14 research outputs found

    Digitalization of The Transport Industry in The Context of Globalization of The World Economy

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    Research background: The article reveals the nature and mechanisms of the influence of the digital economy on the development of the transport industry in the world. The prerequisites for researching the problems of digitalization in the transport sector are determined by several factors. Firstly, the use of digital technologies is especially evident in the transport sector. Secondly, it is the efficiency of using the latest technological achievements that determines the competitiveness of transport companies. Purpose of the article: The aim of the study of this topic is to identify the most significant manifestations of the impact of digitalization on the transport sector, trends and the nature of this impact. Methods: The methodology of the work is to use the method of scientific abstraction, analysis of facts and observation of the real existing picture, as well as induction and deduction to determine the relationship of concepts in general to individual cases. The authors of the study identified the key components of the digitalization process of the economy, and identified those that have the greatest impact on the transport sector. The article contains an analysis of the existing experience of transport digitalization, the consequences of this process. Also in this article, the authors made their forecast for the further development of transport digitalization processes. Findings & Value added: The main result of the study was the conclusion that the objective need of the transport industry for new innovative developments is very high. The economic effect, that the introduction of transport sector digital technologies, brings, is obvious and tangible

    Individual expression features of GPX2, NQO1 and SQSTM1 transcript variants induced by hydrogen peroxide treatment in HeLa cells

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    Abstract Pathway activity assessment-based approaches are becoming highly influential in various fields of biology and medicine. However, these approaches mostly rely on analysis of mRNA expression, and total mRNA from a given locus is measured in the majority of cases. Notably, a significant portion of protein-coding genes produces more than one transcript. This biological fact is responsible for significant noise when changes in total mRNA transcription of a single gene are analyzed. The NFE2L2/AP-1 pathway is an attractive target for biomedical applications. To date, there is a lack of data regarding the agreement in expression of even classical target genes of this pathway. In the present paper we analyzed whether transcript variants of GPX2, NQO1 and SQSTM1 were characterized by individual features of expression when HeLa cells were exposed to pro-oxidative stimulation with hydrogen peroxide. We found that all the transcripts (10 in total) appeared to be significantly individually regulated under the conditions tested. We conclude that individual transcripts, rather than total mRNA, are best markers of pathway activation. We also discuss here some biological roles of individual transcript regulation

    Beam heat load measurements in the cold bore superconductive undulator in ANKA

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    Measurements of the beam-induced heat load in the ANKA cold-bore superconductive undulator are summarized. The strength of the two dominating effects, resistive wall heating and heating by electron bombardment, depends on the beam parameters and the gap width

    Redox Levels of a <i>closo</i>-Osmaborane: A Density Functional Theory, Electron Paramagnetic Resonance and Electrochemical Study

