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Ceiba aesculifolia is an important species in Mexico that generates significant amounts of biomass waste during its exploitation, which can be utilized to produce energy. This study presents the characterization of this waste based on chemical (proximal and elemental) and thermal analyses (TGA-DTG) at different heating rates (ß = 10-30 °C/min (283-303 K/min)) in the presence of nitrogen and in a temperature range of 25-900 °C. Kinetic parameters were calculated and analyzed as well. Activation energy (Ea) and the pre-exponential factor (A) were determined using the Friedman (132.03 kJ/mol, 8.11E + 10 s -1), FWO (121.65 kJ/mol, 4.30E + 09), KAS (118.14 kJ/mol, 2.41E + 09), and Kissinger (155.85 kJ/mol, 3.47E + 11) kinetic methods. Variation in the reaction order, n (0.3937-0.6141), was obtained by Avrami's theory. We also calculated the thermodynamic parameters (ΔH, ΔG, ΔS) for each kinetic method applied. The results for Ea, A, n, ΔH, ΔG, and ΔS show that this biomass waste is apt for use in pyrolysis. Moreover, the moisture (<10%), ash (<2%), volatile material (>80%), and HHV (>19%) contents of C. aesculifolia allowed us to predict acceptable performance in generating energy and fuels. Finally, infrared spectroscopy analysis (FT-IR) allowed us to identify important functional groups, including one that belongs to the family of the aliphatic hydrocarbons.

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Peroxyacid synthesis is the first step in Prilezhaev epoxidation, which is an industrial method to form epoxides. Motivated by the development of a kinetic model as a tool for solvent selection, the effect of solvent type and acid chain length on the lipase-catalyzed peroxyacid synthesis was studied. A thermodynamic activity-based ping-pong kinetic expression was successfully applied to predict the effect of the reagent loadings in hexane. The activity-based reaction quotients provided a prediction of solvent-independent equilibrium constants. However, this strategy did not achieve satisfactory estimations of initial rates in solvents of higher polarity. The lack of compliance with some assumptions of this methodology could be confirmed through molecular dynamics calculations i.e. independent solvation energies and lack of solvent interaction with the active site. A novel approach is proposed combining the activity-based kinetic expression and the free binding energy of the solvent with the active site to predict kinetics upon solvent change. Di-isopropyl ether generated a strong interaction with the enzyme's active site, which was detrimental to kinetics. On the other hand, toluene or limonene gave moderate interaction with the active site rendering improved catalytic yield compared with less polar solvents, a finding sharpened when peroctanoic acid was produced.

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This study examines the gasification kinetics of Brazilian municipal solid waste (MSW) and its components under air, CO2, and air/CO2 (70/30 vol%) atmospheres. The ignition indices of paper and plastic are 6 and 3 times that of food waste, which are 38.6 × 10-3 %/min3 and 19.6 × 10-3 %/min3, respectively, implying a faster separation of volatile compounds from the paper and plastic. The minimum Eα values of 132 kJ/mol and 140 kJ/mol have been obtained for paper waste under air and air/CO2, respectively. On CO2 condition, MSW has an average Ea value of 96 kJ/mol. Under an air/CO2 atmosphere, a high synergistic ΔW of -4.7 wt% has been identified between individual components. The presence of air and CO2 improves the oxidation and char gasification process, thus resulting in better combustion. Hence, the gasification of MSW under an air/CO2 atmosphere would improve the waste-to-energy plant's performance and minimize the CO2 emission.

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Herein, a methodology is employed based on the Flory-Rehner equation for estimating the Flory-Huggins interaction parameter (χ12*) of crosslinked elastomer blends. For this purpose, binary elastomer blends containing polybutadiene rubber (BR), styrene-butadiene rubber (SBR) and nitrile-butadiene rubber (NBR), were prepared in a mixing chamber at a temperature below the activation of the crosslinking agent. Swelling tests with benzene were employed to determine the crosslinked fraction, finding that after 20 min of thermal annealing, the BR and NBR were almost completely crosslinked, while the SBR only reached 60%. Additionally, the BR-SBR blend increased by 2-3 times its volume than its pure components; this could be explained based on the crosslink density. From the mechanical tests, a negative deviation from the rule of mixtures was observed, which suggested that the crosslinking was preferably carried out in the phases and not at the interface. Furthermore, tensile tests and swelling fraction (ϕsw) results were employed to determine the average molecular weight between two crosslinking points (Mc), and subsequently χ12*. Calculated χ12* values were slightly higher than those reported in the literature. The calculated thermodynamic parameters for the blends showed positive ΔGmix values and endothermic behavior, suggesting their immiscible nature.

