Kirkwood Buff Integrals Method Research Articles

Understanding the relationship between preferential interactions of peptides in water-acetonitrile mixtures with protein-solvent contact surface area.

The influence of polar, water-miscible organic solvents (POS) on protein structure, stability, and functional activity is a subject of significant interest and complexity. This study examines the effects of acetonitrile (ACN), a semipolar, aprotic solvent, on the solvation properties of blocked Ace-Gly-X-Gly-Nme tripeptides (where Ace and Nme stands for acetyl and N-methyl amide groups respectively and X is any amino acid) through extensive molecular dynamics simulations. Individual simulations were conducted for each peptide, encompassing five different ACN concentrations within the range of χACN = 0.1-0.9. The preferential solvation parameter (Γ) calculated using the Kirkwood-Buff integral method was used for the assessment of peptide interactions with water/ACN. Additionally, weighted Voronoi tessellation was applied to obtain a three-way data set containing four time-averaged contact surface area types between peptide atoms and water/ACN atoms. A mathematical technique known as N-way Partial Least Squares (NPLS) was utilized to anticipate the preferential interactions between peptides and water/ACN from the contact surface areas. Furthermore, the temperature dependency of peptide-solvent interactions was investigated using a subset of 10 amino acids representing a range of hydrophobicities. MD simulations were conducted at five temperatures, spanning from 283 to 343K, with subsequent analysis of data focusing on both preferential solvation and peptide-solvent contact surface areas. The results demonstrate the efficacy of utilizing contact surface areas between the peptide and solvent constituents for successfully predicting preferential interactions in water/ACN mixtures across various ACN concentrations and temperatures.

Preferential Solvation of Cyclosporin in Aqueous Mixtures of Some Polymeric Cosolvents

Background: Cyclosporin is a cyclic peptide-drug used as immunosuppressant for the prophylaxisof transplant rejection whose physicochemical properties in mixed aqueous solvent systems isstill not well understood. The preferential solvation parameters of cyclosporin in aqueous binarymixtures of diethylene glycol monoethyl ether (DEGME), polyethylene glycol 200 (PEG 200) andpolyethylene glycol 400 (PEG 400) were computed. Methods: Reported mole fraction solubilities of cyclosporin in DEGME-aqueous mixtures,PEG 200-aqueous mixtures, and PEG 400-aqueous mixtures were processed by following theinverse Kirkwood-Buff integrals (IKBI) method as suggested by Marcus and Ben-Naim using somethermodynamic parameters reported in the literature for these aqueous-polymeric mixtures at298.15 K. Results: It is observed that cyclosporin is sensitive to preferential solvation effects in theseaqueous-polymeric binary solvent systems. The preferential solvation parameter by DEGME (δx1,3)is negative in water-rich mixtures but positive in mixtures of 0.12<x1<1.00. It is conjecturablethat hydrophobic hydration around the non-polar methyl and methylene groups of this drug thatcould be present in water-rich mixtures can significantly impact the drug solvation. Otherwise,in mixtures of 0.12<x1<1.00 in DEGME-aqueous mixtures, as well as in almost all the mixtureswith PEGs, the preferential solvation by polymeric cosolvents could be due to the acidic behaviorof cyclosporin in front of ether and hydroxyl oxygen atoms of these polymeric cosolvents. Conclusion: Cyclosporin is preferentially solvated by the polymeric solvents in almost all thestudied mixtures of these aqueous-polymeric binary solvent systems.

Solubility of atenolol in aqueous propylene glycol mixtures revisited: IKBI preferential solvation analysis

ABSTRACT The preferential solvation parameters of atenolol in aqueous binary mixtures of propylene glycol (PG) were derived from reported molar solubility values after conversion to mole fractions by using the inverse Kirkwood–Buff integrals method. This drug is sensitive to preferential solvation effects in this binary system. The preferential solvation parameter by PG (δx 1,3) is negative in water-rich mixtures but positive in mixtures of 0.20 < x 1 < 1.00. It is conjecturable that hydrophobic hydration around the non-polar methyl and phenylene groups of this drug observable in water-rich mixtures could play a relevant role in drug solvation. Otherwise, in mixtures of 0.20 < x 1 < 1.00, the preferential solvation by PG could be due to the acidic behaviour of atenolol.

