Solvatochromic Parameters Research Articles

Physics-informed machine learning to predict solvatochromic parameters of designer solvents with case studies in CO2 and lignin dissolution

The polarity of solvents plays a critical role in various research applications, particularly in their solubilities. Polarity is conveniently characterized by the Kamlet-Taft parameters i.e., the hydrogen bonding acidity (α), basicity (β), and the polarizability (π*). Obtaining Kamlet-taft parameters is very important for solvents namely ionic liquids (ILs) and deep eutectic solvents (DESs). However, given the unlimited theoretical number of combinations of ionic pairs in ILs and hydrogen-bond donor/acceptor pairs in DESs, experimental determination of their Kamlet-Taft parameters is impractical. To address this, the present study developed two different machine learning (ML) algorithms to predict Kamlet-Taft parameters for designer solvents using quantum chemically derived input features. The ML models developed in the present study showed accurate predictions with high R2 and low RMSE values. Further, in the context of present interest in the circular bioeconomy, the relationship between the basicities and acidities of designer solvents and their ability to dissolve lignin and carbon dioxide (CO2) is discussed. Our method thus guides the design of effective solvents with optimal Kamlet-Taft parameter values dissolving and converting biomass and CO2 into valuable chemicals.

Preparation and characterization of novel polyols-based DESs and their use in efficient sequestration of radioactive iodine

The utilization of Novel DESs can be greener alternative to traditional organic solvents. In present study, four polyols-based DESs are synthesized and characterized by several techniques. The prepared DESs are used for the efficient capture of hazardous iodine. In present study by simple combination of two readily accessible, economical, and biodegradable components four polyols-based DESs have been prepared. For the creation of these DESs, a hydrogen bond donors (HBDs) (polyols) and hydrogen bond acceptors (HBAs) (BTEAC) are used, which havemelting points far lower than their respective melting points. The developed DESs were investigated for their physicochemical properties such as density, dynamic viscosity. Our results revealed distinct trends in these properties across different DES compositions, highlighting unique molecular interactions and solvation capabilities. The FTIR and NMR characterization study indicated considerable intermolecular interaction between the various component of the DES system. Further, Kamlet-Taft solvatochromic parameters were determined using Nile red dye, and other solvatochromic dyes. For synthesized DESs, the solvatochromic parameters ENT, normalized polarity parameter, π*, polarity / polarizability; β, hydrogen-bond acceptor basicity and α, hydrogen-bond donor acidity, have been determined. The ENT parameters demonstrate that both non-specific and specific interactions play a significant role in solute–solvent interactions. The synthesized DESs have been utilized for the efficient capture of the iodine. The removal efficiency of DES depends upon the mass of the DESs taken and time duration. These findings deepen our understanding of DES behavior and underscore their versatility in diverse industrial and scientific applications.

On the"Staple" Effect in the d-Glucose Acetylation by Choline-Chloride Ethylene Glycol and Choline-Chloride Urea Deep Eutectic Solvents.

This work employs hybrid quantum mechanics molecular mechanics simulations coupled with an umbrella sampling technique to investigate the acetylation of d-glucose with acetic anhydride in two deep eutectic solvents (DESs): choline-chloride ethylene glycol (ChCl/Etg) and choline-chloride urea (ChCl/U). The reaction proceeds spontaneously, with activation free energy barriers of 18.19 ± 0.15 and 19.83 ± 0.15 kcal/mol for ChCl/Etg and ChCl/U, respectively. These values align with literature data for similar reactions in ionic liquids, highlighting the potential of DESs as green reaction media for wood modifications, while minimizing lignocellulosic matrix degradation. Energy pair distribution analysis, radial distribution functions, and noncovalent interactions reveal a more solvated transition state compared to the initial reactant state within ChCl/Etg, facilitating the acetylation reaction. Interestingly, combined distribution function analysis unveils a "staple" effect in both solvents, potentially hindering efficient product separation. The work further explores hydrogen bond networks and Kamlet-Taft solvatochromic parameters to elucidate the role of solvents in the reaction mechanism. It was observed that a notable decrease in activation energy is accompanied by increasing net basicity, along with a reduction in the "staple" effect. This suggests that solvent parameters could serve as an effective screening tool for identifying novel and efficient DESs for wood modifications.

