Pyrrole and Pyridine in the Water Environment-Effect of Discrete and Continuum Solvation Models.
Ontology highlight
ABSTRACT:
SUBMITTER: Zborowski KK
PROVIDER: S-EPMC8482501 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:We present density functional theory (DFT) calculations at the X3LYP/D95(d,p) level on the solvation of polyalanine α-helices in water. The study includes the effects of discrete water molecules and the CPCM and AMSOL SM5.2 solvent continuum model both separately and in combination. We find that individual water molecules cooperatively hydrogen-bond to both the C- and N-termini of the helix, which results in increases in the dipole moment of the helix/water complex to more than the vector sum of their individual dipole moments. These waters are found to be more stable than in bulk solvent. On the other hand, individual water molecules that interact with the backbone lower the dipole moment of the helix/water complex to below that of the helix itself. Small clusters of waters at the termini increase the dipole moments of the helix/water aggregates, but the effect diminishes as more waters are added. We discuss the somewhat complex behavior of the helix with the discrete waters in the continuum models.
| S-EPMC3271136 | biostudies-literature
Project description:Epithelial tissue, in which cells adhere tightly to each other and to the underlying substrate, is one of the four major tissue types in adult organisms. In embryos, epithelial sheets serve as versatile substrates during the formation of developing organs. Some aspects of epithelial morphogenesis can be adequately described using vertex models, in which the two-dimensional arrangement of epithelial cells is approximated by a polygonal lattice with an energy that has contributions reflecting the properties of individual cells and their interactions. Previous studies with such models have largely focused on dynamics confined to two spatial dimensions and analyzed them numerically. We show how these models can be extended to account for three-dimensional deformations and studied analytically. Starting from the extended model, we derive a continuum plate description of cell sheets, in which the effective tissue properties, such as bending rigidity, are related explicitly to the parameters of the vertex model. To derive the continuum plate model, we duly take into account a microscopic shift between the two sublattices of the hexagonal network, which has been ignored in previous work. As an application of the continuum model, we analyze tissue buckling by a line tension applied along a circular contour, a simplified set-up relevant to several situations in the developmental contexts. The buckling thresholds predicted by the continuum description are in good agreement with the results of stability calculations based on the vertex model. Our results establish a direct connection between discrete and continuum descriptions of cell sheets and can be used to probe a wide range of morphogenetic processes in epithelial tissues.
| S-EPMC4571022 | biostudies-literature
Project description:Theoretical estimation of solvation free energy by continuum solvation models, as a standard approach in computational chemistry, is extensively applied by a broad range of scientific disciplines. Nevertheless, the current widely accepted solvation models are either inaccurate in reproducing experimentally determined solvation free energies or require a number of macroscopic observables which are not always readily available. In the present study, we develop and introduce the Machine-Learning Polarizable Continuum solvation Model (ML-PCM) for a substantial improvement of the predictability of solvation free energy. The performance and reliability of the developed models are validated through a rigorous and demanding validation procedure. The ML-PCM models developed in the present study improve the accuracy of widely accepted continuum solvation models by almost one order of magnitude with almost no additional computational costs. A freely available software is developed and provided for a straightforward implementation of the new approach.
| S-EPMC8213834 | biostudies-literature
Project description:A method is presented to explicitly represent the first solvation shell in continuum solvation calculations. Initial solvation shell geometries were generated with classical molecular dynamics simulations. Clusters consisting of solute and 5 solvent molecules were fully relaxed in quantum mechanical calculations. The free energy of solvation of the solute was calculated from the free energy of formation of the cluster, and the solvation free energy of the cluster was calculated with continuum solvation models. The method has been implemented with two continuum solvation models, a Poisson-Boltzmann model and the IEF-PCM model. Calculations were carried out for a set of 60 ionic species. Implemented with the Poisson-Boltzmann model the method gave an unsigned average error of 2.1 kcal/mol and a rmsd of 2.6 kcal/mol for anions; for cations the unsigned average error was 2.8 kcal/mol and the rmsd 3.9 kcal/mol. Similar results were obtained with the IEF-PCM model.
| S-EPMC2700946 | biostudies-literature
Project description:The paper studies systems of rigid bodies with randomly generated geometry interconnected by normal and tangential bonds. The stiffness of these bonds determines the macroscopic elastic modulus while the macroscopic Poisson's ratio of the system is determined solely by the normal/tangential stiffness ratio. Discrete models with no directional bias have the same probability of element orientation for any direction and therefore the same mechanical properties in a statistical sense at any point and direction. However, the layers of elements in the vicinity of the boundary exhibit biased orientation, preferring elements parallel with the boundary. As a consequence, when strain occurs in this direction, the boundary layer becomes stiffer than the interior for the normal/tangential stiffness ratio larger than one, and vice versa. Nonlinear constitutive laws are typically such that the straining of an element in shear results in higher strength and ductility than straining in tension. Since the boundary layer tends, due to the bias in the elemental orientation, to involve more tension than shear at the contacts, it also becomes weaker and less ductile. The paper documents these observations and compares them to the results of theoretical analysis.