Preferential solvation of triclocarban in N-methyl-2-pyrrolidone + water cosolvent mixtures according to the Inverse Kirkwood-Buff Integrals (IKBI) method and correlation of solubility by means of some mathematical models

Preferential solvation of triclocarban in N-methyl-2-pyrrolidone + water cosolvent mixtures according to the Inverse Kirkwood-Buff Integrals (IKBI) method and correlation of solubility by means of some mathematical models

Musk ketone solubility in binary systems ethyl acetate with methanol, ethanol, and isopropanol: preferential solvation according to the inverse Kirkwood–Buff integrals method

ABSTRACT Three co-solvent mixtures {methanol (1) + ethyl acetate (2), ethanol (1) + ethyl acetate (2), and isopropanol (1) + ethyl acetate} were used to calculate the preferred solvation parameters () of musk ketone (MK) (2). In all co-solvent mixes, values vary non-linearly with the percentage of co-solvent (1). According to the study, values are negative in mixes rich in alcohol but positive in those high in ethyl acetate. The mixtures {methanol (1) + ethyl acetate (2)} and {ethanol (1) + ethyl acetate (2)} show the most favoured solvation of MK by ethyl acetate at 298.15 K and 293.15 K, respectively. When {isopropanol (1) + ethyl acetate (2)} is combined; it is maximum at 298.15 K. Since the values are positive, MK preferentially solvates with ethyl acetate. The most significant values for x 1 = 0.18–0.40 are obtained towards the non-polar regions of MK for the three co-solvent mixes.

Research on sulfenone in four aqueous cosolvent systems at (278.15–323.15) K: solubility, modelling, hansen solubility parameter, preferential solvation and thermodynamic properties

Research on sulfenone in four aqueous cosolvent systems at (278.15–323.15) K: solubility, modelling, hansen solubility parameter, preferential solvation and thermodynamic properties

Solubility measurement of syringic acid, trans-cinnamic acid, p-coumaric acid, and vanillin constituent of Deverra DC. genus in (ethyl acetate + ethyl alcohol) mixtures: Thermodynamic modeling and preferential solvation

Solubility measurement of syringic acid, trans-cinnamic acid, p-coumaric acid, and vanillin constituent of Deverra DC. genus in (ethyl acetate + ethyl alcohol) mixtures: Thermodynamic modeling and preferential solvation

Equilibrium solubility, non-covalent interactions and solvation thermodynamics of thiamphenicol in aqueous cosolvents of n-propanol/acetone/acetonitrile

Equilibrium solubility, non-covalent interactions and solvation thermodynamics of thiamphenicol in aqueous cosolvents of n-propanol/acetone/acetonitrile

Increasing the Equilibrium Solubility of Meloxicam in Aqueous Media by Using Dimethyl Sulfoxide as a Cosolvent: Correlation, Dissolution Thermodynamics and Preferential Solvation

Meloxicam is widely prescribed as an analgesic and anti-inflammatory drug in human therapeutics. Owing the very low aqueous solubility of meloxicam, this property has been studied in dimethyl sulfoxide (DMSO)-aqueous solvent systems at several temperatures from 273.15 to 313.15 K to expand the solubility database about analgesic drugs in mixed solvents. The flask shake method followed by ultraviolet-visible (UV-vis) spectrophotometry analysis were used for meloxicam solubility determinations. A number of cosolvency models, including the Jouyban–Acree model, were challenged for solubility correlation/prediction of this drug in these mixtures. The van’t Hoff and Gibbs equations were employed to calculate the apparent standard thermodynamic quantities relative to dissolution and mixing processes. The inverse Kirkwood–Buff integral method was employed for calculating the preferential solvation parameters of meloxicam by DMSO in the mixtures. Meloxicam solubility increases with increasing temperature and maximum solubilities are observed in neat DMSO at all temperatures studied. Dissolution processes were endothermic in all cases and entropy-driven in the composition interval of 0.40 ≤ x1 ≤ 1.00. A nonlinear enthalpy–entropy relationship was observed in the plot of enthalpy vs. Gibbs energy for drug transfer processes. Meloxicam is preferentially solvated by water in water-rich mixtures but preferentially solvated by DMSO in the composition interval of 0.21 &lt; x1 &lt; 1.00.

