Binary Solvent Research Articles

Instant in situ highlighting of latent fingerprints by a green fluorescent probe based on aggregation-induced emission

Fluorescence sensing of latent fingerprints (LFPs) has gained extensive attention due to its high sensitivity, non-destructive testing, low biotoxicity, ease of operation, and the potential for in situ visualization. However, the realization of in situ visualization of LFPs especially with green emission and rapid speed is still a challenge. Herein, we synthesized an amphibious green-emission AIE-gen TPE–NI–AOH (PLQY = 62%) for instant in situ LFP detecting, which integrates the excellent fluorescence properties of naphthalimide (NI) with a hydrophilic head and the AIE character as well as the donating property of tetraphenylethene (TPE). TPE–NI–AOH in ethanol/water binary solvent was used as an environmentally friendly LFP developer and achieved in situ green-fluorescence visualization of LFPs. The fluorescence signal achieves its 60% saturated intensity in 0.37 s and nearly 100% in 2.50 s, which is an instant process for the naked eye. Moreover, level 3 details and super-resolution images of LFPs could be observed clearly. Besides, the TPE–NI–AOH developer could be stored for at least 6 months, suitable for long-term storage. This instant in situ highlighting method does not require post-processing operations, providing a more convenient, rapid, and efficient detection method of LFPs. This work would inspire the further advancement of fluorescent sensors for fingerprint imaging.

PNIPAM-based ionic hydrogels for enhanced privacy smart windows and flexible sensor

The thermochromic materials are widely used in the smart window field because they can efficiently regulate solar radiation with temperature changes. Currently, most smart windows switch back and forth between opaque and transparent states to control solar radiation, which is very disadvantageous for the visibility of enclosed environments. Herein, in a binary solvent of ethylene glycol-water (EW), we are developing a series of thermoresponsive ion hydrogels suitable for smart windows by in-situ free radical polymerization of the thermoresponsive monomer N-isopropylacrylamide (NIPAM) and ionic monomers (amphiphilic, anionic, cationic). These smart windows exhibit excellent one-way transparency for privacy protection, allowing observation from a relatively dark private space to a public space outside the smart window during the day, while preventing a view from the relatively bright public space into the private space. Furthermore, these hydrogels demonstrate efficient blocking of ultraviolet / near-infrared radiation, low temperature resistance (∼ −40 °C), wide temperature range thermal responsiveness (∼ −25–60 °C), enabling effective regulation of solar heat radiation. Additionally, the anionic-NIPAM complex hydrogel possesses a high diffusion coefficient of water and excellent conductivity of 13.38 mS cm−1, which can be expanded its application in the field of flexible ion-conductive sensors.

High-Performance Flexible Hybrid Silica Membranes with an Ultrasonic Atomization-Assisted Spray-Coated Active Layer on Polymer for Isopropanol Dehydration.

Organic-inorganic hybrid silica materials, incorporating an organic group bridging two silicon atoms, have demonstrated great potential in creating membranes with excellent permselectivity. Yet, the large-scale production of polymer-supported flexible hybrid silica membranes has remained a significant challenge. In this study, we present an easy and scalable approach for fabricating these membranes. By employing a sol-gel ultrasonic spray process with a single-pass method, we deposited a thin and uniform hybrid active layer onto a porous polymer substrate. We first optimized the deposition conditions, including substrate temperature, the binary solvent ratio of the silica sol, and various ultrasonic spray parameters. The resulting flexible hybrid silica membranes exhibited exceptional dehydration performance for isopropanol (IPA)/water solutions (IPA: 90 wt%) in the pervaporation process, achieving a water flux of 0.6 kg/(m2 h) and a separation factor of around 1300. This work demonstrates that the single-pass ultrasonic spray method is an effective strategy for the large-scale production of polymer-supported flexible hybrid silica membranes.