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    A <i>closo</i>-type 11-vertex osmaborane [1-(η<sup>6</sup>-pcym)-1-OsB<sub>10</sub>H<sub>10</sub>] (pcym = <i>para</i>-cymene) has been synthesized and characterized by single-crystal X-ray diffraction and elemental analysis, as well as by <sup>11</sup>B and <sup>1</sup>H NMR, UV–visible, and mass spectrometry. The redox chemistry has been probed by dc and Fourier transformed ac voltammetry and bulk reductive electrolysis in CH<sub>3</sub>CN (0.10 M (<i>n</i>-Bu)<sub>4</sub>NPF<sub>6</sub>) and by voltammetry in the ionic liquid <i>N</i>-butyl-<i>N-</i>methylpyrrolidinium bis­(trifluoromethylsulfonyl)­amide (Pyrr<sub>1,4</sub>-NTf<sub>2</sub>), which allows the oxidative chemistry of the osmaborane to be studied. A single-crystal X-ray diffraction analysis has shown that [1-(η<sup>6</sup>-pcym)-1-OsB<sub>10</sub>H<sub>10</sub>] is isostructural with other metallaborane compounds of this type. In CH<sub>3</sub>CN (0.10 M (<i>n</i>-Bu)<sub>4</sub>NPF<sub>6</sub>), [1-(η<sup>6</sup>-pcym)-1-OsB<sub>10</sub>H<sub>10</sub>] undergoes two well-resolved one-electron reduction processes with reversible potentials separated by ca. 0.63–0.64 V. Analysis based on a comparison of experimental and simulated ac voltammetric data shows that the heterogeneous electron transfer rate constant (<i>k</i><sup>0</sup>) for the first reduction process is larger than that for the second step at GC, Pt, and Au electrodes. <i>k</i><sup>0</sup> values for both processes are also larger at GC than metal electrodes and depend on the electrode pretreatment, implying that reductions involve specific interaction with the electrode surface. EPR spectra derived from the product formed by one-electron reduction of [1-(η<sup>6</sup>-pcym)-1-OsB<sub>10</sub>H<sub>10</sub>] in CH<sub>3</sub>CN (0.10 M (<i>n</i>-Bu)<sub>4</sub>NPF<sub>6</sub>) and electron orbital data derived from the DFT calculations are used to establish that the formal oxidation state of the metal center of the original unreduced compound is Os<sup>II</sup>. On this basis it is concluded that the metal atom in [1-(η<sup>6</sup>-pcym)-1-OsB<sub>10</sub>H<sub>10</sub>] and related metallaboranes makes a 3-orbital 2-electron contribution to the borane cluster. Oxidation of [1-(η<sup>6</sup>-pcym)-1-OsB<sub>10</sub>H<sub>10</sub>] coupled to fast chemical transformation was observed at 1.6 V vs ferrocene<sup>0/+</sup> in Pyrr<sub>1,4</sub>-NTf<sub>2</sub>. A reaction scheme for the oxidation involving formation of [1-(η<sup>6</sup>-pcym)-1-OsB<sub>10</sub>H<sub>10</sub>]<sup>+</sup>, which rearranges to an unknown electroactive derivative, is proposed, and simulations of the voltammograms are provided

    Inappropriate Use of the Quasi-Reversible Electrode Kinetic Model in Simulation-Experiment Comparisons of Voltammetric Processes That Approach the Reversible Limit

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    Many electrode processes that approach the “reversible” (infinitely fast) limit under voltammetric conditions have been inappropriately analyzed by comparison of experimental data and theory derived from the “quasi-reversible” model. Simulations based on “reversible” and “quasi-reversible” models have been fitted to an extensive series of a.c. voltammetric experiments undertaken at macrodisk glassy carbon (GC) electrodes for oxidation of ferrocene (Fc<sup>0/+</sup>) in CH<sub>3</sub>CN (0.10 M (<i>n</i>-Bu)<sub>4</sub>NPF<sub>6</sub>) and reduction of [Ru­(NH<sub>3</sub>)<sub>6</sub>]<sup>3+</sup> and [Fe­(CN)<sub>6</sub>]<sup>3–</sup> in 1 M KCl aqueous electrolyte. The confidence with which parameters such as standard formal potential (<i>E</i><sup>0</sup>), heterogeneous electron transfer rate constant at <i>E</i><sup>0</sup> (<i>k</i><sup>0</sup>), charge transfer coefficient (α), uncompensated resistance (<i>R</i><sub>u</sub>), and double layer capacitance (<i>C</i><sub>DL</sub>) can be reported using the “quasi-reversible” model has been assessed using bootstrapping and parameter sweep (contour plot) techniques. Underparameterization, such as that which occurs when modeling <i>C</i><sub>DL</sub> with a potential independent value, results in a less than optimal level of experiment-theory agreement. Overparameterization may improve the agreement but easily results in generation of physically meaningful but incorrect values of the recovered parameters, as is the case with the very fast Fc<sup>0/+</sup> and [Ru­(NH<sub>3</sub>)<sub>6</sub>]<sup>3+/2+</sup> processes. In summary, for fast electrode kinetics approaching the “reversible” limit, it is recommended that the “reversible” model be used for theory-experiment comparisons with only <i>E</i><sup>0</sup>, <i>R</i><sub>u</sub>, and <i>C</i><sub>DL</sub> being quantified and a lower limit of <i>k</i><sup>0</sup> being reported; e.g., <i>k</i><sup>0</sup> ≥ 9 cm s<sup>–1</sup> for the Fc<sup>0/+</sup> process

