Liquids doi: 10.3390/liquids6010012

Authors: Franz Demmel William Spencer Howells

Liquid sulfur exhibits the famous λ-transition at T = 432 K, changing from a liquid mainly consisting of eight-membered rings into a liquid with chains of different lengths. This transition is accompanied by an increase in viscosity that reaches four orders of magnitude. We present a neutron-scattering study conducted throughout the transition to elucidate the slow relaxation dynamics. The data are analyzed within the frequency domain and, after Fourier transformation, in the time domain as well. The relaxation dynamics between 1 ps and 140 ps deviate strongly from simple exponential decay and can be accurately described as stretched exponential decay. The relaxation times demonstrate a change to faster dynamics above the transition at a wave vector corresponding to nearest-neighbor distances. At smaller wave vectors, however, and hence greater length scales, the relaxation times increase with an increasing temperature, evidencing a significant change in dynamics. The Q-dependence of the relaxation rate above the λ-transition agrees with predictions for polymer melt dynamics. The relaxation dynamics at these length scales are dominated by chain-like structures, and the observed polymer-like dynamics might be the microscopic origin of the increase in viscosity.

Liquids doi: 10.3390/liquids6010011

Authors: Masao Iwamatsu

Hydrophobicity and hydrophilicity are incompatible in the sense that a single substrate cannot exhibit both characteristics simultaneously. On a hydrophobic substrate, for example, a macroscopic droplet always exhibits a morphology with a contact angle higher than 90°, never lower than 90°. In this paper, we theoretically demonstrate the possibility that a nanoscale droplet can exhibit a contact angle lower than 90° on the same hydrophobic substrate. To demonstrate this, we analyze the morphology and contact angle of a sessile droplet on smooth flat substrates, taking into account disjoining pressure of Lennard–Jones type. By constraining the two-dimensional cylindrical droplet and minimizing the free-energy functional, we derive a formula to determine the droplet’s morphology and the boundary between hydrophilic and hydrophobic contact angles for finite-sized droplets. Using this formulation, we reconsider the formula for the macroscopic contact angle, known as the Derjaguin–Frumkin formula. By utilizing a simple disjoining pressure model, we find that the calculated contact angle at the nanoscale is always smaller than the macroscopic contact angle determined by the Derjaguin–Frumkin formula. Consequently, the wettability (hydrophilicity/hydrophobicity) differs at the nanoscale compared to the macroscale. We further discuss the implication of our results on the size-dependent contact angle and line tension at the nanoscale.

Liquids doi: 10.3390/liquids6010010

Authors: Tadeusz Hofman Wojciech Tomaszewski

The research on nonaqueous two-phase systems, i.e., ternary nonaqueous systems with a liquid–liquid phase split induced by a solid component, is discussed. Previous scattered reports are reviewed and summarized. The first systematic studies are described in detail. These included qualitative testing of numerous ternary systems (a solid component and two liquid solvents, significantly different in polarity) to determine whether a liquid–liquid phase split occurred. Some correlations between this occurrence and the Hofmeister series were suggested. The liquid–liquid equilibrium was determined experimentally in a few systems, and the problems encountered during this determination are discussed. Possible applications and further topics of investigation are suggested.

Liquids doi: 10.3390/liquids6010009

Authors: Ioannis Lelidis Giovanni Barbero

Experimentally, adsorption is usually described by adsorption isotherms, which present a saturation effect at high enough concentration or pressure of the adsorbate fluid. This well-known saturation effect was first theoretically discussed by Langmuir, and it is commonly attributed to the finite number of adsorption sites on the substrate surface. Here, we propose an alternative approach to introduce saturation via a repulsive interaction potential, ϕ, among the adsorbate particles, in addition to the attractive potential between the adsorbate particles and the substrate. Using the proposed toy model for a semi-infinite sample, we calculate adsorption isotherms for a typical van der Waals interaction potential. The concentration profile of the adsorbate as a function of the distance from the surface is calculated for several bulk concentrations. The functional dependence of the saturation concentration on the strength of the repulsive inter-particle interaction is extracted by fitting numerical data. Our results are compared to those of the Langmuir model. No assumption of a finite predefined number of adsorption sites is required to obtain saturation.

Liquids doi: 10.3390/liquids6010008

Authors: Cory C. Pye Fernanda de Paola Rodrigues

The energies, structures, and vibrational frequencies of [Fe(H2O)n]3+, n = 0–6, 18 have been calculated at the Hartree–Fock, second-order Møller–Plesset, and density functional (B3LYP) levels of theory using the 6−31G* and 6−31+G* basis sets. The metal–oxygen distances and stretching frequencies were compared with each other, with related crystal structure and solution measurements and with previous calculations. The Fe-O distances and stretching vibrational frequencies were well reproduced with an explicit model for the second hydration shell.

Liquids doi: 10.3390/liquids6010007

Authors: Elias Bürkle Marius Lutz Klara M. Meyer-Hermann Azat Khadiev Dmitri Novikov Patrick Friebel Laura Cattaneo

We present the design and characterization of a fully automated free-standing liquid crystal (FSLC) film holder, enabling remote and precise control of liquid crystal (LC) volume release, wiping speed, and temperature. Using 4-octyl-4′-cyanobiphenyl (8CB) as a test material, we systematically investigated the influence of formation parameters on the resulting film thickness and temporal evolution. Thickness measurements performed by monitoring the difference in optical path lengths of two arms of a standard optical intensity autocorrelation setup reveal that the wiping speed is the dominant factor determining both the initial film thickness and the subsequent annealing dynamics, while temperature becomes relevant only at the highest wiping speeds. Faster wiping speeds consistently produce thinner and more uniform FSLC films on the order of 3 µm, due to reduced LC mass deposition. Time-resolved optical and X-ray scattering measurements confirm the presence of an annealing phase following film formation, which can last for between 1 s and 10 min time scales, until a stable smectic configuration is reached. The holder provides a reliable and fully remote tool for generating high-quality FSLC films at rates up to 1 Hz, suitable for optical to hard X-ray experiments where direct access to the sample environment is limited.

Liquids doi: 10.3390/liquids6010006

Authors: Michele Casoria Marco Pagliai Claudia Andreini Anna Maria Papini Piero Procacci Marina Macchiagodena

An upgraded GAFF2 force field has been used to simulate two fluorinated alcohols, TFE and HFIP, in aqueous solutions at several concentrations. The same force field has also been employed to simulate a 26-residue amphiphilic peptide in several cosolvent/water mixtures to verify and clarify its efficacy in stabilizing the secondary structure. The calculated thermodynamic and structural properties are in agreement with experimental findings. The force field allows a correct description of the secondary structure and affords an accurate characterization of the spatial organization of cosolvent molecules around the peptide.

Liquids doi: 10.3390/liquids6010005

Authors: Diego Ivan Caviedes-Rubio Claudia Patricia Ortiz Rossember Edén Cardenas-Torres Fleming Martinez Daniel Ricardo Delgado

Solubility studies are an essential requirement for the development of more efficient industrial processes. In this context, the use of cosolvents is a relevant strategy in pharmaceutical sciences, especially when dealing with green solvents such as water (W (2)) and Polyethylene glycol 400 (PEG 400 (1)). The objective of this study is to thermodynamically analyze the solubility of isoniazid in {PEG 400 (1) + W (2)} cosolvent mixtures at seven temperatures (288.15 to 318.15 K). The study was conducted by calculating thermodynamic functions from experimental solubility data determined using the flask shaking method, employing UV spectrophotometry as the quantification technique. The dissolution process was shown to be endothermic and entropy-driven. Although maximum solubility would be expected to be achieved in a cosolvent mixture, given that the solubility parameter of isoniazid (30.54 MPa1/2) has an intermediate value between the two pure solvents (PEG 400 ≈ 22.5 MPa1/2; Water ≈47.8 MPa1/2), maximum solubility is achieved in pure PEG 400 and the lowest solubility is achieved in pure water.

Liquids doi: 10.3390/liquids6010004

Authors: Simon Papine-Paktoris Julia Trancoso Fernandes dos Santos Simon Ivar Andersen Alexander A. Shapiro

Filtration of emulsions is an important operation in multiple processes of chemical, environmental, and petroleum engineering. The primary concern of the present study is cleaning of water produced from a petroleum reservoir. The produced water is filtered from the oil droplets before being dumped into the sea or reinjected into the reservoir. Efficiency of filtration is determined, in particular, by the droplet size distribution and interfacial properties. We have developed a new population balance model of emulsion filtration, based on the Boltzmann–Smoluchowski approach. The model accounts for the droplet size distribution, as well as for the different mechanisms of the droplet capture: attachment to the surface and straining in the pore constrictions. The model can not only be applied to filtering of the produced water, but also to more general emulsion processing. It is capable of reproducing experimental data on the droplet production history and dynamic permeability decline. The sensitivity study indicates low sensitivity of the permeability decline curves to the model parameters. The production histories or other kinds of experimental data are necessary to discriminate between the different parametrizations of the model.

Liquids doi: 10.3390/liquids6010003

Authors: Eugene Semenenko Oleksandr Krut’ Artur Zaporozhets

It has been shown for the first time that in the case of a pressure flow of a Newtonian fluid in a circular pipeline, the influence of forces of rheological origin, ion electrostatic and Van der Waals nature on the radius of the undeformed flow core is described by a third-degree polynomial with respect to the thickness of the layer, where the suspension structure is destroyed and its shear flow occurs. In this polynomial, the contributions of rheological forces and the influence of the hydraulic size of the solid-phase particles in the suspension enter as linear terms; ionic electrostatic and Van der Waals forces enter as quadratic and constant terms, respectively. For conditions typical of water–coal fuel, we demonstrate that the hydraulic (size) term is several orders of magnitude smaller than the leading terms and may be neglected, and that the quadratic term is negligible compared with the constant (free) term, so that the limiting value of the undeformed core radius is obtained as the real root of a cubic equation containing cubic, linear and constant terms. At DLVO equilibrium, the constant term vanishes, and the limiting relative core radius reduces to the rheological–hydraulic expression; away from equilibrium, the constant term becomes positive or negative, thereby altering the admissible interval of the relative core radius. Using Cardan’s method, we show analytically that (i) when the cubic discriminant is positive, a single real root exists and physically admissible solutions occur only for a negative constant term; (ii) when the discriminant is negative, three real roots exist and the maximum relative radius at which the suspension structure is preserved shifts above or below the rheological-only radius depending on the sign of the constant term. Numerical evaluation of the proposed lyophobicity model for proportionality coefficients k1 in the range 1–10 yields a lyophobicity function varying approximately from 0.67 to 1.06, confirming the modest but non-negligible role of interparticle interaction energy in modifying the undeformed core size under water–coal fuel conditions. These results quantify the competing roles of rheology and interparticle forces in determining the stability and extent of the undeformed core in pipeline transport of structured suspensions.

Liquids doi: 10.3390/liquids6010002

Authors: Ahmed Ghadhy Amine Lilane Hamza Faraji Said Ettami Abdelkader Boulezhar Dennoun Saifaoui

Arid zones, such as the MENA regions and the Sahara countries, are experiencing significant water stress. To address this global challenge, desalination technologies provide a crucial solution, particularly the reverse osmosis (RO) technique, which is widely used to treat Seawater or Brackish water. Mauritania is among the countries facing a scarcity of potable water resources and relies on desalination technologies to meet its water demand. In this work, a numerical and experimental study was carried out on the functional and productive parameters of the Nouadhibou desalination plant in Mauritania using MATLAB/Simulink (R2016a). The study considered two operating scenarios: with and without the energy recovery unit. The objective of this paper is to perform an analytical study of the operating procedures of the Nouadhibou RO desalination plant by varying several parameters, such as the pressure exchanger, and the feed water mixing ratio in the pressure exchanger unit, etc., in order to determine the system’s optimal operating point. This paper analyzes the system’s performance under different conditions, including recovery rate, feed water temperature, and PEX splitter ratio. In Case No. 1 (without a pressure recovery unit), and with a recovery rate of 20%, doubling the plant’s productivity from 400 to 800 m3/d requires 400 kW of power. In contrast, in Case No. 2 (with a pressure recovery unit), achieving the same productivity requires only 100 kW, with a 75% of energy saving. When the desalination plant operates at a productivity of 400 m3/d@40%, the SPC decreases from 6 kWh/m3 (Case No. 1) to 2.7 kWh/m3 (Case No. 2), resulting in a 55% specific power consumption saving. The results also indicate that power consumption increases with both feed water temperature and PEX splitter ratio, while variations in these parameters have a negligible effect on permeate salinity.

Liquids doi: 10.3390/liquids6010001

Authors: Domenico Paparo Anna Martinez Andrea Rubano

Over the past two decades, terahertz (THz) spectroscopy has demonstrated remarkable potential for the investigation of liquids, including studies of living organisms and biological components in their natural, aqueous environments. The main advantages of THz radiation lie in its ability to interact with collective and low-energy vibrational modes of macromolecules and microorganisms, while being non-harmful due to the low photon energy involved. These characteristics make THz spectroscopy particularly valuable for research in liquids compared to other well-established techniques such as Raman and infrared spectroscopy. In this study, we offer a concise overview and comparison of two case studies from our earlier publications, highlighting how Ultrabroadband THz spectroscopy and Intense THz Spectroscopy serve as complementary methods for advancing research in liquids. Ultrabroadband THz spectroscopy enables simultaneous probing of both intermolecular and intramolecular interactions in a single experiment. On the other hand, intense THz spectroscopy greatly simplifies the determination of the optical constants of liquid solutions, eliminating the need for additional assumptions or prior knowledge. Moreover, it offers high sensitivity, allowing the detection of dilute solutions and subtle spectral variations. Currently, these two techniques typically rely on different THz sources, as achieving both broadband coverage and high intensity in a single setup remains challenging. In fact, the experimental results reviewed here were obtained at two different times and within two distinct scientific collaborations. In particular, the intense source was accessed through a collaboration with Prof. Novelli at Ruhr University in Bochum. Integrating both capabilities into a single apparatus would be highly desirable. Therefore, we also present a theoretical investigation of a novel experimental approach that could enable combined ultrabroadband and intense THz spectroscopy, merging the strengths of both methods.

Liquids doi: 10.3390/liquids5040036

Authors: Samuel Tovey Christian Holm Jens Smiatek

In this article, we discuss the relationship and transition between self- and Fick diffusion coefficients in continuous implicit solvents across different particle densities. By applying the established expressions for self-diffusion and Fick diffusion coefficients in binary solutions, we analyze how the local environment influences diffusion through thermodynamic factors, which can be readily evaluated within the framework of Kirkwood–Buff (KB) theory. These thermodynamic factors, originally defined as derivatives of thermodynamic activity, vary with changes in local particle densities, particularly in the presence of aggregation effects. Consequently, the transition from self- to Fick diffusion coefficients can be understood as a reflection of variations in these thermodynamic factors. Langevin Dynamics simulations at low number densities show excellent agreement with the analytical expressions derived. Overall, our findings provide deeper insight into how local structural environments shape particle dynamics, clarifying the connection between KB theory and the transition from self- to Fick diffusion coefficients.

