Single Solvent Research Articles

Theoretical considerations on single and mixed solvent electrolyte solutions

Theoretical considerations on single and mixed solvent electrolyte solutions

The impact of zwitterionic surfactants on optode-based nanosensors via different fabrication approaches and sensing mechanisms.

In this work, we explored the impact of zwitterionic surfactants, sulfobetaine 16 (SB-16) and a PEG-phospholipid conjugate (DSPE-PEG), on nanosensor performance. We fabricated four sensors (for Na+, K+, Al3+, and O2) and examined how these surfactants influenced various aspects, including fabrication methods, sensing mechanisms, and the incorporation of nanomaterials. Our results highlighted SB-16's role in enhancing selectivity in ion-exchange sensors (Na+ and K+) while maintaining sensitivity akin to its PEG counterpart. The liquid-liquid extraction based sensors (Al3+) were unaffected by surfactant choice, while the O2 sensors that operate via collisional quenching exhibited reduced sensitivity with SB-16 when compared to its PEG-based counterpart. Additionally, the SB-16 sensors proved adaptable to different fabrication approaches (SESE - single emulsion solvent evaporation and FNP - flash nanoprecipitation), showcased good cell viability and maintained a functional lifetime of at least five days. Furthermore, via the use of quantum dots, we showed that it is possible to incorporate other nanomaterials into the sensing phase of SB-16 sensors. Future investigations could target enhancing the pH stability of zwitterionic surfactants to further advance their applicability in sensor technologies.

Inkjet printing high mobility indium-zinc-tin oxide thin film transistor

Metal oxide thin film transistor has been widely used in flat panel display industry because of its low leakage current, high mobility and large area uniformity. Besides, with the development of printed display technology, inkjet printing process can fabricate the customizable patterns on diverse substrates with no need of vacuum or lithography to be used, thus significantly reducing cost and receiving more and more attention. In this paper, we use inkjet printing technology to prepare a bottom gate bottom contact thin film transistor (TFT) by using indium-zinc-tin-oxide (IZTO) semiconductor. The surface morphology of the printed IZTO film is modified by adjusting the solvent composition and solute concentration of the printing precursor ink. The experimental result show that the use of binary solvents can effectively overcome the coffee ring shape caused by the accumulation of solute edge in the volatilization process of a single solvent, ultimately presenting a uniform and flat contour surface. Further increase in solute concentration is in favor of formation of convex surface topology. The reason for the formation of the flat surface of the oxide film is the balance between the inward Marangoni reflux of the solute and the outward capillary flow during volatilization. In addition, IZTO thin film transistor printed with binary solvents exhibits excellent electrical properties. The ratio of width/length = 50/30 exhibits a high on-off ratio of 1.21×10<sup>9</sup>, a high saturation field-effect mobility is 16.6 cm<sup>2</sup>/(V·s), a low threshold voltage is 0.84 V, and subthreshold swing is 0.24 V/dec. The uniform and flat active layer thin film pattern can form good contact with the source leakage electrode, and the contact resistances of TFT devices with different width-to-length ratios are less than 1000 Ω, which can reach the basic conditions of high mobility thin film transistors prepared by inkjet printing. Therefore, using solvent mixture provides a universal and simple way to print oxide films with required surface topology, and present a visible path for inkjet printing of high-mobility thin film transistors.

Ketoconazole-loading strategy to improve antifungal activity and overcome cytotoxicity on human renal proximal tubular epithelial cells

