Magnetic and structural features of amorphous FeMo-based alloys

NANOPERM-type FeMoCuB alloys are studied using magnetic and Mössbauer measurements in the as-prepared amorphous state. It is shown that the Fe₇₆Mo₈Cu₁B₁₅ (A) and Fe₇₄Mo₈Cu₁B₁₇ (B) alloys exhibit the magnetic dipole and electrical quadrupole interactions well detected in the room-temperature Mössbauer spectra. The thermomagnetic measurements above the room temperature indicate a vanishing of the magnetic interactions at approximately 310 K (A) and at 340 K (B), respectively. The low-temperature DC magnetic measurements show an anomaly around 200 K which is also a boundary at which zero-field Mössbauer measurements of both samples reflect the gradual “vanishing” of the electrical quadrupole interactions and appearance of another magnetically ordered component. The Mössbauer measurements in the field of 4 MA/m yield a survival of quadrupole and an enhancement of magnetic dipole interactions.     

Crystal structure and physical characterization of <Emphasis Type="Italic">N</Emphasis>-(3,3-dimethylbutyl)-<Emphasis Type="SmallCaps">l</Emphasis>-α-aspartyl-<Emphasis Type="SmallCaps">l</Emphasis>-phenylalanine,the hydrolysis product of neotame

The hydrolysis product of neotame, N-(3,3-dimethylbutyl)-l--aspartyl-l-phenylalanine (DMBAP), was crystallized from water as an anhydrate with a melting point at 197C with decomposition. Its crystal structure was determined by single crystal X-ray diffractometry. The crystal is orthorhombic with space group P2₁2_₁2₁ with Z=4 and one molecule per asymmetric unit. The cell constants are a=5.520 (2) Å, $b=10.608$ (5) Å and c= 31.92 (2) Å. The ¹³C solid-state nuclear magnetic resonance spectrum of DMBAP is compared with those of neotame monohydrate and neotame methanol solvate.     

Synthesis of 2′-deoxycytidine and its triphosphate bearing tryptophan-based imidazolinone fluorophore for environment sensitive fluorescent labelling of DNA

We synthesized 2′-deoxycytidine and the corresponding nucleoside triphosphate bearing (indol-3-yl)methylene-2-methyl-5-oxo-4,5-dihydroimidazol-1-yl group (a tryptophan-based fluorophore from cyan fluorescent protein) linked through a propargyl group at position 5. The fluorophore is weakly solvatochromic, sensitive to pH, and, as a molecular rotor, it is highly sensitive to viscosity. In low viscosity solvents, the fluorescence is very weak, whereas in more viscous environment it lights up. Primer extension or PCR using the modified dC^TrpTP and KOD XL DNA polymerase was used for construction of labelled oligonucleotides and DNA. Preliminary study showed a 2-fold increase of fluorescence of labelled ON probe in presence of single strand-binding protein indicating a potential of this label for sensing of protein-DNA interactions.     

Catalytic efficiency of iron(III) oxides in decomposition of hydrogen peroxide: competition between the surface area and crystallinity of nanoparticles

Various iron(III) oxide catalysts were prepared by controlled decomposition of a narrow layer (ca. 1 mm) of iron(II) oxalate dihydrate, FeC(2)O(4).2H(2)O, in air at the minimum conversion temperature of 175 degrees C. This thermally induced solid-state process allows for simple synthesis of amorphous Fe(2)O(3) nanoparticles and their controlled one-step crystallization to hematite (alpha-Fe(2)O(3)). Thus, nanopowders differing in surface area and particle crystallinity can be produced depending on the reaction time. The phase composition of iron(III) oxides was monitored by XRD and (57)Fe M?ssbauer spectroscopy including in-field measurements, providing information on the relative contents of amorphous and crystalline phases. The gradual changes in particle size and surface area accompanying crystallization were evaluated by HRTEM and BET analysis, respectively. The catalytic efficiency of the synthesized nanoparticles was tested by tracking the decomposition of hydrogen peroxide. The obtained kinetic data gave an unconventional nonmonotone dependence of the rate constant on the surface area of the samples. The amorphous nanopowder with the largest surface area of 401 m(2) g(-1) revealed the lowest catalytic efficiency, while the highest efficiency was achieved with the sample having a significantly lower surface area, 337 m(2) g(-1), exhibiting a prevailing content of crystalline alpha-Fe(2)O(3) phase. The obtained rate constant, 26.4 x 10(-3) min(-1) (g/L)(-1), is currently the highest value published. The observed rare catalytic phenomenon, where the particle crystallinity prevails over the surface area effects, is discussed with respect to other processes of heterogeneous catalysis.     

