Molecular Solvents Research Articles

O2 solvation cavity in voids of ionic liquids studied by the solvatochromic red shift of O2(1Δg) phosphorescence.

Phosphorescence spectroscopy of singlet oxygen [=O2(1Δg)] was applied to study the solvation properties of small solute molecule, O2, in ionic liquids. Unlike conventional molecular solvents, the spectral red shift of the O2(1Δg) phosphorescence in ionic liquids from the gas phase was found to depend not only on the refractive indexof solvents but also on the vdW volume of anions. This unusual spectral shift of the O2(1Δg) luminescence is interpreted by considering the size of solvation cavities in voids, which is estimated by analyzing the free volume in ionic liquids. These results suggest the potential of the O2(1Δg) phosphorescence spectral shift measurement in the study of molecular-scale voids in ionic liquids.

Microscale Thermophoresis Assay: A Powerful Method to Quantify Protein-Nucleic Acid and Protein-Protein Interactions.

Plant viruses are among the most disastrous pathogens that cause enormous losses in crop yield and crop quality, threatening food security worldwide. These losses are attributed to virus-induced plant physiological disorders and diseases. During the ever-evolving arm race between viruses and their hosts, viruses have evolved multiple strategies to disrupt plant fortification, for example, taking advantage of RNA silencing and plant hormone pathways. Microscale thermophoresis (MST) assay arises as a rapid and precise method to identify the interactions between biomolecules including host and viral factors from plant virus infections.The technique is based on the motion of molecules in temperature gradients, which is termed thermophoresis, and depends on the binding-induced changes in molecular size, charge, and solvation shell. This chapter provides a detailed protocol describing the application of MST assays in analyzing protein-nucleic acid and protein-protein interactions, taking the Rice stripe virus (RSV )-encoded nonstructural protein 3 (NS3) that recognizes primary miR528 transcript (pri-miR528) and Rice dwarf virus (RDV )-encoded capsid protein P2 that recognizes OsIAA10 as examples.

Recovery of dialkylimidazolium-based ionic liquids from their mixtures with acetone or water by flash distillation

In a number of applications for which novel processes based on ionic liquids have been proposed, the recovery of the ionic liquid from its mixture with a molecular solvent is a step of critical importance for the viability of the process. In this work, feasibility and conditions for such recovery by simple flash vapourisation have been explored for the particular case of three dialkylimidazolium-based ionic liquids (namely 1-ethyl-3-methylimidazolium thiocyanate ([C2mim][SCN]), 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), and 1-butyl-3-methylimidazolium acetate ([C4mim][OAc])) and either acetone or water as representative molecular solvents of industrial relevance. The isobaric vapour-liquid equilibria of the binary systems acetone + ([C2mim][SCN] or [C4mim][OAc]) and water + ([C2mim][OAc] or [C4mim][OAc]) have been determined at three different pressures (101.32, 50.00, and 30.00 or 25.00 kPa), and the data have been suitably correlated by means of the NRTL thermodynamic model. These correlations have been used in the software Aspen Plus for the development of reliable simulations of a flash unit to perform the desired separations. The results indicate the difficulty in getting the ionic liquids recovered with high purity, even if operating the flash at a pressure as low as 5 kPa and at temperatures close to the range where the thermal stability of the ionic liquids starts to get compromised.

Molecular structure spectroscopic Elucidation, IEFPCM solvation (UV–Vis, MEP, FMO, NBO, NLO), molecular docking and biological assessment studies of lepidine (4-Methylquinoline)

Quinoline compounds have attracted the curiosity of chemists due to their fascinating biological potential. In the present study, the molecule 4-methylquinoline or lepidine is characterised by DFT/B3LYP with 6–311++G(d,p) basis set to explore the optimised structure. Experimental calculations are compared to the computed FT-IR, FT-Raman and UV–Vis spectra. Theoretical and observed spectra are found to be very comparable. Various polar and non-polar solvents are used to investigate the electronic solvation properties of the title compound using the TD-DFT/IEFPCM model (M062X for UV–Vis and B3LYP for NBO, NLO, HOMO-LUMO, MEP). The occurrence of charge transfer in a molecule is explained by Natural Bond Orbital (NBO) analysis. The local reactivity descriptor describes the reactive regions of the molecule. The title compound's kinetic stability and reactivity are demonstrated using thermodynamic and Frontier Molecular Orbital (FMO) functions. The substance under research has excellent NLO properties. For the head compound, topological analyses such as ELF, LOL and RDG are performed and reported. The biological features (drug-likeness, toxicity and ADME) are calculated, which reveals the pharmaceutical activities of the compound. Molecular docking studies are used to investigate ligand–protein interactions, to show the insulin inhibitor activity of the chemical under research.