Ketoconazole (KTZ), an antifungal agent used to treat localized or systemic fungal infections by inhibiting ergosterol synthesis, exhibits restricted efficacy within eukaryotic cells owing to its elevated toxicity and limited solubility in water. This study aims to improve the biological activity and overcome cytotoxic effects in the renal system of the hydrophobic KTZ by incorporating it into poly(lactic-co-glycolic acid) (PLGA) nanoparticles (NPs) utilizing biomaterial nano-engineering techniques. KTZ-loaded PLGA NPs (KTZ-NPs) were prepared by single emulsion solvent evaporation method and characterized by using dynamic light scattering (DLS), electrophoretic light scattering (ELS), Fourier transform-infrared (FT-IR) spectroscopy and scanning light microscopy (SEM). Particle size and zeta potential of KTZ-NPs were determined as 182.0 ± 3.27 nm and −27.4 ± 0.56 mV, respectively. Antifungal activity was analyzed with the time-kill and top agar dilution methods on Candida albicans (C. albicans) and Aspergillus flavus (A. flavus). Both KTZ and KTZ-NPs caused a significant decrease in A. flavus cell growth; however, the same effect was only observed in time-killing analysis on C. albicans, indicating a methodological difference in the antifungal analysis. According to the top agar method, the MIC value of KTZ-NPs against A. flavus was 9.1 μg ml−1, while the minimum inhibition concentration (MIC) value of KTZ was 18.2 μg ml−1. The twofold increased antifungal activity indicates that nanoparticular drug delivery systems enhance the water solubility of hydrophobic drugs. In addition, KTZ-NPs were not cytotoxic on human renal proximal tubular epithelial cells (HRPTEpCs) at fungistatic concentration, thus reducing fungal colonization without cytotoxic on renal excretion system cells.

Toward High-Quality Sulfide Solid Electrolytes: A Liquid-Phase Approach Featured with an Interparticle Coupled Unification Effect.

Sulfide solid electrolytes (SSEs) are highly wanted for solid-state batteries (SSBs). While their liquid-phase synthesis is advantageous over their solid-phase strategy in scalable production, it confronts other challenges, such as low-purity products, user-unfriendly solvents, energy-inefficient solvent removal, and unsatisfactory performance. This article demonstrates that a suspension-based solvothermal method using single oxygen-free solvents can solve those problems. Experimental observations and theoretical calculations together show that the basic function of suspension-treatment is "interparticle-coupled unification", that is, even individually insoluble solid precursors can mutually adsorb and amalgamate to generate uniform composites in nonpolar solvents. This anti-intuitive concept is established when investigating the origins of impurities in SSEs electrolytes made by the conventional tetrahydrofuran-ethanol method and then searching for new solvents. Its generality is supported by four eligible alkane solvents and four types of SSEs. The electrochemical assessments on the former three SSEs show that they are competitive with their counterparts in the literature. Moreover, the synthesized SSEs presents excellent battery performance, showing great potential for practical applications.

