Aleksey V. Buzyurov

The first evidence of native cyclodextrins fusion was registered using fast scanning calorimetry (FSC) with heating rates up to 40,000 K s⁻¹. The endothermal effects, detected at low heating rates, correspond to the decomposition processes. Upon the increase of the heating rate the onset of these effects shifts to higher temperatures, reaching a limiting value at high heating rates. The limiting temperatures were identified as the melting points of α-, β- and γ-cyclodextrins, as the decomposition processes are suppressed at high heating rates. For γ-cyclodextrin the fusion enthalpy was measured. The activation energies of thermal decomposition of cyclodextrins were determined by dependence of the observed thermal effects on heating rates from 4 K min⁻¹ in conventional differential scanning calorimetry to 40,000 K s⁻¹ in FSC. The lower thermal stability and activation energy of decomposition of β-cyclodextrin than for the other two cyclodextrins were found, which may be explained by preliminary phase transition and chemical reaction without mass loss. The obtained values of fusion parameters of cyclodextrins are needed in theoretical models widely used for prediction of solubility and solution rates and in preparation of cyclodextrin inclusion compounds involving heating.

Heat-induced solid-state decarboxylation of tetra(malonatemethylene) based cyclophane leads to its tetra(2-carboxyethyl) derivative in quantitative yield. This reaction provides more thermostable substance compared to the product of the same cyclophane decarboxylation in solution. The studied cyclophanes have been characterized by means of simultaneous thermal analysis involving thermogravimetry, differential scanning calorimetry, and mass spectrometry of evolved gases as well as fast scanning calorimetry, a method preferable to investigate the compounds with relatively low thermal stability.

Peat has attracted considerable interest as a potential source of alternative fuel in terms of improving hydrocarbons production and satisfying market demand. The next decade is likely to witness a raise in its exploitation. Nevertheless, the characteristics of peat pyrolysis process, via which many experts expect a considerable generation of hydrocarbons, have not been dealt with in depth. In the present study we have applied thermal analysis combined with isoconversional and model methods for clarifying the kinetic and thermodynamic aspects of the process of generating hydrocarbons from peat via pyrolysis in the absence and presence of iron tallates as a catalytic agent. The obtained results showed a positive effect of the opted catalyst on the process of peat pyrolysis. It has been shown that the catalyst is able to reduce the energy of activation of peat pyrolysis process. Moreover, the Gibbs energy, enthalpy and entropy of complex formation values have been found lower in the presence of iron tallates for all the applied isoconversional methods (Friedman and KAS). The evidence from the present study points toward the beneficial effect generated from the utilization of iron tallates in the processes of hydrocarbons generation from peat for improving energy production in the future.

There is still considerable controversy surrounding the mechanisms, thermodynamics, and kinetics of heavy oil aquathermolysis and pyrolysis processes. The present paper aims to widen our knowledge about the effect of iron tallates on pyrolysis and aquathermolysis of Cuban heavy oil. The obtained SARA (S: saturates, A: aromatics, R: resins, A: asphaltenes) analysis has shown a significant increase in light hydrocarbon content during aquathermolysis. Moreover, the elemental analysis has indicated an increase in C and H content by almost 4% and 6%, respectively, with a significant decrease in S and O content by up to 23% in the presence of iron tallates. These results have been further confirmed by infrared spectrometry. The obtained IR data indicated that asphaltene and resin compounds transform into light hydrocarbons after aquathermolysis. On another hand, the activation energy of heavy oil pyrolysis decreased in the presence of the utilized catalyst; meanwhile, the reaction rate increased, especially in the temperature range of 200–480 °C, which may validate a significant effect of the used catalyst in real conditions. Moreover, the obtained thermodynamic data showed a decrease in the enthalpy and entropy of activation of oil pyrolysis in the presence of iron tallates. Our results are encouraging in terms of energy consumption, optimization, and process control and should be validated by a larger sample size.

The vapor pressures of six solid 5-X-1,10-phenanthrolines (where X = Cl, CH₃, CN, OCH₃, NH₂, NO₂) were determined in suitable temperature ranges by Knudsen Effusion Mass Loss (KEML). From the temperature dependencies of vapor pressure, the molar sublimation enthalpies, Δ_cr^gH_m⁰(⟨T⟩), were calculated at the corresponding average ⟨T⟩ of the explored temperature ranges. Since to the best of our knowledge no thermochemical data seem to be available in the literature regarding these compounds, the Δ_cr^gH_m⁰(⟨T⟩) values obtained by KEML experiments were adjusted to 298.15 K using a well known empirical procedure reported in the literature. The standard (p⁰ = 0.1 MPa) molar sublimation enthalpies, Δ_cr^gH_m⁰(298.15 K), were compared with those determined using a recently proposed solution calorimetry approach, which was validated using a remarkable amount of thermochemical data of molecular compounds. For this purpose, solution enthalpies at infinite dilution of the studied 5-chloro and 5-methylphenantrolines in benzene were measured at 298.15 K. Good agreement was found between the values derived by the two different approaches, and final mean values of Δ_cr^gH_m⁰(298.15 K) were recommended. Finally, the standard molar entropies and Gibbs energies of sublimation were also derived at T = 298.15 K. The volatilities of the six compounds were found to vary over a range of three orders of magnitude in the explored temperature range. The large difference in volatility was analyzed in the light of enthalpies and entropies of sublimation. The latter was tentatively put in relation to the rotational contribution of the substituent group on the phenanthroline unit.

Synthetic organic 2D materials are attracting careful attention of researchers due to their excellent functionality in various applications, including storage batteries, catalysis, thermoelectricity, advanced electronics, superconductors, optoelectronics, etc. In this work, thiacalix[4]arene derivatives functionalized by geranyl fragments at the lower rim in cone and 1,3-alternate conformations, that are capable of controlled self-assembly in a 2D nanostructures were synthesized. X-ray diffraction analysis showed the formation of 2D monomolecular-layer nanosheets from synthesized thiacalix[4]arenes, the distance between which depends on the stereoisomer used. It was established by DSC, FSC, and PXRD methods that the obtained macrocycles are capable of forming different crystalline polymorphs, moreover dimethyl sulphoxide (DMSO) is contributing to the formation of a more stable polymorph for cone stereoisomer. The obtained crystalline 2D materials based on synthesized thiacalix[4]arenes can find application in material science and medicine for the development of modern pharmaceuticals and new generation materials.

An efficient strategy of polymorph screening is offered for tert-butylthiacalix[4]arene tetrasubstituted with phenacyloxy groups (1), which is based on saturation of its guest-free solid samples and inclusion compounds with guest vapors inducing solid-solid phase transition, complete or partial exchange or repulsion of included guest. The offered approach makes the preparation of polymorphs more reproducible and predictable as the performed phase transitions are under mostly thermodynamic control even when giving metastable forms. Smart transformation of calixarene states was demonstrated where stable and metastable polymorphs are formed in a kind of on/off switching. Guest repulsion or solid-phase exchange with another guest vapor gives a guest-free form directly or a less stable inclusion compound is prepared that can release guests by drying under milder conditions without host collapse to a stable packing. In total, seven polymorphs of 1 were identified and characterized. Single crystal data reveal the polymorphophore features of 1, which help to variate its polymorphic state. The observed control of polymorphic transitions contributes to the comprehension of their causes and mechanism. The elaborated procedures enable an effective screening of polymorphs through a standardized treatment of the target compound on a click basis with a flexible variation of conditions, which may be scaled up to find more crystal forms.