A concise stereoselective formal total synthesis of the cytotoxic macrolide (+)-Neopeltolide via Prins cyclization

A convergent and highly stereoselective formal total synthesis of the naturally occurring, cytotoxic 14-membered macrolide neopeltolide has been achieved via two Prins cyclizations.     

Effect of the magnetic field on the hydrodynamic permeability of a membrane

The present paper concerns the influence of the magnetic field on the permeability of a membrane of solid cylindrical particles covered with porous layer. Here, we have considered the flow along the axis of cylinder and the alignment of uniform magnetic field is assumed to be perpendicular to the axis. The Brinkman equation is used for flow through porous region and Stokes equation is used for flow through clear fluid region. To model flow through assemblage of particles, cell model technique has been used i.e. the porous cylindrical shell is assumed to be confined within a hypothetical cell of same geometry. The stress jump condition has been employed at the fluid-porous interface and all four alternative conditions Happel, Kuwabara, Kvashnin and Mehta-Morse/Cunningham are used at the hypothetical cell. Effect of the Hartmann number on the hydrodynamic permeability of the membrane is discussed.     

Synthesis of hydrolytically stable phosphorus-containing polymers via polycondensation and their utilization in polymer blends

Amorphous polyarylene ether homo- and copolymers were synthesized which were based upon bisphenol A and either 4, 4'-dichlorodiphenylsulfone, 4, 4'-difluorobenzophenone or 4, 4'-difluorodiphenyl phenylphosphine oxide. Solution blends were prepared from these homo- and copolymers with linear bisphenol A based polyhydroxyether, which was used as a model for the epoxy or vinyl ester thermosetting matrix resins for composite materials. It was observed that transparent, single Tg blends could be prepared from the phosphine oxide containing homopolymer and a 50/50 phosphine oxide/dichlorodiphenylsulfone copolymer. The other homopolymers produced materials with two Tg's, implying that they were definitely phase separated systems. Thermogravimetric analysis was also conducted and the phosphine oxide blends produced high char yields suggesting utilization in fire-resistant applications. The miscibility of the phosphine oxide material has been attributed to specific hydrogen bonding interactions observed between the phosphine oxide bond and the secondary hydroxyl group in the polyhydroxy ether. This hydroxyl functionality is also present in the epoxy and vinylester precursors and it is suggested that these materials could be utilized as interface sizings for carbon fibers, which would produce a graded microstructure between the fiber and the polymer matrix systems.     

Nonequilibrium Phase Transition in a Model of Diffusion, Aggregation, and Fragmentation

We study the nonequilibrium phase transition in a model of aggregation of masses allowing for diffusion, aggregation on contact, and fragmentation. The model undergoes a dynamical phase transition in all dimensions. The steady-state mass distribution decays exponentially for large mass in one phase. In the other phase, the mass distribution decays as a power law accompanied, in addition, by the formation of an infinite aggregate. The model is solved exactly within a mean-field approximation which keeps track of the distribution of masses. In one dimension, by mapping to an equivalent lattice gas model, exact steady states are obtained in two extreme limits of the parameter space. Critical exponents and the phase diagram are obtained numerically in one dimension. We also study the time-dependent fluctuations in an equivalent interface model in (1+1) dimension and compute the roughness exponent and the dynamical exponent z analytically in some limits and numerically otherwise. Two new fixed points of interface fluctuations in (1+1) dimension are identified. We also generalize our model to include arbitrary fragmentation kernels and solve the steady states exactly for some special choices of these kernels via mappings to other solvable models of statistical mechanics.     

Non-spherical magnetic moment in MnAlGe

The magnetic structure factors of MnAlGe (space groupP4/nmm) measured with polarised neutrons have been expressed in terms of the magnetic moment of the Mn atom (site symmetry tetrahedral with tetragonal distortion), the Bessel transforms 〈j _n〉 of the Mn radial functions and the fractional occupancies of the moment density in the various crystal field orbitals. The measured structure factors were least-squares fitted with the theoretical expression involving 〈j _n〉 appropriate to the Mn⁰, Mn⁺ and Mn²⁺ atoms. The best fit was got using Mn⁰ transforms, yielding 1·45µ _B as the Mn magnetic moment. The fractional occupancies of the moment density in the crystal field orbitalsA _1g,B _1g E _g andB _2g were obtained. This analysis shows the magnetic moment to be highly non-spherical with a large fractional occupancy (38%) in theA _1g orbital directed along the tetragonal axis while the fractional occupancies ofB _1g andB _2g are found to be 31% and 30% respectively. The fractional occupancy of the moment in theE _g orbital directed towards the Ge and Al atoms is very low (1%). The spatially averaged moment density of Mn in MnAlGe is more diffuse than that of Mn I and Mn II in isostructural Mn₂Sb.     

Kinetics and mechanisms of oxidation by metal ions. Part XIV(1). Osmium(VIII)-catalysed oxidation of cycloalkanones by alkaline hexacyanoferrate(III)

Transition Metal Chemistry - The OsVIII-catalysed oxidation of cyclopentanone and cyclohexanone by alkaline hexacyanoferrate(III) ions is zeroth-order with respect to $ {? F_{e}(CN)_{6}^{3-}...     

Reactivity investigations of some chosen peroxo-vanadium(V), manganese(III) and chromium(VI) compounds

An interpretative account of the results of reactions in aqueous medium of a highly peroxygenated vanadium(V) complex, K [V(O_{2 3}]·3H₂O, with different organic and inorganic substrates is presented. The reactions were monitored by solution EPR spectroscopy and isolation of products at different stages of the reactions. Redox reactions between diperoxide, K[VO(O₂)₂(H₂O)] and VOSO₄ were conducted. The results of the investigation suggest that secondary oxygen exchange-reaction occurs which not only depends on but also utilises the intermediates in the primary reaction during diperoxovanadate-dependent oxidation of VOSO₄. In an interesting reactiontris(acetylacetonato)-manganese(III), Mn(acac)₃, on being reacted with a hydrogen peroxide adduct, KF·H₂O₂, and bpy and phen afforded crystalline [Mn(acac)₂(bpy)] and [Mn(acac)₂(phen)], respectively. The X-ray structural analysis of [Mn(acac)₂(phen)] showed that the compound crystallised in orthorhombic space groupPbcn. The structure consists of a pseudooctahedral Mn(II) ion being bound to two acac⁻(C₅H₅O ₂ ⁻ ) and a phen ligand with the molecule lying on two-fold axis. Reactivity profiles of two new chromium(VI) reagents viz., pyridinium fluorochromate, C₅H₅NH[CrO₃F] (PFC), and quinolinium fluorochromate C₉H₇NH [CrO₃F] (QFC), have been presented. The compounds are capable of acting as both electron-transfer and oxygen-atom-transfer agents. The X-ray analysis of PFC crystals reveals that the compound crystallises in the orthorhombic space group CmcZ₁. The structure consists of discrete pyridinium cations and CrO₃ F anions with no significant hydrogen bonding. This results in total disorder of the pyridinium cation. The tetrahedral [CrO₃ F]⁻ ion lies on a crystallographic mirror plane.