Tungsten hexachloride nanoparticles loaded on montmorillonite K-10: a novel solid acid catalyst in the synthesis of symmetrical and unsymmetrical azines

In the present investigation, we have developed a novel technique to prepare azines using nano-WCl₆ loaded on Montmorillonite K10 clay as a highly active catalyst. A variety of aldehydes and ketones were efficiently converted to the corresponding azines using catalytic amounts of nanosized WCl₆/Mont. K10 under mild conditions. The nanostructures of WCl₆ loaded on Mont. K10 as solid acid catalyst have been prepared by solid dispersion method. The advantages of this catalyst are rapid completion of the reactions, simplicity of performance, lack of pollution and mild and green reaction conditions. The morphologies, structure, and chemical components of parent and modified clay were successfully characterized using SEM, FT-IR, CV, XRD and EDX measurements.     

Catalytic performance in 4-nitrophenol reduction by Ag nanoparticles stabilized on biodegradable amphiphilic copolymers

Biodegradable copolymers have received much more attention in the last decades due their potential applications in the fields related to environmental protection, medicine, agriculture, and the chemical processes. Silver nanoparticles (Ag NPs) were prepared via reduction of silver nitrate (AgNO₃) using biodegradable amphiphilic copolymers in aqueous solution. The micelles were constructed from the amphiphilic copolymer composed of poly(2-ethyl-2-oxazoline) and poly(ε-caprolactone). The Ag NPs with a diameter of 10–15?nm were found to show a comparable high catalytic activity toward the reduction of 4-nitrophenol (4-NP) in the presence of an excess amount of NaBH₄. The synthesized Ag NPs-loaded copolymer exhibits high catalytic activity for the reduction of 4-NP to 4-aminophenol.     

Peristaltic Wave Locomotion and Shape Morphing with a Millipede Inspired System

We present the mechanical model of a bio-inspired deformable system, modeled as a Timoshenko beam, which is coupled to a substrate by a system of distributed elements. The locomotion action is inspired by the coordinated motion of coupling elements that mimic the legs of millipedes and centipedes, whose leg-to-ground contact can be described as a peristaltic displacement wave. The multi-legged structure is crucial in providing redundancy and robustness in the interaction with unstructured environments and terrains. A Lagrangian approach is used to derive the governing equations of the system that couple locomotion and shape morphing. Features and limitations of the model are illustrated with numerical simulations.     

Cohomogeneity one actions on Minkowski spaces

We study isometric cohomogeneity one actions on the \((n+1)\)-dimensional Minkowski space \(\mathbb {L}^{n+1}\) up to orbit-equivalence. We give examples of isometric cohomogeneity one actions on \(\mathbb {L}^{n+1}\) whose orbit spaces are non-Hausdorff. We show that there exist isometric cohomogeneity one actions on \(\mathbb {L}^{n+1}\), \(n \ge 3\), which are orbit-equivalent on the complement of an n-dimensional degenerate subspace \(\mathbb {W}^n\) of \(\mathbb {L}^{n+1}\) and not orbit-equivalent on \(\mathbb {W}^n\). We classify isometric cohomogeneity one actions on \(\mathbb {L}^2\) and \(\mathbb {L}^3\) up to orbit-equivalence.     

The Use of Bridging Ligand Substituents to Bias the Population of Localized and Delocalized Mixed-Valence Conformers in Solution

The electronic structure and associated spectroscopic properties of ligand-bridged, bimetallic ‘mixed-valence’ complexes of the general form {M}(μ-B){M⁺} are dictated by the electronic couplings, and hence orbital overlaps, between the metal centers mediated by the bridge. In the case of complexes such as [{Cp*(dppe)Ru}(μ-C≡CC₆H₄C≡C){Ru(dppe)Cp*}]⁺, the low barrier to rotation of the half-sandwich metal fragments and the arylene bridge around the acetylene moieties results in population of many energy minima across the conformational energy landscape. Since orbital overlap is also sensitive to the particular mutual orientations of the metal fragment(s) and arylene bridge through a Karplus-like relationship, the different members of the population range exemplify electronic structures ranging from strongly localized (weakly coupled Robin-Day Class II) to completely delocalized (Robin-Day Class III). Here, we use electronic structure calculations with the hybrid density functional BLYP35-D3 and a continuum solvent model in combination with UV-vis-NIR and IR spectroelectrochemical studies to show that the conformational population in complexes [{Cp*(dppe)Ru}(μ-C≡CArC≡C){Ru(dppe)Cp*]⁺, and hence the dominant electronic structure, can be biased through the steric and electronic properties of the diethynylarylene (Ar) moiety (Ar=1,4-C₆H₄, 1,4-C₆F₄, 1,4-C₆H₂-2,5-Me₂, 1,4-C₆H₂-2,5-(CF₃)₂, 1,4-C₆H₂-2,5-ⁱPr₂).     

Nuclear magnetic resonance study of the stoichiometry and stability of several HgX<Subscript>2</Subscript>–acetylemethylentriparatolylphosphorane complexes in various acetone–dimethylformamide mixtures

The reaction of phosphorus ylide, acetylmethylenetriparatolylphosphorane (L) with HgX₂ (X = Cl, Br, I and NO₃) in equimolar ratios using acetone and dimethylformamide as solvents leads to binuclear products. ³¹P NMR spectroscopy was used to investigate the stoichiometry and stability of a HgX₂ complex with CH₃COCHP(p-tolyl)₃ (L) in binary acetone–dimethylformamide mixtures of varying composition. In all cases studied, the variation of ³¹P NMR chemical shift with the [HgX₂]/[L] mole ratio indicated the formation of 1:1 complexes. The formation constants of the resulting complexes were evaluated from computer fitting of the mole ratio data to an equation that relates the observed chemical shifts to the formation constant. In all mercuric salts used, the stabilities of the resulting 1:1 complexes varied in the order Hg(NO₃)₂ > HgCl₂ > HgBr₂ > HgI₂. It was found that, in the case of all complexes, an increase in the percentage of dimethylformamide in the solvent mixtures significantly decreases the stability of the complexes.     

Highly selective oxidation of alcohols using MnO2/TiO2-ZrO2 as a novel heterogeneous catalyst

MnO₂/TiO₂-ZrO₂, which was synthesized by the adsorption method, demonstrated very high catalytic activity in the selective oxidation of benzyl alcohols to benzaldehydes with excellent yields and selectivity in short reaction times. The physical and chemical properties of MnO₂/TiO₂-ZrO₂ were investigated by XRD, XRF, BET, FT-IR and SEM techniques. The influence of the catalyst support (SBA-15, ZSM-5, TiO₂-ZrO₂ and Y), type of metal oxide supported, method of loading and amount of manganese nitrate loading have been thoroughly investigated. Moreover, the catalyst has shown excellent reusability in the process.     

Microwave-assisted expeditious hydrolysis of isobenzofuranone derivatives using silica supported acid under organic solvent-free conditions

Silica sulfuric acid was found to be an efficient, reusable and environment-friendly catalyst for fast hydrolysis of various isobenzofuranone to corresponding 2-ketomethylquinoline derivatives in a high yield under solvent-free using microwave irradiation. As the activator of silica sulfuric acid the wet SiO₂ was chosen. The reactions in conventional conditions were compared with the microwave assisted reactions. This approach can prove beneficial since the recovery of solvents from conventional reaction systems always results in some losses.