Liquids doi: 10.3390/liquids5040035

Authors: Swathy Akhil Owen J. Curnow Ruhamah Yunis

This work reports on novel acid–base conjugate pairs of monocationic allyldiamidinium and dicationic diamidinium salts, some of which are ionic liquids (ILs) at ambient temperatures. A series of allyldiamidinium salts of the general formula [C3H(NRMe)4]X (R = Me, Et, Pr, allyl, CH2CH2OMe; X = Cl, bistriflimide, dicyanamide) were prepared from C3Cl4 or C3Cl5H and the appropriate secondary amine, RNMeH. Alkylated ethylenediamines similarly yield bicyclic allyldiamidinium salts, whereas longer diamines (H2N(CH2)nNH2 (n = 3, 4, 5)) were isolated as their conjugate acids, the diamidinium dicationic salts [C3H2(HN(CH2)nNH)2]X2. The salts were characterized by NMR, ES-MS, DSC, TGA, and miscibility or solubility studies. Additionally, the ILs were characterized by their viscosities. The conductivities of the diamidinium ILs were also measured, and this allowed for an investigation of their Walden parameters. In contrast to expectations, since the ion pairing and clustering were expected to be significant, this showed them to be “superionic”. Previous reports of Walden plots of dicationic ILs were found to be erroneous, and a reanalysis of the literature data found that all reported dicationic and even tetracationic ILs can be classified as superionic. The salts [C3H(NMe2)4]Cl, [C3H(EtN(CH2)2NEt)2]OTf, and [C3H2(HN(CH2)nNH)2]Cl2 (n = 3, 4, 5) were also characterized by single-crystal X-ray diffraction.

Liquids doi: 10.3390/liquids5040034

Authors: Muhammad Faheem Lateef Ahmad Muhammad Hashim

(1) Background: Fixed-dose combination (FDC) improves patient convenience and therapeutic adherence by combining suitable drugs in a single dose form. This study examined the in vitro dissolution of an ibuprofen-loratadine FDC oral suspension to commercial reference formulations. (2) Methods: The FDC suspension (ibuprofen 200 mg/5 mL, loratadine 5 mg/5 mL) was tested against Fenbro 8 Plus and Lorid on USP Apparatus II at 50 rpm and 37 ± 0.5 °C. Dissolution testing was carried out in 900 mL of phosphate buffer (pH 7.2) for ibuprofen and 0.1 N HCl (pH 3.3) for loratadine. Quantification was performed using validated high-performance liquid chromatography linked with ultraviolet detector (HPLC-UV) procedures complying with the ICH Q2 (R2) guidelines. (3) Results: The linearity of the HPLC methods for ibuprofen and loratadine was (R2 > 0.99), accuracy (99.6–100.18%), and precision (%RSD < 2). For both loratadine and ibuprofen, the FDC suspension’s Q15, Q30, T50, T90, and DE% values nearly matched those of the commercial products. Over 95% of both drugs were released within 60 min. The dissolution equivalence between the FDC and the reference formulations was demonstrated by the calculated similarity (f2) and difference (f1) factors, which were f1 = 3 and f2 = 70 for ibuprofen, and f1 = 4 and f2 = 64 for loratadine. (4) Conclusions: The FDC suspension of ibuprofen and loratadine showed dissolving behavior comparable to commercial formulations, confirming its applicability for the practical and efficient treatment of allergy symptoms and inflammatory pain.

Liquids doi: 10.3390/liquids5040033

Authors: Abhishek Saraswat Rajendraprasad Bhattacharyay Paritosh Chaudhuri Sateesh Gedupudi

Specifically engineered heavy liquid metals are proposed as candidate coolants and tritium breeders for advanced nuclear applications. Understanding the wetting behaviours of these liquids on relevant substrate configurations is crucial to tackle the challenges associated with corrosion protection and flow diagnostics development. However, detailed investigations are scarce in the literature. In this experimental study, an apparatus is designed to measure contact angles of different liquid metals over a mirror-polished horizontal SS-304 substrate. This paper presents design aspects of the developed test facility, as well as initial results obtained using direct imaging and the Low-Bond Axisymmetric Drop Shape Analysis algorithm-based image processing technique. Methodological validation is achieved through surrogate liquids/liquid metals (H2O, Hg, Ga, GaInSn), prior to taking measurements from molten lead (Pb) droplets at 425 °C. Estimated contact angles obtained using the two techniques lie within ±10% deviation. Towards the end, the paper lays out plans for future upgrades for studies of wetting behaviours of molten Pb/Pb alloys on substrates with relevant surface properties, including bare P-91 and reduced-activation ferritic–martensitic steels, along with Al2O3/Er2O3-coated versions of these materials, to generate a database for Gen-IV fission reactors and fusion power plants.

Liquids doi: 10.3390/liquids5040032

Authors: Liliya M. Amirova Artur Khannanov Ayrat M. Dimiev Rustem R. Amirov

Graphene oxide (GO) has been successfully used as a filler to modify various properties of polymers and fiber-reinforced composites. The resulting properties depend on the filler content and on the distribution of GO in the polymer matrix. In this work, for the first time, we introduced GO into the highly viscous DEN-438 epoxy novolac resin and investigated rheological properties of the resulting compositions. In particular, we studied the functions of complex viscosity, storage and loss moduli, and mechanical loss tangent on temperature and GO content. The unusual behavior of the newly prepared formulations compared to typical GO/epoxy mixtures was discovered. At low GO content, introduction of GO led not to an increase, but to a decrease in the resin viscosity, with the minimum registered at 0.29 wt.% GO. After this threshold value, viscosity increased with GO content, which we explained by formation of the liquid crystalline structure. At higher GO concentrations, the formulations changed their state from solid-like at rest to liquid-like under load, with the properties being highly desired for film binders. The discovered properties of the GO/novolac epoxy resin formulations suggest their potential use as the new generation of film binders for Resin Film Infusion technology.

Liquids doi: 10.3390/liquids5040031

Authors: Freskida Goni Angela Chemelli Frank Uhlig

In contrast to the typically electrically conductive nanocarbon systems, boron nitride nanosheets (BNNSs) are particularly attractive for the fabrication of polymers that require high thermal conductivity while maintaining electrical insulation. However, their tendency to aggregate and the weak interfacial interaction with the polymer matrix limit their effectiveness in enhancing thermal conductivity. To address these challenges, BNNSs can be chemically modified to improve dispersion and compatibility within the matrix. Nonetheless, the inherent chemical inertness of boron nitride poses a significant obstacle to functionalization. In this work, we demonstrate the successful covalent modification of BNNSs using three different silane coupling agents: (3-aminopropyl)dimethylmethoxysilane, (3-aminopropyl)diethoxymethylsilane, and (3-aminopropyl)trimethoxysilane. FT-IR, SEM/EDX, and WAXS confirm the successful functionalization and reveal that the number of alkoxy groups in the silane strongly influences siloxane network formation and the extent of surface coverage on BNNSs.

Liquids doi: 10.3390/liquids5040030

Authors: Antonella De Ninno Luca Gamberale

This study presents a quantum electrodynamics (QED) framework that explains the anomalous behavior of liquid water. The theory posits that water consists of two coexisting phases: a coherent phase, in which molecules form phase-locked coherence domains (CDs), and an incoherent phase that behaves like a dense van der Waals fluid. By solving polynomial-type equations, we derive key thermodynamic properties, including the minima in the isobaric heat capacity per particle (IHCP) and the isothermal compressibility, as well as the divergent behavior observed near 228 K. The theory also accounts for water’s high static dielectric constant. These results emerge from first-principles QED, integrating quantum coherence with macroscopic thermodynamics. The framework offers a unified explanation for water’s anomalies and has implications for biological systems, materials science, and fundamental physics. Future work will extend the theory to include phase transitions, solute interactions, and the freezing process.

Liquids doi: 10.3390/liquids5040029

Authors: Silvia Varagnolo

Droplets sliding down a partially wetted surface are a ubiquitous phenomenon in nature and everyday life. Despite its apparent simplicity, it hinders complex intricacies for theoretical and numerical descriptions matching the experimental observations, even for the simplest case of a drop sliding down a homogeneous surface. A key aspect to be considered is the distribution of contact angles along the droplet perimeter, which can be challenging to include in the theoretical/numerical analysis. The scenario can become more complex when considering geometrically or chemically patterned surfaces or complex fluids. Indeed, these aspects can provide strategies to passively control the droplet motion in terms of velocity or direction. This review gathers the state of the art of experimental, numerical, and theoretical research about droplets made of Newtonian and non-Newtonian fluids sliding down homogeneous, chemically heterogeneous, or geometrically patterned surfaces.

Liquids doi: 10.3390/liquids5040028

Authors: Kamilla B. Shishkhanova Vyacheslav S. Molchanov Olga E. Philippova

The rheological properties of aqueous solutions of wormlike micelles (WLMs) of cationic surfactant erucyl bis(hydroxyethyl)methylammonium chloride (EHAC) in the presence of hydrotropic salt sodium salicylate (NaSal) and inorganic salt sodium chloride (NaCl) have been studied. The conditions for maximum zero-shear viscosity at fixed surfactant concentration were investigated. It has been shown that charged WLMs in the presence of NaSal have higher viscosities than well-screened micelles in the presence of NaCl. This is because the adsorption of hydrophobic salicylate ions onto the micelles increases their length more significantly than the presence of a large amount of sodium ions in the solution. It was discovered that the effect of temperature on the rheological properties depends on both the type of salt used and the salt/surfactant molar ratio. An unusual increase in zero-shear viscosity and elastic modulus was observed at a NaSal concentration that corresponds to the maximum zero-shear viscosity when the WLMs are linear, charged, and “unbreakable”. These results expand the possibilities of using hydrotropic salts to create stable, highly viscous systems in various fields, and opening up new horizons for applications in oil production, cosmetics, and household chemicals.

Liquids doi: 10.3390/liquids5040027

Authors: Laurence Noirez Eni Kume Patrick Baroni

Liquids like water are not expected to produce a thermal change under shear strain or flow (away from extreme conditions). In this study, we reveal experimental conditions for which the conventional athermal hydrodynamic assumption is no longer valid. We highlight the establishment of non-equilibrium hot and cold thermal states occurring when a mesoscopic confined liquid is set in motion. Two stress situations are considered: low-frequency shear stress at large strain amplitude and microfluidic transport (pressure gradient). Two liquids are tested: water and glycerol at room temperature. In confined conditions (submillimeter scale), these liquids exhibit stress-induced thermal waves. We interpret the emergence of non-equilibrium temperatures as a consequence of the solicitation of the mesoscopic liquid elasticity. In analogy with elastic deformation, the mesoscopic volume decreases or increases slightly, which leads to a change in temperature (thermo-mechanical energy conversion). The energy acquired or released is converted to heat or cold, respectively. To account for these non-equilibrium temperatures, the mesoscopic flow is no longer considered as a complete dissipative process but as a way of propagating shear and thus compressive waves. This conclusion is consistent with recent theoretical developments showing that liquids propagate shear elastic waves at small scales.

Liquids doi: 10.3390/liquids5040026

Authors: Kotaro Kawano Yoshihiro Oka

This study investigates the formation of hydroxyl radicals (OH radicals) in cavitation bubble plasma-treated water (CBPTW) using a chemical probe method. CBPTW samples were prepared with different electrode materials (W, Fe, Cu, and Ag), and the chemical scavenger was added two minutes after the completion of cavitation and plasma treatments. The concentrations of metal ions and hydrogen peroxide (H2O2) generated in the CBPTW were also measured over time. This study reveals a novel mechanism whereby metal nanoparticles and ions released from electrodes catalyze the continuous generation of hydroxyl radicals in CBPTW, which has not been fully addressed in previous studies. The results suggest a continuous generation of OH radicals in CBPTW prepared with W, Fe, and Cu electrodes, with the amount of OH radicals produced in the order Cu > Fe > W. The study reveals a correlation between OH radical production and electrode wear, suggesting that the continuous generation of OH radicals in CBPTW results from the catalytic decomposition of H2O2 by metal nanoparticles or ions released from the electrodes. It should be noted that cavitation bubble plasma (CBP) is fundamentally different from sonochemistry. While sonochemistry utilizes ultrasound-induced cavitation to generate radicals, CBP relies on plasma discharge generated inside cavitation bubbles. No ultrasound was applied in this study; therefore, all observed radical formation is attributable exclusively to plasma processes rather than sonochemical effects. However, the precise mechanism of continuous OH radical formation in CBPTW remains unclear and requires further investigation. These findings provide new insights into the role of electrode materials in continuous OH radical generation in cavitation bubble plasma treated water, offering potential applications in water purification and sterilization technologies.

Liquids doi: 10.3390/liquids5040025

Authors: William E. Acree Costas Panayiotou

A new method is presented for the estimation of contributions to solvation free energy from dispersion, polar, and hydrogen-bonding (HB) intermolecular interactions. COSMO-type quantum chemical solvation calculations are used for the development of four new molecular descriptors of solutes for their electrostatic interactions. The new model needs one to three solvent-specific parameters for the prediction of solvation free energies. The widely used Abraham’s LSER model is used for providing the reference solvation free energy data for the determination of the solvent-specific parameters. Extensive calculations in 80 solvent systems have verified the good performance of the model. The very same molecular descriptors are used for the calculation of solvation enthalpies. The advantages of the present model over Abraham’s LSER model are discussed along with the complementary character of the two models. Enthalpy and free-energy solvation information for pure solvents is translated into partial solvation parameters (PSP) analogous to the widely used Hansen solubility parameters and enlarge significantly their range of applications. The potential and the perspectives of the new approach for further molecular thermodynamic developments are discussed.

Liquids doi: 10.3390/liquids5030024

Authors: Timur A. Mukhametzyanov Mikhail I. Yagofarov Christoph Schick

Experimental data on the folding and unfolding of small globular proteins are often well described assuming a two-state equilibrium process. It means that after careful analysis by a combination of experimental techniques, only folded and unfolded states of the protein are found to be populated under various external conditions with no detectable intermediates. One of the consequences of the two-state behavior is that the equilibrium ratio of the folded to unfolded protein states follows a simple thermodynamic relation, and the enthalpy difference between states can be obtained from the temperature dependence of the equilibrium constant. In this paper, we theoretically investigate the criteria for the two-state equilibrium behavior and discuss the thermodynamic constraint on the properties of the “hidden” folding intermediates. The literature data on the folding mechanism of lysozyme in water and glycerol, which follows a two-state equilibrium behavior but includes kinetic intermediates, is analysed in light of this constraint.