Milrinone solubility in aqueous cosolvent solutions revisited: Inter/intra-molecular interactions, enthalpy-entropy compensation, and preferential solvation

• Intermolecular interactions and charge distribution of milrinone were studied by MEPS and HS analysis. • Solvent effect was studied via linear solvation energy relationships. • Preferential solvation were investigated via inverse Kirkwood–Buff integrals method. • Transfer and dissolution properties together with enthalpy-entropy compensation was studied. Analysis of molecular electrostatic potential surface and Hirshfeld surface were severally employed here to probe into the overall charge distribution and inter/intra-molecular interactions of milrinone. H···H and N···H contacts predominate among all contact interactions and milrinone has powerful ability of hydrogen-bonding donor and acceptor. The solubility profile of milrinone was additionally illustrated by means of three-dimensional Hansen solubility parameters. The mole fraction solubility at 298.15 K in ethanol/ethylene glycol(EG)/isopropanol/ N , N -dimethylformamide(DMF) + water was inspected in the light of molecular interactions via the well-known linear solvation energy relationships. The solubility parameter, dipolarity-polarizability and hydrogen-bonding acidity of systems presented dominant contributions to the solubility variation. The inverse Kirkwood–Buff integrals was applied to probe the local compositions of milrinone in the aqueous solutions of co-solvent. Regarding the aqueous ethanol/isopropanol/DMF solutions within middle and ethanol/isopropanol/DMF-rich mole fractions, preferential solvation of milrinone by ethanol/isopropanol/DMF was observed. Milrinone was not solvated favorably by EG molecule in above regions. The transfer and thermodynamic dissolution properties including entropy, enthalpy and Gibbs free energy change were derived. Moreover, the analysis of enthalpy-entropy compensation was carried out, stating that the milrinone solubility variation in solutions was controlled by two mechanisms, enthalpy-driven and entropy-driven.

Inter-/intra-molecular interactions, preferential solvation, and dissolution and transfer property for tirofiban in aqueous co-solvent mixtures

• Inter-/intra-molecular interactions of tirofiban solutions were studied. • KAT-LSER were used to determine the relative impact of solvent effect. • Preferential solvation were investigated via inverse Kirkwood–Buff integrals method. • Dissolution and transfer properties together with enthalpy-entropy compensation were studied. Using Hirshfeld surface, interaction region indicator and quantitative molecular surface analysis, the microscopic electrostatic features of basicity and acidity of the tirofiban molecule were clearly demonstrated. Both the O atoms in >SO 2 and H atom in –COOH serve as primary electrophilic site and nucleophilic site, respectively. Utilizing solubility data for tirofiban in four different water-based co-solvent mixtures {isopropanol/ethylene glycol (EG)/methanol/ethanol (1) + water (2)}, the inverse Kirkwood–Buff integral method was utilized to determine the preferred solvent for the tirofiban solvation according to the results of preferential solvation analysis. In water-rich composition ranges, the drug is surrounded by water, whereas in isopropanol/methanol/ethanol-intermediate and -rich composition ranges, the drug is surrounded by ethanol/methanol/isopropanol. Isopropanol solutions had the largest magnitude of preferential solvation. Alcohols may have a greater basicity that enhances interactions with the Lewis acidic function groups of tirofiban, giving rise to selective solvation of this drug. The linear solvation energy relationships were used to determine the relative impact of solvent-solvent and solvent-solute interactions in determining the variation of solubility magnitudes. The properties of dissolution and transfer, such as entropy, enthalpy and Gibbs energy change were computed. Entropy-driven and enthalpy-driven mechanisms were shown to be responsible for the change in tirofiban solubility in the four aqueous solutions, according to the enthalpy–entropy compensation analysis.

