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Exploring the microscopic reaction mechanism of dicyandiamide (DCD) synthesis using calcium cyanamide (CaCN2) is highly desirable because of the low conversion of reactants and selectivity of DCD products. DCD synthesis consists of a two-step sequential hydrolysis of CaCN2, followed by dimerization of cyanamide to DCD in an alkaline environment. Density functional theory (DFT) results revealed that the rate-limiting step (RLS) was the formation of a C-N bond between the cyanamide and cyanamide anion in the dimerization of the DCD reaction. Secondary reactions of cyanamide with water, hydrogen sulfide, and DCD were also analyzed. The effects of solvation on the principal and secondary reactions were systematically explored. A single explicit water molecule can significantly lower the free energy barrier of the RLS. Water molecules facilitate the C-N bonding of the reactants in DCD reactions, resulting in a reduction in the free energy barrier of the RLS. The facilitation of double explicit water for the reaction is weaker than that of single explicit water and even yields negative catalysis. The effect of the [OH(H2O)3]− cluster lowering the reaction barrier with the hydrogen-bonding network is the most remarkable, which can alter the reaction path by the direct and indirect involvement of OH− ions. Furthermore, the reaction rate constants were computed by canonical variational theory with the Eckart tunneling correction (CVT/Eckart) and fitted to the Arrhenius expression. The reaction mechanism and kinetics revealed at the microscopic level provide efficient and clean production of DCD with certain theoretical guidance. [ABSTRACT FROM AUTHOR]

Density Functional Theory (DFT) and Molecular docking are pivotal computational techniques in modern chemistry and drug design. This work investigates the electronic structure and reactivity of 2-thiophenecarbonitrile (2TCN) with an emphasis on important factors such as HOMO-LUMO energy gap, MEP, Mulliken atomic charges, natural population analysis, and Mutiwfn (ELF, LOL, ALIE, and RDG) analysis. The MEP and FMO studies were calculated in various solvents like acetonitrile, water, gas, and methanol. The anti-inflammatory and antioxidant investigations revealed substantial activities by 2TCN. Additionally, molecular docking studies are performed to elucidate the binding interaction between the compound and target proteins, providing insights into its potential therapeutic mechanisms. The results demonstrate the binding energies, interaction residues, and the most favorable docking poses. This approach underscores the integration of theoretical and computational methods in advancing molecule design and therapeutic discovery.

Copper (Cu) is an important transition metal, and its isotopes have important applications in geology, environmental science, soil science, and other fields. Cu isotope fractionation can occur in many natural processes. However, the mechanism of Cu isotope fractionation in solution/hydrothermal solution systems is not very clear. In this study, the fractionation effects of complexes of Cu(I) and Cu(II) in solution/hydrothermal solution systems were systematically studied by means of an ab initio method based on first principles. In the simulation of an aqueous solution system, the theoretical treatment method used is the "water-droplet" method. The results show that the heavy Cu isotope (65Cu) enrichment capacity of the Cu-bearing complex solutions is greatly affected by the ligand types both for Cu(I) and Cu(II). For Cu(I) complex solutions, the heavy Cu isotope enrichment sequence is [Cu(HS)2]−·(H2O)42 > [Cu(HS)(H2O)]·(H2O)42 ≈ [Cu(HS)(H2S)]·(H2O)42 > [CuCl]·(H2O)42 > [CuCl2]−·(H2O)42 > [CuCl3]2−·(H2O)42. For the aqueous solutions of Cu(II) with an inorganic ligand (such as H2O, OH−, NO3−, SO42− and CN−), the order of heavy Cu isotope enrichment is as follows: [Cu(H2O)6]2+·(H2O)42 > [Cu(NO3)2]·(H2O)42 > [Cu(OH)2]·(H2O)42 > [CuSO4(H2O)3]·(H2O)42 > [CuNO3(H2O)4]+·(H2O)42 > [CuCN]+·(H2O)42. For the Cu(II) complex solutions with a halogen as ligands, the change order of 1000lnβ is [CuCl]+·(H2O)42 > [CuCl2]·(H2O)42 > [CuBr2]·(H2O)42 > [CuCl3]−·(H2O)42. The sequence of 1000lnβ for Cu(II) organic complex aqueous solutions is [Cu(HOC6H4COO)]+·(H2O)42 > [Cu(CH3CH2COO)]+·(H2O)42 > [Cu(COOHCOO)]+·(H2O)42. The calculation also found that for Cu(I) complex aqueous solutions, the difference in Cu isotope fractionation parameters (1000lnβ) between [CuCl2]−·(H2O)42 and [Cu(HS)2]−·(H2O)42 is relatively large. At 100 °C, the 1000lnβ of the two species are 1.14 and 1.55 (‰), respectively. The difference between the two could be reached up to 0.41 (‰). The Cu isotope fractionation parameter obtained with the "water droplet" method is also very different from the results of previous studies, which indicate that the Cu isotope fractionation behavior of the two is similar. At the same time, the exciting discovery is that the enrichment capacity of heavy Cu isotopes is significantly different between Cu(I) complex aqueous solutions and Cu(II) complex aqueous solutions. At 100 °C, the 1000lnβ of 6 Cu(I) complex aqueous solutions and 13 Cu(II) complex aqueous solutions ranged from 0.90 to 1.55 and 2.24 to 3.25(‰), respectively. It also shows that the REDOX reaction has a significant effect on the Cu isotope fractionation, especially in ore-forming fluids. Therefore, the ligand type is a factor that cannot be ignored when considering the mechanism of Cu isotope fractionation in solution/hydrothermal solution systems. Whether the solvation effect of an aqueous solution is considered or not has a great influence on the numerical values of the final Cu isotope fractionation factors. Hence, the solvation effect of an aqueous solution is an essential determinant in the theoretical calculation of the Cu isotope fractionation factors for Cu-bearing complex solutions. [ABSTRACT FROM AUTHOR]

In this study, 12 phenolic acids were theoretically calculated using the M06-2X functional. To explain their antioxidant and solvation effects, bond dissociation enthalpy (BDE), ionization potential (IP), proton dissociation enthalpy (PDE), proton affinity (PA) and electron transfer enthalpy (ETE) were calculated for each phenolic acid in the gas phase and solvents. The results showed that the BDE of gentianic acid (C5) in the gas phase was the lowest. In terms of BDE, caffeic acid (C6) had the strongest antioxidant effect in benzene, gentianic acid (C5) in acetone, and 3,4-dihydroxybenzyl alcohol (C2) in ethanol and water. In terms of IP, resveratrol had the best antioxidant activity in 4 solvents and in the gas phase. The antioxidant mechanism of phenolic acids was mainly related to hydrogen atom transfer (HAT). It was found that the ability of dehydrogenated anions and cations of phenolic acids to generate dehydrogenated free radicals was consistent with the influence of solvent polarity on IP, BDE, PDE, PA and ETE. In general, the antioxidant capacity of phenolic acids was the strongest in the weakly polar solvent acetone, followed by the strongly polar solvents water and ethanol, and phenolic acids had the weakest antioxidant capacity in non-polar solvents.