Liquids doi: 10.3390/liquids5030023

Authors: Jia-Xin Tan Edgar Acosta

Clove oil is an essential oil used in food and pharmaceutical applications, with a market value of 300+ million dollars per year. Microemulsions have been used as effective clove oil delivery vehicles and could also be used to develop new extraction processes from clove buds. Eugenol, the main component of clove oil, is a polar oil that behaves as a surfactant and as an oil. This bifunctional behavior makes formulating clove oil microemulsions a challenging task. Here, we used a version of the Hydrophilic–Lipophilic Difference (HLD) + Net-Average Curvature (NAC) model that incorporates the bifunctional polar oil model to predict and fit the phase behavior of lecithin (surfactant) + polyglycerol-10 caprylate (hydrophilic linker) microemulsions using mixtures of heptane and clove oil as the oil phase. Using HLD-NAC parameters from the literature, the predicted HLD-NAC curves reproduced the expected phase transitions and the trends in Eugenol segregation toward the surfactant layer. Using these literature parameters as an initial guess to fit the experimental phase volumes produced accurate calculated phase volumes, and predicted interfacial tensions. This work demonstrates the application of heuristics and databases of HLD-NAC parameters in predicting the complex phase behavior of surfactant–oil–water (SOW) systems.

Liquids doi: 10.3390/liquids5030022

Authors: Thomas J. Malinski Ying-Hua Fu Sopida Thavornpradit Yu Ching Wong Yunnuen Avila-Martinez William Dow David E. Bergbreiter

This paper shows that low concentrations of either a low-molecular-weight or a recyclable polymeric cosolvent can be used to design recyclable, tunable alkane polymeric solvent systems. We have shown that dyes experience a microheterogeneous environment that is ca. 40–50% like that of a polar solvent with as little as 0.1 M added cosolvent. Dyes like Nile red or a polyisobutylene (PIB)-bound dansyl fluorophore both detected microheterogeneity in macrohomogeneous mixtures of heptane or a poly(α-olefin) (PAO) with 0.1–2.0 M added polar solvents. H-Bonding cosolvents have greater effects than cosolvents that only interact with dyes by dipole–dipole interactions. Microheterogeneity was also seen when a PIB-bound version of a low-molecular-weight solvent is used as the added polar cosolvent. These microheterogeneous environments can advantageously be used in synthetic and catalytic reactions. This was demonstrated in transesterification and SN2 chemistry. Reactions in PAO solutions polarized by 2 M added THF or by 0.5 M of a PIB-bound HMPA analog both had enhanced reactivity versus reactions in a PAO solution without added cosolvent. In the latter case, the catalyst, the PAO solvent, and the PIB-bound cosolvent were all fully recyclable.

Liquids doi: 10.3390/liquids5030021

Authors: Masaki Ota Naishu Yang Hiroyuki Komatsu Hiroshi Inomata Richard Lee Smith

Peng–Robinson equation of state (PR EoS) has good prediction accuracy for phase diagrams of pure substances or mixtures, but liquid density, especially for high polar substances, is known to be ~20% lower value compared with experimental data at standard atmospheric temperature and pressure (SATP) conditions. To overcome this issue, translation via entropy-based solubility parameter (eSP) Peng–Robinson EoS (eSPT-PR EoS) is proposed in this work. The technique uses eSP for the liquid phase at SATP conditions and correlates the ideal value and a constant C for each substance as a correction. As a result, the C value can be linearly correlated with critical compressibility factor (ZC). Finally, the liquid density was improved and gave an average relative deviation (ARD) value of 4.2% for the generally used 27 chemicals selected at SATP condition. Furthermore, critical density was also improved and gave ARD values of 3.9% compared with the original PR EoS of 21.8%. Thus, a universal calculation method based on PR EoS was developed for improving liquid density representation with the eSPT-PR EoS.

Liquids doi: 10.3390/liquids5030020

Authors: Riko Siewert Vladimir V. Emelyanov Artemiy A. Samarov Matthis Richter Karsten Müller Sergey P. Verevkin

The utilisation of empirical correlations for the estimation of thermodynamic functions is a valuable approach for reducing experimental effort and for validating existing data. Established correlations and group contribution methods provide reliable heat capacity estimates for simple organic compounds. The present work assesses the extent of deviations introduced by employing conventional heat capacity correlations for diols. For this purpose, heat capacity differences between the solid, liquid and gas phases are evaluated based on experimentally determined vapour pressures, enthalpies of vaporisation, heat capacities in the solid and liquid phases, and quantum chemical calculations. It is demonstrated that the structural characteristics of diols result in a significant overestimation of heat capacities when conventional empirical methods are applied. Deviations in the range of 30–50 J·K−1·mol−1 were observed when compared to consistent experimental data. As part of the evaluation, new group contribution parameters were developed for calculating heat capacities in the solid and liquid phases. Based on these improved data, inconsistencies in literature values for enthalpies of vaporisation (on the order of 10–15 kJ mol−1) could be resolved. Furthermore, a new correlation was derived that allows for the reliable prediction of enthalpies of vaporisation for α,ω-alkanediols from pentanediol to decanediol. The resulting data provide significant advantages for the design of technical processes involving diols as renewable sources and for the accurate modelling of their phase behaviour.

Liquids doi: 10.3390/liquids5030019

Authors: Elena Yu. Tyunina Vladimir P. Barannikov Igor N. Mezhevoi

This article presents a mini-review of the available data on the thermodynamics of the complexation of amino acids and peptides with some nucleic bases in a buffer medium. Data on changes in thermodynamic parameters (binding constants, Gibbs energy, enthalpy, entropy) during the complexation of nucleic bases with amino acids and peptides as a function of physicochemical properties are given at T = 298.15 K. The effects of complexation on the volumetric properties of nucleic bases, including apparent molar volumes, standard molar volumes, and limiting molar expansibility, over a temperature range of 288.15 to 313.15 K are considered in detail. Differences in the behavior of amino acids and peptides caused by different modes of coordination with nucleic bases are noted. These manifest in the stoichiometry of the formed complexes, the relationship with the acid dissociation constants of carboxyl and amino groups, enthalpy–entropy compensation in the complexation process, the temperature dependence of the transfer volumes, and the effect of hydrophobicity on volumetric characteristics.

Liquids doi: 10.3390/liquids5030018

Authors: Motoyoshi Kobayashi Takuya Sugimoto Ryoichi Ishibashi Shunsuke Sato

Concentrated suspensions exhibit intriguing behaviors under external forces, including vibration and shear. While previous studies have focused primarily on cornstarch suspensions, this paper reports a novel observation that colloidal silica suspensions also exhibit dancing, bouncing, solidification, and melting under vertical vibration. Unlike cornstarch, silica particles offer high stability, controlled size distribution, and tunable surface properties, making them an ideal system for investigating these phenomena. The 70 wt.% aqueous suspensions of spherical silica particles with a diameter of 0.55 μm were subjected to controlled vertical vibration (60–100 Hz, 100–500 m/s2). High-speed video analysis revealed dynamic transitions, including melting, fingering, squirming, fragmentation, and jumping. The solidified suspension retained its shape after vibration ceased but melted upon weak vibration. This study demonstrates that such dynamic state transitions are not exclusive to starch-based suspensions but can also occur in well-defined colloidal suspensions. Our findings provide a new platform for investigating shear-thickening, jamming, and vibrational solidification in suspensions with controllable parameters. Further work is required to elucidate the underlying mechanisms.

Liquids doi: 10.3390/liquids5020017

Authors: Boris N. Solomonov Mansur B. Khisamiev Mikhail I. Yagofarov

Solvent association and solute–solvent complexation are known to influence the relationship between the thermodynamic functions of solvation, known as the compensation relationship. Here, we accomplish a series of works devoted to the analysis of Gibbs energy–enthalpy relations in the systems with different capabilities of hydrogen bonding. The data on proton acceptors solvated in alcohols were collected, and the quantitative regularities in their solvation thermodynamics were established, depending on the binding degree in solution. The equations connecting the Gibbs energies and enthalpies of solvation in the systems with competition for hydrogen bonding sites were derived from the previously found correlation between the thermodynamic functions of complexation and solvation in simpler solutions. These equations enabled the successful prediction of the solvation enthalpies of 56 proton acceptors in alcohols (RMSD = 1.8 kJ·mol−1). Together with the results of the previous works, the general linear equation connecting the Gibbs energies and enthalpies of solvation in various solute–solvent systems has been obtained. This finding led us to reshaping common understanding of the compensation relationship phenomenon.

Liquids doi: 10.3390/liquids5020016

Authors: Dmitriy M. Makarov Yuliya A. Fadeeva Arkadiy M. Kolker

Ionic liquids (ILs) and deep eutectic solvents (DESs) have been extensively studied as absorbents for CO2 capture, demonstrating high efficiency in this role. To optimize the search for compounds with superior absorption properties, theoretical approaches, including machine learning methods, are highly relevant. In this study, machine learning models were developed and applied to predict Henry’s law constants for CO2 in ILs and DESs, aiming to identify systems with the best absorption performance. The accuracy of the models was assessed in interpolation tasks within the training set and extrapolation beyond its domain. The optimal predictive models were built using the CatBoost algorithm, leveraging CDK molecular descriptors for ILs and RDKit descriptors for DESs. To define the applicability domain of the models, the SHAP-based leverage method was employed, providing a quantitative characterization of the descriptor space where predictions remain reliable. The developed models have been integrated into the web platform chem-predictor, where they can be utilized for predicting absorption properties.

Liquids doi: 10.3390/liquids5020015

Authors: Raheem Akinosho Amr Henni Farhan Shaikh

Carbon dioxide, the primary greenhouse gas responsible for global warming, represents today a critical environmental challenge for humans. Mitigating CO2 emissions and other greenhouse gases is a pressing global concern. The primary goal of this study is to investigate the potential of particular ionic liquids (ILs) in capturing CO2 for the sweetening of natural and other gases. The solubility of CO2 was measured in three distinct ILs, which shared a common anion (triflate, TfO) but differed in their cations. The selected ionic liquids were {1-butyl-3-methylimidazolium triflate [BMIM][TfO], 1-butyl-1-methylpyrrolidinium triflate [BMP][TfO], and 1-butyl-4-methylpyridium triflate [MBPY][TfO]}. The solvents were screened based on results from a molecular computational study that predicted low CO2 Henry’s Law constants. Solubility measurements were conducted at 303.15 K, 323.15 K, and 343.15 K and pressures up to 1.5 MPa using a gravimetric microbalance (IGA-003). The CO2 experimental results were modeled using the Peng–Robinson Equation of state with three mixing rules: van der Waals one (vdWI), van der Waals two (vdWII), and the non-random two-liquid (NRTL) Wong–Sandler (WS) mixing rule. For the three ILs, the NRTL-WS mixing rule regressed the data with the lowest average deviation percentage of 1.24%. The three solvents had similar alkyl chains but slightly different polarities. [MBPY][TfO], with the largest size, exhibited the highest CO2 solubility at all three temperatures. Calculation of its relative polarity descriptor (N) shows it was the least polar of the three ILs. Conversely, [BMP][TfO] showed the highest Henry’s Law constant (lowest solubility) across the studied temperature range. Comparing the results to published data, the study concludes that triflate-based ionic liquids with three fluorine atoms had lower capacity for CO2 compared to bis(trifluoromethylsulfonyl) imide (Tf2N)-based ionic liquids with six fluorine atoms. Additionally, the study provided data on the enthalpy and entropy of absorption. A final comparison shows that the ILs had a lower CO2 capacity than Selexol, a solvent widely used in commercial carbon capture operations. Compared to other ILs, the results confirm that the type of anion had a more significant impact on solubility than the cation.

Liquids doi: 10.3390/liquids5020014

Authors: Vijayakriti Mishra Pramilla D. Sawant Arup Kumar Pathak

Nuclear technology, while offering significant benefits across various sectors, poses potential health risks due to uranium (U) contamination, particularly through its internalization and subsequent interactions with biological systems. This study investigates the binding of uranyl (UO22+) and zinc (Zn2+) ions to Human Serum Albumin (HSA) that is already bound to fatty acids (FAs), using all-atom molecular dynamics (MD) simulations. The analysis focuses on the structural and dynamic alterations in the protein’s multi-metal binding site (MBS-A) caused by FA binding. Results reveal that FA binding induces a conformational change in HSA, disrupting the pre-formed MBS-A binding site, while still allowing uranyl and zinc ions to interact with residue D249 through strong Coulombic interactions. Secondary binding sites, associated with calcium and zinc binding, remain largely unaffected by FAs, providing alternative coordination for metal ions. This study also explores the binding and unbinding pathways of the metal ions using well-tempered meta-dynamics (WT-MtD), showing that while FA binding disrupts the primary metal binding site, it does not completely inhibit the binding of both uranyl and zinc ions. These findings offer new insights into the nature of uranium’s interactions with blood serum proteins and the role of fatty acids in modulating these interactions, which may help in designing future strategies for managing uranium contamination in biological systems.

Liquids doi: 10.3390/liquids5020013

Authors: Jia Lin Lee Gun Hean Chong Yuya Hiraga Yoshiyuki Sato Masaki Ota Richard Lee Smith

Density and viscosity are fundamental properties necessary for processing of red palm oil (RPO). The main fatty acid constituents of RPO were determined to be palmitic acid (C16:0), oleic acid (C18:1), and linoleic acid (C18:2). Rheology measurements confirmed that RPO behaved as a Newtonian fluid. Viscosities and atmospheric densities of RPO were measured at 0.1 MPa and (293 K to 413) K and correlated with the Rodenbush model (0.05% deviation). Dynamic viscosities of RPO were correlated with the Vogel–Fulcher–Tammann model (0.06% deviation) and Doolittle free volume model (0.04% deviation). High-pressure densities of RPO were measured at (10 to 150) MPa and (312 to 352) K. The Tait equation could correlate the high-pressure densities of RPO to within 0.021% deviation and was used to estimate the thermal expansion as 5.1 × 10−4 K−1 (at 312 K, 150 MPa) to 4.8 × 10−4 K−1 (at 352 K, 150 MPa) and isothermal compressibility as 7.3 × 10−4 MPa−1 (at 352 K, 0.1 MPa) to 3.5 × 10−4 MPa−1 (at 352 K, 150 MPa). Parameters for the perturbed-chain statistical associating fluid theory equation of state were determined and gave an average of 0.143% deviation in density. The data and equations developed should be useful in high-pressure food processing as well as in applications considering vegetable oils as heat transfer fluids or as lubricants.