Effect of Solvent Segregation on the Performance of Lithium-Ion Batteries

The pseudo two-dimensional (P2D) model is one of the most powerful tools in modelling lithium-ion batteries (LIBs) 1, in that it can describe the complex electrochemical and thermal behaviours of LIBs with high fidelity yet maintain relatively high computing efficiency. To achieve that, many assumptions have been made, one of which is the single solvent assumption. However, most electrolytes used in LIBs uses multiple solvents to balance the requirements of conductivity, diffusivity and viscosity 2. Therefore, the single solvent assumption indicates that all solvents move as a single entity.However, previous experimental studies have shown that Li+ preferentially attracts cyclic carbonates (like ethylene carbonate, EC) rather than linear carbonates (such as ethyl-methyl carbonate, EMC) to form ion-solvent clusters 3. During charge/discharge, ion-solvent clusters move between the positive and negative electrodes to constitute ionic current. At the electrolyte-electrolyte interface, Li+ de-solvates from the clusters and intercalates into the electrode, or vice versa. Such process will induce concentration gradients of both solvents and lithium ions; the solvent concentration has been ignored in the P2D model. The simplification means the current P2D model fails to capture two important phenomena: (1) many electrolyte properties - including conductivity, diffusivity, and thermodynamic factors - are sensitive to the solvent concentration 4; (2) the solvent components in the ion-solvent clusters are preferentially consumed by interfacial side reactions such as the growth of solid-electrolyte interface (SEI) 3.To fill this gap, we add an extra governing equation for the solvent concentration (in our case, EC) which allows us to describe an electrolyte with two solvents and one salt. We also include a cross diffusion term to consider the dragging effect between the working solvent (EC) and lithium ions. For the charge conservation equation, we directly use measured liquid junction potential as a function of both solvent and lithium-ion concentration, which avoids possible errors brought by identifying the thermodynamic factors.To elucidate the effect of solvent segregation, we compare the overpotential and concentration profile of Li ion and EC at the end of 3C discharge of the normal DFN (single case) and our revised model (double case). The revised model predicts opposite EC concentration compared with Li+, which has been observed by Wang et al. 5 For a high value of , the dragging effect between Li+ and EC is more significant, inducing high concentration gradients of both species. The EC overpotential can be as high as 10 mV and further affects the rate performance of LIBs. This revised model captures more complicated transport mechanisms in the electrolyte and opens the chance of linking the microscopic understanding on solvation structure to a continuum level model. Reference: (1) Newman, J.; Thomas-Alyea, K. E. Electrochemical Systems; 2004.(2) Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem Rev 2014, 114 (23), 11503-11618. DOI: 10.1021/cr500003w.(3) Xu, K. Solvation Sheath of Li+ in Nonaqueous Electrolytes and Its Implication of Graphite/ Electrolyte Interface Chemistry. J. Phys. Chem. C 2007.(4) Ding, M. S.; Xu, K.; Zhang, S. S.; Amine, K.; Henriksen, G. L.; Jow, T. R. Change of Conductivity with Salt Content, Solvent Composition, and Temperature for Electrolytes of LiPF6 in Ethylene Carbonate-Ethyl Methyl Carbonate. Journal of The Electrochemical Society 2001, 148 (10). DOI: 10.1149/1.1403730.(5) Wang, A. A.; Greenbank, S.; Li, G.; Howey, D. A.; Monroe, C. W. Current-driven solvent segregation in lithium-ion electrolytes. Cell Reports Physical Science 2022, 3 (9). DOI: 10.1016/j.xcrp.2022.101047. Figure 1

Purification of Triglyceride from Used Cooking Oil for Biodiesel Feedstock Using Batchwise Solvent Extraction

Green economy and blue economy are essential to applicate. One of the mandatory programs from the Indonesian government is B30, a specification of diesel fuel that has 30 percent of biodiesel content. Based on the biodiesel feedstock specification standard, the free fatty acid content is below 1%. The aim of this research was to produce biodiesel feedstock with high purity of triglyceride from used cooking oil by using batchwise solvent extraction. Batchwise solvent extraction involves the polarity of oil and solvent to separate polar and non-polar lipid fractions. The target of this research was the lowest percentage of free fatty acid and the highest percentage of triglyceride. This method also skipped the general method of refined oil products, such as degumming, neutralization, bleaching, and deodorization. The used cooking oil was mixed with a binary solvent (n-hexane and technical grade ethanol) and a single solvent (food grade ethanol 96% only). Each mixture was stirred at 300 rpm for 15 min and then poured into a separator funnel for 15 min. Polar and non-polar lipid fractions were separated. The non-polar lipid fraction was processed in the same procedure until eight stages. It was found that the batchwise binary solvent extraction produced a non-polar lipid fraction with triglyceride and free fatty acid purities of 88.81% and 2.06%, respectively. Moreover, the batchwise single solvent extraction produced a non-polar lipid fraction with triglyceride and free fatty acid purities of 95.89% and 0.93%, respectively, which is suitable with the standard of biodiesel feedstock below 1%.