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Copper (Cu) is an important transition metal, and its isotopes have important applications in geology, environmental science, soil science, and other fields. Cu isotope fractionation can occur in many natural processes. However, the mechanism of Cu isotope fractionation in solution/hydrothermal solution systems is not very clear. In this study, the fractionation effects of complexes of Cu(I) and Cu(II) in solution/hydrothermal solution systems were systematically studied by means of an ab initio method based on first principles. In the simulation of an aqueous solution system, the theoretical treatment method used is the “water-droplet” method. The results show that the heavy Cu isotope (65Cu) enrichment capacity of the Cu-bearing complex solutions is greatly affected by the ligand types both for Cu(I) and Cu(II). For Cu(I) complex solutions, the heavy Cu isotope enrichment sequence is [Cu(HS)2]−·(H2O)42 > [Cu(HS)(H2O)]·(H2O)42 ≈ [Cu(HS)(H2S)]·(H2O)42 > [CuCl]·(H2O)42 > [CuCl2]−·(H2O)42 > [CuCl3]2−·(H2O)42. For the aqueous solutions of Cu(II) with an inorganic ligand (such as H2O, OH−, NO3−, SO42− and CN−), the order of heavy Cu isotope enrichment is as follows: [Cu(H2O)6]2+·(H2O)42 > [Cu(NO3)2]·(H2O)42 > [Cu(OH)2]·(H2O)42 > [CuSO4(H2O)3]·(H2O)42 > [CuNO3(H2O)4]+·(H2O)42 > [CuCN]+·(H2O)42. For the Cu(II) complex solutions with a halogen as ligands, the change order of 1000lnβ is [CuCl]+·(H2O)42 > [CuCl2]·(H2O)42 > [CuBr2]·(H2O)42 > [CuCl3]−·(H2O)42. The sequence of 1000lnβ for Cu(II) organic complex aqueous solutions is [Cu(HOC6H4COO)]+·(H2O)42 > [Cu(CH3CH2COO)]+·(H2O)42 > [Cu(COOHCOO)]+·(H2O)42. The calculation also found that for Cu(I) complex aqueous solutions, the difference in Cu isotope fractionation parameters (1000lnβ) between [CuCl2]−·(H2O)42 and [Cu(HS)2]−·(H2O)42 is relatively large. At 100 °C, the 1000lnβ of the two species are 1.14 and 1.55 (‰), respectively. The difference between the two could be reached up to 0.41 (‰). The Cu isotope fractionation parameter obtained with the “water droplet” method is also very different from the results of previous studies, which indicate that the Cu isotope fractionation behavior of the two is similar. At the same time, the exciting discovery is that the enrichment capacity of heavy Cu isotopes is significantly different between Cu(I) complex aqueous solutions and Cu(II) complex aqueous solutions. At 100 °C, the 1000lnβ of 6 Cu(I) complex aqueous solutions and 13 Cu(II) complex aqueous solutions ranged from 0.90 to 1.55 and 2.24 to 3.25(‰), respectively. It also shows that the REDOX reaction has a significant effect on the Cu isotope fractionation, especially in ore-forming fluids. Therefore, the ligand type is a factor that cannot be ignored when considering the mechanism of Cu isotope fractionation in solution/hydrothermal solution systems. Whether the solvation effect of an aqueous solution is considered or not has a great influence on the numerical values of the final Cu isotope fractionation factors. Hence, the solvation effect of an aqueous solution is an essential determinant in the theoretical calculation of the Cu isotope fractionation factors for Cu-bearing complex solutions.

Protein unfolding is a ubiquitous process responsible for the loss of protein functionality (denaturation), which, in turn, can be accompanied by the death of cells and organisms. The nature of enthalpy–entropy compensation (EEC) in the kinetics of protein unfolding is a subject of debate. In order to investigate the nature of EEC, the "completely loose" transition state (TS) model has been applied to calculate the Arrhenius parameters for the unfolding of polyglycine dimers as a model process. The calculated Arrhenius parameters increase with increasing dimer length and demonstrate enthalpy–entropy compensation. It is shown that EEC results from the linear correlations of enthalpy and entropy of activation with dimer length, which are derived directly from the properties of the transition state. It is shown that EEC in solvated (hydrated, etc.) proteins is a direct consequence of EEC in proteins themselves. The suggested model allows us also to reproduce and explain "exotic" very high values of the pre-exponential factor measured for the proteins unfolding, which are drastically higher than those known for unimolecular reactions of organic molecules. A similar approach can be applied to analyzing the nature of EEC phenomena observed in other areas of chemistry. [ABSTRACT FROM AUTHOR]

[Display omitted] • Solvation significantly affects energy of species on IIIB-VB TM@GDY, less on VIII/IB. • The performances of OER/ORR are enhanced at Δ G OH* <0.80 eV by weakening OH adsorption. • OER/ORR activities are improved at Δ G OH* >0.90 eV by strengthening OH adsorption. • Find a universal structure descriptor φ with the intrinsic features of the elements. • Ni@GDY, Co@GDY and Cu@GDY are trifunctional electrocatalysts for OER, ORR and HER. Efficient single-atom electrocatalysts show great potential for application in the field of renewable energy. In this work, dispersion-corrected density functional theory (DFT) calculations based on high-throughput screening were used to identify effective graphdiyne (GDY) supported single-atom electrocatalysts (SAECs) for water electrolysis and the oxygen reduction reaction (ORR). The solvation effect on the electrocatalytic performance of the catalysts was carefully discussed. A general design principle was established to evaluate the activities of TM@GDY SAECs for ORR and oxygen evolution reaction (OER). Δ G OH* could serve as the sole descriptor for the onset potential of OER and ORR. Additionally, a universal structural descriptor φ, which is strongly related to Δ G OH* , was identified. This descriptor only includes intrinsic features such as the number of electrons in d orbitals and elemental electronegativity. Consequently, a structure-activity volcano was plotted. Combined with the electronic properties calculations, the mechanism behind the relationship between Δ G OH* and descriptor φ was deeply analyzed. Among the investigated candidates, TM@GDY (TM = Ni, Pt, Pd, Cu, Co, Rh, and Ag) are potential bifunctional electrocatalysts for OER and ORR. Three non-noble metal-based SAECs (Ni@GDY, Co@GDY, and Cu@GDY) and two noble metal-based SAECs (Rh@GDY and Ag@GDY) are potential trifunctional electrocatalysts for OER, ORR, and the hydrogen evolution reaction. [ABSTRACT FROM AUTHOR]

