RESUMEN

This study explores the thermodynamic properties of doped graphene using an adapted electronic spectrum. We employed the one-electron tight-binding model to describe the hexagonal lattice structure. The dispersion relation for graphene is expressed in terms of the hopping energies using a compositional parameter that characterizes the different dopant atoms in the lattice. The focus of the investigation is on the impact of the compositions, specifically the presence of dopant atoms, on the energy spectrum, entropy, temperature, and specific heat of graphene. The numerical and analytical results reveal distinct thermodynamic behaviors influenced by the dopant composition, including topological transitions, inflection points in entropy, and specific heat divergences. In addition, the use of Boltzmann entropy and the revision of Nernst's theorem for doped graphene are introduced as novel aspects.

RESUMEN

This study aimed to produce, characterize and purify a protease from Aspergillus heteromorphus URM0269. After production by solid fermentation of wheat bran performed according to a central composite design, protease was characterized in terms of biochemical, kinetic, and thermodynamic parameters for further purification by chromatography. Proteolytic activity achieved a maximum value of 57.43 U/mL using 7.8 g of wheat bran with 40 % moisture. Protease displayed high stability in the pH and temperature ranges of 5.0-10.0 and 20-30 °C, respectively, and acted optimally at pH 7.0 and 50 °C. The enzyme, characterized as a serine protease, followed Michaelis-Menten kinetics with a maximum reaction rate of 140.0 U/mL and Michaelis constant of 11.6 mg/mL. Thermodynamic activation parameters, namely activation Gibbs free energy (69.79 kJ/mol), enthalpy (5.86 kJ/mol), and entropy (-214.39 J/mol.K) of the hydrolysis reaction, corroborated with kinetic modeling showing high affinity for azocasein. However, thermodynamic parameters suggested a reversible mechanism of unfolding. Purification by chromatography yielded a protease purification factor of 7.2, and SDS-PAGE revealed one protein band with a molecular mass of 14.7 kDa. Circular dichroism demonstrated a secondary structure made up of 45.6 % α-helices. These results show the great potential of this protease for future use in the industrial area.

Asunto(s)

RESUMEN

CONTEXT: New technologies have been developed toward the use of green energies. The production of formic acid (FA) from carbon dioxide (CO[Formula: see text]) hydrogenation with H[Formula: see text] is a sustainable process for H[Formula: see text] storage. However, the FA adduct stabilization is thermodynamically dependent on the type of solvent and thermodynamic conditions. The results suggest a wide range of dielectric permittivity values between the dimethyl sulfoxide (DMSO) and water solvents to stabilize the FA in the absence of base. The thermodynamics analysis and the infrared and charge density difference results show that the formation of the FA complex with H[Formula: see text]O is temperature dependent and has a major influence on aqueous solvents compared to the FA adduct with amine, in good agreement with the experiment. In these conditions, the stability thermodynamic of the FA molecule may be favorable at non-organic solvents and dielectric permittivity values closer to water. Therefore, a mixture of aqueous solvents with possible ionic composition could be used to increase the thermodynamic stability of H[Formula: see text] storage in CO[Formula: see text] conversion processes. METHODS: Using the Quantum ESPRESSO package, density functional theory (DFT) calculations were performed with periodic boundary conditions, and the electronic wave functions were expanded in plane waves. For the exchange-correlation functional, we use the vdW-DF functional with the inclusion of van der Waals (vdW) forces. Electron-ion interactions are treated by the projector augmented wave (PAW) method with pseudopotentials available in the PSlibrary repository. The wave functions and the electronic densities were expanded employing accurate cut-off energies of 6.80[Formula: see text]10[Formula: see text] and 5.44[Formula: see text]10[Formula: see text] eV, respectively. The electronic density was computed from the wave functions calculated at the [Formula: see text]-point in the first Brillouin-zone. Each structural optimization was minimized according to the Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm, with force and energy convergence criteria of 25 meV[Formula: see text]Å[Formula: see text] and 1.36 meV, respectively. The electrostatic solvation effects were performed by the [Formula: see text] package with the Self-Consistent Continuum Solvation (SCCS) approach.

