Insights into the Self-Assembly of Water Reverse Micelles and Solubilization Process in Liquid and Supercritical Solvents: A Molecular Dynamics Study
Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2023. Vol. 676. Article 132200.
Darya L. Gurina, Yury A. Budkov
- This article reports on a full-atomic classical molecular dynamics simulation investigating the self-assembly process of reverse micelles in carbon tetrachloride and supercritical carbon dioxide (scCO2). The study explores the impact of solvent type, surfactant structure (sodium dodecyl sulfate and sodium bis(3,5,5-trimethyl-1-hexyl) sulfosuccinate), water/surfactant ratio, and surfactant concentration on the self-assembly, size, and shape of reverse micelles. The results indicate that at low water/surfactant ratios in scCO2, irregularly shaped reverse micelles are formed, whereas spherical micelles form as the water/surfactant ratio increases. In scCO2, there is always a small fraction of free water molecules present, whereas in CCl4, all water molecules are surrounded by surfactants. The distribution of head groups of di-chain surfactants over the surface of micelles is observed to occur in groups of several surfactants, forming salt bridges through sodium cations. The solubilization of methyl orange by reverse micelles in pure scCO2 and scCO2 modified with ethanol has also been investigated. The study reveals that the hydrophilic part of the solute is located in the water core of the micelle, while the tail is positioned in the hydrophobic crown. Moreover, the presence of ethanol increases the number of reverse micelles compared to the system without ethanol. Ethanol molecules primarily reside on the surface of the water core, forming stable hydrogen bonds with surfactants, as well as shorter-lived hydrogen bonds with water molecules.
Molecular Dynamics Study of the Swelling of Poly(methyl methacrylate) in Supercritical Carbon Dioxide
, , , Materials 2019 Vol. 12 No. 20 P. 3315
The swelling of a poly (methyl methacrylate) in supercritical carbon dioxide was studied by means of full atomistic classical molecular dynamics simulation. In order to characterize the polymer swelling, we calculated various properties related to the density, structure, and dynamics of polymer chains as a function of the simulation time, temperature, and pressure. In addition, ...
Added: October 11, 2019
Computation of drug solvation free energy in supercritical CO2: alternatives to all-atom computer simulations
, , et al., Fluid Phase Equilibria 2021 Vol. 544-545 Article 113096
Despite the modern level of development of computational chemistry methods and technological progress, fast and accurate determination of solvation free energy remains a huge problem for physical chemists. In this paper, we describe two computational schemes that can potentially solve this problem. We consider systems of poorly soluble drug compounds in supercritical carbon dioxide. Considering that the biggest contribution ...
Added: June 1, 2021
, , et al., Russian Journal of Physical Chemistry B 2021 Vol. 15 No. 7 P. 1166-1170
We present the results of calculation of the solvation free energy, based on the classical density functional theory, for a series of 1,2,4-thiadiazole derivatives in supercritical carbon dioxide at three temperatures (308.15, 318.15 and 128.15). Using the obtained data, the solubility values of the chosen compounds are determined. The correlation between the value of the ...
Added: January 28, 2022
, , et al., Journal of Molecular Liquids 2020 Vol. 311 Article 113104
In this paper we present our study of carbamazepine solubility in supercritical carbon dioxide. We have calculated the solubility values along two isochores corresponding to the CO2 densities ρ = 1.1ρcr(CO2) and ρ = 1.3ρcr(CO2), where ρcr(CO2) is the critical density of CO2, in the temperature range from 313 to 383 K, as well as ...
Added: April 9, 2020
Impregnation of Poly(methyl methacrylate) with Carbamazepine in Supercritical Carbon Dioxide: Molecular Dynamics Simulation
, , , Journal of Physical Chemistry B 2020 Vol. 124 No. 38 P. 8410-8417
Fully atomistic molecular dynamics simulations are employed to study impregnation of the poly(methyl methacrylate) (PMMA) matrix with carbamazepine (CBZ) in supercritical carbon dioxide. The simulation box consists of 108 macromolecules of the polymer sample with the polymerization degree of 100, 57 molecules of CBZ, and 242,522 CO2 molecules. The simulation is performed at 333 K and ...
Added: September 16, 2020
Transport properties of imidazolium-based room temperature ionic liquids in confinement of slit charged carbon nanopores: New insights from molecular simulations
, , et al., Journal of Molecular Liquids 2023 Vol. 390 No. A Article 122961
The paper presents a study of the behavior of room-temperature ionic liquids with different alkyl chain lengths and anion types in slit negatively charged carbon nanopores of various widths (1÷15 nm) using all-atom molecular dynamics simulations. The structure of the confined ionic liquids is investigated using number, mass, and charge density profiles and radial distribution ...