As the most productive thermosetting polymer, unsaturated polyester resin (UPR) and its composies were difficult to be chemcycled due to the mass transfer barrier in dense network structure. High temperature/pressure and mechanical crushing were usually applied to improve the mass transfer during chemcycling processes, but at the sacrifice of reaction selectivity and fiber integrity. Here, a unique fragmentation effect of aprotic solvents was observed in UPR, which is a non-reactive solvation that has the potential to replace mechanical fragmentation and improve the recyclability of UPR and its composite materials. The solvation was found to be based on the hydrogen bond between the solvent and ester group of UPR through Hansen solubility parameters and molecular dynamics simulation. It was the intermolecular force between the polyester clusters of UPR that was destroyed, leading to the fragmentation of UPR into micron-sized powder. The fragmentation effect is also applicable to other ester-containing polymers and provides a simple, facile, and energy-efficient method for the chemcycling of thermosetting resins, as well as direct exfoliation of reinforced fillers. A simple solvation method is used to achieve non-reactive fragmentation of thermosets at a low temperature. It is a promising avenue to improve mass transfer and promote degradation efficiency in recovery of thermosets and non-destructive fibers. [Display omitted] • UPR fragmentation/non-deconstructive fiber exfoliation achieved in aprotic solvent. • Solvation is attributed to formation of hydrogen bonds between solvent and ester. • Hansen solubility parameter sphere for the solvation of UPR was established. • Fragmentation effect of solvent is applicable to other ester-containing polymers. [ABSTRACT FROM AUTHOR]

As a rare sugar, D-Tagatose is regarded as an excellent low-energy food sweetener. It is especially beneficial for physical health, such as inhibiting hyperglycemia, improving intestinal flora, and avoiding caries. It is broadly employed in food, medicine, cosmetics, and other fields. Acquiring D-Tagatose solubility is vital to develop D-Tagatose crystallization process to obtain high-quality D-Tagatose production. In this study, the solubility of D-Tagatose in seven pure solvents (methanol, ethanol, n-propanol, water, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone), three binary solvents (ethanol-water mixtures, ethanol-methanol mixtures, and n-propanol-water mixtures) was determined by HPLC method at temperatures from 293.15 K to 323.15 K. Then, the Van't Hoff equation, Apelblat equation, λh equation, NRTL equation, CNIBS/Redlich-Kister model and modified Jouyban-Acree-van't Hoff model were used to correlate the solubility. The correlated solubility accounted for suitable compatibility with the experimental results (ARD

Abstract Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry enable the reversible Mg plating/stripping, while they fail to match most cathode materials toward high-voltage magnesium batteries. Herein, reversible Mg plating/stripping is achieved in conventional carbonate electrolytes enabled by the cooperative solvation/surface engineering. Strongly electronegative Cl from the MgCl2 additive of electrolyte impairs the Mg…O = C interaction to reduce the Mg2+ desolvation barrier for accelerated redox kinetics, while the Mg2+-conducting polymer coating on the Mg surface ensures the facile Mg2+ migration and the effective isolation of electrolytes. As a result, reversible plating and stripping of Mg is demonstrated with a low overpotential of 0.7 V up to 2000 cycles. Moreover, benefitting from the wide electrochemical window of carbonate electrolytes, high-voltage (> 2.0 V) rechargeable magnesium batteries are achieved through assembling the electrode couple of Mg metal anode and Prussian blue-based cathodes. The present work provides a cooperative engineering strategy to promote the application of magnesium anode in carbonate electrolytes toward high energy rechargeable batteries.

The redox potential is a fundamental parameter in electrochemistry and is essential in understanding energy-related applications. A typical redox-active molecule, 2,2,6,6-tetramethyl piperidine-1-oxyl (TEMPO), which has an electrocatalytic effect on organic molecules and functions as a mediator in battery technologies, was selected as a model to investigate the dependence of redox potential on the concentration of the supporting electrolyte LiTFSI. Unusual results from cyclic voltammetry have been obtained, showing that the redox potential of TEMPO shifts negatively upon increasing the concentration of LiTFSI. Solvation energy changes from the tunability of dielectric constants and ion pairing are proposed to explain the phenomenon. This work provides insights into tuning the redox potential through simple methods, with applications in the fields of electrocatalysis and battery technology.

[Display omitted] • [Zn(NA) 2 Cl 2 ] complex, with monoclinic symmetry (P 2 1 /a) was successfully crystallized; • Solvation effect on structural and thermodynamic properties was studied by DFT using PBE1PBE and B3LYP functionals; • DFT allowed vibrational modes adequate assignments in FT-IR and Raman spectra under different solvation conditions; • The complex is thermally stable up to around 200 °C with a decomposition enthalpy of 335.27 kJ/mol; • [Zn(NA) 2 Cl 2 ] exhibited antibacterial activity against Gram-positive and Gram-negative bacteria. A dichlorobis(nicotinamide)zinc(II) complex, [Zn(nicotinamide) 2 Cl 2 ], was crystallized through the slow evaporation method, and its vibrational, electronic, structural, and thermal properties have been characterized. Density functional theory (DFT) was used for the accurate analysis of intramolecular vibrational modes, obtaining chemical reactivity indices and comparative studies of geometric and electronic parameters, including solvation effects in methanol, ethanol, and water, as well as in vacuum. Additionally, the nature and strength of the bonds associated with the coordination sphere (Cl–Zn and N–Zn) were elucidated from the quantum theory of atoms in molecules and natural bond orbital analyses. Powder X-ray diffraction showed that the coordination compound belongs to a monoclinic symmetry with P 2 1 / a (C 2 h 5) space group. Thermal analyses revealed that the material is stable up to 200 °C. From DFT calculations, the complex is chemically more stable in solvents compared to vacuum conditions, with the aqueous medium offering greater stability. The chemical stability was also analyzed by infrared and Raman spectroscopy, with the results showing spectral changes mainly for the vibrational spectra obtained in methanol, ethanol, and water against those obtained in vacuum. Biological experiments showed the complex antibacterial activity against Gram-positive and Gram-negative bacteria, mainly against the Cutibacterium acnes ATCC 6919 strain. A computational study of the absorption, distribution, metabolism, excretion (ADME), and drug-likeness were calculated to support the experimental data. [ABSTRACT FROM AUTHOR]

