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Mn-catalyzed oxidation of the Ashalcha heavy oil in porous media was examined. We used manganese(III) tris(acetylacetonate) as a convinient oil-soluble precatalyst that decomposes to catalytically active species during the temperature ramping. Reaction kinetics in the heavy oil oxidation with air indicated that the presence of the manganese ions changes the mechanism of the oxidation process, especially in the high-temperature region. To study precatalyst transformations in detail, we suggested the approach of combining X-ray powder diffraction (XRPD), thermal analysis, non-isothermal kinetic methods, and electron paramagnetic resonance (EPR). A comprehensive study of the decomposition of pure manganese(III) tris(acetylacetonate) and the subsequent comparison of its behavior to that in porous media in the presence of the oil allows us to shed light on some aspects of the mechanism of catalytic oxidation.

For the first time, a series of catechol-containing Schiff bases, tetrasubstituted at the lower rim thiacalix[4]arene derivatives in three stereoisomeric forms, cone, partial cone, and 1,3-alternate, were synthesized. The structure of the obtained compounds was proved by modern physical methods, such as NMR, IR spectroscopy, and HRMS. Selective recognition (Kb difference by three orders of magnitude) of copper (II) cation in the series of d-metal cations (Cu2+, Ni2+, Co2+, Zn2+) was shown by UV-vis spectroscopy. Copper (II) ions are coordinated at the nitrogen atom of the imine group and the nearest oxygen atom of the catechol fragment in the thiacalixarene derivatives. High thermal stable organic-inorganic copper-based materials were obtained on the base of 1,3-alternate + Cu (II) complexes.

Thermal treatment of oligopeptides is one of the methods for synthesis of organic nanostructures. However, heating may lead not only to self-assembly of the initial molecules, but also to chemical reactions resulting in the formation of new unexpected nanostructures or change in the properties of the existing ones. In the present work, the reaction of cyclization of dipeptide l-leucyl-l-leucine in solid state under heating was studied. The change in morphology of dipeptide thin film and formation of nanostructures after heating was visualized using atomic force microscopy. This method also was used for demonstration of differences in self-assembly of linear and cyclic dipeptides. The chemical structure of reaction product was characterized by NMR spectrometry, FTIR spectroscopy and GC-MS analysis. Kinetic parameters of cyclization were estimated within the approaches of the nonisothermal kinetics ("model-free" kinetics and linear regression methods for detection of topochemical equation). The results of present work are useful for explanation the changes in the properties of nanostructures based on short-chain oligopeptides, notably leucyl-leucine, after thermal treatment, as well as for the synthesis of cyclic oligopeptides.