Наукові засади розвитку інституту юридичної риторики: в контексті теорії юридичної аргументації

Саме аргументація в юридичній риториці є одним із ключових компонентів, який позначається на результативності та якості юридичного дискурсу. Тому для наукового дослідження юридичної риторики як науким провідне значення має вивчення теорії юридичної аргументації, як складової загальної теорії аргументації.Именно аргументация в юридической риторике является одним из ключевых компонентов, который проявляет себя в результативности и качестве юридического дискур­са. Поэтому для научного исследования юридической риторики как науки приоритетное значение имеет изучение теории юридической аргументации, как составляющей общей теории аргументации.The argument in legal rhetoric is one of key components who prover in productivity and quality of a legal discourse. Therefore for scientific research of legal rhetoric science priority has studyind of the legal argument, as making general of the argument

Effect of strontium inclusion on the bioactivity of phosphate-based glasses

We have conducted first-principles and classical molecular dynamics simulations of various compositions of strontium-containing phosphate glasses, to understand how strontium incorporation will change the glasses’ activity when implanted into the body (bioactivity). To perform the classical simulations, we have developed a new interatomic potential, which takes account of the polarizability of the oxygen ions. The Sr-O bond length is ∼ 2.44 − 2.49Å, and the coordination number is 7.5 – 7.8. The Qn distribution and network connectivity were roughly constant for these compositions. Sr bonds to a similar number of phosphate chains as Ca does; based on our previous work [J. K. Christie et al., J. Phys. Chem. B 117, 10652 (2013)], this implies that SrO ↔ CaO substitution will barely change the dissolution rate of these glasses, and that the bioactivity will remain essentially constant. Strontium could therefore be incorporated into phosphate glass for biomedical applications

Теоретико-методологічні засади адаптивного інноваційного розвитку

Подано визначення змісту управління адаптивним інноваційним розвитком, заснованого на використанні його здібностей до трансформації з урахуванням особливостей зовнішнього та внутрішнього середовища суб’єкта сукупності дій, необхідних для здійснення впливу на процеси в усіх сферах управління, що забезпечує інноваційну, організаційно-управлінську, технічну, фінансову та кадрову стійкість. Ключові слова: інновації, інноваційний розвиток, адаптація, адаптивність, механізм, система, процес.Представлено определение содержания управления адаптивным инновационным развитием, основанным на использовании его способностей к трансформации с учетом особенностей внешней и внутренней среды субъекта совокупности действий, необходимых для осуществления влияния на процессы во всех областях управления, обеспечивающих инновационную, организационно-управленческую, техническую, финансовую и кадровую устойчивость. Ключевые слова: инновации, инновационное развитие, адаптация, адаптивность, механизм, система, процесс.The paper presents the definition of management of adaptive innovation-based development that is based on the use of its ability to transform in view of external and internal environment of the subject of actions necessary for making influence on the processes in all areas of management, providing innovative, organizational, administrative, technical, financial and personnel stability of the production company. Keywords: innovation, innovation-based development, adaptation, adaptability, mechanism, system, process

Density functional theory calculations of the hydrazine decomposition mechanism on the planar and stepped Cu(111) surfaces

We have investigated the adsorption of hydrazine (N2H4) and its reactivity on terraces and steps of Cu(111) surfaces by first-principles calculations in order to gain insight into the hydrazine decomposition mechanism. We have investigated different possibilities for the N–N and N–H bond cleavage for any intermediate states by analysing the reaction and barrier energies of each elementary step. We have found that hydrazine dehydrogenation via N–H bond scission is neither energetically nor kinetically favourable on the flat and stepped surfaces, but hydrazine prefers to form NH2via N–N bond decoupling on the Cu(111) with an activation energy below 1 eV. The NH2 molecule reacts fairly easily with co-adsorbed NH2 to form NH3 as well as with N2Hx (x = 1–4) by abstracting hydrogen to produce NH3 and N2 molecules on both the flat and stepped surfaces. We also found that all intermediates except NNH prefer N–N bond breaking as the most likely dissociation pathway, where the amide and imide intermediates produced can be hydrogenated to form NH3 in the presence of hydrogen. NNH is the only intermediate, which prefers to dissociate via a highly exothermic N–H bond breaking process to produce an N2 molecule after overcoming a small barrier energy. We also studied the production of H2 by recombination of hydrogen ad-atoms which, considering the activation energies, is particularly favoured under conditions of moderate temperatures. Our results agree well with experiments suggesting that N2H4 adsorbs dissociatively on copper above ∼300 K leading to N2, NH3 and H2. In general, the lower coordination of the steps is found to lead to higher reactivity than on the flat Cu(111) surface. Furthermore, the calculations show that the influence of step edge atoms is very different for the intra- and intermolecular dehydrogenation mechanisms. They also increase the barrier of N–N decoupling of all the existing species in the reaction

The effect of water on the binding of glycosaminoglycan saccharides to hydroxyapatite surfaces: A molecular dynamics study

Classical molecular dynamics (MD) simulations have been employed to study the interaction of the saccharides glucuronic acid (GlcA) and N-acetylgalactosamine (GalNAc) with the (0001) and (011̄0) surfaces of the mineral hydroxyapatite (HAP). GlcA and GalNAc are the two constituent monosaccharides of the glycosaminoglycan chondroitin sulfate, which is commonly found in bone and cartilage and has been implicated in the modulation of the hydroxyapatite biomineralization process. MD simulations of the mineral surfaces and the saccharides in the presence of solvent water allowed the calculation of the adsorption energies of the saccharides on the HAP surfaces. The calculations show that GalNAc interacts with HAP principally through the sulfate and the carbonyl of acetyl amine groups, whereas the GlcA interacts primarily through the carboxylate functional groups. The mode and strength of the interaction depends on the orientation of the saccharide with respect to the surface and the level of disruption of the layer of water competing with the saccharide for adsorption sites on the HAP surface, suggesting that chondroitin 4-sulfate binds to the layer of solvent water rather than to HAP

