Glycoinsulins: dendritic sialyloligosaccharide-displaying insulins showing a prolonged blood-sugar-lowering activity

Mono-, di-, and trisialyloligosaccharides were introduced to mutant insulins through enzymatic reactions. Sugar chains were sialylated by alpha2,6-sialyltransferase (alpha2,6-SiaT) via an accessible glutamine residue at the N-terminus of the B-chain attached by transglutaminase (TGase). Sia2,6-di-LacNAc-Ins(B-F1Q) and Sia2,6-tri-LacNAc-Ins(B-F1Q), displaying two and three sialyl-N-acetyllactosamines, respectively, were administered to hyperglycemic mice. Both branched glycoinsulins showed prolonged glucose-lowering effects compared to native or lactose-carrying insulins, showing that sialic acid is important in obtaining a prolonged effect. Sia2,6-tri-LacNAc-Ins(B-F1Q), in particular, induced a significant delay in the recovery of glucose levels.     

Photoelectrochemical properties of supramolecular composite of fullerene nanoclusters and 9-mesityl-10-carboxymethylacridinium ion on SnO2

[structure: see text] The photovoltaic cell composed of both fullerene nanoclusters and 9-mesityl-10-carboxymethylacridinium ion exhibits significant enhancement in the photoelectrochemical performance as well as broader photoresponse in the visible and near-infrared regions as compared with the reference system containing only each component.     

Antiferromagnetic transition and electrical conductivity in α-Gd2S3

Magnetic susceptibility and electrical resistivity of α-Gd₂S₃ with an orthorhombic structure (space group: Pnma) have been measured for powder and single-crystal samples. While the magnetic susceptibility of powder sample exhibits a broad peak having a maximum at 4.2 K, the susceptibility for a single crystal with an applied magnetic field along the b-axis demonstrates a sharp drop below 10 K. Nevertheless, the susceptibility with the field perpendicular to the b-axis keeps increasing with decreasing temperature even below 10 K. The electrical resistivity ρ for the powder sample of 4.2×10³ Ω cm around room temperature increases with decreasing temperature and shows a slight discontinuity at about 65 K. In both regions above and below 65 K, is proportional to T^−1/4 with respective coefficients, which is associated with Mott variable-range hopping conductivity. The resistivity of a single crystal along the b-axis is considerably smaller than the value for the powder sample as 0.35 Ω cm at room temperature, and its temperature dependence is fairly weak. While cooling, the resistivity first decreases down to 240 K and then keeps the value independent of the temperature down to 140 K, and subsequently rises gently below 140 K.     

Welding dynamics in an atomistic model of an amorphous polymer blend with polymer–polymer interface

We consider an atomistic model of thermal welding at the polymer-polymer interface of a polyetherimide/polycarbonate blend, motivated by applications to 3D manufacturing in space. We follow diffusion of semiflexible chains at the interface and analyze strengthening of the samples as a function of the welding time t_w by simulating the strain–stress and shear viscosity curves. The time scales for initial wetting, and for fast and slow diffusion, are revealed. It is shown that each component of the polymer blend has its own characteristic time of slow diffusion at the interface. Analysis of strain–stress demonstrates saturation of the Young's modulus at t_w = 240 ns, while the tensile strength continues to increase. The shear viscosity is found to have a very weak dependence on the welding time for t_w > 60 ns. It is shown that both strain–stress and shear viscosity curves agree with experimental data.     

A new ferromagnetic thiospinel CuCrZrS4 with re-entrant spin-glass behaviour

A new thiospinel CuCrZrS₄ has been successfully synthesized by a solid-state chemical reaction. This CuCrZrS₄ exhibits ferromagnetic properties below the Curie temperature at T _c = 60 -2 K. The appearance of irreversible effect between field-cooled and zero-field-cooled magnetization is prominent below around 5 K in a magnetic field of less than 150 Oe. The ac susceptibility χ_AC shows a rapid decrease below about 10 K. This low magnetic-field behaviour indicates the existence of a re-entrant spin-glass phase below about 10 K. The dc magnetic susceptibility above 100 K shows Curie-Weiss behaviour with an effective magnetic moment of 3.61 μ _B, which is a little less than the spin-only value of 3.87 μ _B for the Cr³⁺ ion. The asymptotic Curie temperature θ _P is approximately 65 K, which is a little higher than T _c. The valence state is confirmed to be Cu⁺Cr³⁺Zr⁴⁺S₄ ^2? on the basis of magnetic properties. The electrical resistivity ρ shows a semiconducting temperature dependence over the temperature range from 4.2 to 280 K with an activation energy of 6.84 210^?3 eV in the higher temperature range from 50 to 283 K.     

