Search Results (24)

Arginine plays a critical role in biomolecular interactions due to its guanidinium side chain, which enables multivalent electrostatic and hydrogen bonding contacts. In this study, atomistic molecular dynamics simulations were conducted across a broad concentration range (26–605 mM) to investigate the thermodynamic and structural features of arginine self-assembly in aqueous solution. Key observables—including hydrogen bond count, radius of gyration, contact number, and isobaric heat capacity—were analyzed to characterize emergent behavior. A three-regime aggregation pattern (dilute, cooperative, and saturated) was identified and quantitatively modeled using the Hill equation, revealing a non-linear transition in clustering behavior. Spatial analyses were supplemented with trajectory-based clustering and radial distribution functions. The heat capacity peak observed near 360 mM was interpreted as a thermodynamic signature of hydration rearrangement. Trajectory analyses utilized both GROMACS tools and the MDAnalysis library. While force field limitations and single-replica sampling are acknowledged, the results offer mechanistic insight into how arginine concentration modulates molecular organization—informing the understanding of biomolecular condensates, protein–nucleic acid complexes, and the design of functional supramolecular systems. The findings are in strong agreement with experimental observations from small-angle X-ray scattering and differential scanning calorimetry. Overall, this work establishes a cohesive framework for understanding amino acid condensation and reveals arginine’s concentration-dependent behavior as a model for weak, reversible molecular association. Full article

Pollution by heavy metals such as lead is a major concern, since exposure to these metals can lead to various adverse health effects. In this work, nanofibers composed of CuO (CuONFs) were developed as a novel and promising material for Pb(II) adsorption. There have been no previous reports concerning the production of polyacrylonitrile nanofibers modified with copper sulfate pentahydrate, followed by calcination, to be utilized as a Pb(II) adsorbent. The nanofibers were obtained using the centrifugal spinning method and then were characterized before and after a calcination step using analytical techniques. Adsorption parameters were investigated, including pH, contact time, adsorbate concentration, and temperature. Satisfactory Pb (II) adsorption was reached at 298 K, pH 5.8, and a maximum adsorption of 151.34 mg g⁻¹ was achieved, predicted by the Hill model. The kinetic data proved that Pb (II) adsorption better fitted the pseudo-second-order model, while the Hill model was confirmed to best fit the equilibrium data. Thermodynamic parameters demonstrated that the lead adsorption was favorable, spontaneous, and exothermic. The CuONFs maintained 97.51% of their initial adsorption capacity after two adsorption/desorption cycles. The results showed that CuONFs have excellent potential as an adsorbent for Pb(II), while also showing high stability during reuse. Full article

The aim of the work presented in this paper was development of a thermodynamically consistent constitutive model for orthotopic metals and determination of its parameters based on standard characterisation methods used in the aerospace industry. The model was derived with additive decomposition of the strain tensor and consisted of an elastic part, derived from Helmholtz free energy, Hill’s thermodynamic potential, which controls evolution of plastic deformation, and damage orthotopic potential, which controls evolution of damage in material. Damage effects were incorporated using the continuum damage mechanics approach, with the effective stress and energy equivalence principle. Material characterisation and derivation of model parameters was conducted with standard specimens with a uniform cross-section, although a number of tests with non-uniform cross-sections were also conducted here. The tests were designed to assess the extent of damage in material over a range of plastic deformation values, where displacement was measured locally using digital image correlation. The new model was implemented as a user material subroutine in Abaqus and verified and validated against the experimental results for aerospace-grade aluminium alloy 2024-T3. Verification was conducted in a series of single element tests, designed to separately validate elasticity, plasticity and damage-related parts of the model. Validation at this stage of the development was based on comparison of the numerical results with experimental data obtained in the quasistatic characterisation tests, which illustrated the ability of the modelling approach to predict experimentally observed behaviour. A validated user material subroutine allows for efficient simulation-led design improvements of aluminium components, such as stiffened panels and the other thin-wall structures used in the aerospace industry. Full article

