Properties of the electronic density of states in TiO<Subscript>2</Subscript> nanoparticles surrounded with aqueous electrolyte

Results on the density of sates of nanostructured TiO₂ as a function of particle size and temperature are reported. In TiO₂ nanoparticles with a mean diameter 10 nm, the density of states (DOS) is strongly temperature-dependent, indicating a rearrangement of the bandgap states in which the exponential energy parameter (width of the distribution) increases from 0.080 to 50 °C. For nanoparticles with mean diameters of 20 and 30 nm the DOS is much closer to an exponential distribution, and is much less sensitive to temperature variations. It is suggested that nanometer confinement has a significant influence on the density of electronic states for 10-nm particles, while band tailing is similar to that occurring in bulk semiconductors for the larger particles.

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Core-shell structured electrode materials for lithium ion batteries

Recent progress in studies of several types of core-shell structured electrode materials, including TiO₂/C, Si/C, Si/SiO _x , LiCoO₂/C, and LiFePO₄/C nanocomposites, including details of their preparation and their electrochemical performance is briefly reviewed. Results clearly show that the coating shell can effectively prevent the aggregation of the nanosized cores, which are the electrochemically active materials. In addition, the diffusion coefficients of lithium ions can be increased, and the reversibility of lithium intercalation and deintercalation is improved. As a result, the cycling behavior is greatly improved. The reviewed results suggest that core-shell nanocomposites are a good starting point for further development of new promising electrode materials.

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Core-shell effects of functionalized oxide nanoparticles inside long-range meso-ordered spray-dried silica spheres

Core-shell and homogeneous distributions of functionalized cerium oxide nanoparticles within spray-dried mesostructured silica spheres are achieved by modification of synthesis parameters such as the templating agent and nanoparticle capping functions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

One-step electrochemical synthesis of pure poly(2,5-dicyano-p-phenylenevinylene) films

In this communication we describe the electrochemical synthesis of poly(2,5-dicyano-p-phenylenevinylene) (DCNPPV) polymer films on indium tin oxide substrates. We investigate the purity, morphology, absorption and emission properties of the film. The purity was checked by infrared spectroscopy. The film formed presented spectroscopic purity equivalent to the chemically prepared PPV that was dialyzed for one week. Scanning electron microscopy of the surface revealed a grain-like morphology. The absorption and emission spectra showed absorption and emission bands at 420 nm and 575 nm, respectively, with the absorption onset at 422 nm, which corresponds to an energy gap of 2.25 eV. The electrochemical determination of the energy gap gives 2.05 eV, thus quite close to the optical energy gap at the onset of absorption. The EA and IP were determined by electrochemical measurements and are 3.46 eV and 5.51 eV, respectively.

Semicrystalline morphology in thin films of poly(3-hexylthiophene)

The thermodynamic phase behavior and the morphology in thin films of poly(3-hexylthiophene) (P3HT) has been studied using calorimetry, X-ray scattering, and scanning force microscopy (AFM). Around 225 °C a phase transition from the crystalline state to a layered, liquid crystalline structure occurs in regioregular P3HT, while the regiorandom counterpart material is disordered at all temperatures and displays a glass transition temperature T_g–3 °C. Regioregular P3HT is semicrystalline and forms needle or plate like crystallites which in solution cast thin films are oriented with respect to the substrate. Films produced by spin coating display a non-equilibrium structure with reduced order and orientation. Annealing of these films in the liquid crystalline state leads to the formation of a morphology similar to the one observed in solution cast films.

The Physical and Electronic Structure of M<Subscript>2</Subscript> Quadruply Bonded Complexes: A Density Functional Theory Study

The electronic structures and the physical properties (vertical excitation energies, vibrational stretching frequencies, and bond lengths) of a variety of M–M quadruply bonded (M = Mo, W) complexes are investigated using density functional theory (DFT). By utilizing a variety of pure and hybrid exchange-correlation (XC) functionals and a number basis sets, we are able to recommend a theoretical methodology for most efficiently probing the electronic structures of homoleptic M₂(O₂CR)₄ and bridged M₂(O₂C-X-CO₂)M₂ (R = organic group, typically H; X = conjugated organic group) complexes.

Cytocompatibility of surface ground PE doped with calcium salt of 6-carboxycellulose

We studied the physical–chemical properties of polyethylene (PE) films doped with calcium salt of 6-carboxycellulose (Ca-oxy) in concentrations 0–20 wt.% and their interactions with cells. The interaction between the PE/Ca-oxy composite film and 3T3 cells has not been described so far. Modification by surface grinding to enhance material cytocompatibility was studied. The surface wettability of doped films was tested by contact angle measurements and the surface morphology by SEM microscopy and profilometry. Adhesion and proliferation of tissue cells (3T3 mouse fibroblasts) were studied in vitro on pristine and ground doped PE films. The ground samples have a higher contact angle values and the number of proliferated cells is greater on the ground samples than on pristine ones. The presence of Ca-oxy in PE film increases the adhesion of 3T3 cells on the doped substrate and on ground samples adhere more cells than on pristine ones.

Blue-emitting mesoporous films prepared via incorporation of luminescent Schiff base zinc(II) complex

Highly fluorescent materials have been prepared by incorporation of a zinc complex in mesoporous silica thin films with ordered pore structure. The zinc complex has been introduced into the mesoporous materials via impregnation in an ethanol solution. The incorporation into the films has been monitored by UV–Vis, Fourier transform infrared spectroscopy and spectroscopic ellipsometry. After 18 h of immersion in the doping solution the films showed strong blue emission, increase in the refractive index. Leaching experiments performed by immersing the samples in ethanol or tetrahydrofuran have shown that the chromophore is retained in the porous matrix.

