Immiscible Solvents Research Articles

An Overview of Microfluidic‐Assisted Strategies for Synthesis and Applications of Molecularly Imprinted Polymers

AbstractThis review gives an overview of using microfluidics in conjunction with molecularly imprinted polymers (MIP), which covers two aspects: on the one hand, on‐chip synthesis of polymer and MIP particles on the nano and the micro scale. This comprises both approaches using two different immiscible solvents and homogeneous matrices to obtain the desired particle morphologies. On the other hand, especially paper‐based microfluidic systems have attracted increasing interest as low‐cost analytical tools that are inherently useful for applying at the point of care. By now, there have been several successful attempts to combine them with MIP (instead of biological recognition systems) and to successfully apply them in environmental samples, food matrices, and for diagnostic applications.

Emergent Behavior of a Photoswitchable Solute in a Biphasic Solvent System.

Due to thermal E/Z isomerization, hydrazones in solution typically exist in thermodynamic equilibria between their isomers. Irradiation of such solutions leads to photostationary states that may differ from the equilibrium distribution. Operating such switchable hydrazones in a biphasic system of two immiscible solvents introduces three new degrees of freedom: the E/Z equilibrium in the second solvent and two equilibria for distribution of each of the isomers between the solvents. Irradiation of such a system can be performed in three different ways - the first solvent only, the second solvent only, and both solvents at once - all yielding distinct outcomes. Depending on the choice of materials and the mode of irradiation, such setup may lead to different emergent behaviors that are not immediately intuitive, including net cyclic transport or the accumulation of one photoswitched product in one of the phases, beyond what is reachable by irradiating a simple solution of the same photoswitch.

Core-Sheath Fibers via Single-Nozzle Spinneret Electrospinning of Emulsions and Homogeneous Blend Solutions.

The preparation of core-sheath fibers by electrospinning is a topic of significant interest for producing composite fibers with distinct core and sheath functionalities. Moreover, in core-sheath fibers, low-molecular-weight substances or nanosized inorganic additives can be deposited in a targeted manner within the core or the sheath. Commonly, for obtaining a core-sheath structure, coaxial electrospinning is used. It requires a coaxial spinneret and suitable immiscible solvents for the inner and outer solutions. The single-nozzle spinneret electrospinning of emulsions can address these issues, but use of a stabilizing agent is needed. A third approach-preparation of core-sheath fibers by single-nozzle spinneret electrospinning of homogeneous blend solutions of two polymers or of a polymer/low-molecular-weight substance-has been much less studied. It circumvents the difficulties associated with the coaxial and the emulsion electrospinning and is thoroughly discussed in this review. The formation of core-sheath fibers in this case is attributed to phase-separation-driven self-organization during the electrospinning process. Some possibilities for obtaining core-double sheath fibers using the same method are also indicated. The gained knowledge on potential applications of core-sheath fibers prepared by single-nozzle spinneret electrospinning of emulsions and homogeneous blend solutions is also discussed.

Modular Point-of-Need Tropane Alkaloid Detection at Regulatory Levels: Combining Solid-Liquid Extraction from Buckwheat with a Paper-Immobilized Liquid-Phase Microextraction and Immuno-Detection in Interconnectable 3D-Printed Devices.