Fabrication of highly stretchable composite organohydrogel for strain sensors with high sensitivity and broad temperature tolerance

Elastically stretchable conductive hydrogels have garnered significant scholarly interest for their potential applications in wearable sensing technologies. Yet, these highly elastic hydrogels often display diminished sensory capacities, particularly under conditions of severe thermal variation. This investigation unveils a highly stretchable composite organohydrogel distinguished by its superior sensory proficiency and resilience to harsh thermal environments. Encapsulating carbonized crepe paper (CCP) within a hydrophobic association-driven organohydrogel-crafted through the micellar copolymerization of hydrophobic stearyl methacrylate with hydrophilic acrylamide, and incorporation of polyvinyl alcohol (PVA) and Al3+ in a binary solvent of glycerol and water-we attained a high stretchability of 3865 %, in conjunction with augmented tensile strength and sensory acuity. Moreover, this composite demonstrates a gauge factor of 263.1 for strains ranging from 400 to 550 %, a detection threshold of 0.1 %, swift response/recovery times (161/152 ms), and sustained durability over 1000 cycles at a 100 % strain. Such attributes facilitate its deployment in the realms of health monitoring, activity sensing, gesture recognition, and wireless motion control, even under extreme thermal conditions, heralding a pioneering strategy for the creation of cost-efficient, high-efficacy electronic conductive hydrogels.

Low-Temperature Rapid Polymerization of Intrinsic Conducting PAD/OC Hydrogels with a Self-Adhesive and Sensitive Sensor for Outdoor Damage Repair and Detection.

Intrinsic conducting hydrogels fabricated in situ at low temperatures with self-adhesive properties and excellent flexibility hold significant promise for energy applications and outdoor damage repair. However, challenges such as low polymerization rate and self adhesion, insufficient ionic conductivity, inflexibility, and poor stability under extreme cold conditions have hindered their utilization as high-performance sensors. In this study, we designed an intrinsic conducting hydrogel (PADOC) composed of acrylic acid, acryloyloxyethyltrimethylammonium chloride, N,N'-methylenebis(2-propenamide), self-fabricated oxidized curdlan (OC), and a water/glycerol binary solvent. The novel hydrogel exhibited rapid gelation (30 s) at 0 °C facilitated by the promotion of OC, without the need for external energy input. Our findings from FT-IR, NMR, XPS, XRD, EPR spectra, MS, and DSC analyses revealed that OC underwent selective oxidation via the evolved Fenton reaction at 30 °C, serving as bioaccelerators for PAD polymerization. Due to OC's reductive structure and increased solubility, the reaction activation energy of the PAD polymerization reaction significantly reduced from 103.2 to 54.4 kJ/mol. PADOC ionic hydrogels demonstrated an electrical conductivity of 1.00 S/m, 0.7% low hysteresis, 39.6 kPa self-adhesive strength, and 923% strain-at-break and kept even at -20 °C owing to dense hydrogen and ionic bonds between PAD and OC chains. Furthermore, PADOC ionic hydrogels exhibited antifatigue properties for 10 cycles (0-100%) due to electrostatic interactions and hydrogen bonding. Remarkably, using a self-designed device, the rapid polymerization of PADOC effectively repaired copper pipeline leakage under 86 kPa pressure and detected 1% strain variation as a strain sensor. This study opens a new avenue for the rapid gelation of self-adhesive and flexible intrinsic conducting hydrogels with robust sensor performance.

Solubility of 2,5-Furandicarboxylic Acid in Pure and Mixed Organic Solvent Systems at 293 K Predicted Using Hansen Solubility Parameters.