Solvent pre-selection for extractive distillation using infinite dilution activity coefficients and the three-component Margules equation

• 3-Component Margules equation was used to predict vapor–liquid equilibria. • Infinite dilution activity coefficients are the sole input for solvent pre-selection. • Industrial cases were used to validate the approach. • Molecular solvents, ILs and DESs were incorporated in the screening. We present an easily accessible, open-access approach for fast pre-selection of solvents for extractive distillation at isobaric and isothermal conditions. The method uses the three-component Margules equation, which can predict vapor–liquid equilibria (VLE) in ternary systems with the infinite dilution activity coefficients, γ i ∞ , as sole input parameters. This approach is accessible for anybody regardless of the availability of process simulators or other dedicated software to predict VLE, and can be combined with open access γ i ∞ to perform solvent screening. This approach shows a deviation in VLE of <5% for non-hydrogen bond donating mixtures, while for highly dissimilar (e.g. alkane – alcohol) mixtures the deviation can be >10%. The presented method identifies molecular solvents for case studies where the same or similar solvents have also been reported in literature or are already applied on the industrial level, showing realistic pre-selection outcomes. Furthermore, small, cyclic, polar, molecular solvents are identified to induce preferential interactions and several structurally similar solvents, e.g. ethylene carbonate, dihydrolevoglucosenone and y-valerolactone, are identified to be potential alternative solvents. Among the ionic liquids (ILs) and deep eutectic solvents (DESs), the morpholinium and ammonium structures are identified to have the highest potential for increasing relative volatilities, they also show lower toxicity than other cations. This method thus proves to be able to perform early-stage pre-screening among new classes of solvents which generates information on the minimum required solvent to feed ratio ( S F min ) for energy-efficient distillation from γ i ∞ obtained by measurement or from literature.

An Efficient Synthesis of α, β Unsaturated Ketones via Claisen-schmidt Condensation Reaction using Amino Acid Based Ionic Liquids

: Synthesis of chalcone by Claisen–Schmidt condensation using recyclable L- aspartic acid coupled with imidazolium-based ionic liquid as a green synthetic approach has been developed. Present work offers significant advantages, such as high yield, enhanced reaction speed even at room temperature, catalyst reusability, and the involvement of non-toxic reagents. Background: Chalcones belong to the flavonoid family and possess pharmacological and biological activities, including antibacterial, antifungal, immunosuppressive, and anti-nociceptive properties. Objective: Ionic liquids have emerged as powerful tools for molecular organic solvents. Their wide liquid range, easy recovery, and reusability make them a greener alternative to volatile organic solvents. Thus, in the present work, our objective was to employ them as dual catalysts and solvent systems for the synthesis of chalcone via the CS condensation. Methods: In a typical experiment, benzaldehyde (10 mmol), acetophenone (10 mmol), and 2.5 mol% (L-AAIL) ionic liquid were mixed in a 50 mL round-bottom flask. The reaction was proceeded quickly at room temperature with stirring, and the resulting mixture became a biphasic system with the precipitate at the bottom and the upper phase containing some unreacted substrate which was separated from the catalyst by filtration and decantation. The catalyst was extracted with CH2Cl2 and separated for the next cycle. Results: Claisen–Schmidt condensation accomplished with reasonable to good yields, ranging from 78 to 95% at room temperature in presence of the [L-AAIL], as compared to the traditional route at more than 100°C. Conclusion: [L-AAIL] is found a highly efficient and eco-friendly catalyst for the synthesis of chalcone derivatives at room temperature. [L-AAIL] as a solvent and catalyst will exhibit real advantages by providing a ‘green’ process with a safer operation. Furthermore, short reaction periods, mild reaction conditions, easier separation, and reusability of ionic liquid made this methodology valuable for synthetic organic chemists as well as industry.

