(NH4)6Mo7O24·4H2O as an Efficient,Selective, and Reusable Catalyst for the Oxidation of Thiols to Disulfides Using Potassium Bromate

Abstract

Ammonium molybdate, (NH₄)₆Mo₇O₂₄·4H₂O, is found to be an efficient and selective catalyst for the oxidation of thiols to corresponding disulfides using potassium bromate in aqueous acetonitrile as the solvent. Among various solvents tested, CH₃CN/H₂O showed better results in terms of the reaction yield and rate. In the absence of (NH₄)₆Mo₇O₂₄·4H₂O, the oxidation reaction is not selective for the formation of disulfides. The catalyst can be easily recovered after completion of the reaction and reused without any significant loss of its activity.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.]     

Modeling the framework stability and catalytic activity of pure and transition metal-doped zeotypes

We present a thorough computational study of transition metal-doped zeolite and aluminophosphate (AlPO) frameworks. The structural and electronic chemistry of the dopants is examined with ab initio quantum mechanical calculations, and the results correlated with the Brønsted and Lewis acid strength, and with the redox potential of the dopant ions in the framework. The energetics of doping is provided, and is employed to analyze the mode of dopant incorporation, and its site ordering in the microporous framework. In total, 23 dopant ions are examined in the isostructural framework of chabasite and AlPO-34. These cover most of the isomorphous framework replacements known to occur experimentally, but also framework replacements that have not yet been achieved. In this case, ab initio modeling techniques are employed in a predictive way. Finally, we present a computational study of the alkene epoxidation on titanosilicates, that covers the whole catalytic cycle.     

Differential roles of T-cell subsets in regulation of ultraviolet radiation induced cutaneous photocarcinogenesis

Ultraviolet (UV) radiation, in particular the midwavelength range (UVB; 290-320 nm), is one of the most significant risk factors for the development of nonmelanoma skin cancer. UVB radiation-induced immunosuppression, which occurs in both humans and laboratory animals, contributes to their pathogenesis. However, there are conflicting reports on the relative role of CD4(+) and CD8(+) T cells in UVB induced skin cancer. The purpose of this study was to delineate the contribution of these two cell subpopulations to UVB induced immunosuppression and tumor development using C3H/HeN (WT), CD4 knockout (CD4(-/-) ) and CD8 knockout (CD8(-/-) ) mice. We observed that UVB induced skin carcinogenesis was retarded in terms of number of tumors per group, tumor volume and percentage of mice with tumors, in mice deficient in CD4(+) T cells compared with wild-type mice, whereas significantly greater (P < 0.05) numbers of tumors occurred in CD8(-/-) mice. These results indicate that, CD4(+) T cells promote tumor development while CD8(+) T cells have the opposite effect. Further, we found that CD4(+) T cells from tumor-bearing mice produced interleukin (IL)-4, IL-10, and IL-17 whereas CD8(+) T cells produced interferon-γ. Manipulation of T-cell subpopulations that are induced by UVB radiation could be a means of preventing skin cancers caused by this agent.     

Comparison of the coating properties and corrosion rates in electroless Ni-P/PTFE composites prepared by different types of surfactants

The effects of the addition of three types of surfactants (cationic, anionic, non-ionic) at different concentrations in the plating bath on the deposition rate, PTFE content and surface morphology of electroless Ni-P/PTFE composite coatings were investigated. It was demonstrated that the cationic and non-ionic surfactants created a uniform distribution of PTFE particles in the coatings. The effects of the surfactant type and concentration on the corrosion properties of Ni-P/PTFE coatings were also studied. The corrosion resistance was increased by the incorporation of PTFE particles into the Ni-P matrix. The level of improvement depended largely on the type and concentration of the applied surfactants.     

Obstacles on the Way Toward an Entropic Uncertainty Relation

Deutsch’s entropic uncertainty relation is examined by using two experiments in which the spin of a single spin-half particle is detected after passing through two Stern-Gerlach apparatuses in two successive times. Two experiments differ only in the angle settings of the Stern-Gerlach apparatuses. In the general case where the angles are arbitrarily arranged, Deutsch’s inequality is violated.     

Bending of edge-bonded dissimilar rectangular plates

This study develops the extended Kantorovich method (EKM) to provide a closed form semi analytical solution for the bending analysis of two edge-bonded thin rectangular plates. The constituent plates could be different in thickness, length, material, loading conditions, and Winkler foundation’s stiffness. A combination of clamp, free, and simply supports are applied to the structure. The shared edge in the composite plate is assumed to be perfectly bonded. By applying the EKM together with the idea of weighted residual technique, two sets of ODEs are obtained. Bending is assumed to remain continuous on the bonded edge. The EKM procedure is modified by applying the coordinate of an arbitrary shared point in the boundary conditions for the shared edge, to relate the bending of the two plates. The ODEs are solved iteratively to obtain the deflection function in a fast convergence trend. Two examples of aluminium-steel plate and functionally graded material-steel plate are considered. The deflection results from the boundary modified EKM (BM-EKM) are in high agreement with the finite element solution results. The bending of stepped plates is a special case of the current study. The suggested BM-EKM strengthens the EKM’s ability for solving complex jointed/bonded structures in structural analyses.

     

Synthesis of magnetic nanoparticle‐based molecularly imprinted polymer as a selective sorbent for efficient extraction of ezetimibe from biological samples

In the present study, a novel and efficient adsorbent constructed of molecularly imprinted polymer on the surface of modified magnetic nanoparticles with oleic acid (MNPs) was applied for the selective extraction of ezetimibe. The magnetic molecularly imprinted polymer (MMIP) was polymerized at the surface of modified MNPs using methacrylic acid as functional monomer, ezetimibe as template and ethylene glycol dimethacrylate as cross‐linker. The resulting MMIP showed high adsorption capacity, good selectivity and fast kinetic binding for the template molecule. It was characterized by Fourier transform infrared analysis, scanning electron microscopy and transmission electron microscopy methods. The maximum adsorption capacity of MMIP was obtained as 137.1 mg g^?1 and it took about 20 min to achieve the equilibrium state. The adsorption model of the adsorbent was fitted with the Freundlich and Langmuir isotherm equations. The assay exhibited a linear range of 0.003–20.000 mg L^?1 for ezetimibe with a correlation coefficient of 0.995. The relative standard deviations for the recoveries were <5.2. The method was also examined for the analysis of ezetimibe in the biological samples.