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Experimental and computational approaches were used to study the microstructure of IN718 produced via powder bed fusion additive manufacturing (PBF-AM). The presence, chemical composition, and distribution of stable and metastable phases (γ'', δ, MC, and Laves) were also analyzed. The information obtained from the microstructural study was used to construct a tailored time-temperature transformation (TTT) diagram customized for additive manufacturing of IN718. Experimental techniques, including differential scanning calorimetry (DSC), scanning electron microscopy, energy dispersive X-ray spectroscopy, and electron backscatter diffraction (EBSD), were employed to establish the morphological, chemical, and structural characteristics of the microstructure. The Thermo-Calc software and a Scheil-Gulliver model were used to analyze the presence and behavior of phase transformations during heating and cooling processes under non-thermodynamic equilibrium conditions, typical of AM processes. Unlike conventional TTT diagrams of this alloy, the diagram presented here reveals that the precipitation of γ'' and δ phases occurs at lower temperatures and shorter times in AM-manufactured parts. Significantly, the superposition of γ'' and δ phase curves in the proposed diagram underscores the interdependence between these phases. This TTT diagram is a valuable insight that can help in the development of heat treatment processes and quality control for IN718 produced via PBF-AM.

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The first toxic component identified against mammals in the venom from Centruroides tecomanus scorpion from Colima, Mexico was Ct1a toxin, which was neutralized by human single chain variable fragment (scFv) RAS27. Venom characterization from these scorpions collected on the Pacific coast of Colima, enabled the identification of a second component of medical importance named Ct71 toxin. Amino acid sequence of Ct71 shares a high identity with Chui5 toxin from C. huichol scorpion, which was neutralized by scFv HV. For this reason, the kinetic parameters of interaction between Ct71 toxin and scFv HV were determined by surface plasmon resonance. Results showed a significantly higher affinity for Ct71 as compared to Chui5. As expected, this toxin was neutralized by scFv HV. The injection of a mixture of scFvs HV and RAS27, resulted in the neutralization of C. tecomanus venom, corroborating that human recombinant antibody fragments can efficiently contribute to the neutralization of medically important toxins and their respective venoms from Mexican scorpions.

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 Almost seventy years after its discovery, the sodium-potassium adenosine triphosphatase (the sodium pump) located in the cell plasma membrane remains a source of novel mechanistic and physiologic findings. A noteworthy feature of this enzyme/transporter is its robust stoichiometric ratio under physiological conditions: it sequentially counter-transports three sodium ions and two potassium ions against their electrochemical potential gradients per each hydrolyzed ATP molecule. Here we summarize some present knowledge about the sodium pump and its physiological roles, and speculate whether energetic constraints may have played a role in the evolutionary selection of its characteristic stoichiometric ratio.

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Contamination of water by toxic dyes is a serious environmental problem. Adsorbents prepared by an environmentally safe route have stood out for application in pollutant removal. Herein, iron oxide-based nanomaterial composed of Fe(III)-OOH and Fe(II/III) bound to proanthocyanidins, with particles in the order of 20 nm, was prepared by green synthesis assisted by extract of açaí (Euterpe oleracea Mart.) berry seeds from an agro-industrial residue. The nanomaterial was applied in the adsorption of cationic dyes. Screening tests were carried out for methylene blue (MB), resulting in an outstanding maximum adsorption capacity of 531.8 mg g-1 at 343 K, pH 10, 180 min. The kinetics followed a pseudo-second-order model and the isotherm of Fritz-Schülnder provided the best fit. Thermodynamic data show an endothermic process with entropy increase, typical of chemisorption. The proposed mechanism is based on the multilayer formation over a heterogeneous adsorbent surface, with chemical and electrostatic interactions of MB with the iron oxide nanoparticles and with the proanthocyanidins. The high adsorption efficiency was attributed to the network formed by the polymeric proanthocyanidins that entangled and protected the iron oxide nanoparticles, which allowed the reuse of the nanomaterial for seven cycles without loss of adsorption efficiency.