RESUMEN

The universality of classical thermodynamics rests on the central limit theorem, due to which, measurements of thermal fluctuations are unable to reveal detailed information regarding the microscopic structure of a macroscopic body. When small systems are considered and fluctuations become important, thermodynamic quantities can be understood in the context of classical stochastic mechanics. A fundamental assumption behind thermodynamics is therefore that of coarse graining, which stems from a substantial lack of control over all degrees of freedom. However, when quantum systems are concerned, one claims a high level of control. As a consequence, information theory plays a major role in the identification of thermodynamic functions. Here, drawing from the concept of gauge symmetry-essential in all modern physical theories-we put forward a new possible intermediate route. Working within the realm of quantum thermodynamics, we explicitly construct physically motivated gauge transformations which encode a gentle variant of coarse graining behind thermodynamics. As a first application of this new framework, we reinterpret quantum work and heat, as well as the role of quantum coherence.

RESUMEN

Thermostability is an important and desired feature of therapeutic proteins and is critical for the success or failure of protein drugs development. It can be increased by PEGylation-binding of poly(ethylene glycol) moieties-or glycosylation-post-translational modification to add glycans. Here, the thermostability and thermodynamic parameters of native, PEGylated, and glycosylated versions of the antileukemic enzyme crisantaspase were investigated. First-order kinetics was found to describe the irreversible deactivation process. Activation energy of the enzyme-catalyzed reaction (E*) was estimated for native, PEGylated, and glycosylated enzyme (10.2, 14.8, and 18.8 kJ mol-1 respectively). Half-life decreased progressively with increasing temperature, and longer half-life was observed for PEG-crisantaspase (87.74 min) at 50 °C compared to the native form (9.79 min). The activation energy of denaturation of PEG-crisantaspase (307.1 kJ mol-1) was higher than for crisantaspase (218.1 kJ mol-1) and Glyco-crisantaspase (120.0 kJ mol-1), which means that more energy is required to overcome the energy barrier of the unfolding process. According to our results, PEG-crisantaspase is more thermostable than its native form, while Glyco-crisantaspase is more thermosensitive.

Asunto(s)

RESUMEN

DNA mismatches, that is, base pairs different from the canonical AT and CG, are involved in numerous biological processes and can be a problem for technological applications such as PCR amplification. The nearest-neighbour (NN) model is the standard approach for predicting melting temperatures and is used in methods of secondary structure predictions and modelling of hybridization kinetics. However, despite its biological and technological importance, existing NN parameters that include DNA mismatches are incomplete, and those available were obtained from a limited set of melting temperature at high sodium concentration. To our knowledge, there is currently no NN set of parameters for up to three mismatches covering all configurations at low sodium concentrations. Here, we are applying the NN model to a large set of 4096 published melting temperatures, covering all combinations of single, double and triple mismatches. Dealing with such a large set of temperature is challenging in several ways, bringing new methodological problems. Here, optimizing a large number of 252 independent parameters has required the development of a new method where we readjust the seed parameters using the definition of the Gibbs free energy. The new parameters predict the training set within 1.1 °C and the validation set to 2.7 °C.

Asunto(s)

RESUMEN

The thermodynamic formalism of nonequilibrium systems together with the theory of complex systems and systems biology offer an appropriate theoretical framework to explain the complexity observed at the macroscopic level in physiological phenomena. In turn, they allow the establishment of an appropriate conceptual and operational framework to address the study of phenomena such as the emergence and evolution of cancer.This chapter is organized as follows: In Subheading 1, an integrated vision of these disciplines is offered for the characterization of the emergence and evolution of cancer, seen as a nonlinear dynamic system, temporally and spatially self-organized out of thermodynamic equilibrium. The development of the various mathematical models and different techniques and approaches used in the characterization of cancer metastasis is presented in Subheading 2. Subheading 3 is devoted to the time course of cancer metastasis, with particular emphasis on the epithelial-mesenchymal transition (EMT henceforth) as well as chronotherapeutic treatments. In Subheading 4, models of the spatial evolution of cancer metastasis are presented. Finally, in Subheading 5, some conclusions and remarks are presented.

