Synthesis of benzoxazine and 1,3-oxazine derivatives via ligand-free copper(I)-catalyzed one-pot cascade addition/cyclization reaction

A novel and efficient synthesis of benzoxazine and 1,3-oxazine derivatives via ligand-free copper(I)-catalyzed one-pot cascade addition/cyclization reaction has been developed. A variety of carbodiimides coupled with o-halophenylmethanols and/or substituted (Z)-3-iodoprop-2-en-1-ols to give the corresponding products in moderate to excellent yields under the mild condition.     

Neutron diffraction study of unusual phase separation in the antiperovskite nitride Mn3ZnN

The antiperovskite Mn(3)ZnN is studied by neutron diffraction at temperatures between 50 and 295 K. Mn(3)ZnN crystallizes to form a cubic structure at room temperature (C1 phase). Upon cooling, another cubic structure (C2 phase) appears at around 177 K. Interestingly, the C2 phase disappears below 140 K. The maximum mass concentration of the C2 phase is approximately 85% (at 160 K). The coexistence of C1 and C2 phase in the temperature interval of 140-177 K implies that phase separation occurs. Although the C1 and C2 phases share their composition and lattice symmetry, the C2 phase has a slightly larger lattice parameter (Δa ≈ 0.53%) and a different magnetic structure. The C2 phase is further investigated by neutron diffraction under high-pressure conditions (up to 270 MPa). The results show that the unusual appearance and disappearance of the C2 phase is accompanied by magnetic ordering. Mn(3)ZnN is thus a valuable subject for study of the magneto-lattice effect and phase separation behavior because this is rarely observed in nonoxide materials.     

Amperometric enzyme electrodes of glucose and lactate based on poly(diallyldimethylammonium)-alginate-metal ion-enzyme biocomposites

Sodium alginate (AlgNa) and poly(diallyldimethylammonium chloride) (PDDA) were mixed to obtain an interpenetrating polymer composite via electrostatic interaction and then cast on an Au electrode surface, followed by incorporation of metal ions (e.g. Fe³⁺ or Ca²⁺, to form AlgFe or AlgCa hydrogel) and glucose oxidase (GOx) (or lactate oxidase (LOx)), to prepare amperometric enzyme electrodes. The interactions of PDDA, Alg, and Fe³⁺ are studied by visual inspection as well as microscopic and electrochemical methods. Under optimized conditions, the PDDA-AlgFe-enzyme/Au and PDDA-AlgCa-enzyme/Au electrodes can give good analytical performance (e.g. nM-scale limit of detection of glucose or lactate, and sensitivities > 50 μA cm⁻² mM⁻¹) in the first-generation biosensing mode, which are better than the reported analogs using typical polysaccharide biopolymers as enzyme-immobilization matrices. The enzyme electrodes also worked well in the second-generation biosensing mode in the coexistence of p-benzoquione or ferrocene monocarboxylic acid artificial mediator. Biofuel cells (BFCs) with the enzyme electrodes as the bioanodes and glucose (or lactate) as the biofuel were also fabricated with satisfactory results. The proposed protocols for preparation of high performance Alg-based biocomposites may find wide applications in bioanalysis.     

Correlation of Oscillation Cycles and Crystallization in HDPE Blends with Small Amounts of HMWPE Prepared by Dynamic-Packing Injection Molding

The effect of oscillation cycles on crystal morphology was investigated for high-density polyethylene (HDPE) in blends with 4 wt% high molecular weight polyethylene (HMWPE) (labeled B4) in samples prepared through dynamic-packing injection molding (DPIM). With the aid of differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), a weblike shish-kebab morphology that markedly increased stiffness and toughness was found at a specific oscillation cycle. The DSC and SEM results showed that crystal morphology was altered with changes in the oscillation cycle. The SEM and TEM results showed that a much better weblike shish-kebab structure, in which most of the lamellae connect different columns compared with conventional shish-kebabs, was formed in the B4 samples when the oscillation cycle was 10s. These results show that a proper oscillation cycle favors the improvement of crystal structures in HDPE blends induced by a small amount of HMWPE.     