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This research presents the results of the immobilization of Candida Antarctica Lipase B (CALB) on MOF-199 and ZIF-8 and its use in the production of biodiesel through the transesterification reaction using African Palm Oil (APO). The results show that the highest adsorption capacity, the 26.9 mg·g-1 Lipase, was achieved using ZIF-8 at 45 °C and an initial protein concentration of 1.20 mg·mL-1. The results obtained for the adsorption equilibrium studies allow us to infer that CALB was physically adsorbed on ZIF-8 while chemically adsorbed with MOF-199. It was determined that the adsorption between Lipase and the MOFs under study better fit the Sips isotherm model. The results of the kinetic studies show that adsorption kinetics follow the Elovich model for the two synthesized biocatalysts. This research shows that under the experimental conditions in which the studies were carried out, the adsorption processes are a function of the intraparticle and film diffusion models. According to the results, the prepared biocatalysts showed a high efficiency in the transesterification reaction to produce biodiesel, with methanol as a co-solvent medium. In this work, the catalytic studies for the imidazolate, ZIF-8, presented more catalytic activity when used with CALB. This system presented 95% biodiesel conversion, while the biocatalyst formed by MOF-199 and CALB generated a catalytic conversion percentage of 90%. Although both percentages are high, it should be noted that CALB-MOF-199 presented better reusability, which is due to chemical interactions.

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Understanding how species adapt to different temperatures is crucial to predict their response to global warming, and thermal performance curves (TPCs) have been employed recurrently to study this topic. Nevertheless, fundamental questions regarding how thermodynamic constraints and evolution interact to shape TPCs in lineages inhabiting different environments remain unanswered. Here, we study Drosophila simulans along a latitudinal gradient spanning 3000 km to test opposing hypotheses based on thermodynamic constrains (hotter-is-better) versus biochemical adaptation (jack-of-all-temperatures) as primary determinants of TPCs variation across populations. We compare thermal responses in metabolic rate and the egg-to-adult survival as descriptors of organismal performance and fitness, respectively, and show that different descriptors of TPCs vary in tandem with mean environmental temperatures, providing strong support to hotter-is-better. Thermodynamic constraints also resulted in a strong negative association between maximum performance and thermal breadth. Lastly, we show that descriptors of TPCs for metabolism and egg-to-adult survival are highly correlated, providing evidence of co-adaptation, and that curves for egg-to-adult survival are systematically narrower and displaced toward lower temperatures. Taken together, our results support the pervasive role of thermodynamics constraining thermal responses in Drosophila populations along a latitudinal gradient, that are only partly compensated by evolutionary adaptation.

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A central problem in the cognitive sciences is identifying the link between consciousness and neural computation. The key features of consciousness-including the emergence of representative information content and the initiation of volitional action-are correlated with neural activity in the cerebral cortex, but not computational processes in spinal reflex circuits or classical computing architecture. To take a new approach toward considering the problem of consciousness, it may be worth re-examining some outstanding puzzles in neuroscience, focusing on differences between the cerebral cortex and spinal reflex circuits. First, the mammalian cerebral cortex exhibits exascale computational power, a feature that is not strictly correlated with the number of binary computational units; second, individual computational units engage in noisy coding, allowing random electrical events to gate signaling outcomes; third, this noisy coding results in the synchronous firing of statistically random populations of cells across the neural network, at a range of nested frequencies; fourth, the system grows into a more ordered state over time, as it encodes the predictive value gained through observation; and finally, the cerebral cortex is extraordinarily energy efficient, with very little free energy lost to entropy during the work of information processing. Here, I argue that each of these five key features suggest the mammalian brain engages in probabilistic computation. Indeed, by modeling the physical mechanisms of probabilistic computation, we may find a better way to explain the unique emergent features arising from cortical neural networks.