Exploring solubility and energetics: Dissolution of biologically important l-threonine in diverse aqueous organic mixtures across the temperature range of 288.15 K to 308.15 K

This research provides a thorough investigation into the solubility behavior and solution thermodynamics of l-threonine in significant organic solvent systems. The work was done on measuring the actual solubility and subsequently calculating overall transfer solvation free energetics (∆Genergetic0i) and transfer entropies (∆St0i) at a temperature of 298.15 K. These measurements were performed as l-threonine transitioned from water to different water-organic mixed solvents systems. The saturated solubilities of l-threonine were determined using the ‘gravimetric method’ at five equidistant temperatures namely 288.15 K, 293.15 K, 298.15 K, 303.15 K and 308.15 K. By analyzing the data on solubility, we further obtained the different energies involved in solvation related issues. In the case of single solvents, the nature of solubility of l-threonine was observed like: dimethylsulfoxide (DMSO) < acetonitrile (ACN) < N, N-dimethylformamide (DMF) < ethylene glycol (EG) < water (H2O), irrespective of the experimental conditions. Specifically, at 298.15 K, the solubilities of l-threonine in single solvents were found to be as follows: 0.8220 mol per kg of water, 0.3101 mol per kg of EG, 0.1337 mol per kg of DMF, 0.1107 mol per kg DMSO and 0.1188 mol per kg of ACN. This research critically examines the relationship between the experimental saturated solubility of l-threonine and the complex properties influencing its solvation energy in diverse aqueous organic solvent systems.

An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries

Li metal batteries using Li metal as negative electrode and LiNi1-x-yMnxCoyO2 as positive electrode represent the next generation high-energy batteries. A major challenge facing these batteries is finding electrolytes capable of forming good interphases. Conventionally, electrolyte is fluorinated to generate anion-derived LiF-rich interphases. However, their low ionic conductivities forbid fast-charging. Here, we use CsNO3 as a dual-functional additive to form stable interphases on both electrodes. Such strategy allows the use of 1,2-dimethoxyethane as the single solvent, promising superior ion transport and fast charging. LiNi1-x-yMnxCoyO2 is protected by the nitrate-derived species. On the Li metal side, large Cs+ has weak interactions with the solvent, leading to presence of anions in the solvation sheath and an anion-derived interphase. The interphase is surprisingly dominated by cesium bis(fluorosulfonyl)imide, a component not reported before. Its presence suggests that Cs+ is doing more than just electrostatic shielding as commonly believed. The interphase is free of LiF but still promises high performance as cells with high LiNi0.8Mn0.1Co0.1O2 loading (21 mg/cm2) and low N/P ratio (~2) can be cycled at 2C (~8 mA/cm2) with above 80% capacity retention after 200 cycles. These results suggest the role of LiF and Cs-containing additives need to be revisited.

Investigation of piroctone olamine delivery to the skin from single, binary and ternary solvent systems.

Disruption of the protective stratum corneum barrier increases the skin's vulnerability to microorganisms and facilitates conditions such as dandruff. Dandruff is a disorder of the scalp that causes increased scaling of the SC and is associated with Malassezia fungus. Consequently, many anti-dandruff commercial products use anti-fungal active ingredients such as piroctone olamine also known as Octopirox (OPX). OPX is an active ingredient used in a number of topical preparations for the management of dandruff. The characterization of the physicochemical properties of OPX was previously reported. The aim of the present work was to investigate a range of solvent systems for their effects on OPX interaction with human skin. The solvents used in this study were propylene glycol (PG), diethylene glycol monoethyl ether or Transcutol® (TC), PG monolaurate (PGML), isopropyl myristate (IPM), caprylic/capric triglyceride or Labrafac™ Lipophile WL 1349 (LAB), PG caprylate or Capryol® 90 (CAP), isostearyl isostearate (ISIS) and Plurol® Oleique CC 497 (PIOI). The single solvent systems evaluated were PG, TC, PGML, IPM, ISIS and CAP. For the binary solvent systems, PG and TC were examined. Ternary solvent systems consisted of: PG, TC and LAB; PG, PGML and LAB; and PG, TC and IPM. The concentration of OPX used was 1% (w/v). Heat-separated human epidermis was used for 24 h permeation experiments performed under finite dose conditions; mass balance studies were also conducted. For the six single solvents examined no permeation was evident. Skin permeation of OPX was observed for binary and ternary solvent systems. The highest permeation for all PG:TC binary solvent system ratios tested was from the PG:TC (75:25) system. For the ternary solvent systems investigated, highest cumulative permeation of OPX was observed for PG:PGML:LAB (60:30:10). Considering all systems, PG:TC (75:25) delivered the greatest amount of OPX through the skin. Although OPX is deposited in the skin following the application of neat solvents, higher skin retention values were generally observed for binary and ternary systems. To our knowledge, this is the first study to examine the permeation behaviour of OPX for a range of single, binary and ternary solvent systems.