Acetamiprid in several binary aqueous solutions: Solubility, intermolecular interactions and solvation behavior

• Quantitative surface and HS analysis of acetamiprid molecule were studied. • Acetamiprid solubility in four aqueous solutions were determined and correlated. • Solubility data was analyzed by using extended Hildebrand solubility approach. • Preferential solvation were investigated via inverse Kirkwood–Buff integrals method. • Dissolution properties and enthalpy–entropy compensation were studied. This study focused on the solubility profile, dissolving characteristics, computational methods, and solvation behavior of acetamiprid in aqueous solutions of isopropanol/acetone/methanol/EG (1) . The quantitative analysis of molecular surface, as well as Hirshfeld surface analysis, were used herein to explain the electrostatic features of basicity of acetamiprid molecule. The primary and second electrophilic sites are the CN and N groups, respectively. All solubility tests were carried out in a shake-flask technique at p = 101.2 kPa and temperatures ranging from 278.15 to 318.15 K. The solubility parameter and dipolarity-polarizability of solutions played a significant role in solubility variation. To investigate solubility performance, the three-dimensional Hansen solubility parameter was used. Several common relationships, such as the modified van't Hoff Jouyban–Acree model, the mixture response surface model, and the Jouyban–Acree model, provided acceptable correlation results for the solubility magnitudes with relative average deviations of < 4.98 percent. The preferred solvation of acetamiprid was further investigated by quantification using the inverse Kirkwood–Buff integrals method. Positive preferential solvation values in isopropanol/ethanol/acetone/methanol-rich and -intermediate composition solutions suggest that isopropanol/ethanol/acetone/methanol preferentially solvates acetamiprid. Nonetheless, EG in the EG + water solution didn’t preferentially solvate acetamiprid. Moreover, the dissolution and transfer properties as well as enthalpy–entropy compensation were discussed.

Solubility, solvation analysis and enthalpy–entropy compensation of musk ketone in some cosolvent solutions

• Musk ketone solubility in several cosolvent blends was determined and modelled. • Effect of solvent descriptors on solubility variation was studied. • Solvation behavior was investigated via two approaches of IKBI and EHSA. • Dissolution, transfer properties and enthalpy–entropy compensation were discussed. The present work was mainly devoted to the solubility and modeling, intra- and inter-molecular interactions and solvation behavior for musk ketone dissolved in aqueous solutions of ethanol, N , N -dimethylformamide (DMF), methanol and isopropanol accompanied by various computational methodology. Solubility experiments were conducted by means of the common shake-flask technique under local pressure of p = 101.2 kPa at elevated temperatures from 278.15 to 318.15 K. For each aqueous cosolvent solution, the highest solubility magnitude of musk ketone appeared in neat cosolvent (ethanol, DMF, methanol or isopropanol) at T = 318.15 K; and the lowest one, in water at 278.15 K. The solubility behavior was studied by means of the Hansen solubility parameter. The mixture response surface model, Jouyban–Acree model, modified Wilson model and Jouyban–Acree–van’t Hoff model correlated satisfactorily the solubility magnitudes in mole fraction with relative average deviations of <4.15%. The relative contributions of solute–solvent and solvent–solvent molecular interactions to variation of musk ketone solubility at 298.15 K was quantitatively investigated through the linear solvation energy relationships, demonstrating that the dipolarity-polarizability along with solubility parameter of aqueous solvent systems were chiefly responsible for musk ketone solubility. The solvation performance was studied by an extended Hildebrand solubility approach applied to the solubility in four aqueous solutions and in ethyl acetate + methanol/isopropanol/ethanol solutions at 298.15 K, acquiring RAD of <4.05%. In addition, the preferential solvation of musk ketone was investigated quantitatively by means of the inverse Kirkwood–Buff integrals method in the four aqueous and three non-aqueous solutions. Musk ketone was preferentially solvated by ethanol/DMF/methanol/isopropanol (1) in aqueous solutions within middle and rich ethanol/DMF/methanol/isopropanol (1) compositions, and by ethyl acetate (1) in non-aqueous solutions within middle and rich ethyl acetate (1) compositions. Furthermore, the dissolution and transfer properties as well as enthalpy–entropy compensation were discussed in detail.

