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Numerical simulations of silicone oil–water two-phase turbulent dispersion mixing in Q-type static mixers (QSM) are performed using computational fluid dynamics (CFD) coupled with a population bala...

We investigated the kinematic viscosity and electrical resistivity of the multicomponent Fe74Cu1Nb1.5Mo1.5B8.5Si13.5 melt during three heating–cooling cycles. The temperature dependence of kinematic viscosity and electrical resistivity have the anomalous zones in the same temperature range and they are associated with the liquid–liquid structure transition (LLST). The anomalies were explained by changes in the activation energy and the cluster size. As the cluster size decreases, the activation energy decreases, but the viscosity and electrical resistance increase. LLST begins with the cluster dissolution, and as a result, the Arrhenius plot becomes nonlinear in the transition temperature range. After three cycles of heating–cooling, the temperature dependences of the kinematic viscosity and electrical resistance did not qualitatively change, and this allows us to conclude that LLST is thermoreversible. With an increase in the number of thermal cycles, the activation energy of viscous flow decreases, as well as the onset temperature and temperature range of LLST.

The presence or absence of liquid–liquid phase separation (LLPS) in aerosol particles containing oxidized organic species and inorganic salts affects particle morphology and influences uptake into, diffusion through, and reactivity within those particles. We report here an accessible method, similar to ice core analyses, using solutions that are relevant for both aerosol chemical systems and aqueous two-phase extraction systems and contain ammonium sulfate and one of eight alcohols (methanol, ethanol, 1-propanol, 2-propanol, 2-butaonol, 3-methyl-2-butanol, 1,2-propanediol, or 1,3-propanediol) frozen in articulated (bendable) straws to probe LLPS. For alcohols with negative octanol–water partitioning coefficient (KOW) values and O/C ratios ≥0.5, no LLPS occurs, while for alcohols with positive KOW values and O/C ratios ≤0.33, phase separation always occurs, both findings consistent with observations using different experimental techniques. When a third species, glyoxal, is added, the glyoxal stays in the aqueous phase, regardless of whether LLPS occurs. When phase separation occurs, the glyoxal forms a strong intermolecular interaction with the sulfate ion, red-shifting the ν3(SO42–) peak by 15 cm–1. These results provide evidence of chemical interactions within phase-separated systems that have implications for understanding chemical reactivity within those, and related, systems.

Here, the liquid–liquid phase separation (LLPS) in aqueous solutions containing poly(ethylene glycol) (PEG) methacrylate homopolymers is reported for the first time. In this study, the thermoresponse of concentrated solutions of DEGMA60 (two ethylene glycol, EG, groups) TEGMA71 (three EG groups), OEGMA300x (4.5 in average EG groups) of varying molar masses (MM), and OEGMA50028 (nine in average EG groups) is discussed. Interestingly, the temperature of LLPS (TLLPS) is controlled by the length of the PEG side chain, the MM of the OEGMA300x and the polymer concentration. More specifically, the transition temperature decreases with: (i) Decrease in the length of the PEG side chain, (ii) increase in MM of the OEGMA300x, and increase in concentration. In addition, LLPS is also observed in mixtures of OEGMA300x with Pluronic® F127. In conclusion, these systems present a thermally induced LLPS, with the transition temperature being finely tuned to room temperature when DEGMA is used. These systems find potential use in numerous applications, varying from purification to “water-in-water” emulsions.

Liquid–liquid phase separation (LLPS) during crystallization development of pharmaceuticals is being reported increasingly in recent years. It often causes quality issues such as failure of impurity reject and fragile morphology. In worst cases, crystallization cannot proceed at all after LLPS occurs. Many studies have been published on LLPS during crystallization and an analysis and synthesis of the current state-of-art is needed. In this review, recent advances in LLPS research will be summarized, including brief theoretical interpretations of LLPS, characteristics in phase diagrams and measurement methods for representative model systems, strategies to suppress LLPS, crystallization development in the presence of LLPS and options when direct crystallization fails due to LLPS. This review aims to provide a framework to deal with the occurrence of LLPS during crystallization development.

