Cadmium(II) complexes of (arylazo)imidazoles: synthesis, structure, photochromism, and density functional theory calculation

Reaction between CdX2 and 1-alkyl-2-(phenylazo)imidazole (RaaiR') has isolated complexes of composition Cd(RaaiR')2X2 in MeOH or MeCN. Crystallization of Cd(RaaiR')2I2 from N,N-dimethylformamide (DMF) has separated [Cd(RaaiR')I2.DMF], while Cd(RaaiR')2X2 (X = Cl and Br) remains unchanged in its composition upon crystallization under identical conditions. The structure has been established by spectral (UV-vis and 1H NMR) data and confirmation in the latter case by a single-crystal X-ray diffraction study of [Cd(TaiMe)I2.DMF] [where TaiMe = 1-methyl-2-(p-tolylazo)imidazole]. UV-light irradiation in a MeCN solution of Cd(RaaiR')2I2 and [Cd(RaaiR')I2.DMF] shows trans-to-cis isomerization of coordinated azoimidazole. The reverse transformation, cis-to-trans, is very slow with visible light irradiation. Quantum yields (phit-->c) of trans-to-cis isomerization are calculated, and the free ligand shows higher phi values than their cadmium(II) iodo complexes. The cis-to-trans isomerization is a thermally induced process. The activation energy (Ea) of cis-to-trans isomerization is calculated by a controlled-temperature experiment. The effects of the anions (Cl-, Br-, I-, and ClO4-) and the number of coordinated azoimidazoles (RaaiR') [Cd(RaaiR') or Cd(RaaiR')2] on the rate and quantum yields of photochromism are established in this work. A slow rate of photoisomerization of [Cd(RaaiR')4](ClO4)2 compared to Cd(RaaiR')I2 or Cd(RaaiR')2X2 may be associated with the increased mass and rotor volume of the complexes. The rate of isomerization is also dependent on the nature of X and follows the sequence Cd(RaaiR')2Cl2 < Cd(RaaiR')2Br2 < Cd(RaaiR')2I2. It may be related to the size and electronegativity of halide, which reduces the effective molar association in the order of I < Br < Cl and hence the rate. Gaussian 03 calculations of representative complexes and free ligands are used to explain the difference in the rates and quantum yields of photoisomerization.     

Water‐Splitting Electrocatalysis in Acid Conditions Using Ruthenate‐Iridate Pyrochlores

The pyrochlore solid solution (Na_0.33Ce_0.67)₂(Ir_1?xRu_x)₂O₇ (0≤x≤1), containing B‐site Ru^IV and Ir^IV is prepared by hydrothermal synthesis and used as a catalyst layer for electrochemical oxygen evolution from water at pH<7. The materials have atomically mixed Ru and Ir and their nanocrystalline form allows effective fabrication of electrode coatings with improved charge densities over a typical (Ru,Ir)O₂ catalyst. An in situ study of the catalyst layers using XANES spectroscopy at the Ir L_III and Ru K edges shows that both Ru and Ir participate in redox chemistry at oxygen evolution conditions and that Ru is more active than Ir, being oxidized by almost one oxidation state at maximum applied potential, with no evidence for ruthenate or iridate in +6 or higher oxidation states.     

Concentration of measures via size-biased couplings

Let Y be a nonnegative random variable with mean??? and finite positive variance ?? ², and let Y ^s , defined on the same space as Y, have the Y size-biased distribution, characterized by $$ E[Yf(Y)]=\mu E f(Y^s) \quad {\rm for\,all\,functions}\,f\,{\rm for\,which\,these\,expectations\,exist}. $$ Under a variety of conditions on Y and the coupling of Y and Y ^s , including combinations of boundedness and monotonicity, one sided concentration of measure inequalities such as $$ P\left(\frac{Y-\mu}{\sigma} \ge t\right)\le {\rm exp}\left(-\frac{t^2}{2(A+Bt)} \right) \quad {\rm for\,all}\,t\, > 0 $$ hold for some explicit A and B. The theorem is applied to the number of bulbs switched on at the terminal time in the so called lightbulb process of Rao et?al. (Sankhy?? 69:137?C161, 2007).     

