Journal Description
Liquids
Liquids
is an international, peer-reviewed, open access journal on all aspects of liquid material research published quarterly online by MDPI.
- Open Access— free for readers, with article processing charges (APC) paid by authors or their institutions.
- High Visibility: indexed within AGRIS, and other databases.
- Rapid Publication: manuscripts are peer-reviewed and a first decision is provided to authors approximately 19.6 days after submission; acceptance to publication is undertaken in 5.7 days (median values for papers published in this journal in the first half of 2023).
- Recognition of Reviewers: APC discount vouchers, optional signed peer review, and reviewer names published annually in the journal.
Latest Articles
Photothermal Imaging of Transient and Steady State Convection Dynamics in Primary Alkanes
Liquids 2023, 3(3), 371-384; https://doi.org/10.3390/liquids3030022 (registering DOI) - 01 Sep 2023
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This paper presents a photothermal spectroscopy technique that effectively images convective heat flow in molecular liquids resulting from localized laser-induced heating. The method combines aspects of thermal lensing and photothermal deflection. A high-energy infrared laser is used to induce a thermal lens in
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This paper presents a photothermal spectroscopy technique that effectively images convective heat flow in molecular liquids resulting from localized laser-induced heating. The method combines aspects of thermal lensing and photothermal deflection. A high-energy infrared laser is used to induce a thermal lens in the sample, and a divergent visible laser is used to probe the entire region of the excitation beam within the sample. This approach allows for the observation of the convective flow of the liquid above the excitation beam. The study focuses on the liquid primary alkanes, from n-pentane to n-pentadecane. The paper provides experimental results, including dynamical data for the propagation of the thermal plume, a transient feature, in these alkanes and the exploration of dependence on excitation laser power.
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Solvatochromic and Acid–Base Molecular Probes in Surfactant Micelles: Comparison of Molecular Dynamics Simulation with the Experiment
Liquids 2023, 3(3), 314-370; https://doi.org/10.3390/liquids3030021 - 16 Aug 2023
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This article summarizes a series of seventeen publications by the authors devoted to molecular dynamics modeling of various indicator dyes (molecular probes) enclosed in surfactant micelles. These dyes serve as generally recognized tools for studying various types of organized solutions, among which surfactant
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This article summarizes a series of seventeen publications by the authors devoted to molecular dynamics modeling of various indicator dyes (molecular probes) enclosed in surfactant micelles. These dyes serve as generally recognized tools for studying various types of organized solutions, among which surfactant micelles in water are the simplest and most explored. The modeling procedure involves altogether 50 to 95 surfactant molecules, 16 to 28 thousand water molecules, and a single dye molecule. The presentation of the simulation results was preceded by a brief review of the state of experimental studies. This article consists of three parts. First, despite numerous literature data devoted to modeling the micelles itself, we decided to revisit this issue. The structure and hydration of the surface of micelles of surfactants, first of all of sodium n-dodecylsulfate, SDS, and cetyltrimethylammonium bromide, CTAB, were studied. The values of the electrical potential, Ψ, were estimated as functions of the ionic strength and distance from the surface. The decrease in the Ψ value with distance is gradual. Attempts to consider both DS− and CTA+ micelles in water without counterions result in a decay into two smaller aggregates. Obviously, the hydrophobic interaction (association) of the hydrocarbon tails balances the repulsion of the charged headgroups of these small “bare” micelles. The second part is devoted to the study of seven pyridinium N-phenolates, known as Reichardt’s dyes, in ionic micelles. These most powerful solvatochromic indicators are now used for examining various colloidal systems. The localization and orientation of both zwitterionic and (colorless) cationic forms are generally consistent with intuitive ideas about the hydrophobicity of substituents. Hydration has been quantitatively described for both the dye molecule as a whole and the oxygen atom. A number of markers, including the visible absorption spectra of Reichardt’s dyes, enable assuming a better hydration of the micellar surface of SDS than that of CTAB. However, our data show that it is more correct to speak about the more pronounced hydrogen-bonding ability of water molecules in anionic micelles than about better hydration of the SDS micelles as compared to CTAB ones. Finally, a set of acid–base indicators firmly fixed in the micellar pseudophase were studied by molecular dynamics. They are instruments for estimating electrostatic potentials of micelles and related aggregates as Ψ , where and are indices of so-called intrinsic and apparent dissociation constants. In this case, in addition to the location, orientation, and hydration, the differences between values of and indices of the dissociation constants in water were estimated. Only a semi-quantitative agreement with the experimental data was obtained. However, the differences between of a given indicator in two micellar solutions do much better agree with the experimental data. Accordingly, the experimental Ψ values of ionic micelles, as determined using the in nonionic micelles as , are reproduced with reasonable accuracy for the corresponding indicator. However, following the experimental data, a scatter of the Ψ values obtained with different indicators for given micelles is observed. This problem may be the subject of further research.
