Journal of Solution Chemistry最新文献

Ionic liquid (IL) assisted liquid–liquid-extraction (LLE) has been emerged as fascinating pathway to extract gallium (Ga(III)) from electronic waste. The computational investigation of LLE invokes the UNIQUAC model with extended Pitzer–Debye–Hückel (PDH*) framework to accommodate long range interactions due to the presence of ions. The combination of quantum chemical calculation and global optimization technique have been incorporated to estimate the model parameters. Herein, phosphonium and ammonium-based ILs having 26 tie-lines are used for sole Ga(III) extraction and 14 tie-lines for co-extraction. The sole Ga(III) extraction exhibits deviation between 0.5 and 0.8%, and co-extraction ranges from 0.85 to 1.5% and thus highlights the goodness of estimation.

Three ionic liquids (ILs)(1-ethyl-2,3-dimethylimidazolium acetate, [EMMIM][AC]; tributyl-methylammonium acetate, [N_4,4,4,1][AC]; and tetraethylammonium acetate, [N_2,2,2,2][AC]) were chosen. The vapor–liquid equilibrium (VLE) data of ternary mixtures (acetate + ethanol + IL) were measured at 101.3 KPa. NRTL equation was used to correlate the data. From NRTL model, for [N_2,2,2,2][AC], [EMMIM][AC], and [N_4,4,4,1][AC], minimum mole fractions for completely eliminating azeotrope are 0.015, 0.020 and 0.022, respectively. From the average relative volatility and σ-profiles, it can be obtained that the separation ability order is [EMMIM][AC] > [N_2,2,2,2][AC] > [N_4,4,4,1][AC].

One of the new synthetic cathinones that has a high tendency to replace ecstasy and other established synthetic drugs is N-ethylpentylone, (NEP), due to its high potency, stimulative, hedonic and hallucinatory effects. In order to examine the interactions of N-ethylpentylone, the apparent molar quantities, thermal expansion coefficient and the apparent molar volume at infinite dilution were calculated from the experimental measurements of the density of NEP aqueous solutions in different temperature and molality ranges, from T = (293.15 to 313.15) K and from m = (0.0590 to 0.0977) mol·kg⁻¹, respectively. The taste of N-ethylpentylone was estimated by calculated values of apparent specific molar volume at infinite dilution and it was concluded that its taste in aqueous solutions is bitter. Also, using the spectrofluorimetric technique, an intermolecular deactivation of in situ formed ethidium bromide (EB) complex with DNA (EB-DNA) was investigated in the presence of N-ethylpentylone. Obtained results indicated good affinity and efficiency of NEP to substitute EB from the EB-DNA complex via intercalation mode. Using molecular docking, it was concluded that the binding energy obtained for NEP indicates its higher affinity to interact with DNA, compared to methamphetamine and amphetamine, but lower compared to ecstasy. The affinity of NEP to bind to bovine serum albumin (BSA) was also investigated and discussed. It is shown that N-ethylpentylone could be efficiently transported and distributed through the blood and cells.

Cuminaldehyde, an oxidized aldehyde monoterpene, present in green cumin seeds (Cuminum cyminum Linn, Family—Apiaceae), is traditionally used for the treatment of abdominal colic, dyspepsia, diarrhea, and jaundice. Also, many studies have reported the antioxidant, antibacterial and antifungal effects of cuminaldehyde. Serum albumins are the major soluble and small molecule-binding proteins, present in abundance in the circulatory system of a wide variety of organisms. Studies on the interaction of bioactive molecules with bovine serum albumin (BSA) and human serum albumin (HSA) have attracted enormous interest due to its direct consequence on drug delivery, pharmacokinetics, pharmacodynamics, therapeutic efficacy and drug designing. Our present study is carried out to understand the mechanism of interaction of pharmaceutically important component of spices, cuminaldehyde with BSA and HSA. Fluorescence spectroscopic measurements confirmed that cuminaldehyde interacted with BSA and HSA and quenched its fluorescence intensity via static quenching mechanism. UV–Visible absorption studies and CD-spectroscopy showed the change in secondary conformation of BSA and HSA upon interaction with cuminaldehyde. CD-spectroscopy revealed that HSA is unfolded at lower concentration of cuminaldehyde compared to BSA. The location of binding site for cuminaldehyde in BSA and HSA was investigated by site probe displacement experiments and the results indicated that cuminaldehyde preferred to bind site-I, located in subdomain IIA of both BSA and HSA. Thermodynamic studies revealed that vander Waal’s interaction and hydrogen bonding play a major role in cuminaldehyde-BSA system while hydrophobic interactions play vital role in cuminaldehyde-HSA system. The molecular dockings of cuminaldehyde with BSA/HSA further confirmed the formation of the stable BSA/HSA–cuminaldehyde complex and cuminaldehyde binds at site-I of HSA. On the other hand, docking study showed that cuminaldehyde interacts with some residues close to site-I of BSA. Both experimental and theoretical results showed that the ΔG⁰ values are comparable for both the proteins, which indicate almost equal stability of cuminaldehyde-BSA and cuminaldehyde–HSA complex.