Contamination with tropane alkaloids in cereals is expected to increase globally. However, current identification tools (e.g., liquid chromatography-mass spectrometry) for tropane alkaloids are time-consuming and expensive. Furthermore, their miniaturized alternatives lack sensitivity and robustness. Therefore, there is a pressing need for inexpensive and effective screening methods. Here, an on-site applicable modular workflow for tropane alkaloid detection in buckwheat is presented. The modular workflow combines paper microfluidics and interconnectable 3D-printed sample preparation tools and was evaluated for different tropane alkaloids, including atropine and scopolamine. Furthermore, integration with an indirect competitive lateral flow immunoassay (icLFIA) for atropine detection at relevant levels was demonstrated. In the modular workflow, to minimize matrix coextraction, tropane alkaloids were extracted from the milled buckwheat cereals by a mixture of alkaline aqueous and immiscible organic solvents (extraction recoveries: 66-79%). The tropane alkaloids were subsequently concentrated with a newly developed paper-immobilized liquid-phase microextraction (PI-LPME, extraction recoveries: 34-60%, concentration factor to immobilized solution in paper: 60-108×). After the PI-LPME, with an integrated 3D-printed setup, the tropane alkaloids were directly eluted (elution recoveries: 83-93%) and detected with the icLFIA. Digital read-out of the icLFIA, by employing a hand-held reader, enabled semiquantification of atropine (IC50 = 0.56 ng mL-1 in standard solutions). The modular workflow was validated by analyzing 24 blank and spiked buckwheat cereal samples with 5 and 10 μg kg-1 atropine. A cutoff value was established with an estimated false negative rate of 1% and estimated false positive rate of 0.68%. Therefore, the modular workflow can aid in fast, inexpensive, and on-site atropine detection by nonexperts, and when integrated with a scopolamine-specific icLFIA expanded toward scopolamine detection. Moreover, the developed sample extraction and concentration method (PI-LPME) is suitable for the analysis of many other compounds with pH-dependent polarity.

Gibbs Energy of Cryptand[2.2.2] Transfer from Water to Aqueous Dimethyl Sulfoxide Solvent

We represent the Gibbs energies of cryptand[2.2.2] transfer from water to different composition water–dimethyl sulfoxide solvent. The Gibbs energies were determined by interphase distribution of cryptand[2.2.2] between two immiscible solvents. We conclude, that when the dimethyl sulfoxide concentration increases, the cryptand[2.2.2] solvation is weakening.

How Molecular Orientation Affects the Static Permittivity Profile of the Polar and Nonpolar Liquid-Liquid Interface.

The dielectric permittivity across the liquid-liquid interface presents an intrinsic response, with respect to the instantaneous interface reference. We hypothesize that dielectric responses across the nonpolar and polar liquid-liquid interfaces have different behaviors and underlying mechanisms. Molecular dynamics simulations were used to compare and contrast the dielectric response of a nonpolar (1,2-dichloroethane/water) and a polar (1-octanol/water) liquid-liquid interface system. We found that the enhanced dielectric permittivity at the nonpolar interface is attributed to the increased water dipole orientation and polarization density. In the case of the polar interface, strong association of the immiscible solvents inhibits the molecular dipole orientation, counteracting the effect from the enhanced surface water polarization density and resulting in a standard dielectric response. Detailed knowledge of the hydrogen bond networks and molecular dipole orientation with respect to the specific instantaneous interfacial and bulk regions reveals the effect of molecular proximity and the interaction with the opposing interfacial molecules on the mechanism of the dielectric permittivity response across the liquid-liquid interface phase boundary.

Advancements in Characterization Techniques for Microemulsions: From Molecular Insights to Macroscopic Phenomena.

Microemulsions are thermodynamically stable, optically isotropic, transparent, or semi-transparent mixed solutions composed of two immiscible solvents stabilized by amphiphilic solutes. This comprehensive review explores state-of-the-art techniques for characterizing microemulsions, which are versatile solutions essential across various industries, such as pharmaceuticals, food, and petroleum. This article delves into spectroscopic methods, nuclear magnetic resonance, small-angle scattering, dynamic light scattering, conductometry, zeta potential analysis, cryo-electron microscopy, refractive index measurement, and differential scanning calorimetry, examining each technique's strengths, limitations, and potential applications. Emphasizing the necessity of a multi-technique approach for a thorough understanding, it underscores the importance of integrating diverse analytical methods to unravel microemulsion structures from molecular to macroscopic scales. This synthesis provides a roadmap for researchers and practitioners, fostering advancements in microemulsion science and its wide-ranging industrial applications.

