Manufacturing of Volumetric Glass–Based Composites with Single‐ and Double‐QD Doping

Quantum dot (QD)‐based light‐emitting materials are gaining increased attention because of their easily tunable optical properties desired for various applications in biology, optoelectronics, and photonics. However, few methods can be used to manufacture volumetric materials doped with more than one type of QD other than QD‐polymer hybrids, and they often require complicated preparation processes and are prone to luminescence quenching by QD aggregation and separation from the matrix. Here, simultaneous doping of a volumetric glass‐based nanocomposite with two types of QDs is demonstrated for the first time in a single‐step process using the nanoparticle direct doping method. Glass rods doped with CdTe, CdSe/ZnS, or co‐doped with both QDs, are obtained. Photoluminescence and lifetime experiments confirm temperature‐dependent double emission with maxima at 596 and 720 nm with mean lifetimes up to 16 ns, as well as radiative energy transfer from the short wavelength–emitting QDs to the long wavelength–emitting QDs. This approach may enable the simple and cost‐efficient manufacturing of bulk materials that produce multicolor luminescence with cascade excitation pumping. Applications that could benefit from this include broadband optical fiber amplifiers, backlight systems in LCD screens, high‐power LEDs, or down‐converting solar concentrators used to increase the efficiency of solar panels.     

Luminescence characteristics of undoped and Eu‐doped GdCa4O(BO3)3 single crystals and nanopowders

Single crystals of GdCa₄O(BO₃)₃ (GdCOB) pure and doped with Eu concentration of 1 and 4 at% were grown by the Czochralski and micropulling‐down methods. The distribution of Eu ions in GdCOB crystals was uniform. The substitutions of Eu³⁺ in Gd, Ca(1) and Ca(2) cation sites and eventually formation Eu²⁺ have been investigated. The spectroscopic properties of crystals are compared with the properties of nanopowders obtained by sol‐gel method. Radioluminescence spectra of undoped GdCOB crystal show the characteristic emission of Gd³⁺ at about 312 nm, whereas this emission dramatically decreases in Eu‐doped crystals upon X‐ray excitation, as well as in Eu‐doped nanopowders excited in vacuum ultraviolet (VUV) region. The VUV excitation in the range 125‐333 nm for Eu‐doped samples leads to strong emission in red coming from the ⁵D₀ multiplet of Eu³⁺, only. In the photoluminescence decay kinetics of 312 nm emissions substantial shortening and departure for single exponential decay in Eu‐doped samples is clearly observed. Higher Eu doping results in further acceleration of the decay. In undoped GdCOB crystal, the lifetime of the Gd^{3+ 6}P_7/2 multiplet is 2.79 ms. The Eu^{3+ 5}D₀ decay kinetics monitored at 613 nm are rather constant. Numerical fitting of fully exponential curves, reveals lifetimes 2.7 ms for nanopowder and 2.5 ms for single crystal. The results suggest that this material may be used as a red phosphor in plasma display panels in nanopowder form because of strong excitation band of Eu³⁺ luminescence in the 160‐200 nm regions. Contrary to nanopowder sample, such an excitation band, attributed to the Gd³⁺–O^2– charge transfer was not observed in crystal obtained by the micropulling‐down method. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic properties of a Tm3+:Bi2TeO5 single crystal

Single crystal of bismuth tellurite Bi₂TeO₅ (BTO) doped with trivalent thulium (Tm³⁺) was grown by the Czochralski method and investigated by spectroscopic techniques (absorption, emission). Absorption and emission of the Tm:BTO crystal collected in the VIS‐IR spectral range are presented. Spectroscopic features were investigated as a function of the excitation light polarisation (E//X, Y, and Z axis of optical indicatrix) and sample temperature. The oscillator strength of the ³H₆ → ³F₄ transition at 1.7 μm was determined by numerical integration of the X, Y and Z polarised absorption spectra. The obtained values are: P_X = 4.7 × 10⁻⁶, P_Y = 6.8 × 10⁻⁶ and P_Z = 5.9 × 10⁻⁶ that gives a mean value P_mean = 5.8 × 10⁻⁶. Emission was observed from the ¹G₄ and ³H₄ levels. The ³H₄ and ¹G₄ excited state dynamics was studied. Decay curves and time constants of luminescence were collected at 5 and 300 K and analysed. The ³F₄ → ³H₆ luminescence at around 1.8 μm was too weak to be acquired from the low concentrated sample. However, based on optical data it was possible to estimate the radiative probability A_rad of this transition and the ³F₄ radiative lifetime. The resultant values are: A_rad = 668 ± 0.4 s⁻¹ and τ_rad = 1.5 ms. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,spectroscopic characterization and catalytic activity of cis-dioxidomolybdenum (VI) complexes with chiral tetradentate Schiff bases

