Development of "structure-property" models in nucleophilic substitution reactions involving azides

© 2014 Pleiades Publishing, Ltd. This paper reports a predictive model for the rate constant of the bimolecular nucleophilic substitution involving the azide moiety. It predicts reaction rate constants in different solvents, including organic mixtures, and with different organic and inorganic azides as reactants. The optimal descriptors describing solvent effects and a cation type in the azide salt were suggested. A reasonably good predictive performance of the model in cross-validation has been demonstrated. The model was applied to predict the rates of the reactions between sodium azide with two conformers of calixarenes as well as 3-bromopropyl phenyl ester. For sterically non-hindered molecules, a good agreement between predicted and experimental reaction rates was observed. On the other hand, the model poorly reproduces the results for sterically hindered molecules

QSPR MODELING OF TAUTOMERIC EQUILIBRIA USING LOCAL DESCRIPTORS

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Dispersion of watermelon rinds as secondary raw materials in technologies of pectin-containing extracts and film structures

The development of protective coatings based on pectin substances that serve as natural structure-forming agents developed from a secondary resource base is focused on removing a complex problem in the production of finished products by deep processing of basic raw materials and developing an original film material. At the same time, the technical result of obtaining pectin-containing film structures is their ability to protect food products from microbiological spoilage, natural losses during storage and the preservation of quality and safety indicators. An important preparatory procedure that determines the efficiency and intensity of extraction processes can be attributed to the operation of dispersing the feedstock, since it directly affects the size of the contact surface area of the phases involved in mass transfer. However, it is clear that the greater the degree of grinding, the higher the efficiency of the process, but an excessive increase can lead to additional unjustified energy costs and, as a result, to an increase in the cost of the finished products sold. In this regard, the purpose of the research is to analyze existing technologies for producing pectin-containing extracts, in which watermelon rinds can be used as secondary resources and to intensify the extraction process by conducting a rational preparatory procedure for grinding the raw materials. The object of the research are watermelon rinds as non-recyclable waste from processing watermelon raw materials. According to the obtained graphs, and taking into account the high rates of gelatinization of the obtained pectin extracts, it is possible to recommend a complex treatment of watermelon rinds, including, in addition to the operations of preliminary preparation of raw materials, ultrasonic exposure and acid hydrolysis, and it is desirable to use food acids, for example, acetic or citric, instead of aggressive sulfuric and hydrochloric acids. As a result of the study of the dispersed composition, it has been concluded that the average equivalent particle size of the dispersed raw materials does not exceed the recommended limits, that is, the result obtained can be considered acceptable

Visualization and Analysis of Complex Reaction Data: The Case of Tautomeric Equilibria

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Generative Topographic Mapping (GTM) approach was successfully used to visualize, analyze and model the equilibrium constants (KT) of tautomeric transformations as a function of both structure and experimental conditions. The modeling set contained 695 entries corresponding to 350 unique transformations of 10 tautomeric types, for which KT values were measured in different solvents and at different temperatures. Two types of GTM-based classification models were trained: first, a “structural” approach focused on separating tautomeric classes, irrespective of reaction conditions, then a “general” approach accounting for both structure and conditions. In both cases, the cross-validated Balanced Accuracy was close to 1 and the clusters, assembling equilibria of particular classes, were well separated in 2-dimentional GTM latent space. Data points corresponding to similar transformations measured under different experimental conditions, are well separated on the maps. Additionally, GTM-driven regression models were found to have their predictive performance dependent on different scenarios of the selection of local fragment descriptors involving special marked atoms (proton donors or acceptors). The application of local descriptors significantly improves the model performance in 5-fold cross-validation: RMSE=0.63 and 0.82 logKT units with and without local descriptors, respectively. This trend was as well observed for SVR calculations, performed for the comparison purposes

Alkyl-malonate-substituted thiacalix[4]arenes as ligands for bottom-up design of paramagnetic Gd(III)-containing colloids with low cytotoxicity