Advancing gasoline desulfurization: Multi-objective fuzzy optimization in systems technology

Ultrasonic-assisted oxidative desulfurization (UAOD) is utilized to lessen environmental problems due to sulfur emissions. The process uses immiscible polar solvents and ultrasonic waves to enhance desulfurization efficiency. Prior research focused on comparing the effectiveness of UAOD for gasoline using response surface methodology. This study evaluates the desulfurization efficiency and operating costs, including ultrasonic power, irradiation time, and oxidant amount to determine optimal conditions. The study used a multi-objective fuzzy optimization (MOFO) approach to evaluate the economic viability of UAOD for gasoline. It identified upper and lower boundaries and then optimized the desulfurization efficiency and operating costs while considering uncertainty errors. The fuzzy model employed max-min aggregation to optimize the degree of satisfaction on a scale from 0 (unsatisfied) to 1 (satisfied). Optimal conditions for gasoline UAOD were found at 445.43 W ultrasonic power, 4.74 min irradiation time, and 6.73 mL oxidant, resulting in a 66.79 % satisfaction level. This yielded a 78.64 % desulfurization efficiency (YA) at an operating cost of 13.49 USD/L. Compared to existing literature, gasoline desulfurization was less efficient and less costly. The solutions provided by MOFO demonstrate not only economic viability through decreased overall operating costs and simplified process conditions, but also offer valuable insights for optimizing prospective future industrial-scale UAOD processes.

Water-Oil Interfacial Synthesis of Two-Dimensional Colloidal Lead-Iodide Perovskites with Enhanced Efficiency and Stability.

Two-dimensional Ruddlesden-Popper perovskites L2PbI4 (L = alkylammonium cation) (RPPs) have attracted significant attention due to their unique excitonic characteristics. However, their ultrafast reaction dynamics exacerbates the structural distortion of the inorganic framework, leading to severe deterioration in photoluminescence. Here, we propose a water-oil interfacial synthesis approach to achieve controlled growth of the RPPs nanosheets. By segregating Pb and I precursors in two immiscible solvents, the nucleation and growth of RPPs are prolonged to the minute level. L2PbI4 nanosheets terminated with various alkylammonium are synthesized, and the factors influencing the growth kinetics of RPPs nanosheets are investigated. The resulting (PEA)2PbI4 nanosheets exhibit a 3.6-time enhancement in quantum efficiency and 3.2-time improvement photostability compared to those synthesized using the classical recrystallization method. A white light-emitting diode based on (HDA)2PbI4 nanosheets is fabricated, achieving a color gamut of 119.7% of the NTSC display standards. This innovative approach offers a new method for the controlled growth of 2D RPPs with improved optical quality and stability.

Application of magnetic dispersive solid phase extraction combined with solidification of floating organic droplet-based dispersive liquid–liquid microextraction and GC-MS in the extraction and determination of polycyclic aromatic hydrocarbons in honey

A magnetic dispersive solid phase extraction method combined with solidification of floating organic droplet-based dispersive liquid–liquid microextraction has been validated for the extraction of polycyclic aromatic hydrocarbons from honey samples. For this purpose, a carbonised cellulose–ferromagnetic nanocomposite was used as a sorbent through the magnetic dispersive solid phase extraction. For preparation of the sorbent, first, carbonised cellulose nanoparticles were created by treating cellulose filter paper with concentrated solution of sulfuric acid. Then, the prepared nanoparticles were loaded onto Fe3O4 nanoparticles through coprecipitation. In the extraction process, first, a few mg of the sorbent was added to the diluted honey solution and dispersed in it using vortex agitation. The particles were then separated and the adsorbed analytes were eluted with an organic solvent. The eluent was taken and after mixing with a water–immiscible extraction solvent was used in the following solidification of floating organic droplet-based dispersive liquid–liquid microextraction procedure. By performing the extraction process under the obtained optimum conditions, low limits of detection (0.08–0.17 ng g−1) and quantification (0.27–0.57 ng g−1), satisfactory precision (relative standard deviations ≤ 5.0%), and wide linear range (0.57–500 ng g−1) with great coefficients of determination (r2≥ 0.9986) were obtained.

