New enantiomeric polylactide-block-poly(butylene succinate)-block-polylactides: syntheses, characterization and in situ self-assembly

In situ self-assemblies of new biodegradable triblock PLLA-b-PBS-b-PLLA and PDLA-b-PBS-b-PDLA have been investigated in acetonitrile solution. At first, two series of PLLA-b-PBS-b-PLLA and PDLA-b-PBS-b-PDLA, respectively denoted as the P and Q triblock copolyester series, were prepared with fixed PBS block ((overline) M(n,NMR) = 6.9 kDa) and diverse enantiomeric PLLA/PDLA blocks. Further, their chemical structures and thermal properties were characterized by means of titration, nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), polarimeter, wide-angle X-ray diffraction (WAXD) and thermal analytical instruments. When mixing the synthesized enantiomeric copolyester pairs denoted as P(1)/Q(1) - P(8)/Q(8) in acetonitrile solution at 60 degrees C, in situ self-assemblies were found to happen for the P(4)/Q(4) to P(8)/Q(8) pairs, bearing longer enantiomeric PLA block lengths. DSC and WAXD analysis of the self-assembled microparticles demonstrated that PLLA/PDLA racemic crystals were formed for the P(5)/Q(5) - P(8)/Q(8) systems, as evidenced by their melting points over 200 degrees C, and a new X-ray diffraction peak detected at 2theta = 11.8 degrees . Moreover, morphological studies by scanning electron microscopy (SEM) indicated the formation of disk- or platelet-like microparticles. It was noted that the diameters of the microparticles self-assembled in situ decreased from 1.28-1.50 mum down to 480-660 nm, through tailoring the enantiomeric PLA block length. Other factors, such as a central PBS block, the enantiomeric block length and the preparation conditions were suggested to play important roles in the in situ self-assembly of these enantiomeric triblock copolyesters. These results provide a facile way to self-assemble hydrophobic, biodegradable microparticles, through tuning the important van der Waals stereocomplexation interactions between two enantiomeric blocks in solution.     

17O NMR studies of a triangular-lattice superconductor NaxCoO2 x yH(2)O

We report the first 17O NMR studies of a triangular-lattice superconductor Na(1/3)CoO2 x 4/3H(2)O and the host material Na(x)CoO2 (x=0.35 and 0.72). Knight shift measurements reveal that p-d hybridization induces sizable spin polarization in the O triangular-lattice layers. Water intercalation makes CoO2 planes homogeneous and enhances low frequency spin fluctuations near T(c)=4.5 K at some finite wave vectors different from both the ferromagnetic and "120 degree" modes.     

Velocity profiles in repulsive athermal systems under shear

We conduct molecular dynamics simulations of athermal systems undergoing boundary-driven planar shear flow in two and three spatial dimensions. We find that these systems possess nonlinear mean velocity profiles when the velocity u of the shearing wall exceeds a critical value u(c). Above u(c), we also show that the packing fraction and mean-square velocity profiles become spatially dependent with dilation and enhanced velocity fluctuations near the moving boundary. In systems with overdamped dynamics, u(c) is only weakly dependent on packing fraction phi. However, in systems with underdamped dynamics, u(c) is set by the speed of shear waves in the material and tends to zero as phi approaches phi(c), which is near random close packing at small damping. For underdamped systems with phi相似文献   

Spin dynamics in the carrier-doped S=1/2 triangular lattice of NaxCoO2.yH2O

We probed the local electronic properties of the mixed-valent Co+4-x triangular lattice in NaxCoO2.yH(2)O by 59Co NMR. We observed two distinct types of Co sites for x > or =1/2, but the valence seems averaged out for x approximately 1/3. Local spin fluctuations exhibit qualitatively the same trend down to approximately 100 K regardless of the carrier concentration x, and hence the nature of the electronic ground state. A canonical Fermi-liquid behavior emerges below approximately 100 K only for x approximately 1/3.     

