Chiral arylnickel complexes as highly active initiators for screw‐sense selective living polymerization of 1,2‐diisocyanobenzenes

Optically active chiral organonickel complexes served as efficient chiral initiators for living aromatizing polymerization of 1,2‐diisocyanobenzene derivatives, which afford optically active helical poly(quinoxaline‐2,3‐diyl)s up to 84% s.e. (screw‐sense excess). In comparison with asymmetric polymerization with the corresponding organopalladium initiators, the nickel initiators show a much greater polymerization rate, while the selectivity remains high. The organonickel initiators can be generated in situ from nickel(0) precursors with the corresponding enantiopure (S,S)‐2‐(4,5‐diphenylimidazolin‐2‐yl)phenyl chloride, leading to the convenient synthesis of highly stereo‐controlled poly(quinoxaline‐2,3‐diyl)s. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 898–904, 2010     

Preparation of a Highly Functionalized Cyclopentane Derivative Suitable for the Synthesis of Allosamidin Analogs

Abstract

Methyl 3,6-di-O-benzyl-4-O-benzoyl-2-deoxy-2-methoxycarbonylamino-α-D-glucopyranoside (8) was prepared form D-glucosamine via its 4,6-O-benzylidene derivative. The methyl glycoside moiety of 8 was hydrolyzed in the presence of d-camphorsulfonic acid in acetic acid to give hemiacetal 12. The oxime 14 derived from the latter was subjected to the radical cyclization mediated by tributyltin hydride, providing three types of cyclopentane derivatives. One isomer, 15, having an allosamizoline (2)-like configuration was converted into the N,N′-isopropylidene derivative 3, which is a potential intermediate for the syntheses of analogs of chitinase inhibitor allosamidin (1).     

Oxygen consumption of cell suspension in a poly(dimethylsiloxane) (PDMS) microchannel estimated by scanning electrochemical microscopy

A quantitative analysis of the oxygen concentration profile near a poly(dimethylsiloxane) (PDMS) microfluidic device was performed using scanning electrochemical microscopy (SECM). A microchannel filled with sodium sulfite (Na(2)SO(3)) aqueous solution was imaged by SECM, showing that the oxygen diffusion layer of the PDMS microchannel was observed to be hemicylindrical. Based on a theoretical analysis of the hemicylindrical diffusion layer of the microchannel, the total oxygen mass transfer rates of oxygen to the PDMS microchannel filled with the Na(2)SO(3) solution was calculated to be (4.01 +/- 0.30) x 10(-12) mol s(-1). This is the maximum value of the oxygen transfer rate for this PDMS microchannel device. The oxygen consumption rate increased almost linearly with the logarithm of the concentration of E. coli cells (10(6) approximately 10(8) cells). The respiratory activity for a single E. coli cell was estimated to be approximately 4.31 x 10(-20) mol s(-1) cell(-1).     

Short communication performance of octadecylsilylated monolithic silica capillary columns of 530 microm inner diameter in HPLC

Monolithic silica capillary columns were successfully prepared in a fused silica capillary of 530 microm inner diameter and evaluated in HPLC after octadecylsilylation (ODS). Their efficiency and permeability were compared with those of columns pakked with 5-microm and 3-microm ODS-silica particles. The monolithic silica columns having different domain sizes (combined size of through-pore and skeleton) showed 2.5-4.0-times higher permeability (K= 5.2-8.4 x 10(-14) m2) than capillary columns packed with 3-mm particles, while giving similar column efficiency. The monolithic silica capillary columns gave a plate height of about 11-13 microm, or 11 200-13 400 theoretical plates/150 mm column length, in 80% methanol at a linear mobile phase velocity of 1.0 mm/s. The monolithic column having a smaller domain size showed higher column efficiency and higher pressure drop, although the monolithic column with a larger domain size showed better overall column performance, or smaller separation impedance (E value). The larger-diameter (530 microm id) monolithic silica capillary column afforded a good peak shape in gradient elution of proteins at a flow rate of up to 100 microL/min and an injection volume of up to 10 microL.     