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There is scarce information on the vibrational and thermal properties of small Ni clusters. Here, the outcomes of ab initio spin-polarized density functional theory calculations on the size and geometry effects upon the vibrational and thermal properties of Nin (n = 13 and 55) clusters, are discussed. For theses clusters a comparison is presented between the closed shell symmetric octahedral (Oh) and the icosahedral (Ih) geometries. The results indicate that the Ih isomers are lower in energy. Besides, ab initio molecular dynamics runs at T = 300K show that Ni13 and Ni55 clusters transform from their initial Oh geometries towards the corresponding Ih ones. For Ni13, we also consider the lowest energy less symmetric layered 1-3-6-3 structure, and the cuboid, recently observed experimentally for Pt13, which is competitive in energy but is unstable, as phonon analysis reveals. We calculate their vibrational density of states (νDOS) and heat capacity, and compare with the Ni FCC bulk counterpart. The characteristic features of the νDOS curves of these clusters are interpreted in terms of the clusters' sizes, the interatomic distance contractions, the bond order values as well as the internal pressure and strains of the clusters. We find that the softest possible frequency of the clusters is size and structure-dependent, being the smallest for the Oh ones. We identify mostly shear, tangential type displacements involving mainly surface atoms for the lowest frequency of the spectra of both Ih and Oh isomers. For the maximum frequencies of these clusters the central atom shows anti-phase movements against groups of nearest neighbor atoms. An excess of heat capacity at low temperatures with respect to the bulk is found, while at high temperatures a constant limiting value, close but lower to the Dulong and Petit value, is determined.

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Pomegranate is a fruit desirable for its nutritional and medicinal properties which has a great industrial potential that is yet under-explored. Notable for its integral use, the peels are used in medicinal infusions and the seeds consumed without restrictions. In this sense, the objective of this work is to determine the drying kinetics of pomegranate peels and seeds in a hot air circulation oven, at temperatures of 50, 60, and 70 °C, adjust mathematical models to experimental data, determine the effective diffusivities and thermodynamic properties of the process and the physicochemical characteristics of peels and seeds of fresh pomegranates and in their flours. Twelve models were used to adjust the drying kinetics, obtaining better results with the Diffusion Approximation model, Verma, and modified Henderson and Pabis. The effective diffusivities were well represented by an Arrhenius equation, with activation energies of 31.39 kJ/mol for seeds and 10.60 kJ/mol for peels. In the drying process, the seeds showed higher values of enthalpy, entropy, and Gibbs free energy concerning peels. Pomegranate peel and seed flours have proximal composition and distinct physicochemical characteristics, with high fiber, carbohydrate, and energy content. In addition, peel flours stand out for their mineral content, and seed flours do for their lipid and protein content.

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Capacitive deionization (CDI) is a promising and cost-effective technology that is currently being widely explored for removing dissolved ions from saline water. This research developed materials based on activated carbon (AC) materials modified with zinc oxide (ZnO) nanorods and used them as high-performance CDI electrodes for water desalination. The as-prepared electrodes were characterized by cyclic voltammetry, and their physical properties were studied through SEM and XRD. ZnO-coated AC electrodes revealed a better specific absorption capacity (SAC) and an average salt adsorption rate (ASAR) compared to pristine AC, specifically with values of 123.66 mg/g and 5.06 mg/g/min, respectively. The desalination process was conducted using a 0.4 M sodium chloride (NaCl) solution with flow rates from 45 mL/min to 105 mL/min under an applied potential of 1.2 V. Furthermore, the energy efficiency of the desalination process, the specific energy consumption (SEC), and the maximum and minimum of the effluent solution concentration were quantified using thermodynamic energy efficiency (TEE). Finally, this work suggested that AC/ZnO material has the potential to be utilized as a CDI electrode for the desalination of saline water.

