Spectroscopic studies on Co(II) and Cu(II) complexes of 6-amino-1-methyl-5-nitrosouracil and its 6-methylamine derivative

Four complexes are obtained during the reactions of 6-amino-1-methyl-5-nitrosouracil and its 6-methylamine derivative with Co(II) and Cu(II) ions. Theses complexes were characterized through their elemental, thermal analysis, infrared and 1H NMR spectroscopes. The obtained results indicate that, the exocyclic oxygen and nitrogen atoms are the most probable binding sites rather than ring nitrogen atoms. For cobalt complexes, the two pyrimidine bases act as bidentate ligands in the anionic form with the dissociation of iminic or N3 proton depending upon the nature of substituents on the pyrimidine ring. For copper complexes, the pyrimidine bases interact in the neutral form as monodentate ligands. Octahedral geometries are proposed for all of these complexes.     

Are Unsaturated Isocyanides so Different from the Corresponding Nitriles?

Simple unsaturated and cyclopropylic isocyanides are synthesized by an efficient and simple approach. These compounds with gradually increasing distance between the unsaturated moiety and the isonitrile group are studied by UV photoelectron spectroscopy and quantum chemical calculations, and also compared to the corresponding nitriles. The first photoelectron band of the unsaturated compounds is linked to removal of an electron from the HOMO, which corresponds to CC multiple-bond ionization in antibonding interaction with the π-isocyanide bond (in the same plane) for conjugated systems, or in antibonding interaction with the pseudo-π-CH(2) group for isolated systems. For the 1-ethenyl derivatives, both cyano and isocyano groups act as a π-electron acceptor from the vinyl group, but the isocyano π system is much more strongly destabilized (ionization energies (IEs) shift to smaller values) by vinyl (3.12 eV) than the cyano π system is (2.70 eV). In comparison with the 1-ethynyl derivatives, a less pronounced destabilization (2.69 eV) of π(NC) by the ethynyl system (1.86 eV for π(CN)), and nearly the same order of magnitude of the energetic gap between the total antibonding (π(CC)-π(NC)) and the total bonding (π(CC)+π(NC)) IEs for ethenyl and ethynyl compounds are noted. The huge values of these last-named data for H(2)C=CH-NC (3.85 eV) and for HC≡C-NC (4.04 eV) reflect the strong interaction between the unsaturated carbon-carbon moiety and the isocyanide group, and thus more efficient conjugation than for the corresponding nitriles.     

Pre-organization of the core structure of E-selectin antagonists

A new class of N-acetyl-D-glucosamine (GlcNAc) mimics for E-selectin antagonists was designed and synthesized. The mimic consists of a cyclohexane ring substituted with alkyl substituents adjacent to the linking position of the fucose moiety. Incorporation into E-selectin antagonists led to the test compounds 8 and the 2'-benzoylated analogues 21, which exhibit affinities in the low micromolar range. By using saturation transfer difference (STD)-NMR it could be shown that the increase in affinity does not result from an additional hydrophobic contact of the alkyl substituent with the target protein E-selectin, but rather from a steric effect stabilizing the antagonist in its bioactive conformation. The loss of affinity found for antagonists 10 and 35 containing a methyl substituent in a remote position (and therefore unable to support to the stabilization of the core) further supports this hypothesis. Finally, when a GlcNAc mimetic containing two methyl substituents (52 and 53) was used, in which one methyl was positioned adjacent to the fucose linking position and the other was in a remote position, the affinity was regained.     

Traceless chemical ligations from O-acyl serine sites

Chemical ligation via O- to N-acyl transfer of O-acylated serine containing peptides affords serine containing native peptides via 8- and 11-membered cyclic transition states opening the door to a wide variety of potential applications to peptide elaboration. The feasibility of these traceless chemical ligations is feasible as supported by computation.     

Intersubband resonant enhancement of the nonlinear optical properties in asymmetric (CdS/ZnSe) based quantum wells

In this work, the linear and nonlinear optical properties are studied theoretically in asymmetric (CdS/ZnSe/BeTe)/(ZnSe/BeTe) quantum wells. The electronic states are calculated using the envelope wave function approximation and the intersubband transition energies are studied as a function of CdS and ZnSe well thicknesses as well as doping concentration. The optimum parameters carrying out the transition energy 0.8 eV (1.55 μm wavelength) are given. Results are presented for the linear, the third order nonlinear optical absorption and the refractive index changes in the studied heterostructure. Results show that the changes in the linear and the third order nonlinear optical absorption as well as refractive index change are as important as the temperature is high, the nonlinear terms must be taken into consideration especially near the resonance.     