A designed ZrOCl2/ethylene glycol deep eutectic solvent for efficient lignocellulose valorization

Deep eutectic solvents (DESs) hold great potential in biorefining because they can efficiently deconstruct the recalcitrant structure of lignocellulose. In particular, inorganic salts with Lewis acids have been proven to be effective at cleaving lignin–carbohydrate complexes. Herein, a Zr-based DES system composed of metal chloride hydrate (ZrOCl2·8H2O) and ethylene glycol (EG) was designed and used for poplar powder pretreatment. Zr4+-based salts provide sufficient acidity for lignocellulose depolymerization. The acidity of the DES was analysed by the Kamlet-Taft solvatochromic parameter, and the results demonstrated that the acidity can be regulated by the DES composition. Under the optimum conditions (ZrOCl2·8H2O:EG molar ratio of 1:2), the DES pretreatment removes nearly 100 % hemicellulose and 94.7 % lignin. The recovered lignin exhibited a low polydispersity of 1.7. The cellulose residues deliver an efficiency of 94.4 % upon enzymatic digestion. Moreover, the DES can be easily recovered with high yield and purity, and the recycled DES still maintains high delignification and enzymatic hydrolysis efficiencies. The proposed DES pretreatment technology is promising for biomass valorization.

Cellulose aerogel beads and monoliths from CO2-based reversible ionic liquid solution

The CO2-based reversible ionic liquid solution of 1,1,3,3-tetramethylguanidine (TMG) and ethylene glycol (EG) in dimethyl sulfoxide (DMSO) after capturing CO2, (2[TMGH]+[O2COCH2CH2OCO2]2−/DMSO (χRILs = 0.1), provides a sustainable and effective platform for cellulose dissolution and homogeneous utilization. Highly porous cellulose aerogel beads and monoliths were successfully prepared via a sol-gel process by extruding cellulose solution into different coagulation baths (NaOH aqueous solution or alcohols) and exposing the cellulose solution in open environment, respectively, and followed by different drying techniques, including supercritical CO2-drying, freeze-drying and air-drying. The effect of the coagulation baths and drying protocols on the multi-scale structure of the as-prepared cellulose aerogel beads and monoliths were studied in detail, and the sol-gel transition mechanism was also studied by the solvatochromic parameters determination. High specific surface area of 252 and 207 m2/g for aerogel beads and monoliths were achieved, respectively. The potential of cellulose aerogels in dye adsorption was demonstrated.

Experimental and Computational Kinetic Assessment of Ruthenium (III) Catalyzed Oxidation of Paracetamol by Hexacyanoferrate(III): A Mechanistic Pathway

AbstractThe ruthenium (III) catalyzed redox reaction of paracetamol with hexacyanoferrate (III) in an acidic medium has been investigated. The reaction shows fractional order dependence respecting paracetamol and first‐order dependence respecting the oxidant and ruthenium (III). It is enhanced by medium according to the equation kobs=a+b[H+]. The activation and thermodynamic parameters of the reaction have been estimated using the Arrhenius and Eyring equations. The oxidation product of paracetamol has been identified as quinone oxime through spectral analysis. Furthermore, the reaction has been examined in nine various organic solvents, and the solvents effect has been investigated by Taft's and Swain's multiparametric equations. The rate constants have been found to correlate well with Kamlet‐Taft's solvatochromic parameters (α, β, π*). The reaction constants have been found to be negative, suggesting that the reactivity is influenced mainly by the solute‐solvent interactions. On the basis of kinetic results, a plausible reaction mechanism has been proposed. The proposed mechanism is reinforced by additional evidence from density functional theory (DFT) computations conducted at b3lyp/6‐311*G (d,p) level, which demonstrate that the activation energy barriers align with the reactivity trend observed in the kinetics experiments. Therefore, these computational results provide further support for the proposed mechanism.