The synthesis and X-ray structure of a novel glycoluril derivative are described. The crystal of the glycoluril derivative is obtained by slow evaporation in a refrigerator at about 5 °C. X-ray crystallographic analysis revealed that the compound crystallized in an unusual as conformation instead of the usual clip-shaped aa conformation. Structural analysis shows that the solvation effect, hydrogen bonding, and space-occupying effect influenced the crystallization conformation of the derivative. The X-ray crystallographic analysis in this work provides additional crystallographic evidence of the as conformation of the 3U glycoluril derivative and shows the effect of solvent water on the conformational behavior. [ABSTRACT FROM AUTHOR]

Highlights: A cooperative solvation/surface engineering approach is reported to achieve the reversible Mg plating/stripping in conventional carbonate electrolytes. Benefitting from the strategy, Mg2+ can easily overcome the reduced desolvation barrier and penetrate the Mg2+-conducting polymer coating, deposited on the Mg metal anode successfully, promoting the application of magnesium anode in carbonate electrolytes toward high-energy rechargeable batteries.Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry enable the reversible Mg plating/stripping, while they fail to match most cathode materials toward high-voltage magnesium batteries. Herein, reversible Mg plating/stripping is achieved in conventional carbonate electrolytes enabled by the cooperative solvation/surface engineering. Strongly electronegative Cl from the MgCl2 additive of electrolyte impairs the Mg…O = C interaction to reduce the Mg2+ desolvation barrier for accelerated redox kinetics, while the Mg2+-conducting polymer coating on the Mg surface ensures the facile Mg2+ migration and the effective isolation of electrolytes. As a result, reversible plating and stripping of Mg is demonstrated with a low overpotential of 0.7 V up to 2000 cycles. Moreover, benefitting from the wide electrochemical window of carbonate electrolytes, high-voltage (> 2.0 V) rechargeable magnesium batteries are achieved through assembling the electrode couple of Mg metal anode and Prussian blue-based cathodes. The present work provides a cooperative engineering strategy to promote the application of magnesium anode in carbonate electrolytes toward high energy rechargeable batteries. [ABSTRACT FROM AUTHOR]

Abstract The reaction pathways of PCB-77 in the atmosphere with ·OH, O2, NO x , and 1O2 were inferred based on density functional theory calculations with the 6-31G* basis set. The structures the reactants, transition states, intermediates, and products were optimized. The energy barriers and reaction heats were obtained to determine the energetically favorable reaction pathways. To study the solvation effect, the energy barriers and reaction rates for PCB-77 with different polar and nonpolar solvents (cyclohexane, benzene, carbon tetrachloride, chloroform, acetone, dichloromethane, ethanol, methanol, acetonitrile, dimethylsulfoxide, and water) were calculated. The results showed that ·OH preferentially added to the C5 atom of PCB-77, which has no Cl atom substituent, to generate the intermediate IM5. This intermediate subsequently reacted with O2 via pathway A to generate IM5a, with an energy barrier of 7.27 kcal/mol and total reaction rate of 8.45 × 10−8 cm3/molecule s. Pathway B involved direct dehydrogenation of IM5 to produce the OH-PCBs intermediate IM5b, with an energy barrier of 28.49 kcal/mol and total reaction rate of 1.15 × 10−5 cm3/molecule s. The most likely degradation pathway of PCB-77 in the atmosphere is pathway A to produce IM5a. The solvation effect results showed that cyclohexane, carbon tetrachloride, and benzene could reduce the reaction energy barrier of pathway A. Among these solvents, the solvation effect of benzene was the largest, and could reduce the total reaction energy barrier by 25%. Cyclohexane, carbon tetrachloride, benzene, dichloromethane, acetone, and ethanol could increase the total reaction rate of pathway A. The increase in the reaction rate of pathway A with benzene was 8%. The effect of solvents on oxidative degradation of PCB-77 in the atmosphere is important. Graphical abstract The reaction pathways of PCB-77 in the atmosphere with •OH, O2, NOx, and 1O2 were inferred based on density functional theory calculations with the 6-31G* basis set. Different polar and nonpolar solvents: cyclohexane, benzene, carbon tetrachloride, chloroform, acetone, dichloromethane, ethanol, methanol, acetonitrile, dimethylsulfoxide, and water were selected to study the solvation effect on the favorable reaction pathways. The investigated results showed what kind of pathway was most likely to occur and the solvent effect on the reaction pathway

• An optimization-based framework is developed for reaction solvent design. • The reaction kinetic model is identified through a hybrid method based on CTST. • The GC-COSMO/GC methods are developed for the reaction kinetic model. • An MINLP model is established and a decomposition-based algorithm is applied. • Case studies indicate feasibility and effectiveness of the framework. Solvents have been widely used in chemical manufacturing processes. When involved in liquid homogeneous-phase kinetic reactions, they can have significant impacts on the reaction product yield. In this paper, an optimization-based framework is developed for reaction solvent design. The framework first identifies a reaction kinetic model using a hybrid method consisting of three steps. In step one, a rigorous thermodynamic derivation based on CTST (Conventional Transition State Theory) is performed to formulate a primary reaction kinetic model. In step two, a knowledge-based method is used to select additional solvent properties as supplementary descriptors to account for quantitative correction to the model and thereby improving the prediction accuracy. In step three, model identification is performed to obtain the best regressed reaction kinetic model. This hybrid modelling method is tested through two case studies, namely Diels-Alder and Menschutkin reactions, and an impressive consistency of the results is observed when the infinite dilution activity coefficients (calculated by COSMO-SAC model), hydrogen-bond donor, hydrogen-bond acceptor and solvent surface tension are selected as descriptors in the final reaction kinetic model. The GC-COSMO and GC (Group Contribution) methods are combined for the prediction of these descriptors. Finally, the Computer-Aided Molecular Design (CAMD) technique is integrated with the derived kinetic model for reaction solvent design by formulating and solving a Mixed-Integer Non-Linear Programming (MINLP) model. A decomposition-based solution algorithm is employed to manage the complexity involved with the nonlinear COSMO-SAC equations. Promising reaction solvents are identified and compared with those reported by others, indicating wide applicability and high accuracy of the developed optimization-based framework. [ABSTRACT FROM AUTHOR]