Abstract

Urea, as a nonelectrolyte molecular solute in aqueous solutions, has a vital role in the thermodynamic, thermophysical and physiochemical studies. To a large extent, addition of Urea to water does not alter the structural dynamics of water. Only a little amount of water molecules is supposed to be closely associated with urea molecules. Therefore, study of intramolecular as well as intermolecular interactions in the binary aqueous urea solution by conducting thermophysical and thermodynamic investigations is quite important. In this work, new experimental data on water activity for solutions containing urea under precisely controlled conditions and derived thermodynamic parameters were reported. Water activity of urea was also estimated from the Kirkwood–Buff integrals in a novel way.

Abstract

In this study, we investigate some structural and dynamical properties of aqueous KCl solutions at different temperatures and concentrations. We study a 1.6 mol·kg^–1 aqueous KCl solution at five temperatures and five concentrations at ambient conditions only. Molecular dynamics simulations with the flexible SPC water model were conducted to characterize all partial pair correlation functions, the velocities auto-correlation ones, and the dielectric constants. The analysis of the water pair correlation functions shows a disruption of the H-bond network and a decrease of the oxygen-hydrogen coordination number as temperature or salt concentration increases. The increase of each parameter favors the exchange of molecules between the first and the second hydration shells. Ions pair correlation functions show principally that the fraction of K⁺-Cl⁻ contact ion pairs increases and that of separated ion pairs decreases with increasing temperature or concentration. For all particles, the values of the calculated self-diffusion coefficients rise with temperature and fall with salt concentration. The self-diffusion coefficients of K⁺ and Cl⁻ tend to towards each other at high concentration. Temperature or salt concentration causes a drop in the dielectric constant. For all studied temperatures or salt concentrations, the calculated ratio of the orientational correlation times τ₁/τ₂ for the OH vector indicates that the motion of water molecules can be accounted for by an angular jumps model.

The interaction mechanism between xanthan gum (XG) and bovine serum albumin (BSA) was studied by various spectral and molecular docking techniques. The fluorescence spectrum analysis reveals that XG and BSA are quenched, with XG quenching BSA in a static manner according to the Stern-Volmer equation. The Vant’s Hoff equation indicates negative values for the thermodynamic parameters ΔH, ΔG, and ΔS during the binding process. Therefore, it can be concluded that hydrogen bonding and van der Waals forces dominate the interaction between XG and BSA, resulting in a spontaneous and exothermic quenching process. The results of molecular docking simulation show that hydrogen bond and van der Waals force are the main forces between XG and BSA. Through multispectral analysis, it is observed that XG affects the microenvironment of BSA by increasing its polarity and hydrophilicity while weakening its hydrophobicity. This leads to changes in the secondary structure of BSA molecules. The binding distance between XG and BSA is calculated to demonstrate energy transfer between them, and overlap integral calculations confirm the presence of non-radiative energy transfer from XG to BSA. Analysis of the circular dichroism spectrum reveals that interaction between BSA and XG leads to protein relaxation, a decrease in α-helix structure, and an increase in β-sheet structure, providing further evidence for alterations in the secondary structure of BSA. Through the study of the interaction between XG and BSA, the interaction mechanism of both is analyzed, which provides data support for their future discussion and research.

Motivated by the scarcity of prior research, in this study we report the synthesis and photophysical characteristics of newly obtained benzanthrone ethynyl derivatives. Fourier-transform infrared spectroscopy, ¹H and ¹³C nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry elucidated the structures of the compounds. To study photophysical characteristics, absorbance and emission spectra were measured in solvents with different polarities. Photofading proved high stability of the synthesized compounds (up to 96% of initial absorption after irradiation for 4 h). The analyzed compounds are fluorescent (quantum yields from 0.01 to 0.74 in ethanol) with a significant solvatochromic effect (from 466 nm in benzene to 720 nm in dimethyl sulfoxide). Based on these findings, there is a correlation between the electronic nature of substituents and photophysical parameters. Hence, these compounds could find applications as probes in fluorescence microscopy and sensors to detect polarity variations.

Graphical Abstract

Non-ionic hydrophobic eutectic solvents have emerged as a new class of eutectic solvents. They are prepared by mixing two non-ionic components. They have gained significant interest compared to their counterpart ionic hydrophobic eutectic solvents and hydrophobic ionic liquids due to the availability of a wide array of non-ionic substances that can be used to prepare these solvents. Understanding the distinct physical characteristics of these solvents is crucial to their practical application within process industries and associated fields. The present work reports the development of a density model for these solvents based on the conductor-like screening model (COSMO), a dielectric continuum solvation model. For this purpose, a comprehensive literature search was carried out, and 485 density points of 37 different hydrophobic non-ionic eutectic solvents were collected. COSMO volume, one of the outputs of the COSMO calculations, was correlated with the experimental molar volume for the model development. Two different models were developed, one at 298.15 K and another a general model that can predict the density over a wide temperature range at atmospheric pressure. The developed model only requires the molar ratio and COSMO volumes of the components forming the eutectic solvents to predict the density. The proposed general model performed better than most other models and was comparable with the best one reported in the literature, with an average relative deviation percent (ARD%) of 1.34%.