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(This article belongs to the Special Issue Solvatochromic Probes and Their Applications in Molecular Interaction Studies—a Themed Issue to Honor Professor Dr. Christian Reichardt)
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Reichardt’s Dye-Based Solvent Polarity and Abraham Solvent Parameters: Examining Correlations and Predictive Modeling
Liquids 2023, 3(3), 303-313; https://doi.org/10.3390/liquids3030020 - 02 Aug 2023
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The concept of “solvent polarity” is widely used to explain the effects of using different solvents in various scientific applications. However, a consensus regarding its definition and quantitative measure is still lacking, hindering progress in solvent-based research. This study hopes to add to
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The concept of “solvent polarity” is widely used to explain the effects of using different solvents in various scientific applications. However, a consensus regarding its definition and quantitative measure is still lacking, hindering progress in solvent-based research. This study hopes to add to the conversation by presenting the development of two linear regression models for solvent polarity, based on Reichardt’s ET(30) solvent polarity scale, using Abraham solvent parameters and a transformer-based model for predicting solvent polarity directly from molecular structure. The first linear model incorporates the standard Abraham solvent descriptors s, a, b, and the extended model ionic descriptors j+ and j−, achieving impressive test-set statistics of R2 = 0.940 (coefficient of determination), MAE = 0.037 (mean absolute error), and RMSE = 0.050 (Root-Mean-Square Error). The second model, covering a more extensive chemical space but only using the descriptors s, a, and b, achieves test-set statistics of R2 = 0.842, MAE = 0.085, and RMSE = 0.104. The transformer-based model, applicable to any solvent with an associated SMILES string, achieves test-set statistics of R2 = 0.824, MAE = 0.066, and RMSE = 0.095. Our findings highlight the significance of Abraham solvent parameters, especially the dipolarity/polarizability, hydrogen-bond acidity/basicity, and ionic descriptors, in predicting solvent polarity. These models offer valuable insights for researchers interested in Reichardt’s ET(30) solvent polarity parameter and solvent polarity in general.
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(This article belongs to the Special Issue Solvatochromic Probes and Their Applications in Molecular Interaction Studies—a Themed Issue to Honor Professor Dr. Christian Reichardt)
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An X-ray and Neutron Scattering Study of Aqueous MgCl2 Solution in the Gigapascal Pressure Range
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, , , , and
Liquids 2023, 3(3), 288-302; https://doi.org/10.3390/liquids3030019 - 04 Jul 2023
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The structure of electrolyte solutions under pressure at a molecular level is a crucial issue in the fundamental science of understanding the nature of ion solvation and association and application fields, such as geological processes on the Earth, pressure-induced protein denaturation, and supercritical
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The structure of electrolyte solutions under pressure at a molecular level is a crucial issue in the fundamental science of understanding the nature of ion solvation and association and application fields, such as geological processes on the Earth, pressure-induced protein denaturation, and supercritical water technology. We report the structure of an aqueous 2 m (=mol kg−1) MgCl2 solution at pressures from 0.1 MPa to 4 GPa and temperatures from 300 to 500 K revealed by X-ray- and neutron-scattering measurements. The scattering data are analyzed by empirical potential structure refinement (EPSR) modeling to derive the pair distribution functions, coordination number distributions, angle distributions, and spatial density functions (3D structure) as a function of pressure and temperature. Mg2+ forms rigid solvation shells extended to the third shell; the first solvation shell of six-fold octahedral coordination with about six water molecules at 0 GPa transforms into about five water molecules and one Cl− due to the formation of the contact ion pairs in the GPa pressure range. The Cl− solvation shows a substantial pressure dependence; the coordination number of a water oxygen atom around Cl− increases from 8 at 0.1 MPa/300 K to 10 at 4 GPa/500 K. The solvent water transforms the tetrahedral network structure at 0.1 MPa/300 K to a densely packed structure in the GPa pressure range; the number of water oxygen atoms around a central water molecule gradually increases from 4.6 at 0.1 MPa/298 K to 8.4 at 4 GPa/500 K.