Injectable long-acting ivacaftor-loaded poly (lactide-co-glycolide) microparticle formulations for the treatment of cystic fibrosis: In vitro characterization and in vivo pharmacokinetics in mice

Optimizing a sustained-release drug delivery system for the treatment of cystic fibrosis (CF) is crucial for decreasing the dosing frequency and improving patients’ compliance with the treatment regimen. In the current work, we developed an injectable poly(D,L-lactide-co-glycolide) (PLGA) microparticle formulation loaded with ivacaftor, a cystic fibrosis transmembrane conductance regulator (CFTR) potentiator that increases the open probability of the CFTR anion channel, using a single emulsion solvent evaporation technique. We aimed to study the effect of different parameters on the characteristics of the prepared formulations to select an optimized microparticle formulation to be used in an in vivo pharmacokinetic study in mice. First, a suite of ivacaftor-loaded microparticles were prepared using different formulation parameters in order to study the effect of varying these parameters on microparticle size, morphology, drug loading, encapsulation efficiency, and in vitro release profiles. Prepared microparticles were spherical with diameters ranging from 1.91–6.93 µm, percent drug loading (% DL) of 3.91–10.3%, percent encapsulation efficiencies (% EE) of 26.6–100%, and an overall slow cumulative release profile. We selected the formulation that demonstrated optimal combined % DL and % EE values (8.25 and 90.7%, respectively) for further studies. These microparticles had an average particle size of 6.83 µm and a slow tri-phasic in vitro release profile (up to 6 weeks). In vivo pharmacokinetic studies in mice showed that the subcutaneously injected microparticles resulted in steady plasma levels of ivacaftor over a period of 28 days, and a 6-fold increase in AUC 0 – t (71.6 µg/mL*h) compared to the intravenously injected soluble ivacaftor (12.3 µg/mL*h). Our results suggest that this novel ivacaftor-loaded microparticle formulation could potentially eliminate the need for the frequent daily administration of ivacaftor to people with CF thus improving their compliance and ensuring successful treatment outcomes.

Ten-Fold Solvent Kinetic Isotope Effect for the Nonradiative Relaxation of the Aqueous Ferrate(VI) Ion.

Hypervalent iron intermediates have been invoked in the catalytic cycles of many metalloproteins, and thus, it is crucial to understand how the coupling between such species and their environment can impact their chemical and physical properties in such contexts. In this work, we take advantage of the solvent kinetic isotope effect (SKIE) to gain insight into the nonradiative deactivation of electronic excited states of the aqueous ferrate(VI) ion. We observe an exceptionally large SKIE of 9.7 for the nanosecond-scale relaxation of the lowest energy triplet ligand field state to the ground state. Proton inventory studies demonstrate that a single solvent O-H bond is coupled to the ion during deactivation, likely due to the sparse vibrational structure of ferrate(VI). Such a mechanism is consistent with that reported for the deactivation of f-f excited states of aqueous trivalent lanthanides, which exhibit comparably large SKIE values. This phenomenon is ascribed entirely to dissipation of energy into a higher overtone of a solvent acceptor mode, as any impact on the apparent relaxation rate due to a change in solvent viscosity is negligible.

