Search Results (6,395)

This study presents a thorough investigation of chemical outcomes during the reaction of cisplatin and 2-thiohydantoin ligands in the presence of DMSO. Aided by NMR spectroscopy and quantum chemical calculations, the influence of DMSO substitution on the reaction factors is specified, and key intermediates and products in the reaction mechanism are identified and characterized. Coordination modes, reaction orders, and important thermodynamic parameters, such as Gibbs free energies, stabilization energies, and reaction rate constants, are determined. Molecular docking was utilized to propose the binding modes of the final products to DNA and predict their anticancer properties. The results of this study represent a unique kinetic and mechanistic outlook into the influence of DMSO on platinum(II) coordination, as ligand substitution with DMSO was previously found to alter the coordination environment in a biologically relevant manner. Full article

Rapid changes in Arctic summer sea ice exert substantial influences on the polar climate system, maritime navigation, and resource exploitation, while subseasonal-to-seasonal (S2S) prediction of sea ice state remains highly uncertain. Using daily observations and reanalysis data of sea ice concentration (SIC) and thickness (SIT) from 1979 to 2023, together with concurrent atmospheric and oceanic fields, this study develops a multivariate linear Markov model to perform S2S predictions of Arctic summer sea ice. Sensitivity experiments with different variable combinations, weighting strategies, and modal truncation schemes are conducted, and predictive skill is systematically evaluated against persistence and climatological baselines. Results indicate that the model exhibits stable forecast skill without pronounced error accumulation at extended lead times. SIC predictability is primarily governed by its intrinsic spatiotemporal persistence and is significantly modulated by oceanic thermodynamic forcing, particularly sea surface temperature and surface net energy flux, highlighting a pronounced oceanic memory effect. In contrast, local atmospheric dynamic variables provide limited incremental skill. For SIT, predictability is dominated by its own historical state, with SIC contributing marginal short-term improvement and air–sea coupling exerting weak influence. Overall, the proposed framework effectively extracts dominant predictable signals with clear physical interpretability, providing a computationally efficient statistical approach for S2S prediction of Arctic summer sea ice. Full article

This study proposes a CO₂ re-liquefaction system utilizing the cold energy of LNG and liquid hydrogen (LH₂) to efficiently manage boil-off gas in alternative fuel-based CO₂ carriers. Process simulations using Aspen HYSYS V11 under 100% and 70% propulsion loads evaluated the Specific Energy Consumption (SEC), Coefficient of Performance (COP), UA of heat exchangers, and Specific Life Cycle Cost (SLCC). The results demonstrate that under both 100% and 70% propulsion load conditions, the utilization of cold energy decreases the SEC by 24.5% and improves the COP by approximately 34% compared to the reference model without cold energy utilization. Sensitivity analysis on the minimum temperature approach indicates limited impact on performance. The UA of the heat exchangers decreased by up to 83% (LNG) and 87% (LH₂), offering significant downsizing advantages. Economically, SLCC was reduced by up to 14.8% and 15.9% for the LNG and H₂ models, respectively, due to lower Capital Expenditure (CAPEX) and Operating Expenditure (OPEX). Consequently, this study demonstrates that exploiting the cold energy of alternative fuels significantly improves both the thermodynamic performance and economic feasibility of CO₂ re-liquefaction systems, providing foundational data for future optimization. Full article

Magnetic superconductor EuRbFe₄As₄ is a quite unique system in which macroscopic superconductivity and magnetic ordering coexist, with interesting interactions between Abrikosov vortices and Eu²⁺ spins that were investigated mostly by static (DC) magnetization measurements. Our aim is to study the dynamic interactions between the two sub-systems using AC susceptibility measurements in a wide range of temperatures and superimposed DC fields. In low DC fields, the magnetic transition at 15 K is clearly visible. We have observed very little difference between the AC susceptibility in different cooling regimes, but large difference for different field orientation. For field perpendicular to the superconducting planes, we have observed an anomalous dependence just below the critical temperature, which is absent in the parallel field orientation. We explained the anomaly by the interplay between the sample dimensions and the temperature dependence of the London penetration depth which may allow the paramagnetic Meissner-like response to be detected in the temperature dependence of the AC susceptibility. We stress that the newly reported phenomenon reflects an AC-susceptibility manifestation of a field-stabilized critical state rather than a thermodynamic phase. In addition, we have observed a paramagnetic AC response in the normal phase, in both field orientations, indicative of interactions between Eu²⁺ spins and flux lines. Full article