Liquids doi: 10.3390/liquids5020012

Authors: William E. Acree Costas Panayiotou

This work is a continuation of our recent work on the prediction of hydrogen-bonding (HB) interaction enthalpies. In the present work, a simple method is proposed for the prediction of the HB interaction free energies. Quantum chemical (QC) calculations are combined with the Linear Solvation Energy Relationship (LSER) approach for the determination of novel QC-LSER molecular descriptors and the development of the method. Each hydrogen-bonded molecule is characterized by an acidity or proton donor capacity, αG, and/or a basicity or proton acceptor capacity, βG. These descriptors suffice for the prediction of HB interaction free energy when the interacting molecules possess one acidic and or one basic site. In this case of two interacting molecules, 1 and 2, their overall HB interaction free energy is cαG1βG2+βG1αG2, where c is a universal constant equal to (ln10)RT = 5.71 kJ/mol at 25 °C. This holds true over the full composition range, that is, regardless of which molecule is solute and which solvent. In the case of complex multi-sited molecules possessing more than one distant acidic site and/or more than one type of distant basic sites, two sets of αG and βG descriptors are needed, one for the molecule as solute in any solvent and one for the same molecule as the solvent of any solute. Descriptors αG and βG are reported for a number of common hydrogen-bonded molecules but they may be obtained for any other hydrogen-bonded molecule of interest from its molecular surface charge distribution already available or easily obtained via relatively cheap DFT/basis-set QC calculations. The new predictive scheme is validated against corresponding estimations of the widely used Abraham’s LSER model. The developments in the present work and the previous one are useful for solvation studies in chemical and biochemical systems and, particularly, for equation-of-state developments in molecular thermodynamics. The strengths and limitations of the new predictive method are critically discussed.

Liquids doi: 10.3390/liquids5020011

Authors: Amr Seifelnasr Farhad Zare Xiuhua Si Jinxiang Xi

This study investigated the role of synthetic mucus coatings in enhancing the physiological relevance of in vitro nasal spray deposition assessments using 3D-printed nasal cavity models. Synthetic mucus solutions, representing normal (0.25% w/v xanthan gum) and diseased (1% w/v xanthan gum) nasal conditions, were developed to mimic the viscoelastic properties of human nasal mucus. Their physical properties, including viscosity, surface tension, contact angle, and adhesivity on dry and synthetic mucus-coated stereolithography (SLA) surfaces, were systematically characterized. Comparative experiments evaluated the behavior of saline drops and liquid films on dry versus synthetic mucus-coated SLA surfaces at inclinations of 30°, 45°, and 60°. Observational deposition experiments using anatomically accurate nasal models were conducted under a 45° backward-tilted head position with gentle sniff airflow across uncoated, 0.25% w/v mucus-coated, and 1% w/v mucus-coated surfaces. Synthetic mucus coatings significantly influenced saline spray deposition patterns. On uncoated surfaces, deposition consisted of scattered droplets and limited film formation, mainly in the anterior and turbinate regions. In contrast, synthetic mucus coatings facilitated broader and more uniform liquid distribution due to diffusion and lubrication effects. These findings highlight the value of synthetic mucus coatings for better simulating nasal environments, offering insights to optimize nasal spray formulations and delivery devices.

Liquids doi: 10.3390/liquids5020010

Authors: Ioannis Lelidis Giovanni Barbero

The well-known Poisson–Nernst–Planck model is a classical approach usedto describe ion transport in liquids. Extended versions of this model account for thegeneration–recombination of ions at equilibrium. In this paper, we investigate the influenceof the generation–recombination term on dielectric relaxation in an electrolytic cell shapedlike a slab, bounded by two parallel blocking electrodes. We show that in the adiabaticlimit—which holds when the reaction time is much longer than the dielectric relaxationtime—the electric current in the external circuit does not follow a simple relaxation mechanism.Instead, it is characterized by two distinct relaxation times: a short relaxationtime associated with dielectric relaxation and a longer relaxation time related to the iondissociation–association process. Conversely, this information could be used to assess thepresence and/or significance of the generation–recombination effect in an electrolytic cell.

Liquids doi: 10.3390/liquids5020009

Authors: Eleonora Guarini Ubaldo Bafile Daniele Colognesi Alessandro Cunsolo Alessio De Francesco Ferdinando Formisano

This work provides a comprehensive picture of the advances that the exponential expansion theory (EET) of autocorrelation functions relevant to liquids dynamics made possible in the last decade up to very recent times. The role of both longitudinal and transverse collective excitations in liquids is investigated by studying the main autocorrelation functions typically obtained either experimentally (when possible) or through molecular dynamics simulations. Examples for some classes of liquids are provided, especially intended for the understanding of dispersion curves, i.e., the collective mode frequencies as a function of the wavevector Q, which is inversely proportional to the length scale at which microscopic processes are probed. The main result of this work is the ubiquitous observation that the EET method works extremely well for all considered autocorrelation functions or spectra, either experimental or simulated. This paper provides also, in its final part, important hints for future research, based on an integration of the EET lineshape description within Bayesian inference analysis.

Liquids doi: 10.3390/liquids5010008

Authors: Márta Gődény Christian Schröder

Ionic liquids exhibit distinctive solvation and reactive properties, making them highly relevant for applications in energy storage, catalysis, and CO2 capture. However, their complex molecular interactions, including proton transfer and physisorption/chemisorption, necessitate advanced computational efforts to model them at the atomic scale. This review examines key molecular dynamics approaches for simulating ionic liquid reactivity, including quantum-mechanical methods, conventional reactive force fields such as ReaxFF, and fractional force fields employed in PROTEX. The strengths and limitations of each method are assessed within the context of ionic liquid simulations. While quantum-mechanical simulations provide detailed electronic insights, their high computational cost restricts system size and simulation timescales. Reactive force fields enable bond breaking and formation in larger systems but require extensive parameterization. These approaches are well suited for investigating reaction pathways influenced by the local environment, which can also be partially addressed using multiscale simulations. Fractional force fields offer an efficient alternative for simulating significantly larger reactive systems over extended timescales. Instead of resolving individual reaction mechanisms in full detail, they incorporate reaction probabilities to model complex coupled reactions. This approach enables the study of macroscopic properties, such as conductivity and viscosity, as well as proton transport mechanisms like the Grotthuß process—phenomena that remain inaccessible to other computational methods.

Liquids doi: 10.3390/liquids5010007

Authors: Pavel V. Maslennikov Alex V. Zakharov

Based on data from broadband dielectric spectroscopy (BDS) and a molecular model based on the Landau–de Gennes concept, the effect of confinement on the structural, dielectric, and dynamic properties of 4-n-pentyl-4′-cyanobiphenyl (5CB) in the nematic phase is studied. The dielectric permittivity and relaxation times were previously obtained by the BDS technique in a wide frequency range (1MHz≤f≤1GHz) in the nematic phase composed of 5CB molecules confined to Anopore membranes with pore sizes of 0.2 μm. The distance-dependent values of the order parameter P2(r), the relaxation time τ(r)≡τ001(r), the rotational diffusion coefficient D⊥(r), and both rotational viscosity coefficients γi(r) (i=1,2) as functions of the distance r away from the bounding surface are calculated by a combination of existing statistical-mechanical approaches and data obtained by the BDS technique. Reasonable agreement between the calculated and experimental values of γi(i=1,2) for bulk 5CB is obtained.

Liquids doi: 10.3390/liquids5010006

Authors: Franco Cataldo

Dimer and trimer acids are interesting viscous liquids produced from fatty acids derived from renewable sources. The chemical structures of dimer and trimer acids are known and quite complex and are presented here, discussed and further elucidated through electronic absorption spectroscopy, FT-IR and Raman spectroscopy. Dimer and trimer acids have a number of applications in their original form or in the form of derivatives. In the present study, a series of esters of dimer and trimer acids with alcohols from renewable sources were synthesized for use as plasticizers for rubber and plastics. The polarity of the dimer and trimer acids as well as their esters with alcohols from renewable sources (dimerates and trimerates) were systematically studied using a Nile red solvatochromic probe. The resulting E(NR) values were compared with the E(NR) values of the most common types of rubber and plastics. Compatibility and other physical properties expected from the E(NR) scale were studied and successfully confirmed in tire tread rubber compound formulations and in nitrile rubber and PVC matrices, confirming once again the sensitivity and the validity of the Nile red solvatochromic polarity scale for the development of new plasticizers. The validity of the liquids polarity measured with the Nile Red dye is supported by the correlation found between the E(NR) scale and the dielectric constants (ε) of carboxylic acids (including dimer and trimer acids, hydrogenated dimer acids and isostearic acid) and alcohols. A correlation was even found linking the E(NR) values the with the ε values of thin solid films of rubbers and plastics. In the case of the esters the correlation of their E(NR) values was found with the length of the aliphatic chains of the alcohols used in the esterification.

Liquids doi: 10.3390/liquids5010005

Authors: Homa Rezaei Abolghasem Jouyban

Utilizing the shake-flask technique under atmospheric pressure (101 kPa) within the temperature range of 293.2 to 313.2 K, the experimental solubility and density values of deferiprone were determined in binary mixtures of polyethylene glycol 400 and 1-propanol. The mole fraction solubility of deferiprone exhibited an augmentation with elevated temperature and increased polyethylene glycol 400 mass ratio in polyethylene glycol 400 + 1-propanol compositions. A subsequent regression analysis of the solubility data was conducted employing the van’t Hoff, λh, Yalkowsky, modified Wilson, Jouyban–Acree and Jouyban–Acree–van’t Hoff models upon the comprehensive evaluation of the entire dataset; the van’t Hoff equation demonstrated the most favorable regression. Furthermore, the findings of this study hold significance for advancing the understanding of the basic thermodynamic data pertinent to the crystallization and industrial separation processes of deferiprone.

Liquids doi: 10.3390/liquids5010004

Authors: Noah Kalicki Kyle Ruhland Fangzheng Chen Dante G. Quirinale Zengquan Wang Douglas L. Abernathy K. F. Kelton Nicholas A. Mauro

When examined at the nanometer length scale, metallic liquids exhibit extensive ordering. Bonding enthalpies are balanced against entropic tendencies resulting in a rich complicated behavior that leads to clustering that depends on temperature but evolves on picosecond time scales. The structural organization of metallic liquids affects their thermophysical properties, such as viscosity and density, thus influencing the ability of a metallic liquid to form useful technological phases, such as metallic glasses. The time-dependent pair correlation function (the Van Hove function) was determined for metallic-glass forming Cu49Zr45Al6 at 1060 °C from time-of-flight inelastic neutron scattering measurements made using the Neutron Electrostatic Levitation facility at the Spallation Neutron Source. The time for changes in local atomic connectivity, which is the timescale of atomic ordering, was determined by examining the decay of the nearest neighbor peak. The results of rigorous statistical analyses were used to distinguish between competing models of ordering, suggesting that a stretched exponential model of coordination number change is valid for this system.

Liquids doi: 10.3390/liquids5010003

Authors: Javier Catalán

The behavior of the energy of the peaks of the first UV/Vis absorption band and the presence or absence of isosbestic points in this band with changing temperature for all-trans-DPH and all-trans-β-carotene, dissolved in 1-chlorobutane or hydrocarbon solvents, allows us to show conclusively whether these compounds transform their all-trans-molecular structures into a structure of their conformers. From these analyses, it is concluded that in these solvents, all-trans-DPH is not thermally transformed to its conformer s-cis-DPH in a temperature range from 133 K to 350 K. On the other hand, all-trans-β-carotene, as a model-compound, does show changes in its molecular structure in these solvents with changing temperature. We also show that a portion of all-trans-DPH dissolved in cis-Decalin, at room temperature, slowly transforms into its conformer s-cis-DPH.

Liquids doi: 10.3390/liquids5010002

Authors: Heinz Langhals

The relation between the pressure and molar concentration (in mol/L) of real gases in a low- to medium-pressure range is precisely described by a logarithmic two-parameter equation. Increasing the concentration caused an increase in pressure and also the weakening of the effect due to intermolecular interactions, forming the basis for an equation with an adjusted parameter. Exceeding a critical concentration by a further increase caused a switch to another set of parameters in the same equation. At high pressure, a second switch to an exponential term was observed. This equation of state, defined segment by segment, was attributed to three different structures of the medium. The validity of the equations found was verified with experimental data reported in the literature for helium, neon, argon, krypton, and xenon and is discussed in more detail for argon. The temperature dependence of the parameters of the equations is reported and the formation of a liquid phase is discussed.

Liquids doi: 10.3390/liquids5010001

Authors: Toshio Yamaguchi Kousei Li Yuki Matsumoto Nami Fukuyama Koji Yoshida

Raman scattering measurements were performed on 1 mol dm−3 aqueous calcium nitrate (Ca(NO3)2) and sodium nitrate (NaNO3) solutions containing 4% (w/w) D2O in a temperature range from 25 to 350 °C and pressure of 40 MPa. As the temperature increased, the N–O symmetric stretching vibrational band (ν1) of NO3− at 1045–1047 cm−1 shifted to a lower wavenumber by 5~6 cm−1. The band analysis using one Lorentzian component showed that the full-width at half maximum (FWHM) did not change significantly below 175 °C but increased rapidly above 200 °C for both solutions. The peak area for an aqueous Ca(NO3)2 solution showed a breakpoint between 225 and 250 °C, suggesting a change in the coordination shell of NO3− at 175~250 °C. The OD symmetric stretching vibrational band of HDO water was deconvoluted into two Gaussian components at 2530 and 2645 cm−1; the former component has high temperature dependence that is ascribed to the hydrogen bonds, whereas the latter one shows less temperature dependence due to the non-hydrogen bonds of water. X-ray scattering measurements were performed on a 1 mol dm−3 aqueous Ca(NO3)2 solution at 25 to 210 °C and 40 MPa. Empirical potential structure refinement (EPSR) modeling was used to analyze the X-ray scattering data. Ca2+ forms a rigid coordination shell consisting of about seven water molecules at 2.48 Å and one NO3− at 25~170 °C, with further water molecules substituted by NO3− at 210 °C. NO3− is surrounded by 13~14 water molecules at an N–Ow distance of 3.6~3.7 Å. The tetrahedral network structure of solvent water pertains from 25 to 170 °C but is transformed to a dense packing arrangement at 210 °C.