Analysis of agomelatine (Form Ⅱ) dissolution behavior in different mono-solvents: Solubility, solvation thermodynamics as well as inter-molecular interactions

Form II of Agomelatine (AG) is a stable crystal which can be applied to industrial production, and it is mainly used for the treatment of depression. In this paper, the solubility of AG in ten single solvents was determined by the laser dynamic method, and the solubility data were fitted and analyzed using the activity coefficient model and empirical equations (NRTL,λh, Apelblat and Van't Hoff). Besides, the thermodynamic properties of the mixing and dissolution processes were estimated. The compatibility between Agomelatine and selected solvents was analyzed based on HSP, the Hansen Solubility Parameter. On the basis of the Hirshfeld partition (IGMH), the study applied the independent gradient model and the molecular surface to qualitatively elaborate the electrostatic characteristics of the acidity and basicity of Agomelatine. The results show that compared with the other ester solvents, the = O, and > NH groups in the Agomelatine molecule have priority over forming hydrogen bonds with the alcohol solvents. The molecular dynamics simulation of Agomelatine in different solvent systems was conducted by using the Materials studio software, the interaction force between the solute–solvent molecules in the solution was calculated, and the reasons for the solubility difference of Agomelatine in various solvents were analyzed.

Effects of pyrolysis and incineration on the phosphorus fertiliser potential of bio-waste- and plant-based materials

Land application of biomass materials and their products of thermal treatment (biochars and ashes) can offset the unsustainable use of soluble P fertilisers. However, few evaluations of P fertiliser potential have systematically addressed diverse biomass types with contrasting P contents.This paper evaluates the relative P fertiliser potential of four P-rich biowastes (animal bone, poultry manure, pig slurry, and a municipal sewage sludge) and three low-P, plant-based materials (reeds [Phragmites australis L.], rice husks [Oryza sativa L.] and cocoa prunings [Theobroma cacao L.]) and their biochars and ashes. We utilised three complementary approaches: P extractability in single solvents (2% formic and citric acids, and 1 M neutral ammonium citrate); sequential chemical P fractionation, and P dissolution/desorption kinetics.In most cases, pyrolysis and incineration of the P-rich biowastes increased P extractability (% TP) in the single solvents, whilst decreasing water-soluble P. For pig slurry, for example, pyrolysis reduced water-soluble P 20-fold, with corresponding increases observed not only in the solvent-extractable P but also in the pool of potentially plant available, NaHCO3-Pi fraction (e.g., 17 to 35% TP). These complementary datasets were also evident for the low-P feedstocks and thermal products; e.g., pyrolysis increased the NaHCO3-Pi fraction in reed feedstock from 6 to 15% TP. For all biomass feedstocks, biochars and ashes, pseudo-second order P-release kinetics provided the best fit with the experimental data.The data demonstrate scope for using pyrolysis to upgrade the P fertiliser value of a wide range of biomass materials whilst reducing their environmental impact.

Measurement and molecular simulation of the solubility properties of 4-tert-Butyl-2, 6-dinitro-3-methoxytoluene in single and binary solvents

The solubility of 4-tert-Butyl-2, 6-dinitro-3-methoxytoluene (musk amberette) in methanol, ethanol, n-propanol, n-butanol, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran and methanol + tetrahydrofuran at 278.15 K to 318.15 K were determined. All measurement data obtained good results by merging Van’t Hoff, modified Apelblat, λh, Yaws, NRTL, Wilson, Jouyban-Acree and Sun model. The deviation analysis between fitting values and experimental values indicates that the Yaws model was more effectively in fitting the solubility of musk amberette. In addition, the ΔsolH°, ΔsolG°, ΔsolS° of musk amberette solution were discussed by Van’t Hoff equation. Their fruits implied that the dissolution of musk amberette is found to be accompanied by heat absorption and entropy gain processes. This is consistent with the positive slope of the T-x1 curve, which means that high temperature is advantage for the continued dissolution of musk amberette. In contrast, the presence of strong hydrogen bonds between alcohol solvents results in their lowest solubility for musk amberette. As an important task, the melting performance and crystal structure of musk amber were tested through instruments. The same characteristics exclude the presence of solvates or polymorphs. Finally, molecular visualization analysis was used to summarize the interatomic interactions within the crystal of musk amberette. The relationship between HSP, π, α, β, CED and their ability to dissolve musk amberette was discussed. It has been proven that high CED of the solvent is the main obstacle to the dissolution of musk amberette. The interaction between the O atom of musk amberette and hydroxyl H atom of alcohol in binary mixed solutions was obtained through molecular dynamics. Further, elucidated the relationship between mixed solvents and solubility. In summary, these studies will provide strong guidance for the upgrading of musk amberette production processes.