In this work, three functionalized hybrid composites, CS/PVA-VAN, CS/PVA-VAN@TiO₂ and CS/GO/PVA-VAN@TiO₂, were synthesized and applied for adsorption evaluation on two common non-steroidal anti-inflammatory drugs, i.e., diclofenac (DCF) and ketoprofen (KTP). The structural and morphological characteristics of new composites were identified via Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and BET techniques. BET analysis demonstrated that the CS/GO/PVA-Van@TiO₂ composite has a surface area 64.86 m²/g, which is twice that of CS/PVA-Van. Moreover, adsorption evaluation was achieved at an optimum pH condition (pH 5.0) for both drugs. In addition, the kinetic data fitted better in a pseudo-second-order kinetic model, while the adsorption was heterogeneous and multilayer. The adsorption capacity of CS/GO/PVA-VAN@TiO₂ was found to be 114.53 mg/g and 65.20 mg/g for diclofenac and ketoprofen, respectively. Thermodynamic analysis confirmed that the adsorption process was endothermic and spontaneous for all pollutants. Moreover, the kinetic swelling and stability studies demonstrated that graphene oxide contributed to improving the structural compactness and stability of composite. Finally, the adsorption performance of the optimal composite material was investigated in a binary system of non-steroidal anti-inflammatory drugs in various ratios. Full article

Industrial volatile organic compound (VOC) emissions from large-scale petroleum storage represent a persistent environmental challenge, particularly in agricultural perimeters where atmospheric “breathing” cycles drive localized soil loading. This study investigates the thermodynamic and spatial relationship between gasoline storage emissions and chemical contamination in the Constanta South terminal area using a multi-layered analytical approach. By integrating gas chromatography (GC-MS) headspace analysis with an artificial intelligence (AI) framework utilizing high-order polynomial regression, we quantified the source–path–receptor dynamics across a thermal gradient (12 °C to 70 °C). The results reveal a non-linear surge in VOC emissions at temperatures exceeding 37 °C, characterized by a shift toward medium-weight hydrocarbons (C4–C6) that act as carriers for heavier aromatics. The AI risk model identified a significant spatial gradient, identifying a 500 m “critical zone” where the Hazard Quotient (HQ) is elevated, necessitating technological upgrades like Vapor Recovery Units (VRUs) to mitigate ecological risks. Full article

Hot-air drying is widely adopted for herbs because it is robust and easy to control, yet it is often energy-intensive and may operate far from optimal conditions when industrial dryers rely on fixed airflow paths and large air recirculation rates. This work investigates a conventional basket-type, adiabatic hot-air dryer through an instrumented 30 h drying campaign and a psychrometric energy analysis. The hot-air drier is designed to reduce the relative humidity of herbs from the environmental value (highly variable as a function of the species, the weather conditions, and, mostly, the seasonality) to 20%. Temperature and relative humidity were measured at four positions to characterize the shelf-by-shelf drying sequence and to identify process phases. A mass balance indicated that approximately 3.8 t of water was removed during the trial. Based on the measured thermodynamic states of the moist air and estimated airflow rates (35,000–53,000 m³/h), the baseline configuration was analyzed and an upgrade strategy was proposed to improve dehumidification and overall efficiency while preserving the conventional hot-air-drying concept. The alternative solution integrates a refrigeration-based dehumidification loop (heat pump) to decouple moisture removal from sensible heating; three plant layouts and seasonal boundary conditions (summer/winter) were simulated. For the most favorable configurations, the specific final–primary energy demand and the associated CO₂-equivalent emissions were reduced by about 70–85% compared with the baseline, depending on the airflow rate and recirculation strategy. The results highlight practical retrofit options for existing herb dryers and provide a transparent framework for translating measured psychrometric states into energy and emission indicators. The results, achieved and discussed in this study, were used to optimize the utilization of an already existing and operative hot-air dryer. Based on the proposed working configuration, the dryer now allows achieving the fixed target for herb mixtures of the previous configuration and, at the same time, reducing the energy consumption and associated equivalent CO₂ emitted, as well as achieving process completion in less time. Full article

