Mechanical mixtures of Me (Ni, Pd) Ce oxides and silica-supported heteropolyacids: Role and optimal concentration of each active species in n-hexane isomerization

Catalytic properties of silica-supported heteropolyacids (HPA) in a mechanical mixture with reduced Me-Ce oxides (Me = Ni, Pd) in n-hexane isomerization are studied. The role of each component of the mixed oxides (Ce and, typically, Ni and Pd) and their optimum content has been illuminated: cerium is not only beneficial for eliminating or preventing coke deposition but is also effective for maintaining the Keggin structure of the highly-organized HPA during the reaction and probably allows a better dispersion of the second metal species. Nickel and palladium, present as Ni⁰ and Pd⁰, reinforce the activation of the alkane, which is difficult to obtain by means of a direct attack by an acid, and, thus, enhance noticeably the activity of the catalyst. The best mechanical mixtures are obtained with 30–70 wt % NiCeO-HPW/SiO₂ and 50–50 wt % Pd_0.1CeO-HPW/SiO₂. These mixtures have the highest efficiency for a Ni/(Ni + W) atomic ratio of 0.66 and a Pd/(Pd + W) ratio of 0.40, respectively. Finally, the conversion of n-hexane is in the order HPW > HSiW > HBW, which seems to be consistent with the order of their acid strength as per the literature, but the isomerization selectivity appears to be slightly higher on HSiW. Published in Russian in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 24–28. The text was submitted by the authors in English.     

Rapid determination of 5-hydroxytryptamine in whole blood by liquid chromatography with fluorimetric detection.

A rapid and simple reversed-phase (using muBondapak C18 as the stationary phase) liquid chromatographic method with fluorimetric detection is described for the quantitation of 5-hydroxytryptamine in whole blood. The rapidity and simplicity of the method are explained by the absence of a pretreatment. 5-Fluoro-dl-tryptophan was used as internal standard. The mobile phase was 0.01 M phosphate buffer (pH 4.5) with 0.0025 M 1-heptanesulfonic acid and 20% methanol. The detection wavelength were 302 nm for excitation and 340 nm for emission. Analysis time was 10 min with retention times for 5-hydroxytryptamine of 9 min and for 5-fluoro-dl-tryptophan of 7 min. This method is proposed for biological exploration of psychiatric disorders involving 5-hydroxytryptamine and would be useful for tryptophan.     

Efficient nickel-mediated intramolecular amination of aryl chlorides

The use of an in situ generated Ni(0) catalyst associated with 2,2'-bipyridine or N,N'-bis(2,6-diisopropylphenyl)dihydroimidazol-2-ylidene (SIPr) as a ligand and NaO-t-Bu as the base for the intramolecular coupling of aryl chlorides with amines is described. The procedure has been applied to the formation of five-, six-, and seven-membered rings. [reaction: see text]     

Dual phosphorescence from 5-methylbicyclo[4.3.01,5]non-1-en3-one

Phosphorescence has been simultaneously observed from both a ³π, π* and a ³n,π* level of 5-methylbicyclo-[4.3.0^1,5non-1-en-3-one. The emission from the higher energy ³n,π* state, which is in thermal equilibrium with the ³π,π* state, is quenched by lowering the temperature and also quenched by increasing the solvent polarity so as to raise the energy of the ³n,π* state relative to the ³π,π* state.     

Warm tachyon inflation and swampland criteria

In this study, the scenario of a two-component warm tachyon inflation is considered, where the tachyon field plays the role of the inflaton by driving the inflation. During inflation, the tachyon scalar field interacts with the other component of the Universe, which is assumed to be photon gas, i.e., radiation. The interacting term contains a dissipation coefficient, and the study is modeled based on two different and familiar choices of the coefficient that were studied in the literature. By employing the latest observational data, the acceptable ranges for the free parameters of the model are obtained. For any choice within the estimated ranges, there is an acceptable concordance between the theoretical predictions and observations. Although the model is established based on several assumptions, it is crucial to verify their validity for the obtained values of the free parameters of the model. It is found that the model is not self-consistent for all values of the ranges, and for some cases, the assumptions are violated. Therefore, to achieve both self-consistency and agreement with the data, the parameters of the model must be constrained. Subsequently, we consider the recently proposed swampland conjecture, which imposes two conditions on the inflationary models. These criteria rule out some inflationary models; however, warm inflation is among those that successfully satisfy the swampland criteria. We conduct a precise investigation, which indicates that the proposed warm tachyon inflation cannot satisfy the swampland criteria for some cases. In fact, for the first case of the dissipation coefficient, in which, there is dependency only on the scalar field, the model agrees with observational data. However, it is in direct tension with the swampland criteria. Nevertheless, for the second case, wherein the dissipation coefficient has a dependency on both the scalar field and temperature, the model exhibits acceptable agreement with observational data, and suitably satisfies the swampland criteria.     

Cleavage of Menger’s aliphatic amide: A model for peptidase enzyme solely explained by proximity orientation in intramolecular proton transfer

Ab initio HF/6-31G and DFT B3LYP/6-31G (d,p) calculations for the cleavage of Menger’s aliphatic amide 3 (a peptidase model) under physiological conditions, indicate that the rate limiting step in the cleavage process is a proton transfer from one of the carboxyl groups onto the amidic carbonyl oxygen. The acceleration in rates is mainly due to proximity orientation, and the effect of pseudoallylic strain relief on the rates is negligible. Moreover, the calculations reveal that the mode and the mechanism of the amide cleavage are largely dependent on the pH of the reaction. These results explain the findings that peptidase enzymes are reactive around neutral pH while their activities vanish under basic medium.     

Issue Information ‐ TOC

Numerical modeling of multiphase flow generally requires a special procedure at the solid wall in order to be consistent with Young's law for static contact angles. The standard approach in the lattice Boltzmann method, which consists of imposing fictive densities at the solid lattice sites, is shown to be deficient for this task. Indeed, fictive mass transfer along the boundary could happen and potentially spoil the numerical results. In particular, when the contact angle is less than 90 degrees, the deficiencies of the standard model are major. Various videos that demonstrate this behavior are provided (Supporting Information). A new approach is proposed and consists of directly imposing the contact angle at the boundaries in much the same way as Dirichlet boundary conditions are generally imposed. The proposed method is able to retrieve analytical solutions for static contact angles in the case of straight and curved boundaries even when variable density and viscosity ratios between the phases are considered. Although the proposed wetting boundary condition is shown to significantly improve the numerical results for one particular class of lattice Boltzmann model, it is believed that other lattice Boltzmann multiphase schemes could also benefit from the underlying ideas of the proposed method. The proposed algorithm is two‐dimensional, and the D2Q9 lattice is used. Copyright © 2016 John Wiley & Sons, Ltd.     

On the reduction of S-alkyl-thionocarbonates (xanthates) with phosphorus compounds

[reaction: see text] Reductive cleavage of the carbon-sulfur bond present in S-alkyl-thionocarbonates (xanthates) was achieved by high-yielding, tin-free radical reactions based on phosphorus reagents. The combination hypophosphorous acid/triethylamine/AIBN led to fast, efficient, and smooth formation of the alkane. Reduction with diethyl phosphite was sufficiently slow to permit sequential intermolecular addition of a 2-oxoalkyl xanthate onto an olefin followed by cleavage of the newly formed carbon-sulfur bond.