Exploiting new interface-active solid catalysts is crucial to construct efficient Pickering emulsion systems for biphasic catalysis. In this work, ultrathin g-C3N4 nanosheets (g-C3N4-NSs) were developed as a new solid emulsifier to directly position catalytic sites at oil-water interfaces for improving the reaction efficiency of a biphasic reaction. Exemplified by a metal-involved biphasic reaction of nitroarenes reduction, the developed Pd/g-C3N4-NSs catalyst with Pd nanoparticles loaded on the surface of g-C3N4-NSs exhibited excellent activity with a catalytic efficiency of 1220 h-1. Such activity was 4.2 and 17.9 times higher than those of Pd/g-C3N4-bulk and the ordinary Pd/C8-SiO2 catalyst, respectively. Also, in the biphasic oxidation reaction of alcohols, Pd/g-C3N4-NSs achieved a 2.3-fold activity enhancement. It was found by analyzing the solidified emulsion droplets that the Pd/g-C3N4-NSs catalyst was parallelly assembled at the oil-water interfaces. Because of the ultrathin thickness of g-C3N4-NSs, such a unique interfacial assembly behavior allowed precise positioning of Pd nanoparticles at the oil-water interfaces. As a result, the oil-soluble reactant could directly react with the water-soluble reactant at the oil-water interface hosting the Pd nanoparticles. Our elaborately designed reaction interface was believed to substantially avoid the diffusion barrier between oil-soluble and water-soluble reactants and then to significantly enhance the reactivity of biphasic reactions. This work highlights the importance of the interfacial location of catalytic sites in biphasic catalysis.

Dispersive liquid-liquid microextraction is one of the most widely used microextraction techniques currently in the Analytical Chemistry field, mainly due to its simplicity and rapidity. The operational mode of this approach has been constantly changing since its introduction, adapting to new trends and applications. Most of these changes are related to the nature of the solvent employed for the microextraction. From the classical halogenated solvents (e.g., chloroform or dichloromethane), different alternatives have been proposed in order to obtain safer and non-pollutants microextraction applications. In this sense, low density solvents, such as alkanols, switchable hydrophobicity solvents and ionic liquids were the first and most popular replacements for halogenated solvents, which provided similar or better results than these classical dispersive liquid-liquid microextraction solvents. However, despite the good performances obtained with low density solvents and ionic liquids, researchers have continued investigating in order to obtain even greener solvents for dispersive liquid-liquid microextraction. For that reason, in this review, the evolution over the last five years of the three types of solvents already mentioned and two of the most promising solvent alternatives (i.e., deep eutectic solvents and supramolecular solvents), have been studied in detail with the purpose of discussing which one provides the greenest alternative. This article is protected by copyright. All rights reserved.

The occurrence of unidirectional ejection phenomena (both continuous & intermittent), during mass transfer in binary and ternary systems respectively; reported earlier, have been explained on the b...

The aim of this study is the extraction and determination of di(2-ethylhexyl) adipate and three phthalate esters including di-iso-butyl phthalate, di-n-butyl-phthalate, and di-(2-ethylhexyl) phthal...

The jamming of nanoparticle surfactants (NPSs) at liquid-liquid interface imparts attractive properties to the interfacial assemblies and enables the structuring of liquids. Herein, we report photoresponsive supramolecular microcapsules with jammed NPS assemblies at the oil-water interface, taking advantage of host-guest molecular recognition. The permeability of the colloidal membrane can be effectively manipulated by switching the NPSs from a jammed state to an unjammed state with a photo trigger, leading to a controlled molecular diffusion and release, affording a versatile platform for the construction of next generation smart microcapsule systems.

In this work, magnetic dispersive micro-solid phase extraction (MDMSPE) coupled with dispersive liquid-liquid microextraction (DLLME) was developed for Se(IV) and Se(VI) followed by graphite furnace atomic absorption spectrometry. MDMSPE involved the use of magnetic ZnFe

Flow transport in confined spaces is ubiquitous in technological processes, ranging from separation and purification of pharmaceutical ingredients by microporous membranes and drug delivery in biomedical treatment to chemical and biomass conversion in catalyst-packed reactors and carbon dioxide sequestration. In this work, we suggest a distinct pathway for enhanced liquid transport in a confined space via propelling microdroplets. These microdroplets can form spontaneously from localized liquid-liquid phase separation as a ternary mixture is diluted by a diffusing poor solvent. High speed images reveal how the microdroplets grow, break up and propel rapidly along the solid surface, with a maximal velocity up to ∼160 μm s-1, in response to a sharp concentration gradient resulting from phase separation. The microdroplet propulsion induces a replenishing flow between the walls of the confined space towards the location of phase separation, which in turn drives the mixture out of equilibrium and leads to a repeating cascade of events. Our findings on the complex and rich phenomena of propelling droplets suggest an effective approach to enhanced flow motion of multicomponent liquid mixtures within confined spaces for time effective separation and smart transport processes. This journal is

The Green, delicate and rapid ultrasound-assisted ionic liquid-based dispersive liquid-liquid microextraction technique was developed to preconcentrate trace quantities of zirconium Zr(IV) ion in r...

An ultrasonic-assisted demulsified dispersive liquid–liquid microextraction based on solidification of floating organic droplet (UA-DE-DLLME-SFO) technique was considered for the preconcentration o...