Total synthesis of mycestericin A and its 14-epimer

The total synthesis of mycestericin A (1) and its 14-epimer 34 is described herein. The Overman rearrangement of an allylic trichloroacetimidate derived from l-tartrate generated a tetra-substituted carbon with nitrogen and subsequent stereoselective transformations afforded the highly functionalized left-half segment, vinyl iodide. Cross-coupling of the vinyl iodide with a chiral organometallic species synthesized from d-tartrate under the Negishi or Suzuki-Miyaura coupling conditions, followed by deprotection, completed the total synthesis of 1. The 14-epimer of mycestericin A was also synthesized, and a comparison of [α]_D values of peracetyl γ-lactone derivatives of mycestericin A and its 14-epimer as well as degradation studies of 1 and 34 fully confirmed the proposed absolute structure of mycestericin A.     

Large time behavior of solutions of Hamilton–Jacobi equations with periodic boundary data

We study the large time behavior of viscosity solutions of Hamilton–Jacobi equations with periodic boundary data on bounded domains. We establish a result on convergence of viscosity solutions to state constraint asymptotic solutions or periodic asymptotic solutions depending on the sign of critical value as time goes to infinity.     

Control of emission peaks of X-ray phosphor using dye-silica nanoparticles

Simple method yielding new emission peaks to the X-ray phosphor and its mechanism were investigated using concentrated-dye-molecule-doped silica nanoparticles (dye-silica nanoparticles) and X-ray phosphors. The dye-silica nanoparticles were coated on the sheet of the X-ray phosphor using 20 wt% polyvinyl alcohol solution. The fluorescence of the dye-silica nanoparticle coated onto X-ray phosphor was successfully observed by X-ray irradiation. The fluorescent cascade from the X-ray-irradiated phosphor could be used in the excitation of the dye-silica nanoparticles by coating on the calcium tungstate (X-ray phosphor). The observed new fluorescence was based on the extent of the overlapping of wavelengths between the emission of the X-ray phosphor and the excitation of the dye-silica nanoparticles. The fluorescent peak of the calcium tungstate as the X-ray phosphor shifted from 434 to 425 nm. The dye-silica particle-calcium tungstate hybrid material showed new emission peaks from 543 to 601 nm due to the addition of fluorescein, rhodamine red-X, or cy5. The new emission peaks changed by the content of dye and the size of the silica nanoparticles. The fluorescence intensity ratio of the new fluorescence peaks at 543 nm against that of the X-ray phosphor depended on the fluorescent cascade from the X-ray-irradiated X-ray phosphor. It can closely match the overall emission of the phosphorous intensity screens to the sensitivity of the film allowing lower dose X-rays to obtain the same image clarity.     

Vertex corrections to the anomalous Hall effect in spin-polarized two-dimensional electron gases with a Rashba spin-orbit interaction

We study the effect of disorder on the intrinsic anomalous Hall conductivity in a magnetic two-dimensional electron gas with a Rashba-type spin-orbit interaction. We find that anomalous Hall conductivity vanishes unless the lifetime is spin-dependent, similar to the spin Hall conductivity in the nonmagnetic system. In addition, we find that the spin Hall conductivity does not vanish in the presence of magnetic scatterers.     

Laser energy dependence on femtosecond laser-induced nucleation of protein

We have investigated femtosecond laser-induced nucleation of hen egg-white lysozyme (HEWL) as a function of the laser pulse energy and pulse time width. This is the first recorded study to confirm that the femtosecond laser-induced nucleation of HEWL can be induced at a specific threshold laser energy. The threshold energy is comparable to that of cavitation bubble generation. The results strongly suggest that morphological changes in the solution are key factors for protein nucleation.     

Bulk ammonothermal GaN

In this work, results of structural characterization of high-quality ammonothermal GaN are presented. Besides expected low dislocation density (being of the order of 10³ cm⁻²) the most interesting feature seems perfect flatness of the crystal lattice of studied crystals. Regardless the size of crystals, lattice curvature radius exceeds 100 m, whereas better crystals reveal radius of several hundred meters and the best above 1000 m. Excellent crystallinity manifests in very narrow X-ray diffraction peaks of full-width at half-maximum (FWHM) values about 16 arcsec.