Dynamical behavior of one-dimensional water molecule chains in zeolites: nanosecond time-scale molecular dynamics simulations of bikitaite

Nanosecond scale molecular dynamics simulations of the behavior of the one-dimensional water molecule chains adsorbed in the parallel nanochannels of bikitaite, a rare lithium containing zeolite, were performed at different temperatures and for the fully and partially hydrated material. New empirical potential functions have been developed for representing lithium-water interactions. The structure and the vibrational spectrum of bikitaite were in agreement both with experimental data and Car-Parrinello molecular dynamics results. Classical molecular dynamics simulations were extended to the nanosecond time scale in order to study the flip motion of water molecules around the hydrogen bonds connecting adjacent molecules in the chains, which has been observed by NMR experiments, and the dehydration mechanism at high temperature. Computed relaxation times of the flip motion follow the Arrhenius behavior found experimentally, but the activation energy of the simulated system is slightly underestimated. Based on the results of the simulations, it may be suggested that the dehydration proceeds by a defect-driven stepwise diffusion. The diffusive mechanism appears as a single-file motion: the molecules never pass one another, even at temperatures as high as about 1000 K, nor can they switch between different channels. However, the mean square displacement (MSD) of the molecules, computed with respect to the center of mass of the simulated system, shows an irregular trend from which the single-file diffusion cannot be clearly evidenced. If the MSDs are evaluated with respect to the center of mass of the molecules hosted in each channel, the expected dependence on the square root of time finally appears.     

Impact of Dose-Rate on Rheology,Structure and Wear of Irradiated UHMWPE

Ultrahigh molecular weight polyethylene (UHMWPE) is used as a bearing material in total joint replacements (TJR). UHMWPE for TJR is usually modified by irradiation and thermal treatment to increase wear resistance. We modified UHMWPE in three ways, differing in radiation dose-rate and/or atmosphere during irradiation. Rheological properties before and after irradiation were determined by means of oscillatory shear measurements. Structural changes were followed by X-ray diffraction, infrared spectroscopy, electron spin resonance, and solubility measurements. Wear resistance of selected samples was obtained by the pin-on-disk method. Rheological properties changed sensitively with modification conditions including radiation dose rate. Moreover, rheological results correlated well with both crosslinking extent and wear resistance. Finally, it was demonstrated that the optimal radiation dose, i.e. the dose leading to maximum crosslinking density and wear resistance, was different for each of the three modification procedures.     

New and Simple Staining Method for Visualizing UHMWPE Lamellar Structure in TEM

Ultra-high-molecular-weight polyethylene (UHMWPE) is used in arthroplasty as a key component of total joint replacements. In order to increase its wear resistance, the polymer is often cross-linked in a two-step procedure comprising irradiation and thermal treatment. Both modification steps impact UHMWPE lamellar structure. In this study we introduce a new staining method that makes it possible to visualize the UHMWPE lamellae by transmission electron microscopy (TEM). The method consists of one-step staining with oleum (H ₂ SO ₄ solution of SO ₃ ) for 4 days and ultramicrotomy; this is significantly simpler than previously described techniques and yields micrographs of the same quality. The lamellar thicknesses from TEM correlated well with those from small- and wide-angle X-ray scattering and differential scanning calorimetry. It has also been demonstrated that the exact values of lamellar thicknesses obtained from TEM micrographs strongly depend on the place selected for image analysis.     

On the origin of diastereoselectivity in [2 + 2 + 2] cycloisomerization of chiral triynes: controlling helicity of helicene-like compounds by thermodynamic factors

Diastereoselective CoI-mediated [2 + 2 + 2] cycloisomerization of CH(3)O-substituted optically pure aromatic triynes to obtain nonracemic functionalized helicene-like compounds (comprising a penta-, hexa-, and heptacyclic helical scaffold) was studied. The stereochemical outcome of the reaction at 140 degrees C using CpCo(CO)(2) was controlled by thermodynamic factors yielding diastereomeric ratios up to 91:9. Using CpCo(ethylene)(2) at room temperature, a kinetic control took place leading to the loss of stereoselectivity. Barriers to epimerization for selected helicene-like compounds were measured indicating their lower configurational stability in comparison to the parent carbohelicenes. Free energy differences between corresponding pairs of diastereomers (calculated at the DFT B3LYP/TZV+P level) were in excellent agreement with the experimental data and allowed for the prediction of the stereochemical outcome of the reaction. An optically pure hexacyclic helicene-like alcohol was prepared on a multigram scale. Its X-ray structure confirmed the previous helicity assignments being based on (1)H-(1)H correlations in ROESY (1)H NMR spectra.     

Electromagnetic scattering by a homogeneous chiral obstacle in a chiral environment

Time-harmonic electromagnetic waves are scattered by a homogeneouschiral obstacle embedded in a chiral environment. The correspondingtransmission problem is reduced, via Bohren's decomposition,to an integral equation over the interface between the obstacleand the surrounding medium. This integral equation is shownto be uniquely solvable except for a discrete set of electromagneticparameters of the obstacle.     

A novel microplate-based HPLC-fluorescence assay for determination of NADPH-cytochrome P450 reductase activity

A 96‐well microplate‐based HPLC endpoint assay is described for the determination of NADPH‐cytochrome P450 reductase (CPR) activity. Novel sampling of NADPH into microplates was optimized. Separation was performed on a Zorbax Eclipse XDB‐C₁₈ analytical 4.6 × 150 mm, 5 µm column. To validate the method, recombinant human NADPH‐P450 reductase and microsomes with cytochrome P450 CYP1A1 were used. The mobile phase consisted of 80% acetonitrile and 20% water at a flow‐rate of 0.8 mL/min. The CPR activity was quantified using NADPH fluorescence at λ_Ex = 340 nm and λ_Em = 450 nm. Enzymatic activity was directly proportional to the decrease in NADPH fluorescence. This analytical process enables a highly sensitive endpoint determination for reductase activity in vitro and monitoring of the consumption of NADPH in enzymatic reactions. The method avoids the use of substrates and of organic solvents that may affect CPR and cytochrome P450 activity. In the reaction, molecular oxygen served as a proton source. The method can substitute spectrophotometric detection methods for its accuracy, high reproducibility (~100%) and sensitivity. The lower limit of detection, shown using the Agilent 1200 aparatus, is in the 250 nmol range. In addition, using this method it is possible to set up reactions in a high‐throughput format. Copyright © 2011 John Wiley & Sons, Ltd.     

Analysis and numerical studies of a problem of shape design

Communicated by R. V. Kohn