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(This article belongs to the Special Issue Hydration of Ions in Aqueous Solution)
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Hydration of Phosphate Ion in Polarizable Water: Effect of Temperature and Concentration
by
and
Liquids 2023, 3(3), 278-287; https://doi.org/10.3390/liquids3030018 - 21 Jun 2023
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The hydration of phosphate ions, an essential component of many biological molecules, is studied using all-atom molecular dynamics (MD) simulation and quantum chemical methods. MD simulations are carried out by employing a mean-field polarizable water model. A good linear correlation between the self-diffusion
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The hydration of phosphate ions, an essential component of many biological molecules, is studied using all-atom molecular dynamics (MD) simulation and quantum chemical methods. MD simulations are carried out by employing a mean-field polarizable water model. A good linear correlation between the self-diffusion coefficient and phosphate anion concentration is ascertained from the computed mean-square displacement (MSD) profiles. The HB dynamics of the hydration of the phosphate anion is evaluated from the time-dependent autocorrelation function CHB(t) and is determined to be slightly faster for the phosphate–anion system as compared to that of the water–water system at room temperature. The coordination number (CN) of the phosphate ion is found to be 15.9 at 298 K with 0.05 M phosphate ion concentration. The average CN is also calculated to be 15.6 for the same system by employing non-equilibrium MD simulation, namely, the well-tempered meta-dynamics method. A full geometry optimization of the PO43−·16H2O cluster is investigated at the ωB97X-D/aug-cc-pVTZ level of theory, and the hydration of the phosphate anion is observed to have both singly and doubly bonded anion–water hydrogen bonds and inter-water hydrogen bonds in a range between 0.169–0.201 nm and 0.192–0.215 nm, respectively. Modified Stokes–Einstein relation is used to calculate the conductivity of the phosphate ion and is found to be in good agreement with the experimentally observed value.
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(This article belongs to the Special Issue Hydration of Ions in Aqueous Solution)
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Effects of Dispersed Carbon Nanotubes and Emerging Supramolecular Structures on Phase Transitions in Liquid Crystals: Physico-Chemical Aspects
Liquids 2023, 3(2), 246-277; https://doi.org/10.3390/liquids3020017 - 29 May 2023
Cited by 1
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The current state of the study of different liquid crystalline (LC) systems doped with carbon nanotubes (CNTs) is discussed. An attempt is endeavored to outline the state-of-the-art technology that has emerged after two past decades. Systematization and analysis are presented for the integration
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The current state of the study of different liquid crystalline (LC) systems doped with carbon nanotubes (CNTs) is discussed. An attempt is endeavored to outline the state-of-the-art technology that has emerged after two past decades. Systematization and analysis are presented for the integration of single- and multi-walled carbon nanotubes in thermotropic (nematic, smectic, cholesteric, ferroelectric, etc.) and lyotropic LCs. Special attention is paid to the effects of alignment and supramolecular organization resulting from orientational coupling between CNTs and the LC matrix. The effects of the specific inter-molecular and inter-particle interactions and intriguing microstructural, electromagnetic, percolation, optical, and electro-optical properties are also discussed.