Added: August 31, 2023
, , et al., Journal of Molecular Liquids 2021 Vol. 334 Article 115997
We investigate a well-known phenomenon of the appearance of the crossover points, corresponding to the intersections of the solubility isotherms of the solid compound in supercritical fluid. Opposed to the accepted understanding of the existence of two fixed crossover points, which confine the region of the inverse isobaric temperature dependence of the solubility, we have found that these ...
Added: April 8, 2021
Polylactide nanoparticle impregnation with carbamazepine in supercritical media and its subsequent release in liquid solvents: insights from molecular simulation
, , , Journal of Molecular Liquids 2022 Vol. 352 Article 118758
A full-atomic classical molecular dynamics simulation of polylactide nanoparticle impregnation with carbamazepine in supercritical carbon dioxide was performed. The effect of temperature (333 K, 373 K), pressure (20 MPa, 40 MPa) and ethanol addition (1.7 mol.%) on the impregnation process was studied. Based on the solvent accessible surface area values it was concluded that a pressure increase and cosolvent addition ...
Added: February 19, 2022
Possibility of pressure crossover prediction by classical DFT for sparingly dissolved compounds in scCO2
, , et al., Journal of Molecular Liquids 2019 Vol. 276 P. 801-805
A new method of solubility estimations, applied to sparingly dissolved compounds in supercritical carbon dioxide has been introduced in this paper. The method is based on determination of solubility contributions along the thermodynamic path consisting of sublimation and solvation processes. The contribution of the sublimation process is taken from the experiment, while the free energy of ...
Added: December 19, 2018
, Physical Chemistry Chemical Physics 2020 Vol. 22 P. 14756-14772
In this article, I summarize my theoretical developments in the statistical field theory of salt solutions of zwitterionic and multipolar molecules. Based on the Hubbard-Stratonovich integral transformation, I represent configuration integrals of dilute salt solutions of zwitterionic and multipolar molecules in the form of functional integrals over the space-dependent fluctuating electrostatic potential. In the mean-field ...
Added: June 11, 2020
, , et al., Journal of Physical Chemistry C 2019 Vol. 123 No. 16 P. 10333-10338
In this manuscript, we study the electrically induced breathing of Metal-Organic Framework (MOF) within a 2D lattice model. The Helmholtz free energy of the MOF in electric eld consists of two parts: the electrostatic energy of the dielectric body in the external electric eld and elastic energy of the framework. The rst contribution is calculated ...
Added: April 1, 2019
МОЛЕКУЛЯРНО-ДИНАМИЧЕСКОЕ МОДЕЛИРОВАНИЕ СТРУКТУРНЫХ, ДИНАМИЧЕСКИХ И КОЛЕБАТЕЛЬНЫХ СВОЙСТВ ВОДНОГО РАСТВОРА NaNO2
, Журнал физической химии 2022 Т. 96 № 7 С. 1004-1009
The properties of an aqueous solution of NaNO2 were studied by classical molecular dynamics based on the newly performed parameterization of the interaction potential of the ion with water molecules. It was shown that the first hydration shell around the ion had a radius of at least 3.8 Å, and the weakest hydrogen bonds formed ...
Added: May 16, 2022
, , Physical Review E - Statistical, Nonlinear, and Soft Matter Physics 2023 Vol. 107 No. 2 Article 024503
In this paper, we present a self-consistent field theory of macroscopic forces in spatially inhomogeneous flexible chain polyelectrolyte solutions. We derive an analytical expression for a stress tensor which consists of three terms: isotropic hydrostatic stress, electrostatic (Maxwell) stress, and stress rising from conformational entropy of polymer chains—conformational stress. We apply our theory to the ...
Added: February 15, 2023
, , Applied Physics A: Materials Science and Processing 2018 Vol. 124 P. 365
Hummer’s method was used to prepare graphene oxide (GO) by chemical exfoliation of graphite. Simple precipitation method was used for the preparation of hybrid nanocomposites MgO–rGO and Fe2O3–rGO. A 0.3 Molar of corresponding metal nitrate solution and GO solution are used for the preparation process. XRD, FT-IR, and XPS were used to characterize the prepared ...
Added: January 28, 2020
Dielectric Mismatch Effects on Polyelectrolyte Solutions in Electrified Nanopores: Insights from Mean-Field Theory
, , Polymer Science - Series C 2023
We utilize the self-consistent field theory to explore the mechanical and electrical properties of charged surfaces immersed in polyelectrolyte solutions that could be potentially useful for electrochemical applications. Our research focuses on how the dielectric heterogeneity of the solution could affect the disjoining pressure and differential capacitance of the electric double layer. Relying on the ...
