Preparation, preservation and application of pure isotope-enriched phenyltin species

A method combining liquid/liquid extraction and chromatographic fractionation has been developed for the preparation of pure monophenyltin (MPhT), diphenyltin (DPhT), and triphenyltin (TPhT), synthesized from isotope-enriched Sn metal using phenylation of SnI₄ in diethylether (DEE) followed by quenching with HBr and water. After two successive extractions of the aqueous HBr phase with DEE, >99% of both DPhT and TPhT was recovered in the combined DEE phase and 94% of the MPhT remained in the aqueous phase. The MPhT in the aqueous phase was extracted into dichloromethane. The organic phases were vaporized and the PhTs were redissolved in MeOH/water/acetic acid/sodium acetate (59/30/6/8, v/v/v/w), which was also used as storing solution. Aliquots of the two solutions containing either DPhT and TPhT or MPhT were injected into a silica-based C₁₈ column for isolating and purifying single species. The yields of pure MPhT, DPhT, and TPhT, each synthesized from isotope-enriched ¹¹⁸Sn metal, ¹²²Sn metal, and ¹²⁴Sn metal, were better than 99%. After chromatographic separation, the single phenyltin compounds were mixed to prepare a spike for multiple-isotope species-specific isotope dilution (MI-SSID). MI-SSID was successfully used to determine phenyltin compounds in the certified reference material, mussel tissue BCR CRM-477. At −20 °C, all of the fractionated phenyltin species were stable in the storage solution for at least 197 days. When these standards were stored at 4 °C or 22 °C, 4–6% of the DPhT and TPhT degraded within 27 days. The degradation of DPhT and TPhT increased with the ionic strength and acidity of the storage solution.      

Theoretical study of the substituent effects on the S-H bond dissociation energy and ionization energy of 3-pyridinethiol: Prediction of novel antioxidant

The S-H bond dissociation enthalpies [BDE(S-H)] of a set of 5-X- and 6-X-3-pyridinethiols (X = F, Cl, CH3, OCH3, NH2, N(CH3)2, CF3, CN, and NO2) have been computed using the density functional theory based (RO)B3LYP procedure with 6-311++G(2df,2p) basis set. The effects of substituents on the BDE(S-H), proton affinity of the pyridinethiol anion [PA(S-)] and ionization energy (IE) are analyzed and their correlations with Hammett's substituent constants are examined. Subsequently, a series of 6-substituted 3-pyridinethiols have been explored to find out their antioxidant potentials. Finally, a number of 3-pyridinethiol based compounds are theoretically proposed as novel antioxidants.     

Temperature‐dependent Raman scattering study of multiferroic MnWO4

We have measured polarized Raman spectra of MnWO₄ single crystals at low temperatures, and studied the temperature dependence of the various phonon modes. From our Raman studies of the MnWO₄, a new transition temperature, ∼180 K, was found. We have completely assigned the symmetries of the 18 observed Raman modes of the MnWO₄, as expected from a group theoretical analysis. These Raman modes have been classified into three groups according to weak, intermediate and strong temperature dependence of the modes in each group. Six internal modes have been identified by their weak temperature dependence of the Raman wavenumbers. The temperature dependence of the wavenumbers of the B_g modes in Mg O bonds, modes of intermediate temperature dependence group, shows an anomalous behavior under 50 K. The phonon modes of strong temperature dependence show an anomalous change at ∼180 K in the linewidths. This is believed to be a new transition temperature which involves the changes in the inter‐WO₆ octahedra structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Squark Pair Production at Muon Colliders in the MSSM with CP Violation

We study the pair production of scalar quark in a muon collider within the MSSM with CP violation. We show that including the CP phases can strongly affect the cross section of the process: \(\mu^{+}\mu^{-}\rightarrow \tilde{q}_{i}\bar{\tilde{q}}_{j}\). This could have an important impact on the search for squarks and the determination of the MSSM parameters at future colliders.     

Bandgap optimization of two-dimensional photonic crystals using semidefinite programming and subspace methods

In this paper, we consider the optimal design of photonic crystal structures for two-dimensional square lattices. The mathematical formulation of the bandgap optimization problem leads to an infinite-dimensional Hermitian eigenvalue optimization problem parametrized by the dielectric material and the wave vector. To make the problem tractable, the original eigenvalue problem is discretized using the finite element method into a series of finite-dimensional eigenvalue problems for multiple values of the wave vector parameter. The resulting optimization problem is large-scale and non-convex, with low regularity and non-differentiable objective. By restricting to appropriate eigenspaces, we reduce the large-scale non-convex optimization problem via reparametrization to a sequence of small-scale convex semidefinite programs (SDPs) for which modern SDP solvers can be efficiently applied. Numerical results are presented for both transverse magnetic (TM) and transverse electric (TE) polarizations at several frequency bands. The optimized structures exhibit patterns which go far beyond typical physical intuition on periodic media design.     

Electronic transitions of fluorene, dibenzofuran, carbazole, and dibenzothiophene: From the onset of absorption to the ionization threshold

A comparative study of the electronic transitions of fluorene and its hetero-analogues dibenzofuran, carbazole, and dibenzothiophene was performed in a wide energy range. Gas phase, crystal phase, and linear dichroism electronic transmittance spectra were measured with synchrotron radiation. Electronic transitions to excited singlet states were predicted with time-dependent density functional theory, TD-B3LYP/6-31+G(d,p). Based on the experimental and theoretical results, symmetry assignments of electronic transitions in the vacuum and near-UV region are suggested. The correspondence between excited states in these molecules, similarities, and differences between their electronic spectra are discussed.     

Deterministic Raman crosstalk effects in amplified wavelength division multiplexing transmission

We study the deterministic effects of inter-pulse Raman-induced crosstalk in amplified wavelength division multiplexing (WDM) optical fiber transmission lines. We show that the dynamics of pulse amplitudes in an N-channel transmission system is described by an N-dimensional predator-prey model. We find the equilibrium states with non-zero amplitudes and prove their stability by obtaining the Lyapunov function. The stability is independent of the exact details of the approximation for the Raman gain curve. Furthermore, we investigate the impact of cross phase modulation and Raman self and cross frequency shifts on the dynamics and establish the stability of the equilibrium state with respect to these perturbations. Our results provide a quantitative explanation for the robustness of differential-phase-shift-keyed WDM transmission against Raman crosstalk effects.     

Event excess in the MiniBooNE search for ¯νμ→¯νe oscillations

The MiniBooNE experiment at Fermilab reports results from a search for ˉν_{μ}→ˉν_{e} oscillations, using a data sample corresponding to 5.66×102? protons on target. An excess of 20.9±14.0 events is observed in the energy range 475相似文献   

Existence of metastable kinetic modes

The nonlinear evolution of resonantly driven systems, such as suprathermal particle driven modes in magnetically confined plasmas, is shown to strongly depend on the existence and nature of an underlying damping mechanism. When background resonant damping is present, subcritical states can take place. In particular, purely nonlinear steady-state regimes are found, whose destabilization threshold and saturation levels are calculated and validated using numerical simulations. This nonlinear behavior can be of relevance for acoustic modes in magnetically confined plasmas.     

Coulomb energy determination of a single Si dangling bond

Determination of the Coulomb energy of single point defects is essential because changing their charge state critically affects the properties of materials. Based on a novel approach that allows us to simultaneously identify a point defect and to monitor the occupation probability of its electronic state, we unambiguously measure the charging energy of a single Si dangling bond with tunneling spectroscopy. Comparing the experimental result with tight-binding calculations highlights the importance of the particular surrounding of the localized state on the effective charging energy.