Si/Si1−xGex/Si-based quantum wells infrared photodetector operating at 1.55 μm

A quantum well infrared photodetector consisting of self-assembled type II SiGe/Si based quantum wells operating around 1.55 μm at room temperature has been investigated. The Si_1−yGe_y/Si/Si_1−xGe_x/Si/Si_1−yGe_y stack results in a ‘W’ like profiles of the conduction and valence bands strain-compensated in the two low absorption windows of silica fibers infrared photodetectors have been proposed. Such computations have been used for the study of the p-i-n infrared photodetectors operating, around (1.3–1.55 μm) at room temperature. The quantum transport properties of electrons and holes were approved with Schrödinger and kinetic equations resolved self-consistently with the Poisson equation. The theoretical performances of the photodetector were carried out such as the dark current mechanisms, the temperature dependence of normalized dark current and the zero-bias resistance area product (R₀A).     

Influence of substrate temperature and Cobalt concentration on structural and optical properties of ZnO thin films prepared by Ultrasonic spray technique

Pure and Cobalt doped zinc oxide were deposited on glass substrate by Ultrasonic spray method. Zinc acetate dehydrate, Cobalt chloride, 4-methoxyethanol and monoethanolamine were used as a starting materials, dopant source, solvent and stabilizer, respectively. The ZnO samples and ZnO:Co with Cobalt concentration of 2 wt.% were deposited at 300, 350 and 400 °C. The effects of substrate temperature and presence of Co as doping element on the structural, electrical and optical properties were examined. Both pure and Co doped ZnO samples are (0 0 2) preferentially oriented. The X-ray diffraction results indicate that the samples have polycrystalline nature and hexagonal wurtzite structure with the maximum average crystallite size of ZnO and ZnO:Co were 33.28 and 55.46 nm. An increase in the substrate temperature and presence doping the crystallinity of the thin films increased. The optical transmittance spectra showed transmittance higher than 80% within the visible wavelength region. The band gap energy of the thin films increased after doping from 3.25 to 3.36 eV at 350 °C.     

Surface waves at the interface between tunable LC–MTMs and nonlinear media

The surface wave propagation at the interface between tunable metamaterials (MTMs) and nonlinear media is investigated. Tunable MTMs have a refractive index which can be tuned to negative?Czero?Cpositive values. The nonlinear media are assumed to have a Kerr-like refractive index. The dispersion equation is analytically derived and solved numerically. Results display the different behaviors of the propagating waves as the refractive index is tuned.     

Oscillation criteria for quasi-linear functional dynamic equations on time scales

This paper is concerned with oscillation of the second-order quasilinear functional dynamic equation

$$(r(t)(x^\Delta (t))^\gamma )^\Delta + p(t)x^\beta (\tau (t)) = 0,$$

on a time scale \(\mathbb{T}\) where γ and β are quotient of odd positive integers, r, p, and τ are positive rd-continuous functions defined on \(\mathbb{T},\tau :\mathbb{T} \to \mathbb{T}\) and \(\mathop {\lim }\limits_{t \to \infty } \tau (t) = \infty \). We establish some new sufficient conditions which ensure that every solution oscillates or converges to zero. Our results improve the oscillation results in the literature when γ = β, and τ(t) ≤ t and when τ(t) > t the results are essentially new. Some examples are considered to illustrate the main results.

     

Decay property of Timoshenko system in thermoelasticity

We investigate the decay property of a Timoshenko system of thermoelasticity in the whole space for both Fourier and Cattaneo laws of heat conduction. We point out that although the paradox of infinite propagation speed inherent in the Fourier law is removed by changing to the Cattaneo law, the latter always leads to a solution with the decay property of the regularity‐loss type. The main tool used to prove our results is the energy method in the Fourier space together with some integral estimates. We derive L² decay estimates of solutions and observe that for the Fourier law the decay structure of solutions is of the regularity‐loss type if the wave speeds of the first and the second equations in the system are different. For the Cattaneo law, decay property of the regularity‐loss type occurs no matter what the wave speeds are. In addition, by restricting the initial data to with a suitably large s and γ ∈ [0,1], we can derive faster decay estimates with the decay rate improvement by a factor of t^?γ/2. Copyright © 2011 John Wiley & Sons, Ltd.