Role of gallium wetting layer in high-quality ZnO growth on sapphire (0001) substrates

ZnO is a wide direct bandgap (Eg=3.37 eV at room temperature) II-VI compound semiconductor of wurtzite structure (a = 3.249 ? c = 5.207 ?. Compared to GaN and ZnS, ZnO has a larger exciton binding energy, ~60 meV (cf. ~25 meV for GaN and ~40 meV for ZnS), which is advantageous to realizing low-threshold excitonic lasers. Since optically pumped UV lasing of ZnO at room temperature was reported in 1997[1], much attention has been paid to the crystal quality improvement and p-type conduc…     

Separation of proteins on surface-modified poly(dimethylsiloxane) microfluidic devices

Separation and detection of proteins have been realized on nonionic surfactant-modified poly(dimethylsiloxane) (PDMS) microfabricated devices with end-column amperometric detection. The hydrophobic PDMS channels are turned into hydrophilic ones after being modified with Brij35 and facilitate the separation of proteins. The coating can remarkably reduce the adsorption of large protein molecules and is stable in the range of pH 6-12. The detection of proteins in such channels needs less rinsing time and thus efficiency is raised. Even large molecules of proteins can also be detected with better reproducibility and enhanced plate numbers. The relative standard deviation (RSD) of the migration time for glucose oxidase (GOD) is 2.2% (n = 19). Separation of GOD and myoglobin has been developed in modified channels. Predominant operational variables, such as the coating conditions, the concentration of surfactant and buffer, are studied in detail.     

Tetronamides as latent acyclic vinylogous amides in formal aza-[3 + 3] cycloaddition reactions with alpha,beta-unsaturated iminium salts. An unexpected rearrangement and an approach to synthesis of substituted piperidines

A detailed account regarding formal aza-[3 + 3] cycloaddition reactions of tetronamides with alpha,beta-unsaturated iminium salts is described here. This investigation uncovers regioisomeric cycloadducts that were not found in previous studies involving this formal cycloaddition and an unexpected rearrangement that led to pyridines and dihydropyridines. Both stereochemical and regiochemical issues raised in this study provide further mechanistic insights into this cycloaddition. With careful control of reaction temperatures, the desired formal cycloadducts are obtained. Ensuing transformation of these cycloadducts into functionalized piperidines establishes the concept of employing tetronamides as latent acyclic vinylogous amides for the formal aza-[3 + 3] cycloaddition.     

Building Pb nanomesas with atomic-layer precision

We demonstrate a novel scheme for manipulating metallic nanostructures involving a macroscopic number of atoms, yet with precise control in their local structures. The scheme entails a two-step process: (a) a triggering step using a scanning tunneling microscope, followed by (b) self-driven and self-limiting mass-transfer process. By using this scheme, we construct Pb nanomesas on Si(111) substrates whose thickness can be controlled with atomic-layer precision. The kinetic barrier for the mass transfer and the underlying mechanism behind this novel manipulation are determined.     

Far-field emission of a semiconductor nanowire laser

The polarization properties and angular distribution of intensity of the far fields from a nanowire laser are investigated. The far-field emission depends strongly on the mode type (HE11, TE01, TM01) and the radius of the nanowire. The emission is weakly directional, and a large part of it can be emitted in the backward direction. Our results can be applied for experimental determination of a lasing mode by its far fields as well as for optimization of laser emission.     

Rescaling Symmetry Flow of the Kadomtsev--Petviashvili Hierarchy

We present a new symmetry flow of the Kadomtsev-Petviashvili (KP) hierarchy, which origins from the rescaling of whole “multi-time“ valuables. This flow describes the deformation of solutions of the KP hierarchy with respect to a noncommutative parameter. It is shown that the introduced rescaling symmetry flow does not commute with the ordinary evolution flows of the KP hierarchy, but commutes with the evolution flows with respect to slow-variables.