Invariants of ratio of crystal-mobile, liquid-mobile, and vaporized chaotized particles in solid, liquid, and gas states of substance

The authors of the article have developed the concept of chaotic particles based on the Boltzmann distribution over the kinetic energy of the particles’ chaotic motion. This distribution allows to combine the solid, liquid, and gaseous states of matter with the help of energetic particles called crystal-mobile, liquid-mobile, and vapor-mobile. The ratio of the proportions of such randomized particles determines a certain state of matter aggregation. The sum of the shares of these particles in all combinations at any temperature is equal to unity. During the study it has identified that qualitative and quantitative analysis of states with a priority basic effect of a randomized component of a substance can be conducted. Certain regularities of states were discovered, independent of the specific type of substance and consistent with the physicochemical properties. The entropy of mixing of all three energy classes of chaotic particles was calculated for simple substances. It was characterized by a maximum in the interval of the boiling point of substances. This feature testifies to the unique variety of possibilities for the implementation of the most complex heterogeneous processes in terrestrial conditions at atmospheric pressure, which ultimately ensured the self-organization of life

ANALYSIS OF THERMAL EFFECTS WITH MULTI-FOCI STRUCTURING

The possibility of a thermal imaging technique for studying the setting of composite materials in the light of the paradigm of multifocal structure formation is analyzed. Since thermal violated observations are characterized by a high thermal sensitivity to temperature gradients up to hundredths of degrees, they make it possible to distinguish the temperature differences arising in the adjacent sections of the hardening binding. A technique for obtaining thermal images (thermograms) of a hardening composite binder is implemented. A series of thermograms of setting processes was obtained, for two of them a quantitative study was carried out, including the temperature gauge and the construction of several types of graphic mappings of the obtained patterns ‒ the normalized frequency of the distribution of the area of the binder for those temperatures and two types of densitograms ‒ radial and circular, allowing to visualize the structure of thermal foci arising in a binder. The hardening of binding materials is considered as a multistage exothermic process, in which hydration processes is accompanied by heating. The speed of heterogeneous processes associated with hydration depends, in turn, on the characteristics of the forming structure of binding materials. The observed thermal processes are considered as an indirect response, "shadow" of structure formation processes. The information consisting in this indirect response, however, is enough to make a number of conclusions on the nature of the emerging structure. The study revealed a high probability of the formation of foci near the macroscopic boundaries of the section (walls and bottom of the form), inconsistency of the structural processes, the occurrence of diverse foci of structure formation corresponding to temperature foci. The interpretation of the data obtained is the conclusion about formation of the regions of high plastic deformations near the boundaries of the contact of the foci. This regions are considered as a cluster of microscopic boundaries of the section, cracks and pores, which give rise to the structure of the destruction of the hardened material. The emergence of such areas is associated with nonynchronouspassage of structuring in different parts of the binder.

Leveraging the interplay between homogeneous and heterogeneous catalytic mechanisms: copper-iron nanoparticles working under chemically relevant tumor conditions

The present work sheds light on a generally overlooked issue in the emerging field of bio-orthogonal catalysis within tumor microenvironments (TMEs): the interplay between homogeneous and heterogeneous catalytic processes. In most cases, previous works dealing with nanoparticle-based catalysis in the TME, focus on the effects obtained (e.g. tumor cell death) and attribute the results to heterogeneous processes alone. The specific mechanisms are rarely substantiated and, furthermore, the possibility of a significant contribution of homogeneous processes by leached species –and the complexes that they may form with biomolecules- is neither contemplated nor pursued. Herein, we have designed a bimetallic catalyst nanoparticle containing Cu and Fe species and we have been able to describe the whole picture in a more complex scenario where both homogeneous and heterogeneous processes are coupled and fostered under TME relevant chemical conditions. We investigate the preferential leaching of Cu ions in the presence of a TME overexpressed biomolecule such as glutathione (GSH). We demonstrate that these homogeneous processes initiated by the released by Cu-GSH interactions are in fact responsible for the greater part of the cell death effects found (GSH, a scavenger of reactive oxygen species is depleted and highly active superoxide anions are generated in the same catalytic cycle). The remaining solid CuFe nanoparticle becomes an active catalase-mimicking surrogate able to supply oxygen from oxygen reduced species, such as superoxide anions (by-product from GSH oxidation) and hydrogen peroxide, another species that is enriched in the TME. This enzyme-like activity is essential to sustain the homogeneous catalytic cycle in the oxygen-deprived tumor microenvironment. The combined heterogeneous-homogeneous mechanisms revealed themselves as highly efficient in selectively killing cancer cells, due to their higher GSH levels compared to healthy cell lines.

