Isomeric states in180Os

Two new isomers have been observed in¹⁸⁰Os. A high-K isomer withI, K ≧20 and a half-life ofT _1/2=12+4 ns have been established. It deexcites via two transitions into the 18⁺ level of the yrare band indicating an unusually smallK-hindrance factor. Evidence for an isomer withI, K>16 and a half-life ofT _1/2=41±10 ns was found. A half-life of 17±3 ns was measured for the previously known 7^? state at 1862 keV. The decay scheme of the previously known 7^? isomer at 1928 keV has been extended and a revised version is presented.     

Optimization of Verapamil Drug Analysis by Excitation-Emission Fluorescence in Combination with Second-order Multivariate Calibration

Excitation emission fluorescence matrices (EEMs) of Verapamil drug were obtained by direct and by derivatization fluorescence spectroscopy. The fluorescence excitation and emission wavelengths were displaced to longer wavelengths and the fluorescence intensity was enhanced upon derivation with respect to the native fluorescence of the drug. The complete EEM of the native fluorescence of the drug and of the derivatization product were rapidly acquired by using a charged-coupled device detector (CCD), which is advantageous in terms of speed in the analysis, with respect to the use of a conventional photomultiplier detector. The EEMs were analyzed by several second-order multivariate calibration methods exploiting the second order advantage. The three-dimensional decomposition methods used, based in different assumptions about the trilinearity of the three way data structure under analysis, were parallel factor analysis (PARAFAC), bilinear least squares (BLLS), parallel factor analysis 2 (PARAFAC2) and multivariate curve resolution—alternating least squares (MCR-ALS). The determination was performed by using the standard addition approach. The figures of merit of the PARAFAC and BLLS methods were calculated, obtaining a lower limit of detection with the derivatization procedure, when compared with the direct measurement of the fluorescence of the drug. In Verapamil drug the best estimations were found with the BLLS and the MCR-ALS models. In the quantification of Verapamil in a pharmaceutical formulation the best estimation, when compared with the result obtained by the US Pharmacopeia high performance liquid chromatography approach, was obtained by direct fluorescence spectroscopy with MCR-ALS and by derivatization fluorescence spectroscopy with the PARAFAC2 model.     

Kinetics and mechanisms of gas‐phase elimination of 2,2‐diethoxyethyl amine and 2,2‐diethoxy‐N,N‐diethylethanamine

The gas‐phase elimination kinetics of 2,2‐diethoxyethyl amine and 2,2‐diethoxy‐N,N‐diethylethanamine (320–380 °C; 40–150 Torr) in a seasoned reaction vessel are homogeneous, unimolecular and obey a first‐order rate law. These elimination processes involve two parallel reactions. The first gives ethanol and the corresponding 2‐ethoxyethenamine. The latter compound further decomposes to ethylene, CO and the corresponding amine. The second parallel reaction produce ethane and the corresponding ethyl ester of an α‐amino acid. The following Arrhenius expressions are given as: For 2,2‐diethoxyethyl amine For 2,2‐diethoxy‐N,N‐diethylethanamine Comparative kinetic and thermodynamic parameters of the overall, the parallel and the consecutive reactions lead to consider two types of mechanisms in terms of a concerted polar cyclic transition state structures. Copyright © 2008 John Wiley & Sons, Ltd.     

On the blue emission of a novel solution-processed stilbenoid dendrimer thin film for OLED displays

A novel blue fluorescent first generation stilbenoid dendrimer built on the 1,3,5-benzene core and endowed with a periphery of hexyloxy branches has been synthesized and is proposed as an active layer for organic light-emitting diodes processed by spin coating. In this work, we have obtained homogeneous thin films with blue emission (2.8 eV) by spin coating instead of the usual evaporation method used for low-weight molecular materials. The absorption and emission spectra of the films are analyzed and compared to that of the molecule. The obtained results show the dependence of the absorption and emission properties on the morphology and the dendrimer aggregation in the film. The effect of inter-dendrimer interactions leads to a broadening of the absorption bands and to a reduction of the threshold as the aggregation increases. The most efficient solid-state emission is for the films obtained from chloroform as solvent in the precursor solution.     

Tip-induced reduction of the resonant tunneling current on semiconductor surfaces

We report scanning tunneling microscope measurements showing a substantial decrease of the current, almost to zero, on the Si(111)-(7x7) reconstruction in the near-to-contact region under low bias conditions. First principles simulations for the tip-sample interaction and transport calculations show that this effect is driven by the substantial local modification of the atomic and electronic structure of the surface. The chemical reactivity of the adatom dangling bond states that dominate the electronic density of states close to the Fermi level and their spatial localization result in a strong modification of the electronic current.