Measurement of the solubility and density of the saturated solution of 3-aminophenol in different pure solvents from 283.1 to 323.1 K: Correlative to pure predictive thermodynamic modeling and molecular dynamic simulation

The solubility of 3-aminophenol was measured in water, isopropanol, ethyl acetate, chloroform, and tert-butyl methyl ether (MTBE) from 283.1 to 323.1 K at atmospheric pressure. In addition, the density of pure solvents and the saturated 3-aminophenol solutions was measured. The experimental solubility data were correlated and predicted using four types of thermodynamic models, including correlative (Wilson, NRTL, and UNIQUAC), semi-predictive (NRTL-SAC, and UNIQAUC-SAC), predictive group contribution methods (UNIFAC, and UNIFAC-DMD), and pure predictive COSMO-SAC model. The NRTL-SAC and UNIQUAC-SAC as semi-predictive models were used to obtain 3-aminophenol conceptual segment numbers, and then, using the NRTL-SAC model, the solubility of 3-aminophenol was predicted in 58 FDA approved solvents in the pharmaceutical industry. The predictive models including UNIFAC and UNIFAC-DMD were also used to predict the 3-aminophenol solubility and compared with the experimental data. The results of the COSMO-SAC model have a large deviation from experimental data. In addition, the experimental solubility data were correlated using the PR equation of state with relative success. The segment-based models such as NRTL-SAC and UNIQUAC-SAC are suggested in the fast solvent screening procedure. Finally, the standard dissolution enthalpy (ΔdisH), the standard dissolution entropy (ΔdisS), and the standard dissolution Gibbs energy (ΔdisG) of 3-aminophenol in the selected solvents were calculated by the Van’t Hoff model and the Gibbs-Helmholtz equation. These values imply that the solubility of 3-aminophenol is an entropy-driven non-spontaneous endothermic process in all chosen single solvents. Using the molecular dynamic (MD) simulation the solvation free energy of 3-aminophenol was calculated. The order of the absolute value of free energy of solvation is as ethyl acetate > isopropanol > MTBE > water > chloroform which is consistent with the order of solubility data.

Room Temperature Evaporation Behavior of Homogeneous Azeotropes Used in Art Conservation Cleaning Treatments

Cleaning painted surfaces of their grime, aged varnishes, and discolored overpaint is one of the most common interventive treatments for art conservators. Carefully concocted solvent mixtures navigate the solubility differences between the material removed and the original paint underneath. However, these solutions may be altered by differential evaporation rates of the component solvents (zeotropic behavior), potentially leading to ineffectively weak cleaning or conversely overly strong residual liquid capable of damaging the underlying paint. Azeotropic solvent blends, which maintain a constant composition during evaporation, offer a promising solution. These blends consist of two or more solvents combined at precise concentrations to function as a single solvent. Additionally, pressure-maximum azeotropes feature higher vapor pressure compared to other mixtures, further minimizing contact time and sorption of the solvents into artworks. This study examines azeotropes of isopropanol with n-hexane and 2-butanone in cyclohexane, which have been used previously in art conservation. The evaporation behavior at room temperature of these boiling point azeotropes was assessed using vapor pressure measurements, refractive index determinations, gravimetric analysis, and gas chromatography. Results showed changes in composition during evaporation and found that the actual room temperature azeotropic composition can vary between 1 and 10% v/v in concentration with those commonly reported at their boiling points. Art conservators should be cautious when using azeotropic blends reported at boiling points significantly higher than room temperature. To ensure the safety and efficacy of these mixtures, it is recommended to determine individual azeotropic cleaning blends experimentally before their use.