Asunto(s)

RESUMEN

This paper presents so-called thermoelectric generators (TEGs), which are considered thermal engines that transform heat into electricity using the Seebeck effect for this purpose. By using linear irreversible thermodynamics (LIT), it is possible to study the thermodynamic properties of TEGs for three different operating regimes: maximum power output (MPO), maximum ecological function (MEF) and maximum power efficiency (MPE). Then, by considering thermoelectricty, using the correspondence between the heat capacity of a solid and the metabolic rate, and taking the generation of energy by means of the metabolism of an organism as a process out of equilibrium, it is plausible to use linear irreversible thermodynamics (LIT) to obtain some interesting results in order to understand how metabolism is generated by a particle's released energy, which explains the empirically studied allometric laws.

RESUMEN

The use of chicken waste can contribute to the development of new processes and obtaining molecules with high added value. An experimental design was applied to evaluate the effect of moisture, temperature, and inoculum size on the production of antioxidant peptides and proteases by A. oryzae IOC3999 through solid-state fermentation (SSF) of chicken viscera meal. As a result, the process conditions strongly influenced protease production and antioxidant activity of the fermented products. A global analysis of the results indicated that the most adequate conditions for SSF were (assay 9): 40% initial moisture, 30 °C as the incubation temperature, 5.05 × 106 spores/g as the inoculum size, and 48-h fermentation as the fermentation time. Under this condition, the antioxidant activities for the ABTS- and DPPH-radicals inhibition and ferric reducing antioxidant power (FRAP) methods were 376.16, 153.29, and 300.47 (µmol TE/g), respectively, and the protease production reached 428.22 U/g. Ultrafiltration of the crude extract obtained under optimized fermentation conditions was performed, and the fraction containing peptides with molecular mass lower than 3 kDa showed the highest antioxidant activity. The proteases were biochemically characterized and showed maximal activity at pH values ranging from 5.0 to 6.0 and a temperature of 50 °C. The thermodynamic parameters indicated that the process of thermal protease inactivation is not spontaneous (ΔG*d > 88.78 kJ/mol), increasing with temperature (ΔH*d 27.01-26.88 kJ/mol), and with reduced disorder in the system (ΔS*d < - 197.74 kJ/mol) probably caused by agglomeration of partially denatured enzymes.

Asunto(s)

RESUMEN

Solubility is one of the most important physicochemical properties due to its involvement in physiological (bioavailability), industrial (design) and environmental (biotoxicity) processes, and in this regard, cosolvency is one of the best strategies to increase the solubility of poorly soluble drugs in aqueous systems. Thus, the aim of this research is to thermodynamically evaluate the dissolution process of triclocarban (TCC) in cosolvent mixtures of {N-methyl-2-pyrrolidone (NMP) + water (W)} at seven temperatures (288.15, 293.15, 298.15, 303.15, 308.15, 313.15 and 318.15 K). Solubility is determined by UV/vis spectrophotometry using the flask-shaking method. The dissolution process of the TCC is endothermic and strongly dependent on the cosolvent composition, achieving the minimum solubility in pure water and the maximum solubility in NMP. The activity coefficient decreases from pure water to NMP, reaching values less than one, demonstrating the excellent positive cosolvent effect of NMP, which is corroborated by the negative values of the Gibbs energy of transfer. In general terms, the dissolution process is endothermic, and the increase in TCC solubility may be due to the affinity of TCC with NMP, in addition to the water de-structuring capacity of NMP generating a higher number of free water molecules.

RESUMEN

We studied the thermodynamic properties such as the entropy, heat (JQ), and work (JW) rates involved when an atom passes through a Ramsey zone, which consists of a mode field inside a low-quality factor cavity that behaves classically, promoting rotations on the atomic state. Focusing on the atom, we show that JW predominates when the atomic rotations are successful, maintaining its maximum purity as computed by the von Neumann entropy. Conversely, JQ stands out when the atomic state ceases to be pure due to its entanglement with the cavity mode. With this, we interpret the quantum-to-classical transition in light of the heat and work rates. Besides, we show that, for the cavity mode to work as a Ramsey zone (classical field), several photons (of the order of 106) need to cross the cavity, which explains its classical behavior, even when the inside average number of photons is of the order of unity.

RESUMEN

In this article, we introduce a quasiprobability distribution of work that is based on the Wigner function. This proposal rests on the idea that the work conducted on an isolated system can be coherently measured by coupling the system to a quantum measurement apparatus. In this way, a quasiprobability distribution of work can be defined in terms of the Wigner function of the apparatus. This quasidistribution contains the information of the work statistics and also holds a clear operational definition that can be directly measured in a real experiment. Moreover, it is shown that the presence of quantum coherence in the energy eigenbasis is related with the appearance of features related to non-classicality in the Wigner function such as negativity and interference fringes. On the other hand, from this quasiprobability distribution, it is straightforward to obtain the standard two-point measurement probability distribution of work and also the difference in average energy for initial states with coherences.