Study of the Ternary Mixture of Methanol/Formamide/Acetonitrile via Solvatochromic Probes.

Following previous studies, the ternary mixture of methanol/formamide/acetonitrile (MeOH/Formamide/MeCN) was studied using the UV-Vis absorption spectra at 298.15 K with a set of five probes, 4-nitroaniline, 4-nitroanisole, 4-nitrophenol, N,N-dimethyl-4-nitroaniline and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio)phenolate (Reichardt betaine dye), for a total of 22 mole ternary fractions. In addition, nine mole fractions of the underling binary mixtures, MeOH/Formamide and Formamide/MeCN were also tested. Spectroscopic results were used to model the preferential solvation order for each probe in the mixtures. The Kamlet-Taft solvatochromic solvent parameters, α, β, and π*, were also computed through the use of the solvatochromic shifts of the five probe indicators. Moreover, discrepancies in the spectroscopic behavior of 4-nitrophenol in formamide-rich mixtures were observed and analyzed.

Ether-type co-solvents of excellence for aqueous base-free Pt-catalyzed oxidation of concentrated 5-(hydroxymethyl)furfural to 2,5-furandicarboxylic acid

The biomass-derived 5-(hydroxymethyl)furfural (5-HMF) is readily converted in water to 2,5-furandicarboxyl acid (FDCA) that is well known as a renewable diacid monomer. However, the limited solubility of FDCA in water posed serious challenges to process development. Herein, the base-free Pt-catalyzed oxidation of 5-HMF was explored in aqueous binary solvent systems containing organic co-solvents such as dimethyl sulfoxide, N,N-dimethylformamide, gamma-valerolactone, dioxane, diethylene glycol dimethyl ether, and 1,2-dimethoxyethane (DME). The FDCA solubility and 5-HMF oxidation performance were investigated in co-solvent/H2O systems with different co-solvent fractions. When correlated with the solvatochromic parameters of co-solvents, the FDCA yield appeared to be in harmony with their polarizability and hydrogen bonding acceptance ability. Thus, infrared spectra were collected with three systems such as co-solvent/H2O, 5-HMF in co-solvent, and 5-HMF in co-solvent/H2O. The employed co-solvent was found to have different abilities to interact with the O–H and C=O moieties of 5-HMF via H-bonding and dipole-induced dipole attraction (related with the polarizability), respectively. Consequently, a high FDCA yield was achieved using three ether-type co-solvents in which these interactions are relatively weak. In a continuous-flow pattern for the base-free oxidation of 3 wt% 5-HMF solution, a FDCA yield of >98 % was achieved with 60 wt% DME/H2O under the optimized conditions.

Determination of Hansen Solubility Parameters of Raw Muscovite

AbstractMuscovite has been used increasingly as a substrate in flexible electronics and fillers in high-performance nanocomposites. Muscovite-based interfacial interactions play a crucial rule in material fabrication. Hansen solubility parameters (HSPs) have proven useful in characterizing molecular interactions within/between condensed phases. The present study aimed to determine the HSPs of raw muscovite (RM) and to investigate solvent dispersion mechanisms of RM. To achieve this, the solubilities of RM in 17 solvents were evaluated by dispersion tests, and the HSPs of RM were calculated as the center of the optimal solubility rotated-ellipsoid in HSP space, which included all good solvents, had the smallest number of outliers, and had the smallest volume. The resulting dispersion, polar, and hydrogen bonding components of RM were 18.301, 2.366, and 3.727 MPa1/2, respectively. By considering the HSPs and Kamlet-Taft's solvatochromic parameters of solvents, we concluded that the low polarity of RM is due to hindered K+/H+ exchange on the RM surface, resulting from limited water/moisture contact. For solvent dispersion of RM, essential conditions include strong dispersion forces and weak polar forces, finely tuned to match the surface property of RM at a certain hydration level. The HSPs of RM determined from dispersion tests were restricted to predicting/characterizing RM-based interfacial phenomena in an environment with strictly controlled water/moisture content. The HSP calculation method proposed herein was applicable to any clay mineral.