In this work, we propose a modified Schwarzschild geometry inspired by the Asymptotic Safety approach to quantum gravity, in which the Newtonian coupling becomes a running quantity depending on the radial coordinate. We employ an infrared cutoff at the proper distance and obtain a new quantum-corrected black hole metric. We provide a thermodynamical analysis, first using standard methods and then proceeding to a geometrothermodynamical study of the phase space and to a topological analysis of phase transitions. We also calculate the grey-body factors of our solution, providing exact lower bounds in the quantum-corrected transmission coefficients. Finally, we present the shadow size and intensity profile of our solution, showing its consistency with current observational constraints. Full article

Hematocrit (HCT) fluctuations and ambient temperature variations are two critical interference factors limiting the accuracy of electrochemical glucose test strips in self-monitoring of blood glucose (SMBG). In this study, a high-precision screen-printed glucose sensor incorporating in situ impedance-based HCT correction and temperature compensation was developed. The system employs a time-division multiplexing strategy, integrating a normalized thermodynamic model and an in situ impedance-based HCT correction algorithm, to achieve synergistic decoupling and precise compensation of temperature and HCT interferences. Experimental results demonstrate that after multi-parameter synergistic correction, the system exhibits excellent stability across a wide temperature range (10–35 °C) and a broad HCT range (10–70%). The accuracy indicators significantly surpass ISO 15197:2013 standards. In contrast, uncorrected measurements showed deviations ranging from approximately −80% to +30% due to HCT fluctuations. This multiple correction strategy effectively resolves systematic errors in whole blood testing without increasing electrode complexity or requiring pretreatment steps, providing a robust technical solution for high-precision, low-cost personal glucose monitoring. Full article

In structural health monitoring, purely data-driven methods for deformation prediction are often susceptible to time-varying boundary conditions under complex operating scenarios, leading to insufficient physical interpretability and limited generalization across different conditions. To address these challenges, this study proposes a Physics-Informed Dual-branch Long Short-Term Memory framework (PINN-DualSHM). The framework employs dual-branch LSTMs to separately extract temporal features of structural mechanical responses and environmental thermal effects. Dynamic decoupling and fusion of these heterogeneous features are achieved through an adaptive cross-attention mechanism. Furthermore, physical priors, including the thermodynamic superposition principle and structural settlement monotonicity, are embedded into the loss function as regularization terms, complemented by a dual uncertainty quantification system based on heteroscedastic regression and MC Dropout. Experimental results based on long-term measured data from an industrial base project in Shenzhen demonstrate that PINN-DualSHM significantly outperforms baseline models such as LSTM, CNN-LSTM, and GAT-LSTM. Specifically, the Root Mean Square Error (RMSE) is reduced by 65.25%, and the coefficient of determination (R²) reaches 0.925. Physical consistency analysis confirms that the introduction of physical constraints effectively suppresses anomalous predictive fluctuations that violate mechanical laws. Uncertainty decomposition reveals that aleatoric uncertainty is dominant (93.7%), objectively indicating that the current system’s accuracy bottleneck lies in sensor noise rather than model capability. By enhancing prediction accuracy while providing credible quantitative assessments and physical interpretability, the proposed method provides a scientific basis for the operation, maintenance optimization, and upgrading decisions of SHM systems. Full article