Liquids doi: 10.3390/liquids4040043

Authors: Alexandros G. Vanakaras Edward T. Samulski Demetri J. Photinos

Recently, two new polymorphs have been added to the nematic class: the polar-twisted nematic (NPT) in 2016 and the ferroelectric nematic (NF) in 2020. Comprised of achiral molecules, both exhibit local polar ordering and adopt modulated structures, right- and left-handed helical organizations—form chirality—albeit on vastly different dimensional scales; modulations have a ~10 nanometer pitch in the NPT and ~500 nm in the NF. Here, we focus on the structure and symmetries of the NPT phase and the ensuing physical properties. Based on an array of order parameters that fully describe the molecular ordering and the nano-modulations thereof, we present a consistent formulation of the dielectric, optical, surface anchoring, and elasticity properties of the NPT materials. We show that these properties are distinctly different from those associated with an elastically modulated, locally uniaxial, nematic.

Liquids doi: 10.3390/liquids4040042

Authors: Lintao Li Yuming Liu Yanzun Li Ziyi Wang Kai Guo Qianli Ma Yingying Cui Kaibang Liu Cong Chen

With the continuous growth of global energy demand, greenhouse gas emissions are also rising, leading to serious challenges posed by climate change. Carbon Capture, Utilization, and Storage (CCUS) technology is considered one of the key pathways to mitigate climate change. Among the CCUS technologies, CO2 storage in offshore saline aquifers has gained significant attention in recent years. This paper conducts an in-depth analysis of the Sleipner and Snøhvit projects in Norway and the Tomakomai project in Japan, exploring key issues related to the application, geological characteristics, injection strategies, monitoring systems, and simulation methods of CO2 storage in offshore saline aquifers. This study finds that CO2 storage in offshore saline aquifers has high safety and storage potential but faces several challenges in practical applications, such as geological reservoir characteristics, technological innovation, operational costs, and social acceptance. Therefore, it is necessary to further strengthen technological innovation and policy support to promote the development and application of CO2 storage in offshore saline aquifers. This study provides valuable experiences and insights for similar projects worldwide, contributing to the sustainable development of CO2 storage in offshore saline aquifers and making a greater contribution to achieving global net-zero emission targets.

Liquids doi: 10.3390/liquids4040041

Authors: Reese W. Anderson Allison I. Anderson Mark W. Gealy Darin J. Ulness

This study investigates the dynamics of thermal plumes interacting with the liquid–air interface in straight-chain alcohols and their mixtures using a photothermal imaging technique based on thermal lensing. This method enables the indirect measurement of temperature gradients via changes in refractive index caused by localized laser heating. Employing a collimated laser beam, the results show the formation and evolution of cylindrical heated zones and their interactions with the liquid–air interface. The study reveals that, while some alcohols exhibit stable surface behaviors, others demonstrate complex dynamical behaviors, including strong stable steady-state oscillations. The findings contribute to understanding fluid dynamics in molecular liquids near their liquid–air interfaces.

Liquids doi: 10.3390/liquids4040040

Authors: Jonathan G. M. Conn Abdullah Ahmad David S. Palmer

Understanding the interactions between solutes and solvents is vital in many areas of the chemical sciences. Solvation free energy (SFE) is an important thermodynamic property in characterising molecular solvation and so accurate prediction of this property is sought after. The One-Dimensional Reference Interaction Site Model (RISM) is a well-established method for modelling solvation, but it is known to yield large errors in the calculation of SFE. In this work, we show that a single machine learning free energy functional for RISM can accurately model solvation thermodynamics in multiple solvents. A convolutional neural network is trained on solvation free energy density functions calculated by RISM for small organic molecules in approximately 100 different solvent systems. We achieve an average RMSE of 1.41 kcal/mol and an R2 of 0.89 across all solvent systems. We also compare the performance for the most and least commonly represented solvents and show that higher accuracy is generally seen with higher volumes of data, with RMSE values of 0.69–1.29 kcal/mol and R2 values of 0.78–0.97 for solvents with more than 50 data points. We have shown that machine learning can greatly improve solvation free energy predictions in RISM, while demonstrating that the methodology is generalisable across solvent systems. This represents a significant step towards a universal machine learning SFE functional for RISM.

Liquids doi: 10.3390/liquids4040039

Authors: M. Melia Rodrigo Ana M. T. D. P. V. Cabral Sónia I. G. Fangaia Afonso C. Nogueira Artur J. M. Valente Ana C. F. Ribeiro Miguel A. Esteso

In this work, we propose a comprehensive experimental study of the diffusion of isoniazid, one of the first-line anti-tuberculosis drugs, in combination with another drug (ethambutol dihydrochloride) and with different cyclodextrins as carrier molecules, for facilitated transport and enhanced solubility. For that, ternary mutual diffusion coefficients measured by the Taylor dispersion method (D11, D22, D12, and D21) are determined for aqueous solutions containing isoniazid and different cyclodextrins (that is, α–CD, β–CD, and γ–CD) at 298.15 K. From the significant effect of the presence of these carbohydrates on the diffusion of this drug, interactions between these components are suggested. Support for this arose from models, which shows that these effects may be due to the formation of 1:1 (CDs:isoniazid) complexes.

Liquids doi: 10.3390/liquids4040038

Authors: Vera L. S. Freitas Carlos A. O. Silva Maria D. M. C. Ribeiro da Silva

The standard molar enthalpies of formation in the liquid phase for ethyl (E)-cinnamate and ethyl hydrocinnamate, two cinnamate derivatives with notable flavor and fragrance characteristics, were determined experimentally using combustion calorimetry in an oxygen atmosphere. To derive the gas-phase enthalpies of formation for these derivatives, their enthalpies of vaporization were measured using a high-temperature Calvet microcalorimeter and the vacuum drop microcalorimetric technique. Additionally, a computational analysis employing the G3(MP2)//B3LYP composite method was conducted to calculate the gas-phase standard enthalpies of formation at T = 298.15 K for both compounds. These findings enabled a detailed assessment and analysis of the structural and energetic effects of the vinyl and ethane moieties between the phenyl and carboxylic groups in the studied compounds. Considering the structural features of ethyl (E)-cinnamate and ethyl hydrocinnamate, a gas-phase enthalpy of hydrogenation analysis was conducted to explore their energetic profiles more thoroughly.

Liquids doi: 10.3390/liquids4040037

Authors: Costas Panayiotou

A new method, based on quantum chemical calculations, is proposed for the thermodynamically consistent reformulation of QSPR-type Linear Free-Energy Relationship (LFER) models. This reformulation permits the extraction of valuable information on intermolecular interactions and its transfer in other LFER-type models, in acidity/basicity scales, or even in equation-of-state models. New molecular descriptors of electrostatic interactions are derived from the distribution of molecular surface charges obtained from COSMO-type quantum chemical calculations. The widely used and very successful Abraham’s Linear Solvation Energy Relationship (LSER) model is selected as the reference LSER model for the calculations in solute–solvent systems as well as in solute self-solvation. Hydrogen-bonding free energies, enthalpies, and entropies are now derived for a variety of common solutes. The capacity of the method to address the role of conformational changes in solvation quantities is discussed. The perspectives of the LSER model with the implementation of the new descriptors are also discussed.

Liquids doi: 10.3390/liquids4030036

Authors: Jocelyn Chen Audrey Chen Yixuan Yang William E. Acree

Solute descriptors derived from experimental solubility data for oxybenzone dissolved in 21 different organic solvents indicate that the hydrogen atom on the hydroxyl functional group forms an intramolecular hydrogen bond with the lone electron pair on the oxygen atom of the neighboring >C=O functional group. Group contribution methods developed for estimating the Abraham model solute descriptors from the molecule’s Canonical SMILES code significantly over-estimate the Abraham model’s hydrogen bond acidity solute descriptor of oxybenzone. An informed user-modified Canonical SMILES code is proposed to identify which hydrogen atoms are involved in intramolecular H-bond formation. The identified hydrogen atom(s) can be used to define a new functional/fragment group and numerical group contribution value.

Liquids doi: 10.3390/liquids4030035

Authors: Timur I. Magsumov Igor A. Sedov

Many ionic liquids, including alkylimidazolium salts, form a nanoheterogeneous structure with polar and apolar domains in their liquid phase. Using molecular dynamics simulations, the influence of the structure of the cations of a series of aprotic ([CnC1Im][TFSI], [CnCnIm][TFSI]) and protic ([HCnIm][TFSI]) alkylimidazolium bistrilimides on the domain structure of their liquid phase was studied. The characteristic sizes of domains and the extent of domain segregation in different liquids have been compared. It has been shown that the latter, but not the former, is a key factor determining the magnitude of the Gibbs free energy of cavity formation in nanostructured ionic liquids, which in turn governs their solvation properties.

Liquids doi: 10.3390/liquids4030034

Authors: Boris N. Solomonov Mansur B. Khisamiev Mikhail I. Yagofarov

In this work, an approach to the calculation of hydrogen bonding enthalpies is proposed. It employs the correlation proposed by M.H. Abraham, establishing the connection between the equilibrium constant (KHB) and acidity (α2H) and basicity (β2H) parameters: log KHB = 7.354 · α2H · β2H − 1.099. Hydrogen bonding enthalpy (ΔHBH) is found using the compensation relationship with Gibbs energy (ΔHBG): ΔHBG = 0.66 · ΔHBH + 2.5 kJ·mol−1. This relationship enables the calculation of the enthalpy, Gibbs energy and entropy of hydrogen bonding. The validity of this approach was tested against 122 experimental hydrogen bonding enthalpies values available from the literature. The root mean square deviation and average deviation equaled 1.6 kJ·mol−1 and 0.5 kJ·mol−1, respectively.

Liquids doi: 10.3390/liquids4030033

Authors: Ariel A. Chialvo

We review the statistical mechanic foundations of the fundamental structure-making/breaking functions, leading to the rigorous description of the solute-induced perturbation of the solvent environment for the understanding of the solvation process of any species regardless of the type and nature of the solute–solvent interactions. Then, we highlight how these functions are linked to unambiguous thermodynamic responses resulting from changes in state conditions, composition, and solute–solvent intermolecular interaction asymmetries. Finally, we identify and illustrate the pitfalls behind the use of surrogate approaches to structure-making/breaking markers, including those based on Jones–Dole’s B-coefficient and Hepler’s isobaric-thermal expansivity, while highlighting their ambiguities and lack of consistency and the sources of misinterpretations.

Liquids doi: 10.3390/liquids4030032

Authors: Sergey P. Verevkin Dzmitry H. Zaitsau

New experimental vapour pressures and vaporisation enthalpies of the ionic liquids [2,4-dimethyl-1,2,4-triazolium][NTf2], [2-methyl-4-ethyl-1,2,4-triazolium][NTf2], and [2-ethyl-4-methyl-1,2,4-triazolium][NTf2] were measured using the Langmuir method in combination with the quartz crystal microbalance. New experimental vapour pressures and vaporisation enthalpies of the molecular liquids 1H-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-ethyl-1,2,4-triazole, and 1H-1,2,3-triazole were measured using the transpiration method. Structure–property relationships between molecular and ionic liquids were studied. These results will facilitate chemical engineering calculations of processes involving ILs.

Liquids doi: 10.3390/liquids4030031

Authors: Barbara L. Goodall Jane P. Ferguson Cory C. Pye

The geometries and vibrational frequencies of various configurations of XO4m−(H2O)n, X = Fe, Ru, Os, m = 0; X = Mn, Tc, Re, m = 1; X = Cr, Mo, W, m = 2; and X = Nb, Ta, m = 3; n = 0–6 are calculated at various levels up to MP2/6-31+G* and B3LYP/6-31+G*. These properties are studied as a function of increasing cluster size. The experimental and theoretical bond distances and vibrational spectra are compared where available, and predictions are made where they are not.

Liquids doi: 10.3390/liquids4030030

Authors: Sergei F. Vyboishchikov

A dense artificial neural network, ESE-ΔH-DNN, with two hidden layers for calculating both solvation free energies ΔG°solv and enthalpies ΔH°solv for neutral solutes in organic solvents is proposed. The input features are generalized-Born-type monatomic and pair electrostatic terms, the molecular volume, and atomic surface areas of the solute, as well as five easily available properties of the solvent. ESE-ΔH-DNN is quite accurate for ΔG°solv, with an RMSE (root mean square error) below 0.6 kcal/mol and an MAE (mean absolute error) well below 0.4 kcal/mol. It performs particularly well for alkane, aromatic, ester, and ketone solvents. ESE-ΔH-DNN also exhibits a fairly good accuracy for ΔH°solv prediction, with an RMSE below 1 kcal/mol and an MAE of about 0.6 kcal/mol.

Liquids doi: 10.3390/liquids4030029

Authors: Andrew S. I. D. Lang Youngmin Lee

This study explores the application of fine-tuned large language models for predicting physicochemical properties, specifically focusing on Abraham model solute descriptors (E, S, A, B, V) and modified solvent parameters (e0, s0, a0, b0, v0). By leveraging ChemLLaMA, a specialized version of the LLaMA model for cheminformatics tasks, we developed the AbraLlama-Solvent and AbraLlama-Solute models using curated datasets of experimentally derived solute descriptors and solvent parameters. Our findings demonstrate that AbraLlama-Solvent and AbraLlama-Solute predict modified solvent parameters and solute descriptors with high accuracy, comparable to existing methods. The AbraLlama-Solvent model shows varying prediction accuracy across different solvents, influenced by their position within the chemical space, while the AbraLlama-Solute model consistently predicts solute descriptors with high accuracy. Both models are available as applications on Hugging Face, facilitating easy predictions from SMILES strings. This research highlights the potential of LLMs in chemistry applications, offering practical tools for solvent comparison and expanding the applicability of Abraham solvation equations to a broader range of organic solvents.

Liquids doi: 10.3390/liquids4030028

Authors: Anushis Patra Vaishali Khokhar Siddharth Pandey

Deep eutectic solvents (DESs) have emerged as viable alternatives to toxic organic solvents. The most intriguing aspect of these solvents is perhaps the widely varying physicochemical properties emerging from the changes in the constituents that form DESs along with their composition. Based on the constituents, a DES can be hydrophilic/polar or hydrophobic/non-polar, rendering a vastly varying spectrum of polarity a possibility. DESs formed by mixing urea (U) with hydrated lanthanide salts, lanthanum nitrate hexahydrate (La : U), cerium nitrate hexahydrate (Ce : U), and gadolinium nitrate hexahydrate (Gd : U), respectively, exhibit very high polarity as manifested via the probe-reported empirical parameters of dipolarity/polarizability (π*). The highest π* of 1.70 exhibited by the DES (Gd : U) in a 1 : 2 molar ratio is unprecedented. The π* ranges from 1.50 to 1.70 for these DESs, which is almost the highest reported for any solvent system. The π* decreases with an increasing amount of urea in the DES; however, the anomalous trends in H-bond donating acidity (α) and H-bond accepting basicity (β) appear to be due to the hydrated water of the lanthanide salt. The emission band maxima of the fluorescence probe of the “effective” dielectric constant (εeff) of the solubilizing media, pyrene-1-carboxaldehyde (PyCHO), in salt-rich DESs reflect higher cybotactic region dipolarity than that offered by water. Probe Nile red aggregates readily in these DESs to form non-fluorescent H-aggregates, which is a characteristic of highly polar solvents. The behavior of probe pyranine also corroborates these outcomes as the (lanthanide salt : urea) DES system supports the formation of the deprotonated form of the probe in the excited state. The (lanthanide salt : urea) DES system offers solubilizing media of exceptionally high polarity, which is bound to expand their application potential.