Central to the production of polyethylene furanoate (PEF), a bioplastic that could potentially replace petroleum-derived plastics, is 2,5-furandicarboxylic acid (FDCA). FDCA is a chemical derived from biomass that has low solubility in traditionally used solvents such as water. Thus, identifying solvents that can solubilize significant amounts of FDCA could allow for lower PEF production costs. In this study, FDCA solubility was investigated in nine pure solvents including H2O, acetonitrile (ACN), γ-valerolactone (GVL), γ-butyrolactone (GBL), ethanol (EtOH), methanol (MeOH), dimethyl sulfoxide (DMSO), sulfolane (SULF), and tetrahydrofuran (THF), eight binary, and three ternary solvent blends at 293 K. For all binary systems excluding DMSO and MeOH, the solubility of FDCA increased 1.5-65 times compared to the pure organic solvent, and the FDCA solubility was at least 10 times higher when compared to pure water. Specifically, the 20/80 w/w H2O/DMSO system solubilized 23.1 wt % FDCA, the highest of any binary blend studied, and 190 times more solubility than in pure water. In 20/80 w/w H2O/THF, the FDCA solubility was 60 times higher than pure water. In ternary blends that included DMSO, H2O, and either GVL, THF, or SULF, solubility increased by at least 6.6 times relative to the pure secondary organic component and 54 times relative to pure water. Using Hansen solubility parameters (HSPs), the radius of interaction (R i,j ) was found to be more strongly correlated to FDCA solubility than individual HSPs or the total solubility parameter. A MATLAB-based optimization code was developed and successful in minimizing the R i,j of a solvent blend to maximize FDCA solubility in binary and ternary aqueous solvents.

Investigation of the Functional Components in Health Beverages Made from Polygonatum cyrtonema Rhizomes Provides Primary Evidence to Support Their Claimed Health Benefits.

This study aims to understand the functional component compositions of traditional herbal health beverages made from Polygonatum cyrtonema rhizomes and to reveal the pharmacodynamic chemical basis for their claimed health benefits. Two traditional methods, rhizome decoction and rhizome infusion, were used to make health herbal beverages, including "Huangjin" tea and "Huangjin" wine, respectively. The secondary metabolites of "Huangjin" beverages were investigated and compared by widely targeted metabolomics. The results clearly showed that the major functional components in "Huangjin" beverages were phenolic acids, flavonoids, and alkaloids. The "Huangjin" wine has a greater variety of flavonoids and alkaloids than "Huangjin" tea, and the functional components in "Huangjin" wine were more abundant than those in "Huangjin" tea. Homoisoflavones and amide alkaloids were the dominating flavonoids and alkaloids in "Huangjin" wine, respectively. Continuous rhizome infusion could not increase the content of functional components in "Huangjin" wine. In conclusion, this study not only provides primary evidence to support the claimed health benefits of "Huangjin" beverages but also suggests that making traditional herbal beverages by rhizome infusion has superior health benefits than making them by rhizome decoction, which is attributed to the higher yields of functional components extracted by Chinese liquor than hot water. Therefore, Chinese liquor shows advantages in its use as a superior binary ethanol-water solvent in making herbal health beverages to enhance the solubility of poorly water-soluble functional components.

Determination and Correlation of the Solubility of Potassium Fluoride in Eight Single Solvents and Four Binary Solvent Mixtures at Different Temperatures

Determination and Correlation of the Solubility of Potassium Fluoride in Eight Single Solvents and Four Binary Solvent Mixtures at Different Temperatures

Mobility-induced kinetic effects in multicomponent mixtures

We give an overview exploring the role of kinetics in multicomponent mixtures. Compared to the most commonly studied binary (single species plus solvent) case, multicomponent fluids show a rich interplay between kinetics and thermodynamics due to the possibility of fractionation, interdiffusion of mixture components and collective motion. This leads to a competition between multiple timescales that change depending on the underlying kinetics. At high densities, crowding effects are relevant and non-equilibrium structures can become long-lived. We present the main approaches for the study of kinetic effects in multicomponents mixtures, including the role of crowding, and explore their consequences for equilibrium and non-equilibrium scenarios. We conclude by identifying the main challenges in the field.

Significant Improvements to Si Calendar Lifetime Using Rapid Electrolyte Screening via Potentiostatic Holds