Of Hex1 is a potential target for the rational design of pesticides. TMG-chitotriomycin is one of the most highly specific known inhibitors of chitinolytic β-GlcNAcases from bacteria, fungi and insects. TMG-chitotriomycin and its analogues show different activities to O f Hex1, dependent on the number of GlcNAc units. Subsequently, it is essential to explore how these GlcNAc unit number changes cause alterations in activity. In this study, we examined the free energy patterns and per residue decomposition of binding within the complexes of Of Hex1 and a series of inhibitors, utilizing restricted molecular dynamics (MD) and water-mediated MM/GBSA calculations. The results indicated Glu328 could form a stronger polar interaction with Of Hex1 inhibitors, while Trp448 and Trp490 had important non-polar contributions. Interestingly, the conformation of Trp448 was different in the open or closed state, when O f Hex1 bound different inhibitors. Moreover, the water molecule that mediates the GlcNAc Ⅱ and Trp490 may be critical to stabilizing the hydrophobic interaction. Further study showed that isomerization of TMG-chitotriomycin analogs did not decrease binding affinity, however, there was a highly positive correlation between the calculated binding affinities and the experimental activity data (r2 = 0.92) when water molecules were explicitly taken into account. Moreover, the water molecules that mediated GlcNAc II and Trp490 might be critical to the stabilization of the hydrophobic interaction and cause the activity difference between TMG-(GlcNAc) 2 and TMG-(GlcNAc). Image 1 • The correlation between binding free energy and experimental values calculated by MM/GBSA was high (r2 = 0.91). • Explicit water molecules were considered to calculate the binding free energy with MM/GBSA. • An important water molecule mediates the second GlcNAc II and Trp490. [ABSTRACT FROM AUTHOR]

[Display omitted] • The ability to shuttle protons in the reaction media is key to achieve measurable benzene reduction reaction on Pd catalysts. • Aprotic solvents inhibit the stimulus-responsive behavior of the p-NIPAM. • Remote interaction between p-NIPAM and surface species is possible only in aqueous media. The impact of solvent composition on the reaction rates and apparent activation barriers for the reduction of nitrobenzene on Pd has been investigated by changing the solvent from pure water to mixtures with increasing concentrations of 1-methyl-2-pyrrolidone (NMP). When using pure NMP as the solvent, the activity was negligible and a high activation energy barrier was observed. Surprisingly, switching to water led to faster reaction rates and lower apparent barriers. Considering that previous research has demonstrated that water molecules near the catalyst surface facilitate the hydrogen insertion on R-NO* and R-HNO* surface species via proton-electron transfer, it is possible to link the herein observed trends in activity for the nitrobenzene hydrogenation to the ability of the reaction media to shuttle protons during the reaction. Furthermore, the polymer-induced solvation effects were investigated using thermo-responsive Pd/SiO 2 -p-NIPAM catalyst. Here, we observed that the utilization of NMP inhibits the thermo-responsive behaviour of poly N-isopropylacrylamide (p-NIPAM). This explains the constant particle size of Pd/SiO 2 -p-NIPAM catalyst observed at different temperatures during dynamic light scatting characterization (DLS). We speculate that this non-responsive behaviour of the p-NIPAM in the presence of NMP is the cause of the constant activation energy barrier at temperatures above and below the lower critical solution temperature (LCST) of the polymer (32 °C). When the reaction was conducted in pure water, the polymer-coated catalyst showed significant changes in both the apparent enthalpy and entropy of activation for temperatures below and above the LCST. This suggests that the microenvironment induced by the polymer can significantly influence the reaction rate. [ABSTRACT FROM AUTHOR]

• MD simulation is conducted for Nafion membrane with Pt redeposition. • Effect of Pt particle size on gas permeation and solvation effect is analyzed. • Interaction of Pt particles and Nafion membrane is revealed. During the operation of proton exchange membrane fuel cell, Pt particles in the catalytic layer inevitably dissolve into the membrane, which affects the performance of fuel cell. In this work, molecular dynamics is employed to investigate the effect of the redeposition of Pt particles on gas diffusion and solvation characteristics in the hydration membrane. Gas diffusion, hydrophilic cluster and its connectivity are analyzed. The interaction between Pt particles, Nafion membrane and water molecules is discussed. The influence of Pt particles on the thermal conduction of membrane is also evaluated. The results demonstrate that the presence of Pt particles affects the solvation effect of membrane, leading to a weak water cluster connectivity of membrane, which in turn leads to a poor gas diffusion performance. In addition, the thermal conductivity gradually deteriorates during the redeposition of Pt particles. [ABSTRACT FROM AUTHOR]

Antagonistic salts are composed of hydrophilic and hydrophobic ions. In a binary mixture, such as water and organic solvent, these ion pairs preferentially dissolve to those phases, respectively, and there is a coupling between the charge density and the composition. The heterogeneous distribution of ions forms a large electric double layer at the interface between these solvents. This reduces the interfacial tension between water and organic solvent, and stabilizes an ordered structure, such as a membrane. These phenomena have been extensively studied from both theoretical and experimental point of view. In addition, the numerical simulations can reproduce such ordered structures.