Liquids doi: 10.3390/liquids4030027

Authors: Xiaohui Wang Zhe Huai Lei Zheng Meili Liu Zhaoxi Sun

Years of massive applications of high-throughput atomistic modeling tools such as molecular docking and end-point free energy calculations in the drug industry and academic exploration have made them indispensable parts of hierarchical screening. While the similarities between host–guest and protein–ligand complexes lead to the direct extension of techniques for protein–ligand screening to host–guest systems, the practical performance of these hit identification tools remains unclear in host-–-guest binding. Recent reports on specific host–guest complexes suggest that the experience on the accuracy ladder accumulated from protein–ligand cases could be invalid in host–guest complexes, which makes it an urgent need to perform a systematic benchmark to secure solid numerical supports and guidance of practical setups. Concerning molecular docking, there still lacks a comprehensive benchmark considering popular docking programs. As for end-point reranking, quantitative and rigorous free energy estimation via end-point formulism requires establishing statistically meaningful measurements of uncertainties due to finite sampling, which is neglected or underestimated by a significant portion in almost all main-stream applications. Further, a face-to-face comparison between different screening tools is required for the design of a hierarchical workflow. To fill the above-mentioned critical gaps, in this work, using a dataset containing tens of host–guest complexes involving basket-like macromolecular hosts from the octa acid family, we extensively benchmark seven academic docking protocols and perform post-docking end-point rescoring with twenty protocols. The resulting comprehensive benchmark provides conclusive pictures of the practical value of docking and end-point screening in OA host–guest binding.

Liquids doi: 10.3390/liquids4030026

Authors: Ramya Motati Trisha Kandi Jilawan Francis Jocelyn Chen Emily Yao Saikiran Motati Audrey Chen Dhishithaa Kumarandurai Nikita Shanmugam William E. Acree

Mole fraction of solubilities are reported for the: o-acetoacetanisidide, anthracene, benzoin, 4-tert-butylbenzoic acid, 3-chlorobenzoic acid, 3-chlorobenzoic acid, 2-chloro-5-nitrobenzoic acid, 4-chloro-3-nitrobenzoic acid, 3,4-dichlorobenzoic acid, 2,3-dimethoxybenzoic acid, 3,4-dimethoxybenzoic acid, 3,5-dimethoxybenzoic acid, 3,5-dinitrobenzoic acid, diphenyl sulfone, 2-ethylanthraquinone, 2-methoxybenzoic acid, 4-methoxybenzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 2-methyl-3-nitrobenzoic acid, 3-methyl-4-nitrobenzoic acid, 4-methyl-3-nitrobenzoic acid, 2-naphthoxyacetic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, salicylamide, thioxanthene-9-one, 3,4,5-trimethoxybenzoic acid, and xanthene dissolved in isobutyl acetate at 298.15 K. The results of our experimental measurements, combined with the published literature data, were used to obtain Abraham model equations for isobutyl acetate. The mathematical correlations presented in the current study describe the observed molar solubility ratios of the solutes dissolved in isobutyl acetate to within an overall standard deviation of 0.12 log units or less.

Liquids doi: 10.3390/liquids4030025

Authors: Christian Fischer-Lodike Mohammad Albinsaad James S. Chickos

Vaporization enthalpies and vapor pressures of 5α-androstane and 5α-cholestane are reported using correlation gas chromatography (CGC). The results for 5α-cholestane are compared to both estimated and experimental values reported previously for 5α-cholestane. The results are generally in agreement with the literature within the reported uncertainties. A simple method for reducing the amount of curvature in logarithm plots of vapor pressures as a function of K/T when using n-alkanes as standards in CGC experiments is also reported. This may prove useful in evaluating vapor pressures of rigid hydrocarbons at high temperatures.

Liquids doi: 10.3390/liquids4020024

Authors: Fleming Martínez María Ángeles Peña Abolghasem Jouyban

Published equilibrium mole fraction solubilities of phenothiazine in ethanol, propylene glycol and water as mono-solvents at several temperatures were investigated to find standard apparent thermodynamic quantities of dissolution mixing and solvation based on the van’t Hoff and Gibbs equations. Further, by processing the reported mole fraction solubility values of phenothiazine in some aqueous cosolvent mixtures at T/K = 298.2, the inverse Kirkwood–Buff integrals treatment demonstrated preferential hydration of phenothiazine in water-rich mixtures and preferential solvation of this agent by cosolvents in mixtures of 0.24 < x1 < 1.00 in the {ethanol (1) + water (2)} mixed system and mixtures of 0.18 < x1 < 1.00 in the {propylene glycol (1) + water (2)} mixed system.

Liquids doi: 10.3390/liquids4020023

Authors: Keizo Watanabe Satoshi Ogata

In this study, the friction factor of a turbulent pipe flow for dried rice malt extract solutions was experimentally reduced to that of a Newtonian fluid. The friction factor was measured for four types of solutions at different culture times and concentrations. The results indicate that the experimental data points of the test solutions diverged from the maximum drag reduction asymptote at and above Re√f ≅ 200~250 and aligned parallel to those of Newtonian fluids. This drag reduction phenomenon differed from that observed in artificial high-molecular-weight polymer solutions, called Type A drag reduction, in which the drag reduction level is dependent on the Reynolds number in the intermediate region. This is classified as a Type B drag reduction phenomenon in biopolymer solutions and fine solid particle suspensions. The order of drag reduction corresponded to approximately 5–50 ppm xanthan gum solutions, as reported previously. Furthermore, the velocity profile in a turbulent pipe flow was predicted using a semi-theoretical equation in which the friction factors were determined using the difference between the experimental results of the tested solutions and Newtonian fluids. The results indicate considerable thickening of the viscous sublayer in the turbulent pipe flow of the test solutions compared with that of Newtonian fluids.

Liquids doi: 10.3390/liquids4020022

Authors: Amr Seifelnasr Xiuhua Si Peng Ding Jinxiang Xi

Swallowing disorders, or dysphagia, can lead to bolus aspiration in the airway, causing serious adverse health effects. Current clinical interventions for dysphagia are mainly empirical and often based on symptoms rather than etiology, of which a thorough understanding is still lacking. However, it is challenging to study the swallowing process that involves sequential structural motions and is inaccessible to standard visualization instruments. This study proposed an in vitro method to visualize swallowing hydrodynamics and identify the fundamental mechanisms underlying overflow aspirations. An anatomically accurate pharynx–epiglottis model was developed from patient-specific CT images of 623 µm isotropic resolution. A compliant half-pharynx cast was prepared to incorporate dynamic structures and visualize the flow dynamics in the mid-sagittal plane. Three locations of frequent overflow aspiration were identified: the epiglottis base, cuneiform tubular recesses, and the interarytenoid notch. Water had a consistently higher aspiration risk than a 1% w/v methylcellulose (MC) solution. The contracting–relaxing pharynx and flapping epiglottis spread the liquid film, causing a delayed esophageal entry and increased vallecular residual, which was more pronounced with the MC solution. Dispensing the liquid too slowly resulted in water aspiration, whereas this was not observed with the MC solution. An incomplete epiglottis inversion, such as horizontal or down-tilt 45°, aggravated the aspiration risks of water. This study suggests that it is practical to use anatomically accurate respiratory–digestive models to study the swallowing process by incorporating varying physiological details.

Liquids doi: 10.3390/liquids4020021

Authors: Hannah S. Slocumb Gerald R. Van Hecke

Density, viscosity, refractive index, and ultrasonic velocity were measured for the pure materials anisole, methanol, and toluene, and for the binary mixtures: methanol—anisole and methanol—toluene. Excess molar volume VE, isobaric thermal compressibility α, excess Gibbs activation energy for fluid flow ΔGE*, and excess isentropic compressibility κSE were calculated from the measured quantities. For both binary mixtures VE and κSE were <0 while Δn > 0 and ΔGE* > 0 over the entire mole fraction composition range. Anisole mixtures exhibited more negative values for VE and κSE while more positive values were displayed for Δn and ΔGE* compared to toluene mixtures. For Δη, negative values were observed at low alcohol concentrations but positive values at high alcohol concentrations for both systems.

Liquids doi: 10.3390/liquids4020020

Authors: Yasuko Noritomi Takashi Kuboki Hidetaka Noritomi

We have kinetically estimated the enzymatic redox reaction at the horseradish peroxidase (HRP)-modified electrode combined with ionic liquids by adding N-(2-methoxythethyl)-N-methylpyrrolidinium bis(trifluoromethane sulfonyl)imide (MEMPTFSI) to HRP/carbon paste (CP)/Ketjenblack EC600JC (EC). The fluctuation of the steady-state reduction current of HRP at the HRP/CP-modified electrode progressively increased as the applied potential was lowered. The enzymatic redox reaction with hydrogen peroxide as a substrate at the HRP/CP/EC/MEMPTFSI-modified electrode and the HRP/CP-modified electrode could be correlated by the Michaelis–Menten equation. The Michaelis constant of the enzymatic redox reaction at the HRP/CP/EC/MEMPTFSI-modified electrode was the same as that at the HRP/CP-modified electrode. On the other hand, the turnover number of the enzymatic redox reaction at the HRP/CP/EC/MEMPTFSI-modified electrode was six times larger than that at the HRP/CP-modified electrode. Consequently, the specificity constant of the enzymatic redox reaction at the HRP/CP/EC/MEMPTFSI-modified electrode was much higher than that at the HRP/CP-modified electrode.

Liquids doi: 10.3390/liquids4020019

Authors: Kay Bischoff Dominik Mücke Andreas Schubert Cemal Esen Ralf Hellmann

In this article, the particle concentration of finely dispersed copper(II) oxide nanosuspensions as precursors for reductive laser sintering (RLS) is optimized on the basis of rheological investigations. For this metallization process, a smooth, homogeneous and defect-free precursor layer is a prerequisite for adherent and reproducible copper structures. The knowledge of the rheological properties of an ink is crucial for the selection of a suitable coating technology as well as for the adjustment of the ink formulation. Different dilutions of the nanosuspension were examined for their rheological behavior by recording flow curves. A strong shear thinning behavior was found and the viscosity decreases exponentially with increasing dilution. The viscoelastic behavior was investigated by a simulated doctor blade coating process using three-interval thixotropy tests. An overshoot in viscosity is observed, which decreases with increasing thinning of the precursor. As a comparison to these results, doctor blade coating of planar glass and polymer substrates was performed to prepare precursor layers for reductive laser sintering. Surface morphology measurements of the resulting coatings using laser scanning microscopy and rheological tests show that homogeneous precursor layers with constant thickness can be produced at a particle–solvent ratio of 1.33. A too-high particle content results in an irregular coating layer with deep grooves and a peak-to-valley height Sz of up to 7.8 μm. Precise dilution control allows the fabrication of smooth surfaces with a Sz down to 1.5 μm.

Liquids doi: 10.3390/liquids4020018

Authors: Jia Lin Lee Gun Hean Chong Masaki Ota Haixin Guo Richard Lee Smith

An overview of solvent replacement strategies shows that there is great progress in green chemistry for replacing hazardous di-polar aprotic solvents, such as N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), and 1,4-dioxane (DI), used in processing active industrial ingredients (APIs). In synthetic chemistry, alcohols, carbonates, ethers, eucalyptol, glycols, furans, ketones, cycloalkanones, lactones, pyrrolidinone or solvent mixtures, 2-methyl tetrahydrofuran in methanol, HCl in cyclopentyl methyl ether, or trifluoroacetic acid in propylene carbonate or surfactant water (no organic solvents) are suggested replacement solvents. For the replacement of dichloromethane (DCM) used in chromatography, ethyl acetate ethanol or 2-propanol in heptanes, with or without acetic acid or ammonium hydroxide additives, are suggested, along with methanol acetic acid in ethyl acetate or methyl tert-butyl ether, ethyl acetate in ethanol in cyclohexane, CO2-ethyl acetate, CO2-methanol, CO2-acetone, and CO2-isopropanol. Supercritical CO2 (scCO2) can be used to replace many organic solvents used in processing materials from natural sources. Vegetable, drupe, legume, and seed oils used as co-extractants (mixed with substrate before extraction) can be used to replace the typical organic co-solvents (ethanol, acetone) used in scCO2 extraction. Mixed solvents consisting of a hydrogen bond donor (HBD) solvent and a hydrogen bond acceptor (HBA) are not addressed in GSK or CHEM21 solvent replacement guides. Published data for 100 water-soluble and water-insoluble APIs in mono-solvents show polarity ranges appropriate for the processing of APIs with mixed solvents. When water is used, possible HBA candidate solvents are acetone, acetic acid, acetonitrile, ethanol, methanol, 2-methyl tetrahydrofuran, 2,2,5,5-tetramethyloxolane, dimethylisosorbide, Cyrene, Cygnet 0.0, or diformylxylose. When alcohol is used, possible HBA candidates are cyclopentanone, esters, lactone, eucalytol, MeSesamol, or diformylxylose. HBA—HBA mixed solvents, such as Cyrene—Cygnet 0.0, could provide interesting new combinations. Solubility parameters, Reichardt polarity, Kamlet—Taft parameters, and linear solvation energy relationships provide practical ways for identifying mixed solvents applicable to API systems.

Liquids doi: 10.3390/liquids4020017

Authors: Johnathan Biebighauser Johan Dominguez Lopez Krys Strand Mark W. Gealy Darin J. Ulness

The results of a photothermal spectroscopy technique that effectively images convective and conductive heat flow in liquids via a thermal lensing effect are described. Pure water; sodium chloride solutions at salinities of approximately 5, 15, 25, and 35 g/kg; and an artificial seawater of 35 g/kg were studied across a range of temperatures. This system was studied because of the importance of thermal pluming in seawater. ‘Frustrated’ thermal starting plumes were observed near the temperature of maximum density. The physical characteristics of these thermal starting plumes are reported.