RESEARCH OF GENERAL HYDROGEN TECHNOLOGY ACCORDING TO OPTIMAL PARAMETERS AS A COMPONENT OF COMPLEX DEVELOPMENT OF EFCE AND CFE-UA ASSOCIATIONS

The analysis of the prospects for the development of hydrogen energy in the EU and Ukraine is carried out. The possibilities of implementing projects and technologies for the production of green hydrogen for industrial use are considered. The conditions for the implementation of the project for the creation of a research and development center for hydrogen and hydrogen fuel cell technology are presented. A review of publications devoted to the process of obtaining hydrogen from water has been completed. The main factors influencing the course of reactions in the production of hydrogen from water using alloys are considered. Recommended alloys for producing hydrogen at autonomous facilities. The components of the research algorithm are given taking into account the system of process factors based on the analysis of literature data on the technology of hydrogen production by the electrolysis of water. The general principles of calculating gas generators have been established, which should be based on the basic principles of the thermodynamics of heterogeneous processes: classical thermodynamics of multiphase and heterogeneous systems.

Functionality-Based Formation of Secondary Organic Aerosol from m-Xylene Photooxidation

Photooxidation of volatile organic compounds (VOCs) produces condensable oxidized organics (COOs) to yield secondary organic aerosol (SOA), but the fundamental chemical mechanism for gas-to-particle conversion remains uncertain. Here we elucidate the production of COOs and their roles in SOA and brown carbon (BrC) formation from m-xylene oxidation by simultaneous monitoring the evolutions of gas-phase products and aerosol properties in an environmental chamber. Four COO types with the distinct functionalities of dicarbonyls, carboxylic acids, polyhydroxy aromatics/quinones, and nitrophenols are identified from early-generation oxidation, with the yields of 25 %, 37 %, 5 %, and 3 %, respectively. SOA formation occurs via several heterogeneous processes, including interfacial interaction, ionic dissociation/acid-base reaction, and oligomerization, with the yields of (20 ± 4) % and (32 ± 7) % at 10 % and 70 % relative humidity (RH), respectively. Chemical speciation shows the dominant presence of oligomers, nitrogen-containing organics, and carboxylates at RH and carboxylates at low RH. The identified BrC includes N-heterocycles/N-heterochains and nitrophenols, as evident from reduced single scattering albedo. The measured uptake coefficient (γ) for COOs is dependent on the functionality, ranging from 3.7 × 10−4 to 1.3 × 10−2. A kinetic framework is developed to predict SOA production from the concentrations and uptake coefficients for COOs. This functionality-based approach well reproduces SOA formation from m-xylene oxidation and is broadly applicable to VOC oxidation for other species. Our results reveal that photochemical oxidation of m-xylene represents a major source for SOA and BrC formation under urban environments, because of its large abundance, high reactivity with OH, and high yields for COOs.

Redistribution of total reactive nitrogen in the lowermost Arctic stratosphere during the cold winter 2015/2016

During winter 2015/2016 the Arctic stratosphere was characterized by extraordinarily low temperatures in connection with the occurrence of extensive polar stratospheric clouds. From mid of December 2015 until mid of March 2016 the German research aircraft HALO (High Altitude and Long–Range Research Aircraft) was deployed to probe the lowermost stratosphere in the Arctic region within the POLSTRACC (Polar Stratosphere in a Changing Climate) mission. More than twenty flights have been conducted out of Kiruna/Sweden and Oberpfaffenhofen/Germany, covering the whole winter period. Besides total reactive nitrogen (NOy), observations of nitrous oxide, nitric acid, ozone and water were used for this study. Total reactive nitrogen and its partitioning between gas- and particle phase are key parameters for understanding processes controlling the ozone budget in the polar winter stratosphere. The redistribution of total reactive nitrogen was evaluated by using tracer–tracer correlations. In January air masses with extensive nitrification were encountered at altitudes between 12 and 15 km. The excess NOy amounted up to about 6 ppb. During several flights, along with gas–phase nitrification, indications for extensive occurrence of nitric acid containing particles at flight altitude were found. These observations support the assumption of sedimentation and subsequent evaporation of nitric acid containing particles leading to redistribution of total reactive nitrogen. Remnants of nitrified air masses have been observed until mid of March. Between end of February and mid of March also de-nitrified air masses have been observed in connection with high potential temperatures. Using tracer–tracer correlations, missing total reactive nitrogen was estimated to amount up to 6 ppb. This indicates the downward transport of air masses that have been denitrified during the earlier winter phase. Observations within POLSTRACC, at the bottom of the vortex, reflect heterogeneous processes from the overlying Arctic winter stratosphere. The comparison of the observations with CLaMS model simulations confirm and complete the picture arising from the present measurements. The simulations confirm, that the ensemble of all observations is representative for the vortex–wide vertical NOy-redistribution.