Silicon-based lithium-ion batteries exhibit severe time-based degradation resulting in poor calendar lives. This has been identified as the major impediment towards commercialization with cycle life considered a solved issue through nanosizing and protective coatings allowing over 1000 cycles of life to be achieved. In this work, rapid screening of sixteen electrolytes for calendar life extension of Si-rich systems (70 wt% Si) is performed using the voltage hold (V-hold) protocol. V-hold significantly shortens the testing duration over the traditional open circuit voltage reference performance test allowing us to screen electrolytes within a span of two months. We find a novel ethylene carbonate (EC) free electrolyte formulation containing lithium hexafluorophosphate (LiPF6) salt, and binary solvent mix of fluoroethylene carbonate (FEC), ethyl methyl carbonate (EMC) that extends calendar life of Si cells as compared to conventional EC based electrolyte. Our coupled experimental-theoretical analysis framework provides a decoupling of the parasitic currents during V-hold, allowing us to extrapolate the capacity loss to predict semiquantitative calendar lifetimes. Subsequently, cycle aging and oxidative stability tests of the EC free system also show enhanced performance over baseline electrolyte.

A “Hand‐In‐Hand” Thermal‐Responsive Cyclodextrin Material Designed for Liquid Smart Windows

AbstractThermochromic smart windows have emerged as a focal point in energy research. In this study, a novel approach is introduced for developing thermoresponsive materials for smart windows, utilizing microscopic agglomeration of molecules to regulate incident light. The groundbreaking material, β‐CD‐Val‐IBAm4, is constructed by grafting four isobutylated valines onto natural β‐cyclodextrins. This material exhibits a unique “hand‐in‐hand” effect, resulting from the interaction of isobutylated valine side chains, which leads to molecular aggregation and reduced light transmission at elevated temperatures. The hydration–dehydration process is related to molecular aggregation rather than crosslinking, ensuring the structural integrity and uniformity of the smart windows. Molecular dynamics simulations and 2D NOESY confirm the thermal response mechanism of β‐CD‐Val‐IBAm4. When dissolve in a glycerol‐water binary solvent system, the material forms a thermochromic liquid with outstanding optical performance (ΔTsol of 1 mm liquid can reach 69.8%) and long‐term stability. This innovative approach opens new avenues for the advancement of next‐generation smart window technologies.

The solvation thermodynamics of rose acetate in four mixed solvents: Molecular dynamics simulation, molecular conformation analysis, machine learning and solubility prediction

The solubility of rose acetate (alpha-(trichloromethyl) benzyl acetate) in four binary solvent mixtures was measured by static gravimetric method at the temperature ranging from 288.15 K to 328.15 K under atmosphere pressure. The dissolution behavior and solubility prediction were performed through simulations and calculations, using Materials Studio software and Back Propagation Neural Network. The modified Apelblat equation, λh model, Van’t Hoff equation, and NRTL model were employed to correlate the solubility data respectively. And the modified Apelblat equation provided the best fitting performance, corresponding to the lowest average value of average relative deviation and root mean square deviation. After analyzing the solvent properties, it was obsersved that the solubility of rose acetate in selected solvents was influenced by the polarity of the solvent. The mixing thermodynamic properties including ΔmixH, ΔmixS and ΔmixG indicated that the dissolution process of rose acetate was exothermic and spontaneous.Molecular dynamics (MD) simulations were utilized to analyze the interaction mechanism between rose acetate and binary solvent mixtures. The results revealed that the hydrogen bonding interaction played an insignificant role in the dissolution process. Moreover, the solute molecules were characterized in both crystal and solution state based on their conformation and molecular energies. A back-propagation (BP) neural network was constructed to predict the solubility of rose acetate, and the predicted data exhibited good agreement with the measured valuses.

Co-Solvent effect and Kinetics of Alkaline Hydrolysis of Butyle Salicylate

The base catalised hydrolysis of buyl salicylate has been carred out in water-DMF binary solvent mixture covering range of 30 to 70% (v/v) of solvent composition at different Temperature (20 to 400 C). The reaction followed second order rate constant which decreases with increase of solvent composition. The salvation and desolvation concept are used to explain the solvent influence on rate and mechanism is the reaction. The relation between changes in dielectric constant due to variation of reaction mixture and change in specific rate constant has been explained on the basis of electrostatic and non-electrostatic contribution of solvent mixture. Calculated value of Iso-composition activation energy is found to be increases with increase of solvent composition. The thermodynamic parameters (ΔG*, ΔH* & ΔS*) has been determined with help of Wynne Jone and Eyring equation which show the great dependency on solvent composition.

