The GC/AED studies on the reactions of sulfur mustard with oxidants

A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive.     

Spatial distributions of residuals produced inside a spallation target

The spallation target model of an accelerator driven system (ADS), consisting of six 5 cm thick and 16 cm in diameter Pb segments, was constructed. Three sets of 17 Bi samples (1/2 inch in diameter and 1 mm thick) were placed in 3 Pb disc-shaped holders inside the target at 5, 10 and 15 cm from its front. After irradiation with 660 MeV proton beam gamma-spectra of radioisotopes produced in Bi were collected several times for each sample with the use of HPGe detectors in order to identify the radioisotopes and to determine their absolute activities. Their spatial distributions were then compared with respective values obtained in the calculations made with the use of FLUKA and/or MCNPX code. A fair agreement with the experiment has been observed.     

Lipidic membranes are potential "catalysts" in the ligand activity of the multifunctional pentapeptide neokyotorphin

Neokyotorphin (NKT) is a multifunctional pentapeptide that is involved in biological functions as diverse as analgesia, antihibernatic regulation and proliferation stimulus of tumour cells. The interaction of neokyotorphin with cell membranes is potentially important to all these multiple biological processes since receptor-mediated processes are thought to be involved in neokyotorphin action. Sargent and Schwyzer proposed in their "membrane catalysis" model that ligands interact with membrane lipids in order to adopt the necessary conformation for cell receptors. We have used fluorescence techniques to study the depth, orientation and extent of incorporation of NKT with model membrane systems (lipidic vesicles). The roles of lipid charge, membrane phase and sterol presence were investigated. The phenolic ring of tyrosine is located in a shallow position in membranes. The extent of partition is less in gel crystalline membranes than in liquid crystalline membranes. Addition of cholesterol causes a reorientation of the tyrosine ring at the interface of lipidic bilayers. Lipidic membranes meet all the conditions required for acting as potential "catalysts" in the ligand activity of the multifunctional pentapeptide NKT, because they modulate the exposure and orientation of the phenolic ring, which is most likely involved in docking to receptors.     

IMAGE-WARP: a real-space restoration method for high-resolution STEM images using quantitative HRTEM analysis

We have developed a new method for processing distorted high-resolution scanning transmission electron microscopy (STEM) images. The method is based on finding the displaced vertices in the experimental STEM image and warping to geometrically correct reference grid of the object. As a reference grid for warping a structural model obtained using a high-resolution transmission electron microscopy (HRTEM) analysis of the area of interest is utilised. Combined with quantitative HRTEM analysis the IMAGE-WARP method provides a real-space restoration of high-resolution high-angle annular dark-field (HAADF) STEM images without affecting the original Z-contrast information. The method can be applied to extract valuable compositional atomic-column data from any HAADF-STEM image of any kind of bulk crystals with local occupancy or chemistry fluctuations, stacking faults, special grain boundaries or interfaces, for which we have an available structural model. After the warping, distortion-corrected images can be further enhanced using conventional image-filtering techniques, and finally quantified with HAADF-STEM image simulations. The applicability of the IMAGE-WARP method was illustrated using experimental HAADF-STEM images of a strontium titanate crystal disrupted with a Ruddlesden-Popper-type antiphase boundary.     

Untersuchungen über den Kohlenmonoxydzerfall und seine katalytische Vergiftung

Untersuchung über den Einfluß von Schwefelwasserstoffzusätzen zu Kohlenmonoxyd und gichtgasähnlichen Gasgemischen auf den Kohlenmonoxydzerfall an Gichtstaub und reinem Eisen(III)-oxyd. Erörterung der Analysenverfahren. Diskontinuierliche Vergiftungsversuche. Betriebsversuche an kleinen Rekuperatoren. Versuche an feuerfesten Steinen.     

Phenolic compounds and antioxidant activity of extracts of Ginkgo leaves

The aim of the present study was to determine the flavonol contents of crude extracts from Ginkgo (Ginkgo biloba L.) leaves, their antioxidant properties in model system studies, and their inhibitory action of linoleic acid oxidation in an emulsion system and of triacylglycerols (TAG) in rapeseed oil. Extracts were prepared from both green and yellow leaves of Ginkgo trees using water, aqueous acetone, and ethanol. Extracts were analyzed by HPLC for their presence and content of selected flavonols; these included myricetin, quercetin, kaempferol, isorhamnetin, and morin. The highest level of flavonols, especially quercetin, myricetin and kaempferol, were found in the aqueous acetonic extracts. Crude extracts from yellow Ginkgo leaves contained greater amounts of flavonols. The best DPPH radical‐scavenging activity amongst the Ginkgo extracts examined was determined for aqueous acetonic extracts, while the lowest was noted for the ethanolic extract of green leaves. Water infusion extracts exhibited the highest iron(II) chelating activity. The reducing power of extracts from yellow leaves was 2 higher than that of crude extracts from green leaves. Nevertheless, extracts from green Ginkgo leaves imparted a greater protection factor against TAG oxidation, as assessed by the Rancimat method. Crude extracts from yellow Ginkgo leaves were more efficacious than green ones at inhibiting oxidation of the linoleic acid emulsion.     