Insight into molecular interactions and solvation properties of methylammonium perchlorate in acetonitrile-dimethylsulfoxide binary mixtures: Compressibility, viscometric and dissolution thermodynamic studies

Densities (ρ), ultrasonic velocities (u) and viscosities (ƞ) of Methylammonium perchlorate (CH3NH3ClO4) in binary solvent mixtures of Acetonitrile (AN) and Dimethylsulfoxide (DMSO) containing 0.0, 0.20, 0.40, 0.60, 0.80 and 1.0 ​mol fraction of DMSO at various temperatures ranging from 298K–328K at atmospheric pressure, have been measured. From the experimental data important parameters, namely, apparent molal volume (VΦ), isentropic compressibility (Ks), limiting apparent molal isentropic compressibility (Kos,ɸ), A and B-viscosity coefficients from Jones-Dole equation, B/Vɸo values and viscous flow related thermodynamic properties have been derived. Interpretation of the obtained thermodynamic parameters was done with regards to solute-solvent and solute-solute interactions and structure breaking and making potential of the solutes in solution. To evaluate the extent of preferential solvation, Kos,ɸ values and B-coefficients for the electrolytes have been further split up into the contribution of individual ion (Kos,ɸ± and B± values) by reference electrolyte method.

Nonaqueous Solvent Extraction for Enhanced Metal Separations: Concept, Systems, and Mechanisms.

Efficient and sustainable separation of metals is gaining increasing attention, because of the essential roles of many metals in sustainable technologies for a climate-neutral society, such as rare earths in permanent magnets and cobalt, nickel, and manganese in the cathode materials of lithium-ion batteries. The separation and purification of metals by conventional solvent extraction (SX) systems, which consist of an organic phase and an aqueous phase, has limitations. By replacing the aqueous phase with other polar solvents, either polar molecular organic solvents or ionic solvents, nonaqueous solvent extraction (NASX) largely expands the scope of SX, since differences in solvation of metal ions lead to different distribution behaviors. This Review emphasizes enhanced metal extraction and remarkable metal separations observed in NASX systems and discusses the effects of polar solvents on the extraction mechanisms according to the type of polar solvents and the type of extractants. Furthermore, the considerable effects of the addition of water and complexing agents on metal separations in terms of metal ion solvation and speciation are highlighted. Efforts to integrate NASX into metallurgical flowsheets and to develop closed-loop solvometallurgical processes are also discussed. This Review aims to construct a framework of NASX on which many more studies on this topic, both fundamental and applied, can be built.

Zwitterionic materials with disorder and plasticity and their application as non-volatile solid or liquid electrolytes.

Zwitterionic materials can exhibit unique characteristics and are highly tunable by variation to the covalently bound cationic and anionic moieties. Despite the breadth of properties and potential uses reported to date, for electrolyte applications they have thus far primarily been used as additives or for making polymer gels. However, zwitterions offer intriguing promise as electrolyte matrix materials that are non-volatile and charged but non-migrating. Here we report a family of zwitterions that exhibit molecular disorder and plasticity, which allows their use as a solid-state conductive matrix. We have characterized the thermal, morphological and structural properties of these materials using techniques including differential scanning calorimetry, scanning electron microscopy, solid-state NMR and X-ray crystallography. We report the physical and transport properties of zwitterions combined with lithium salts and a lithium-functionalized polymer to form solid or high-salt-content liquid electrolytes. We demonstrate that the zwitterion-based electrolytes can allow high target ion transport and support stable lithium metal cell cycling. The ability to use disordered zwitterionic materials as electrolyte matrices for high target ion conduction, coupled with an extensive scope for varying the chemical and physical properties, has important implications for the future design of non-volatile materials that bridge the choice between traditional molecular and ionic solvent systems.

Effects of Ionic Liquids on the Nucleofugality of Chloride.

The nucleofugality of chloride has been measured in solvent mixtures containing ionic liquids for the first time, allowing reactivity in these solvents to be put in context with molecular solvents. Using well-described electrofuges, solvolysis rate constants were determined in mixtures containing different proportions of ethanol and the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; the different solvent effects observed as the mixture changed could be explained using interactions of the ionic liquid with species along the reaction coordinate, determined using temperature dependent kinetic studies. The solvolysis data allowed determination of the nucleofugality of chloride in these mixtures, which varied with the proportion of salt in the reaction mixture, demonstrating quantitatively the importance of the amount of ionic liquid in the reaction mixture in determining reaction outcome. Nucleofugality data for chloride were determined in seven further ionic liquids, with the reactivity shown to vary over more than an order of magnitude. This outcome illustrates that the components of the ionic liquid are critical in determining reaction outcome. Overall, this work quantitatively extends the understanding of solvent effects in ionic liquids and demonstrates the potential for such information to be used to rationally select an ionic liquid to control reaction outcome.