2,2′-Biazulene diimide-based conjugate polymers for highperformance field-effect transistors

正Azulene,which is one of the non-alternating 10π-electron aromatic compounds,has attracted the interest of many research groups due to the application to material sciences utilizing the unique optoelectronic properties[1,2].Therefore,the construction ofπ-conjugated system incorporating azulene skeleton is actively researched in recent years.Gao and co-workers[3,4]at Shanghai Institute of Organic Chemistry have demonstrated the preparation of diimide     

The α‐Glycosidation of Partially Unprotected N‐Acetyl and N‐Glycolyl Sialyl Donors in the Absence of a Nitrile Solvent Effect

The synthesis of α‐sialosides is one of the most difficult reactions in carbohydrate chemistry and is considered to be both a thermodynamically and kinetically disfavored process. The use of acetonitrile as a solvent is an effective solution for the α‐selective glycosidation of N‐acetyl sialic acids. In this report, we report on the α‐glycosidation of partially unprotected N‐acetyl and N‐glycolyl donors in the absence of a nitrile solvent effect. The 9‐O‐benzyl‐N‐acetylthiosialoside underwent glycosidation in CH₂Cl₂ with a good α‐selectivity. On the other hand, the 4,7,8‐O‐triacetyl‐9‐O‐benzyl‐N‐acetylthiosialoside was converted to β‐sialoside as a major product under the same reaction conditions. The results indicate that the O‐acetyl protection of the sialyl donor was a major factor in reducing the α‐selectivity of sialylation. After tuning of the protecting groups of the hydroxy groups at the 4,7,8 position on the sialyl donor, we found that the 9‐O‐benzyl‐4‐O‐chloroacetyl‐N‐acetylthiosialoside underwent sialylation with excellent α‐selectivity in CH₂Cl₂. To demonstrate the utility of the method, straightforward synthesis of α(2,9) disialosides containing N‐acetyl and/or N‐glycolyl groups was achieved by using the two N‐acetyl and N‐glycolyl sialyl donors.     

Direct numerical simulation of homogeneous stratified rotating turbulence

The effects of the Prandtl number on stratified rotating turbulence have been studied in homogeneous turbulence by using direct numerical simulations and a rapid distortion theory. Fluctuations under strong stable-density stratification can be theoretically divided into the WAVE and the potential vorticity (PV) modes. In low-Prandtl-number fluids, the WAVE mode deteriorates, while the PV mode remains. Imposing rotation on a low-Prandtl-number fluid makes turbulence two-dimensional as well as geostrophic; it is found from the instantaneous turbulent structure that the vortices merge to form a few vertically-elongated vortex columns. During the period toward two-dimensionalization, the vertical vortices become asymmetric in the sense of rotation. Communicated by S. Obi PACS 47.55.Hd     

Viscosity reduction of cellulose + 1-butyl-3-methylimidazolium acetate in the presence of CO2

Viscosities of microcrystalline cellulose + 1-butyl-3-methylimidazolium acetate ([bmIm][Ac]) solutions (0.6–1.2 wt%) in contact with CO₂ were measured at 312 K with a resonant vibrational viscometer. At 4 MPa and 312 K, the CO₂ could reduce the viscosity of 1.2 wt% cellulose + [bmIm][Ac] solution by about 80 %, whereas N₂ at the same conditions gave less than a 10 % reduction in viscosity. The viscosity-averaged degree of polymerization and IR spectrum showed that cellulose did not decompose during experiments and that [bmIm][Ac] acted as a non-derivatizing solvent during the dissolution and viscosity reduction process. Further, although CO₂ does react with [bmIm][Ac] to form 1-butyl-3-methylimidazolium-2-carboxylate, the reaction seems to be reversible and it does not affect the cellulose. Thus, [bmIm][Ac] with CO₂ provides an effective solvent for cellulose and the solvent system can probably be recycled or reused.     

Effects of Nb and Y substitution on negative thermal expansion of ZrV 2−XPXO7 (0≦X≦0.8)

Zirconium vanadates with a novel chemical composition including niobium and yttrium were synthesized by the sol-gel method. An aqueous solution of NH₄H₂PO₄ and NH₄V O₃ and an ethanol solution of ZrOCl₂,NbCl₅, and Y Cl₃ were prepared. These two solutions were stirred and mixed to prepare precursors of zirconium vanadates at 333 K, following the evaporation of the solvent at 363 K. The precursor gels obtained were heated at 373-973 K in air. A zirconium vanadate phase began to crystallize above 673 K and a single phase of zirconium vanadate was synthesized at 973 K. Although ZrV ₂O₇ generally had a positive thermal expansion in the temperature range above RT, the degree of positive thermal expansion decreased with the two types of substitution of P for V and a set of Nb and Y for Zr of ZrV ₂O₇. X-ray diffraction peaks due to a superlattice structure, causing a positive thermal expansion from RT, were not observed in the synthesized (Nb, Y)-substituted zirconium vanadates.