Chemical and Mechanical Aspect of Entropy-Exergy Relationship

The present research focuses the chemical aspect of entropy and exergy properties. This research represents the complement of a previous treatise already published and constitutes a set of concepts and definitions relating to the entropy–exergy relationship overarching thermal, chemical and mechanical aspects. The extended perspective here proposed aims at embracing physical and chemical disciplines, describing macroscopic or microscopic systems characterized in the domain of industrial engineering and biotechnologies. The definition of chemical exergy, based on the Carnot chemical cycle, is complementary to the definition of thermal exergy expressed by means of the Carnot thermal cycle. These properties further prove that the mechanical exergy is an additional contribution to the generalized exergy to be accounted for in any equilibrium or non-equilibrium phenomena. The objective is to evaluate all interactions between the internal system and external environment, as well as performances in energy transduction processes.

Observations of Cyanogen Bromide (BrCN) in the Global Atmosphere during the NASA Atmospheric Tomography mission (ATom) and Implications for Active Bromine Chemistry.

<p>Bromine activation (the production of Br in an elevated oxidation state) represents a mechanism for ozone destruction and mercury removal in the global troposphere, and has been a common feature of both polar boundary layers, often accompanied by nearly complete ozone destruction. The chemistry and budget of active bromine compounds (e.g. Br<sub>2</sub>, BrCl, HOBr) reflects the cycling of Br and ultimately its impact on the environment. Cyanogen bromide (BrCN) has recently been measured by iodide ion high resolution time-of-flight mass spectrometry (I<sup>-</sup> CIMS) during the NASA Atmospheric Tomography mission, and could be a previously unquantified participant in active Br chemistry. BrCN mixing ratios ranged from below detection limit (1.5pptv) up to as high as 48 pptv (10sec avg) and enhancements were almost exclusively confined to the polar boundary layers (PBL). Likely BrCN formation pathways involve the reactions of active Br (Br<sub>2</sub>, HOBr) with reduced nitrogen compounds. Gas phase loss processes due to reaction with radical species are likely quite slow and photolysis is known to be relatively slow. These features, and the lack of BrCN enhancements above the PBL, imply that surface reactions must be the major loss processes. Known liquid phase reactions of BrCN result in the conversion of the Br to bromide (Br<sup>-</sup>) or formation of C-Br bonded organic species, hence a loss of atmospheric active Br from that chemical cycle. Thus, accounting for the chemistry of BrCN will be an important aspect of understanding polar Br cycling.</p>

The ATPase mechanism of myosin 15, the molecular motor mutated in DFNB3 human deafness

Cochlear hair cells each possess an exquisite bundle of actin-based stereocilia that detect sound. Unconventional myosin 15 (MYO15A) traffics and delivers critical molecules required for stereocilia development and thus is essential for building the mechanosensory hair bundle. Mutations in the human MYO15A gene interfere with stereocilia trafficking and cause hereditary hearing loss, DFNB3, but the impact of these mutations is not known, as MYO15A itself is poorly characterized. To learn more, we performed a kinetic study of the ATPase motor domain to characterize its mechano-chemical cycle. Using the baculovirus-Sf9 system, we purified a recombinant minimal motor domain (S1) by co-expressing the mouse MYO15 ATPase, essential and regulatory light chains that bind its IQ domains, and UNC45 and HSP90A chaperones required for correct folding of the ATPase. MYO15 purified with either UNC45A or UNC45B co-expression had similar ATPase activities (kcat = ~ 6 s-1 at 20°C). Using stopped-flow and quenched-flow transient kinetic analyses, we measured the major rate constants describing the ATPase cycle, including ATP , ADP and actin binding, hydrolysis and phosphate release. Actin-attached ADP release was the slowest measured transition (~ 12 s-1 at 20°C), although this did not rate-limit the ATPase cycle. The kinetic analysis shows the MYO15 motor domain has a moderate duty ratio (~ 0.5) and weak thermodynamic coupling between ADP and actin binding. These findings are consistent with MYO15 being kinetically adapted for processive motility when oligomerized. Our kinetic characterization enables future studies into how deafness-causing mutations affect MYO15 and disrupt stereocilia trafficking necessary for hearing.

Oxidative Stress-induced Toxicity and DNA Stability in Some Agri-field Based Livestock/Insect by Widely used Pesticides

Aim and Objectives: Humans continuously use pesticides in the field to control the pest population and weeds for considerable agricultural productivity. Side-by species like grazinganimals, insects and other species are adversely affected by or become resistant to pesticides. Insects, birds and cattle are highly abundant dwellers of the agriculture-field and represent three distinct phyla having versatile physiological features. Besides higher agricultural-productivity, protection to several species will maintain ecological/environmental balance. Studies on the effect of widely used pesticides on their DNA-stability and important enzymatic-activities are insufficient. Materials and Methods: Antioxidant-activity (Superoxide-dismutase; SOD/Catalase- by gelzymogram- assay) and DNA-stability (fragmentation-assay) in hepatic/gut tissues were studied after in vitro exposure of Chlorpyrifos, Fenvalerate, Nimbecidine or Azadirachtin to goat/cow/poultry-hen/insect. Results: In general, all pesticides were found to impair enzymatic-activities. However, lower organisms were affected more than higher vertebrates by azadirachtin-treatment. DNA fragmentation was found more in insects/poultry-birds than that of the cattle in hepatic/gut tissues. Inversely, toxicity/antioxidant marker-enzymes were more responsive in insect gut-tissues. However, mitochondrialtoxicity revealed variable effects on different species. It has been noticed that chlorpyrifos is the most toxic pesticide, followed by Fenvalerate/Nimbecidine (Azadirachtin, AZT). Nevertheless, AZT revealed its higher DNA-destabilizing effects on the field-insects as compared to the other animals. Conclusion: Field-insects are highly integrated into the ecosystem and the local bio-geo-chemical cycle, which may be impaired. Pesticides may have toxic effects on higher vertebrates and may sustain in the soil after being metabolized into their different derivatives. Some of the sensitive biochemical parameters of this organism may be used as a biomarker for pesticide toxicity.