Extended Hildebrand Solubility Approach and Inverse Kirkwood–Buff Integrals Method Applied to Chloroxine Solubility in Several Blended Solvents

ABSTRACT Extended Hildebrand solubility approach (EHSA) was used in this work to analyse the chloroxine solubility in mixtures at temperature of 298.15 K. A good prediction results of EHSA were observed to correlate the interaction parameter (W) and solubility parameter of blends in the absence of chloroxine (δ 1+2). Nonetheless, the forecasting outcomes of EHSA were similar with that attained when natural logarithm of solubility (lnx 3) was associated with δ 1+2. Additionally, the local mole fraction of ethyl acetate and n-propanol/methanol/isopropanol/ethanol in the vicinity of chloroxine were quantitatively derived by the inverse Kirkwood–Buff integrals method. It could be conjectured that in the alcohol-rich solutions, the interactions of acidic sites of alcohols on basic sites of chloroxine have crucial responsibility for the solvation. It is remarkable the present work does expand the preferential solvation analysis of chloroxine by the particular solvent species in the ethyl acetate + alcohol mixtures.

Thermodynamic study and preferential solvation of sulfamerazine in acetonitrile + methanol cosolvent mixtures at different temperatures

This paper discusses sulfamerazine (SMR) solubility in Acetonitrile (MeCN) + Methanol (MeOH) cosolvents at nine temperatures (278.15–318.15 K). Herein, the maximum SMR solubility was reached in a cosolvent mixture at the highest studied temperature, and the minimum SMR solubility was reached in neat methanol at the lowest studied temperature. Using experimental data, thermodynamic functions were calculated for both the solution and mixture using the Gibbs and van’t Hoff equations, thus determining that the solution process is endothermic with entropic favoring. In addition, the preferential solvation parameters (δx3,1), calculated using the inverse Kirkwood-Buff integrals (IKBI) method, are reported; SMR is preferentially solvated by MeOH in MeOH-rich mixtures, and in intermediate and MeCN-rich mixtures, the δx3,1 values indicate that SMR is not preferentially solvated by any of the two solvents in the mixture (MeCN + MeOH). Finally, eight models were assessed (Apelblat, van’t Hoff, Yaws, λh, Weibull, NRTL, Wilson, and Wilson modified), with all presenting mean relative deviation percentages (MRD%) under 6%, which indicates a good correlation with the experimental data.

Solubility, solvent effect, enthalpy–entropy compensation and solvation thermodynamics of 4-(bromomethyl)-2(1H)-quinolinone in several aqueous blends

• Solubility of BMQ in four solutions was determined and mathematically correlated. • Inter and intra-molecular interactions were studied by KAT-LSER model. • Preferential solvation was made through IKBI method. • Dissolution and transfer properties were detailed discussed. The current study was mainly devoted to solubility for the systems formed by 4-(bromomethyl)-2(1H)-quinolinone (BMQ) and blended solvents of isopropanol, N -methyl-2-pyrrolidinone (NMP), ethanol and n -propanol with water. Experiments for solubility determination were conducted by employing the shake-flask equilibration method from 278.15 to 318.15 K under 101.2 kPa. For each aqueous cosolvent mixture, the minimum solubility was recorded in water at 278.15 K; and the maximum value, in neat organic solvents at 318.15 K. The solubility performance was illustrated by Hansen solubility parameters of water, BMQ and co-solvents. No occurrence of polymorphic transformation or solvation was observed after experiments based on the XRD spectra of raw BMQ and excess solids analyzed. The satisfactory correlation results for solubility data was obtained by modified Wilson model, mixture response surface model, modified van’t Hoff-Jouyban–Acree model and Jouyban–Acree model. The relative average deviations were calculated to be no more than 8.72 %. Investigation on the relative contributions from inter- and intra-molecular interactions to the solubility variation of BMQ at temperature of 298.15 K was quantitatively performed via the linear solvation energy relationships (LSER). The descriptors of solvent blends including solubility parameter, dipolarity-polarizability and hydrogen-bond basicity were primarily responsible for the solubility variation. As well, the preferential solvation of BMQ was researched quantitatively via the inverse Kirkwood–Buff integrals method on the basis of some obtainable properties of solvent blends. The positive preferential solvation parameters for BMQ in middle and cosolvent-rich blends strongly suggest that the crystalline solute of BMQ is preferentially solvated by cosolvents of isopropanol, NMP, ethanol and n -propanol. The transfer and apparent dissolution properties including apparent Gibbs energy change (298.15 K), dissolution enthalpy and dissolution entropy (298.15 K) were derived and discussed. Analysis of enthalpy–entropy compensation indicates the entropy-driven mechanism of BMQ dissolved in all blend solvents.

