Absorption spectra and photolysis of methyl peroxide in liquid and frozen water

Methyl peroxide (CH(3)OOH) is commonly found in atmospheric waters and ices in significant concentrations. It is the simplest organic peroxide and an important precursor to hydroxyl radical. Many studies have examined the photochemical behavior of gaseous CH(3)OOH; however, the photochemistry of liquid and frozen water solutions is poorly understood. We present a series of experiments and theoretical calculations designed to elucidate the photochemical behavior of CH(3)OOH dissolved in liquid water and ice over a range of temperatures. The molar extinction coefficients of aqueous CH(3)OOH are different from the gas phase, and they do not change upon freezing. Between -12 and 43 °C, the quantum yield of CH(3)OOH photolysis is described by the following equation: Φ(T) = exp((-2175 ± 448)1/T) + 7.66 ± 1.56). We use on-the-fly ab initio molecular dynamics simulations to model structures and absorption spectra of a bare CH(3)OOH molecule and a CH(3)OOH molecule immersed inside 20 water molecules at 50, 200, and 220 K. The simulations predict large sensitivity in the absorption spectrum of CH(3)OOH to temperature, with the spectrum narrowing and shifting to the blue under cryogenic conditions because of constrained dihedral motion around the O-O bond. The shift in the absorption spectrum is not observed in the experiment when the CH(3)OOH solution is frozen suggesting that CH(3)OOH remains in a liquid layer between the ice grains. Using the extinction coefficients and photolysis quantum yields obtained in this work, we show that under conditions with low temperatures, in the presence of clouds with a high liquid-water content and large solar zenith angles, the loss of CH(3)OOH by aqueous photolysis is responsible for up to 20% of the total loss of CH(3)OOH due to photolysis. Gas phase photolysis of CH(3)OOH dominates under all other conditions.     

Capability of laboratories to determine core nutrients in foods: results of an international proficiency test

A proficiency test (PT) to assess the capabilities of laboratories to determine nutrients in a biscuit sample was carried out in September 2009. The need for such interlaboratory comparison arose from an increasing nutrition labeling requirements of different countries around the world. Forty-eight laboratories worldwide participated in this PT program for the determination of total lipids, saturated fat, trans-fat, protein, sugars, total dietary fiber (TDF), ash and sodium in food. This program was organized under the auspices of the Asia-Pacific Laboratory Accreditation Cooperation (APLAC). APLAC considers PT programs as one of the objective means of assessing the performance of the accredited laboratories. The program is one of the APLAC PT series whose primary purposes are to establish mutual agreement on the equivalence of the operation of APLAC member laboratories and to provide an opportunity to identify testing deficiency so that corrective actions can be taken, if necessary. The results of this program indicated that the consensus mean values estimated by robust statistics were in good agreement with the corresponding values obtained in the homogeneity tests except for trans-fat and TDF. The relative standard deviations of participant results for trans-fat and TDF were also found to be higher (19 and 24%, respectively) than the other test parameters. The relative standard deviations for other test parameters were less than 10%. One-half of the laboratories obtained satisfactory z-scores (| z | < 3) (\left| z \right| < 3) for all their reported results. Although participants were instructed to provide the measurement uncertainties of their reported results, only 27.5% of them had done so. Albeit many of the measurement uncertainties appear to be reasonable, some of them were found to vary widely, indicating that some laboratories still have difficulties in estimating measurement uncertainties. Although the overall measurement capability can be considered to be satisfactory, there is still room for improvement of analytical procedures.     