Chemistry,commentary and community: Discussion of “The NaDyBr<Subscript>4</Subscript> complex: its molecular structure and thermodynamic properties” by Varga and Hargittai

The molecular geometries, relative stabilities, binding energies, and dissociation energies of NaDyBr₄ and its molecular ion are discussed. Both the bidentate and tridentate isomers are stable for the neutral species, while only the bidentate form is stable for NaDyBr₄ ⁺.

Food anaphylaxis

    Figure Avoidance is the primary measure in food allergy confirmed

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A comparative study of hydrothermal and sol–gel methods in the synthesis of MnO<Subscript>2</Subscript> nanostructures

In this work, MnO₂ nanostructure powders with different crystalline phases have been successfully prepared by hydrothermal and sol–gel methods. The obtained products were characterized by XRD and SEM techniques and their crystallographic phases and morphological properties compared. Results showed that α-MnO₂, β-MnO₂, and δ-MnO₂ nanorods were synthesized by hydrothermal method and γ-MnO₂ polymorph was obtained by sol–gel method.

Chemistry, commentary, and community: discussion of “an examination of the vaporization enthalpies and vapor pressures of pyrazine, pyrimidine, pyridazine, and 1,3,5-triazine” by Lipkind and Chickos

Vaporization enthalpies for the isomeric diazines were discussed within the context of recent measurements and estimation techniques. It is suggested that pyridazine shows enigmatic behavior.

Branched trichain sulfosuccinates as novel water in CO2 dispersants

A series of highly branched trichain sulfosuccinate surfactants have been synthesized and studied in condensed CO₂ and aqueous environments. Aqueous critical micelle concentrations (CMCs) showed a general trend of increasing CMC with decreasing chain length, whereas increased branching appeared to increase solubility in CO₂ and aid the dispersion of water. Near infrared spectra confirmed observed cloud with a large increase in solubility above the cloud pressures in this solvent.

A novel Ce<Superscript>III</Superscript>-cyclam type complex and its redox chemistry in aqueous solutions

A new Ce^III complex was synthesized by mixing the ligand “dioxocyclam” with Ce^III ions at pH 8.0 and its redox properties were investigated.

Modeling of solvent viscosity effects on the electroreduction of Pt(II) aquachlorocomplexes

Solvent dynamics effects on the electroreduction of [PtCl₃(H₂O)]⁻ at a mercury electrode are explored in the framework of Sumi–Marcus model using an efficient computational scheme. According to results of density functional calculations, the second electron transfer step may be regarded as rate controlling. The nonmonotonous influence of solvent viscosity on the reaction rate is predicted and explained in terms of the saddle point avoidance. The results of model calculations are employed to interpret experimental data reported earlier in the literature.

Encapsulating of single quantum dots into polymer particles

Single semiconductor quantum dots were embedded into polymer particles with diameters below 0.1 μm by an emulsion polymerization procedure or via a secondary dispersion approach. The photoluminescence properties of the nanocrystals are retained upon encapsulation, as demonstrated by fluorescence confocal microscopy.

Electrochemistry and catalytic behavior of immobilized binuclear complexes of copper(II) and nickel(II) with Robson type ligand

Various systems containing immobilized binuclear copper(II) and nickel(II) complexes with Robson type ligand ([M₂L]Cl₂) are studied and compared in relation to catalysis of hydrogen peroxide reduction. Molecular complexes adsorbed on mercury and gold, crystalline complexes immobilized in the carbon paste electrode, and complex species entrapped into polyphenol-modified gold electrodes are considered. Electrocatalysis is assumed to result from the formation of H₂O₂–[M₂L]Cl₂ adduct, not from mediating redox transformations. Possible geometry of the formed reaction layers supporting adduct formation is discussed.

Preparation, structural, and optical features of two-dimensional cross-linked DNA/gold-nanoparticle conjugates

The formation and the optical features of two-dimensional aggregates formed by DNA-directed immobilization and cross-linking of bifunctional DNA–gold nanoparticles at flat gold substrates are analyzed. The samples are structurally characterized by atomic force microscopy to evaluate the particle size, the particle densities, and the degree of aggregation. The optical characteristics determined by UV/visible measurements are correlated with the structural features observed.

Kinetics of substitution at [tris(3,5-dimethylpyrazolyl)-hydroborato]molybdenum nitrosyl dihalides by alcohols and by aniline

The kinetics of substitution by alcohols and by aniline at [tris(3,5-dimethylpyrazolyl)hydroborato]molybdenum nitrosyl dihalides in toluene solution at 298.2 K and at atmospheric pressure are reported and interpreted in terms of an associative mechanism.

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Comparison of synthetic procedures for the preparation of sol–gel derived phenoxy-silica hybrid materials

Novel phenoxy-silica hybrid materials (with 3 wt.% SiO₂) have been synthesized using different synthetic procedures. Differential scanning calorimetric (DSC) (T_g), FT-IR and transmission electron microscopy (TEM) results, as well as thermal and mechanical properties, are reported for these hybrids, which can be classified into three different groups, depending on the number of components synthesized in situ. Best results in terms of homogeneity (TEM) and mechanical properties have been obtained when the sol–gel process has been carried out in the presence of a phenoxy resin modified with a pendant alkoxysilane monomer.