Oxo- and oxoperoxo-molybdenum(VI) complexes with aryl hydroxamates: synthesis, structure, and catalytic uses in highly efficient, selective, and ecologically benign peroxidic epoxidation of olefins

A solution obtained by dissolving MoO3 in H2O2 reacts separately with secondary hydroxamic acids (viz., N-benzoyl N-phenyl hydroxamic acid (BPHAH), N-benzoyl N-ortho-, -meta-, -para-tolyl hydroxamic acids, (BOTHAH, BMTHAH, and BPTHAH, respectively), and N-cinnamoyl N-phenyl hydroxamic acid (CPHAH) affording [MoO(O2)(BPHA)2] (1), [MoO(O2)(BOTHA)2] (2), [MoO(O2)(BMTHA)2] (3), [MoO(O2)(BPTHA)2] (4), and [Mo(O)2(CPHA)2](5), respectively. The O and O2 are situated cis to each other in 2-4, but in each case, they are disordered and distributed over four sites. This disorder does not exist in the 6-coordinate cis dioxo complex 5, to which crude MoO(O2)(CPHA)2 (5') was converted during recrystallization. An aqueous molybdate solution readily reacts with all those hydroxamic acids producing [Mo(O)2(hydroxamate)2] (6). While 2, 3, and 4 possess a very distorted pentagonal bipyramidal structure, 5 has a distorted octahedral geometry. In the solid state, as well as in solution, 5 exists as two apparently enantiomerically related molecules differing in the orientation of the pendant phenyl rings. To emphasize that the formation and structural uniqueness of 5 compared to 1-4 is caused by the influence of the cinnamoyl residue, one compound of the 6 series, namely, [Mo(O)2(BPHA)2] (6A), was structurally characterized to prove directly that the special stereochemical properties of 5 rely on the special electronic structure of CPHA- ligand. Complexes 1-5, as well as 6, show high potential and selectivity as catalysts in the epoxidation of olefins at room temperature in the presence of NaHCO3 as a promoter and H2O2 as a terminal oxidant. A comparative epoxidation study has been performed to determine the relative efficiency of the catalysts. To make the epoxidation method cost effective, a study to optimize the use of H2O2 has also been performed. To obtain evidence in favor of our suggested mechanism to this homogeneous olefin --> epoxide conversion, it was necessary to synthesize a peroxo-rich compound, namely, [MoO(O2)2BMTHA]- (7), but the attempted synthesis culminated in the isolation of [MoO(O2)2(C6H5COO)]- (8), obviously, via the hydrolysis of coordinated BMTHA.     

Rotating beams and non-rotating beams with shared eigenpair for pinned-free boundary condition

In this paper we look for a rotating beam, with pinned-free boundary conditions, whose eigenpair (frequency and mode-shape) is same as that of a uniform non-rotating beam for a particular mode. It is seen that for any given mode, there exists a flexural stiffness function (FSF) for which the ith mode eigenpair of a rotating beam with uniform mass distribution, is identical to that of a corresponding non-rotating beam with same length and mass distribution. Inserting these derived FSF’s in a finite element code for a rotating pinned-free beam, the frequencies and mode shapes of a non-rotating pinned-free beam are obtained. For the first mode, a physically realistic equivalent rotating beam is possible, but for higher modes, the FSF has internal singularities. Strategies for addressing these singularities in the FSF for finite element analysis are provided. The proposed functions can be used as test functions for rotating beam codes and also for targeted destiffening of rotating beams.     

Analytical test functions for free vibration analysis of rotating non-homogeneous Timoshenko beams

In this paper, the governing equations for free vibration of a non-homogeneous rotating Timoshenko beam, having uniform cross-section, is studied using an inverse problem approach, for both cantilever and pinned-free boundary conditions. The bending displacement and the rotation due to bending are assumed to be simple polynomials which satisfy all four boundary conditions. It is found that for certain polynomial variations of the material mass density, elastic modulus and shear modulus, along the length of the beam, the assumed polynomials serve as simple closed form solutions to the coupled second order governing differential equations with variable coefficients. It is found that there are an infinite number of analytical polynomial functions possible for material mass density, shear modulus and elastic modulus distributions, which share the same frequency and mode shape for a particular mode. The derived results are intended to serve as benchmark solutions for testing approximate or numerical methods used for the vibration analysis of rotating non-homogeneous Timoshenko beams.     

