Laboratory vacuum spectrometer for the soft x‐ray region

A laboratory surface x‐ray absorption near edge structure ((S)XANES) spectrometer used for measurements in the soft x‐ray region is described. The x‐ray beam path of the spectrometer is enclosed in a vacuum chamber directly connected to the x‐ray generator output port. With this setup, the absorption of the x‐rays in the air is avoided. The developed spectrometer uses a monochromator equipped with cylindrically bent PET(002), KAP(001), and Ge(111) crystals of different Rowland radii working in the Johann focusing geometry. Nine stepping motors are used to control the positions of the monochromator, receiving slit, sample, and detectors. An x‐ray photon energy available in experiment ranges from about 1 keV to 5 keV. A registration of the photoelectrons emitted from the sample with the channeltron is used to carry out surface‐sensitive measurements. The performance of the developed spectrometer is illustrated by spectra measured at the absorption K‐edges of several elements from the Na‐Ti set. Copyright © 2008 John Wiley & Sons, Ltd.     

Molecular beam epitaxy of GaSb on ZnTe/GaAs: Influence of the chemical composition of ZnTe surface

We have studied the molecular beam epitaxy (MBE) of GaSb films on GaAs (0 0 1) substrates by using ZnTe as a new buffer layer. GaSb films were grown on two distinct ZnTe surfaces and the influence of surface chemical composition of ZnTe on the morphological and structural properties of GaSb films has been investigated. Initial 2-dimensional (2D) growth of GaSb films is obtained on Zn-terminated surface consequently smooth morphology and high crystal quality GaSb films are achieved. The thin GaSb film (0.4 μm) grown on Zn-terminated ZnTe surface reveals considerably narrow X-ray diffraction linewidth (113 arcsec) along with small residual strain, which strongly supports the availability of ZnTe buffer for the growth of high-quality GaSb film.     

Interface resistance dependence of spin transport in a ferromagnet–semiconductor hybrid structure

The spin transport signals from NiFe and Co into two-dimensional electron gas layers are measured for various thicknesses of transmission barriers. A stable and reproducible electrical detection of spin transport was obtained only when the barrier thickness is less than 10 nm. The typical interface resistance to observe spin signals in this experiment is about 0.5–250 Ω, which is a neither transparent nor a severe tunneling limit. The optimal interface resistance depends on the ferromagnetic materials, but severe tunneling barrier is not proper for fully electrical spin transport. Device size is also a critical factor to decide the proper range of interface resistance.     

Synthesis of Functionalized Tetrahydropyridines by SnCl4-Mediated [4+2] Cycloaddition between Donor–Acceptor Cyclobutanes and Nitriles

Cycloadditions of strained carbocycles promoted by Lewis acids are powerful methods to construct heterocyclic frameworks. In fact, the formal [3+2] cycloadditions of donor–acceptor (DA) cyclopropanes with nitriles has seen particular success in synthesis. In this work, we report on the first [4+2] cycloaddition of nitriles with DA cyclobutanes by Lewis acid activation. Tetrahydropyridine derivatives were obtained in up to 91 % yield from various aryl-activated cyclobutane diesters and aliphatic or aromatic nitriles.     

Quantitative determination of enzalutamide,an anti‐prostate cancer drug,in rat plasma using liquid chromatography–tandem mass spectrometry,and its application to a pharmacokinetic study

This report details a method using liquid chromatography–tandem mass spectrometry (LC‐MS/MS) that allows one to determine the concentration of an atypical anticancer drug, enzalutamide, in rat plasma. Specifically, this method involves the addition of an acetonitrile and bicalutamide (internal standard) solution to plasma samples. Following centrifugation of this mixture, an aliquot of the supernatant was directly injected into the LC‐MS/MS system. Separation was achieved using a column packed with octadecylsilica (5 µm, 2.1 × 50 mm) with 10 mM ammonium acetate in acetonitrile as the mobile phase; detection was accomplished using MS/MS by multiple‐reaction monitoring via an electrospray ionization source. This method demonstrated a linear standard curve (r = 0.997) over a concentration range of 0.001–1 µg/mL, as well as an intra‐ and inter‐assay precision of 2.7 and 5.1%, respectively, and an accuracy range from 100.8 to 105.6%. The lower limit of quantification was 1.0 ng/mL in 50 μL of rat plasma sample. We also demonstrated that this analytical method could be successfully applied to the pharmacokinetic study of enzalutamide in rats. Copyright © 2014 John Wiley & Sons, Ltd.     