Four kinds of solvents, methylene chloride (CH2Cl2), toluene (TOL), ethyl acetate (EtoAc), and dimethyl carbonate (DMC), were added into the 1-butyl-3-methylimidazolium chloroaluminate ionic liquid ([BMIM]Cl/AlCl3 IL) to improve the property of the IL-based electrolyte for aluminum (Al) electrolysis. Solvation effects of these solvents on the physical properties, electrochemical properties, and electroactive ion of the [BMIM]Cl/AlCl3 IL-based electrolyte were investigated. It was found that the viscosity of the IL electrolyte decreased after adding CH2Cl2 or TOL, and the conductivity increased while the change of the conductivity and the viscosity moved in the opposite direction with the addition of EtoAc or DMC. The UV-Vis spectra showed that the electroactive Al ion continued existence after adding CH2Cl2 or TOL, but there was solvation effect between TOL and BMIM+. On the other hand, both EtoAc and DMC had solvation effects with electroactive Al ion and BMIM+. The results illustrated that solvation effect was the key effect on the reduction of Al on the cathode, and further influenced the morphology of the Al deposits. In addition, the concentration polarization reduced and the efficiency of electrolysis improved after adding CH2Cl2 or TOL. Furthermore, bright Al coatings were obtained finally by adding CH2Cl2 into [BMIM]Cl/AlCl3 IL electrolyte (when the mole ratio of CH2Cl2 is around 66.7~75%). [ABSTRACT FROM AUTHOR]

The solvation effect of compressed CO 2 on the curing reaction process of epoxy resin was investigated by using the in-situ FTIR. The isothermal curing kinetic constant and activation energy of diglycidyl ether of bisphenol A (DGEBA) with m-xylylenediamine (MXDA) was calculated via Kamal autocatalytic model. The autocatalyzed rate constants and activation energy under 0.1 MPa CO 2 are 0.7139 min −1 and 50.83 kJ/mol at 393 K, while those under 18 MPa CO 2 are 1.0928 min −1 and 36.36 kJ/mol, respectively. The increased kinetic constant and reduced activation energy suggests that the plasticization effect of CO 2 eases the chain movement, promotes the curing of epoxy resin, and increases the final conversion at relatively low temperature. Then, an amended Kamal model involving the diffusion factor was applied to better describe the curing process, which suggests that the high pressure CO 2 plays an important role to reduce the mass transfer resistance and intensify the curing process. Meanwhile, the activation energy determined by the isoconversional method, also decreases with CO 2 pressure at the same conversion. Especially, the activation energy at 90% conversion under 0.1 and 18 MPa CO 2 are 46.52 and 36.19 kJ/mol, respectively, which further confirms the solvation effect of CO 2 accelerates the curing of epoxy resin. [ABSTRACT FROM AUTHOR]

• A DFT framework considering a complicated solvent model was developed for the lithium extraction system. • The extraction reaction mechanism was determined based on solvation ability analysis. • The intramolecular repulsion and intermolecular hydrogen bonds of TBP and diluent inhabited lithium extraction. The polar diluent plays an important role in the TBP-diluent-FeCl 3 system for lithium recovery from salt lake brine. In this study, a DFT model considering a complicated solvent model was developed to understand the role of diluent in the lithium extraction process at the molecular level. The theoretical framework contains the main analysis items on the solvation ability, intermolecular and intramolecular interactions. The results indicate that the atomic charge of the electronegative atom in the diluent was one of the key factors influencing solvation ability. TBP had the strongest solvation ability with Li+ to form the Li(TBP) 2 (H 2 O) 2 + complex, and the diluent molecule had the potential to replace the water molecule to further form the Li(TBP) 2 (Dil)(H 2 O)+ complex. In this process, both the hydrogen bond and intramolecular repulsive interaction between TBP and the diluent molecule had adverse effects on lithium extraction. The simulation results were consistent with the experimental results. [ABSTRACT FROM AUTHOR]

The complexation of alkali-metal cations with calix[4]arene tertiary amide derivative (L) was studied in N-methylformamide (NMF), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) by means of microcalorimetric and UV spectrophotometric titrations. The Gibbs energies, enthalpies, and entropies for transfer of reactants and products from W-methylformamide to other solvents were determined. Favorable enthalpic contribution to overall stability was found to be the most important for all complexation reactions, especially in the case of NaL+ formation, resulting in an affinity peak of L for this cation. The complexation entropy changes were always unfavorable. The ligand dissolution was endothermic in all solvents, accompanied by positive solution entropy. The highest complex stability constants were determined in NMF, whereas in DMSO the affinity of L towards alkali metal cations was the lowest. An interesting interplay between the transfer enthalpies and entropies of the reactants and complexes was revealed and discussed in detail. [ABSTRACT FROM AUTHOR]

We report the molecular dynamics studies on the interfacial behavior of cesium (Cs + ) extraction by bis(2-propyloxy)calix [4]crown-6 (BPC6) and dicyclohexano-18-crown-6 (DCH18C6). For the benchmarking study, the phase separation for [BMIM][Tf 2 N]-water was validated. Thereafter, to understand the mechanism of complexation and the behavior of the crown ether ligand, crown ether (CE) molecules and Cs + NO 3 − ions were inserted randomly in the ionic liquid (IL)–water biphasic system. It was observed that the 2:1 Cs + -BPC6 complex formed during the simulation was more stable at the interface and was found to diffuse slowly to the IL side of the interface. On the contrary the 1:1 Cs + -DCH18C6 complex was found to be fully solvated in the bulk IL phase. The [BMIM] + cation was found to partition to the aqueous phase and exchange with Cs + ion in presence or absence of CE. The solubility, density plots and the snapshots of the [BMIM] + cation at the IL–water interface indicates the dual cationic exchange. A comparison of the interfacial behavior of Cs + -BPC6 complex and Cs + -DCH18C6 complex in IL–water preformed interface system, depicted that the Cs + -BPC6 complex was stable at the interface till the end of the simulation. One the other hand, the uncomplexed DCH18C6 resided at the interface, while the Cs + ion diffused to the bulk aqueous phase. The calculated interaction energy of Cs + -BPC6 was found to higher as compared to Cs + -DCH18C6. These results display the importance of the dual cationic exchange properties of IL and the extraction efficiency of CE for extraction of metal ions. [ABSTRACT FROM AUTHOR]

