A study into Stille cross‐coupling reaction mediated by palladium catalysts deposited over siliceous supports bearing N‐donor groups at the surface

Mesoporous molecular sieve SBA‐15 and conventional silica gel were grafted with 3‐[2‐(diethylamino)ethylamino]propyl groups and used as supports for the preparation of deposited palladium catalysts, which were subsequently evaluated in Stille cross‐coupling reaction of aryl bromides. The highest conversions were achieved with the metal‐saturated catalyst resulting from the modified SBA‐15. Influence of various reaction parameters (solvent, additive, temperature, etc.) on the overall yield and selectivity was studied. Copyright © 2013 John Wiley & Sons, Ltd.     

The Kinetics of Reduction of Sulfoxides by the Iodide Ion in Aqueous Perchloric Acid

Abstract

The kinetics of the acid-catalyzed reactions of di-n-butyl -sulfoxide (BuSOBu), di-phenylsulfoxide (PhSOPh), and di-benzyl -sulfoxide (PhCH₂SOCH₂Ph) with iodide in a medium of HCLO₄ has been followed; the reaction orders with respect to sulfoxide and iodide have been determined and a possible mechanism discussed.     

A simple polymer electrolyte membrane system for enrichment of low-level tritium (3H) in environmental water samples

Tritium (³H) is an essential tracer of the Earth's water cycle; yet widespread adoption of tritium in hydrologic studies remains a challenge because of analytical barriers to quantification and detection of ³H by electrolytic pre-concentration. Here, we propose a simple tritium electrolytic enrichment system based on the use of solid polymer electrolyte membranes (PEMs) that can be used to enrich ³H in 250–3000?mL environmental water samples to a 10-mL final volume. The IAEA PEM-³H system reported here can produce high enrichment factors (>70-fold) and, importantly, removes some of the deterrents to conventional ³H enrichments methods, including the use of toxic electrolysis and neutralization chemicals, spike standards, a complex electrolysis apparatus that requires extensive cooling and temperature controls, and improves precision by eliminating the need for tracking recovery gravimetrics. Preliminary results with varying operating conditions show ³H enrichments to 70-fold and higher are feasible, spanning a wide range of tritium activities from 5 to 150 TU with a precision of ～4.5?%. Further work is needed to quantify inter-sample memory and to establish lower ³H detection limits. The IAEA PEM-³H system is open source, with 3-D CAD and design files made freely available for adoption and improvement by others.     

Influence of Fe-doping on the microstructure and electromagnetic performance of manganese oxides

A simple wet chemical method was used to synthesize Fe-doped MnO₂ composites with iron amount ranging from 0 to 90 M percent. X-ray diffraction, electron probe micro-analyzer, scanning electron microscopy and vector network analyzer were employed to investigate the effect of iron doping on the microstructure and electromagnetic performance of the as-synthesized samples. Results indicate that relative small content of Fe-doping cannot change the α-MnO₂ structure but can promote the formation of hollow-structural morphology. The as-obtained products are transformed into a novel compound (Fe_0.67Mn_0.33)OOH with the increase of Fe-doping to 30 mol%. The possible formation mechanism was proposed in detail. Compared with the pure MnO₂, the Fe-doped samples exhibit decreased dielectric loss but increased magnetic loss with increasing the iron content below 20 mol% while relatively poor electromagnetic properties with the iron content above 30 mol%.     

Online induction heating for determination of isotope composition of woody stem water with laser spectrometry: a methods assessment

Application of stable isotopes of water to studies of plant–soil interactions often requires a substantial preparatory step of extracting water from samples without fractionating isotopes. Online heating is an emerging approach for this need, but is relatively untested and major questions of how to best deliver standards and assess interference by organics have not been evaluated. We examined these issues in our application of measuring woody stem xylem of sagebrush using a Picarro laser spectrometer with online induction heating. We determined (1) effects of cryogenic compared to induction-heating extraction, (2) effects of delivery of standards on filter media compared to on woody stem sections, and (3) spectral interference from organic compounds for these approaches (and developed a technique to do so). Our results suggest that matching sample and standard media improves accuracy, but that isotopic values differ with the extraction method in ways that are not due to spectral interference from organics.     