    A Comparison of Fully Automated Methods of Data Analysis and Computer Assisted Heuristic Methods in an Electrode Kinetic Study of the Pathologically Variable [Fe(CN)<sub>6</sub>]<sup>3–/4–</sup> Process by AC Voltammetry

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    Fully automated and computer assisted heuristic data analysis approaches have been applied to a series of AC voltammetric experiments undertaken on the [Fe­(CN)<sub>6</sub>]<sup>3–/4–</sup> process at a glassy carbon electrode in 3 M KCl aqueous electrolyte. The recovered parameters in all forms of data analysis encompass <i>E</i><sup>0</sup> (reversible potential), <i>k</i><sup>0</sup> (heterogeneous charge transfer rate constant at <i>E</i><sup>0</sup>), α (charge transfer coefficient), <i>R</i><sub>u</sub> (uncompensated resistance), and <i>C</i><sub>dl</sub> (double layer capacitance). The automated method of analysis employed time domain optimization and Bayesian statistics. This and all other methods assumed the Butler–Volmer model applies for electron transfer kinetics, planar diffusion for mass transport, Ohm’s Law for <i>R</i><sub>u</sub>, and a potential-independent <i>C</i><sub>dl</sub> model. Heuristic approaches utilize combinations of Fourier Transform filtering, sensitivity analysis, and simplex-based forms of optimization applied to resolved AC harmonics and rely on experimenter experience to assist in experiment–theory comparisons. Remarkable consistency of parameter evaluation was achieved, although the fully automated time domain method provided consistently higher α values than those based on frequency domain data analysis. The origin of this difference is that the implemented fully automated method requires a perfect model for the double layer capacitance. In contrast, the importance of imperfections in the double layer model is minimized when analysis is performed in the frequency domain. Substantial variation in <i>k</i><sup>0</sup> values was found by analysis of the 10 data sets for this highly surface-sensitive pathologically variable [Fe­(CN)<sub>6</sub>]<sup>3–/4–</sup> process, but remarkably, all fit the quasi-reversible model satisfactorily

    New Insights into the Analysis of the Electrode Kinetics of Flavin Adenine Dinucleotide Redox Center of Glucose Oxidase Immobilized on Carbon Electrodes

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    New insights into electrochemical kinetics of the flavin adenine dinucleotide (FAD) redox center of glucose-oxidase (GlcOx) immobilized on reduced graphene oxide (rGO), single- and multiwalled carbon nanotubes (SW and MWCNT), and combinations of rGO and CNTs have been gained by application of Fourier transformed AC voltammetry (FTACV) and simulations based on a range of models. A satisfactory level of agreement between experiment and theory, and hence establishment of the best model to describe the redox chemistry of FAD, was achieved with the aid of automated e-science tools. Although still not perfect, use of Marcus theory with a very low reorganization energy (≤0.3 eV) best mimics the experimental FTACV data, which suggests that the process is gated as also deduced from analysis of FTACV data obtained at different frequencies. Failure of the simplest models to fully describe the electrode kinetics of the redox center of GlcOx, including those based on the widely employed Laviron theory is demonstrated, as is substantial kinetic heterogeneity of FAD species. Use of a SWCNT support amplifies the kinetic heterogeneity, while a combination of rGO and MWCNT provides a more favorable environment for fast communication between FAD and the electrode
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