The reaction pathways of PCB-77 in the atmosphere with ·OH, O, NO, and O were inferred based on density functional theory calculations with the 6-31G* basis set. The structures the reactants, transition states, intermediates, and products were optimized. The energy barriers and reaction heats were obtained to determine the energetically favorable reaction pathways. To study the solvation effect, the energy barriers and reaction rates for PCB-77 with different polar and nonpolar solvents (cyclohexane, benzene, carbon tetrachloride, chloroform, acetone, dichloromethane, ethanol, methanol, acetonitrile, dimethylsulfoxide, and water) were calculated. The results showed that ·OH preferentially added to the C5 atom of PCB-77, which has no Cl atom substituent, to generate the intermediate IM5. This intermediate subsequently reacted with O via pathway A to generate IM5a, with an energy barrier of 7.27 kcal/mol and total reaction rate of 8.45 × 10 cm/molecule s. Pathway B involved direct dehydrogenation of IM5 to produce the OH-PCBs intermediate IM5b, with an energy barrier of 28.49 kcal/mol and total reaction rate of 1.15 × 10 cm/molecule s. The most likely degradation pathway of PCB-77 in the atmosphere is pathway A to produce IM5a. The solvation effect results showed that cyclohexane, carbon tetrachloride, and benzene could reduce the reaction energy barrier of pathway A. Among these solvents, the solvation effect of benzene was the largest, and could reduce the total reaction energy barrier by 25%. Cyclohexane, carbon tetrachloride, benzene, dichloromethane, acetone, and ethanol could increase the total reaction rate of pathway A. The increase in the reaction rate of pathway A with benzene was 8%. The effect of solvents on oxidative degradation of PCB-77 in the atmosphere is important. [ABSTRACT FROM AUTHOR]

In our work, the transfer reactions of four cations (Na+, K+, Mg2+, Ca2+) and seven anions (Br-, NO HPO SO CO ClO NO 3 4 2 4 2 3 2 4 2 -, -, -, , -, -) across the micropipette supported water/1,2-dichloroethane (W/1,2-DCE) interface facilitated by propylene carbonate (PC) were investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. Well-defined voltammetric behaviors were obtained for all ions. The electrochemical data were used to determine the thermodynamic parameters (diffusion coefficient, standard Gibbs energy of transfer, stoichiometric ratio and the apparent association constant) of the facilitated ion transfer processes. [ABSTRACT FROM AUTHOR]

• Environment-dependent fluorescence quenching mechanism of 2-phenylbenzo[ b ]phospholium salts was theoretically analyzed. • Several stable structures of ion pairs are obtained in the solution phase. • Absorption and fluorescence processes are characterized by ππ* local excitation. • Fluorescence quenching can be explained by the relaxation to the charge transfer state. • In the electronic excited states, the drastic change in solvation structure is observed by the 3D-RISM-SCF method. Recently reported highly fluorescent 2-phenylbenzo[ b ]phospholium salt shows an interesting photochemical property. While the counter anion and solvent dependency indicate that the salt is mainly responsible for the absorption and fluorescence spectra, the fluorescence decay clearly depends on the counter anion. In the present study, the detailed mechanism is elucidated using quantum chemical computation and its hybrid with statistical mechanics called 3D-RISM-SCF. Based on the careful exploration of plausible structures of the ion pairs in the methanol and dichloromethane solution, we identify the structure of the charge transfer state, the key on the photoprocess. [ABSTRACT FROM AUTHOR]

• Influence of solvents on the molecular structure and dynamic properties. • 1-(4-Fluorophenyl)-1-propanone) was characterized by FMOs, MEP, NLO, & NBO. • AIM and RDG were used to evaluate the compound's covalent interactions in solvents. • Anti-cancer activity was evaluated with the best binding score and inhibition constant. • Investigations on the toxicity of the molecule. 1-(4-Fluorophenyl)-1-propanone) has been extensively investigated in this work due to its significant theoretical and experimental interest and potential pharmacological implications in the evaluation of cytotoxicity. To rationalize compound structure in solution phases through potential energy scan (PES) with optimization of the compound and its stable structure was validated with spectral analysis. Further structural characteristics of weak interactions with chemical functionalities are obtained by topological studies of the AIM and RDG parameters. In LOL and EFL studies, the strongest delocalized zones were found to occur at the locations C7-C10-C11 and C8-C4-C5 of the molecule. When the electronic properties of the title chemical were studied in solutions, the FMOs energies and MEP analysis showed that the compound was more reactive in the aqueous phase and the lower electronic absorption band gap was given by the ethanol solvent. Moreover, variations in the hyperpolarizability (α) and NBO characteristics of the compound were observed in different media. The efficiency of the title compound's anti-cancer activity was evaluated using molecular docking studies, and drug affinity & toxicity of the compound were also anticipated by SwissADME. [ABSTRACT FROM AUTHOR]

• Detailed study on structural properties of the title compound is carried out. • DFT/B3LYP methods with extensive experimental studies on the compound were carried out. • AIM, LOL, and ELFmaps investicated for covalent and non-covalent aspects. • Solvation effects on UV–vis absortion spectra was predicted. • Molecular docking was performed for biological evaluation of antimicrobial activity. In this study, the (4Z)-4-{2-[amino(hydroxy)methyl]hydrazinylidene}-2,6-di(furan-2-yl)-3 methylpiperidin-1-ol [AHMH-DFMP] was synthesized, characterized using spectroscopic and DFT analyses, and its antimicrobial activity was assessed. On this synthesized material, theoretical computations with spectroscopy studies have been carried out utilizing B3LYP level density functional theory (DFT) with a 6-311++(d,p) basis set. The cyclic voltammetry method is used to determine the electrochemical properties of produced heterocyclic compounds. The shape of the voltammetry curves and their peak potential virtually fingerprint the electrochemical reduction of the compound. Structural assignment of the product was concluded based on elemental analysis, infrared, mass and NMR spectroscopy with DFT. In the compound's higher excitation state (TD-DFT approach), the effects of polar and non-polar solvents on UV–vis absorption were examined. The electronic structure of the molecule was extensively studied using topological features of AIM, LOL, and ELF. Furthermore, MEP, FMOs, NLO, Fukui functions, and NBO were calculated for the reactivity and biological needs of the synthesized compound in this work. The final product was evaluated for its anti-microbial activities using disc diffusion method and molecular docking studies. [ABSTRACT FROM AUTHOR]