Novel synthesis of highly ordered mesoporous Fe2O3/SiO2 nanocomposites for a room temperature VOC sensor

The controlled synthesis of mesoporous silica and metal oxide nanocomposites with a highly ordered porous structure and large specific surface area for specific applications has been an attractive topic in the field of porous materials. Herein, we introduce a novel method for the fabrication of highly ordered mesoporous structured and large specific surface area Fe₂O₃/SiO₂ nanocomposites, and consider their application in room temperature gas sensors. The mesoporous Fe₂O₃/SiO₂ nanocomposites were synthesised by a two-step method, which combines the hydrothermal growth of Fe₂O₃ nanoparticles and the microemulsion phase of Brij 56 (C₁₆EO₁₀) surfactant as templates in instantly direct-templating synthesis. This synthesis method enables the fabrication of mesoporous Fe₂O₃/SiO₂ nanocomposites without distortion of the ordered porous structure after calcination at high temperature. The synthesised materials were found to be efficient in a room temperature VOC sensor application, with good recovery.     

Long time stability of four methods for splitting the evolutionary Stokes–Darcy problem into Stokes and Darcy subproblems

This report analyzes the long time stability of four methods for non-iterative, sub-physics, uncoupling for the evolutionary Stokes–Darcy problem. The four methods uncouple each timestep into separate Stokes and Darcy solves using ideas from splitting methods. Three methods uncouple sequentially while one is a parallel uncoupling method. We prove long time stability of four splitting based partitioned methods under timestep restrictions depending on the problem parameters. The methods include those that are stable uniformly in _S0$S_0$, the storativity coefficient, for moderate _kmin$k_{min}$, the minimum hydraulic conductivity, uniformly in _kmin$k_{min}$ for moderate _S0$S_0$ and with no coupling between the timestep and the spacial meshwidth.     

On Half-Way AZ-Style Identities

The Ahlswede–Zhang identity is an elegant sharpening of the famous LYM-inequality. Recently, we have found a parametrised identity which implies the AZ identity and characterizes deficiencies of other inequalities in combinatorics. In this paper, we show identities of half-way extraction from AZ-style identities. These identities aim to characterize more clearly terms participating in AZ identities or LYM-style inequalities.     

Dual extragradient algorithms extended to equilibrium problems

In this paper we propose two iterative schemes for solving equilibrium problems which are called dual extragradient algorithms. In contrast with the primal extragradient methods in Quoc et al. (Optimization 57(6):749–776, 2008) which require to solve two general strongly convex programs at each iteration, the dual extragradient algorithms proposed in this paper only need to solve, at each iteration, one general strongly convex program, one projection problem and one subgradient calculation. Moreover, we provide the worst case complexity bounds of these algorithms, which have not been done in the primal extragradient methods yet. An application to Nash-Cournot equilibrium models of electricity markets is presented and implemented to examine the performance of the proposed algorithms.     

Controlled SnO2 nanocrystal growth in SiO2–SnO2 glass‐ceramic monoliths

Crack‐free (100–x) SiO₂–x SnO₂ glass‐ceramic monoliths have been prepared by the sol–gel method obtaining for the first time SnO₂ concentrations of 20% with annealing at 1100 °C. Heat‐treatment resulted in the formation and growth of SnO₂ nanocrystals within the silica matrices. Combined use of Fourier transform–Raman spectroscopy and in situ high‐temperature X‐Ray diffraction shows that SnO₂ particles begin to crystallize in the cassiterite‐type phase at 80 °C and that their average apparent size remains around 7 nm, even after annealing at 1100 °C. Nanocrystal sizes and size distributions determined by low‐wavenumber Raman are in good agreement with those obtained from transmission electron microscopy measurements. Results indicate that the formation and the growth of SnO₂ nanocrystals impose a residual porosity in the silica matrix. Copyright © 2011 John Wiley & Sons, Ltd.     

Stability radii of higher order linear difference systems under multi-perturbations

We study stability radii of higher order linear difference systems under multi-perturbations. A formula for complex stability radius of higher order linear difference systems under multi-perturbations is given. Then, for the class of positive systems, we prove that the complex stability radius and real stability radius of the system under multi-perturbations coincide and they are computed via a simple formula. These are extensions of corresponding results of Hinrichsen and Son, Hinrichsen et al., Ngoc and Son, and Pappas and Hinrichsen. An example is given to illustrate the obtained results.