The stories behind supercooled bulk and confined water can be different. Bulk water has a metastable liquid-liquid phase transition at deeply supercooled conditions, but the existence of such a phenomenon in confined water is in question. Herein we show simulation results of first-order phase transitions between high- and low-density liquid (HDL and LDL) in confined water in both positive and negative pressures. A mid-density state between these two local states appears, which lets the transition show the hysteresis loop with transiently stable intermediate states. On the basis of Landau theory that we have adapted for mixing of moieties with high- and low-density states, we explain the phase transitions with the order parameter-dependent free energy change which is governed by second- to higher-order interactions among those moieties.

The phase behavior of atmospheric aerosol particles influences processes like gas-particle partitioning, solar light scattering, and cloud formation, ultimately affecting atmospheric air quality an...

Host–guest molecular recognition at the liquid–liquid interface endows the interface with unique properties, including stimuli-responsiveness and self-regulation, due to the dynamic and reversible nature of non-covalent interactions. Increasing research efforts have been put into the preparation of supramolecular interfacial systems such as films and microcapsules by integrating functional components (e.g., colloidal particles, polymers) at the interface, providing tremendous opportunities in the areas of encapsulation, delivery vehicles, and biphasic reaction systems. In this review, we summarize recent progress in supramolecular interfacial systems assembled by host–guest chemistry, and provide an overview of the fabrication process, functions, and promising applications of the resultant constructs.

Summary Imbibition is one of the most common physical phenomena in nature, and it plays an important role in enhanced oil recovery, hydrology, and environmental engineering. The imbibition in a capillary is one of the fluid transports in porous media, and the effect of a dynamic contact angle that changes with the imbibition rate on liquid-liquid imbibition is not clear. In this paper, the molecular kinetic theory (MKT) is used to study the effect of a dynamic contact angle on spontaneous capillary-liquid-liquid imbibition at a micrometer scale. The results show that: Using a scaling time, the effects of various forces in different imbibition systems can be compared, the influence of a dynamic contact angle on imbibition can be characterized by a frictional effect of the three-phase contact line, and the proposed model considering the effect of a dynamic contact angle is better than the model neglecting the effect of a dynamic contact angle. As the displacing phase viscosity increases, the influence of a dynamic contact angle on imbibition strengthens, which is attributed to a decrease in the viscous effect and an increase in the frictional effect during the imbibition process; as the displaced phase viscosity increases, the influence of a dynamic contact angle on imbibition weakens, which is attributed to an increase in the viscous effect and a decrease in the frictional effect during the imbibition process. As the interfacial tension increases, the frictional effect increases, with the result that the effect of a dynamic contact angle on imbibition increases. As the capillary becomes more hydrophilic, the effect of a dynamic contact angle on imbibition becomes stronger because of a decreasing viscous effect and an increasing frictional effect. As the capillary length increases, the viscous effect increases, whereas the frictional effect decreases, leading to a decrease in the dynamic contact angle effect. As the capillary radius increases, the frictional force decreases, whereas its proportion in total resistance or the frictional effect increases, resulting in an increase in the effect of a dynamic contact angle. This work sheds light on the effect of a dynamic contact angle on capillary-liquid-liquid imbibition, including displacing phase viscosity, displaced phase viscosity, interfacial tension, capillary wettability, length, and radius. It will provide new insights into manipulating a capillary imbibition process and provide a fundamental theory for enhanced oil recovery by imbibition in conventional or unconventional reservoirs. Supplementary materials are available in support of this paper and have been published online under Supplementary Data at https://doi.org/10.2118/205490-PA. SPE is not responsible for the content or functionality of supplementary materials supplied by the authors.

Background: Tramadol, (±)-trans-2-[(dimethylamino) methyl]-1-(3-methoxyphenyl) cyclohexanol, is a synthetic centrally acting analgesic used in the treatment of moderate to chronic pain. Tramadol, like other narcotic drugs, is used for the treatment of pain and may also be abused. Its overdose can cause adverse effects such as dizziness, vomiting, and nausea. The aim of this paper is to develop a sample preparation method for the determination of tramadol in human plasma samples, followed by CE analysis. Methods: Ultrasound assisted-dispersive liquid-liquid microextraction using binary mixed extractant solvent (chloroform and ethyl acetate) was used for the extraction of one hundred microliters of tramadol spiked human plasma samples and in real human plasma samples obtained from the patients with abuse of tramadol. After evaporation of the extractant solvent, the residue was reconstituted in 100 μL deionized water and subsequently analyzed by CE-UV. Results: The developed method has remarkable characteristics, including simplicity, good repeatability and appreciable accuracy. Under the best extraction conditions, a low limit of detection at 7.0 μg per liter level with good linearity in the range of 0.02-10 μg mL-1 was obtained. Conclusion: UA-DLLME, using a binary mixed extraction solvent, was established for the determination of tramadol in human plasma samples via the CE method with UV-detection. In addition, the analysis of tramadol in some plasma samples of patients with abuse of tramadol indicated that the method has acceptable performance for the determination of tramadol in plasma samples, which indicates that the method is suitable for clinical applications.