The high viscosity of biodiesel fuel, caused by the presence of saturated fatty acid esters, limits its application, particularly at low temperatures. Supercritical fluid extraction (SFE) using carbon dioxide represents a promising method for selective fractionation, enabling the removal of high-viscosity saturated components and the enrichment of the fuel with less viscous unsaturated esters. However, the rational design of such processes requires a deep understanding of the interrelationship between flow hydrodynamics, thermodynamic conditions, and mass transfer in a supercritical medium. In this work, a comprehensive computational fluid dynamics (CFD) modeling study of the fractionation process was performed for a model ethyl oleate/ethyl palmitate mixture (25.28:74.72 wt.%) in supercritical CO₂ at pressures of 11 and 14 MPa and a temperature of 40 °C. A three-dimensional model of a laboratory-scale extractor was developed using the Ansys Fluent software version 2020 R1 environment. Since the target esters are absent from the standard material database, a custom property library and compiled User-Defined Function (UDF) routines were developed. These describe the temperature dependence of density, viscosity, heat capacity, and thermal conductivity for both the individual components and their mixture using established mixing rules. The calculations employed an Eulerian multiphase model, the realizable k–ε turbulence model, and species transport equations. The modeling revealed pronounced selectivity: under the chosen thermodynamic conditions, ethyl palmitate is extracted preferentially over ethyl oleate, with this difference becoming more pronounced as pressure increases. The developed and verified CFD model deepens the fundamental understanding of hydrodynamics and mass transfer during supercritical fractionation and serves as a basis for optimizing process parameters to produce biodiesel with reduced viscosity. The regime at P = 14 MPa and t = 40 °C provides the most favorable thermodynamic and hydrodynamic conditions for the selective removal of saturated esters. Full article

The current study explored the martensite structures of Fe₃Pt alloys, specifically $Cmmm$-Fe₃Pt, $P{6}_3/mmc$-Fe₃Pt, $P4/mmm$-Fe₃Pt, and $R\overline{3}m$-Fe₃Pt, aiming to provide a comprehensive understanding of the mechanisms that govern their physical and chemical properties. We have focused on their structural, thermodynamical, magnetic, electronic, mechanical, and dynamical characteristics, utilizing the density functional theory (DFT) technique. Our study revealed that in addition to the previously reported austenitic cubic $Pm\overline{3}m$-Fe₃Pt and martensite tetragonal $I4/mmm$-Fe₃Pt with L1₂ structure, there exist additional Fe₃Pt phases that exhibit excellent structural, thermodynamic, magnetic, and mechanical properties. The calculated enthalpies of formation were found to be negative and less than −0.39 eV in all the structures considered, indicating thermodynamic stability and formation under experimental synthetic conditions. Moreover, the computed magnetic moments are in the range 2.94 to 3.04 ${\mathsf{\mu }}_{\mathrm{B}}$, which is relatively comparable to 3.24 ${\mathsf{\mu }}_{\mathrm{B}}$ of the widely reported $Pm\overline{3}m$-Fe₃Pt alloy. The analysis of the electronic structure also revealed strong magnetism due to the presence of asymmetry in the spin-up and -down states of the density of states (DOS) plots. To determine the mechanical response of Fe₃Pt structures under loading conditions, we computed the independent elastic constants, macroscopic properties, and stress–strain relationship under hydrostatic stress. All four phases were studied, but the hypothetical $P{6}_3/mmc$-Fe₃Pt showed excellent mechanical stability at ambient conditions and exceptional hardness and resistance to compression in the elastic region 0% ≤ strain ≤ 10%. This evidence is provided by satisfying the Born necessary stability conditions, large bulk modulus, and a strong linear relationship fit ($R^2$) of greater than 0.94. Moreover, the phonon dispersion curves revealed dynamical stability for $Cmmm$-Fe₃Pt and $R\overline{3}m$-Fe₃Pt, and metastability for $P4/mmm$-Fe₃Pt, while the hypothetical $P{6}_3/mmc$-Fe₃Pt is unstable. Full article

