Szczepan Roszak

Exploring relative thermodynamic stabilities of formic acid and formamide dimers - Role of low-frequency hydrogen-bond vibrations

The low-frequency fundamentals together with the high-frequency modes, responsible for hydrogen bonding (OH/NH stretching modes), were analyzed to correlate the intensities with the hydrogen-bond strengths/binding energies of the formic acid and formamide dimers using Møller-Plesset second-order perturbation (MP2) and coupled cluster computations with explicit anharmonicity corrections. Linear correlations were observed for both the formic acid and formamide dimers, and as consequence of such correlation an additive properties of binding energies with respect to the local hydrogen-bond energies of fragments involved (for these dimers) has been proposed. It has been further observed that (i) the nature of their six low-frequency fundamentals are very similar, and (ii) the in-plane bending and stretch-bend fundamentals of different dimers of these two species (depending on the dimer structure), in this low-frequency region, modulate their strength of hydrogen-bond/binding hence their relative stability order. These results were further verified against the results from Gaussian-G4-MP2 (G4MP2), Gaussian-G2-MP2 (G2MP2), and complete basis set (CBS-QB3) methods of high accuracy energy calculations.

Comparative study of hydrolytic and electron-driven processes in carboplatin biotransformation

The results of computational simulation of reaction courses mimicking the transformation of carboplatin from pro-drug into its active shape, responsible for cytotoxic effect, are reported. Implementing the density functional theory (DFT) calculations and the supermolecular approach, we explored the pathways representing two disparate models of carboplatin bioactivation: (1) based on paradigm of carboplatin aquation, and (2) based on new hypothesis that transformation is controlled by electron-transfer processes. The calculated geometrical and thermodynamic parameters were used for evaluation of pathways. In contrast to carboplatin hydrolysis, representing a typical two stage SN2 mechanism, the postulated electron-driven reactions proceed under the dissociative electron attachment (DEA) mechanism. The reaction profiles predict endothermic effect in both stages of hydrolytic course and final exothermic effects for electron-driven processes. The most effective are hybrid processes including two-stages: water and subsequent electron impact on transformed carboplatin. The aqua-products, manifesting strong electron-affinity, can be the active form of drug capable to cytotoxic interaction with DNA, not only as alkylating agent but also as electron-acceptor. Concluding, the hybrid transformation of carboplatin is more favourable than hydrolytic.

Interactions of Substituted Nitroaromatics with Model Graphene Systems: Applicability of Hammett Substituent Constants To Predict Binding Energies

Applicability of Hammett parameters (σm and σp) was tested in extended π-systems in gas phase. Three different model graphene systems, viz. 5,5-graphene (GR), 3-B-5,5-graphene (3BGR), and 3-N-5,5-graphene (3NGR), were designed as extended π-systems, and interactions of various nitrobenzene derivatives (mainly m- and p-substituted together with some multiple substitutions) on such platforms were monitored using density functional theory (M06/cc-pVDZ, M06/cc-pVTZ, M06/sp-aug-cc-pVTZ) and Møller–Plesset second-order perturbation (MP2/cc-pV-DZ) theory. Offset face to face (OSFF) stackings were found to be the favored orientations, and reasonable correlations were found between binding energies (ΔEB) and the ∑|σm| values of the substituted nitrobenzenes. It was proposed previously that |σm| contains information about the substituents’ polarizability and controls electrostatic and dispersion interactions. The combination of ∑|σm| and molar refractivity (as ∑Mr) or change in polarizability (Δα: with respect to benzene) of nitrobenzene derivatives generated statistically significant correlation with respect to ΔEB, thereby supporting the hypothesis related to the validity of |σm| correlations. The |σp| parameters also maintain similar correlations for the various p-substituted nitrobenzene derivatives together with several multiply-substituted nitrobenzene derivatives. The correlation properties in such cases are similar to the |σm| cases, and the energy partition analysis for both the situations reveled importance of electrostatic and dispersion contributions in such interactions. The applicability of Hammett parameters was observed previously on the restricted parallel face to face orientation of benzene···substituted benzene systems, and the present results show that such an idea could be used to predict ΔEB values in OSFF orientations, if the scaffolds are designed in such a way that substituted benzene systems cannot escape their π-clouds.

Enhancing mercury removal across air pollution control devices for coal-fired power plants by desulfurization wastewater evaporation

ABSTRACT Desulfurization wastewater evaporation technology is used to enhance the removal of gaseous mercury (Hg) in conventional air pollution control devices (APCDs) for coal-fired power plants. Studies have affirmed that gaseous Hg is oxidized and removed by selective catalytic reduction (SCR), an electrostatic precipitator (ESP) and wet flue gas desulfurization (WFGD) in a coal-fired thermal experiment platform with WFGD wastewater evaporation. Effects of desulfurization wastewater evaporation position, evaporation temperature and chlorine ion concentration on Hg oxidation were studied as well. The Hg0 oxidation efficiency was increased ranging from 30% to 60%, and the gaseous Hg removal efficiency was 62.16% in APCDs when wastewater evaporated before SCR. However, the Hg0 oxidation efficiency was 18.99% and the gaseous Hg removal efficiency was 40.19% in APCDs when wastewater evaporated before ESP. The results show that WFGD wastewater evaporation before SCR is beneficial to improve the efficiency of Hg oxidized and removed in APCDs. Because Hg2+ can be easily removed in ACPDs and WFGD wastewater in power plants is enriched with chlorine ions, this method realizes WFGD wastewater zero discharge and simultaneously enhances Hg removal in APCDs.