Stacking effect of polyfluorene on the chemical shift and electron transport

We investigate the structures, NMR chemical shifts, absorption spectra, frontier molecular orbitals, and transition density matrices of pi-stacked polyfluorenes by ab initio calculations. For F1-F4, we consider two different conformations, syn and anti. The simulated 1H NMR chemical shifts are in good agreement with the previous experiment, and the significantly upfielded chemical shifts explain that the fluorene moieties are stacked on each other. It is found that the relative stability for syn and anti conformers is almost equivalent in B3LYP calculations; however, the syn conformer becomes much more stable than the anti conformer in MP2 calculations, which is consistent with the experimental finding that only the syn conformers are relevant. The vertical detachment energy, which is linearly proportional to the ionization potential, shows the same size dependence as the previous experiment. The electron attachment energy decreases exponentially as the size increases, which implies that the electron transport would be possible even for long chains such as F3 and F4. This was evident from the frontier molecular orbitals (HOMO and LUMO). Also, it is found that the syn conformers are very favorable for electron transport through the pi-stacked fluorene moieties.     

Patterned cell culture inside microfluidic devices

This paper describes a simple plasma-based dry etching method that enables patterned cell culture inside microfluidic devices by allowing patterning, fluidic bonding and sterilization steps to be carried out in a single step. This plasma-based dry etching method was used to pattern cell-adhesive and non-adhesive areas on the glass and polystyrene substrates. The patterned substrate was used for selective attachment and growth of human umbilical vein endothelial cells, MDA-MB-231 human breast cancer cells, NIH 3T3 mouse fibroblasts, and primary rat cortical neurons. Finally, we have successfully combined the dry-patterned substrate with a microfluidic device. Patterned primary rat neurons were maintained for up to 6 days inside the microfluidic devices and the neurons' somas and processes were confined to the cell-adhesive region. The method developed in this work offers a convenient way of micropatterning biomaterials for selective attachment of cells on the substrates, and enables culturing of patterned cells inside microfluidic devices for a number of biological research applications where cells need to be exposed to well-controlled fluidic microenvironment.     

Liquid chromatography-tandem mass spectrometry for the determination of a new oxazolidinone antibiotic DA-7867 in human plasma

A liquid chromatography-tandem mass spectrometric (LC/MS/MS) method for the determination of a new ox-azolidinone antibiotic DA-7867, (S)-[N-3-(4-(2-(1-methyl-5-tetrazolyl)-pyridine-5-yl)-3- fl uorophenyl)-2-oxo-5-oxazolidinyl]methyl acetamide, in human plasma was developed. DA-7867 and internal standard, linezolid, were extracted from human plasma with ethyl acetate at acidic pH. A reverse-phase LC separation was performed on Luna C(8) column with the mixture of acetonitrile-ammonium formate (10 mm, pH 4.5; 35:65, v/v) as mobile phase. The analytes were determined using an electrospray ionization tandem mass spectrometry in the multiple-reaction-monitoring mode. The lower limits of quanti fi cation for DA-7867 was 2.5 ng/mL. The single liquid-liquid extraction quantitatively recovered DA-7867 and internal standard from plasma samples at the ranges of 82.2-86.7%. DA-7867 was stable in blank human plasma at room temperature for 24 h and following three freeze-thaw cycles.     

