High pressure mössbauer studies of magnetic actinide systems

Due to the wider radial extent of 5f electrons when compared to their 4f counterparts, intermetallics of the light actinides show a broad spectrum of magnetic properties ranging from the localized magnetism of the lanthanides to the itinerant magnetism often found in transition metal compounds. One parameter which strongly influences the magnetic character of the compound is the actinide-actinide separation which can experimentally be varied by the application of high pressure. The question of 5f electron delocalization will be reviewed with respect to Moesshauer high pressure data on NpCo₂si₂, NpAl₂, NpOs₂ and new results will be presented of NpAs. The connection of hyperfine parameters with results of X-ray diffraction studies will be discussed.Work supported by the Bundesministerium für Forschung und Technologie, Federal Republic of Germany     

Polarization-mixing optical parametric oscillator

We report the experimental realization of a new type of optical parametric oscillator in which oscillation is achieved by polarization rotation in a linear retarder, followed by nonlinear polarization mixing. The mixing is performed by a type II degenerate parametric downconversion in a periodically poled KTP crystal pumped by a 1064 nm pulsed Nd:YAG pump. A single, linearly polarized beam, precisely at the degenerate wavelength is generated. The output spectrum has a narrow linewidth (below the instrumentation bandwidth of 1 nm) and is highly stable with respect to variations in the crystal temperature.     

Assessment of the nature of interactions of cations with cycloheptatriene derivatives using change in the aromaticity: Comparison with electron density and NBO results

ABSTRACT

Interactions of cycloheptatriene derivatives, C₇H₆X, (X?=?NH, PH, AsH, O, S, Se) with the cations H⁺, CH₃⁺, Cu⁺, Al⁺, Li⁺, Na⁺, and K⁺ are studied using B3LYP functional and 6-311++G(d,p) basis set. The calculated gas-phase cation affinities (CA) and cation basicities (CB) for all molecules decrease as H⁺ > CH₃⁺ > Cu⁺ > Al⁺ > Li⁺ > Na⁺ > K⁺. We used the induced aromaticity in the 7-membered ring of C₇H₆X upon interaction with the cations, M⁺, as a measure of C₇H₆X/M⁺ interaction. Nucleus-independent chemical shift (NICS) and harmonic oscillator model of aromaticity (HOMA) were used as two indices of aromaticity. The highest and lowest induced aromaticities were observed for interactions of H⁺ and K⁺, respectively. Also, the aromaticity induced by interaction with a cation in C₇H₆AsH and C₇H₆PH was larger than that in C₇H₆NH and C₇H₆O. Hence, the aromaticity was considered as a measure of covalency for the C₇H₆X/M⁺ interactions showing a rational dependence on both the molecule and cation. The nature of the interactions was also assessed using electron density, charge distribution analysis and NBO calculations. The results of the aromaticity indices, NICS and HOMA, were compared with the electron density and NBO results.     

Synthesis of Poly(ϵ-caprolactone) Grafted Poly(2-hydroxyethyl methacrylate) Functionalized Hydroxyapatite by RAFT and ROP

Poly(?-caprolactone) grafted poly(2-hydroxyethyl methacrylate) functionalized hydroxyapatite (HAP@PHEMA-g-PCL) nanocomposites were synthesized by the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP). The RAFT agent was anchored on the surface of hydroxyapatite nanocrystals (HAPs) through the silane condensation process of 3-chloropropyltrimethoxysilane followed by reaction with potassium xanthogenate. Poly(2-hydroxyethyl methacrylate) (PHEMA) was covalently functionalized on the surface of HAPs by RAFT polymerization. Then, poly(?-caprolactone) (PCL) was grafted on HAPs by ROP based on the hydroxyl groups of PHEMA to afford HAP@PHEMA-g-PCL. The structure and composition of HAP@PHEMA-g-PCL nanocomposites were characterized by FT-IR, XRD, and TGA analyses. The morphology and formation of the polymer encapsulating HAPs were demonstrated from SEM and TEM images, while the ¹H MNR analysis of the cleaved PHEMA-g-PCL confirmed the grafting.     

In situ chemical fabrication of polyaniline/multi-walled carbon nanotubes composites as supports of Pt for methanol electrooxidation

Science China Chemistry - In this study, platinum (Pt)-polyaniline(PANI)/MWNTs catalysts were synthesized by two sequential reactions. First, core-shell structural PANI/MWNTs composites were...     

Instability of two-phase flows: A lower bound on the dimension of the global attractor of the Cahn-Hilliard-Navier-Stokes system

We consider a model for the flow of a mixture of two viscous and incompressible fluids in a two or three dimensional channel-like domain. The model consists of the Navier-Stokes equations governing the fluid velocity coupled with a convective Cahn-Hilliard equation for the relative density of atoms of one of the fluids. We prove the instability of certain stationary solutions for such a system endowed with periodic boundary conditions on elongated domains (0,2π/α₀)×(0,2π) or (0,2π/α₀)×(0,2π)×(0,2π/β₀) for a special class of periodic body forces, provided that α₀ and β₀ are small enough. As a consequence, we deduce a lower bound for the Hausdorff dimension of the global attractor.     

First order magnetic phase transition in tetragonal NpCu2Si2

Magnetization and Np²³⁷ Mössbauer studies of the tetragonal compounds NpM₂Si₂ (M = Cr, Mn, Fe, Co, Ni, Cu) were performed. NpMn₂Si₂ is ferromagnetic. All other compounds order antiferromagnetically. Only in NpCu₂Si₂ the Mössbauer studies reveal a first order magnetic phase transition at T_N = 34 K. It is interpreted in terms of Blume's model, originally developed for cubic UO₂.