Experimental and theoretical study on gas-phase ion/molecule reactions of silver trimer cation, Ag3+, with 12-crown-4

The reaction mechanisms of silver trimer cation, Ag3+, with 12-crown-4 (12C4) were studied experimentally and theoretically. Using a cylindrical ion trap time-of-flight mass spectrometer, gas-phase ion/molecule reactions of Ag3+ with 12C4 were observed. Metal-ligand complexes of [Ag(12C4)]+, [Ag3(12C4)]+ and [Ag3(12C4)2]+, and of [Ag(12C4)2]+ and [Ag3(12C4)3]+, were observed as the reaction intermediates and terminal products, respectively. The formations of the [Ag12C4]+ and [Ag(12C4)2]+ complexes indicated that the neutral dimer (Ag2) had been eliminated from the trimer cation. From the results of ab initio calculations at the HF/LanL2DZ level of theory and the experiments, it is suggested that three 12C4 molecules can attach to Ag3+ through consecutive reactions and that neutral Ag2 can be easily eliminated from [Ag3(12C4)]+.     

MacNeille completions and canonical extensions

Let be a variety of monotone bounded lattice expansions, that is, bounded lattices endowed with additional operations, each of which is order preserving or reversing in each coordinate. We prove that if is closed under MacNeille completions, then it is also closed under canonical extensions. As a corollary we show that in the case of Boolean algebras with operators, any such variety is generated by an elementary class of relational structures.

Our main technical construction reveals that the canonical extension of a monotone bounded lattice expansion can be embedded in the MacNeille completion of any sufficiently saturated elementary extension of the original structure.

     

Pyridine-thermal synthesis and high catalytic activity of CeO2/CuO/CNT nanocomposites

Carbon nanotubes (CNTs) were controllably coated with the uninterrupted CuO and CeO₂ composite nanoparticles by a facile pyridine-thermal method and the high catalytic performance for CO oxidation was also found. The obtained nanocomposites were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction as well as X-ray photoelectron spectroscopy. It is found that the CuO/CeO₂ composite nanoparticles are distributed uniformly on the surface of CNTs and the shell of CeO₂/CuO/CNT nanocomposites is made of nanoparticles with a diameter of 30-60 nm. The possible formation mechanism is suggest as follows: the surface of CNTs is modified by the pyridine due to the π-π conjugate role so that the alkaline of pyridine attached on the CNT surface is more enhanced as compared to the one in the bulk solvent, and thus, these pyridines accept the proton from the water molecular preferentially, which result in the formation of the OH⁻ ions around the surface of CNTs. Subsequently, the metal ions such as Ce³⁺ and Cu²⁺ in situ react with the OH⁻ ions and the resultant nanoparticles deposit on the surface of CNTs, and finally the CeO₂/CuO/CNT nanocomposites are obtained. The T₅₀ depicting the catalytic activity for CO oxidation over CeO₂/CuO/CNT nanocomposites can reach ∼113 °C, which is much lower than that of CeO₂/CNT or CuO/CNT nanocomposites or CNTs.     

Improving mechanical properties of a-CNx films by Ti-TiN/CNx gradient multilayer

Amorphous carbon nitride (a-CN_x) films with functional gradient Ti-TiN/CN_x underlayer were deposited by direct current magnetron sputtering. Microstructure and composition of the films were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, atomic force microscope (AFM) and transmission electron microscopy (TEM). Mechanical and tribological properties were investigated by nanoindenter, scratch and ball-on-disk tribometer. The a-CN_x-based films suffer a graphitization process with the increasing deposition temperature, thus the hardness and elastic modulus decrease. With the design of the Ti-TiN/CN_x gradient underlayers, some important advantages of relatively thick CN_x films can be achieved, such as increased hardness, improved adhesion strength, and the wear resistance of the a-CN_x-based films can be also improved significantly.     

On division subrings normalized by almost subnormal subgroups in division rings

Periodica Mathematica Hungarica - Let D be a division ring with infinite center, K a proper division subring of D and N an almost subnormal subgroup of the multiplicative group $$D^*$$ of D. The...     

Synthesis, structure, and optical and electrochemical properties of star-shaped porphyrin-triarylamine conjugates

A series of novel star-shaped porphyrin-triarylamine conjugates were synthesized by palladium-catalyzed cross-coupling reactions. The spectroscopic and electrochemical studies show that pi-conjugation of the porphyrin core is extended to the triarylamine moieties.