© 2017 The Authors. The present work introduces thiacalix[4]arene adopting 1,3-alternate conformation with alkyl-malonate terminal substituents as ligands for Gd(III) ions. pH-dependent complex formation of Gd(III) ions via alkyl-malonate substituents in aqueous DMSO solutions results in a precipitation. The precipitated complexes were converted into hydrophilic colloids of "plum-pudding" morphology, where the Gd(III) complexes form hard small (1.5-4nm) cores included into larger (about 180nm) soft PSS shells. The precipitate-to-colloid transformation is facilitated by polystyrolsulfonate (PSS) for Gd(III) complexes with thiacalix[4] arene bearing propyl-malonate groups, while the presence of PSS triggers a dissolution of the precipitated complexes for thiacalix[4]arenes with pentyl-malonate substituents. To a lesser extent the similar tendency disturbs the formation of PSS-stabilized colloids on the basis of butyl-malonate substituted thiacalix[4] arene. The PSS-stabilized colloids exhibit high longitudinal and transverse relaxivities (r 1 =23.8 and r 2 =29.4mM -1 s -1 at 0.47T, respectively), while the recoating of the PSS-stabilized colloids with polyethyleneimine is accompanied by the dissolution of the hard cores. High relaxivity along with low cytotoxicity of PSS-stabilized colloids indicates their applicability as contrast agents in MRI

Borexino's search for low-energy neutrinos associated with gravitational wave events from GWTC-3 database

The search for neutrino events in correlation with gravitational wave (GW) events for three observing runs (O1, O2 and O3) from 09/2015 to 03/2020 has been performed using the Borexino data-set of the same period. We have searched for signals of neutrino-electron scattering with visible energies above 250 keV within a time window of 1000 s centered at the detection moment of a particular GW event. The search was done with three visible energy thresholds of 0.25, 0.8 and 3.0 MeV.Two types of incoming neutrino spectra were considered: the mono-energetic line and the spectrum expected from supernovae. The same spectra were considered for electron antineutrinos detected through inverse beta-decay (IBD) reaction. GW candidates originated by merging binaries of black holes (BHBH), neutron stars (NSNS) and neutron star and black hole (NSBH) were analysed separately. Additionally, the subset of most intensive BHBH mergers at closer distances and with larger radiative mass than the rest was considered. In total, follow-ups of 74 out of 93 gravitational waves reported in the GWTC-3 catalog were analyzed and no statistically significant excess over the background was observed. As a result, the strongest upper limits on GW-associated neutrino and antineutrino fluences for all flavors (\nu_e, \nu_\mu, \nu_\tau) have been obtained in the (0.5 - 5.0) MeV neutrino energy range.Comment: 13 pages, 8 figure

Experimental Detection of the CNO Cycle

Borexino recently reported the first experimental evidence for a CNO neutrino. Since this process accounts for only about 1% of the Sun’s total energy production, the associated neutrino flux is remarkably low compared to that of the pp chain, the dominant hydrogen-burning process. This experimental evidence for the existence of CNO neutrinos was obtained using a highly radio-pure Borexino liquid scintillator. Improvements in the thermal stabilization of the detector over the last five years have allowed us to exploit a method of constraining the rate of 210Bi background. Since the CNO cycle is dominant in massive stars, this result is the first experimental evidence of a major stellar hydrogen-to-helium conversion mechanism in the Universe

Identification of the cosmogenic 11C background in large volumes of liquid scintillators with Borexino

Cosmogenic radio-nuclei are an important source of background for low-energy neutrino experiments. In Borexino, cosmogenic 11C decays outnumber solar pep and CNO neutrino events by about ten to one. In order to extract the flux of these two neutrino species, a highly efficient identification of this background is mandatory. We present here the details of the most consolidated strategy, used throughout Borexino solar neutrino measurements. It hinges upon finding the space-time correlations between 11C decays, the preceding parent muons and the accompanying neutrons. This article describes the working principles and evaluates the performance of this Three-Fold Coincidence (TFC) technique in its two current implementations: a hard-cut and a likelihood-based approach. Both show stable performances throughout Borexino Phases II (2012–2016) and III (2016–2020) data sets, with a 11C tagging efficiency of ∼90 % and ∼ 63–66 % of the exposure surviving the tagging. We present also a novel technique that targets specifically 11C produced in high-multiplicity during major spallation events. Such 11C appear as a burst of events, whose space-time correlation can be exploited. Burst identification can be combined with the TFC to obtain about the same tagging efficiency of ∼90% but with a higher fraction of the exposure surviving, in the range of ∼ 66–68 %