Parahydrogen-Induced Polarization in Heterogeneous Hydrogenations over Silica-Immobilized Rh Complexes

The use of heterogeneous catalysts for parahydrogen-induced polarization (PHIP) of nuclear spins opens new horizons for production of hyperpolarized substances. Immobilization of homogeneous hydrogenation catalysts is a promising approach for designing the efficient heterogeneous catalytic systems capable of PHIP generation. Herein, we study the formation of PHIP in the gas-phase and in the liquid-phase hydrogenations of propyne and propylene catalyzed by silica-immobilized Rh complexes synthesized by the ligand-exchange anchoring of the Wilkinson’s complex RhCl(PPh₃)₃, the binuclear complex Rh₂Cl₂(C₈H₁₂)₂ and the cationic complex [Rh(C₈H₁₂)₂]⁺[BF₄]^? to the phosphine-modified silica gel. We consider the stability and the mechanistic aspects of the hydrogenation over the immobilized Wilkinson’s catalyst in terms of PHIP observation. Using a PASADENA (parahydrogen and synthesis allow dramatically enhanced nuclear alignment) effect, it is found, in particular, that liquid-phase propyne hydrogenation over the immobilized Wilkinsons’s catalyst at 70°C proceeds in a stable regime with a stereoselective cis addition of a hydrogen molecule, while in the gas phase at the same temperature the hydrogenation stereoselectivity is observed only for a short time after the reaction is started, and then the catalyst rapidly loses its activity. The reasons of the catalyst deactivation are discussed based on the literature data, the results of infrared spectroscopy study, and the comparison to the behavior of the immobilized binuclear and cationic Rh complexes. In addition, it is shown that the immobilized Wilkinson’s catalyst is reduced as temperature increases in the range of 90–130°C, as confirmed by X-ray photoelectron spectroscopy.     

Effect of montmorillonite on the structure and properties of powder epoxy compounds for polymeric coatings

Procedures for preparing nanomodified powder epoxy compounds with various concentrations of montmorillonite were examined. The dispersion of particles in the epoxy oligomers was studied by X-ray diffraction analysis and electron microscopy. The influence of the content of the modifiers on the physicomechanical properties of cured block specimens was analyzed.     

Complete assignment of the 1H and 13C NMR spectra of antimicrobial 4‐arylamino‐ 3‐nitrocoumarin derivatives

Herein, we describe the synthesis and complete assignment of the ¹H and ¹³C NMR chemical shifts of a series of antimicrobial 4‐arylamino‐3‐nitrocoumarin derivatives based on a combination of ¹H and ¹³C NMR, ¹H‐¹H‐COSY, NOESY, HSQC and HMBC experiments. Conformational effects upon the chemical shifts of the coumarin moiety arising from the anisotropy of the aryl side group are briefly discussed. This study provides the first complete and fully assigned NMR data for this important group of antimicrobial compounds and bridges the gap existing in the literature with regard to NMR structural data for 4‐arylamino‐3‐nitrocoumarins. Copyright © 2010 John Wiley & Sons, Ltd.     

Crystal Structure of Bis -(2,2′-bipyridine-N,N′)-(dicyanamide-N)-copper(II) Tricyanomethanide. Electronic and Structural Parameters Describing the Shape of Coordination Polyhedra in Five-Coordinated Copper(II) Compounds

 The structure of the new compound [Cu(bpy)₂N(CN)₂]C(CN)₃ (6) is compared with thestructures of six copper(II) coordination compounds with phenanthroline or bipyridine ligands and N-donor pseudohalide anions: [Cu(phen)₂NCS]C(CN)₃ (1), [Cu(bpy)₂NCS]C(CN)₃ (2), [Cu(phen)₂NCS]ONC(CN)₂ (3), [Cu(phen)₂N(CN)₂]C(CN)₃ (4), [Cu(bpy)₂C(CN)₃]C(CN)₃ (5), and [Cu(bpy)₂NCO]C(CN)₃ (7). The Cu(II) atoms in all above compounds are five-coordinated with an N-donor atom of the pseudohalide anion located in the equatorial plane of a deformed trigonal bipyramid. The shape of the coordination polyhedra and the degree of trigonal bipyramidal distortion towards a tetragonal pyramid are discussed and described using one electronic and several structural criteria which are discussed and compared.     

Magnetic superlattices and multilayers

We briefly review the active areas of current research in magnetic superlattices, emphasizing later years. With recent widening use of advanced technologies, more emphasis has been made on quantitative atomic level chemical and structural characterization. Examples where the multilayer structure has been controlled, characterized and correlated with the physical properties are discussed. The physical properties are categorized according to the complexity of a structure needed to observe a particular effect. We outline a number of general important unsolved problems, which could considerably benefit from theoretical and experimental input. An extensive list of magnetic multilayer materials is provided, with references to recent publications.     

Thermal Behavior of Hexogen Phlegmatized with Montan Waxes

Hexogen can be used pressed only if its crystals are covered by some polymeric material [1], either natural or artificial. Montan waxes, as natural polymeric materials, were used for the phlegmatization. The melting process of seven types of waxes was analyzed by differential scanning calorimetry. The thermal decomposition processes of hexogens and phlegmatized hexogens were investigated by dynamic differential scanning calorimetry and dynamic thermogravimetric analyses. Kinetic parameters of the decomposition processes of hexogens were evaluated by using data obtained from differential scanning calorimetric curves. This revised version was published online in August 2006 with corrections to the Cover Date.     

The generator coordinate method for tertiary reactions of light composite nuclei

A theory of nuclear reactions with three composite fragments in a final channel, based on a variational principle of Kohn type and the generatorcoordinate (GC) representation of the trial function, is proposed and tested numerically. The Hamiltonian operator is microscopic, and the GC basis enables the inclusion of any rearrangement channels. The trial function is totally antisymmetrized and exactly projected on the eigenstates of the angular momentum and parity operators. It consists of a correlation term and channel terms which have to be specified only in the regions not covered by the correlation term, in which a pair of fragments is not close together. The channel relative-motion wave functions, from which the GC representation of the channel terms is obtained, are calculated from an asymptotic series. The three-fragment part of the trial function is expanded in hyperspherical harmonics. In this paper we study primarily the convergence of the reaction parameters with respect to the GC basis applying the formalism to the reaction³He(³He,pp)⁴He without inclusion of the Coulomb interaction. The part of the rearrangement differential corss section corresponding to well-separated final fragments is compared to experimental data.