Influence of Polymer Gate Dielectric on Organic Field‐Effect Transistors: Interdependence of Molecular Weight, Solvent Polarity, and Surface Energy—A Case Study with PMMA and Pentacene

AbstractThe semiconductor/dielectric interface controls the performance of organic field‐effect transistors (OFETs). Herein, the influence of both the molecular weight and the polarity of the solvent of a poly(methyl methacrylate) (PMMA)‐based gate dielectric on the performance of pentacene OFETs is systematically investigated, by studying surface energy, surface roughness, morphology, leakage current, and capacitance of the dielectric. Various existing views on the role of the surface energy are considered while deriving a correlation. Larger pentacene grains are observed when the film is grown on high molecular weight‐PMMA films cast from high dipole moment‐solvent. The electrical properties of the corresponding OFETs show great improvement compared to those of OFETs fabricated with low molecular weight‐PMMA film as the gate dielectric, irrespective of the solvent. The authors attribute this enhanced performance to the increased surface energy of the polymeric dielectric which turns out to be a strong function of its molecular weight and the dipole moment of the solvent. Bias‐stress measurements on the OFETs confirm this correlation.

Advances in environmentally-friendly organic thermoelectric and organic thin-film transistor materials

<p indent=0mm>Organic semiconductors (OSCs) are significant systems of next-generation optoelectronic materials, which are widely applied in flexible devices, power generation and sensors. However, most of the organic semiconductors are prepared in chlorinated solvents which are harmful to human health and ecological environment. Nowadays, accompanied with the trends of environmentally-friendly optoelectronics, the OSCs processed with green solvents attracted extensive attention and developed rapidly. In this article, we reviewed the advances in environmentally-friendly OSCs in molecular design, solvent selection and processing method. The application of those materials in organic thin-film transistor and organic thermoelectric devices was highlighted. Finally, challenges and perspectives of the environmentally-friendly OSCs are also summarized.

Bulk and interfacial nanostructure and properties in deep eutectic solvents: Current perspectives and future directions

Deep eutectic solvents (DESs) are a tailorable class of solvents that are rapidly gaining scientific and industrial interest. This is because they are distinct from conventional molecular solvents, inherently tuneable via careful selection of constituents, and possess many attractive properties for applications, including catalysis, chemical extraction, reaction media, novel lubricants, materials chemistry, and electrochemistry. DESs are a class of solvents composed solely of hydrogen bond donors and acceptors with a melting point lower than the individual components and are often fluidic at room temperature. A unique feature of DESs is that they possess distinct bulk liquid and interfacial nanostructure, which results from intra- and inter-molecular interactions, including coulomb forces, hydrogen bonding, van der Waals interactions, electrostatics, dispersion forces, and apolar-polar segregation. This nanostructure manifests as preferential spatial arrangements of the different species, and exists over several length scales, from molecular- to nano- and meso-scales. The physicochemical properties of DESs are dictated by structure–property relationships; however, there is a significant gap in our understanding of the underlying factors which govern their solvent properties. This is a major limitation of DES-based technologies, as nanostructure can significantly influence physical properties and thus potential applications. This perspective provides an overview of the current state of knowledge of DES nanostructure, both in the bulk liquid and at solid interfaces. We provide definitions which clearly distinguish DESs as a unique solvent class, rather than a subset of ILs. An appraisal of recent work provides hints towards trends in structure–property relationships, while also highlighting inconsistencies within the literature suggesting new research directions for the field. It is hoped that this review will provide insight into DES nanostructure, their potential applications, and development of a robust framework for systematic investigation moving forward.

Novel room temperature ionic liquids and low melting mixtures based on imidazolium: Cheap ionic solvents for chemical and biological applications

Novel protic ionic liquids (PILs) and low melting mixtures (LMMs) have been synthesized based on green components, cheap sources, the high purity, and easy way of preparation. PILs include [Im][For], [Im][Ace], [Im][Pro], [Im][But], and [Im][Pen]. LMMs include [ImCl][EG], [ImCl][Gly], [ImCl][PEG], [ImCl][ETA], and [ImCl][carbohydrate] + DMSO. These solvents contain imidazolium/imidazolium chloride as a cation/salt. NMR spectroscopy was used to analyze the structures of solvents. Melting points, and thermal stabilities were measured via thermal analyses. We were looking to synthesize new DESs with imidazolium chloride (ImCl); Due to lack of observation the melting points for mixtures of ImCl + hydrogen bond donors (HBDs), these mixtures were called low melting mixtures (LMMs) in this work. The mixtures of PILs/LMMs with molecular solvents showed good implications for homogenous and heterogenous systems which can be used for separation goals. Solubilities of carbohydrates, and some amino acids were tested in pure and mixed of ILs with molecular liquids. Adding DMSO to ILs/LMMs increased the dissolution of carbohydrates. As well, adding water to ILs had a remarkable effect for increasing the solubility of amino acids.

