Self-Similar Solutions to a Kinetic Model for Grain Growth

We prove the existence of self-similar solutions to the Fradkov model for two-dimensional grain growth, which consists of an infinite number of nonlocally coupled transport equations for the number densities of grains with given area and number of neighbors (topological class). For the proof we introduce a finite maximal topological class and study an appropriate upwind discretization of the time-dependent problem in self-similar variables. We first show that the resulting finite-dimensional dynamical system admits nontrivial steady states. We then let the discretization parameter tend to zero and prove that the steady states converge to a compactly supported self-similar solution for a Fradkov model with finitely many equations. In a third step we let the maximal topology class tend to infinity and obtain self-similar solutions to the original system that decay exponentially. Finally, we use the upwind discretization to compute self-similar solutions numerically.     

Dinuclear Rh(II) pyrazolates as CVD precursors for rhodium thin films

New dinuclear rhodium(II) pyrazolate (Pz) complexes of formula Rh(2)(3-R,5-R'Pz)(4)·2L (R = R' = CF(3), L = H(2)O (1), CH(3)CN (2)) and Rh(2)(3-R,5-R'Pz)(4) (R = R' = (t)Bu (3); R = CF(3), R' = (t)Bu (4)) have been synthesized from the interaction of the lithium salt of the corresponding pyrazole with Rh(2)(OAc)(4) in diethyl ether. The complexes were characterized by X-ray crystallography and spectroscopic methods. They were further evaluated as precursors for the chemical vapor deposition (CVD) of Rh thin films using H(2) as the carrier gas. The resulting films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).     

Stannyl derivatives of naphthalene diimides and their use in oligomer synthesis

2-Stannyl and 2,6-distannyl naphthalene diimides (NDIs) can be synthesized through the palladium-catalyzed reaction of the appropriate bromo derivatives with hexabutylditin. The utility of these precursors in palladium catalyzed cross-coupling reactions is demonstrated by the synthesis of bi- and ter-NDI derivatives, UV-vis, cyclic voltammetry, and n-channel organic field-effect transistor data for which are compared to those of the monomeric parent NDI.     

A rapid analytical method for cholecalciferol (vitamin D3) in fortified infant formula, milk and milk powder using Diels-Alder derivatisation and liquid chromatography-tandem mass spectrometric detection

A method for analysing vitamin D₃ (VD3, cholecalciferol) has been established and validated. This method is rapid and cost effective and is intended for use in quality control in the manufacture of fortified infant formulae and milk powders. Milk or reconstituted milk powder was solubilised in methanol and extracted in one step into isooctane, which was separated by centrifugation. A portion of the isooctane layer was then transferred, and an aliquot of 4-phenyl-1,2,4-triazoline-3,5-dione was added to derivatise VD3. The analyte was then re-extracted into a small volume of acetonitrile and analysed by reverse-phase chromatography. Detection was by triple quadrupole mass spectrometer using a selective transition, m/z 560 → 298. An internal standard, deuterium-labelled VD3, was used to correct for losses in extraction and any variation in derivatisation and ionisation efficiencies. The method has been subjected to a single-laboratory validation and has been found to be linear, highly selective and accurate with respect to National Institute of Standards and Technology Standard Reference Material 1849, analyte spiking experiments and comparison with an LC–UV-based method. The repeatability standard deviation was 4.23 %. Significantly for routine laboratories, the method returns results within 2 h, generates minimal waste and minimises health and safety concerns to the analyst.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

Assessment of the performance of MP2 and MP2 variants for the treatment of noncovalent interactions

For many years, MP2 served as the principal method for the treatment of noncovalent interactions. Until recently, this was the only technique that could be used to produce reasonably accurate binding energies, with binding energy errors generally below ~35%, at a reasonable computational cost. The past decade has seen the development of many new methods with improved performance for noncovalent interactions, several of which are based on MP2. Here, we assess the performance of MP2, LMP2, MP2-F12, and LMP2-F12, as well as spin component scaled variants (SCS) of these methods, in terms of their abilities to produce accurate interaction energies for binding motifs commonly found in organic and biomolecular systems. Reference data from the newly developed S66 database of interaction energies are used for this assessment, and a further set of 38 complexes is used as a test set for SCS methods developed herein. The strongly basis set-dependent nature of MP2 is confirmed in this study, with the SCS technique greatly reducing this behavior. It is found in this work that the spin component scaling technique can effectively be used to dramatically improve the performance of MP2 and MP2 variants, with overall errors being reduced by factors of about 1.5-2. SCS versions of all MP2 variants tested here are shown to give similarly accurate overall results.     

Noise-immune cavity-enhanced optical heterodyne detection of HO2 in the near-infrared range

Accurate measurements of the absolute concentrations of radical species present in the atmosphere are invaluable for better understanding atmospheric processes and their impact on Earth systems. One of the most interesting species is HO(2), the hydroperoxyl radical, whose atmospheric daytime levels are on the order of 10 ppt and whose observation therefore requires very sensitive detection techniques. In this work, we demonstrate the first steps toward the application of external-cavity diode-laser-based noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) to the detection of the HO(2) radical in the near-infrared range. Measurements of stable species and of HO(2) were made in a laboratory setting, and the possibilities of extending the sensitivity of the technique to atmospheric conditions are discussed.     

2+2] photocycloadditions of thiomaleimides

Thiomaleimides, generated by the addition of bromomaleimides to thiols including cysteine, undergo highly efficient [2+2] photocycloadditions.     

Terahertz single pixel imaging based on a Nipkow disk

We describe a terahertz single pixel imaging system based on a Nipkow disk. Nipkow disks have been used for fast scanning imaging systems since the first experimental television was invented in 1926. In our work, a Nipkow disk with 24 scanning lines was used to provide an axial resolution of 2 mm/pixel. We also show that by implementing a microscanning technique the axial resolution can be further improved to 0.5 mm/pixel. Imaging of several objects was demonstrated to show that this simple scanning system is promising for fast or real time terahertz imaging applications.