On the origin of cis selectivity in the cyclization of N-protected 2-substituted 3-aza-5-hexenyl radicals: a density functional study

Cyclization of the N-dimethylphosphinoyl-2-methyl-3-aza-5-hexenyl radical has been studied at the UB3LYP/6-31+G(d)//UB3LYP/6-31G(d) hybrid density functional level. The corresponding radical precursor has been synthesized and found to give cis/trans ratios of up to 10/1 in reductive radical cyclizations. The relative energies of reactant and transition state conformers were determined. In discord with the Beckwith-Houk model, it has been found that chair-axial transition states, which lead to cis products, are lowest in energy, rationalizing the observed experimental diastereoselectivity.     

Structural and thermal interpretation of the synergy and interactions between the fire retardants magnesium hydroxide and zinc borate

The mechanism of cooperative action of commercial fire retardants is interpreted as resulting from specific chemical reaction and phase changes. This investigation focuses on the thermally initiated interactions between two forms of commercially available fire retardant compounds. The fire performance of a polyolefin with a metal hydroxide fire retardant, magnesium hydroxide, can significantly reduce the heat release rate through absorption of heat during conversion to its metal oxide. Formation of water, followed by vaporisation, decreases heat and dilutes volatiles from polymer degradation. The second form of fire retardant compounds are zinc borates (2ZnO·3B₂O₃·3H₂O and 4ZnO·B₂O₃·H₂O), that undergo dehydration with increasing temperature. Differential thermal analysis and wide-angle X-ray spectroscopy indicated that various structural changes occurred during heating. Endothermic transitions were observed for all components, while zinc borate (2ZnO·3B₂O₃·3H₂O) showed an exothermic crystallisation transition at relatively high temperature. The exotherm was modified by the development of a new crystalline phase, magnesium orthoborate (3MgO·B₂O₃) that formed on reaction with magnesium oxide (MgO) at temperatures greater than 500 °C. Formation of crystalline zinc oxide (ZnO) was also detected. From zinc borate (4ZnO·B₂O₃·H₂O), ZnO was primarily formed. No new crystalline phases were observed in the presence of MgO over the temperature range investigated.     

Effect of the ionic aggregation on the crystallisation behavior of poly(ethylene) part of ionomer

The influence of ionic interaction on the melt-crystallization behavior of the ethylene ionomer was studied using modulated DSC (MDSC^TM), wide angle X-ray scattering (XRD) and hot stage microscopy. The kinetics of the crystallization process of the ionomer was evaluated using isothermal differential scanning calorimetry (iso-DSC). Wide-angle X-ray scattering was used to examine the d spacing of poly(ethylene) part. The crystallinity of the poly(ethylene) part of ionomer measured from XRD is found to be 24%, which is comparable to that obtained from MDSC^TM. Small-angle X-ray scattering (SAXS) results show that the clusters and multiplets exist in the ionomer, and the cluster is about 127Ĺ. The kinetics of crystallization process obtained using Avrami equation shows that the crystallization process is fundamentally similar to poly(ethylene) as it goes through nucleation and propagation stages of the crystals. However, the morphology of the crystal appears to be different and influenced by clusters (platelike and/or needle-shaped) as evident from Avrami constant. This is different from the poly(ethylene) (which is spherulitic in nature) due to polar cluster and hydrophobic PE melt interaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Separation and identification of multicomponent mixture by thin-layer chromatography coupled with Fourier transform-infrared microscopy

A fast and convenient method based on coupled thin-layer chromatography (TLC) with Fourier transform infrared (FTIR) microscopy has been established for separation and identification of multicomponent mixtures. In this study, the method was developed and consummated with more perfect TLC spots transferral process and consistent FTIR testing conditions. A newly developed technique, solid-phase extract (SPE) was introduced for sample pre-treatment instead of using traditional column chromatography. It is a new field for SPE that has already been widely applied in many other fields. It not only overcomes the backwards (low separation efficiency, time consuming and solvent consumption) of column chromatography but also makes it much easier to choose an optimum TLC sheet and to set suitable TLC loading. With all the above-mentioned modifications and supplements, the analytical method of coupled TLC with FTIR microscopy for separation and identification of multicomponent mixtures becomes more convenient and more efficient. In addition, a very complex sample (a die-cast release agent) was used as an example to demonstrate the technique.     