Interface‐Driven Spontaneous Differentiation‐Repulsion Behavior in Isochemical Droplet Populations

AbstractAn important exercise for understanding the emergent behavior in biology is to study it using minimal synthetic systems. Current biomimetic systems involving directed motion and collective migration require at least three components: two immiscible solvents to form an emulsion, and external agent(s), usually surfactants, to give rise to asymmetric interactions and induce transient non‐equilibrium conditions. Here, the most minimal system thinkable, consisting of only two components, is presented, in the form of micron‐sized oil (1‐decanol) droplets dispersed in a finite water reservoir. Spontaneous emergent dynamics within chemically identical droplet populations is reported, in the form of physical differentiation of droplets in a stochastic manner leading to an immediate repulsive behavior amongst their neighbors. Using a microfluidic production platform, fluorescence microscopy experiments, and modelling, it is showed that this cyclic phenomenon of differentiation‐repulsion results from oil droplets entering the air‐water interface leading to Marangoni flows and their coupling with evaporative flux of decanol. The potential of this platform is illustrated by demonstrating control over the event frequency, its use as Marangoni tweezers to trap droplet clusters, and proof‐of‐principle reorganization of multi‐component assemblies. The presented collective behavior with exceptional chemical simplicity makes it amenable for potentially developing self‐assembled biomimetic and bioengineered structures.

Neat and rapid preparation of hydrophobic magnetic ionic liquids composed of transition metal chelates featuring in situ formation capabilities in aqueous matrices

Nitrogen and oxygen-donor ligands comprised of alkylimidazoles, tertiary amides, and diglycolamides were employed to form transition metal chelates in the preparation of twelve magnetic ionic liquids. Viscosities as low as 198 cP were achieved.

Pro-apoptotic effect of chloroform fraction of Moraea sisyrinchium bulb against glioblastoma cells

IntroductionGlioblastoma is a common malignant brain tumor, with limited therapeutic options. In our previous study, the Moraea sisyrinchium plant showed cytotoxicity against glioblastoma and hepatocellular carcinoma cells. Among different parts of this plant (flower, stem, and bulb), the bulb showed better anticancer potential. The present work aimed to test the anticancer activity of different fractions of the bulb extract, to determine its phytochemicals, and to study its mechanism action on glioblastoma. MethodsThe bulb extract was partitioned into different fractions using immiscible solvents. The U87 glioblastoma cells were incubated with the obtained fractions. Then, the cell proliferation assay (MTT), cell migration test (scratch), cell cycle analysis (propidium iodide staining), apoptosis/necrosis assay (annexin V/propidium iodide staining), and real-time PCR (PTEN, Akt, mTOR, BAX and BCL-2 genes) were performed. Phytochemicals were determined using liquid chromatography-mass spectroscopy. ResultsThe chloroform fraction showed more antiproliferative effect than n-hexane, ethyl acetate, and n-butanol fractions. Also, chloroform fraction induced cell cycle arrest, increased apoptosis, and inhibited cell migration ability (P < 0.05). The expression of PTEN, mTOR, and BAX genes was significantly up-regulated, while the expression of Akt and Bcl-2 showed down-regulation. The phytochemicals identified in the chloroform fraction were mainly xanthones, phytosterols, and isoflavones. ConclusionThe chloroform fraction of Moraea sisyrinchium bulb inhibits the proliferation and migration of glioblastoma cells by inducing cell cycle arrest and apoptosis by upregulation of the PTEN gene and Bax/Bcl-2 ratio. The identified compounds in the chloroform fraction are potential candidates for further investigation as anticancer agents against glioblastoma.

Interfacial Tension-Impelled Self-Assembly and Morphology Tuning of Poly(3,4-ethylene dioxythiophene)/Tellurium Nanocomposites at Various Liquid/Liquid Interfaces.

