Influence of ligand coordination of cobalt ions on structural properties of ZnO-ZnF2-B2O3 glass system by means of spectroscopic studies

The glasses of the composition 10ZnO-30ZnF₂-60B₂O₃ doped with different concentrations of CoO were prepared. Differential scanning calorimetric (DSC) studies, optical absorption, photoluminescence and infrared spectra of these glasses have been carried out. DSC studies have indicated that the resistance of the glass against devitrification increases with the increase in the concentration of CoO. Optical absorption spectra have exhibited one octahedral band due to ⁴T_1g(F)→²T_1g(H) and two tetrahedral bands due to ⁴A₂(⁴F)→⁴T₁(⁴P) ⁴A₂(⁴F)→⁴T₁(⁴F) transitions of Co²⁺ ions at about 525, 570 and 1400 nm, respectively. As the concentration of CoO is increased the tetrahedral bands are observed to grow at the expense of octahedral band. The luminescence spectra have exhibited two emission bands in the spectral regions of 600-700 nm and 800-900 nm due to ⁴T₁(⁴P)→⁴A₂(⁴F) and ⁴T₁(⁴P)→⁴T₂(⁴F) tetrahedral transitions of Co²⁺ ions, respectively. With the increasing content of cobalt ions in the glass matrix, the half width and intensity of these bands are observed to increase. The analysis of the results of these two spectra coupled with IR spectra has indicated that as the concentration of CoO is increased in the glass matrix, the tetrahedral occupancy of cobalt ions dominates over the octahedral occupancy and increase the rigidity of the glass network.     

Improving microwave dielectric properties of La2.98/3Sr0.01(Mg0.5Sn0.5)O3 ceramics with CuO additive

The microwave dielectric properties of CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were investigated with a view to their application in microwave devices. CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method. The X-ray diffraction patterns of CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics exhibited no significant variation of phase with sintering temperature. By adding 0.75 wt.% CuO, a dielectric constant of 20.07, a quality factor (Q × f) of 63,000 GHz, and a temperature coefficient of resonant frequency τ_f (−77.0 ppm/°C) were obtained when La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were sintered at 1500 °C for 4 h.     

Exchange bias behavior of monodisperse Fe3O4/γ-Fe2O3 core/shell nanoparticles

We have carried out systematic studies on well-characterized monodisperse Fe₃O₄/γ-Fe₂O₃ core/shell nanoparticles of 2-30 nm having a very narrow size distribution and possessing a uniquely mono-layer of surface γ-Fe₂O₃. This unique core-shell structure, probably having a disordered magnetic surface state, leads us to three key observations of unusual magnetic properties: i) a very large magnetic exchange anisotropy reaching over 7 × 10⁶ erg/cm³ for the smaller particles, ii) exchange bias behavior in the magnetization data of the core/shell Fe₃O₄/γ-Fe₂O₃ nanoparticles, and iii) the temperature dependence of the coercive field following an unusual exponential behavior.     

Determination of elastic, piezoelectric, and dielectric constants of an R:BaTiO3 single crystal by Brillouin scattering

From the sound velocity measured using the Brillouin scattering technique, the elastic, piezoelectric, and dielectric constants of a high-quality monodomain tetragonal Rh：BaTiO3 single crystal are determined at room temperature. The elastic constants are in fairly good agreement with those of the BaTiO3 single crystal, measured previously by Brillouin scattering and the low-frequency equivalent circuit methods. However, their electromeehanical properties are significantly different. Based on the sound propagation equations and these results, the directional dependence of the compressional modulus and the shear modulus of Rh：BaTiO3 in the （010） plane is investigated. Some properties of sound propagation and electromechanical coupling in the crystal are discussed.     