Use of green analysis methods to determine the ionization constant values of isoxazolyl penicillins

In this study, an environmentally friendly analysis of penicillinase-resistant antibiotics oxacillin, dicloxacillin, and cloxacillin was carried out by liquid chromatography methods using ethanol solvent that is not harmful to human health and the environment. Ionization constant (wwpKa) values of isoxazolyl penicillins in ethanol–water binary mixtures containing 20–35% (v/v) ethanol at 37 °C were obtained by green reverse phase liquid chromatography and micellar liquid chromatography methods known as green chromatography. The developed methods are based on a model that relates the chromatographic behavior of the identified analytes to pH. The linear relationship between the microscopic solvatochromic parameter ETN and the retention values of the compounds was determined depending on the change of organic solvent in the mobile phase. Using the obtained chromatographic data, conditions that ensure the simultaneous separation of the compounds for both methods were determined. The relationship between the calculated sspKa values and the macroscopic properties of ethanol was investigated. The agreement between the pKa (wwpKa) values in the water medium determined by this approach was determined by t-test at a 95% confidence level for both methods. The wwpKa values of the compounds at 25 °C were also estimated using Abraham solute parameters without any experimental work.

Comparative study on the physicochemical properties of N-SO3H functionalized ammonium and imidazolium ionic liquids

Twelve N-SO3H functionalised ammonium and imidazolium based Brønsted acidic ionic liquids were synthesised by varying four anions (Cl-, CF3COO-, BF4- and OTf-). They were characterised using various spectroscopic techniques. A detailed study on Brønsted acidity, thermal stability, conductivity, density, polarity, and electrochemical window of the ionic liquids (ILs) was carried out to analyse the effects of different cations and anions. The conductivity of these ILs in molecular solvents (MeOH, MeCN and acetone) were measured at a particular mole fraction (XIL = 0.001) of the ILs and the results were correlated with Kamlet-Taft solvatochromic parameters (ETN, α, β) of the solvents. Their Brønsted acidity order was determined using the Hammett plots. The polar nature of synthesized ionic liquids was studied by taking fluorescence emission spectrum of pyrene as a probe molecule in two illustrative 2-ethyl-1,3-disulfoimidazolium ionic liquids. The electrochemical stabilities of twelve ILs in the same molecular solvents were determined by Cyclic Voltammetry. The results revealed highest electrochemical stability window for the imidazolium ILs in acetone. Among the four types of anions, the ionic liquids of CF3COO- and Cl- anions were found to be thermally stable up to 250–260 °C as compared to the ionic liquids of BF4- and OTf- anions.

Investigation of physical and electrochemical behaviour of N-sulfonic acid functionalized cyclic-ammonium based Brӧnsted acidic ionic liquids in molecular solvents

Two types of six Brӧnsted acidic ionic liquids of N-SO3H tethered cyclic ammonium cations (five, six and seven membered) with four anions namely [AcO]−, [HSO4]−, [BF4]−, [PF6]− were synthesized to evaluate their physical and electrochemical behavior in polar solvents (water, MeOH & CH3CN) using conductivity and Cyclic Voltammetry techniques. Their comparative Brönsted acidic orders were determined using UV–visible Hammett plots. Except the ionic liquid of [PF6]− anion with N,N-disulfopiperidinium cation, the thermal stabilities of other ionic liquids found within 230–250 °C. Solvent dependent aggregative nature was observed in polar solvents for the ionic liquids at a particular temperature and concentration. Their aggregative properties were also evidenced by comparison of experimental and computed chemical shift values of additional acidic protons of 1H NMR spectra. Kamlet-Taft solvatochromic parameters of molecular solvents (ETN, α, β) were correlated with their observed conductivities. Piperidinium ionic liquids showed wider electrochemical windows (2.99 V to 2.55 V) in acetonitrile as compared to other cyclic ammonium ionic liquids in polar solvents.