Polycaprolactone/Anthocyanin-Based Electrospun Volatile Amines Gas Indicator with Improved Visibility by Varying Bi-Solvent Ratio: A Case of Intelligent Packaging of Mackerel.

Electrospun nanofibers have been applied as a new technology for gas indicators in food intelligent packaging. A poly(ε-caprolactone) (PCL)/red cabbage anthocyanin (RCA)-based nanofiber volatile amines gas indicator was developed by applying a bi-solvent of acetic acid (AA) and formic acid (FA) in electrospinning. The visibility of color change was improved from pink to blue, compared to blue to yellow-green, when using a single solvent of AA. The solutes of PCL (12.5, 15, 17.5, and 20%) and RCA (10, 20, 30, and 40%) and the solvents of AA/FA (9:1, 7:3, 5:5, 3:7, and 1:9) were applied in electrospinning under the condition of 12.5 cm, 1.0 mL/h, and 20 kV. The optimal microstructure with the thinnest fiber diameter and constant arrangement without forming NF beads appeared under the 7:3 FA/AA, 15% PCL, and 20% RCA condition. The indicator changed from pink to blue with the values of total color change (ΔE) of 10, 14, and 18 when exposed to the saturated gas of ammonia solutions of 8, 80, and 800 mM, respectively. The indicator was stable and unchanged in color for 28 days when exposed to light at room temperature. In the application to mackerel packaging, the built-in indicator changed from pink to purple regardless of storage temperature when the spoilage point was reached.

Sustainable approach towards isolation of photosynthetic pigments from Spirulina and the assessment of their prooxidant and antioxidant properties

Carotenoids, chlorophyll and phycocyanin are three types of photosynthetic pigments found in Spirulina that differ in colour, composition, stability, solubility, and commercial importance. Such diversity of structures creates a challenge to extract these pigments simultaneously from the same batch of raw material in an efficient and sustainable manner. This study demonstrates that water can be successfully used as a single solvent together with combined (non)mechanical cell membrane disruption techniques (ultrasonication, centrifugation, freezing/thawing cycle) to extract these photosynthetic pigments from the same batch. This water-based approach delivers a significant improvement in isolating green pigments, which are often overlooked during extraction due to a preference for blue and yellow pigments. Chlorophyll was quantitatively converted to its stable derivatives to carry out a comparative analysis of antioxidant properties (DPPH, TEAC, FRAP), singlet oxygen production and intracellular activities (MTT, ROS assays) using Caco-2 cells.

Electron Delocalization Enables Sulfone‐based Single‐solvent Electrolyte for Lithium Metal Batteries

AbstractLi‐metal batteries (LMB), although providing high energy density, face the grand challenge of identifying good electrolyte solvents for cycling. Common solvents are either only stable against lithium metal anode or only stable against LiNixMnyCo1‐x‐yO2 (NMC) cathode. There is significant effort trying to increase the cathode stability for ether electrolytes, which are in general stable against lithium metal anode. In comparison, there is much less effort trying to increase the anode stability of electrolytes that are stable against NMC cathode. One example is the sulfone‐based electrolyte. It has good cathode stability but is hindered from practical application because of (1) high viscosity and poor wetting capability and (2) poor anode stability. Here, we solve these issues by modifying the sulfone molecules using resonance and electron withdrawing effect. The viscosity is significantly reduced by delocalizing the electrons through introducing additional oxygen on the molecular backbone and applying appropriate fluorination. The resulting molecule 2,2,2‐trifluoroethyl mesylate (TFEM) has decreased Lewis basicity and less reactivity toward Li+. The electrolyte based on TFEM as single solvent enables cycling of LMB under harsh conditions of low N/P ratio (21 mg/cm2 NMC811 and 50 μm Li) with 90 % capacity retention after 160 cycles at C/3 discharge rate.