RESUMEN

Shortcuts to adiabaticity (STA) are relevant in the context of quantum systems, particularly regarding their control when they are subjected to time-dependent external conditions. In this paper, we investigate the completion of a nonadiabatic evolution into a shortcut to adiabaticity for a quantum field confined within a one-dimensional cavity containing two movable mirrors. Expanding upon our prior research, we characterize the field's state using two Moore functions that enables us to apply reverse engineering techniques in constructing the STA. Regardless of the initial evolution, we achieve a smooth extension of the Moore functions that implements the STA. This extension facilitates the computation of the mirrors' trajectories based on the aforementioned functions. Additionally, we draw attention to the existence of a comparable problem within nonrelativistic quantum mechanics.

RESUMEN

The majority vote model is one of the simplest opinion systems yielding distinct phase transitions and has garnered significant interest in recent years. This model, as well as many other stochastic lattice models, are formulated in terms of stochastic rules with no connection to thermodynamics, precluding the achievement of quantities such as power and heat, as well as their behaviors at phase transition regimes. Here, we circumvent this limitation by introducing the idea of a distinct and well-defined thermal reservoir associated to each local configuration. Thermodynamic properties are derived for a generic majority vote model, irrespective of its neighborhood and lattice topology. The behavior of energy/heat fluxes at phase transitions, whether continuous or discontinuous, in regular and complex topologies, is investigated in detail. Unraveling the contribution of each local configuration explains the nature of the phase diagram and reveals how dissipation arises from the dynamics.

RESUMEN

The western tropical North Atlantic (WTNA) is a very complex region, with the influence of intense western boundary currents in connection with equatorial zonal currents, important atmospheric forcings (e.g Intertropical Convergence Zone), mesoscale activities (e.g NBC rings), and the world's largest river discharge as the Amazon River runoff. The volume discharge is equivalent to more than one-third of the Atlantic river freshwater input, with a plume that spreads over the region reaching the northwestward Caribbean Sea and eastward longitudes of 30°W, and influencing from physical to biological structures. Therefore, in order to enable and encourage more understanding of the region, here we present a dataset based on an idealized scenario of no river runoff of the Amazon River and Par ´a River in the WTNA. The numerical simulations were conducted with a regional oceanic modeling system (ROMS) model and three pairs of files were generated with the model outputs: (i) ROMS-files, with the parameters of the ROMS-outputs raw data in a NetCDF format and monthly and weekly frequencies; (ii) MATLAB-files, which contain oceanographic parameters also in monthly and weekly frequencies; and (iii) NetCDF-files, with oceanographic parameters again in monthly and weekly frequencies. For each file, we present the coordinates and variable names, descriptions, and correspondent units. The dataset is available in the Science Data Bank repository (doi: https://doi.org/10.57760/sciencedb.02145).

RESUMEN

A grafting of N1-(3-trimethoxysilylpropyl)diethylenetriamine (TMSPDETA) on natural clay was carried out to obtain an organic-inorganic hybrid clay material that was applied as an adsorbent to the uptake of Reactive Blue 19 (RB-19) and Reactive Green 19 (RG-19) dyes from aqueous wastewaters. This research demonstrates the effect of TMSPDETA contents on amino-functionalized clay materials' hydrophobic/hydrophilic behavior. The resultant material was utilized to uptake reactive dyes in aqueous solutions. The clay@TMSPDETA hybrid material was characterized by isotherm of adsorption and desorption of nitrogen, FTIR, elemental analysis, TGA, pHpzc, total acidity, total basicity groups, and hydrophilic balance. The hybrid samples were more hydrophilic than the pristine clay for ratios from 0.1 up to 0.5 due to adding amino groups to the pristine clay. FTIR spectra suggest that TMSPDETA was grafted onto the clay. The hybrid material presents a surface area 2.17-fold (42.7 m2/g) lower than pristine clay (92.7 m2/g). The total volume of pores of hybrid material was 0.0822 cm3/g, and the pristine clay material was 0.127 cm3/g, corresponding to a diminution of the total pore volume (Vtot) of 1.54 times. The kinetic data followed the pseudo-second-order (PSO) model for RB-19 and RG-19 reactive dyes. The equilibrium data were better fitted to the Liu isotherm model, displaying a Qmax as 178.8 and 361.1 mg g-1 for RB-19 and RG-19, respectively, at 20.0 °C. The main mechanism of interactions of the reactive dyes with the hybrid clay is electrostatic interaction. The clay@TMSPDETA has a very good effect on treating synthetic dye-textile wastewater. The removal percentage of simulated wastewater was up to 97.67% and 88.34% using distilled water and plastic industry wastewater as the solvents, respectively. The clay@TMSPDETA-0.1 could be recycled up to 5 cycles of adsorption and desorption of both dyes, attaining recoveries of 98.42% (RB-19) and 98.32% (RG-19) using 0.1 M HCl + 10% ethanol.

