We examine the microscopic structure of a hard-sphere fluid confined to a small cylindrical pore by means of Monte Carlo simulation. In order to analyze finite-size effects, the simulations are carried out in the framework of different statistical mechanics ensembles. We find that the size effects are specially relevant in the canonical ensemble where noticeable differences are found with the results in the grand canonical ensemble (GCE) and the isothermal isobaric ensemble (IIE) which, in most situations, remain very close to the infinite system results. A customary series expansion in terms of fluctuations of either the number of particles (GCE) or the inverse volume (IIE) allows us to connect with the results of the canonical ensemble.
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Environ Res
January 2025
Faculty of Exact Sciences and Technology, Federal University of Grande Dourados, Dourados, MS, 79804-970, Brazil. Electronic address:
Transforming lignocellulosic biomass waste into value-added materials like porous carbons offers a sustainable and increasingly important solution for its efficient management within a circular economy framework. Although the heteroatom-doping process enhances oxygen- or nitrogen-containing functionalities on porous carbons, it often leads to losses in structural integrity and other key functionalities. This study presents a novel protocol to produce N-doped porous carbons that efficiently introduces nitrogen groups while improving surface area, microporosity definition and the concentration of oxygen-containing functionalities.
View Article and Find Full Text PDFJ Chem Inf Model
January 2025
Max-Planck-Institut für Immunbiologie und Epigenetik (MPI-IE), Stübeweg 51, 79108 Freiburg im Breisgau, Germany.
Intrinsically disordered regions are found in most eukaryotic proteins and are enriched with positively and negatively charged residues. While it is often convenient to assume that these residues follow their model-compound p values, recent work has shown that local charge effects (charge regulation) can upshift or downshift side chain p values with major consequences for molecular function. Despite this, charge regulation is rarely considered when investigating disordered regions.
View Article and Find Full Text PDFCurr Biol
January 2025
Department of Pharmacology, Vanderbilt Brain Institute, Vanderbilt Center for Addiction Research, Vanderbilt University, Nashville, TN 37232, USA; Department of Anatomy, Cell Biology, & Physiology, Indiana University School of Medicine, Indianapolis, IN 46202, USA. Electronic address:
Human and non-human primate studies clearly implicate the dorsolateral prefrontal cortex (dlPFC) as critical for advanced cognitive functions. It is thought that intracortical synaptic architectures within the dlPFC are the integral neurobiological substrate that gives rise to these processes. In the prevailing model, each cortical column makes up one fundamental processing unit composed of dense intrinsic connectivity, conceptualized as the "canonical" cortical microcircuit.
View Article and Find Full Text PDFPhys Rev E
November 2024
Dipartimento di Scienze Matematiche, Politecnico di Torino, Corso Duca degli Abruzzi 24, Turin, Italy and INFN, Sezione di Torino, Via P. Giuria 1, 10125 Turin, Italy.
The physical significance of the stochastic processes associated to the generalized Gibbs ensembles is scrutinized here with special attention to the thermodynamic fluctuations of small systems. Differently from the so-called stochastic thermodynamics, which starts from stochastic versions of the first and second law of thermodynamics and associates thermodynamic quantities to microscopic variables, here we consider stochastic variability directly in the macroscopic variables. By recognizing the potential structure of the Gibbs ensembles, when expressed as a function of the potential entropy generation, we obtain exact nonlinear thermodynamic Langevin equations (TLEs) for macroscopic variables, with drift expressed in terms of entropic forces.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Department of Chemistry and Biochemistry, University of California, Los Angeles, California, 90095-1569, USA.
Restructuring of surfaces and interfaces plays a key role in the activation and/or deactivation of a wide spectrum of heterogeneous catalysts and functional materials. The statistical ensemble representation can provide unique atomistic insights into this fluxional and metastable realm, but constructing the ensemble is very challenging, especially for the systems with off-stoichiometric reconstruction and varying coverage of mixed adsorbates. Here, we report GOCIA, a versatile global optimizer for exploring the chemical space of these systems.
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