In this study, several adsorption models were studied to predict the adsorption kinetics of turbidity on an electro-generated adsorbent throughout the electrocoagulation remediation of real groundwater. A new design for an electrocoagulation reactor consisting of a finned anode positioned concentrically in a tube-shaped cathode was fabricated, providing a significant active area compared to its immersed volume. This work completed a previous electrochemical study through a deep investigation of adsorption technology that proceeded throughout the electrocoagulation reactor under optimal operating conditions, namely a treatment period of 2–30 min, a 2.3-Ampere current, and a stirring speed of 50 rpm. The one-, two-, and three-parameter adsorption models investigated in this study possess significant regression coefficients: Henry (R² = 1.000), Langmuir (R² = 0.9991), Freundlich (R² = 0.9979), Temkin (R² = 0.9990), Kiselev (R² = 0.8029), Harkins–Jura (R² = 0.9943), Halsey (R² = 0.9979), Elovich (R² = 0.9997), Jovanovic (R² = 0.9998), Hill–de Boer (R² = 0.8346), Fowler–Guggenheim (R² = 0.8834), Dubinin–Radushkevich (R² = 0.9907), Sips (R² = 0.9834), Toth (R² = 0.9962), Jossens (R² = 0.9998), Redlich–Peterson (R² = 0.9991), Koble–Carrigan (R² = 0.9929), and Radke–Prausnitz (R² = 0.9965). The current behavior of the adsorption–electrocoagulation system follows pseudo-first-order kinetics (R² = 0.8824) and the Bangham and Burt mass transfer model (R² = 0.9735). The core findings proved that an adsorption-method-based electrochemical cell has significant outcomes, and all the adsorption models could be taken into consideration, along with other kinetic and thermodynamics investigations as well. Full article

The crystal structures, stability, mechanical properties and electronic structures of Nb-free and Nb-doped Ti-Al intermetallic compounds were investigated via first-principles calculations. Seven components and eleven crystal configurations were considered based on the phase diagram. The calculated results demonstrate that hP8-Ti₃Al, tP4-TiAl, tP32-Ti₃Al₅, tI24-TiAl₂, tI16-Ti₅Al₁₁, tI24-Ti₂Al₅, and tI32-TiAl₃ are the most stable phases. Mechanical properties were estimated with the calculated elastic constants, as well as the bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and Pugh’s ratio following the Voigt–Reuss–Hill scheme. As the Al content increases, the mechanical strength increases but the ductility decreases in the Ti-Al compounds. This results from the enhanced covalent bond formed by the continuously enhanced Al-sp hybrid orbitals and Ti-3d orbitals. Nb doping (~5 at.% in this study) keeps the thermodynamical and mechanical stability for the Ti-Al compounds, which exhibit slightly higher bulk modulus and better ductility. This is attributed to the fact that the Nb 4d orbitals locate near the Fermi level and interact with the Ti-3d and Al-3p orbitals, improving the metallic bonds based on the electronic structures. Full article

Almost every model of muscle contraction in the literature to date is a molecular power stroke model, even though this corpuscular mechanism is opposed by centuries of science, by 85 years of unrefuted evidence that muscle is a thermodynamic system, and by a quarter century of direct observations that the molecular mechanism of muscle contraction is a molecular switch, not a molecular power stroke. An ensemble of molecular switches is a binary mechanical thermodynamic system from which A.V. Hill’s muscle force–velocity relationship is directly derived, where Hill’s parameter a is the internal force against which unloaded muscle shortens, and Hill’s parameter b is the product of the switch displacement, d, and the actin–myosin ATPase rate. Ignoring this model and the centuries of thermodynamics that preceded it, corpuscularians continue to develop molecular power stroke models, adding to their 65-year jumble of “new”, “innovative”, and “unconventional” molecular mechanisms for Hill’s a and b parameters, none of which resemble the underlying physical chemistry. Remarkably, the corpuscularian community holds the thermodynamicist to account for these discrepancies, which, as outlined here, I have done for 25 years. It is long past time for corpuscularians to be held accountable for their mechanisms, which by all accounts have no foundation in science. The stakes are high. Molecular power stroke models are widely used in research and in clinical decision-making and have, for over half a century, muddied our understanding of the inner workings of one of the most efficient and clean-burning machines on the planet. It is problematic that corpuscularians present these models to stakeholders as science when in fact corpuscularians have been actively defending these models against science for decades. The path forward for scientists is to stop baseless rejections of muscle thermodynamics and to begin testing corpuscular and thermodynamic mechanisms with the goal of disproving one or the other of these hypotheses. Full article

