Preparation of Y2O3:Eu thin films by excimer-laser-assisted metal organic deposition

Europium-doped yttrium oxide (Y₂O₃:Eu) thin films were successfully deposited on quartz and ITO/glass substrates by excimer-laser-assisted metal organic deposition (ELAMOD) at low temperatures. The effects of laser wavelength and thermal temperature on the films’ crystallinity and photoluminescence properties were investigated. Films irradiated by an ArF laser at 80 mJ/cm² and 400–500°C were highly crystallized compared with those prepared by thermal MOD. In contrast, when the film was irradiated by a KrF laser at 500°C, no crystalline Y₂O₃:Eu was formed. The Y₂O₃:Eu film irradiated by the ArF laser at 80 mJ/cm² and 500°C showed typical PL spectra of Eu³⁺ ions with cubic symmetry and a ⁵D₀→⁷F₂ transition at ∼612 nm. The PL intensity at 612 nm was much higher for the film prepared with ELAMOD than for that prepared by the thermal-assisted process, and the photoemission intensity of the film prepared with ELAMOD strongly depended on the substrate material.     

Iron-Chloranilate Intercalation Compounds: Synthesis,Crystal Structures,and Thermal Properties

Abstract

Hydrogen bond supported new iron-chloranilate assemblies, {(Hpy)[Fe(CA)₂(H₂O)₂](H₂O)}_n (py = pyridine, H₂CA = chloranilic acid, C₆H₂O₄Cl₂) (1), and [(phz)₂[Fe(CA)₂(H₂O)₂](H₂O)₂]_n (phz = phenazine, C₁₂H₈N₂) (2) have been synthesized and characterized. Compound 2 crystallizes in the monoclinic, space group C2/m (#12), with a= 29.135(6) Å, b= 16.886(6) Å, c = 15.017(5) Å, ß = 165.907(1)°, V= 1798(2) ų, Z = 2. In both the compounds two chloranilate dianions and two water molecules are coordinated to the iron ion making anionic monomers [Fe(CA)₂(H₂O)₂]^?, which are the building blocks of the compounds. The coordination environment around the iron ion in the building block is a distorted octahedron, where two water molecules sit on the trans position to each other. [Fe(CA)₂(H₂O)₂]^? anions form common layer structures, supported by hydrogen bonds. Hpy⁺ are intercalated in between the layers of 1 by electrostatic and hydrogen bonding interactions and phz are intercalated in that of 2 by electrostatic interactions. DSC traces of 1 show anomaly at 174 K, indicating phase transition in the compound.     

Markov Chain Approximations to Nonsymmetric Diffusions with Bounded Coefficients

We consider a certain class of nonsymmetric Markov chains and obtain heat kernel bounds and parabolic Harnack inequalities. Using the heat kernel estimates, we establish a sufficient condition for the family of Markov chains to converge to nonsymmetric diffusions. As an application, we approximate nonsymmetric diffusions in divergence form with bounded coefficients by nonsymmetric Markov chains. This extends the results by Stroock and Zheng to the nonsymmetric divergence forms. © 2012 Wiley Periodicals, Inc.     

Achiral Trisubstituted Thioureas as Secondary Ligands to CuI Catalysts: Direct Catalytic Asymmetric Addition of α‐Fluoronitriles to Imines

Thioureas have emerged as effective hydrogen‐bonding catalysts over the last two decades, and they are broadly utilized in asymmetric catalysis. We report that achiral trisubstituted thioureas function as beneficial secondary ligands to Cu^I catalysts, thereby enabling highly diastereo‐ and enantioselective addition of α‐fluoronitriles to imines. The structure of the thiourea significantly affects the reaction outcome, and kinetic experiments indicate that the thioureas enhance the stereocontrol by binding to the Cu^I complex. The reaction products can be readily transformed into valuable β‐amino acid derivatives bearing a fluorinated tetrasubstituted stereogenic center.     

