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.     

Non-isothermal short-range-order kinetics of binary alloys as influenced by solute-vacancy complexes

A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach. The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures. An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use of DSC trace data. A value of 89.12±0.32 kJ mol^-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation energy corresponding to the ordering process as influenced by quenching temperature was also assessed. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Thermal conductivity of crystalline chrysotile asbestos

The thermal conductivity of crystalline chrysotile asbestos made up of hollow tubular Mg₃Si₂O₅(OH)₄ filaments is measured in the range 5–300 K. The paper discusses the possibility of using this material in studies of the thermal conductivity of thin filaments of metals and semiconductors incorporated into the channels of crystalline chrysotile asbestos tubes.     

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.     

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