Syntheses of four iron(II)-azo amino acid complexes ( 1-4) with the general formula [FeL(HO)]Cl· nHO, where L represents azo amino acid ligands, were carried out by direct mixing of N, N-diethylamino-4-nitrosoaniline, amino acids (alanine, histidine, tryptophan or phenylalanine) and Fe(II) ions in aqueous-methanol media. Azo ligands act as bidentate ligands and coordinate to Fe(II) ions through O-carboxylic and N-azo groups. Complexes 1-4 were characterized by IR, UV-visible spectra, thermogravimetric analyses (TGA) and conductance measurements. Kinetics of 1-4 oxidation by peroxydisulfate ions were studied spectrophotometrically in an aqueous media and in various aqueous-methanol binary mixtures at 25 °C. Kinetics of the oxidation followed pseudo-first-order reaction kinetics, $$ k_{\text{obs}} = (k_{2} [{\text{S}}_{2} {\text{O}}_{8}^{2 - } ])[{\text{complex}}] $$ . Reactivity trends and their rate constants are discussed in terms of polarity, hydrophobicity of 1-4, and solvation effect of methanol. The effect of methanol ratios on the oxidation reaction is analyzed into initial ( is) and transition state ( ts) components. The decrease in the rate constant of the 1-4 oxidation, as the ratio of methanol increases, is predominantly caused by the effect of methanol on the initial state ( ts) or by an increase in the Gibbs energy difference between is and ts. [ABSTRACT FROM AUTHOR]

The accumulation of H 2 O 2 on the surface of WO 3 in the process of photoelectrochemical (PEC) water splitting leads to the decrease of photoactivity of WO 3 . To solve this problem, a thin layer of FeOOH acting as water splitting catalyst was coated on the active sites of WO 3 surface. The WO 3 /FeOOH anode, with a deposition time of 20 min, showed a maximum photocurrent of 1.3 mA/cm 2 at 1.23 V vs reversible hydrogen electrode (RHE) under simulated solar illumination (AM 1.5G, 100 mW/cm 2 ). Furthermore, long time photostability of WO 3 was achieved by depositing the FeOOH layer ascribed to its water oxidation ability to generate O 2 rather than H 2 O 2 . Interestingly, we found that a p–n junction between WO 3 and FeOOH formed due to the different solvation effects on WO 3 and FeOOH. The existence of p–n junction favored the transfer of holes from the WO 3 to the FeOOH. [ABSTRACT FROM AUTHOR]

[Display omitted] • The solvation effects of organic anions are investigated in OSN. • Solvation structures exhibit solvent-separated ion pairs and contacting ion pairs. • Pseudo-solvation structure undergoes desolvation due to Na+ transmembrane. • Mixed solvents can be used to regulate solvation size for efficient separations. The solvation effect plays a critical role in chemical reactions and ion transport process, but most studies focus on the solvation effect of metal ions, such as Li+, Mg2+ and so on. Few studies have explored the solvation of organic ions with more complex structures than metal ions. In this work, the solvation effect of organic ions in the organic solvent nanofiltration (OSN) process is investigated, in which methyl orange (MO) is selected as the model organic anions. The solvent-separated ion pairs (SSIP) and contact ion pairs (CIP) are found to form in protic and aprotic solvents, respectively, caused by the differences in solvent polar groups, and the transmembrane mechanism of organic anions in protic and aprotic solvents. Then, the solvation structure of mixed solvent is studied from molecule level, which is further validated by experiment. The addition of water can regulate the solvent environment around MO and weaken adverse effect on rejection performance due to the desolvation process in aprotic solvents. This work is of great significance for achieving high-efficiency separation by adjusting solvation structures, which expands the application scenarios of single membranes. [ABSTRACT FROM AUTHOR]

• Optimized structure of Fmoc-OSu was confirmed by FT-IR and FT-Raman spectra. • The effects of polar and non-polar solvents on Fmoc-OSu studied with solute–solvent interactions parameters. • AIM, LOL, and ELFmaps investicated for topological aspects. • Solvation effects on reactivity sites (FMOs, ESP, & Fukui) predictions. • Biological evaluation with molecular docking for anti-breast cancer activity. In this study, the solvation effects, and spectroscopic characterization of the N-(9-Fluorenylmethoxycarbonyloxy)succinimide (Fmoc-OSu) were described using experimental approaches (FT-IR, FT-Raman, and UV–Vis) with quantum computations. The stable optimized structure in various media was evaluated with the structural and topological (AIM, LOL, and ELF) parameters. The vibrational investigation was utilized to determine the structure of the chemical as well as to find the relation between potential energy distribution and molecular structure. FMOs analysis, Electrostatic potential energy map, and Fukui chemical reactivity descriptors were utilized to study the influence of the solvents on the reactivity of the compound. UV–Vis absorptions with vertical excitations are to detect where there is a greater probability of electron transfer in the compound. Furthermore, the Solvent parameters have described the effects of polar and non-polar solvents on the title molecule. The bioactivity of the chemical was further examined via molecular docking with cancer cell proteins. The Fmoc-OSu produces the most non-covalent interactions against the breast cancer cell development protein (PDB code: 1OQA), which has the highest binding energy of −8.08 kcal/mol. [ABSTRACT FROM AUTHOR]

• The redox potential of TEMPO can be regulated by electrolyte concentration. • The diffusion coefficients of TEMPO decrease as the concentration of LiTFSI increases. • The redox potential of TEMPO shifts negatively with an increase in LiTFSI concentration. • Solvation energy changes and ion pairing are the main contributors to these effects. The redox potential is a fundamental parameter in electrochemistry and is essential in understanding energy-related applications. A typical redox-active molecule, 2,2,6,6-tetramethyl piperidine-1-oxyl (TEMPO), which has an electrocatalytic effect on organic molecules and functions as a mediator in battery technologies, was selected as a model to investigate the dependence of redox potential on the concentration of the supporting electrolyte LiTFSI. Unusual results from cyclic voltammetry have been obtained, showing that the redox potential of TEMPO shifts negatively upon increasing the concentration of LiTFSI. Solvation energy changes from the tunability of dielectric constants and ion pairing are proposed to explain the phenomenon. This work provides insights into tuning the redox potential through simple methods, with applications in the fields of electrocatalysis and battery technology. [ABSTRACT FROM AUTHOR]

The effects of adding an antagonistic salt, sodium tetraphenylborate ( $$\hbox {NaBPh}_4$$ ), to a binary mixture of deuterated water and 2,6-dimethylpyridine were investigated by visual inspection, optical microscopy, and small-angle neutron scattering. With increasing salt concentration, the two-phase region shrinks. When the concentration of $$\hbox {NaBPh}_4$$ is $$85\hbox { mmol}{\cdot} \hbox {L}^{-1}$$ , a temperature-induced lamellar/disorder phase transition is observed at 338 K. These trends are similar to those observed for a mixture of water/3-methylpyridine/ $$\hbox {NaBPh}_4$$ (Sadakane et al., Phys. Rev. Lett. 103, 167803 ). [ABSTRACT FROM AUTHOR]