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(This article belongs to the Special Issue Nanocarbon–Liquid Systems)
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Determination of the Dissociation Constants (pKa) of Eight Amines of Importance in Carbon Capture: Computational Chemistry Calculations, and Artificial Neural Network Models
Liquids 2023, 3(2), 214-245; https://doi.org/10.3390/liquids3020016 - 20 May 2023
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This work focuses on determining the dissociation constants (pKa) of eight amines, namely, 3-(Diethylamino) propylamine, 1,3-Diaminopentane, 3-Butoxypropylamine, 2-(Methylamino) ethanol, Bis(2-methoxyethyl) amine, α-Methylbenzylamine, 2-Aminoheptane, and 3-Amino-1-phenylbutane, within temperatures ranging from 293.15 K to 323.15 K. The thermodynamic properties of the protonated
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This work focuses on determining the dissociation constants (pKa) of eight amines, namely, 3-(Diethylamino) propylamine, 1,3-Diaminopentane, 3-Butoxypropylamine, 2-(Methylamino) ethanol, Bis(2-methoxyethyl) amine, α-Methylbenzylamine, 2-Aminoheptane, and 3-Amino-1-phenylbutane, within temperatures ranging from 293.15 K to 323.15 K. The thermodynamic properties of the protonated reactions were regressed from the pKa work. In addition, the protonated order of both 3-(Diethylamino) propylamine and 1,3-Diaminopentane were determined using computational chemistry methods owing to their unsymmetrical structures. In addition to the experimental methods, the dissociation constants at the standard temperature (298.15 K) were also estimated using group functional models (paper–pencil) and computational methods. The computational methods include COSMO-RS and computational chemistry calculations. An artificial neural network (ANN) method was employed to model the data by collecting and combining the experimental properties to estimate the missing pKa values. Although the ANN models can provide acceptable results, they depend on the availability of the data. Instead of using the experimental properties, they were generated using software such as Aspen Plus or CosmothermX. The simulated ANN model can also provide very good fits to the experimental constant values.
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(This article belongs to the Section Chemical Physics of Liquids)
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Translational Dynamics of Imidazolium-Based Ionic Liquids in Acetonitrile Solutions
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and
Liquids 2023, 3(2), 203-213; https://doi.org/10.3390/liquids3020015 - 19 Apr 2023
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The dynamics of pure ionic liquids and solutions with acetonitrile have been investigated through quasielastic neutron scattering (QENS). The translational diffusive motion of the 1-butyl-3-methyl-imidazolium cation was revealed as a function of concentration and temperature. The diffusion coefficients obtained are in reasonably good
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The dynamics of pure ionic liquids and solutions with acetonitrile have been investigated through quasielastic neutron scattering (QENS). The translational diffusive motion of the 1-butyl-3-methyl-imidazolium cation was revealed as a function of concentration and temperature. The diffusion coefficients obtained are in reasonably good agreement with molecular dynamics (MD) computer simulations based on a classical potential. The diffusive mobility of the cation dramatically increases when adding acetonitrile. This increase in diffusivity is directly related to a maximum in conductivity of these ionic liquid solutions and might pave the way for new design of electrolytes. The translational motions in pure ionic liquids are too slow to be resolved by our experiment. However, localized motion resembling rotation on a sphere of the measured proton signal could be identified in the pure ionic liquids.
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(This article belongs to the Section Molecular Liquids)
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Density, Excess Molar Volume and Vapor–Liquid Equilibrium Measurements at 101.3 kPa for Binary Mixtures Containing Ethyl Acetate and a Branched Alkane: Experimental Data and Modeling
Liquids 2023, 3(2), 187-202; https://doi.org/10.3390/liquids3020014 - 11 Apr 2023
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Vapor–liquid equilibrium (VLE) and density data for binary systems of branched alkanes + ethyl acetate are scarce in the literature. In this study, the binary mixtures 3-methylpentane + ethyl acetate and 2,3-dimethylbutane + ethyl acetate were investigated. Density measurements at atmospheric pressure were
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Vapor–liquid equilibrium (VLE) and density data for binary systems of branched alkanes + ethyl acetate are scarce in the literature. In this study, the binary mixtures 3-methylpentane + ethyl acetate and 2,3-dimethylbutane + ethyl acetate were investigated. Density measurements at atmospheric pressure were performed using a vibrating tube density meter at 293.15, 298.15 and 303.15 K. Large and positive excess molar volumes were calculated and correlated using a Redlich–Kister-type equation. Isobaric VLE data at 101.3 kPa were obtained using a Gillespie-type recirculation ebulliometer. Equilibrium compositions were determined indirectly from density measurements. The experimental data were checked for consistency by means of the Fredenslund test and the Wisniak (L-W) test and were then successfully correlated using the NRTL model. The newly studied binary systems display high deviations from ideality and minimum boiling azeotropes, the coordinates of which are reported in this work.