Preferential solvation and solute-solvent interactions of posaconazole in mixtures of (ethyl acetate + ethanol/isopropanol) at several temperatures

• Research the solubility profile of posaconazole in two mixtures. • The influence of solvent properties on the solubility was analyzed by KAT-LSER method. • Preferential solvation parameters were evaluated by using the inverse Kirkwood-Buff integrals method. • The solubility profile was correlated by Jouyban-Acree model. • The apparent thermodynamic properties in dissolution process were evaluated. In this work, the dissolution process of stable crystalline form I in mixtures of (ethyl acetate + ethanol/isopropanol) at several temperatures was studied and represented by using Jouyban-Acree model, which was considered to be useful in the development of a pharmaceutical product. The influence of solvent properties of mixed solvents on the solubility of posaconazole was analyzed by KAT-LSER method. The solubility of posaconazole in mixture of ethyl acetate + isopropanol increased monotonically with the increasing mass fraction of ethyl acetate. However, it increased firstly and then decreased with the rising mass fraction of ethyl acetate in ethyl acetate + ethanol, and the maximum mole solubility was 4.871 × 10 −4 when the mass fraction of ethyl acetate is w = 0.50 at T = 313.15 K. The co-solvency phenomenon was investigated by solubility parameters method. More importantly, preferential solvation parameters (δ x 1,3 ) of posaconazole in two mixtures were calculated by using the inverse Kirkwood-Buff integrals method, and it was all negative in ethyl acetate + ethanol system and ethanol-rich mixture in ethyl acetate + isopropanol, but positive at the mole compositions of ethyl acetate from 0.44 to 1.0 in ethyl acetate + isopropanol. Furthermore, some apparent thermodynamic properties including apparent molar standard dissolution enthalpy ( Δ H sol o ), apparent molar standard Gibbs energy ( Δ G sol o ), apparent molar standard dissolution entropy ( Δ S sol o ), the relative contributions by enthalpy ( ζ H ) and by entropy ( ζ TS ) toward to Gibbs energy were calculated by the van’t Hoff equation. Consequently, the experimental solubility and thermodynamic parameters could be used as the reference for simulation in the purification and separation of posaconazole.

Solubility of N-(9-fluorenylmethoxycarbonyloxy)-succinimide in several aqueous co-solvent solutions revisited: Solvent effect, preferential solvation and dissolution and transfer properties

• Preferential solvation of N-(9-fluorenylmethoxycarbonyloxy)-succinimide were studied by IKBI method. • Solvent-solvent and solvent–solute interactions were investigated using KAT-LSER model. • Dissolution and transfer properties were derived and discussed. • Enthalpy–entropy compensation were analyzed. Preferential solvation of N -(9-fluorenylmethoxycarbonyloxy)-succinimide (Fmoc-OSu) in mixtures of DMF (1) + water (2), ethanol (1) + water (2), ethylene glycol (EG, 1) + water (2) and DMSO (1) + water (2) was investigated by inverse Kirkwood–Buff integrals method. In ethanol-rich and intermediate contents, ethanol preferentially solvated Fmoc-OSu; and for the four aqueous co-solvent blends in water-rich composition regions, Fmoc-OSu was preferentially solvated by water. The solvent effect was described through modeling the Gibbs energy change of Fmoc-OSu solubility by linear solvation energy relationships. The main contribution to solubility variation of Fmoc-OSu was the solvent dipolarity-polarizability and solubility parameter. The dissolution and transfer enthalpy, entropy and Gibbs free energy were discussed in detail. Analysis outcomes of thermodynamic dissolution and enthalpy–entropy compensation demonstrated that two different mechanisms, enthalpy-driven and entropy-driven controlled the solubility variation of Fmoc-OSu in the DMF/EG/DMSO + water mixtures; and enthalpy-driven, in the ethanol + water mixture.