The effects of various structural and operating parameters on liquid–liquid dispersion and selectivity of chemical reactions in inline single-row teethed high shear mixers (HSMs) were studied by a ...

We report on the dynamic response of aqueous solution containing poly(N-isopropylacrylamide)-capped gold (pNIPAM-capped Au) nanoparticles to the introduction of NaCl. The addition of NaCl increases...

In the field of industrial crystallization, liquid–liquid phase separation (LLPS) easily makes the crystallization process into an uncontrollable state, making it extremely difficult for people to ...

The adsorption of two-dimensional (2-D) graphene oxide (GO) nanosheets at liquid-liquid interfaces has broad technological implications from functional material preparations to oil-water emulsification. Molecular-level understanding of the adsorption thermodynamics and the interfacial behavior is of great significance. Here, the adsorption free energy of GO nanosheets at the water-cyclohexane system was simulated, in which the effect of oxygen-containing groups and deprotonation has been investigated. It was observed that the neutral GO (GO-COOH) has obvious interfacial activity with a reduction of interfacial tension, while the deprotonated GO (GO-COO-) shows a weak interface affinity. There exists an optimal oxidization degree that could cause the best interfacial stability, which is attributed to the balance of interfacial hydrophilic-hydrophobic interactions. The interaction arising from water is the main factor determining interfacial activity. The interfacial morphology and dynamics of GO nanosheets have also been simulated, in which an anisotropic 2-D translation and rotation along the interface were revealed. Our simulation results provide new insight into the adsorption mechanism and dynamics behavior of GO at the oil-water interface.

In the present study, liquid–liquid flow dynamics are compared in three different geometries experimentally. These are straight glass capillary, serpentine geometry made of glass capillary, and ser...

Intrinsically disordered proteins (IDPs) populate an ensemble of dynamic conformations, making their structural characterization by experiments challenging. Many IDPs undergo liquid-liquid phase separation into dense membraneless organelles with myriad cellular functions. Multivalent interactions in low-complexity IDPs promote the formation of these subcellular coacervates. While solution NMR, Förster resonance energy transfer (FRET), and small-angle X-ray scattering (SAXS) studies on IDPs have their own challenges, recent computational methods draw a rational trade-off to characterize the driving forces underlying phase separation. In this Perspective, we critically evaluate the scope of approximation-free field theoretic simulations, well-tempered ensemble methods, enhanced sampling techniques, coarse-grained force fields, and slab simulation approaches to offer an improved understanding of phase separation. A synergy between simulation length scale and model resolution would reduce the existing caveats and enable theories of polymer physics to elucidate finer details of liquid-liquid phase separation (LLPS). These computational advances offer promise for rigorous characterization of the IDP proteome and designing peptides with tunable material and self-assembly properties.

The approach coupling computational fluid dynamics and a population balance model (PBM) was adopted to simulate the hydraulic performance of liquid–liquid dispersions in a pump-mixer. Behaviors of ...

In this work, the Dispersive Liquid-Liquid Microextraction (DLLME) method has intensified the extraction of Zinc from aqueous solution utilizing 1-butyl-3-methylimidazolium hexafluorophosphate [BMI...

Background: Aflatoxin B1 is a secondary toxic metabolite produced by several aspergillus species. This study was conducted to determine the presence of aflatoxin in tomato paste samples. Methods: A total of 30 tomato pastes were analyzed for Aflatoxin B1 contamination via HPLC-FLD. Analyte extraction was done by dispersive liquid-liquid microextraction. Results: The limit of detection (LOD) and limit of quantitation (LOQ) were 0.14 and 0.44 µg/kg, respectively. The recovery rates ranged from 91 to 94%. The findings showed all samples were contaminated with Aflatoxin B1 and the average concentration was 1.1 ± 0.02 µg/kg. The amount of aflatoxin B1 in 6 samples was higher than the limit set by the European Union. Conclusion: The proposed method was successfully applied to the analysis of tomato paste samples with quantitative results. The main advantages of the developed method include its simplicity in operation, rapid achievement of a very high sample, and low cost.

Hydrocyclones are widely used in industry and CFD has been used to compute them. Reynolds stress turbulence models (RSM), which are computationally costly and oftentimes hard to converge, are often...