Asunto(s)

RESUMEN

The Brazil nut shell was used as a precursor material for preparing activated carbon by chemical activation with potassium hydroxide. The obtained material (BNSAC) was characterized, and the adsorptive features of phenol were investigated. The characterization showed that the activated carbon presented several rounded cavities along the surface, with a specific surface area of 332 m2 g-1. Concerning phenol adsorption, it was favored using an adsorbent dosage of 0.75 g L-1 and pH 6. The kinetic investigation revealed that the system approached the equilibrium in around 180 min, and the Elovich model represented the kinetic curves. The Sips model well represented the equilibrium isotherms. In addition, the increase in temperature from 25 to 55 °C favored the phenol adsorption, increasing the maximum adsorption capacity value (qs) from 83 to 99 mg g-1. According to the estimated thermodynamic parameters, the adsorption was spontaneous, favorable, endothermic, and governed by physical interactions. Therefore, the Brazil nut shell proved a good precursor material for preparing efficient activated carbon for phenol removal.

Asunto(s)

RESUMEN

In this work, we fabricated and characterized ZnO and TiO2 thin films, determining their structural, optical, and morphological properties. Furthermore, we studied the thermodynamics and kinetics of methylene blue (MB) adsorption onto both semiconductors. Characterization techniques were used to verify thin film deposition. The semiconductor oxides reached different removal values, 6.5 mg/g (ZnO) and 10.5 mg/g (TiO2), after 50 min of contact. The pseudo-second-order model was suitable for fitting the adsorption data. ZnO had a greater rate constant (45.4 × 10-3) than that of TiO2 (16.8 × 10-3). The removal of MB by adsorption onto both semiconductors was an endothermic and spontaneous process. Finally, the stability of the thin films showed that both semiconductors maintained their adsorption capacity after five consecutive removal tests.

RESUMEN

Torpor is used in small sized birds and mammals as an energy conservation trait. Considerable effort has been put towards elucidating the mechanisms underlying its entry and maintenance, but little attention has been paid regarding the exit. Firstly, we demonstrate that the arousal phase has a stereotyped dynamic: there is a sharp increase in metabolic rate followed by an increase in body temperature and, then, a damped oscillation in body temperature and metabolism. Moreover, the metabolic peak is around two-fold greater than the corresponding euthermic resting metabolic rate. We then hypothesized that either time or energy could be crucial variables to this event and constructed a model from a collection of first principles of physiology, control engineering and thermodynamics. From the model, we show that the stereotyped pattern of the arousal is a solution to save both time and energy. We extended the analysis to the scaling of the use of torpor by endotherms and show that variables related to the control system of body temperature emerge as relevant to the arousal dynamics. In this sense, the stereotyped dynamics of the arousal phase necessitates a certain profile of these variables which is not maintained as body size increases.

Asunto(s)

RESUMEN

We study the performance of an endoreversible magnetic Otto cycle with a working substance composed of a single quantum dot described using the well-known Fock-Darwin model. We find that tuning the intensity of the parabolic trap (geometrical confinement) impacts the proposed cycle's performance, quantified by the power, work, efficiency, and parameter region where the cycle operates as an engine. We demonstrate that a parameter region exists where the efficiency at maximum output power exceeds the Curzon-Ahlborn efficiency, the efficiency at maximum power achieved by a classical working substance.