Nature of π-Electronic Transitions in UV Spectra of Deoxyvasicinone and Its Derivatives

The principal types of electronic transitions in absorption spectra of deoxyvasicinone and its 6-amino- and 6-nitro-derivatives were determined by analyzing the electron-density distributions in excited states calculated using ZINDO/S.     

Structure of solid monolayers and multilayers of n -hexane on graphite

We present all-atom molecular dynamics simulations ofn-hexane on the basal plane of graphite at monolayer and multilayer coverages. In keeping with experimental data, we find the presence of ordered adsorbed layers both at single monolayer coverage and when the adsorbed layer coexists with excess liquid adsorbate. Using a simulation method that does not impose any particular periodicity on the adsorbed layer, we quantitatively compare our results to the results of neutron diffraction experiments and find a structural transition from a uniaxially incommensurate lattice to a fully commensurate structure on increasing the coverage from a monolayer to a multilayer. The zig-zag backbone planes of all the alkane molecules lie parallel to the graphite surface at the multilayer coverage, while a few molecules are observed to attain the perpendicular orientation at monolayer coverage. Dedicated to Professor C N R Rao on his 70th birthday     

Evidence of a Photo‐Radical Pathway Responsible of the Rearrangement of a Manganese(III)‐Schiff Base Complex in Solution

A new Mn^III‐Schiff base complex, [MnL(OH₂)](ClO₄) ( 1 ) (H₂L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode Mn^III EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement.     

Sorption Behaviour of Molybdenum on Different Antimonates Ion Exchangers

Various antimonate compounds are well known as important inorganic ion exchangers, since they resist radiation and chemical degradation and also exhibit selectivities towards different cations. Ceric, silicon, titanium and ferric antimonates were prepared as inorganic ion exchangers. Characterization of these materials has been described using different techniques, including thermal analysis, surface area measurements, X-ray diffraction and IR-spectroscopy. In batch distribution experiments the influence of HNO₃ molarity and Mo concentration for Mo sorption on different matrices is described in terms of their retention capacities and distribution coefficients.The selectivities of these exchangers towards molybdenum are in the order: CeSb > SiSb > FeSb > TiSb.     

Indirect Oxidation of Organic Substances by Intermediates of the Oxygen Reduction

Results of two urgent and practically important directions of research on the indirect oxidation of organic compounds by highly reactive intermediates generated electrochemically from oxygen (HO₂ ^–, HO₂ ^·, HO^·) are considered and orderly arranged. The studies in question are the indirect synthesis and mineralization of organic toxicants in waste water.     

Transport of Neutrally Buoyant and Dense Variably Sized Colloids in a Two-Dimensional Fracture with Anisotropic Aperture

The transport of monodisperse as well as polydisperse colloid suspensions in a two-dimensional, water saturated fracture with spatially variable and anisotropic aperture is investigated with a particle tracking model. Both neutrally buoyant and dense colloid suspensions are considered. Although flow and transport in fractured subsurface formations have been studied extensively by numerous investigators, the transport of dense, polydisperse colloid suspensions in a fracture with spatially variable and anisotropic aperture has not been previously explored. Simulated snapshots and breakthrough curves of ensemble averages of several realizations of a log-normally distributed aperture field show that polydisperse colloids exhibit greater spreading than monodisperse colloids, and dense colloids show greater retardation than neutrally buoyant colloids. Moreover, it is demonstrated that aperture anisotropy oriented along the flow direction substantially increases colloid spreading; whereas, aperture anisotropy oriented transverse to the flow direction retards colloid movement.     

NMR Detection of Phase Transition in a ZSM-5 Silicalite Caused by the Adsorbed Hexane and Decane Molecules

Times of longitudinal T _1b and transverse T _2b magnetic relaxation of hexane and decane molecules in micropores of ZSM-5 silicalite were measured as functions of the content of these liquid n-alkanes in zeolite and of temperature. The stepwise changes in the T _1b and T _2b times were revealed in the region of 8% content of hydrocarbons. The observed changes in the concentration and temperature dependences of T _1b and T _2b times are explained by the rearrangement of silicalite crystal lattice under the action of adsorbed molecules.