An investigation of partial radial distribution functions and atomic pair potentials within a system has established that the existing potential functions are rooted in the assumption of a static arrangement of atoms, overlooking their distribution and vibration. In this study, Hill’s proposed radial distribution function polynomials are applied for the pure gaseous state to a binary liquid alloy to derive the pair potential energy. The partial radial distribution functions of 36 binary liquid alloy from literatures were used to obtain the binary model parameters of four thermodynamic models for validation. Results show that the regular solution model (RSM) and molecular interaction volume model (MIVM) outperform other models when the asymmetric method calculates the partial radial distribution function. RSM demonstrates an average SD of 0.078 and an ARD of 32.2%. Similarly, MIVM exhibits an average SD of 0.095 and an average ARD of 32.2%. Wilson model yields an average SD of 0.124 and an average ARD of 226%. Nonrandom two-liquid (NRTL) model exhibits an average SD of 0.225 and an average ARD of 911%. On applying the partial radial distribution function symmetry method, MIVM and RSM outperform the other models, with an average SD of 0.143 and an average ARD of 165.9% for MIVM. RSM yields an average SD of 0.117 and an average ARD of 208.3%. Wilson model exhibits average values of 0.133 and 305.6% for SD and ARD, respectively. NRTL model shows an average SD of 0.200 and an average ARD of 771.8%. Based on this result, the influence of the symmetry degree on the thermodynamic model is explored by examining the symmetry degree as defined by the experimental activity curves of the two components. Full article

The current work aims to study the thermal degradation of the flame retardant polyurethane aerogel (FR_PU_aerogel) through multiple milligram-scale experimental methods. A systemic methodology for measuring the reaction kinetics and thermodynamics of the thermal degradation of FR_PU_aerogel is detailed. Specifically, the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed simultaneously in inert atmosphere to measure the mass loss and heat flow data, and a numerical framework called ThermaKin2Ds was used to inversely model these experimental data. First, a reaction mechanism with six first-order consecutive reactions was developed based on the inverse analysis of the TGA data. The corresponding reaction kinetics were optimized using the hill climbing optimization algorithm. Subsequently, the heat capacities of each condensed phase component and the heat of the reactions were obtained through inversely modeling the heat flow data. Furthermore, the heat of the complete combustion of each gaseous component were derived based on the heat release rates measured in the milligram-scale combustion calorimeter (MCC) experiments. It is noted that the developed reaction mechanism was further validated against the mass loss data obtained at different heating rates. The parameters determined in this work serve as a core subset of inputs for the pyrolysis model development, which is essential for the quantitative understanding of the ignition and the combustion behavior of solid materials. Full article

YTaO₄ and the relevant modification are considered to be a promising new thermal barrier coating. In this article, phase stability and mechanical properties of the monoclinic (M), monoclinic-prime (M′), and tetragonal (T) REMO₄ (M = Ta, Nb) are systematically investigated from first-principles calculations method based on density functional theory (DFT). Our calculations show that M′-RETaO₄ is the thermodynamically stable phase at low temperatures, but the stable phase is a monoclinic structure for RENbO₄. Moreover, the calculated relative energies between M (or M′) and T phases are inversely proportional to the ionic radius of rare earth elements. It means that the phase transformation temperature of M′→T or M→T could decrease along with the increasing ionic radius of RE³⁺, which is consistent with the experimental results. Besides, our calculations exhibit that adding Nb into the M′-RETaO₄ phase could induce phase transformation temperature of M′→M. Elastic coefficient is attained by means of the strain-energy method. According to the Voigt–Reuss–Hill approximation method, bulk modulus, shear modulus, Young’s modulus, and Poisson’s ratio of T, M, and M’ phases are obtained. The B/G criterion proposed by Pugh theory exhibits that T, M, and M’ phases are all ductile. The hardness of REMO₄ (M = Ta, Nb) phases are predicted based on semi-empirical equations, which is consistent with the experimental data. Finally, the anisotropic mechanical properties of the REMO₄ materials have been analyzed. The emerging understanding provides theoretical guidance for the related materials development. Full article