Sorption property, excess enthalpy, and solvatochromic parameters of choline lactate

Sorption properties, including isotherm shape, adsorption energy, maximum uptake, and cyclic hydrothermal stability, have a significant influence on the optimization of absorbents for diverse desiccant air conditioning systems. The sorption behavior of the water/choline lactate ([ch][lac]) pair was examined using a dynamic vapor sorption (DVS) analyzer. Data analysis identified type-III isotherms. The Dubinin-Astakhov (D-A) formulation, defined by a temperature-independent Polani potential, was successfully applied to the sorption equilibrium curve. The Kamlet-Taft polarity parameters were tested using solvatochromic probes with a UV/Vis spectrophotometer. Multivariate regression analysis was performed to correlate the water affinity coefficient of the D-A model with the Kamlet-Taft polarity parameters using linear solvation energy relationships (ISERs). The solvatochromic parameter of dipolarity/palarizability (π*) had a positive contribution to the water affinity coefficient of ionic liquid (IL) desiccants, and the general trend of influence was hydrogenbondacidity(α)>π*>hydrogenbondbasicity(β). Excess enthalpies were correlated well with solvatochromic parameters. The differential enthalpies and entropies, first virial coefficient (A0), and isosteric enthalpies of sorption at zero surface coverage were also discussed. The enthalpy of activation at zero surface coverage was deduced from sorption kinetics. The hydrothermal cyclic stabilities and ambient regenerabilities were determined by cycle stress tests.

Is it possible to correlate various physicochemical properties of Natural Deep eutectic systems in order to predict their behaviours as solvents?

The classification of Natural Deep Eutectic Systems (NADES) as promising alternative solvents for the 21st century has been reported. Although this is mainly due to their very interesting characteristics that have attracted the attention of the scientific community, there is, however, a lack of information regarding many physicochemical properties of these compounds. Therefore, the main objective of this work was to characterize and relate the properties, both of hydrophilic and hydrophilic NADES, regarding their water content, density, viscosity, refractive index, dielectric constant, dipole moment, surface tension, as well solvatochromic parameters. Comparatively to the set of organic solvents also explored, it was observed that for these parameters studied, the values of hydrophilic systems are mostly higher than those of organic solvents, which in turn tend to be higher than those of hydrophobic systems. Moreover, the analysis of solvatochromic parameters (polarity and Kamlet-Taft parameters) provided new evidence for the usefulness of NADES as potential substitute solvents for sustainable development. Finally, regarding the general list of compounds, it was proved with statistical parameters (Pearson correlation coefficient and p-value) that most of the studied properties are strong and significantly correlated with each other.

Mechanistic insights into the lignin dissolution behavior in amino acid based deep eutectic solvents

Deep eutectic solvents (DESs) composed by amino acids (L-arginine, L-proline, L-alanine) as the hydrogen bond acceptors (HBAs) and carboxylic acids (formic acid, acetic acid, lactic acid, levulinic acid) as hydrogen bond donors (HBDs) were prepared and used for the dissolution of dealkaline lignin (DAL). The mechanism of lignin dissolution in DESs was explored at molecular level by combining the analysis of Kamlet-Taft (K-T) solvatochromic parameters, FTIR spectrum and density functional theory (DFT) calculations of DESs. Firstly, it was found that the formation of new hydrogen bonds between lignin and DESs mainly drove the dissolution of lignin, which were accompanied by the erosion of hydrogen bond networks in both lignin and DESs. The nature of hydrogen bond network within DESs was fundamentally determined by the type and number of functional groups in both HBA and HBD, which affected its ability to form hydrogen bond with lignin. One hydroxyl group and carboxyl group in HBDs provided active protons, which facilitated proton-catalyzed cleavage of β-O-4, thus enhancing the dissolution of DESs. The superfluous functional group resulted in more extensive and stronger hydrogen bond network in the DESs, thus decreasing the lignin dissolving ability. Moreover, it was found that lignin solubility had a closed positive correlation with the subtraction value of α and β (net hydrogen donating ability) of DESs. Among all the investigated DESs, L-alanine/formic acid (1:3) with the strong hydrogen-bond donating ability (acidity), weak hydrogen-bond accepting ability (basicity) and small steric-hindrance effect showed the best lignin dissolving ability (23.99 wt%, 60 °C). On top of that, the value of α and β of L-proline/carboxylic acids DESs showed some positive correlation with the global electrostatic potential (ESP) maxima and minima of the corresponding DESs respectively, indicating the analysis of ESP quantitative distributions of DESs could be an effective tool for DESs screening and design for lignin dissolution as well as other applications.