Unsteady RANS method for surface ship boundary layer and wake and wave field

Results are reported of an unsteady Reynolds‐averaged Navier–Stokes (RANS) method for simulation of the boundary layer and wake and wave field for a surface ship advancing in regular head waves, but restrained from body motions. Second‐order finite differences are used for both spatial and temporal discretization and a Poisson equation projection method is used for velocity–pressure coupling. The exact kinematic free‐surface boundary condition is solved for the free‐surface elevation using a body‐fitted/free‐surface conforming grid updated in each time step. The simulations are for the model problem of a Wigley hull advancing in calm water and in regular head waves. Verification and validation procedures are followed, which include careful consideration of both simulation and experimental uncertainties. The steady flow results are comparable to other steady RANS methods in predicting resistance, boundary layer and wake, and free‐surface effects. The unsteady flow results cover a wide range of Froude number, wavelength, and amplitude for which first harmonic amplitude and phase force and moment experimental data are available for validation along with frequency domain, linear potential flow results for comparisons. The present results, which include the effects of turbulent flow and non‐linear interactions, are in good agreement with the data and overall show better capability than the potential flow results. The physics of the unsteady boundary layer and wake and wave field response are explained with regard to frequency of encounter and seakeeping theory. The results of the present study suggest applicability for additional complexities such as practical ship geometry, ship motion, and maneuvering in arbitrary ambient waves. Copyright © 2001 John Wiley & Sons, Ltd.     

Pyrazolidine derivatives with heteroaryl urea as dipeptidyl peptidase IV inhibitors

In the continuation of efforts to modify the structure of our novel DP-IV inhibitors, a series of pyrazolidine derivatives with heteroaryl urea was synthesized and evaluated for their ability to inhibit dipeptidyl peptidase IV (DP-IV).     

Noncollinear phase matching in fluorescence upconversion

We investigate noncollinear sum-frequency generation in a time-resolved fluorescence upconversion experiment to eliminate group-velocity mismatch (GVM), a major mechanism that deteriorates time resolution. The noncollinear geometry inherently causes phase-front mismatch (PFM) that also spoils time resolution. The effects of GVM and PFM on the time resolution are studied by numerical calculations and experiments. Based on the investigation, a fluorescence upconversion apparatus with time resolution better than 45 fs (FWHM) is demonstrated.     

Attosecond pulse extreme-ultraviolet photoionization in a two-color laser field

Attosecond-pulse extreme-ultraviolet (XUV) photoionization in a two-color laser field is investigated. Attosecond pulse trains with different numbers of pulses are examined, and their strong dependence on photoelectronic spectra is found. Single-color driving-laser-field-assisted attosecond XUV photoionization cannot determine the number of attosecond pulses from the photoelectronic energy spectrum that are detected orthogonally to the beam direction and the electric field vector of the linearly polarized laser field. A two-color-field-assisted XUV photoionization scheme is proposed for directly determining the number of attosecond pulses from a spectrum detected orthogonally.     

Simulation on the response of new phosphate glass RPC for <Emphasis Type="Italic">γ</Emphasis>-rays and e<Superscript>+</Superscript>/e<Superscript>−</Superscript> particles using GEANT3

The influence of phosphate glass electrode in the configuration of resistive plate chamber has been studied using GEANT3.21 Monte Carlo code. Bakelite electrodes were replaced by phosphate glass electrodes, as these glass materials have low bulk resistivity, are portable and easy to handle. These types of RPCs in their compact form of all materials are suitable for high rate background environment. We find that these new types of RPCs give little higher response to γ-rays and e⁺/e⁻ particles, both for single-and double gap RPCs. The results of simulation are discussed.      

Dendritic chiral auxiliaries on silica: a new heterogeneous catalyst for enantioselective addition of diethylzinc to benzaldehyde

This article reports the first work on the use of silica supported dendritic chiral auxiliaries for the enantioselective addition of diethylzinc to benzaldehyde: the control of dendrimer propagation on the silica surface is of prime importance to obtain enhanced conversion, selectivity, and enantioselectivity.     

Characterization and growth of ZnSTe epilayers by hot-wall epitaxy

ZnS_1−xTe_x epilayers were grown on GaAs(1 0 0) substrates by hot-wall epitaxy in a wide range of Te composition. The Te composition was determined by Rutherford backscattering spectrometry and the lattice constant was measured by double-crystal rocking curve. It was found that the lattice of the epilayer matches well with that of the substrate at x=0.37 as expected by Vegard's rule, and the energy gap was also determined as a function of Te composition by spectrophotometer. It showed that a quadratic relation with the composition: E_g(x)=3.71−5.27x+3.83x². Photoluminescence characteristics were also studied.