Added: August 31, 2023
, , Journal of Molecular Liquids 2021 Vol. 341 Article 117438
Modeling aggregation of ionic micelles in solution is an important task that has been attracting attention for years. The molecular-thermodynamic micellization models describe the electrostatic interactions within the Poisson-Boltzmann theory that does not take into account fluctuations of the surfactant heads in the micelle. In this work we apply the statistical field theory to spherical ...
Added: September 1, 2021
Параллельные вычислительные технологии – XVII всероссийская конференция с международным участием, ПаВТ'2023, г. Санкт-Петербург, 28–30 марта 2023 г. Короткие статьи и описания плакатов
, , Издательский центр ЮУрГУ, 2023
Данный сборник содержит статьи, включенные в программу всероссийской научной конференции с международным участием «Параллельные вычислительные технологии 2023». Конференция проходила 28–30 марта 2023 года в Университете ИТМО (г. СанктПетербург). Подробную информацию о конференции можно найти в сети Интернет по адресу http://agora.guru.ru/pavt. Отпечатано с авторских оригиналов. ...
Added: November 27, 2023
Formation of Nanowires of Various Types in the Process of Galvanic Deposition of Iron Group Metals into the Pores of a Track Membrane
, , et al., Membranes 2022 No. 12 P. 1-19
The processes of formation of one-dimensional nanostructures by the method of matrix synthesis was studied in this work. Nanowires (NWs) from magnetic metals of iron-group and copper (3-d metals) were synthesized in the pores of matrix-track membranes by galvanic deposition. NWs with both homogeneous elemental distribution (alloys) and with periodically alternating parts with different composition (layers) were obtained in ...
Added: December 5, 2023
, , et al., Journal of Materials Chemistry C 2023 Vol. 11 No. 25 P. 8570-8576
In spite of decades of comprehensive studies phenomenon of single semiconductor colloidal quantum dots (QD) photoluminescence (PL) blinking require theoretical retreatment. Here we present enhanced model which proposes, that the blinking is caused by fluctuations in the rate of nonradiative relaxation due to temporal variations of the electron-phonon interaction coupling. The model quantitatively reproduces the ...
Added: May 16, 2023
, , , Carbon 2021 Vol. 175 P. 202-214
Based on the quantum-mechanical theory of electron transfer (ET), the parameter was proposed to describe the electrochemical activity of doped graphenes. The parameter is calculated using the density of states (DOS), local density of state (LDOS) values, which are in turn obtained from the density functional theory (DFT) calculations and reorganization energies of redox system. ...
Added: January 12, 2021
, , et al., Journal of Physical Chemistry C 2021 Vol. 125, No. 10 P. 5549-5558
Defects introduced to the surface of Bi(111) break the translational symmetry and modify the surface states locally. We present a theoretical and experimental study of the 2D defects on the surface of Bi(111) and the states that they induce. Bi crystals cleaved in ultrahigh vacuum (UHV) at low temperature (110 K) and the resulting ion-etched ...
Added: December 5, 2021
, М. : ЛЕНАНД, 2020
Within the presented monograph for the first time statistical approaches, based on the self-consistent field theory, were presented for the theoretical description of the thermodynamic properties of the ion-molecular systems (electrolyte solutions, ionic liquids, dielectric polymers and metal-organic frameworks) in the bulk solution and at the interfaces with the account for their molecular structure. In ...
Added: November 18, 2019
, , , Materials 2023 Vol. 16 No. 14 Article 5026
The nitrite admixtures in cement and concrete are used as corrosion inhibitors for steel reinforcement and also as anti-freezing agents. The characterization of the protective properties should account for the decrease in the concentration of free NO2− ions in the pores of cement concretes due to their adsorption. Here we applied the classical molecular dynamics computer ...
Added: July 21, 2023
Density Functional Theory Model for Adsorption-Induced Deformation of Mesoporous Materials with Nonconvex Pore Geometry
, , , Journal of Physical Chemistry C 2020 Vol. 124 No. 37 P. 20046-20054
Adsorption of fluids in nanoporous media causes mechanical stresses which results in deformation. This phenomenon is ubiquitous and its magnitude depends on the pore size and geometry. Adsorption and adsorption-induced deformation are typically modeled in slit-shape or convex (cylindrical or spherical) pores. However, many porous materials are composed of spherical grains, so that the pores ...
Added: August 13, 2020