Complete Oxidation of Methane over Palladium Supported on Alumina Modified with Calcium,Lanthanum,and Cerium Ions

The activity and thermal stability of Pd/Al_2O_3 and Pd/(Al_2O_3 MO_x)(M=Ca,La,Ce) palladium catalysts in the reaction of complete oxidation of methane are presented in this study.The catalyst supports were prepared by sol-gel method and they were dried either conventionally or with supercritical carbon dioxide.Then they were impregnated with palladium nitrate solution.The catalysts with unmodified alumina had a high surface area.The activity and thermal stability of the alumina- supported catalyst was also very high.The introduction of calcium,lanthanum,or cerium oxide into alumina support caused a decrease of the surface area in the way dependent on the support precursor drying method.These modifiers decreased the activity of palladium catalysts,and they required higher temperatures for the complete oxidation of methane than unmodified Pd/Al_2O_3.The improvement of the palladium activity by lanthanum and cerium support modifier was observed only at low temperatures of the reaction.     

The investigation of femoroacetabular impingement using motion capture,FEM and multi-body simulations

In recent years, femoroacetabular impingement (FAI) has become increasingly common. As published in the literature, FAI is caused by an unphysiological contact between the proximal femur and the acetabular rim, which may lead to pain, limitation of movement, and damage of cartilage. In this paper, patient-specific finite element simulations of the movement of the hip based on gait motion data and MRI segmentation were conducted to check stresses of the acetabulum and femur, and additionally whether a bony contact is present or not. The study's findings show no bony contact between femur and acetabulum, which may lead to the hypothesis that the labrum and its deformation and/or the articular capsule are involved in the mechanism of FAI. In order to verify this hypothesis more simulations including labrum and capsule must be performed. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Conformational analysis of nine-membered cyclic acetals. Stereoelectronic effect in 2,4- and 3,5-benzodioxonine derivatives

Conformations of the title compounds were examined using DFT calculations and NBO analysis in order to find the origins of their conformational preferences. The most stable conformations were TBC and TCBtype-1 for the 2,4- and 3,5-benzodioxonine derivatives, respectively. In both of these conformations the acetal moiety adopts the g+/-g+/- geometry. The NBO analysis yielded values of the stabilization energy associated with the stereoelectronic nO --> sigmaC-O* interactions that were highest for conformations other than the global minima. Conformers displaying the strongest interactions followed different patterns of atom arrangement within the acetal moiety, namely g+g-, and those in which one or both of the torsion angles within the C-O-C-O-C segment were close to 90 degrees . Steric repulsion caused by alkyl substituents at the anomeric carbon was found to influence the strength of the nO --> sigmaC-O* stabilization through modification of bond lengths and torsion angles. The adopted ground-state conformations result from accommodation of steric repulsions and stabilizing stereoelectronic interactions. It was shown that DFT calculations of conformational preferences of acetals together with GIAO prediction of 13C chemical shifts should be a useful methodology for studies on conformation and conformational equilibria of acetals in solution.     

Identification of Bacteria Associated with Post-Operative Wounds of Patients with the Use of Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Approach

The bacterial infection of post-operative wounds is a common health problem. Therefore, it is important to investigate fast and accurate methods of identifying bacteria in clinical samples. The aim of the study was to analyse the use of the MALDI-TOF MS technique to identify microorganism wounds that are difficult to heal. The most common bacteria are Escherichia coli, Staphylococcus spp., and Enterococcus spp. We also demonstrate the effect of culture conditions, such as the used growth medium (solid: Brain Heart Infusion Agar, Mueller Hilton Agar, Glucose Bromocresol Purple Agar, and Vancomycin Resistance Enterococci Agar Base and liquid: Tryptic Soy Broth and BACTEC Lytic/10 Anaerobic/F), the incubation time (4, 6, and 24h), and the method of the preparation of bacterial protein extracts (the standard method based on the Bruker guideline, the Sepsityper method) to identify factors and the quality of the obtained mass spectra. By comparing the protein profiles of bacteria from patients not treated with antibiotics to those treated with antibiotics based on the presence/absence of specific signals and using the UniProt platform, it was possible to predict the probable mechanism of the action of the antibiotic used and the mechanism of drug resistance.     

Analysis of flammability and smoke emission of rigid polyurethane foams modified with nanoparticles and halogen-free fire retardants

Using one-step method, rigid polyurethane foams were made, modified with developed fire retardant systems containing halogen-free flame retardants and nanofillers in the form of multi-walled carbon nanotubes or nanoscale titanium dioxide. The materials were subjected to a test using a cone calorimeter and smoke-generating chamber, and selected samples were further analyzed via thermogravimetry and oxygen index. Moreover, the products of thermal degradation of selected samples were identified using gas chromatography with mass spectrometer. Conducted flammability tests confirmed the presence of a synergistic effect between the used nanofillers and halogen-free flame retardants. It has been observed that the carbonized layer, the formation of which favored the presence of nanoadditives, inhibits the combustion process. Furthermore, nanofillers influenced favorably reduction in the amount and the number of occurring products of thermal degradation.     

CHEMILUMINESCENCE IN THE PEROXIDATION OF TANNIC ACID

Abstract— Peroxidation of tannins with alkaline H₂O₂ is accompanied by weak chemiluminescence in the spectral region 480–800 nm. o-Di and tri-hydroxy groups of polyphenols undergo oxidation by a free-radical mechanism and a green intermediate anion-radical with absorption Δ_max= 600 nm is formed. The radical mechanism is supported by the low activation energy 14–20 kJ/mol and the quenching effect of radical scavengers. The reaction of the green intermediate with peroxy anions is the chemiluminescence rate limiting step. In the presence of a-hydroxy-methylperoxide formed from H₂O₂ and formaldehyde, the alkaline peroxidation of tannins is accompanied by strong red luminescence (420–800 nm). The base catalyzed decomposition of peroxides gives only a weak red emission (460–800 nm). Light intensity is enhanced in D₂O by a factor 6.5. Quenchers of O₂(¹Δ_g) and 1,3-di-phenylisobenzofurane diminish light intensity in non-aqueous solutions. The data suggest ¹O₂ participation in the observed chemiluminescence. Thermo-chemical calculations give —ΔH values from 250–1000 kJ/mol for one elementary reaction step which limits the mechanism of chemi-enereization. Chemiexcitation of tannins is relevant to biochemical mechanisms of aerobic degradation of aromatic compounds, energy utilization as well as to defense and resistance processes in plants.     

Stereochemical studies of the formation of chiral internucleotide linkages by phosphoramidite coupling in the synthesis of oligodeoxyribonucleotides

HPLC-fractionated ($\text{R}$_p)- and ($\text{S}$_p)-phosphoramidites underwent tetrazole-catalyzed coupling to support-bound nucleosides to give intermediary phosphates with epimerization at phosphorus, as shown by conversion to epimerized mixtures of dinucleoside phosphorothioates.