Characterization Electrospun Nanofibers Based on Cellulose Triacetate Synthesized from Licorice Root Cellulose

Cellulose triacetate (CTA) nanofibers were formed by electrospinning using two binary solvent systems: methylene chloride/ethanol and chloroform/acetone. Previously, licorice root cellulose (LRC) with a degree of polymerization (DP) of 710 was extracted from licorice root waste by alkaline treatment and hydrogen peroxide bleaching at high temperatures. Then CTA with a degree of substitution (DS) of 2.9 and an average molecular weight of 175 kDa was synthesized from LRC using acetic acid and acetic anhydride, sulfuric acid was as a catalyst. The influence of the electrospinning process and various solvent systems on the morphology and structure of nanofibers is studied. The structure and morphology of the nanofibers were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and the sorption characteristics were also investigated. The results showed that the morphology and structure of nanofibers depended on the solvent mixture used. The average diameters of the CTA nanofibers with grooved morphology varied 200-700 nm (solvent methylene chloride/ethanol) and the dumbbell-shaped (flat ribbon) CTA nanofibers in a wide range from 200 nm to 4 mkm (solvent chloroform/acetone).

Fully Physically Crosslinked PNIPAM Ionogels with High Mechanical Properties and Temperature‐Managed Adhesion Achieved by H2O/Ionic Liquid Binary Solvents

AbstractPoly(N‐isopropylacrylamide) (PNIPAM) gels change their volume and hydrophilicity in response to temperature stimulus in flexible actuators, flexible sensors, and energy storage management. However, traditional PNIPAM gels exhibit low mechanical properties and poor self‐recovery ability due to weak intermolecular (chain) interactions and necessary covalent crosslinking. Herein, a water/ionic liquid (H2O/IL) binary solvent system that provides additional hydrogen bonding and hydrophobic interactions as well as can significantly increase the solubility (up to 60 wt.%) of NIPAM is developed. The fully physically crosslinked PNIPAM ionogel is prepared by utilizing the H2O/IL binary solvent and exhibited excellent mechanical performances, rapid self‐recovery properties, and strong adhesion strength. In addition, the lower critical solution temperature of the PNIPAM ionogel can also be tuned over a wide range (37‐70 °C) by adjusting the IL ratio in the binary solvent. Furthermore, based on the temperature sensitivity and ionic conductivity of the PNIPAM ionogel, applications of PNIPAM ionogels in smart devices, temperature‐managed adhesion, and flexible sensing are demonstrated, respectively. This work improves various performances of PNIPAM gels by using the H2O/IL binary solvent to adjust non‐covalent interactions and provided new ideas for developing high‐performance temperature‐sensitive gels.

Solvatochromism in Mixtures of Hydrogen Bond Acceptor (HBA) Solvents with Water.

The UV/Vis absorption energies νmax of Reichardt's dye B30 with respect to ET(30) and 4-nitroaniline (NA) are investigated as a function of the solvent composition Nav,z. in co-solvent/water mixtures. Nav,z. is the average molar concentration of the solvent mixture at a given solvent fraction z. The z can be the mole, the volume or the mass fraction. The co-solvents considered were acetonitrile, acetone, tetrahydrofuran, pyridine, piperidine and 2-(diethylamino)-ethanol. Acetone and acetonitrile can be expected to slightly enhance the water structure at low co-solvent concentrations. This interpretation is supported by the analysis of the refractive index as a function of the solvent composition. In general, it can be stated that the structural complexity of the binary solvent mixtures is mainly responsible for the evolution of the absorption energies ET(30) or νmax(NA) as a function of the mixture composition. In particular, the endothermic solvation of NA in co-solvent/water mixtures and its effect on the νmax(NA) is highlighted.