Solubility, solvation thermodynamics and solvent effect of thiabendazole in several cosolvent blends

• Solubility of thiabendazole in four mixtures was determined. • Solubility data was correlated by four co-solvency models. • Solvent effect was studied by linear solvation energy relationships. • Preferential solvation were investigated via IKBIs method. • Solubility data was analyzed by using EHSA. Equilibrium solubility determination and model correlation were performed in the present research for the systems formed by solid solute of thiabendazole and binary aqueous blends of acetonitrile, methanol, n -propanol and isopropanol. Experiments at temperatures ranging from 283.15 to 323.15 K were conducted by the use of the shake-flask saturation technique at 101.2 kPa. For the given binary solvent blends, the minimum mole fraction solubility was recorded in water at 283.15 K; and the maximum one, in neat organic solvent at 323.15 K. The generated equilibrium solubility was satisfactorily described by two models, modified van’t Hoff-Jouyban–Acree and Jouyban–Acree, with the relative average deviations (%) of no more than 6.08. Good prediction results of extend Hildebrand solubility approach (relative average deviations < 4.10%) were observed in terms of quartic polynomial for the four solution systems to correlate the interaction parameter ( W ) and solubility parameters of the solvents’ blends in the absence of thiabendazole ( δ 1+2 ). Analysis of the relative contributions from intra- and inter-molecular interactions to solubility variation of solid solute of thiabendazole (298.15 K) was quantitatively carried out via the linear solvation energy relationships (LSER). The descriptors of blended solvents comprising solubility parameter and hydrogen-bond basicity were principally responsible for the variation of determined solubility. Besides, the preferential solvation of thiabendazole was quantitatively researched via the inverse Kirkwood–Buff integrals method on the basis of some accessible properties for blended solvent systems. The positive preferential solvation parameters for thiabendazole in the middle and cosolvent-rich blends powerfully suggested that thiabendazole was preferentially solvated by cosolvents of isopropanol, acetonitrile, n -propanol, ethanol and methanol. The conjecture was reasonable that in above compositions, thiabendazole mainly served as Lewis acidic in terms of its interactions with alcohol molecules; while for the acetonitrile mixtures, this behavior was contributed by polarization effect. Besides, thiabendazole was preferentially solvated by ethanol (2) in ethyl acetate (1) + ethanol (2) solutions with ethyl acetate-rich compositions, and by water (2) solvent in aqueous blends with rich water compositions.

Rimsulfuron solubility in several aqueous solutions revisited: Solvent effect, dissolution behavior and preferential solvation

• Preferential solvation of rimsulfuron in four aqueous co-solvent solutions were studied by IKBI method. • Performance of solubility was investigated by three-dimensional Hansen solubility parameter. • Solvent-solvent and solvent–solute interactions were investigated using KAT-LSER model. • Dissolution and transfer properties were derived and discussed. • Enthalpy–entropy compensation were analyzed. Preferential solvation was analyzed with the help of the inverse Kirkwood–Buff integrals method based on the available equilibrium solubility of rimsulfuron in four solutions of EG (1) + water (2), ethanol (1) + water (2), DMF (1) + water (2) and methanol (1) + water (2). Rimsulfuron was preferentially surrounded by water solvent in water-rich composition regions. For the aqueous ethanol/methanol mixtures in intermediate and methanol/ethanol-rich composition ranges, methanol/ethanol preferentially solvated rimsulfuron; while EG/DMF didn’t preferentially solvate the rimsulfuron for the EG/DMF in the ranges. Selective solvation of rimsulfuron by methanol/ethanol was perhaps resulted from higher basicity of methanol/ethanol that was in favor of interactions with the acidic groups of rimsulfuron. The performance of rimsulfuron solubility was investigated by means of Hansen solubility parameter concept in detail. The study on relative prominence of solvent–solvent and solute–solvent molecule interactions on rimsulfuron solubility variation identified the hydrogen-bond basicity, dipolarity-polarizability and solubility parameter of solution descriptors analyzed in terms of the linear solvation energy relationships. As well, the dissolution and transfer Gibbs free energy change, enthalpy and entropy were resulted, representing the solubilization capacity more favorable with the rising compositions of EG/ethanol/DMF/methanol. Thermodynamic analysis of enthalpy–entropy compensation demonstrated a shift of dominant dissolution mechanism from entropy-driven (water-rich regions) to enthalpy-driven (organics-rich regions).