The Dongsha Island (DS) is located in the mid-northern South China Sea continental margin. The waters around it are underlain by the Chaoshan Depression, a relict Mesozoic sedimentary basin, blanketed by thin Cenozoic sediments but populated with numerous submarine hills with yet less-known nature. A large hill, H110, 300 m high, 10 km wide, appearing in the southeast to the Dongsha Island, is crossed by an ocean bottom seismic and multiple channel seismic surveying lines. The first arrival tomography, using ocean bottom seismic data, showed two obvious phenomena below it: (1) a low-velocity (3.3 to 4 km/s) zone, with size of 20 × 3 km², centering at ~4.5 km depth and (2) an underlying high-velocity (5.5 to 6.3 km/s) zone of comparable size at ~7 km depth. MCS profiles show much-fragmented Cenozoic sequences, covering a wide chaotic reflection zone within the Mesozoic strata below hill H110. The low-velocity zone corresponds to the chaotic reflection zone and can be interpreted as of highly-fractured and fluid-rich Mesozoic layers. Samples dredged from H110 comprised of illite-bearing authigenic carbonate nodules and rich, deep-water organisms are indicative of hydrocarbon seepage from deep source. Therefore, H110 can be inferred as a mud volcano. The high-velocity zone is interpreted as of magma intrusion, considering that young magmatism was found enhanced over the southern CSD. Furthermore, the origin of H110 can be speculated as thermodynamically driven, i.e., magma from the depths intrudes into the thick Mesozoic strata and promotes petroleum generation, thus, driving mud volcanism. Mud volcanism at H110 and the occurrence of a low-velocity zone below it likely indicates the existence of Mesozoic hydrocarbon reservoir, which is in favor of the petroleum exploration. Full article

A thermodynamic description of porous media must handle the size- and shape-dependence of media properties, in particular on the nano-scale. Such dependencies are typically due to the presence of immiscible phases, contact areas and contact lines. We propose a way to obtain average densities suitable for integration on the course-grained scale, by applying Hill’s thermodynamics of small systems to the subsystems of the medium. We argue that the average densities of the porous medium, when defined in a proper way, obey the Gibbs equation. All contributions are additive or weakly coupled. From the Gibbs equation and the balance equations, we then derive the entropy production in the standard way, for transport of multi-phase fluids in a non-deformable, porous medium exposed to differences in boundary pressures, temperatures, and chemical potentials. Linear relations between thermodynamic fluxes and forces follow for the control volume. Fluctuation-dissipation theorems are formulated for the first time, for the fluctuating contributions to fluxes in the porous medium. These give an added possibility for determination of the Onsager conductivity matrix for transport through porous media. Practical possibilities are discussed. Full article

β-Cyclodextrin nanosponge (β−CD−M) was used for the adsorption of ibuprofen (IBU) from water and sewage. The obtained material was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller (BET), Barrett–Joyner–Halenda (BJH), Harkins and Jura t-Plot, zeta potential, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and elementary analysis (EA). Batch adsorption experiments were employed to investigate the effects of the adsorbent dose, initial IBU concentration, contact time, electrolyte ions and humic acids, and sewage over adsorption efficiency. The experimental isotherms were show off using Langmuir, Freundlich, Hill, Halsey and Sips isotherm models and thermodynamic analysis. The fits of the results were estimated according to the Sips isotherm, with a maximum adsorption capacity of 86.21 mg g⁻¹. The experimental kinetics were studied by pseudo-first-order, pseudo-second-order, Elovich, modified Freundlich, Weber Morris, Bangham’s pore diffusion, and liquid film diffusion models. The performed experiments revealed that the adsorption process fits perfectly to the pseudo-second-order model. The Elovich and Freundlich models indicate chemisorption, and the kinetic adsorption model itself is complex. The data obtained throughout the study prove that this nanosponge (NS) is extremely stable, self-separating, and adjusting to the guest structure. It also represents a potential biodegradable adsorbent for the removal IBU from wastewaters. Full article