Environment-tolerant gelatin based ionic conductive organohydrogel for flexible sensor

Flexible wearable devices based on hydrogels have attracted more and more attention, however, the preparation of hydrogels with high toughness, conductivity and anti-freezing and anti-drying is still a challenge. In this study, a chemical-physical cross-linked double network conductive organohydrogel was designed by incorporating gelatin and Lithium chloride (LiCl) into polyacrylamide (AM) network with water-glycerol binary solvent. The results displayed that the organohydrogel exhibited high toughness, high stretchability, anti-freezing and anti-drying capability. With the addition of glycerol and LiCl, the organohydrogel has shown good conductivity in wide ranges of temperature. Moreover, the organohydrogel could be used as a strain sensor for the detection of various human body motions. Meanwhile, it was found that the introduction of LiCl enhanced the strain sensing performance, the stability and working temperature range. The sensors exhibited a high thermal sensitivity (5.72 % /℃), broad temperature detection range (0–65℃). These outstanding advantages indicated that the organohydrogels have potential application as strain and temperature sensors.

Hydroxypropyl methylcellulose reinforced bilayer hydrogel dressings containing L-arginine-modified polyoxometalate nanoclusters to promote healing of chronic diabetic wounds

Diabetes-related slow healing of wounds is primarily driven by bacterial infections and angiogenesis disorder and presents a substantial hurdle in clinical treatment. To solve the above problems, an advanced multifunctional hydrogel system based on natural polymer was created here to facilitate wound healing in patients with chronic diabetes. The prepared dressing was composed of an outer hydrogel containing polyvinyl alcohol and hydroxypropyl methyl cellulose in dimethyl sulfoxide and water as binary solvents, and an inner hydrogel containing chitosan quaternary ammonium salt, flaxseed gum, and polyvinyl alcohol. Thus, a polysaccharide based bilayer hydrogel (BH) with superior mechanical strength and biocompatibility was created. This bilayer hydrogel could easily bind to dynamic tissue surfaces, thereby generating a protective barrier. Meanwhile, L-arginine-modified polyoxometalate (POM@L-Arg) nanoclusters were loaded in the inner hydrogel. They released NO when stimulated by the peroxide microenvironment of diabetic wounds. NO as a signal molecule regulated vascular tension and promoted cell proliferation and migration. Additionally, because of the synergistic effect of NO and the chitosan quaternary ammonium salt, the hydrogel system exhibited excellent antibacterial performance. The NO released reduced the levels of proinflammatory factors IL-6 and TNF-α in the diabetic wounds, which thus accelerated wound healing. In short, BH + POM@L-Arg is expected to serve as an ideal wound dressing as it exerts a good promotion effect on diabetes-related wound healing.

Experimental and model-based approach to evaluate solvent effects on the solubility of the pharmaceutical artemisinin

The separation and purification of plant-based Active Pharmaceutical Ingredients (API) from extracts is a crucial part in pharmaceutical process development. For the purification of the antimalarial drug component artemisinin (ARTE) from an Artemisia anna L. toluene extract, antisolvent crystallization is considered. Solubilities of ARTE in binary solvent mixtures of toluene and two potential antisolvents, n-heptane and ethanol, were determined at temperatures from 278.15 K to 313.15 K. The experimental work was supported by the application of various models, utilizing varying amounts of experimental input data. The goal was the identification of models that are able to predict solubilities in binary solvent mixtures sufficiently accurate and, thus, can help to reduce the experimental effort for future solvent screenings. In this study, we applied the PC-SAFT model both with and without fitting the binary interaction parameter kij between ARTE and the respective solvent, as well as the empirical Jouyban-Acree model. From the experiments, n-heptane demonstrated to be a promising antisolvent, while ethanol acted more as a cosolvent. All models tested were capable of distinguishing between effective and ineffective antisolvents. The purely predictive PC-SAFT model applied with kij = 0 exhibited the largest deviation from the experimental data. This was followed by the PC-SAFT model including fitted kij values, based on at least four experimental data points. The Jouyban-Acree model fitted the data most accurately. Its parametrization required a minimum of ten experimental data points.

Solubility Measurement, Model Correlation, and Solvent Effect Analysis of Spectinomycin Dihydrochloride Pentahydrate in Three Binary Solvents

Solubility Measurement, Model Correlation, and Solvent Effect Analysis of Spectinomycin Dihydrochloride Pentahydrate in Three Binary Solvents