Synthesis, spectroscopic, and structural studies of substituent effect on the solvatochromic, tautomeric, and halochromic behavior of 2-methylated arylazoquinoline dyes along with DFT calculations

Six methylated heteroarylazo quinoline dyes with different electron-withdrawing/donating substituents, namely 5-(4-substituted arylazo)-8-hydroxy-2-methyl quinoline dyes, were synthesized by coupling reaction and their chemical structures were elucidated by conventional spectroscopic methods. The photophysical properties of the dyes were examined and systematically compared in a range of solvents of various solvatochromic parameters and at various pH values through UV–Vis spectroscopy. 2-methylated arylazoquinoline dye (the unsubstituted dye) was prepared and chosen for comparison purposes. The dyes show different chromic behavior including tautomerism, solvatochromism, ionochromism, and halochromism. The chromic and azo/hydrazone tautomeric properties of the dyes were found to depend on the substituent nature, solvent polarity/polarizability, and the acidity/basicity of the solvent environment. The Kamlet-Abboud-Taft, Katritzky, and Catalán linear solvation energy relationships (LSER) were used to correlate the dye spectral data. The acid-base equilibria between neutral and anionic forms of the dyes were studied in buffer solutions in a range of pH 1.0–13.0 and the ionization constants,pKa, were determined. Finally, the DFT calculations on the studied compounds provide an overall supportive and complementary picture of the spectral measurements of representative structure of the azo model.

Spectroscopic study of solvent effects on the electronic absorption spectra of morpholine and its complexes

The electronic absorption spectra of morpholine and its five morpholine complexes have been studied in different solvents of various polarities. The regression and correlation coefficients have been calculated with the SPSS program. Solvation energy relationships were deduced from spectral shifts and correlated with solvent parameters α (solvent hydrogen bond donor acidity), β (solvent hydrogen bond acceptor basicity), and π* (dipolarity/polarizability). The percentage contributions of the calculated solvatochromic parameters show that classic solvation effects play a major role in explaining the spectral shifts in all investigated complexes. The blue shift of [Fe(MOR)3Cl3]·4H2O, [Ni(MOR)4Cl2]·4H2O, and [Cu(MOR)4Cl2]·6H2O complexes is due to the formation of hydrogen bonds, which suggests the stabilization of the ground electronic state compared with the excited state. [CuNi(MOR)2Cl4]·4H2O and [CuZn(MOR)3Cl4]·2H2O are mixed metal complexes that suffer a red shift due to the solute-solvent interactions, which causes stabilization of the excited solute state with increasing solvent polarity. The bands are affected by specific solute-solvent interactions including hydrogen bond donor ability (acidity) and hydrogen bond acceptor ability (basicity) and nonspecific solute-solvent interactions including electromagnetic interaction between the dipole moments of solute and polar solvents.

Dissolution kinetics of cellulose in ionic solvents by polarized light microscopy

Aiming to increase the scarce information available on the kinetics of cellulose dissolution, we have applied an image-assisted technique based on the luminance evolution as cellulose dissolves to study this process under different experimental conditions. This protocol was validated via direct determination of the cellulose dissolved. In all cases datapoints were linearly fitted assuming a pseudo-zero order reaction which facilitates the comparison between datasets. To study the solvent effect we have used three ionic liquids with large basicity and found significantly different rates of dissolution, from faster to slower: [C_2C_1Im][OAc]>[C_1C_1Im][DMP]>[C_2C_1Im][DEP]. Solvatochromic parameters and viscosity of the solvent media were determined and the latter was identified as a key factor slowing the process as it reduces ionic mobility. The weight of viscosity was estimated by removing the viscosity effect with a tuned solvent media doped with DMSO. Activation energy was 70% lower at constant viscosity. On the substrate side, particle size is the main factor affecting the dissolution rate. All samples were milled to homogenise the starting material and minimise the distortions caused by the size distribution. After, dissolution of three cellulose substrates under the same experimental conditions was analysed. Dissolution of natural fibers took twice as long as dissolving pulp which dissolves slower than lyocell fibers. This trend correlates with the roughness of the samples obtained by optical perfilometry which is consistent with the dissolution mechanism proposed in the literature.Graphical abstract