Influence of Carbon Nanotubes on the Crystallization and Directional Tensile Behavior of High-Density Polyethylene Prepared by Dynamic-Packing Injection Molding

The influence of multi-walled carbon nanotubes (MWCNTs) on the crystallization and directional tensile properties of high-density polyethylene (HDPE) was studied for samples prepared by dynamic-packing injection molding (DPIM). Oscillatory shear was imposed on the gradually cooled melt during the packing solidification stage of DPIM. For the oriented composites containing 1.8 wt% MWCNTs, the tensile fracture behavior showed typical brittle features along the flow direction (FD) and perpendicular direction (PD), which were almost the same as those that occurred in oriented pure HDPE. The elongation at break along both directions decreased due to the incorporation of MWNCTs in the oriented composites compared with the oriented pure HDPE. However, the tensile strength of the oriented HDPE/MWCNT composites was greatly improved along the FD due to the presence of carbon nanotubes; meanwhile, it was not weakened along the PD. In scanning electron microscopy observations, it was found that there were some oriented hybrid shish-kebab structures in a nanometre scale in the oriented HDPE/MWCNT composites, but not in its isotropic composites. This suggests that MWCNTs were involved in the shear-induced crystallization of HDPE. Differential scanning calorimetry measurements confirmed that the crystallinity of oriented HDPE composites with 1.8 wt% MWCNTs was higher than those of isotropic HDPE and isotropic composites, but was not obviously higher than that of oriented pure HDPE. These findings demonstrate that MWCNTs indeed affected the formation of crystalline structures, but did not greatly influence the crystallinity of HDPE under shear flow. The transition of crystalline morphology might be the reason for change in tensile behavior for the oriented HDPE/MWCNT composites compared with the oriented pure HDPE.     

Advantages of Surface‐Initiated ATRP (SI‐ATRP) for the Functionalization of Electrospun Materials

Surface‐initiated atom transfer radical polymerization (SI‐ATRP) is successfully applied to electrospun constructs of poly(L ‐lactide). ATRP macroinitiators are adsorbed through polyelectrolyte complexation following the introduction of negative charges on the polyester surface through its blending with a six‐armed carboxy‐terminated oligolactide. SI‐ATRP of glycerol monomethacrylate (GMMA) or 2‐(N,N‐diethylamino)ethyl methacrylate (DEAEMA) allows then to grow surface films with controllable thickness, and in this way also to control the wetting and interactions of the construct.     

Observation of low‐wavenumber out‐of‐plane optical phonon in few‐layer graphene

Few‐layer graphene grown by chemical vapor deposition has been studied by Raman and ultrafast laser spectroscopy. A low‐wavenumber Raman peak of ~120 cm⁻¹ and a phonon‐induced oscillation in the kinetic curve of electron–phonon relaxation process have been observed, respectively. The Raman peak is assigned to the low‐wavenumber out‐of‐plane optical mode in the few‐layer graphene. The phonon band shows an asymmetric shape, a consequence of so‐called Breit‐Wigner‐Fano resonance, resulting from the coupling between the low‐wavenumber phonon and electron transitions. The obtained oscillation wavenumber from the kinetic curve is consistent with the detected low‐wavenumber phonon by Raman scattering. The origin of this oscillation is attributed to the generation of coherent phonons and their interactions with photoinduced electrons. Copyright © 2012 John Wiley & Sons, Ltd.     

3D skyrmion and knot in two-component Bose–Einstein condensates

We present exact solutions to the two-component Bose–Einstein condensates by adopting a method of separating the variables, which exhibit nontrivial topology. These solitonic solutions can form 3D skyrmion and knot in the three-dimensional system.     

Molecular dynamics study on water self-diffusion in aqueous mixtures of methanol,ethylene glycol and glycerol: investigations from the point of view of hydrogen bonding

Molecular dynamics simulations have been performed to investigate the aqueous binary mixtures of alcohols, including methanol, ethylene glycol (EG) and glycerol of molalities ranging from 1 to 5 m at the temperatures of 273, 288 and 298 K, respectively. The primary purpose of this paper is to investigate the mechanism of water self-diffusion in water-alcohol mixtures from the point of view of hydrogen bonding. The effects of temperature and concentration on water self-diffusion coefficient are evaluated quantitatively in this work. Temperature and concentration to some extent affect the hydrogen bonding statistics and dynamics of the binary mixtures. It is shown that the self-diffusion coefficient of water molecules decreases as the concentration increases or the temperature decreases. Moreover, calculations of mean square displacements of water molecules initially with different number n of H-bonds indicate that the water self-diffusion coefficient decreases as n increases. We also studied the aggregation of alcohol molecules by the hydrophobic alkyl groups. The largest cluster size of the alkyl groups clearly increases as the concentration increases, implying the emergence of a closely connected network of water and alcohols. The clusters of water and alcohol that interacted could block the movement of water molecules in binary mixtures. These findings provide insight into the mechanisms of water self-diffusion in aqueous binary mixtures of methanol, EG and glycerol.