Experimental Critical-Exponent Values for Fluids

After a review of the history and an assessment of the current status of the subject, we present light-scattering data to determine the critical correlation-function exponents for an aqueous electrolyte solution yielding the experimental values γ=1.238±0.012, ν=0.629±0.003, η=0.032±0.013. We conclude the paper with some comments concerning the temperature dependence of non-asymptotic effective critical-exponent values of fluids.     

Hydrogen on WO3(001)

Ultraviolet photoemission measurements of the (001) surface of WO₃ show that after exposure to atomic hydrogen new states appear in the energy gap region at 2.3 and 0.9 eV below the Fermi energy. A peak at 2.2 eV was also produced by hydrogen ion bombardment. To investigate whether these surface effects were due to the formation of hydrogen tungsten bronze H_xWO₃, comparison was made with spectra from the electronically similar sodium bronze. The form of the spectra were different both in the valence band and energy gap regions indicating that hydrogen adsorption or loss of oxygen from the surface rather than formation of H_xWO₃ is the major effect.     

Two dimensional Kohn anomally in NbSe2

Phonon dispersion curves for several low frequency branches in the layered compound NbSe₂ have been measured. The results indicate the possible existence of a two dimensional Kohn anomaly in this material.     

Enhancement of the superconducting transition temperature near a phase instability in NaxWO3

The superconducting transition temperature of tetragonal I sodium tungsten bronze (Na_xWO₃) has been found to increase rapidly as the x-value is decreased to the metal-semiconductor phase transition. It is suggested that a soft mode instability is responsible for the increased electron-phonon interaction near the phase transition.     

Solvent and enzyme induced recrystallization of mechanically degraded hemp cellulose

The structural degradation of cellulose fibre from hemp (Cannabis Sativa L.) by a ball-milling process and the recrystallization behavior of the product were studied. A linear increase in the Brunauer–Emmett–Teller specific surface area was observed; indicating the fibre bundles were being crushed and disrupted to single fibres, which was confirmed by SEM. An increase in the milling duration gradually destroyed the crystalline structure of the cellulose fibres, observed by a reduction of the 002 plane intensity in wide angle X-ray scattering measurements. The crystalline order index calculated from the area ratio of the 002 to the 021, 10 and 002 planes was decreased from 65 to 36 after milling for 330 min. Subsequently the lower thermal stability of ball-milled fibre was observed from a decrease in the temperature at the maximum mass loss rate using thermogravimetry. An increase in solvent polarity, solvent-fibre ratio, agitation speed and drying rate resulted in the rearrangement of ball-milled cellulose crystalline structure to a greater order. Moreover, an increase in the BET specific surface area and the amorphous fraction improved the scouring efficiency of the ball-milled cellulose using the pectate lyase enzyme (EC. 4.2.2.2).     

TMDSC analysis of single-site copolymer blends after thermal fractionation

Temperature-modulated differential scanning calorimetry (TMDSC) has been used to study the melting of a series of blends containing linear low-density polyethylene (LLDPE) and very low-density polyethylenes (VLDPE) with long chain branches. After the blends were subjected to different thermal histories including thermal fractionation by stepwise isothermal cooling, they were examined by TMDSC. TMDSC curves have been interpreted in terms of a combination of the reversing and non-reversing specific heats that result from reversible and irreversible events at the time and temperature, which they are detected, respectively. It was found that crystals formed at different crystallisation conditions had different internal order; hence they showed different amounts of reversing and non-reversing contributions. There is no exothermic activity seen in the non-reversing signal for the thermally fractionated polymers and their blends suggesting formation of crystals approaching equilibrium. In contrast, polymers and blends cooled at 10°C min^-1 cooling rate showed large exothermic contributions corresponding to irreversible effects. In addition, a true reversible melting contribution is also detected for both fast-cooled and thermally-fractionated samples during the quasi-isothermal measurements. This revised version was published online in July 2006 with corrections to the Cover Date.