Spectroscopic and microscopic investigation of gold nanoparticle formation: ligand and temperature effects on rate and particle size

We report a spectroscopic and microscopic investigation of the synthesis of gold nanoparticles (AuNPs) with average sizes of less than 5 nm. The slow reduction and AuNP formation processes that occur by using 9-borabicyclo[3.3.1]nonane (9-BBN) as a reducing agent enabled a time-dependent investigation based on standard UV-vis spectroscopy and transmission electron microscopy (TEM) analyses. This is in contrast to other borohydride-based syntheses of thiolate monolayer protected AuNPs which form particles very rapidly. We investigated the formation of 1-octadecanethiol (ODT) protected AuNPs with average diameters of 1.5-4.3 nm. By studying the progression of nanoparticle formation over time, we find that the nucleation rate and the growth time, which are interlinked with the amount of ODT and the temperature, influence the size and the size dispersion of the AuNPs. High-resolution TEM (HRTEM) analyses also suggest that the nanoparticles are highly single crystalline throughout the synthesis and appear to be formed by a diffusion-controlled Ostwald-ripening growth mechanism.     

Distinguishing a SM-like MSSM Higgs boson from SM Higgs boson at muon collider

We explore the possibility of distinguishing the SM-like MSSM Higgs boson from the SM Higgs boson via Higgs boson pair production at future muon collider. We study the behavior of the production cross-section in SM and MSSM with Higgs boson mass for various MSSM parameters tan β and m _A . We observe that at fixed CM energy, in the SM, the total cross-section increases with the increase in Higgs boson mass whereas this trend is reversed for the MSSM. The changes that occur for the MSSM in comparison to the SM predictions are quantified in terms of the relative percentage deviation in cross-section. The observed deviations in cross-section for different choices of Higgs boson masses suggest that the measurements of the cross-section could possibly distinguish the SM-like MSSM Higgs boson from the SM Higgs boson.      

Bounds on neutrino mixing with exotic singlet neutrinos

We examine the effects of mixing induced non-diagonal light-heavy neutrino weak neutral currents on the amplitude for the process (with a=e, μ or τ). By imposing constraint that the amplitude should not exceed the perturbative unitarity limit at high energy , we obtain bounds on light-heavy neutrino mixing parameter sin² where is the mixing angle. In the case of one heavy neutrino (mass mξ) or mass degenerate heavy neutrinos, for Λ=1 TeV, no bound is obtained for mξ<0.50 TeV. However, sin² ≤3.8 × 10⁻⁶ for mξ=5 TeV and sin ≤6.0 × 10⁻⁸ for mξ=10 TeV. For Λ=∞, no constraint is obtained for mξ<0.99 TeV and sin² ≤3.8 × 10⁻² (for mξ=5 TeV) and sin² ≤9.6 × 10⁻³ (for mξ=10 TeV).     

Asymptotic analysis of Neumann periodic optimal boundary control problem

An optimal boundary control problem in a domain with oscillating boundary has been investigated in this paper. The controls are acting periodically on the oscillating boundary. The controls are applied with suitable scaling parameters. One of the major contribution is the representation of the optimal control using the unfolding operator. We then study the limiting analysis (homogenization) and obtain two limit problems according to the scaling parameters. Another notable observation is that the limit optimal control problem has three controls, namely, a distributed control, a boundary control, and an interface control. Copyright © 2016 John Wiley & Sons, Ltd.     

Syntheses,Spectral Studies and Bioanalyses of Some Triorganotin（IV） Complexes of Cephlaxine

Five novel triorganotin（IV） complexes have been synthesized by refluxing trimethyl, triethyl, tributyl, triphenyl and tribenzyltin chloride with Cephlaxine. These compounds were characterized by spectroscopic （IR, IH, 13C, 119Sn NMR） techniques and elemental analysis. The results obtained through these techniques are in full agreement with the proposed 1：1 stoichiometry. The synthesized compounds were than tested against various microorganisms and fungi. The results of new products obtained showed that the triphenyltin（IV） complex displayed promising activity against all types of bacteria and fungi used while all other compounds showed significant antibacterial and antifungal activity.