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Natural pigments are bioactive compounds that can present health-promoting bioactivities in the human body. Due to their strong coloring properties, these compounds have been widely used as color additives as an alternative to artificial colorants. However, since these pigments are unstable under certain conditions, such as the presence of light, oxygen, and heat, the use of complexation and encapsulation techniques with biopolymers is in demand. Moreover, some functional properties can be achieved by using natural pigments-biopolymers complexes in food matrices. The complexation and encapsulation of natural pigments with biopolymers consist of forming a complex with the aim to make these compounds less susceptible to oxidative and degrading agents, and can also be used to improve their solubility in different media. This review aims to discuss different techniques that have been used over the last years to create natural pigment-biopolymers complexes, as well as the recent advances, limitations, effects, and possible applications of these complexes in foods. Moreover, the understanding of thermodynamic parameters between natural pigments and biopolymers is very important regarding the complex formation and their use in food systems. In this sense, thermodynamic techniques that can be used to determine binding parameters between natural pigments and potential wall materials, as well as their applications, advantages, and limitations are presented in this work. Several studies have shown an improvement in many aspects regarding the use of these complexes, including increased thermal and storage stability. Nonetheless, data regarding the biological effects on the human body and the sensory acceptance of natural pigments-biopolymers complexes in food systems are scarce in the literature.

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O objetivo geral desse trabalho foi desenvolver compostos de coordenação com os metais cobre, manganês, zinco, cobalto, níquel e magnésio com os aminoácidos L- ácido aspártico e glutâmico para aplicação como fertilizantes foliares e elucidação de seus prováveis mecanismos de absorção pela planta. Como plano de trabalho, pretendeu-se produzir alguns complexos metálicos com agentes complexantes que confiram características específicas: alta estabilidade termodinâmica e cinética quando comparado a quelatos usados comercialmente dos mesmos metais; alta solubilidade; compatibilidade com herbicidas e fungicidas e alta estabilidade frente a variações de pH. Os compostos foram caracterizados no estado sólido e/ou em solução aquosa, através de técnicas disponíveis em nosso laboratório, na Central Analítica do IQ-USP e/ou nos laboratórios da ICL América do Sul Ind. e Com. SA. Com o desenvolvimento dos compostos de coordenação, foram avaliados alguns parâmetros considerados imprescindíveis para garantia da qualidade do produto gerado, que foram então comparados aos de quelatos de EDTA (ácido etilenodiaminotetraacético) comercializados atualmente e que demonstraram vantagens. Para avaliar a eficiência dos produtos gerados foi realizada aplicação foliar em ao menos uma cultura e verificado o teor de cada nutriente após período de absorção e resposta produtiva, evidenciando e determinando o mecanismo de absorção realizado pela planta. Como resultado, desenvolveu-se uma série de produtos com alta tecnologia agregada que trouxeram benefícios nutricionais, sustentando uma nutrição de qualidade além de serem ecologicamente favoráveis (eco-friendly portfolio)

This project aims the development of copper, manganese, zinc, cobalt, nickel and iron metal complexes with L-amino acids aspartic and glutamic acids for application as foliar fertilizers and elucidation of the probable incorporation/absorption mechanism by plants. As a work plan, it was intended to produce these metal complexes with complexing agents that provide specific characteristics: high thermodynamic and kinetic stabilities when compared to the corresponding EDTA chelates; high solubility; compatibility with herbicides and fungicides and high stability against pH variations. With the development of such coordination compounds, some parameters considered indispensable to quality assurance were then evaluated, in comparison to that of currently available commercial EDTA chelates. To evaluate the performance of the obtained compounds, two foliar applications in the same crop were carried out. Further, the content of each nutrient after the production period and the productive capacity were evaluated, aiming to elucidate the absorption mechanism of the plant. As a result, elaborated products with high added technology were obtained, capable of ameliorating the nutritional benefits, that can support an eco-friendly portfolio

