Copolymers of modified starches with polyacrylonitrile

A study was made of the ceric ammonium nitrate-initiated graft polymerization of acrylonitrile (AN) onto a number of modified starches that had been reduced in molecular weight by either acid, hypochlorite, or enzyme treatment. With highly soluble starches, much of the starting material was recovered as ungrafted carbohydrate, and the reaction product was largely dimethylformamide-soluble polymer with a high polyacrylonitrile (PAN) content. The molecular weight of grafted PAN was lower when the modified starches existed as granules in water dispersion; however, heating (60°C) an aqueous slurry of an acid-modified corn starch (with intact granules) before the reaction had relatively little effect on the composition of the copolymer. Decreasing the concentrations in water of modified starch and AN resulted in more frequent and lower molecular weight grafts of PAN. Aqueous methanol as a reaction medium for an acid-modified starch with intact granules led to more frequent grafting of lower molecular weight PAN than when water alone was used. The number of grafted chains, however, was fewer than found with unmodified wheat starch under comparable conditions. A modified starch with the granule structure completely broken down gave no detectable reaction in aqueous methanol.     

Electronic states in hyperbolic-boundary crescent-shaped quantum wires

A fully two-dimensional study of the electronic sub-bands in crescent-shaped quantum wires is presented. The confinement energies and the wave functions are compared by means of an aspect ratio to those produced by the adiabatic approximation. Guidelines for applying the adiabatic model are provided and the adiabatic quantum number classification scheme is discussed. Non- adiabatic states are determined among the first few sub-bands and a built-in dipole is identified. The energy spectrum is explored as a function of wire dimensions achievable by present-day technology. Wire parameters corresponding to maximized sub-band separations are determined.     

A Self‐Binding,Melt‐Castable,Crystalline Organic Electrolyte for Sodium Ion Conduction

The preparation and characterization of the cocrystalline solid–organic sodium ion electrolyte NaClO₄(DMF)₃ (DMF=dimethylformamide) is described. The crystal structure of NaClO₄(DMF)₃ reveals parallel channels of Na⁺ and ClO₄⁻ ions. Pressed pellets of microcrystalline NaClO₄(DMF)₃ exhibit a conductivity of 3×10⁻⁴ S cm⁻¹ at room temperature with a low activation barrier to conduction of 25 kJ mol⁻¹. SEM revealed thin liquid interfacial contacts between crystalline grains, which promote conductivity. The material melts gradually between 55–65 °C, but does not decompose, and upon cooling, it resolidifies as solid NaClO₄(DMF)₃, permitting melt casting of the electrolyte into thin films and the fabrication of cells in the liquid state and ensuring penetration of the electrolyte between the electrode active particles.     

Ionic liquid-supported TEMPO as catalyst in the oxidation of alcohols to aldehydes and ketones

We describe an efficient synthesis of an ionic liquid-supported TEMPO which was used for the oxidation of alcohols to aldehydes and ketones. The predictable solubility of ionic liquids allows an easy separation of the oxidation products from reagents. Furthermore, the oxidation can be carried out using an ionic liquid as the solvent instead of dichloromethane; and the IL-supported TEMPO can be recycled and used several times without the loss of efficiency.     

精确的甲烷分子价轨道的电子动量谱学研究

电子动量谱学（EMS）已发展成为探测原子分子电子结构的强有力工具．借助电子动量谱学可获得精确的分子轨道电子密度分布，并能提供非常详细的电子运动和电子关联信息．分子电子密度分布和电子运动的详细了解对分子的识别和化学活性的理解非常重要，并且也有助于计算机辅助的分     

Shear thickening and migration in granular suspensions

We study the emergence of shear thickening in dense suspensions of non-Brownian particles. We combine local velocity and concentration measurements using magnetic resonance imaging with macroscopic rheometry experiments. In steady state, we observe that the material is heterogeneous, and we find that the local rheology presents a continuous transition at low shear rate from a viscous to a shear thickening, Bagnoldian, behavior with shear stresses proportional to the shear rate squared, as predicted by a scaling analysis. We show that the heterogeneity results from an unexpectedly fast migration of grains, which we attribute to the emergence of the Bagnoldian rheology. The migration process is observed to be accompanied by macroscopic transient discontinuous shear thickening, which is consequently not an intrinsic property of granular suspensions.     

Yielding and shear banding in soft glassy materials

Yield stress fluids have proven difficult to characterize, and a reproducible determination of the yield stress is difficult. We study two types of yield stress fluids (YSF) in a single system: simple and thixotropic ones. This allows us to show that simple YSF are simply a special case of thixotropic ones, and to pinpoint the difference between static and dynamic yield stresses, one of the major problems in the field. The thixotropic systems show a strong time dependence of the viscosity due to the existence of an internal percolated structure that confers the yield stress to the material. Using loaded emulsions to control the thixotropy, we show that the transition to flow at the yield stress is discontinuous for thixotropic materials, and continuous for ideal ones. The discontinuity leads to a critical shear rate below which no steady flows can be observed, accounting for the ubiquitous shear banding observed in these materials.