New approach to environmentally benign epoxidation: the solid-phase-system using urea–H2O2 and recyclable dodecatungstate on apatite

On the basis of new concept using a solid disperse phase we have developed an efficient catalytic solid-phase-system for epoxidations of alkenes using urea–hydrogen peroxide (urea–H₂O₂) complex and cetylpyridinium dodecatungstate ((CetylPy)₁₀[H₂W₁₂O₄₂]) catalyst on fluorapatite (FAp). The recovered solid catalyst phase was reused to keep the catalytic activity after several times. In the conceptual idea it is a key point that in situ solid-phase-activation of the catalyst with urea–H₂O₂ proceeds to form microcrystals of the active species dispersed on the solid phase. The dispersion of the catalyst on FAp in the case of tungstic acid (H₂WO₄) was suggested by EPMA analysis. We proposed the peroxo type of species keeping the parent polyoxometalate framework as novel active species from FT-IR spectroscopic studies. FAp phase plays important roles of dispersing the active species on its surface to have high catalytic activity and of stabilizing the active species to lead to high reusability.     

Interfacial reaction between CO2-CO gas and molten iron oxide containing P2O5

The interfacial reaction between CO₂-CO gas and molten iron oxide containing P₂O₅ was investigated by the ¹³CO₂-CO isotope exchange technique at 1773 K with CO₂/CO=1.0. The apparent rate constant rapidly decreased with the addition of P₂O₅ up to 2.86 mol pct PO_2.5 and the Fe³⁺/Fe²⁺ ratio kept constant at approximately 0.2. By the classic site blockage model, in which the reaction only occurs on the vacant sites, and the modified site blockage model, in which the reaction occurs on the vacant sites and the sites occupied by phosphorus simultaneously, the effect of the addition of P₂O₅ was analyzed and the reaction mechanism of CO₂ dissociation was discussed. It may be concluded that the dissociation of the adsorbed CO₂ molecule is reasonable as a rate-determining step and that the effect of phosphorus on the interfacial reaction is caused by the decrease in the number of active sites with the increase of phosphorus content as a surface active element in molten iron oxide.     

Multivariate analysis of the associations between laboratory data and clinical features among patients with infectious mononucleosis syndrome

Infectious mononucleosis (IM) syndrome is typically caused by EBV, but also by drugs and other organisms such as CMV and HBV. It demonstrates a wide range of clinical and laboratory characteristics, presumably depending on the age of onset. However, associations of laboratory abnormalities with the clinical features have not been well documented. We evaluated here, the associations among patients with IM syndrome using of multiple regression (MR) and multiple logistic regression (MLR) analyses. We examined 90 (40 males, 50 females) patients, who were admitted to our hospital with IM syndrome. The diagnostic criteria were fever and presence of atypical lymphocytes (> 5% of the WBC or the count including monocytes > 5000/microliter), and at least 3 of 7 clinical features: tonsillitis, lymphadenopathy, skin rash, hepato-, spleno-megaly, hepatic dysfunction. The diagnosis of EBV was serologically confirmed in 41 cases. MR revealed that the higher age group tended to have lower platelet counts, and that lower platelet counts were associated with higher ALT levels. In addition, MLR revealed that patients with skin rash tended not to have splenomegaly. The frequency of splenomegaly was not related to age, contrary to the findings of previous reports. These findings are useful to differentiate IM syndrome based on laboratory data.     

Solid-state high-resolution 13C-NMR studies of regenerated cellulose samples with different crystallinities

Summary CP/DD/MASS ¹³C-NMR spectra have been obtained for regenerated cellulose samples with different crystallinities as well as for cotton, -D-glucose, -D-cellobiose, and cellopentaose. The spectra of the regenerated cellulose samples exhibit broad multiplicities of the C-4 and C-6 resonance lines in a similar manner as those of native cellulose samples such as cotton and ramie, and, in addition, another broad tailing of the C-1 resonance. Since these multiplicities change linearly with crystallinity, it is concluded that they are ascribed to the contributions from the crystalline and noncrystalline components. Effects of hydrogen bonds and conformations of the -1,4-glycosidic linkage on the chemical shifts are also discussed.     