Nature of high reactivity of metal/solid oxidizer nanocomposites prepared by mechanoactivation: a review

In this review, the regularities of formation, structure and high reactivity of two types of energetic metal/solid oxidizer nanocomposites (Al(Mg)/X (X = MoO₃, (–C₂F₄–) _n )) prepared by mechanoactivation are examined. One reason for the high reactivity is an increase in contact surface between the components occurring after mechanoactivation. Two methods for determination of area of contact surface S _C between the components are used, and the values of S _C for all the systems are estimated. Considerable attention is paid to the role of highly reactive defects (grain sizes, dislocations and stacking faults, paramagnetic centers, “weakly bound” oxygen in MoO₃, etc.), formed in the components under mechanical stress. For the Me/MeO₃ systems, the formation of point defects in the oxide is an important factor. It was found that, after mechanoactivation, the evolution of O₂ from MoO₃ occurs at 230–450 °C. It is argued that this process is associated with the thermal destruction of “weak” Mo–O bonds in the “bridge” oxygen. It was suggested that the formation of defect structure in MoO₃ and increasing of the oxygen mobility under heating give rise to a low-temperature peak in DSC curves and initiated self-ignition on the fuel–air mixture. For composites Mg/MoO₃, self-ignition occurs at temperature 100 °C lower than that for Al/MoO₃: The decreasing of temperature can be connected with larger S _C in the first system. In the Mg/(–C₂F₄–) _n system, the reactions of magnesium defects with (–C₂F₄–) _n are accompanied by a weak heat evolution, too low to initiate ignition. In this case, the reaction is initiated by the thermal depolymerization of (–C₂F₄–) _n , while a high values of S _C provide a complete conversion. In the case of shock-wave initiation, defects in the components play only a minor role in the conversion, whereas the value of S _C remains to be highly important.     

Rippling Colloidal Polyelectrolyte Complex for Customized Fingerprints with High Tactile Perception

Fingerprints possess wide applications in personal identification, tactile perception, access control, and anti-counterfeiting. However, latent fingerprints are usually left on touched surfaces, leading to the leakage of personal information. Furthermore, tactile perception greatly decreases when fingerprints are covered by gloves. Customized fingerprints are developed to solve these issues, but it is a challenge to develop fingerprints with various customized patterns using traditional techniques due to their requiring special templates, materials, or instruments. Inspired by ripples on the lake, blowing air is used to generate surface waves on a colloidal polyelectrolyte complex, leading to vertical stratification and the accumulation of particles near the top of the film layer. As water rapidly evaporates, the viscosity of these particles significantly increases and the wave is solidified, forming fingerprint patterns. These customized fingerprints integrate functions of grasping objects, personal identification without leaving latent fingerprints and tactile perception enhancement, which can be applied in information security, anti-counterfeiting, tactile sensors, and biological engineering.     

A 3D Cu-Naphthalene-Phosphonate Metal–Organic Framework with Ultra-High Electrical Conductivity

A conductive phosphonate metal–organic framework (MOF), [{Cu(H₂O)}(2,6-NDPA)_0.5] (NDPA = naphthalenediphosphonic acid), which contains a 2D inorganic building unit (IBU) comprised of a continuous edge-sharing sheet of copper phosphonate polyhedra is reported. The 2D IBUs are connected to each other via polyaromatic 2,6-NDPA's, forming a 3D pillared-layered MOF structure. This MOF, known as TUB40, has a narrow band gap of 1.42 eV, a record high average electrical conductance of 2 × 10² S m⁻¹ at room temperature based on single-crystal conductivity measurements, and an electrical conductance of 142 S m⁻¹ based on a pellet measurement. Density functional theory (DFT) calculations reveal that the conductivity is due to an excitation from the highest occupied molecular orbital on the naphthalene-building unit to the lowest unoccupied molecular orbital on the copper atoms. Temperature-dependent magnetization measurements show that the copper atoms are antiferromagnetically coupled at very low temperatures, which is also confirmed by the DFT calculations. Due to its high conductance and thermal/chemical stability, TUB40 may prove useful as an electrode material in supercapacitors.