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Partial Denaturation of Double-Stranded DNA on Pristine Graphene under Physiological-like Conditions
Liquids 2023, 3(2), 168-186; https://doi.org/10.3390/liquids3020013 - 30 Mar 2023
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Interactions between DNA and graphene are paramount for a wide range of applications, such as biosensing and nanoelectronics; nonetheless, the molecular details of such interactions remain largely unexplored. We employ atomically detailed molecular dynamics simulations with an enhanced sampling technique to investigate the
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Interactions between DNA and graphene are paramount for a wide range of applications, such as biosensing and nanoelectronics; nonetheless, the molecular details of such interactions remain largely unexplored. We employ atomically detailed molecular dynamics simulations with an enhanced sampling technique to investigate the adsorption and mobility of double-stranded DNA along the basal plane of graphene, in an electrolytic aqueous medium. The study focuses on physiologically relevant conditions, using a buffer of [NaCl] = 134 mM. DNA physisorption is shown to be fast and irreversible, leading to deformation and partial melting of the double helix as a result of π–π stacking between the terminal nucleobases and graphene. Denaturation occurs primarily at the termini, with ensemble averaged H-bond ratios of 47.8–62%; these can, however, reach a minimum of 15%. Transition between free-energy minima occurs via a thermodynamical pathway driving the nucleic acid from a radius of gyration of 1.5 nm to 1.35 nm. Mobility along the basal plane of graphene is dominant, accounting for ~90% of all centre-of-mass translation and revealing that the DNA’s apparent diffusivity is similar to diffusion along the endohedral volume of carbon nanotubes, but one order of magnitude faster than in other 2D materials, such as BC3 and C3N.
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Conformational Dependence of the First Hyperpolarizability of the Li@B10H14 in Solution
Liquids 2023, 3(1), 159-167; https://doi.org/10.3390/liquids3010012 - 20 Feb 2023
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Using the ASEC-FEG approach in combination with atomistic simulations, we performed geometry optimizations of a Cs conformer of the lithium decahydroborate (Li@B10H14) complex in chloroform and in water, which has been shown to be the most stable in
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Using the ASEC-FEG approach in combination with atomistic simulations, we performed geometry optimizations of a Cs conformer of the lithium decahydroborate (Li@B10H14) complex in chloroform and in water, which has been shown to be the most stable in the gas phase and calculated its first hyperpolarizability. At room temperature, ASEC-FEG calculations show that this conformer is stable only in chloroform. However, it is found that the nonlinear response of the Cs conformer in chloroform is mild, and the result for the hyperpolarizability is markedly decreased in comparison with the result of the C2v conformer.