The effect of water content on lignin solubilization in deep eutectic solvents

Highly efficient, reversible and green dissolution of lignin is still a challenge, which hinders its wide scale-up applications. In this study, amino acid-polyol deep eutectic solvents (DESs) by employing l-arginine (l-Arg) and l-proline (l-Pro) as HBA and ethylene glycol (EG) and glycerol (Gly) as HBD were prepared as well as applied for dealkaline lignin (DAL) dissolution, to explore the efficient system for lignin dissolution and unveil the solubilization mechanism. The mostly used choline chloride (ChCl) based DESs were also evaluated as controlled groups. It was found that the higher value of α (hydrogen-bond donating ability) of DESs was conducive for DAL dissolution, due to the high content of β-O-4 bond in DAL. Among all the investigated DESs at water content of 2 wt%, ChCl/LA with the highest value of α (2.35) presented the best lignin dissolving ability (29.09 wt%). The effects of water content on the lignin dissolving ability of hydrated DESs were tested and discussed detailly, from a microcosmic perspective by using Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance (1H NMR), solvatochromic parameters and quantum chemistry calculations. It was remarkable to find that added water greatly improved the mass transfer and activated the reaction sites in both l-Pro and l-Arg based DESs, thus enhancing or maintaining the lignin solubilities at high water concentrations. The hydrated l-Arg/EG DESs allowed a solubility enhancement of 3.49 and 2.16 times at 70 and 90 wt% water concentration, compared to l-Arg/EG/2 wt%H2O at 60 °C, which was environmentally friendly and economically attractive. However, the addition of water was a negative factor for ChCl based DESs, because water preferred to interact with Cl− with strong electronegativity, resulting in stronger interaction energy between hydrogen bond donors (HBD) and Ch+. This work provided a bridge connecting the microstructure and dissolving behavior of hydrated DESs, indicating that the addition of water could make DESs more versatile and flexible, thus boosting various potential applications such as gas capture, the dissolution and delivery of medicine.

Evaluation of the Polarity in Binary Liquid Mixtures as a Function of Volume Fraction

The variation of solvatochromic polarity parameters as a function of mole fraction data may not represent the realistic environment of the solvatochromic probe molecule. This is because of the fact that the solvation environment of the solvatochromic probe molecules is not only determined by the number of individual solvent molecules around it but also by the size of those individual solvent molecules. In this regard we wish to understand the variation of ET N polarity parameter of binary liquid mixtures as a fuction of volume fractions. Representation of the ET N parameter as a function of volume fraction data leads to a completely different dataset for binary liquid mixtures where water is used as one of the solvents. These mixtures usually display negative deviations from linearity for the ET N values, when ET N values are plotted as a function of mole fraction values of the solvents. On the other hand, if the ET N values are plotted as a function of volume fraction values of the solvents in binary liquid mixtures containing water, these deviations are minimized to a large extent and even reversed to the positive deviations in some of these mixtures. This study gives an insight into a long lasting problem of understanding the negative deviations of the ET N values from linearity observed in binary liquid mixtures of water, as these deviations are either minimized or reversed into positive deviations when ET N values are plotted versus volume fraction of solvents. This study opens up a whole new discussion about the solvatochromic data of the solvent mixtures, whether this data must be represented as a function of mole fraction values or as a function of volume fraction of the solvents. The representation of the solvatochromic data as a function of volume fraction of solvents might lead to new insights in studying the solute-solvent interactions in binary solvent mixtures.