The ATPase mechanism of myosin 15, the molecular motor mutated in DFNB3 human deafness

Cochlear hair cells possess an exquisite bundle of actin-based stereocilia that detect sound. Unconventional myosin 15 (MYO15A) traffics and delivers critical molecules required for stereocilia development and is essential for building the mechanosensory hair bundle. Mutations in the human MYO15A gene interfere with stereocilia trafficking and cause hereditary hearing loss, DFNB3. To understand the molecular mechanism of how MYO15A delivers proteins within stereocilia, we performed a kinetic study of the ATPase motor domain to characterize its mechano-chemical cycle. Using the baculovirus-Sf9 system, we purified a recombinant minimal motor domain (S1) by co-expressing the mouse MYO15 ATPase, essential and regulatory light chains that bind its IQ domains, and UNC45 and HSP90A chaperones required for correct folding of the ATPase. MYO15 purified with either UNC45A or UNC45B co-expression had similar ATPase activities (kcat = ~ 6 s−1 at 20°C). Using stopped-flow and quenched-flow transient kinetic analyses, we measured the major rate constants describing the ATPase cycle, including ATP, ADP and actin binding, hydrolysis and phosphate release. Actin-attached ADP release was the slowest measured transition (~ 12 s−1 at 20°C), although this did not rate-limit the ATPase cycle. The kinetic analysis shows the MYO15 motor domain has a moderate duty ratio (~ 0.5) and weak thermodynamic coupling between ADP and actin binding. This is consistent with MYO15 being adapted for strain sensing as a monomer, or processive motility if oligomerized into ensembles. Our kinetic characterization enables future studies into how deafness-causing mutations affect MYO15 and ultimately disrupt stereocilia trafficking necessary for normal hearing.

Kinetic Control over Droplet Ripening in Fuel-Driven Active Emulsions

Active droplets are made of phase-separated molecules that are activated and deactivated by a metabolic reaction cycle. Such droplets play a crucial role in biology as a class of membrane-less organelles. Moreover, theoretical studies show that active droplets can evolve to the same size or spontaneously self-divide when energy is abundant. All of these exciting properties, i.e., emergence, decay, collective behavior, and self-division, are pivotal to the functioning of life. However, these theoretical predictions lack experimental systems to test them quantitively. Here, we describe the synthesis of synthetic active droplets driven by a metabolic chemical cycle and we find a surprising new behavior, i.e., the dynamics of droplet-growth is regulated by the kinetics of the fuel-driven reaction cycle. Consequently, these droplets ripen orders of magnitude faster compared to Ostwald ripening. Combining experiments and theory, we elucidate the underlying mechanism, which could help better understand how cells regulate the growth of membrane-less organelles.<br>

Kinetic Control over Droplet Ripening in Fuel-Driven Active Emulsions

Active droplets are made of phase-separated molecules that are activated and deactivated by a metabolic reaction cycle. Such droplets play a crucial role in biology as a class of membrane-less organelles. Moreover, theoretical studies show that active droplets can evolve to the same size or spontaneously self-divide when energy is abundant. All of these exciting properties, i.e., emergence, decay, collective behavior, and self-division, are pivotal to the functioning of life. However, these theoretical predictions lack experimental systems to test them quantitively. Here, we describe the synthesis of synthetic active droplets driven by a metabolic chemical cycle and we find a surprising new behavior, i.e., the dynamics of droplet-growth is regulated by the kinetics of the fuel-driven reaction cycle. Consequently, these droplets ripen orders of magnitude faster compared to Ostwald ripening. Combining experiments and theory, we elucidate the underlying mechanism, which could help better understand how cells regulate the growth of membrane-less organelles.<br>

Вплив кінетичних параметрів на ефективність виділення водню шляхом розчинення сплаву АК7 в лужних розчинах з домішками активаторів

The aim of the article is to study the influence of the main factors on the hydrogen evolution performance, in particular, the concentration of components, the nature of the electrolyte, the composition and surface condition of the aluminum alloy. For research, a MICROmed device was used, which has a temperature control and a mixing function. Weight corrosion tests were evaluated gravimetrically using the brand scales CERTUS Balance CBA-150-0.02. pH of solutions was measured using pH - meters mark 150 MA. Processing of the results was carried out by mathematical planning of experiments using the software package Exel 2016. It proposed a low-temperature chemical synthesis method by reacting hydrogen alloys of aluminum with alkali solutions with additives activators. The basic patterns of change in the dissolution rate of the AK7 alloy and formation of hydrogen halide from the impact of ions in alkaline solutions and its influence on the process condition of the alloy surface and reaction products. In this alloy, the most influential is the admixture of silicon, which is 3–6% by weight. The influence of the kinetic parameters of dissolution of the AK7 aluminum alloy on the synthesis of hydrogen as a source of environmentally safe thermal energy is determined. The dependences of the process of hydrogen evolution in alkaline solutions by the mechanism of hydrogen depolarization on the nature of the aluminum alloy and impurities of activators in the electrolyte are established. The processes of the metal chemical cycle of hydrogen production have been studied; they create the conditions for the further development of the technological process of aluminodepolarization synthesis of hydrogen without the use of membrane electrolyzers. This method is important for the needs of small energy in small quantities.