Computation and conversion of brain pH values obtained with two algorithms of phosphorus magnetic resonance spectroscopy data analysis

The intracellular brain pH in phosphorus magnetic resonance spectroscopy is calculated using the chemical shift between the inorganic phosphate and phosphocreatine with the Henderson–Hasselbalch equations. Researchers use various mathematical formulas that have different parameters and get various results for the same input data as a consequence. Thus, the aim of this article was to determine the mathematical formulas that allow the conversion of the pH values obtained by the most popular analysis methods to each other. To determine the relationships between pH results and the applied mathematical formula, the pH values were calculated using two algorithms for the theoretical chemical shift values. The pH results were compared with each other using the appropriate t-tests. Mathematical formulas were designed to simplify the conversion of pH values obtained by two data analysis methods to each other. The pH values with were obtained this way did not differ significantly from the pH values calculated directly from the given formula. The computed mathematical formulas will make it possible to simplify pH conversions without knowing the chemical shift between inorganic phosphate and phosphocreatine but only basing on the final pH values obtained by one of the formulas.     

Rheological Technique as a Sensitive Method to Characterize the Chain Diffusion across the Interface between Polystyrene and Carbon Black Filled Polystyrene

The mutual diffusion process and interphase development taking place at the interface between disks of polystyrene (PS) and carbon black filled polystyrene (CB-PS) in the molten state were investigated by a small-amplitude, oscillatory shear, rheological technique. The rheological method was employed to probe the thermorheological complexity of these polymer disks. It was found that the dynamic complex shear modulus, G*(t), increased with the time of contact in two time regimes at a fixed frequency. The time of transition between the two regimes was observed to be close to the time needed for the transition from the Rouse mode to the reptation mode. The results showed that the content of the carbon black and the temperature affected the slope of the G*(t) – t curve. Scanning electron microscopy revealed the interface disappeared when the diffusion process was complete.     

The FDTD simulation for the performance of dispersive cloak devices

In this paper, we defined the scattering energy intensity based on the Poynting vector to quantitatively study the cloak effect of electromagnetic waves in the time domain. The influences of the effective working frequency bands of four kinds of electromagnetic cloak materials, incidence angle of electromagnetic waves and the number of approximately cloak layers on the cloak effect are studied. To the best of our knowledge, this is the first time to use the time domain method to quantitatively study the effective working frequency band and the scattering energy intensity of cloak materials.     

Flux and fluence dependence of disorder produced during implantation of 11B in silicon

The flux and fluence dependence of disorder produced in silicon during the implantation of ¹¹B has been investigated at room temperature, -50°C. and -120°C. Implantations were carried out with 200 keV ¹¹B ions using current densities in the range from 0.06μA/cm² to 15μA/cm², and the disorder monitored by measuring the energy spectra of backscattered protons which were incident on the sample at 450 keV parallel to a (110) axis. Significant differences in the dependence of the disorder on ¹¹B flux and fluence were observed between the implantations performed at room temperature and those carried out at the two lower temperatures.     

Application of electromagnetic processing for development of high-performance sintered powder metal parts

Electromagnetic processing was used to study the effects of electro-magneto forming on the dimensional control and thermal stability of sintered powder metal (PM) parts. The investigation was carried out on sinter-hardened, low chromium-molybdenum bainitic steel. The results show an increase in the microhardness of about 14% for the electromagnetic processed parts compared to the as-sintered parts. This was attributed to the 2% increase in the density, 17% and 29% reduction in the volume fraction of porosity and width of the bainitic lath, respectively, due to the electromagnetic processing. Dimensional characterization was carried out using a vertically aligned push-rod dilatometer. After four thermal cycles of heating and cooling, at a controlled rate of 5 °C/min to 1000 °C, the electromagnetic processed parts exhibited reduced dimensional change of about 44% lower than for the as-sintered parts. This is significantly important for applications that demand high dimensional tolerance and performance, especially at elevated temperatures.