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The von Willebrand disease (vWD) is the most common hereditary bleeding disorder caused by defects of the von Willebrand Factor (vWF), a large extracellular protein in charge of adhering platelets to sites of vascular lesions. vWF performs this essential homeostatic task via specific protein-protein interactions between the vWF A1 domain and the platelet receptor, the glycoprotein Ib alpha (GPIBα). The two naturally occurring vWF A1 domain mutations G1324A and G1324S, near the GPIBα binding site, induce a dramatic decrease in platelet adhesion, resulting in a bleeding disorder classified as type 2M vWD. However, the reason for the drastic phenotypic response induced by these two supposedly minor modifications remains unclear. We addressed this question using a combination of equilibrium-molecular dynamics (MD) and nonequilibrium MD-based free energy simulations. Our data confirms that both mutations maintain the highly stable Rossmann fold of the vWF A1 domain. G1324A and G1324S mutations hardly changed the per-residue flexibility of the A1 domain but induced a global conformational change affecting the region near the binding site to GPIBα. Furthermore, we observed two significant changes in the vWF A1 domain upon mutation, the global redistribution of the internal mechanical stress and the increased thermodynamic stability of the A1 domain. These observations are consistent with previously reported mutations increasing the melting temperature. Overall, our results support the idea of thermodynamic conformational restriction of A1-before the binding to GPIBα-as a crucial factor determining the loss-of-function of the G1324A(S) vWD mutants.

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Centruroides huichol scorpion venom is lethal to mammals. Analysis of the venom allowed the characterization of four lethal toxins named Chui2, Chui3, Chui4, and Chui5. scFv 10FG2 recognized well all toxins except Chui5 toxin, therefore a partial neutralization of the venom was observed. Thus, scFv 10FG2 was subjected to three processes of directed evolution and phage display against Chui5 toxin until obtaining scFv HV. Interaction kinetic constants of these scFvs with the toxins were determined by surface plasmon resonance (SPR) as well as thermodynamic parameters of scFv variants bound to Chui5. In silico models allowed to analyze the molecular interactions that favor the increase in affinity. In a rescue trial, scFv HV protected 100% of the mice injected with three lethal doses 50 (LD50) of venom. Moreover, in mix-type neutralization assays, a combination of scFvs HV and 10FG2 protected 100% of mice injected with 5 LD50 of venom with moderate signs of intoxication. The ability of scFv HV to neutralize different toxins is a significant achievement, considering the diversity of the species of Mexican venomous scorpions, so this scFv is a candidate to be part of a recombinant anti-venom against scorpion stings in Mexico.

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For decades, there was an intense debate in relation to the mechanism behind the entry into metabolic depression (EMD) of mammals and birds. The fulcrum of the argument was whether the depression of metabolic rate ([Formula: see text]) was caused by the drop in body temperature, the so-called "Q10 effect", or whether it was caused by a metabolic downregulation. One present-day model of this process is a qualitative (textual) description: the initial step of EDM would be a downregulation in [Formula: see text] from the value maintaining euthermia at a given ambient temperature to the basal metabolic rate of the animal and, then, Q10 effect would take over and drop [Formula: see text] to its lower levels. Despite widely accepted, this qualitative description still misses a theoretical analysis. Here, we transpose the descriptive model to a formal quantitative one and analyze it under necessary thermodynamic conditions of a system. We, then, compare the results of the formal model to empirical data of EMD by mammals and birds. The comparisons indicate that the metabolic evolution in the course of the entry phase does not follow the descriptive model. Instead, as proposed by alternate models, EMD is a downregulated process as a whole until a new equilibrium Tb is attained.

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In this work, a transient analysis of a dual-skin chest-freezer refrigeration system, operating with R290, is studied numerically with the purpose of performing the characterization of the system through the second law of thermodynamics. A mathematical model which accounts for refrigerant mass distribution inside the system is used. In addition, this work addresses the calculation of entropy generation and exergy destruction for characterizing the system performance during its operations. In order to validate the model, a comparison with measured experimental data is performed for both pull-down and on-off operations. The characterization of the system through the second law of thermodynamics is conducted using two different methods. One consists of a direct calculation of the entropy generation rate and the second one in the calculation of exergy destruction rate. The equivalence of these two methods is used as an indicative of the "correctness" of the performed calculations. The model results agree near 97% with the experimental data used in the comparisons. Entropy generation and exergy destruction results along time for the whole system and in its individual components are characterized with the second law. These results are very useful for improving refrigeration system design.