Evaluating pediatric and adult simulated fluids solubility: Abraham solvation parameters and multivariate analysis

PurposeTo understand drug solubilization as a function of age and identify drugs at risk of altered drug solubility in pediatric patients. To assess the discrimination ability of the Abraham solvation parameters and age-related changes in simulated media composition to predict in vitro drug solubility differences between pediatric and adult gastrointestinal conditions by multivariate data analysis.MethodsDifferences between drug solubility in pediatric and adult biorelevant media were expressed as a % pediatric-to-adult ratio [Sp/Sa (%)]. Solubility ratios of fourteen poorly water-soluble drugs (2 amphoteric; 4 weak acids; 4 weak bases; 4 neutral compounds) were used in the analysis. Partial Least Squares Regression was based on Abraham solvation parameters and age-related changes in simulated gastrointestinal fluids, as well as their interactions, to predict the pediatric-to-adult solubility ratio.ResultsThe use of Abraham solvation parameters was useful as a theory-informed set of molecular predictors of drug solubility changes between pediatric and adult simulated gastrointestinal fluids. Our findings suggest that the molecular solvation environment in the fasted gastric state was similar in the pediatric age-groups studied, which led to fewer differences in the pediatric-to-adult solubility ratio. In the intestinal fasted and fed state, there was a high relative contribution of the physiologically relevant surfactants to the alteration of drug solubility in the pediatric simulated conditions compared to the adult ones, which confirms the importance of an age-appropriate composition in biorelevant media.ConclusionStatistical models based on Abraham solvation parameters were applied mostly to better understand drug solubility differences in adult and pediatric biorelevant media.

Ionic Liquid for Perovskite Solar Cells: An Emerging Solvent Engineering Technology

ConspectusPerovskite solar cells (PSCs) have, in recent years, become one of the most in-depth photovoltaic materials in many different disciplines due to their long-range charge carrier diffusion lengths, strong light absorption, easy tuning of the band gaps, low defect density, and solution processability. The power conversion efficiency (PCE) of single-junction PSCs has reached a certified value of 25.5%, which has caught up with or even surpassed traditional photovoltaic technologies, such as silicon (Si) solar cells, thin film solar cell, etc. In addition to the performance of PSCs comparable to traditional photovoltaic technology, its biggest feature is that it can be prepared by a solution method. The preparation process of the solution method simplify the film preparation process and greatly reduce the preparation cost. In addition, the solution method provides a favorable option for the energy supply of flexible wearable devices in the future.At present, the preparation of PSCs mainly uses organic molecular solvents, including N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and their mixed solvents. However, most of these commonly used organic solvents are unsafe and are likely to cause water and soil pollution, harm to the human body, and safety accidents. In addition, most solvents have a high coordination number, which limits the crystallization of perovskite. Furthermore, high-quality perovskite films require the introduction of a large amount of high boiling point, polar and aprotic antisolvents to assist crystallization, such as chlorobenzene, ether, and ethyl acetate. In addition to the toxicological problems of the antisolvent, the technology has a relatively narrow operating time window, relatively high operating environment requirements, and relatively low repeatability, which greatly limits the large-scale production of PSCs. Therefore, It is very necessary to develop a new solvent engineering technology for PSCs, which is green and pollution-free, is a simple process, and has high efficiency, long-term stability, and low cost. Recently, we have developed a series of ionic liquids, including MAAc, MAFa, BAAc, etc., which can be used as solvents to prepare efficient and stable PSCs. It allows the production of smooth and continuous polycrystalline perovskite thin films in ambient air through a simple spin coating methodIn this Account, we started with the discovery of ionic liquids as solvents to PSCs. We have proposed new strategies for improving and enhancing ionic liquid-based PSCs, including interface engineering, solvent engineering, and additive engineering. Furthermore, the stable and efficient mechanism of ionic liquid-based perovskite solar cells has been revealed. In view of the designable characteristics of ionic liquids, some functional ionic liquids have been designed and applied to different systems of halide perovskites, which has important guiding significance for the development of more functional ionic liquids for PSCs. Finally, the challenges and future directions of ionic liquid-based PSCs from both large-scale production and technological perspectives are proposed to provide a new method for the commercialization of PSCs.

