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Pudlarz Agnieszka Małgorzata Ranoszek-Soliwoda Katarzyna Czechowska Ewa Tomaszewska Emilia Celichowski Grzegorz Grobelny Jarosław Szemraj Janusz 《Applied biochemistry and biotechnology》2019,187(4):1551-1568
Applied Biochemistry and Biotechnology - Superoxide dismutase (SOD) is one of the best characterized enzyme maintaining the redox state in the cell. A bacterial expression system was used to... 相似文献
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Another Unprecedented Wieland Mechanism Confirmed: Hydrogen Formation from Hydrogen Peroxide,Formaldehyde, and Sodium Hydroxide
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Robert Czochara Prof. Grzegorz Litwinienko Dr. Hans‐Gert Korth Dr. Keith U. Ingold 《Angewandte Chemie (International ed. in English)》2018,57(29):9146-9149
In 1923, Wieland and Wingler reported that in the molecular hydrogen producing reaction of hydrogen peroxide with formaldehyde in basic solution, free hydrogen atoms (H.) are not involved. They postulated that bis(hydroxymethyl)peroxide, HOCH2OOCH2OH, is the intermediate, which decomposes to yield H2 and formate, proposing a mechanism that would nowadays be considered as a “concerted process”. Since then, several other (conflicting) “mechanisms” have been suggested. Our NMR and Raman spectroscopic and kinetic studies, particularly the determination of the deuterium kinetic isotope effect (DKIE), now confirm that in this base‐dependent reaction, both H atoms of H2 derive from the CH2 hydrogen atoms of formaldehyde, and not from the OH groups of HOCH2OOCH2OH or from water. Quantum‐chemical CBS‐QB3 and W1BD computations show that H2 release proceeds through a concerted process, which is strongly accelerated by double deprotonation of HOCH2OOCH2OH, thereby ruling out a free radical pathway. 相似文献
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Grzegorz Makomaski 《Journal of Thermal Analysis and Calorimetry》2018,133(3):1345-1352
The study results of porous structure and thermal properties of carbon adsorbents (AC) obtained from pitch–polymer compositions were presented. The compositions were carbonized and activated with steam, potassium hydroxide, and magnesium and potassium carbonates. For the obtained AC, the thermal analysis and the determination of adsorption value of iodine and porous structure by adsorption/desorption of nitrogen at 77 K were carried out. The possibility of obtained activated carbons from pitch–polymer compositions was demonstrated. The use of untypical feedstock, as an effect of combination of bituminous substance with polymeric waste and improvement of the methods of production, creates the potential possibility to produce carbon adsorbents of interesting properties and porous structure. 相似文献
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Agnieszka Tomaszewska Grzegorz Moskal Damian Migas Marta Mikuśkiewicz Tomasz Maciąg 《Journal of Thermal Analysis and Calorimetry》2018,134(1):157-164
The γ–γ′ Co-based superalloys are newly developed class of refractory alloys which may replace commercial Ni-based superalloys owing to their favorable properties at high temperature. In case of new Co-based superalloys, the heat treatment aims to obtain microstructure composed of appropriate volume fraction of small cuboidal γ′-Co3(Al,W) precipitates within the γ-Co matrix. However, due to a high tendency to interdendritic segregations of alloying elements, the alloys based on Co–Al–W system should be normally homogenized before further steps of heat treatment (solutionizing and aging). In this study, thermal analysis was applied for determination of temperature range for primary heat treatment of the Co–9Al–9W (at.%). The differential thermal analysis (DTA) measurements were carried out on the thermal analyzer NETZSCH STA 449 F3 Jupiter. On the base of obtained results, respectively, solvus of γ′ phase and solidus temperatures were determined, as well as the thermal range of Co3W (DO19) phase precipitation. As a consequence, the heat treatment without homogenizing (only solution and aging) was proposed as a most suitable way to obtain beneficial microstructure. 相似文献
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Jezierski A Skrzypek G Jezierski P Paul D Jedrysek MO 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,69(5):1311-1316
EPR spectroscopy was performed on four peat cores (1-2.5 m depth) collected from Yellowstone National Park (USA), Scotland (UK) and Lower Silesia (Poland) to study peat formation process. The stable free radicals identified in all investigated samples are semiquinone type and g-parameters range from 2.0030 to 2.0048. The highest g-values are characteristic of upper well-aerated peat layers and gradually decrease with depth. The lowest g-values are typical of relatively old fens and bogs where anaerobic conditions are expected and carbonization processes are advanced. The decrease in g-parameter value is connected with conjugation of semiquinone units with gradually augmented polyaromatic units in the peat substance. Generally the radical concentration increases with depth (0.05-5x10(17) spins/gram). However the g-values, line width parameters, and spin concentrations exhibit strong variations in some peat layers. Variation of these parameters observed for certain peat horizons correlate with the variation of carbon stable isotopic composition. For the old well-conserved peat deposits (e.g. Scotland/UK, approximately 5600 BP), variation of EPR parameters may be used to study paleo redox conditions. 相似文献
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The paper concerns two aspects of the entropy in mesogenic systems: (i) the entropy jump (Delta S (0) NI) at the phase transition from the isotropic liquid (I) to the nematic liquid crystalline state (N), and (ii) the entropy increment (Delta S) caused by the ordering action of the probing electric field applied to the dipolar system. The system studied are the mixtures of strongly polar mesogenic solvent n-hexylcyanobiphenyl (C 6H 13PhPhCN, 6CB) and the nonpolar nonmesogenic admixture 4-ethylcyclohexyl-4'- n-nonylphenyl (C 2H 5CyHxPhC 9H 19, 2CyPh9). The entropy jump at the I-N phase transition in pure 6CB [Delta S (0) NI= 1.52 J/(mol K)] was evaluated from the analysis of the phase diagram of the mixture 6CB + 2CyPh9 with use of the Landau-Lifshitz theory; the resulting value of the transition enthalpy (Delta H (0) NI = T NIDelta S (0) NI = 0.50 kJ/mol) agrees well to that obtained with the calorimetric methods. The field-induced entropy increment (Delta S) was calculated, at the given temperature, from the static dielectric permittivity derivative value (depsilon s/d T), with use of the Fr?hlich theory. The singularities in dependence of the entropy increment on the temperature and on the mixtures composition are discussed in terms of the prenematic molecular self-organization extent in mesogenic liquids of different density of dipoles. 相似文献
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A straightforward route for the stereoselective synthesis of unsaturated quinolizidines and related higher homologs has been developed. Our results revealed that the rhodium complex [RhCl(cod)]2 is an effective catalyst for the intramolecular conjugate addition of vinylstannanes to the dihydropyridones leading to the corresponding 1-azabicyclo[m.n.0]alkenes in a moderate to good yield and an excellent diastereoselectivity under neutral conditions at room temperature. This methodology has been successfully applied to the stereoselective synthesis of the racemic lasubine I. 相似文献