Liquids doi: 10.3390/liquids4020016

Authors: Cory C. Pye Champika Mahesh Gunasekara

The energies, structures, and vibrational frequencies of [Sb(H2O)n]3+, n = 0–9, 18 have been calculated at the Hartree–Fock and second-order Møller–Plesset levels of theory using the CEP, LANL2, and SDD effective core potentials in combination with their associated basis sets, or with the 6-31G* and 6-31+G* basis sets. The metal–oxygen distances and totally symmetric stretching frequency of the aqua ions were compared with each other and with related crystal structure measurements where available.

Liquids doi: 10.3390/liquids4020015

Authors: Franco Cataldo

After a survey on polymer plasticization theories and conventional criteria to evaluate polymer–plasticizer compatibility through the solubility parameter, an attempt to create a polymer–plasticizer polarity scale through solvatochromic dyes has been made. Since Reichardt’s ET(30) dye is insoluble in rubber hydrocarbon polymers like polyisoprene, polybutadiene and styrene–butadiene copolymers and is not useful for the evaluation of the hydrocarbons and ester plasticizers, the Nile Red solvatochromic dye was instead used extensively and successfully for this class of compounds. A total of 53 different compounds were evaluated with the Nile Red dye and wherever possible also with Reichardt’s ET(33) dye. A very good correlation was then found between the Nile Red scale E(NR) and Reichardt’s ET(30) scale for this class of compounds focusing on diene rubbers and their typical hydrocarbons and new ester plasticizers. Furthermore, the E(NR) scale also shows a reasonable correlation with the total solubility parameter calculated according to the Van Krevelen method. Based on the above results, some conclusion was made about the compatibility between the diene rubbers and the conventional plasticizers, as well as a new and green plasticizer proposed for the rubber compounds.

Liquids doi: 10.3390/liquids4010014

Authors: Stuart J. Brown Andrew J. Christofferson Calum J. Drummond Qi Han Tamar L. Greaves

Solvation properties are key for understanding the interactions between solvents and solutes, making them critical for optimizing chemical synthesis and biochemical applications. Designable solvents for targeted optimization of these end-uses could, therefore, play a big role in the future of the relevant industries. The tailorable nature of protic ionic liquids (PILs) as designable solvents makes them ideal candidates. By alteration of their constituent structural groups, their solvation properties can be tuned as required. The solvation properties are determined by the polar and non-polar interactions of the PIL, but they remain relatively unknown for PILs as compared to aprotic ILs and their characterization is non-trivial. Here, we use solvatochromic dyes as probe molecules to investigate the solvation properties of nine previously uncharacterized alkyl- and dialkylammonium PILs. These properties include the Kamlet–Aboud–Taft (KAT) parameters: π* (dipolarity/polarizability), α (H-bond acidity) and β (H-bond basicity), along with the ET(30) scale (electrophilicity/polarizability). We then used molecular dynamics simulations to calculate the radial distribution functions (RDF) of 21 PILs, which were correlated to their solvation properties and liquid nanostructure. It was identified that the hydroxyl groups on the PIL cation increase α, π* and ET(30), and correspondingly increase the cation–anion distance in their RDF plots. The hydroxyl group, therefore, reduces the strength of the ionic interaction but increases the polarizability of the ions. An increase in the alkyl chain length on the cation led to a decrease in the distances between cations, while also increasing the β value. The effect of the anion on the PIL solvation properties was found to be variable, with the nitrate anion greatly increasing π*, α and anion–anion distances. The research presented herein advances the understanding of PIL structure–property relationships while also showcasing the complimentary use of molecular dynamics simulations and solvatochromic analysis together.

Liquids doi: 10.3390/liquids4010013

Authors: Javier Catalán Henning Hopf

The solvent-dependent intensity changes in the first UV/Vis absorption band of the three polyenes DPH, DPHb, and ttbP3 dissolved in a hydrocarbon solvent with temperature allow for the conclusion that, at temperatures above 233 K, the two phenyl groups of DPH are rotated out-of-plane to yield a non-coplanar molecular structure. This leads to the conclusion that DPH becomes increasingly less coplanar as the temperature rises above 233 K. When the phenyl groups rotate out-of-plane, the polarizability decreases, and the energy of the first electronic transition increases by an extra value. Therefore, below 233 K, the correlation lines between the absorption energy of the 0–0 component of the UV/Vis absorption band and the solvent polarizability, as measured by the SP values, show bilinear behavior. The unexpected behavior shown by DPH dissolved in tetrachloro- and dichloromethane is discussed. We dedicate this research as a tribute to the very important contribution to the solvent effect made by Prof. Christian Reichardt and also to his generous and altruistic scientific help that he has always shown.

Liquids doi: 10.3390/liquids4010012

Authors: Eirini Maria Kanakaki Vassilis Gaganis

A computational model that can accurately describe the thermodynamics of a hydrocarbon system and its properties under various conditions is a prerequisite for running reservoir and pipeline simulations. Cubic Equations of State (EoS) are mathematical tools used to model the phase and volumetric behavior of reservoir fluids when compositional effects need to be considered. To anticipate uncertainty and enhance the quality of their predictions, EoS models must be adjusted to adequately match the available lab-measured PVT values. This task is challenging given that there are many potential tuning parameters, thus leading to various tuning results of questionable validity. In this paper, we present an automated EoS tuning workflow that employs a Generalized Pattern Search (GPS) optimizer for efficient tuning of a cubic EoS model. Specifically, we focus on the Peng–Robinson (PR) model, which is the oil and gas industry standard, to accurately capture the behavior of diverse multicomponent, complex hydrocarbon mixtures encountered in subsurface reservoirs. This approach surpasses the limitations of conventional gradient-based (GB) methods, which are susceptible to getting trapped in local optima. The proposed technique also allows physical constraints to be imposed on the optimization procedure. A gas condensate and an H2S-rich oil were used to demonstrate the effectiveness of the GPS algorithm in finding an optimized solution for high-dimensional search spaces, and its superiority over conventional gradient-based optimization was confirmed by automatically tracking globally optimal and physically sound solutions.

Liquids doi: 10.3390/liquids4010011

Authors: Rudolf Naef William E. Acree

Assessment of the environmental impact of organic chemicals has become an important subject in chemical science. Efficient quantitative descriptors of their impact are their partition coefficients logPow, logKoa and logKaw. We present a group-additivity method that has proven its versatility for the reliable prediction of many other molecular descriptors for the calculation of the first two partition coefficients and indirectly of the third with high dependability. Based on the experimental logPow data of 3332 molecules and the experimental logKoa data of 1900 molecules at 298.15 K, the respective partition coefficients have been calculated with a cross-validated standard deviation S of only 0.42 and 0.48 log units and a goodness of fit Q2 of 0.9599 and 0.9717, respectively, in a range of ca. 17 log units for both descriptors. The third partition coefficient logKaw has been derived from the calculated values of the former two descriptors and compared with the experimentally determined logKaw value of 1937 molecules, yielding a standard deviation σ of 0.67 log units and a correlation coefficient R2 of 0.9467. This approach enabled the quick calculation of 29,462 logPow, 27,069 logKoa and 26,220 logKaw values for the more than 37,100 molecules of ChemBrain’s database available to the public.

Liquids doi: 10.3390/liquids4010010

Authors: Stefan Spange

The UV/Vis absorption energies (νmax) of different solvatochromic probes measured in co-solvent/water mixtures are re-analyzed as a function of the average molar concentration (Nav) of the solvent composition compared to the use of the mole fraction. The empirical ET(30) parameter of Reichardt’s dye B30 is the focus of the analysis. The Marcus classification of aqueous solvent mixtures is a useful guide for co-solvent selection. Methanol, ethanol, 1,2-ethanediol, 2-propanol, 2-methyl-2-propanol, 2-butoxyethanol, formamide, N-methylformamide (NMF), N,N-dimethylformamide (DMF), N-formylmorpholine (NFM), 1,4-dioxane and DMSO were considered as co-solvents. The ET(30) values of the binary solvent mixtures are discussed in relation to the physical properties of the co-solvent/water mixtures in terms of quantitative composition, refractive index, thermodynamics of the mixture and the non-uniformity of the mixture. Significant linear dependencies of ET(30) as a function of Nav can be demonstrated for formamide/water, 1,2-ethanediol/water, NMF/water and DMSO/water mixtures over the entire compositional range. These mixtures belong to the group of solvents that do not enhance the water structure according to the Marcus classification. The influence of the solvent microstructure on the non-linearity ET(30) as a function of Nav is particularly clear for alcohol/water mixtures with an enhanced water structure.

Liquids doi: 10.3390/liquids4010009

Authors: Daniela Babusca Andrei Vleoanga Dana Ortansa Dorohoi

This article contains a comparative spectral analysis corroborated with the quantum mechanical computations of four cycloimmonium ylids. The spectral shift of the visible electronic absorption band of the studied molecules in 20 solvents with different empirical parameters is expressed by linear multi-parametric dependences that emphasize the intramolecular charge transfer (ICT) process. The nature of molecular interactions and their contribution to the spectral shift of the visible ICT band of solutes are also established in this manuscript. The results of the statistical analysis are used to estimate the cycloimmonium ylids’ excited dipole moment by the variational method, using the hypothesis of McRae. The importance of the structure of both the heterocycle and carbanion substituents to the stability and reactivity of the studied cycloimmonium ylids is underlined by the quantum mechanical computations of the molecular descriptors.

Liquids doi: 10.3390/liquids4010008

Authors: W. Earle Waghorne

Catalan’s SPPN, a measure of solvent polarity/polarizability has been analysed in terms of molecular properties derived from computational chemistry. The results show that SPPN correlates positively with the molecular dipole moment and quadrupolar amplitude and negatively with the molecular polarizability. These correlations are shared with Kamet and Taft’s π* and Reichardt and Dimroth’s ET(30). Thus, one can associate the solvent polarity with non-specific interactions involving the permanent charges on solvent molecules. It is also noted that the opposite correlations, all three parameters increasing with increasing solvent polarity but decreasing with increasing solvent polarizability, creates an ambiguity in their use, for example, in linear free energy relationships.

Liquids doi: 10.3390/liquids4010007

Authors: Cynthia M. Dupureur

The intramolecular charge transfer behavior of push–pull dyes is the origin of their sensitivity to environment. Such compounds are of interest as probes for bioimaging and as biosensors to monitor cellular dynamics and molecular interactions. Those that are solvatochromic are of particular interest in studies of lipid dynamics and heterogeneity. The development of new solvatochromic probes has been driven largely by the need to tune desirable properties such as solubility, emission wavelength, or the targeting of a particular cellular structure. DFT calculations are often used to characterize these dyes. However, if a correlation between computed (dipole moment) and experimentally measured solvatochromic behavior can be established, they can also be used as a design tool that is accessible to students. Here, we examine this correlation and include case studies of the effects of probe modifications and conformation on dipole moments within families of solvatochromic probes. Indeed, the ground state dipole moment, an easily computed parameter, is correlated with experimental solvatochromic behavior and can be used in the design of new environment-sensitive probes before committing resources to synthesis.

Liquids doi: 10.3390/liquids4010006

Authors: Jianwei Li

The thermodynamic and kinetic contributions to the over-extraction of extractables by nonpolar organic solvents relative to biological lipids in exhaustive and exaggerated extractions of medical devices are studied based on the Abraham solvation model and solvent–material interactions, using low-density polyethylene (LDPE) as an exemplary material. The thermodynamic effect is evaluated by the partition constant of extractables between LDPE and extraction solvents, hexane and lipids, defined as the concentration in the polymer phase divided by the concentration in the solvent phase. The Abraham solvation model is used to correlate the measured LDPE-lipid partition constant (log10Pldpe/lipid) to construct the predictive model. Similar models are also derived from the thermodynamic cycle conversion, using the system constants of LDPE-water and Lipid-water partition systems. These constructed models, together with the predictive LDPE-hexane (log10Pldpe/hexane) model established from a previous study, are used to predict and compare the ranges and values of Pldpe/s (s = lipids and hexane) for the observed LDPE extractables over a wide hydrophobicity range in log10Po/w from zero to 30. The solvent-LDPE interactions are examined by the degree of swelling of LDPE by hexane (or other nonpolar solvents) and lipids, including the solvent diffusion rates into the material. These parameters allow the evaluation of kinetic effect on the over-extraction. The extent of over-extraction is compiled directly by experimental “overall” or “specific” migration data or indirectly calculated by the diffusion coefficient of extractables when extracted by hexane or lipids. It is concluded from this study that the extractables distribution between LDPE and lipids highly favors the lipid phase thermodynamically (Pldpe/lipid<1), and the values of Pldpe/lipid are always lower than those of Pldpe/hexane, thereby indicating that the thermodynamic effect is not the cause of over-extraction. It is the kinetic effect that dominantly contributes to the over-extraction, as supported by the material swelling and solvent diffusion rates. Finally, the extent of over-extraction has been established from a few folds to over a hundred-fold, and the median value is 7. Furthermore, the methods adopted and developed in this study can be invaluable tools in other disciplines such as the reliable prediction of extractables from other device materials and environmental sampling.

Liquids doi: 10.3390/liquids4010005

Authors: Pedro P. Madeira Luisa A. Ferreira Vladimir N. Uversky Boris Y. Zaslavsky

This short review describes the expansion of the solvatochromic approach utilizing water-soluble solvatochromic dyes to the analysis of solvent features of aqueous media in solutions of various compounds. These solvent features (polarity/dipolarity, hydrogen bond donor ability (HBD acidity), and hydrogen bond acceptor ability (HBA basicity)) vary depending on the nature and concentration of a solute. Furthermore, the solvent features of water (the solvent dipolarity/polarizability and hydrogen bond donor ability) in solutions of various compounds describe multiple physicochemical properties of these solutions (such as the solubility of various compounds in aqueous solutions, salting-out and salting-in constants for polar organic compounds in the presence of different inorganic salts, as well as water activity, osmotic coefficients, surface tension, viscosity, and the relative permittivity of aqueous solutions of different individual compounds) and are likely related to changes in the arrangement of hydrogen bonds of water in these solutions.

Liquids doi: 10.3390/liquids4010004

Authors: Henry J. Castejón

Molecular dynamics simulations have been used to investigate the structural changes in confined liquids. The density distribution functions for weakly and strongly interacting liquids were determined and compared to those of a non-interacting system in order to assess the impact of the entropic forces on the equilibrium state of the systems. The effect of the entropic forces was assessed by quantifying the layering on the liquid structure upon confinement. The more pronounced layering obtained for weakly interacting and non-interacting systems indicated that entropic forces are more effective in these systems where an increase in the multiplicity of states does not require a prohibitively high cost in energy.