ClnH6-nSiGe compounds for CMOS compatible semiconductor applications: synthesis and fundamental studies

We describe the synthesis of a new family of chlorinated Si-Ge hydrides based on the formula ClnH6-nSiGe. Selectively controlled chlorination of H3SiGeH3 is provided by reactions with BCl3 to produce ClH2SiGeH3 (1) and Cl2HSiGeH3 (2). This represents a viable single-step route to the target compounds in commercial yields for semiconductor applications. The built-in Cl functionalities are specifically designed to facilitate selective growth compatible with CMOS processing. Higher order polychlorinated derivatives such as Cl2SiHGeH2Cl (3), Cl2SiHGeHCl2 (4), ClSiH2GeH2Cl (5), and ClSiH2GeHCl2 (6) have also been produced for the first time leading to a new class of highly reactive Si-Ge compounds that are of fundamental and practical interest. Compounds 1-6 are characterized by physical and spectroscopic methods including NMR, FTIR, and mass spectroscopy. The results combined with first principles density functional theory are used to elucidate the structural, thermochemical, and vibrational trends throughout the general sequence of ClnH6-nSiGe and provide insight into the dependence of the reaction kinetics on Cl content in the products. The formation of 1 was also demonstrated by an alternative route based on the reaction of (SO3CF3)SiH2GeH3 and CsCl. Depositions of 1 and 2 at very low temperatures (380-450 degrees C) produce near stoichiometric SiGe films on Si exhibiting monocrystalline microstructures, smooth and continuous surface morphologies, reduced defect densities, and unusual strain properties.     

Machine-learning classifiers for imbalanced tornado data

Learning from imbalanced data, where the number of observations in one class is significantly larger than the ones in the other class, has gained considerable attention in the machine learning community. Assuming the difficulty in predicting each class is similar, most standard classifiers will tend to predict the majority class well. This study applies tornado data that are highly imbalanced, as they are rare events. The severe weather data used herein have thunderstorm circulations (mesocyclones) that produce tornadoes in approximately 6.7 % of the total number of observations. However, since tornadoes are high impact weather events, it is important to predict the minority class with high accuracy. In this study, we apply support vector machines (SVMs) and logistic regression with and without a midpoint threshold adjustment on the probabilistic outputs, random forest, and rotation forest for tornado prediction. Feature selection with SVM-recursive feature elimination was also performed to identify the most important features or variables for predicting tornadoes. The results showed that the threshold adjustment on SVMs provided better performance compared to other classifiers.     

Fatigue crack growth simulations of homogeneous and bi-material interfacial cracks using element free Galerkin method

In this paper, quasi-static fatigue crack growth simulations of homogeneous and bi-material interfacial cracks have been performed using element free Galerkin method (EFGM) under mechanical as well as thermo-elastic load. The thermo-elastic fracture problem is decoupled into thermal and elastic problems. The temperature distribution obtained by solving heat conduction equation is used as input in the elastic problem to get the displacement and stress fields. Discontinuities in the temperature and displacement fields are captured by extrinsic partition of unity enrichment technique. The values of stress intensity factors have been extracted from the EFGM solution by domain based interaction integral approach. The standard Paris fatigue crack growth law has been implemented for the life estimation of various model problems. The results obtained by EFGM under mechanical and thermo-elastic loads were compared with those obtained by FEM using remeshing approach.     

Mössbauer investigation of the reaction of ferrate(VI) with sulfamethoxazole and aniline in alkaline medium

Mechanisms on the oxidation of sulfamethoxazole (SMX) and aniline by ferrate(VI) (Fe^VIO $_{4}{^{2-}}$ , Fe(VI)) in alkaline medium suggested the formation of Fe(VI)-SMX or Fe(VI)-aniline intermediates, respectively. Fe(V) and Fe(IV) as other intermediate iron species have also been proposed in the mechanism. In this paper, rapid freeze Mössbauer spectroscopy was applied in rapidly frozen samples to explore intermediate iron species in the reactions of SMX and aniline with Fe(VI). In both reactions, Fe(VI)-SMX and Fe(VI)-aniline intermediates were not seen in second-minute time scale. Fe(V) and Fe(IV) were also not observed. Fe(III) was the only final species of the reactions.