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Investigation of the Impact of High Concentration LiTFSI Electrolytes on Silicon Anodes with Reactive Force Field Simulations
Liquids 2023, 3(1), 132-158; https://doi.org/10.3390/liquids3010011 - 06 Feb 2023
Cited by 1
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The initial formation cycles are critical to the performance of a lithium-ion battery (LIB), particularly in the case of silicon anodes, where the high surface area and extreme volume expansion during cycling make silicon susceptible to detrimental side reactions with the electrolyte. The
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The initial formation cycles are critical to the performance of a lithium-ion battery (LIB), particularly in the case of silicon anodes, where the high surface area and extreme volume expansion during cycling make silicon susceptible to detrimental side reactions with the electrolyte. The solid electrolyte interface (SEI) that is formed during these initial cycles serves to protect the surface of the anode from a continued reaction with the electrolyte, and its composition reflects the composition of the electrolyte. In this work, ReaxFF reactive force field simulations were used to investigate the interactions between ether-based electrolytes with high LiTFSI salt concentrations (up to 4 mol/L) and a silicon oxide surface. The simulation investigations were verified with galvanostatic testing and post-mortem X-ray photoelectron spectroscopy, revealing that highly concentrated electrolytes resulted in the faster formation and SEIs containing more inorganic and silicon species. This study emphasizes the importance of understanding the link between electrolyte composition and SEI formation. This ReaxFF approach demonstrates an accessible way to tune electrolyte compositions for optimized performance without costly, time-consuming experimentation.
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(This article belongs to the Special Issue Electrolytes for High-Performance Rechargeable Batteries)
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Determination of Abraham Model Solute Descriptors for 62 Additional C10 through C13 Methyl- and Ethyl-Branched Alkanes
Liquids 2023, 3(1), 118-131; https://doi.org/10.3390/liquids3010010 - 01 Feb 2023
Cited by 3
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Abraham model solute descriptors are reported for the first time for 62 additional C10 through C13 methyl- and ethyl-branched alkanes. The numerical values were determined using published gas chromatographic retention Kováts retention indices for 157 alkane solutes eluted from a squalane
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Abraham model solute descriptors are reported for the first time for 62 additional C10 through C13 methyl- and ethyl-branched alkanes. The numerical values were determined using published gas chromatographic retention Kováts retention indices for 157 alkane solutes eluted from a squalane stationary phase column. The 95 alkane solutes that have known descriptor values were used to construct the Abraham model KRI versus L-solute descriptor correlation needed in our calculations. The calculated solute descriptors can be used in conjunction with previously published Abraham model correlations to predict a wide range of important physico-chemical and biological properties. The predictive computations are illustrated by estimating the air-to-polydimethylsiloxane partition coefficient for each of the 157 alkane solutes.
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(This article belongs to the Collection Feature Papers in Solutions and Liquid Mixtures Research)
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How Does Heat Propagate in Liquids?
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Liquids 2023, 3(1), 92-117; https://doi.org/10.3390/liquids3010009 - 30 Jan 2023
Cited by 1
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In this paper, we proceed to illustrate the consequences and implications of the Dual Model of Liquids (DML) by applying it to the heat propagation. Within the frame of the DML, propagation of thermal (elastic) energy in liquids is due to wave-packet propagation
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In this paper, we proceed to illustrate the consequences and implications of the Dual Model of Liquids (DML) by applying it to the heat propagation. Within the frame of the DML, propagation of thermal (elastic) energy in liquids is due to wave-packet propagation and to the wave-packets’ interaction with the material particles of the liquid, meant in the DML as aggregates of molecules swimming in an ocean of amorphous liquid. The liquid particles interact with the lattice particles, a population of elastic wave-packets, by means of an inertial force, exchanging energy and momentum with them. The hit particle relaxes at the end of the interaction, releasing the energy and momentum back to the system a step forward and a time lapse later, like in a tunnel effect. The tunnel effect and the duality of liquids are the new elements that suggest on a physical basis for the first time, using a hyperbolic equation to describe the propagation of energy associated to the dynamics of wave-packet interaction with liquid particles. Although quantitatively relevant only in the transient phase, the additional term characterizing the hyperbolic equation, usually named the “memory term”, is physically present also once the stationary state is attained; it is responsible for dissipation in liquids and provides a finite propagation velocity for wave-packet avalanches responsible in the DML for the heat conduction. The consequences of this physical interpretation of the “memory” term added to the Fourier law for the phononic contribution are discussed and compiled with numerical prediction for the value of the memory term and with the conclusions of other works on the same topic.
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(This article belongs to the Section Physics of Liquids)
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Acknowledgment to the Reviewers of Liquids in 2022
Liquids 2023, 3(1), 90-91; https://doi.org/10.3390/liquids3010008 - 13 Jan 2023
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High-quality academic publishing is built on rigorous peer review [...]
