Synthesis of 2-butyl-4,9-decadienoic and 2-butyl-4,9-dimethyl-4,9-decadienoic acids,structural analogues of cygerol

2-Butyl-4,9-decadienoic and 2-butyl-4,9-dimethyl-4,9-decadienoic acids, structural isomers of 2-cyclohexylgeranylacetic acid, which is an active component of the wound healing ointment cygerol, have been synthesized. Hydrocarbon chains C₁₀ have been obtained by the one-pot method of formation of long-chain hydrocarbons, namely, by the telomerization reaction of 1,3-dienes with nucleophiles catalyzed by palladium complexes. A heterogeneous palladium-zeolite catalyst has been used for the first time in telomerization of isoprene with piperidine.     

Trends in formation of the nanocrystalline structure and cationic ordering in the Dy2O3-HfO2 (1: 1) system

Evolution of the nanocrystalline structure of the complex oxide Dy₂HfO₅ in the course of thermal annealing at temperatures to 1600°C has been studied by a combination of X-ray and synchrotron methods, including traditional and anomalous X-ray diffraction, PDF, EXAFS, and SAXS. The changes in crystallite size upon annealing of the as-synthesized amorphous precursor have been analyzed in detail. The systematic distortions of a fluorite-type perfect crystal structure (space group $Fm\bar 3m$ ) related to the nonequivalence of the local environment of the Dy and Hf cations but not resulting in formation of a pyrochlore-type cationordered structure in this system have been examined.     

Local atomic environments and magnetic properties of copper binuclear azomethine complexes

Local atom environment in binuclear chelate Cu(II) complexes on the basis of azomethine ligands was investigated by extended X-ray absorption fine structure spectroscopy. The temperature magnetic measurements indicated ferro- or antiferromagnetic exchange in these complexes. A direct correlation between the character of the exchange magnetic interaction and the type of the ligand coordination in these complexes was established.     

Atomic structure of nickel phthalocyanine probed by X-ray absorption spectroscopy and density functional simulations

The local atomic structure of Ni in nickel phthalocyanine was studied by K-edge X-ray absorption fine structure spectroscopy. The obtained inter atomic nickel-nitrogen distance differs from the reference X-ray diffraction data so an additional study was performed within density functional theory framework. The justification of the used theoretical approach was provided by a comparison of theoretical free electron densities of states with experimental Ni K-edge X-ray absorption near edge spectra. The refined Ni local environment retain the reference structure of the molecule except for the length of Ni-N bond which increases to 1.90 Å.     

ChemInform Abstract: Explaining Stability of Transition Metal Carbides — and Why TcC Does Not Exist.

The formation of transition metal (M) carbides M_xC_y and trends of their stability are systematically investigated using the USPEX code within the DFT.     

Hybrid materials based on polymethylsilsesquioxanes containing Fe,Pt, and Fe–Pt metallic nanoparticles

New hybrid materials based on Pt, Fe, and Pt–Fe nanoparticles stabilized in a matrix of polymethylsilsesquioxane nanogel and ultrahigh molecular weight polyethylene (UHMWPE) were prepared. Metal vapor synthesis was used to produce mono- and bimetallic nanoparticles. It was shown that organosilicon nanogel effectively stabilizes Pt nanoparticles with an average size of 0.9 nm. Using the nanogel results in the formation of superparamagnetic Fe particles 3–5 nm in size that consist of ferromagnetic Fe⁰ core and antiferromagnetic shells of Fe oxides. It is established that using an organosilicon matrix in the formation of Pt-Fe/UHMWPE systems helps reduce the average particle size of Fe in the material from 6.5 to 4.5 nm and narrow their particle size distribution. The composition, magnetic and electronic characteristics of the nanocomposites are studied via transmission electron microscopy, X-ray photoelectron spectroscopy, Mössbauer spectroscopy, XANES, and EXAFS.     

Short- and long-range order balance in nanocrystalline Gd2Zr2O7 powders with a fluorite-pyrochlore structure

A series of nanocrystalline Gd₂Zr₂O₇ powders has been studied using a combination of X-ray diffraction and X-ray spectroscopy with synchrotron radiation. It has been shown that isothermal annealing of an X-ray amorphous mixed hydroxide first leads to the formation of an oxide nanomaterial with a defect fluorite structure and clearly pronounced nonequivalence of the local environment of the Gd³⁺ and Zr⁴⁺ ions. Increasing heat treatment temperature results in initiation and growth of nanodomains with pyrochlore-type superstructure ordering of cations inside bulkier crystallites of defect fluorite. To adequately describe the evolution of the real nanocrystalline structure of gadolinium zirconate, a combination of X-ray structural methods sensitive to the averaged crystal structure and local atomic structure should be used.     

Solid-state near-edge X-ray absorption fine structure spectra of glycine in various charge states

The experimental solid-state near-edge X-ray absorption fine structure spectra for a series of glycine-related samples including alpha-glycine, beta-glycine, glycinium chloride, glycinium trifluoroacetate, and sodium glycinate at the C, N, and O K-edges measured under identical conditions are reported and compared. An assignment of spectral features for alpha-glycine is proposed on the basis of extended theoretical simulations of polarization-dependent spectra performed within the real-space multiple-scattering formalism explicitly taking into account the intermolecular environment of a glycine molecule in a crystal.     

Studying the structure of siloxane-urethane-ethylene oxide block copolymers

The structure of siloxane-urethane-ethylene oxide block copolymers is studied by means of atom force microscopy (AFM) and scanning electron microscopy (SEM). The degree of copolymer crystallinity is determined by X-ray diffraction. A correlation between the obtained results is established.     

EXAFS study of copper complexes with azomethinic ligand environment

A series of copper metallochelates C₂₂H₁₈CuN₄O₂ X (X = Se, S, O) as models of active centers of natural metalloproteins have been synthesized on the basis of new azomethine ligand systems. The structure of the complexes has been studied by extended X-ray absorption fine-structure spectroscopy. It is shown that, in the metallochelates with X = Se or S, one azomethine chalcogen-containing ligand undergoes tridentate interaction with copper ions, while the other ligand is an acetate group. As a result, a complex with the N₂O₂ X environment is formed, where one of the oxygen atoms of the acetate group is at a large distance from the metal ion: R = 2.56–2.68 Å. For the metallochelate with X = O, coordination of the acetate group by a copper ion is found to be absent, and only interaction with azomethine ligands having average Cu-N/O distances R = 1.96–2.04 Å is observed.