Theoretical analysis of uranium-doped thorium dioxide: Introduction of a thoria force field with explicit polarization

Thorium dioxide is used industrially in high temperature applications, but more insight is needed into the behavior of the material as part of a mixed-oxide (MOX) nuclear fuel, incorporating uranium. We have developed a new interatomic potential model including polarizability via a shell model, and commensurate with a prominent existing UO2 potential, to conduct configurational analyses and to investigate the thermophysical properties of uranium-doped ThO2. Using the GULP and Site Occupancy Disorder (SOD) computational codes, we have analyzed the distribution of low concentrations of uranium in the bulk material, where we have not observed the formation of uranium clusters or the dominance of a single preferred configuration. We have calculated thermophysical properties of pure thorium dioxide and Th(1−x)UxO2 which generated values in very good agreement with experimental data

Gadolinium-vacancy clusters in the (111) surface of gadolinium-doped ceria: a density functional theory study

Solid-oxide fuel cells are promising devices for sustainable power generation. Electrolyte materials play an important role in connecting the anode and cathode, and they influence the performance of the device. In this context, gadolinium-doped ceria (GDC) has proven to be an efficient electrolyte material, although the presence of dopant clusters can lower its efficiency. After usage, dopant clusters start appearing at dislocations, translocations, grain boundaries, or surfaces. Hence, the study of dopant clustering at the atomic level near these regions becomes of vital importance, as it allows us to understand the reasons for the occurrence of this phenomenon and its impact on the oxygen conduction. In this context, the present paper studies the impact of dopant clustering near the (111) GDC surface. We have studied two different gadolinium concentrations in the material, of approximately 7% and 14%, which are close to the optimum concentration of 10%. Our results indicate that surface relaxation is a key factor in determining the preference of defect clusters to be found in the surface. We have also calculated the relative abundance of different defect clusters at different temperatures, including the configurational entropy term. It was revealed that working temperatures (650–1100 K) show the relative abundance of different cluster structures, displaying that, at high concentrations, preferred dopant clusters resemble the structure of Gd2O3, showing the formation of gadolinia domains. Finally, we show that oxygen diffusion will be affected by the formation of these domains. After evaluating the oxygen mobility, we conclude that oxygen vacancies will be trapped by the gadolinium clusters at the surface. These vacancy traps prevent oxygen diffusion, thereby affecting negatively the performance of the material and the fuel cell in general

CuO surfaces and CO2 activation: a dispersion-corrected DFT plus U Study

We have used computational methodology based on the density functional theory to describe both copper(I) and copper(II) oxides, followed by the investigation of a number of different low index CuO surfaces. Different magnetic orderings of all the surfaces were studied, and reconstructions of the polar surfaces are proposed. A detailed discussion on stabilities, electronic structure, and magnetic properties is presented. CuO(111) and CuO(111) were found to have the lowest surface energies, and their planes dominate in the calculated Wulff morphology of the CuO crystal. We next investigated the adsorption of CO2 on the three most exposed CuO surfaces, viz., (111), (111), and (011), by exploring various adsorption sites and configurations. We show that the CO2 molecule is activated on the CuO surfaces, with an adsorption energy of −93 kJ/mol on the (011) surface, showing exothermic adsorption, while (111) and (111) surfaces show comparatively weak adsorption. The activation of the CO2 molecule is characterized by large structural transformations and significant charge transfer, i.e., forming a negatively charged bent CO2–δ species with elongated C–O bonds, which is further confirmed by vibrational analyses showing considerable red shift in the frequencies as a result of the activation

Activation and dissociation of CO2 on the (001), (011), and (111) surfaces of mackinawite (FeS): a dispersion-corrected DFT study

Iron sulfide minerals, including mackinawite (FeS), are relevant in origin of life theories, due to their potential catalytic activity towards the reduction and conversion of carbon dioxide (CO2) to organic molecules, which may be applicable to the production of liquid fuels and commodity chemicals. However, the fundamental understanding of CO2 adsorption, activation, and dissociation on FeS surfaces remains incomplete. Here, we have used density functional theory calculations, corrected for long-range dispersion interactions (DFT-D2), to explore various adsorption sites and configurations for CO2 on the low-index mackinawite (001), (110), and (111) surfaces. We found that the CO2 molecule physisorbs weakly on the energetically most stable (001) surface but adsorbs relatively strongly on the (011) and (111) FeS surfaces, preferentially at Fe sites. The adsorption of the CO2 on the (011) and (111) surfaces is shown to be characterized by significant charge transfer from surface Fe species to the CO2 molecule, which causes a large structural transformation in the molecule (i.e., forming a negatively charged bent CO2−δ species, with weaker C—O confirmed via vibrational frequency analyses). We have also analyzed the pathways for CO2 reduction to CO and O on the mackinawite (011) and (111) surfaces. CO2 dissociation is calculated to be slightly endothermic relative to the associatively adsorbed states, with relatively large activation energy barriers of 1.25 eV and 0.72 eV on the (011) and (111) surfaces, respectively