Electronic absorption and emission spectra of Alq3 in solution with special attention to a delayed fluorescence

Tris(8-quinolinolato)aluminum(III) (Alq₃) shows electronic absorption bands at 378, 360 (in a 1:1 mixed solvent of methanol and ethanol (ME) at 77 K), 334, 316, 300, 263, 255.8, and 233 nm in ethanol at room temperature. According to the polarized fluorescence excitation spectrum together with MO calculations, for instance, the 360 nm band is assigned to an LL CT transition (an intramolecular charge transfer transition between two ligands), and the 378 nm band to an LM/ML CT one (an intramolecular charge transfer transition between ligand and metal). Alq₃ shows a broad fluorescence band peaking at around 478 nm in the ME matrix at 77 K. The emission spectrum measured with a phosphoroscope has two emission bands at 567 and 478 nm. The 567 nm band accompanies vibronic bands at 578 and 605 nm, being safely assigned to a phosphorescence of Alq₃. The lifetimes of the 478 and 567 nm bands are both 5.4 ms. The lifetime of the 478 nm band together with the band position and its band shape indicate that this band can be assigned to a delayed fluorescence.     

Topological aspects of excitons in artificial structure

The exciton properties of thin nanotube structures are investigated theoretically. Anisotropic size dependencies have been found in the exciton binding energy, the kinetic energy for the relative motions of an electron and a hole, and the wavefunction. These anisotropies arise from the different boundary conditions in the tube-length and circumferential directions, namely, the topological features of nanotubes. We also found that it is possible to change the topology of exciton wavefunctions by varying the tube-length and the tube-radius. These findings suggest that the optical properties of nanotubes such as oscillator strength or nonlinear susceptibilities can be controlled by tuning the structural parameters, thus yielding a novel guiding principle for designing optical functional materials.     

Thermal extrusion of cellulose using hydroxypropyl methylcellulose

Cellulose - Hydroxypropyl methylcellulose (HPMC), a cellulose derivative, is highly water soluble, viscoelastic, and thermoplastic. However, the thermoplasticity of HPMC has not yet been studied in...     

Synergistic Biophysical Techniques Reveal Structural Mechanisms of Engineered Cationic Antimicrobial Peptides in Lipid Model Membranes

In the quest for new antibiotics, two novel engineered cationic antimicrobial peptides (eCAPs) have been rationally designed. WLBU2 and D8 (all 8 valines are the d -enantiomer) efficiently kill both Gram-negative and -positive bacteria, but WLBU2 is toxic and D8 nontoxic to eukaryotic cells. We explore protein secondary structure, location of peptides in six lipid model membranes, changes in membrane structure and pore evidence. We suggest that protein secondary structure is not a critical determinant of bactericidal activity, but that membrane thinning and dual location of WLBU2 and D8 in the membrane headgroup and hydrocarbon region may be important. While neither peptide thins the Gram-negative lipopolysaccharide outer membrane model, both locate deep into its hydrocarbon region where they are primed for self-promoted uptake into the periplasm. The partially α-helical secondary structure of WLBU2 in a red blood cell (RBC) membrane model containing 50 % cholesterol, could play a role in destabilizing this RBC membrane model causing pore formation that is not observed with the D8 random coil, which correlates with RBC hemolysis caused by WLBU2 but not by D8.     

Nucleophilic and Electrophilic Activation of Non‐Heteroaromatic Amides in Atom‐Economical Asymmetric Catalysis

Recent advances in catalytic asymmetric carbon–carbon bond‐forming reactions of non‐heteroaromatic amide substrates are highlighted. Among carbonyl compounds, amides have received limited attention in catalytic asymmetric transformations mainly owing to their lower reactivity. Amides are reluctant to form enolates for nucleophilic addition, and α,β‐unsaturated amides exhibit diminished electrophilicity at the β‐carbon. Recent advances in asymmetric catalysis rendered these amides amenable to enantioselective reactions with perfect atom economy, producing synthetically useful chiral building blocks. This Minireview summarizes recent developments in the field.     

Effects of meniscus on the directional growth of potassium niobate single crystals

The study of meniscus effects on the directional growth of single crystals of potassium niobate (KNbO₃) with a [110]_pc oriented seed by the top-seeded-solution-growth technique has been described. The directional growth of KNbO₃ single crystals has been illustrated for different crystallographic orientations of the crystal. Experimental results show that the shape of the solution flux meniscus, which is determined by a number of growth parameters, has a significant effect on growth rates on different 100_pc, 010_pc and 001_pc type surfaces. Findings based on this work enable one to select a dominant growth direction and hence to engineer the geometrical shaping of resultant KNbO₃ single crystals through careful control of growth parameters. Maximum crystal dimensions for the grown KNbO₃ along [100]_pc and [001]_pc achieved in this work are 34.0 and 31.2 mm, respectively.