Metal hydrides store hydrogen in the solid state with high density and inherent safety, and their thermodynamic characteristics are typically described by the pressure–composition–isotherm (PCI) curve. In the plateau pressure region of the PCI curve, the equilibrium pressure remains nearly constant over a wide hydrogen concentration range, making conventional pressure-based methods unsuitable for quantifying the hydrogen amount in metal hydride vessels. This study proposes a strain-based method to quantify the hydrogen amount in a metal hydride vessel by measuring the strain induced on the metal hydride vessel surface due to the volumetric change of the metal hydride during hydrogen adsorption and desorption. The installation of strain gauges on the metal hydride vessel was verified using argon pressurization tests. The metal hydride was activated prior to controlled hydrogen desorption experiments aimed at quantifying the amount of hydrogen remaining in the vessel. A correlation between strain and hydrogen amount was obtained from experiments conducted at discrete measurement points. The hydrogen amount estimated using the strain-based method was further evaluated through continuous time-series desorption tests and showed good agreement with the results obtained from the mass flow controller (MFC)-based method, with a maximum difference of 4.5%. These results demonstrate that the proposed method provides a simple and reliable approach for quantifying the hydrogen amount in metal hydride vessels. Full article

The Earth’s climate is an open nonlinear system, sustained far from thermodynamic equilibrium by solar radiation and energy and matter exchange among its four major subsystems: atmosphere, ocean, land, and cryosphere. Among these four subsystems, the ocean significantly influences and sustains Earth’s climate over decadal to millennial timescales. Although modern numerical models increasingly capture intricate dynamical details, the fundamental concepts of large-scale ocean variability are less frequently explored. This study revisits ocean circulation through the lens of self-organization theory and synergetics. The key synergetic concepts of mode competition, order parameters, and the slaving principle are interpreted within the framework of general ocean circulation and the Atlantic Meridional Overturning Circulation (AMOC). The Brusselator, a simplified model of a nonlinear dynamical system initially developed in chemical kinetics, serves as a conceptual analog for ocean circulation energy conversion. Despite its high abstraction, this proxy model effectively captures essential bifurcation behaviors, such as Hopf bifurcation transitions and limit-cycle behaviors. This clarifies feedback regulation, instability, and potential regime transitions in the AMOC. The synthesis in this study is intended for an interdisciplinary readership and highlights the broader applicability of synergetic principles to the complex Earth climate system maintained far from equilibrium. Full article

The removal of water pollutants, specifically the organophosphorus pesticides chlorpyrifos (CHP) and azinphos-methyl (AZM), as well as the dye Rhodamine B (RB), was investigated through the valorization of grape pomace, an abundant agricultural byproduct. For the first time, hydrochars derived from grape pomace were utilized as adsorbents for these contaminants following KOH activation (HCK) and pyrolysis at 400 °C (PHC). The study aimed to evaluate the adsorption performance, determine the optimal conditions, and elucidate the adsorption mechanisms. Physicochemical characterization using SEM, FTIR, BET surface area analysis, stability, and pH_PZC measurements revealed distinct differences in surface morphology, functional groups, porosity, and surface charge. Under optimized conditions, maximum adsorption capacities reached 751.0, 3.98, and 1.39 mg g⁻¹ for RB, CHP, and AZM, respectively, on HCK, and 616.0 (RB), 30.10 (CHP), and 9.15 mg g⁻¹ (AZM) on PHC, indicating that the selected hydrochars efficiently removed the investigated pollutants from water. Kinetic modeling demonstrated pseudo-first-order adsorption for RB and CHP on HCK and pseudo-second-order adsorption for AZM on HCK and all pollutants on PHC. Thermodynamic analysis confirmed that adsorption processes were spontaneous and favorable, with enhancements dependent on temperature. These findings suggest that HCK is particularly effective for cationic dyes, while PHC exhibits greater affinity toward organophosphorus pesticides, offering complementary applications and providing new mechanistic insights into hydrochar-based pollutant removal. Full article