A Kinetic Study for the Noncatalytic Esterification of Palm Fatty Acid Distillate

In this work, the reaction scheme for the esterification of palm fatty acid distillate performed under the noncatalytic and high‐temperature condition (230–290°C) was investigated with a rigorous mathematical modeling. The esterification reaction was assumed to be the pseudo–homogeneous second‐order reversible reaction, and the mass transfer effectiveness factor (η) was introduced in the modeling framework to systematically and collectively consider both evaporation and reaction, which are simultaneously and competitively occurred in the liquid phase. The nonlinear programming problem was constructed with the objective function consisting of the errors between experimental data and the estimated values from the reaction model. The problem was solved by using the Nelder–Mead simplex algorithm to identify kinetic parameters, reaction rate constants, and mass transfer coefficients. The values of mass transfer coefficients were found to follow the Hertz–Knudsen relation and expressed as a function of reaction temperature. From the reaction rate constants obtained from the proposed kinetic models, the apparent activation energy was estimated to be 43.98 kJ/mol, which is lower than the value obtained from the reaction using heterogeneous catalysts. This low value indicates that reactants and products behave as an acid catalyst at relatively high operating temperature and constant pressure.     

Spectrochemical analysis of powder using 355 nm Nd-YAG laser-induced low-pressure plasma

The applicability of spectrochemical analysis of minute amounts of powder samples was investigated using an ultraviolet Nd-YAG laser (355 nm) and low-pressure ambient air. A large variety of chemical powder samples of different composition were employed in the experiment. These included a mixture of copper(II) sulfate pentahydrate, zinc sulfide, and chromium(III) sulfate n-hydrate powders, baby powder, cosmetic powders, gold films, zinc supplement tablet, and muds and soils from different areas. The powder samples were prepared by pulverizing the original samples to an average size of around 30 μm in order to trap them in the tiny micro holes created on the surface of the quartz subtarget. It was demonstrated that in all cases studied, good quality spectra were obtained with low background, free from undesirable contamination by the subtarget elements and featuring ppm sensitivity. A further measurement revealed a linear calibration curve with zero intercept. These results clearly show the potential application of this technique for practical qualitative and quantitative spectrochemical analysis of powder samples in various fields of study and investigation.     

A facile approach to synthesize uniform hydrogel shells with controllable loading and releasing properties

We present a facile and straightforward method to synthesize uniform poly(vinyl amine) hydrogel shells with excellent loading capability for active materials and controllable responsiveness to applied stimuli, providing tunable releasing properties.     

The kinetics of competing multiple-barrier unimolecular dissociations of o-, m-, and p-chlorotoluene radical cations

The kinetics of competing multiple-barrier unimolecular dissociations of o-, m-, and p-chlorotoluene radical cations to C7H7(+) (benzyl and tropylium) are studied by ab initio/Rice-Ramsperger-Kassel-Marcus (RRKM) calculations. This system presents a very intriguing kinetic example in which the conventional approach assuming a single-barrier or a double-well potential surface with one transition state cannot predict or explain the outcome. The molecular parameters obtained at the SCF level of theory with the DZP basis set are utilized for the evaluation of microcanonical RRKM rate constants with no adjustable parameters. First-principles calculations provide the microscopic details of the reaction kinetics along the two competing multiple-barrier reaction pathways: the rate-energy curves for all elementary steps; temporal variations of the reactants, the reaction intermediates, and the products; and the product yield as a function of energy. The rate constant for each channel is calculated as a function of the internal energy at 0 K. After the thermal correction, the calculated rate-energy curves for the benzyl channel agree well with the photoelectron photoion coincidence data obtained at room temperature for all three isomers. Close agreement between experiments and theory suggests that first-principles calculations taking the full sequence of kinetic steps into account offer a useful kinetic model capable of correctly predicting the outcome of competing multiple-barrier reactions. The slowest process is identified as [1,2] and [1,3] alpha-H migration at the entrance to the tropylium and benzyl channel, respectively. However, the overall rate is determined not by the slowest process, but by the combination of the slowest rate and the net flux toward the product, which is multiplicatively reduced with an increasing number of reaction intermediates. The product yield calculation confirms the benzyl cation as the predominant product. For all isomers, the thermodynamically most stable tropylium ion is produced much less than expected because a large fraction of flux coming into the tropylium channel goes back to the benzyl channel. The benzyl channel is kinetically favored because it involves a lower entrance barrier with fewer rearrangements than the tropylium channel.