| S-EPMC5459208 | biostudies-other
Project description:An empirical continuum solvation model, solvation free energy density (SFED), has been developed to calculate solvation free energies of a molecule in the most frequently used solvents. A generalized version of the SFED model, generalized-SFED (G-SFED), is proposed here to calculate molecular solvation free energies in virtually any solvent. G-SFED provides an accurate and fast generalized framework without a complicated description of a solution. In the model, the solvation free energy of a solute is represented as a linear combination of empirical functions of the solute properties representing the effects of solute on various solute-solvent interactions, and the complementary solvent effects on these interactions were reflected in the linear expansion coefficients with a few solvent properties. G-SFED works well for a wide range of sizes and polarities of solute molecules in various solvents as shown by a set of 5,753 solvation free energies of diverse combinations of 103 solvents and 890 solutes. Octanol-water partition coefficients of small organic compounds and peptides were calculated with G-SFED with accuracy within 0.4 log unit for each group. The G-SFED computation time depends linearly on the number of nonhydrogen atoms (n) in a molecule, O(n).
| S-EPMC3581891 | biostudies-other
Project description:Solvent-mediated electrostatic interactions were well recognized to be important in the structure and function of molecular systems. Ionic interaction is an important component in electrostatic interactions, especially in highly charged molecules, such as nucleic acids. Here, we focus on the quality of the widely used Poisson-Boltzmann surface area (PBSA) continuum models in modeling ionic interactions by comparing with both explicit solvent simulations and the experiment. In this work, the molality-dependent chemical potentials for sodium chloride (NaCl) electrolyte were first simulated in the SPC/E explicit solvent. Our high-quality simulation agrees well with both the previous study and the experiment. Given the free-energy simulations in SPC/E as the benchmark, we used the same sets of snapshots collected in the SPC/E solvent model for PBSA free-energy calculations in the hope to achieve the maximum consistency between the two solvent models. Our comparative analysis shows that the molality-dependent chemical potentials of NaCl were reproduced well with both linear PB and nonlinear PB methods, although nonlinear PB agrees better with SPC/E and the experiment. Our free-energy simulations also show that the presence of salt increases the hydrophobic effect in a nonlinear fashion, in qualitative agreement with previous theoretical studies of Onsager and Samaras. However, the lack of molality-dependency in the nonelectrostatics continuum models dramatically reduces the overall quality of PBSA methods in modeling salt-dependent energetics. These analyses point to further improvements needed for more robust modeling of solvent-mediated interactions by the continuum solvation frameworks.
| S-EPMC5730473 | biostudies-literature
Project description:We present a multiwavelet-based implementation of a quantum/classical polarizable continuum model. The solvent model uses a diffuse solute-solvent boundary and a position-dependent permittivity, lifting the sharp-boundary assumption underlying many existing continuum solvation models. We are able to include both surface and volume polarization effects in the quantum/classical coupling, with guaranteed precision, due to the adaptive refinement strategies of our multiwavelet implementation. The model can account for complex solvent environments and does not need a posteriori corrections for volume polarization effects. We validate our results against a sharp-boundary continuum model and find a very good correlation of the polarization energies computed for the Minnesota solvation database.
| S-EPMC10100532 | biostudies-literature
Project description:Nucleophilic addition onto a carbonyl moiety is strongly affected by solvent, and correctly simulating this solvent effect is often beyond the capability of single-scale quantum mechanical (QM) models. This work explores multiscale approaches for the description of the reversible and highly solvent-sensitive nucleophilic N|···C═O bond formation in an Me2N-(CH2)3-CH═O molecule. In the first stage of this work, we rigorously compare and test four recent quantum mechanical/molecular mechanical (QM/MM) explicit solvation models, employing a QM description of water molecules in spherical regions around both the oxygen and the nitrogen atom of the solute. The accuracy of the models is benchmarked against a reference QM simulation, focusing on properties of the solvated Me2N-(CH2)3-CH═O molecule in its ring-closed form. In the second stage, we select one of the models (continuous adaptive QM/MM) and use it to obtain a reliable free energy profile for the N|···C bond formation reaction. We find that the dual-sphere approach allows the model to accurately account for solvent reorganization along the entire reaction path. In contrast, a simple microsolvation model cannot adapt to the changing conditions and provides an incorrect description of the reaction process.
| S-EPMC6023263 | biostudies-literature
Project description:In this study, the inhibitive performance of pyridine-2-thiol added to a corrosive solution was investigated for brass using potentiodynamic polarization, electrochemical impedance spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical experiments were performed with different inhibitor concentrations in 0.5 M H2SO4 as the corrosive medium. For potentiodynamic polarization, icorr values decreased significantly for the inhibited solutions in contrast with the uninhibited solution. Pyridine-2-thiol had an optimum inhibition concentration of 0.25 mM, giving an icorr value of 1.8 µA/cm2 compared to 26 µA/cm2 for the blank solution. EIS data indicated that Rp and Rct values increased substantially after the addition of the corrosion inhibitor and corrosion inhibition efficiencies of more than 85% was achieved for the majority of the inhibited solutions. Scanning electron microscopy showed defect free and less scale formation for the inhibited surface but the bare brass surface had larger amounts of scale formation. X-ray photoelectron spectroscopy and UV-vis spectroscopy was used to investigate surface chemical composition and inhibitor structural changes over time.
| S-EPMC9573544 | biostudies-literature