that the transformation is isothermal, then the cooled gas will heat up to the original temperature of the rock in a very short time (<1 s). Because the quantity of energy in the case of isothermal transformation is almost three times as high as in the adiabatic case, obtaining the correct energy balance for gas-induced geodynamic phenomena requires detailed analysis of this question. For this purpose, a unique experimental study was carried out to determine the time required for heat exchange in conditions of very rapid flows of gas around rock grains of different sizes. Numerical simulations reproducing the experiments were also designed. The results of the experiment and the simulation were in good agreement, indicating a very fast rate of heat exchange. Taking account of the parameters of the experiment, the thermodynamic transformation may be considered to be close to isothermal.     

Enhancement of the Efficacy of Photodynamic Inactivation of Candida albicans with the Use of Biogenic Gold Nanoparticles

This study reports on successful photodynamic inactivation of planktonic and biofilm cells of Candida albicans using Rose Bengal (RB) in combination with biogenic gold nanoparticles synthesized by the cell‐free filtrate of Penicillium funiculosum BL1 strain. Monodispersed colloidal gold nanoparticles coated with proteins were characterized by a number of techniques including SEM–EDS, TEM, UV–Vis absorption and fluorescence spectroscopy, as well as Fourier transform infrared spectroscopy to be 24 ± 3 nm spheres. A Xe lamp (output power of 20mW, delivering intensity of 53 mW cm^?2) was used as a light source to study the effects of RB alone, the gold nanoparticles alone and the RB‐gold nanoparticle mixture on the viability of C. albicans cells. The most effective reduction in the number of planktonic cells was found after 30 min of Xe lamp light irradiation (95.4 J cm^?2) and was 4.89 log₁₀ that is 99.99% kill for the mixture of RB with gold nanoparticles compared with 2.19 log₁₀ or 99.37% for RB alone. The biofilm cells were more resistant to photodynamic inactivation, and the highest effective reduction in the number of cells was found after 30 min of irradiation in the presence of the RB–gold nanoparticles mixture and was 1.53 log₁₀, that is 97.04% kill compared with 0.6 log₁₀ or 74.73% for RB. The probable mechanism of enhancement of RB‐mediated photodynamic fungicidal efficacy against C. albicans in the presence of biogenic gold nanoparticles is discussed leading to the conclusion that this process may have a multifaceted character.     

Silver nanoparticles formed in bio- and chemical syntheses with biosurfactant as the stabilizing agent

In this work, the comparison of the physical properties of silver nanoparticles (AgNPs) obtained via the reduction of silver nitrate (AgNO₃) in biological and chemical (model) syntheses supplemented with the biosurfactant surfactin is described. In the studies, two strains of Bacillus subtilis (denoted T’1 and I’1a) were used. The biological synthesis of AgNPs was performed using supernatants obtained from cultures of bacteria growing on brewery effluents, molasses, and Luria–Bretani (LB) medium. In model experiments, ascorbic acid served as the reductant; surfactin acted as the stabilizing agent. The surfactin concentrations were adjusted to 5 and 30?mg/L, which corresponded to minimum and maximum surfactin concentrations as measured in the supernatants obtained from the B. subtilis cultures. The chemical synthesis was carried out at acidic as well as alkaline pH. Dynamic light scattering (DLS) revealed that in model and biological samples, single AgNPs were accompanied by aggregated structures. Transmission electron microscopy showed that the contribution of the aggregates in bacterial supernatants and in chemical synthesis is negligible under acidic conditions. However, in the alkaline environment, this contribution predominates. In the model experiments, smaller nanoparticles were formed with higher concentrations of surfactant. The presence of surfactin significantly increased the stability of AgNPs in both bio- and chemical syntheses.     

The design, synthesis, and application of a chiral coupling reagent derived from strychnine for the enantioselective activation of a carboxylic group

The concept of a chiral coupling reagent for the enantioselective synthesis of peptides with a predictable configuration and enantiomeric purity from racemic substrates is presented. The reagent was prepared by treatment of strychninium tetrafluoroborate with 2-chloro-4,6-dimethoxy-1,3,5-triazine in the presence of sodium bicarbonate yielding N-(4,6-dimethoxy-1,3,5-triazin-2-yl)strychninium tetrafluoroborate in high yield, which is stable at room temperature, and in a broad range of solvents gave enriched Z-Ala-Phe-OMe (dr from 95/5 to 60/40) in high yield with d-configuration on the alanine residue starting from rac-Z-Ala-OH.     

Tri(mesityloxy)silanethiol – The First Structurally Characterized Organoxysilanethiol (Contributions to the Chemistry of Silicon–Sulfur Compounds. 77 [1])

Tri(mesityloxy)silanethiol (TMST) was isolated as the only product of the reaction between SiS₂ and 2,4,6‐trimethylphenol. TMST crystallizes in the triclinic system. Good quality of the crystal allowed the unrestricted refinement of the mercapto group; the resulting S–H distance is 1.29(4) Å and the Si–S–H bond angle is 95.4(17)°. Molecules of TMST show no hydrogen bonds in the crystal – the FT‐IR spectrum of the solid sample exhibits a very sharp, well‐resolved band of isolated –SH group at 2562 cm^–1.