Expanding the Structural Diversity and Functional Scope of Diphenylalanine-Based Peptide Architectures by Hierarchical Coassembly.

Modulation of the structural diversity of diphenylalanine-based assemblies by molecular modification and solvent alteration has been extensively explored for bio- and nanotechnology. However, regulation of the structural transition of assemblies based on this minimal building block into tunable supramolecular nanostructures and further construction of smart supramolecular materials with multiple responsiveness are still an unmet need. Coassembly, the tactic employed by natural systems to expand the architectural space, has been rarely explored. Herein, we present a coassembly approach to investigate the morphology manipulation of assemblies formed by N-terminally capped diphenylalanine by mixing with various bipyridine derivatives through intermolecular hydrogen bonding. The coassembly-induced structural diversity is fully studied by a set of biophysical techniques and computational simulations. Moreover, multiple-responsive two-component supramolecular gels are constructed through the incorporation of functional bipyridine molecules into the coassemblies. This study not only depicts the coassembly strategy to manipulate the hierarchical nanoarchitecture and morphology transition of diphenylalanine-based assemblies by supramolecular interactions but also promotes the rational design and development of smart hydrogel-based biomaterials responsive to various external stimuli.

Benchmarking Free Energy Calculations in Liquid Aliphatic Ketone Solvents Using the 3D-RISM-KH Molecular Solvation Theory

The three-dimensional reference interaction site model of the molecular solvation theory with the Kovalenko–Hirata closure is used to calculate the free energy of solvation of organic solutes in liquid aliphatic ketones. The ketone solvent sites were modeled using a modified united-atom force field. The successful application of these solvation models in calculating ketone–water partition coefficients of a large number of solutes supports the validation and benchmarking reported here.

Phase-separation of cellulose from ionic liquid upon cooling: preparation of microsized particles

Cellulose is an historical polymer, for which its processing possibilities have been limited by the absence of a melting point and insolubility in all non-derivatizing molecular solvents. More recently, ionic liquids (ILs) have been used for cellulose dissolution and regeneration, for example, in the development of textile fiber spinning processes. In some cases, organic electrolyte solutions (OESs), that are binary mixtures of an ionic liquid and a polar aprotic co-solvent, can show even better technical dissolution capacities for cellulose than the pure ILs. Herein we use OESs consisting of two tetraalkylphosphonium acetate ILs and dimethyl sulfoxide or γ-valerolactone, as co-solvents. Cellulose can be first dissolved in these OESs at 120 °C and then regenerated, upon cooling, leading to micro and macro phase-separation. This phenomenon much resembles the upper-critical solution temperature (UCST) type thermodynamic transition. This observed UCST-like behavior of these systems allows for the controlled regeneration of cellulose into colloidal dispersions of spherical microscale particles (spherulites), with highly ordered shape and size. While this phenomenon has been reported for other IL and NMMO-based systems, the mechanisms and phase-behavior have not been well defined. The particles are obtained below the phase-separation temperature as a result of controlled multi-molecular association. The regeneration process is a consequence of multi-parameter interdependence, where the polymer characteristics, OES composition, temperature, cooling rate and time all play their roles. The influence of the experimental conditions, cellulose concentration and the effect of time on regeneration of cellulose in the form of preferential gel or particles is discussed.Graphical abstractRegular micro-sized particles regenerated from a cellulose-OES mixture of tetrabutylphosphonium acetate:DMSO (70:30 w/w) upon cooling

A molecular solvation theory simulation of liquid alkyl esters of acetic acid with the 3D Reference Interaction Site Model

The liquid states of three aliphatic esters, viz. methyl-, ethyl-, and n-butyl-acetate are modeled using the three-dimensional reference interaction site model with the Kovalenko-Hirata closure in combination with the united atom AMBER force field. The distributions of different solvent sites were compared with those obtained from all-atom molecular dynamics simulations. The possibility of existence of dimeric and tetrameric clusters in liquids were explored using the dispersion corrected density functional theory. The molecular solvation theory showed good accuracy in solvation free energy calculations and in ester to water partition coefficient calculations for a large set of organic compounds.