Improvement of dielectric tunability and loss tangent of (Ba,Sr)TiO3 thin films with K doping

Ba_0.6Sr_0.4TiO₃ thin films doped with K were deposited on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method. The structure, surface morphology, and dielectric and tunable properties of Ba_0.6Sr_0.4TiO₃ thin films have been studied in detail. The K content in Ba_0.6Sr_0.4TiO₃ thin films has a strong influence on the material's properties including surface morphology, dielectric and tunable properties. It is found that the Curie temperature of K-doped Ba_0.6Sr_0.4TiO₃ films shifts to higher values compared with that of undoped Ba_0.6Sr_0.4TiO₃ thin films, which leads to a dielectric enhancement of K-doped Ba_0.6Sr_0.4TiO₃ films at room temperature. At the optimized content of 0.02 mol, the dielectric loss tangent is reduced significantly from 0.057 to 0.020. Meanwhile, the tunability is enhanced obviously from 26% to 48% at the measured frequency of 1 MHz and the maximum value of the figure of merit is 23.8. This suggests that such films have potential applications for tunable devices.     

Intense up-conversion emissions of Yb3+/Dy3+ co-doped Al2O3 nanopowders prepared by non-aqueous sol—gel method

Yb³⁺/Dy³⁺ co-doped Al₂O₃ nanopowders have been prepared by the non-aqueous sol-gel method and their up- conversion photoluminescence spectra are measured under excitation by 980-nm semiconductor laser. The results show that there are comparatively abundant spectra of up-conversion emissions centered at 378, 408, 527 and 543, and 663 nm, corresponding to ⁴G_9/2 → ⁶H_13/2, ⁴G_9/2 → ⁶H_11/2, ⁴I_15/2 → ⁶H_13/2, and ⁴F_9/2 → ⁶H_11/2 transitions of Dy³⁺, respectively. Two-photon and three-photon processes are involved in ultraviolet, violet, green, and red up-conversion emissions. The energy transition between Yb³⁺ and Dy³⁺ is discussed.     

TDDFT方法研究两个基于Michael反应的氰离子传感器的不同传感机理

利用含时密度泛函方法计算了两个具有类似结构的传感器分子a和b的氰离子传感机理. 结果证实,传感器分子a在基态和S₁态下有着类似的几何构型. 在质子性溶剂水中,氰离子能与传感器分子a发生Michael加成反应,水溶液提供质子,促使最终的α,β-加成产物的生成. 而此加成产物在S₁态下会发生构型变化,导致荧光的猝灭. 传感器分子b的S₁态与基态构型相比发生了构型扭转,并且在非质子性溶剂乙腈中,也可以与氰离子发生Michael加成反应. 由于乙腈     

How glucosylation triggers physical–chemical properties of curcumin: an experimental and theoretical study

In the present study, we investigate the structures of glucosylated curcumin derivatives with DFT at B3LYP/6‐31G* level. A conformational analysis is performed in order to determine the conformational minimum (GS) and rotational transition state (TS) of curcumin derivatives and then their electronic features are evaluated. HOMO and LUMO frontier orbitals and maps of electron density potential (MEPs) are plotted and compared. In order to correlate their predicted spectroscopic properties with IR, UV–vis and NMR experimental data we extended the theoretical study on electronic properties to different solvents (H₂O, MeOH, ACN, DMSO). The main finding is that the curcuminic core maintains the same geometrical and electronic structures in all compounds miming the metal coordination capability showed by curcumin. Therefore, we may confirm that the presence of glucose does not affect the electronic properties of the derivatives. Copyright © 2010 John Wiley & Sons, Ltd.     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

Growth of β-Ga2O3 nanorods by ammoniating Ga2O3/V thin films on Si substrate

This paper reports that/3-Ga2O3 nanorods have been synthesized by ammoniating Ga2O3 films on a V middle layer deposited on Si（111） substrates. The synthesized nanorods were confirmed as monoclinic Ga2O3 by x-ray diffraction,Fourier transform infrared spectra. Scanning electron microscopy and transmission electron microscopy reveal that the grown β-Ga2O3 nanorods have a smooth and clean surface with diameters ranging from 100 nm to 200 nm and lengths typically up to 2μm. High resolution TEM and selected-area electron diffraction shows that the nanorods are pure monoclinic Ga2O3 single crystal. The photoluminescence spectrum indicates that the Ga2O3 nanorods have a good emission property. The growth mechanism is discussed briefly.