Phase separation behavior and morphology development of phenolic resin/PMMA/hexamethylenetetrarnine blends

Summary In order to obtain materials with nanopores which will be applicable for many fields, the structures of the cured blends of phenolic resin (PhN), poly(methyl methacrylate) (PMMA) and curing agent were studied. After PMMA was extracted from cured blends, the structures of cured phenolic resins were observed with SEM. As a results, it was found that nanosized continuous pore structures were formed in extremely wide composition region if curing temperature was high.     

Thermodynamics of calcium and oxygen in molten titanium and titanium-aluminum alloy

The deoxidation equilibrium of molten titanium and titanium-aluminum alloys saturated with solid CaO has been measured in the temperature range from 1823 to 2023 K. The equilibrium constant of reaction CaO (s)=Ca (mass pct in Ti,Ti-Al)+O (mass pct in Ti,Ti-Al) and the interaction parameter between calcium and oxygen were determined for Ti, TiAl, and TiAl₃. The standard Gibbs energy of reaction for TiAl was obtained as follows: $$\Delta G^\circ = 279,000 - 103TJ/mol$$ The possibilities for the deoxidation of titanium and titanium-aluminum alloys by using calcium-based fluxes are discussed.     

A generalized finite-difference time-domain quantum method for the N-body interacting Hamiltonian

The Quantum Finite-Difference Time-Domain (FDTD-Q) method is a numerical method for solving the time evolution of the Schrödinger equation. It can be applied to systems of interacting particles, allowing for realistic simulations of quantum mechanics of various experimental systems. One of the drawbacks of the method is that divergences in the numerical evolution occur rather easily in the presence of interactions, which necessitates a large number of evolution steps or imaginary time evolution. We present a generalized (GFDTD-Q) method for solving the time-dependent Schrödinger equation including interactions between the particles. The new scheme provides a more relaxed condition for stability when the finite difference approximations for spatial derivatives are employed, as compared with the original FDTD-Q scheme. We demonstrate our scheme by simulating the time evolution of a two-particle interaction Hamiltonian. Our results show that the generalized method allows for stable time evolutions, in contrast to the original FDTD-Q scheme which produces a divergent solution.     

Evolution of TiS and TiN in Fe-40 MassPctNi Austenitic Alloy During Heating at 1273 K (1000 °C)

Metallurgical and Materials Transactions B - Evolution of TiS in composition and morphology as well as the change in size distribution of TiS and TiN in Fe-40 masspctNi austenitic alloy during...     

Fast and Almost Complete Nitridation of Mesoporous Silica MCM-41 with Ammonia in a Plug-Flow Reactor

The title reaction proceeded well to yield silicon (oxy)nitride at 973–1323 K using a plug-flow reactor. The degree of nitridation was studied as a function of temperature and time of nitridation, the sample weight, and the flow rate of ammonia. It was dependent on the reaction temperature and the amount of ammonia supplied per sample weight. The nitridation at 1273 K for 10–25 h yielded the oxynitride with 36–39 wt% nitrogen, which was very close to 40 wt% of Si₃N₄. Characterization with X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy measurements, and nitrogen adsorption revealed the conversion of MCM-41 to the corresponding oxynitride without essential loss of the mesoporous structure, the decrements of the lattice constant and the pore diameter by 20–35%, and the increments of the wall thickness by ca. 45%. Solid-state ²⁹Si nuclear magnetic resonance spectra during the nitridation clearly showed fast decrease in SiO₄ species and slow in SiO₃(OH). Various intermediate species, SiO _x N _y (NH₂ or NH) _z , were observed to be formed and finally, ca. 70% SiN₄ species, ca. 20% SiN₃(NH₂ or NH), and ca. 10% SiON₂(NH₂ or NH) were produced, being consistent with the results of the above mentioned elemental analysis.