New chiral mononuclear cis-dioxidomolybdenum (VI) complexes, MoO ₂ L ¹ –MoO ₂ L ¹⁰ , with tetradentate Schiff bases derived from various substituted salicylaldehydes and 1S,2S-(+)-2-amino-1-(4-nitrophenyl)-1,3-propanediol were synthesized. All complexes were characterized by elemental analysis, circular dichroism, electronic and IR spectroscopy. ¹H NMR and also two-dimensional (COSY, NOESY and gHSQC) NMR measurements made for MoO ₂ L ¹ –MoO ₂ L ¹⁰ complexes show that Schiff bases are coordinated to the MoO₂²⁺ cation, creating facial (fac) and meridional (mer) types of geometrical isomers. Moreover, catalytic activity studies were also performed for all complexes in asymmetric sulfoxidation of thioanisole and epoxidation of styrene, cyclohexene and two monoterpenes, i.e. S(−)-limonene and (−)-α-pinene, using aqueous 30% H₂O₂ or tert-butyl hydroperoxide as the oxygen source.     

Detection of PAH of molecular weight between 300 and 402 in airborne particulate matter by fused silica capillary GC and GC/MS

Gas chromatography (GC), low-voltage mass spectrometry (LV MS), and gas chromatography/mass spectrometry (GC/MS) have been used for detecting polycyclic aromatic hydrocarbons (PAH) of molecular weight between 300 and 402 in airborne particulate matter. Nearly 200 high molecular PAH separated by fused silica capillary columns could be characterized by their El mass spectra. The lack of reference substances precluded further structure elucidation.     

Simulation of polycrystalline ferroelectrics based on discrete orientation distribution functions

Ferroelectric materials exhibit a spontaneous polarization, which can be reversed by an applied electric field of sufficient magnitude. The resulting nonlinearities are expressed by characteristic dielectric and butterfly hysteresis loops. These effects are correlated to the structure of the crystal and especially to the axis of spontaneous polarization in case of single crystals. We start with a representative meso scale, where the domains consist of unit cells with equal spontaneous polarization. Each domain is modeled within a coordinate invariant formulation for an assumed transversely isotropic material as presented in [10], in this context see also [8]. In this investigation we obtain the macroscopic polycrystalline quantities via a simple homogenization procedure, where discrete orientation distribution functions are used to approximate the different domains. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization from a reactive pulse plasma

The Al₂O₃ unstable γ phase and A1N stable phase were crystallized from LTE pluse plasma. It was explained as the result of shifting the equilibrium of configurations s²p⁶ ? sp³ into the sp³ direction under influence of plasma.     

Sleep disturbances in highly stress reactive mice: Modeling endophenotypes of major depression

Background  

Neuronal mechanisms underlying affective disorders such as major depression (MD) are still poorly understood. By selectively breeding mice for high (HR), intermediate (IR), or low (LR) reactivity of the hypothalamic-pituitary-adrenocortical (HPA) axis, we recently established a new genetic animal model of extremes in stress reactivity (SR). Studies characterizing this SR mouse model on the behavioral, endocrine, and neurobiological levels revealed several similarities with key endophenotypes observed in MD patients. HR mice were shown to have changes in rhythmicity and sleep measures such as rapid eye movement sleep (REMS) and non-REM sleep (NREMS) as well as in slow wave activity, indicative of reduced sleep efficacy and increased REMS. In the present study we were interested in how far a detailed spectral analysis of several electroencephalogram (EEG) parameters, including relevant frequency bands, could reveal further alterations of sleep architecture in this animal model. Eight adult males of each of the three breeding lines were equipped with epidural EEG and intramuscular electromyogram (EMG) electrodes. After recovery, EEG and EMG recordings were performed for two days.     

Numerical calculation of overlap and kinetic integrals in prolate spheroidal coordinates

The efficient algorithm calculating the overlap and the kinetic integrals for the numerical atomic orbitals is presented. The described algorithm exploits the properties of the prolate spheroidal coordinates. The overlap and the kinetic integrals in ?³ are reduced to the integrals over the rectangular domain in ?², what substantially reduces the complexity of the problem. We prove that the integrand over the rectangular domain is continuous and does not have any slope singularities. For calculation of the integral over the rectangle any adaptive algorithm can be applied. The exemplary results were obtained by application of the adaptive Gauss quadrature. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008