In this study, twenty five partially vitrified rocks and four samples of vitrified rocks collected on the top hill called Serravuda (Acri, Calabria, Italy) are analyzed. The goal is to shed light on the origin of these enigmatic vitrified materials. The analyzed vitrified rocks are a breccia of cemented rock fragments (gneiss, granitoid, and amphibolite fragments) which extends for more than 10 m, forming a continuous mass along the northern and north-west border of the flat top hill. Surrounded by the vitrified accumulation, exposed Paleozoic granitoid substrate rocks show limited melting or heat-alteration processes. By mapping minerals embedded in the glass matrix via X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM), an interpretation of source rock material, reactions, and thermometric indications to form vitrified materials on the top hill of Serravuda, Acri (Italy), is provided. The mineralogical composition of heated or partially vitrified samples is heterogeneous owing to the effects of heating events, but it mostly recalls the parent rock composition (gneiss, granitoid, and amphibolite). The presence of quartz, cristobalite, tridymite, mullite, plagioclase, hercynite, cordierite, and olivine in Serravuda partially vitrified rocks and glasses suggests that samples were subjected to pyrometamorphism and the temperature range at which the glass formed was about 1000–1100 °C in the presence of hydrous gas, burning organic material (e.g., wood), and assuming thermodynamic equilibrium. Lithologies of the heated or partially vitrified rock fragments are a mixture of parent rocks not outcropping on the top of the hill such as gneiss and amphibolite. Data suggest that Serravuda vitrified rocks are most likely the result of anthropic activities and could represent remnants of vitrified fort walls. The mineral assemblage of partially vitrified rocks and glasses suggests that the fort walls were made of slabs derived from the local metamorphic rocks with the addition of Serravuda substrate Paleozoic granitoid rocks to improve the strength and insulation of the fort walls. Full article

Myofibroblasts are contractile cells found in multiple tissues. They are physiological cells as in the human placenta and can be obtained from bone marrow mesenchymal stem cells after differentiation by transforming growth factor-β (TGF-β). They are also found in the stroma of cancerous tissues and can be located in non-muscle contractile tissues. When stimulated by an electric current or after exposure to KCl, these tissues contract. They relax either by lowering the intracellular Ca²⁺ concentration (by means of isosorbide dinitrate or sildenafil) or by inhibiting actin-myosin interactions (by means of 2,3-butanedione monoxime or blebbistatin). Their shortening velocity and their developed tension are dramatically low compared to those of muscles. Like sarcomeric and smooth muscles, they obey Frank-Starling’s law and exhibit the Hill hyperbolic tension-velocity relationship. The molecular motor of the myofibroblast is the non-muscle myosin type IIA (NMIIA). Its essential characteristic is the extreme slowness of its molecular kinetics. In contrast, NMIIA develops a unitary force similar to that of muscle myosins. From a thermodynamic point of view, non-muscle contractile tissues containing NMIIA operate extremely close to equilibrium in a linear stationary mode. Full article

We have described for the first time the thermodynamic state of a highly confined single-phase and single-component fluid in a slit pore using Hill’s thermodynamics of small systems. Hill’s theory has been named nanothermodynamics. We started by constructing an ensemble of slit pores for controlled temperature, volume, surface area, and chemical potential. We have presented the integral and differential properties according to Hill, and used them to define the disjoining pressure on the new basis. We identified all thermodynamic pressures by their mechanical counterparts in a consistent manner, and have given evidence that the identification holds true using molecular simulations. We computed the entropy and energy densities, and found in agreement with the literature, that the structures at the wall are of an energetic, not entropic nature. We have shown that the subdivision potential is unequal to zero for small wall surface areas. We have showed how Hill’s method can be used to find new Maxwell relations of a confined fluid, in addition to a scaling relation, which applies when the walls are far enough apart. By this expansion of nanothermodynamics, we have set the stage for further developments of the thermodynamics of confined fluids, a field that is central in nanotechnology. Full article