Superconductivity in the 100–120 K region in oxides of the Tl-Ca-Ba-Cu-O system

Oxides with different cation ratios 2122, 2212, 2213 and 2223 in the Ti-Ca-Ba-Cu-O system exhibit onset of superconductivity in the 110–125 K range with zero-resistance in the 95–105 K range. Electron microscopic studies show dislocations, layered morphology and other interesting features. These oxides absorb electromagnetic radiation (9.11 GHz) in the superconducting phase.     

Investigation of ionic conduction in the mixed AgI-PbI2 system

Study of ionic conductivity in AgI-PbI₂ system has a function of composition and temperature shows that PbI₂ has a definite role in the process of superionic phase transition. It has been found that at 80 mole % of AgI, superionic phase transition temperature passes through a minimum value of as low as 105°C. The maximum conductivity (at room temperature) is also obtained in this region. The results are discussed qualitatively in terms of a lattice loosening model.     

Arthrichitin. A New Cell Wall Active Metabolite from Arthrinium phaeospermum

Arthrichitin (1), C(33)H(46)N(4)O(9), is a new cell wall active depsipeptide isolated from the fermentation broth of Arthrinium phaeospermum (HIL Y-903022). Its structure was elucidated on the basis of spectroscopic and chemical degradation studies. Arthrichitin consists of serine, beta-keto tryptophan, glutamic acid, and 2,4-dimethyl-3-hydroxydodecanoic acid units.     

Sol-Emulsion-Gel Synthesis of Shaped Powders in the System BaO-TiO2

Shaped tetragonal barium titanate (BaTiO₃) particles were prepared by the sol-emulsion-gel method with systematic variation of the concentration of a non-ionic surfactant in the organic phase (oil phase) of water-in-oil (w/o) emulsions above or below the critical micelle concentration (CMC). An acetate-based sol with equivalent oxide ratio BaO : TiO₂ = 1 : 1 was selected for the study. Micelle formation of the surfactant and their self-aggregation apparently played an important role in controlling the shape and size of the droplets and accordingly shape and size of the final barium titanate particles resulting therefrom. Transmission electron microscopy (TEM) revealed that with low concentration of the surfactant (2–5 vol%) ill-formed spheres were obtained. Spherical particles were formed with increasing the surfactant concentration to 7 vol%. At 12 vol% of the surfactant, rod-like particles were first found to form, which with further increase in surfactant concentration to 15–20 vol%, gradually transformed to cube-like/lamellar type particles. Attempts have been made to explain the various particle shapes in terms of surfactant aggregation.     

A relation between RF values of unidimensional and circular paper chromatography

1. R_F values of 12 amino acids were determined in phenol-water and benzyl alcohol-acetic acid-water using unidimensional and circular techniques of paper chromatography. 2. It has been observed that the square of circular R_F values (considering frontal boundary of solute) equals the linear R_F values, and this relation is valid for the amino acids as well as the sugars studied. 3. The relation is found to be independent of the distance traversed by the solvent in the case of both amino acids and sugars. 4. A theoretical support has been given to the experimental observations.     

Mullite Fibre Mats by a Sol-Gel Spinning Technique

Fine grained, microcrystalline mullite (Al_4+2x Si_2–2x O_10–x) fibre mats with a web-like structure were fabricated by a sol-gel spinning technique using a multi-orifice spinneret. Points of contact in gel fibre mats helped in the formation of a web-like fibrous body having reasonable strength and very little dust formation after calcination. Strong and resilient fibres with diameters in the range 3–12 m were obtained by a single-step sol-gel method from spinnable sols devoid of organics as the binder aid. Crystallization of -alumina and mullite at about 900°C and 1250°C, respectively was confirmed by differential thermal analysis (DTA) and X-ray diffraction (XRD). Thermogravimetry (TG) indicated the removal of most of the volatiles at about 500°C accompanied by a weight loss of about 48%. Scanning electron microscopy (SEM) shows the presence of small grains (80–150 nm in size) in the fibres calcined at 1250°C. Fourier transformed infrared spectroscopy (FTIR) indicated the sequence of transformations taking place during heat-treatment of gel fibres at different temperatures. The individual fibres in the mats calcined at 1250°C exhibited a tensile strength of 1300–1600 MPa.     

Neutral strange particle correlations in 360 GeV/cpp interactions

Production properties and correlations forK _s ⁰ K _s ⁰ ,K _s ⁰ Λ,K _s ⁰ ¯Λ and Λ¯Λ systems in 360 GeV/cpp interactions are presented. All rapidity gap distributions are observed to peak at Δy=0 and the azimuthal angular distributions between the two particles are consistent with being flat. Experimental results are compared with the quark fusion and Lund models of particle production.