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Linear Solvation–Energy Relationships (LSER) and Equation-of-State Thermodynamics: On the Extraction of Thermodynamic Information from the LSER Database
Liquids 2023, 3(1), 66-89; https://doi.org/10.3390/liquids3010007 - 11 Jan 2023
Cited by 3
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There is a remarkable wealth of thermodynamic information in freely accessible databases, the LSER database being a classical example. The LSER, or Abraham solvation parameter model, is a very successful predictive tool in a variety of applications in the (bio)chemical and environmental sector.
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There is a remarkable wealth of thermodynamic information in freely accessible databases, the LSER database being a classical example. The LSER, or Abraham solvation parameter model, is a very successful predictive tool in a variety of applications in the (bio)chemical and environmental sector. The model and the associated database are very rich in thermodynamic information and information on intermolecular interactions, which, if extracted properly, would be particularly useful in various thermodynamic developments for further applications. Partial Solvation Parameters (PSP), based on equation-of-state thermodynamics, are designed as a versatile tool that would facilitate this extraction of information. The present work explores the possibilities of such an LSER–PSP interconnection and the challenging issues this effort is faced with. The thermodynamic basis of the very linearity of the LSER model is examined, especially, with respect to the contribution of strong specific interactions in the solute/solvent system. This is done by combining the equation-of-state solvation thermodynamics with the statistical thermodynamics of hydrogen bonding. It is verified that there is, indeed, a thermodynamic basis of the LFER linearity. Besides the provenance of the sought linearity, an insight is gained on the thermodynamic character and content of coefficients and terms of the LSER linearity equations. The perspectives from this insight for the further development of LSER and related databases are discussed. The thermodynamic LSER–PSP interconnection is examined as a model for the exchange in information between QSPR-type databases and equation-of-state developments and the associated challenges are examined with representative calculations.
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(This article belongs to the Special Issue Modeling of Liquids Behavior: Experiments, Theory and Simulations)
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Open AccessReview
The Relevance of Cavity Creation for Several Phenomena Occurring in Water
Liquids 2023, 3(1), 57-65; https://doi.org/10.3390/liquids3010006 - 09 Jan 2023
Abstract
The solvent-excluded volume effect is an under-appreciated general phenomenon occurring in liquids and playing a fundamental role in many cases. It is quantified and characterized by means of the theoretical concept of cavity creation and its Gibbs free energy cost. The magnitude of
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The solvent-excluded volume effect is an under-appreciated general phenomenon occurring in liquids and playing a fundamental role in many cases. It is quantified and characterized by means of the theoretical concept of cavity creation and its Gibbs free energy cost. The magnitude of the reversible work of cavity creation proves to be particularly large in water, and this fact plays a key role for, among other things, the poor solubility of nonpolar species, the formation of host–guest complexes, and the folding of globular proteins. An analysis of some examples is provided in the present review.
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(This article belongs to the Special Issue Modeling of Liquids Behavior: Experiments, Theory and Simulations)
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Open AccessCommunication
Density and Dynamic Viscosity of Perfluorodecalin-Added n-Hexane Mixtures: Deciphering the Role of Fluorous Liquids
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Liquids 2023, 3(1), 48-56; https://doi.org/10.3390/liquids3010005 - 04 Jan 2023
Cited by 1
Abstract
Fluorous solvents are deputed as prominent solvent systems owing to their salient features, unique physical properties, and ecological importance. In this study, the temperature- and composition-dependence of physical properties, density (ρ/g·cm−3), and dynamic viscosity (η/mPa·s), of neat
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Fluorous solvents are deputed as prominent solvent systems owing to their salient features, unique physical properties, and ecological importance. In this study, the temperature- and composition-dependence of physical properties, density (ρ/g·cm−3), and dynamic viscosity (η/mPa·s), of neat perfluorodecalin (PFD) and PFD-added n-hexane mixtures with select compositions are reported. Density follows a linear decrease with temperature and a quadratic increase with the mole fraction of PFD. The sensitivity or dependence of density on temperature increases with an increase in PFD mole fraction. The temperature-dependence of the dynamic viscosity of the investigated mixtures follows the Arrhenius-type expression from which the resultant activation energy of the viscous flow (Ea,η) is determined. Interestingly, the composition-dependence of dynamic viscosity shows exponential growth with an increase in PFD mole fraction. Excess molar volumes (VE) and deviation in the logarithmic viscosities ∆(ln η) of the mixtures are calculated to highlight the presence of strong repulsive interactions between the two mixture components.