Liquids doi: 10.3390/liquids4010003

Authors: Omar A. El Seoud Shirley Possidonio Naved I. Malek

Many reactions are carried out in solvent mixtures, mainly because of practical reasons. For example, E2 eliminations are favored over SN2 substitutions in aqueous organic solvents because the bases are desolvated. This example raises the question: how do we chose binary solvents to favor reaction outcomes? This important question is deceptively simple because it requires that we understand the details of all interactions within the system. Solvatochromism (solvent-dependent color change of a substance) has contributed a great deal to answer this difficult question, because it gives information on the interactions between solvents, solute-solvent, and presumably transition state-solvent. This wealth of information is achieved by simple spectroscopic measurements of selected (solvatochromic) substances, or probes. An important outcome of solvatochromism is that the probe solvation layer composition is almost always different from that of bulk mixed solvent. In principle, this difference can be exploited to “tune” the composition of solvent mixture to favor the reaction outcome. This minireview addresses the use of solvatochromic probes to quantify solute-solvent interactions, leading to a better understanding of the complex effects of solvent mixtures on chemical phenomena. Because of their extensive use in chemistry, we focus on binary mixtures containing protic-, and protic-dipolar aprotic solvents.

Liquids doi: 10.3390/liquids4010002

Authors: Nikolay O. Mchedlov-Petrossyan Mykyta O. Marfunin Nika N. Kriklya

This review article is devoted to the colloidal properties of fullerene solutions. According to generally accepted understandings, all solvents in relations to fullerenes are divided into “good”, “poor”, and “reactive”. We have consistently considered the state of fullerenes in these systems. In “good”, predominantly non-polar aromatic solvents and CS2, non-equilibrium dissolution methods lead to the formation of colloidal aggregates, whereas the utilization of equilibrium methods results in the formation of molecular solutions. The latter, however, have some unusual properties; new results considered in this review confirm previously expressed ideas about colloidal properties of these solutions. In “poor” (polar) solvents, lyophobic colloidal systems appear. Both “bottom-up” and “top-down” methods of preparation are well documented in the literature. However, N-methylpyrrolidine-2-one, DMSO, and DMF dissolve fullerenes quite easily and with less energy consumption. These solvents can be considered a subset of “poor” solvents that have some features of being “reactive” at the expense of basic properties. New data confirm that hydrosols of fullerenes are typical hydrophobic colloids that obey the Schulze–Hardy rule and other regularities in the presence of electrolytes. Organosols in acetonitrile and methanol are much less stable with respect to the effects of electrolytes. This allows us to assume a non-DLVO stabilizing factor in the hydrosols. Accordingly, a new estimate of the Hamaker constant of fullerene–fullerene interaction is proposed. In DMSO and DMF, the coagulation of fullerene sols is hindered due to strong solvation with these basic solvents.

Liquids doi: 10.3390/liquids4010001

Authors: András Szabadi Robert Klausser Oliver Spadiut Christian Schröder

The pivotal role of proteins in pharmaceuticals is challenged by stability issues, making the study of inclusion bodies—a source of insoluble protein aggregates—increasingly relevant. This review outlines the critical procedures in inclusion body processing, focusing on ’mild solubilization concepts’ and refolding methodologies. Attention is afforded to the emerging role of ionic liquids with unique and tunable physicochemical properties in optimizing protein unfolding and refolding processes. The review critically assesses the existing literature at the intersection of inclusion bodies and ionic liquids, identifying recent advancements, potential applications, and avenues for future research. This comprehensive analysis aims to elucidate the complexities in efficient protein processing from inclusion bodies.

Liquids doi: 10.3390/liquids3040032

Authors: Elaheh Rahimpour Abolghasem Jouyban

The objective of this research is to propose a general model utilizing the solvatochromic polarity of electronic transition energy (ET) of the Reichardt indicator to predict paracetamol solubility in the solvent mixtures. In order to model validation, the available ET (30) values of nine aqueous mixtures obtained from existing literature sources were utilized. The trained model yielded a relatively accurate estimation of paracetamol solubility in the investigated systems.

Liquids doi: 10.3390/liquids3040031

Authors: Heinz Langhals

Intermolecular interactions form the basis of the properties of solvents, such as their polarity, and are of central importance for chemistry; such interactions are widely discussed. Solvent effects were reported on the basis of various polarity probes with the ET(30) polarity scale of Dimroth and Reichardt being of special interest because of its sensitivity, precise measurability and other advantages, and has been used for the investigation of solvent interactions. A two-parameter equation for the concentration dependence of medium effects has been developed, providing insights into structural changes in liquid phases. Moving from condensed gases to binary solvent mixtures, where the property of one solvent can be continuously transformed to the other, it was shown how the polarity of a solvent can be composed from the effect of polar functional groups and other structural elements that form the matrix. Thermochromism was discussed as well as the effect of very long-range interactions. Practical applications were demonstrated.

Liquids doi: 10.3390/liquids3040030

Authors: Darío A. Tinjacá Fleming Martinez María Angeles Peña Abolghasem Jouyban William E. Acree

The reported total Hildebrand solubility parameter (δ2) value of meloxicam, as calculated based on the group contribution method proposed by Fedors, was compared with those estimated based on the maximum solubility peaks observed in different aqueous cosolvent systems at T = 298.15 K. Thus, the observed δ2 values varied from (19.8 to 29.1) MPa1/2, respectively. Moreover, the Hansen solubility parameters (HSPs) and the total Hildebrand solubility parameter were also determined by using the Bustamante regression method with the reported experimental solubility values of meloxicam in 31 neat solvents (30 organic solvents and water), obtaining the values: δd = 19.9 MPa1/2, δp = 16.9 MPa1/2, δh = 5.7 MPa1/2, and δT = 26.7 MPa1/2. Furthermore, the HSPs of meloxicam were also estimated based on the Hoftyzer–van Krevelen group contribution method, obtaining the values: δd = 17.9 MPa1/2, δp = 20.3 MPa1/2, and δh = 9.2 MPa1/2, and the total solubility parameter as: δT = 28.6 MPa1/2. In addition, the Kamlet–Abboud–Taft linear solvation energy relationship (KAT-LSER) model was also employed to evaluate the role of different intermolecular interactions on the dissolution of meloxicam in different solvents that varied in terms of polarity and hydrogen bonding capability.

Liquids doi: 10.3390/liquids3040029

Authors: Linh Dinh Bingfang Yan

Lyotropic liquid crystals (LLCs) are liquids that have crystalline structures. LLCs as drug delivery systems that can deliver hydrophobic, hydrophilic, and amphiphilic agents. Due to their unique phases and structures, LLCs can protect both small molecules and biologics from the gastrointestinal tract’s harsh environment, thus making LLCs attractive as carriers for oral drug delivery. In this review, we discuss the advantages of LLCs and LLCs as oral formulations targeting intestinal lymphatic transport. In oral LLC formulations, the relationship between the micelle compositions and the resulting LLC structures as well as intestinal transport and absorption were determined. In addition, we further demonstrated approaches for the enhancement of intestinal lymphatic transport: (1) lipid-based LLCs promoting chylomicron secretion and (2) the design of LLC nanoparticles with M cell-triggered ligands for targeting the M cell pathway. In this review, we introduce LLC drug delivery systems and their characteristics. Our review focuses on recent approaches using oral LLC drug delivery strategies targeting the intestinal lymphatic system to enhance drug bioavailability.

Liquids doi: 10.3390/liquids3040028

Authors: Andrew T. Nguyen Heather M. Childs William M. Salter Afroditi V. Filippas Bridget T. McInnes Kris Senecal Timothy J. Lawton Paola A. D’Angelo Walter Zukas Todd E. Alexander Victoria Ayotte Hong Zhao Christina Tang

Materials that generate structural color may be promising alternatives to dyes and pigments due to their relative long-term stability and environmentally benign properties. Liquid crystal (LC) mixtures of cholesteryl esters demonstrate structural color due to light reflected from the helical structure of the self-assembled molecules. The apparent color depends on the pitch length of the liquid crystal. While a wide range of colors have been achieved with such LC formulations, the nature of the pitch–concentration relationship has been difficult to define. In this work, various machine learning approaches to predict the reflected wavelength, i.e., the position of the selective reflection band, based on LC composition are compared to a Scheffe cubic model. The neural network regression model had a higher root mean squared error (RMSE) than the Scheffe cubic model with improved predictions for formulations not included in the dataset. Decision tree regression provided the best overall performance with the lowest RMSE and predicted position of the selective reflection band within 0.8% of the measured values for LC formulations not included in the dataset. The predicted values using the decision tree were over two-fold more accurate than the Scheffe cubic model. These results demonstrate the utility of machine learning models for predicting physical properties of LC formulations.

Liquids doi: 10.3390/liquids3040027

Authors: Xiaohui Wang Mao Wang Zhaoxi Sun

Due to the similarity of host–guest complexes and protein–ligand and protein–protein assemblies, computational tools for protein–drug complexes are commonly applied in host–guest binding. One of the methods with the highest popularity is the end-point free energy technique, which estimates the binding affinity with gas-phase and solvation contributions extracted from simplified end-point sampling. Our series papers on a set of carboxylated-pillararene host–guest complexes have proven with solid numerical evidence that standard end-point techniques are practically useless in host–guest binding, but alterations, such as slightly increasing interior dielectric constant in post-processing calculation and shifting to the multi-trajectory realization in conformational sampling, could better the situation and pull the end-point method back to the pool of usable tools. Also, the force-field selection plays a critical role, as it determines the sampled region in the conformational space. In the current work, we continue the efforts to explore potentially promising end-point modifications in host–guest binding and further extend the sampling time to an unprecedent length. Specifically, we comprehensively benchmarked the shift from the original MM description to QM Hamiltonians in post-processing the popular single-trajectory sampling. Two critical settings in the multi-scale QM/GBSA regime are the selections of the QM Hamiltonian and the implicit-solvent model, and a scan of combinations of popular semi-empirical QM Hamiltonians and GB models is performed. The multi-scale QM/GBSA treatment is further combined with the three-trajectory sampling protocol, introducing a further advanced modification. The sampling lengths in the host–guest complex, solvated guest and solvated host ensembles are extended to 500 ns, 500 ns and 12,000 ns. As a result, the sampling quality in end-point calculations is unprecedently high, enabling us to draw conclusive pictures of investigated forms of modified end-point free energy methods. Numerical results suggest that the shift to the QM Hamiltonian does not better the situation in the popular single-trajectory regime, but noticeable improvements are observed in the three-trajectory sampling regime, especially for the DFTB/GBSA parameter combination (either DFTB2 or its third-order extension), the quality metrics of which reach an unprecedently high level and surpass existing predictions (including costly alchemical transformations) on this dataset, hinting on the applicability of the advanced three-trajectory QM/GBSA end-point modification for host–guest complexes.

Liquids doi: 10.3390/liquids3040026

Authors: Onofrio Annunziata

Diffusiophoresis is the migration of a macromolecule in response to a concentration gradient of a cosolute in liquids. Diffusiophoresis of polyethylene glycol (PEG) in water occurs from high to low concentration of trimethylamine-N-oxide (TMAO). This is consistent with the preferential hydration of PEG observed in the presence of TMAO. In other words, PEG migrates in the direction in which it lowers its chemical potential. On the other hand, although PEG is found to preferentially bind urea in water, PEG diffusiophoresis still occurs from high to low urea concentration. Thus, PEG migrates in the direction that increases its chemical potential in the urea case. Here, a ligand-binding model for polymer diffusiophoresis in the presence of a cosolute that preferentially binds to polymer is developed. It includes both actual polymer–ligand binding and the effect of the polymer on cosolute thermodynamic activity. This model shows that polymer–cosolute binding has a marginal effect on polymer diffusiophoresis and indicates that weak repulsive interactions, such as hard-core exclusion forces, are the main factor responsible for the observed PEG diffusiophoresis from high to low urea concentration. This work contributes to a better understanding of diffusiophoresis of macromolecules in response to gradients of nonelectrolytes.

Liquids doi: 10.3390/liquids3040025

Authors: Saikiran Motati Ramya Motati Trisha Kandi William E. Acree

Spectrophotometric measurements were used to determine the mole fraction solubilities of vitamin K4 dissolved in cyclohexane, methylcyclohexane, 1-heptanol, 2-butanol, 2-pentanol, 2-methyl-1-butanol, 4-methyl-2-pentanol, and cyclopentanol at 298.15 K. Results from our experimental measurements, combined with the published solubility data, are used to calculate the solute descriptors of the vitamin K4 solute. The calculated solute descriptors describe the observed solubility data to within an overall standard deviation of 0.110 log units. The calculated solute descriptors were also used to estimate the several blood-to-rat tissue partition coefficients of vitamin K4, as well as the equilibrium vapor pressure above the solid vitamin at 298 K, and the vitamin’s enthalpy of solvation in both water and in 1,4-dioxane organic mono-solvent.

Liquids doi: 10.3390/liquids3040024

Authors: Manish Kumar Abhishek Kumar Siddharth Pandey

Deep eutectic solvents (DESs) have emerged as novel alternatives to common solvents and VOCs. Their employment as electrolytes in batteries has been an area of intense research. In this context, understanding changes in the physicochemical properties of DESs in the presence of Li salts becomes of utmost importance. Solvatochromic probes have the potential to gauge such changes. It is reported herein that one such UV–vis molecular absorbance probe, Reichardt’s betaine dye 33, effectively manifests changes taking place in a DES Glyceline composed of H-bond accepting salt choline chloride and H-bond donor glycerol in a 1:2 molar ratio, as salt LiCl is added. The lowest energy intramolecular charge–transfer absorbance band of this dye exhibits a 17 nm hypsochromic shift as up to 3.0 molal LiCl is added to Glyceline. The estimated ETN parameter shows a linear increase with the LiCl mole fraction. Spectroscopic responses of betaine dye 33, N,N-diethyl-4-nitroaniline and 4-nitroaniline are used to assess empirical Kamlet–Taft parameters of dipolarity/polarizability (π*), H-bond-donating acidity (α) and H-bond-accepting basicity (β) as a function of LiCl concentration in Glyceline. LiCl addition to Glyceline results in an increase in α and no change in π* and β. It is proposed that the added lithium interacts with the oxygen of the –OH functionalities on the glycerol rendering of the solvent with increased H-bond-donating acidity. It is observed that pyrene, a popular fluorescence probe of solvent polarity, does respond to the addition of LiCl to Glyceline, however, the change in pyrene response starts to become noticeable only at higher LiCl concentrations (mLiCl ≥ 1.5 m). Reichardt’s betaine dye is found to be highly sensitive and versatile in gauging the physicochemical properties of DESs in the presence of LiCl.