Direct Observations of Anthracene Clusters at Ice Surfaces

Heterogeneous processes can control atmospheric composition. Snow and ice present important, but poorly understood, reaction media that can greatly alter the composition of air in the cryosphere in polar and temperate regions. Atmospheric scientists struggle to reconcile model predictions with field observations in snow-covered regions due to experimental challenges associated with monitoring reactions at air-ice interfaces, and debate regarding reaction kinetics and mechanisms has persisted for over a decade. In this work, we use wavelength-resolved fluorescence microscopy to determine the distribution and chemical speciation of the pollutant anthracene at the surfaces of environmentally relevant frozen surfaces. We show that anthracene adsorbs to frozen surfaces in monomeric form, but that following lateral diffusion, molecules ultimately reside within brine channels at saltwater ice surfaces, and in micron-sized clusters at freshwater ice surfaces; emission profiles indicate extensive self-association. We also measure anthracene photodegradation kinetics in aqueous solution and artificial snow prepared from frozen freshwater and saltwater solutions and use the micro-spectroscopic observations to explain the rate constants measured in different environments. These results resolve long-standing debates and will improve predictions of pollutant fate in the cryosphere. The techniques used can be applied to numerous surfaces within and beyond the atmospheric sciences.

Quantifying heterogeneous monsoonal melt on a debris-covered glacier in Nepal Himalaya using repeat uncrewed aerial system (UAS) photogrammetry

The ablation zones of debris-covered glaciers in Himalaya exhibit heterogeneous processes and melt patterns. Although sub-debris melt is measured at ablation stakes, the high variability of debris thickness necessitates distributed melt measurements at the glacier scale. Focusing on Annapurna III Glacier, we used uncrewed aerial system (UAS) photogrammetry to estimate total volume loss and slope-perpendicular glacier melt between May and November 2019 using flow-corrected point clouds. Results indicated the average elevation change was −1.10 ± 0.19 m, while the mean melt was −0.87 m w.e., equating to a mean melt rate of −0.47 cm w.e. d−1. However, the spatial pattern was highly variable due to complex local processes necessitating future study over short intervals. The evaluation of specific areas showed the interplay of debris thickness variability, subseasonal debris redistribution, supraglacial channel reconfiguration and the imprint of relict ice cliffs in leading to contemporary melt rates. Ice cliffs had higher melt distances (mean −3.9 ± 0.19 m) compared to non-cliff areas (mean −0.75 ± 0.19 m) and were the predominant control on the spatial patterns of seasonal melt rates. Crucially, the definition of ice cliff areas from thinning data has a profound impact on derived melt rates and melt enhancement. Our study demonstrates the possibility and utility of deriving fully-distributed slope-perpendicular melt measurements.

Ionic Liquids for Development of Heterogeneous Catalysts Based on Nanomaterials for Biocatalysis

The development of effective methods of enzyme stabilization is key for the evolution of biocatalytic processes. An interesting approach combines the stabilization process of proteins in ionic liquids and the immobilization of the active phase on the solid support. As a result, stable, active and heterogeneous biocatalysts are obtained. There are several benefits associated with heterogeneous processes, as easy separation of the biocatalyst from the reaction mixture and the possibility of recycling. Accordingly, this work focused on the supported ionic liquid phases as the efficient enzyme stabilization carriers, and their application in both continuous flow and batch biocatalytic processes.