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(This article belongs to the Special Issue Modeling of Liquids Behavior: Experiments, Theory and Simulations)
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Climbing Colloidal Suspension
Liquids 2023, 3(1), 40-47; https://doi.org/10.3390/liquids3010004 - 02 Jan 2023
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Mixtures of powder and liquid are ubiquitous in nature as well as industries and exhibit complex flowing and deforming behaviors, including sol to gel transition under shear stress. In order to better understand the characteristic features of this type of mixture, we observed
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Mixtures of powder and liquid are ubiquitous in nature as well as industries and exhibit complex flowing and deforming behaviors, including sol to gel transition under shear stress. In order to better understand the characteristic features of this type of mixture, we observed the behavior of a mixture of colloidal silica particles and water as a model system under vibration. The mixture showed different states, from powder-like to viscous fluid-like, with increasing content of water. At certain concentrations of silica particles (around 70 wt. %) and under relatively faster vibration (over 17 Hz), we observed that the colloidal suspension of silica particles and water climbed up the wall of a container against gravity. The main purpose of this paper is to report how we can observe the climbing suspension of colloidal silica. The rheological measurements of the climbing suspension demonstrated that the climbing suspension showed shear-thickening behavior, where force chain networks and normal stress differences are considered to develop. Therefore, we speculate that the transient formation and breaking of force networks and normal stress differences under vibration contribute to the occurrence of the climbing suspension. The tunable nature of colloidal suspensions may help to elucidate the climbing mechanism in the future.
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Vibrational Raman Spectroscopy of the Hydration Shell of Ions
Liquids 2023, 3(1), 19-39; https://doi.org/10.3390/liquids3010003 - 27 Dec 2022
Cited by 1
Abstract
Ionic perturbation of water has important implications in various chemical, biological and environmental processes. Previous studies revealed the structural and dynamical perturbation of water in the presence of ions, mainly with concentrated electrolyte solutions having significant interionic interactions. These investigations highlighted the need
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Ionic perturbation of water has important implications in various chemical, biological and environmental processes. Previous studies revealed the structural and dynamical perturbation of water in the presence of ions, mainly with concentrated electrolyte solutions having significant interionic interactions. These investigations highlighted the need of selective extraction of the hydration shell water from a dilute electrolyte solution that is largely free from interionic interactions. Double-difference infrared (DDIR) and Raman multivariate curve resolution (Raman-MCR), as well as MD simulation, provided valuable insight in this direction, suggesting that the perturbed water mainly resides in the immediate vicinity of the ion, called the hydration shell. Recently, we have introduced Raman difference spectroscopy with simultaneous curve fitting (Raman-DS-SCF) analysis that can quantitatively extract the vibrational response of the perturbed water pertaining to the hydration shell of fully hydrated ions/solute. The DS-SCF analysis revealed novel hydrogen-bond (H-bond) structural features of hydration water, such as the existence of extremely weakly interacting water–OH (νmax ~ 3600 cm−1) in the hydration shell of high-charge-density metal ions (Mg2+, Dy3+). In addition, Raman-DS-SCF retrieves the vibrational response of the shared water in the water–shared-ion pair (WSIP), which is different from the hydration shell water of either the interacting cation and anion. Herein, we discuss the perturbation of water H-bonding in the immediate vicinity of cation, anion, zwitterion and hydrophobes and also the inter-ionic interactions, with a focus on the recent results from our laboratory using Raman-DS-SCF spectroscopy.
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(This article belongs to the Special Issue Hydration of Ions in Aqueous Solution)
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