Compared to the enormous number of nanostructures that have been documented, the variety of nanostructures produced by organic polymerization is rather limited. We devised an unconventional route and a sustainable approach to distribute tellurium nanoparticles (Te NPs) in a poly(3,4-ethylene dioxythiophene) (PEDOT) matrix to form semiconducting organic-inorganic nanocomposites for potential applications in electrochemical sensing. The adopted strategy of in situ liquid/liquid interface-assisted polymerization aids in the formation of intimately tethered Te NPs on the PEDOT polymer chains, thereby preventing the aggregation of Te NPs. The untapped versatility inherent to using biphasic systems for interfacial polymerization is explored at three interface systems of immiscible solvents: chloroform/water, dichloromethane/water, and hexane/water, giving rise to PEDOT/Te nanocomposite (PTeNC) of distinct morphology. Chemical nature, crystallinity, and morphology investigations proved the successful formation of PTeNC in different interface systems. Consequently, the temporal evolution of interfacial tension in the preferential adsorption of nanoparticles and final product morphology was monitored by pendant drop tensiometry. Owing to the role of morphology, PTeNC synthesized at the hexane/water interface showcased the best electrocatalytic behavior toward nonenzymatic detection of l-ascorbic acid, an essential nutritional factor, and a neuromodulator with a limit of detection of 0.66 μM and excellent sensitivity, selectivity, and reproducibility. Hence, we envision that interface-assisted polymerization offers a nascent and robust strategy for encapsulating unusual electrode materials in polymeric matrices.

Separation of 1,2-diols from ethylene glycol via biphasic-solvent extraction and thermodynamic insights

Impurities 1,2-propylene glycol (PG), 1,2-butylene glycol (BG), 2,3-butylene glycol (23BG), 1,2-pentanediol (PDO), and 1,2-hexanediol (HDO) were isolated from ethylene glycol (EG) via biphasic-solvent extraction, which involves immiscible solvents saline water (S1) and ethyl acetate (S2). After adding S1 to the diol-S2 system, the partition coefficients were almost unaltered, while the selectivity coefficients were doubled or tripled. The larger the carbon-atom number of diol was, the higher the removal rate was. The removal rates of PG, BG, 23BG, PDO, and HDO reached 68%, 95.3%, 90.1%, 100%, and 100%, respectively. The EG content was increased from 72.7 to 91.2 wt%, and EG recovery reached 80.1%. The phase diagrams showed that the S1-EG-S2, S1-PDO-S2, and S1-HDO-S2 systems exhibited Treybal's type-II behaviors, while the S1-PG-S2 and S1-BG-S2 systems showed type-I characteristics. In addition, the low-carbon-number diols were miscible with S1 and rejected S2, while the high-carbon-number diols exhibited opposite characteristics. The intense endotherm during the dissolution of EG in ester implied that the increase of enthalpy of system is an important reason for the high chemical potential of EG. The obvious Tyndall phenomena of C3–6 diols dispersed in saline water indicated that these diols formed into ordered micelles with low entropy, resulting in their high chemical potentials. The chemical potentials of diols in the biphasic solvents synergistically contributed to the separation selectivity.

Minimize Precolumn Band Broadening with Immiscible Solvent Sandwich Injection.

We investigated the possibility of reducing the effect of precolumn band broadening (PreCBB) by sandwiching the sample between two small plugs of an immiscible liquid. It has been found that in cases of severe PreCBB, improvements in peak efficiency can amount up to 20 times for the early-eluting compounds. For smaller degrees of PreCBB, the gain on the efficiency of early-eluting compounds is smaller (order of 50%), yet it is still significant. It has been verified that the presence of the immiscible fluid sandwich does not affect the repeatability of the analysis nor the linearity of the calibration curves used for analyte quantitation. It is also shown that the main effect of the two sandwich plugs is the minimization of the dispersion in the precolumn transfer tubing itself, which makes the method fundamentally different from pure on-column focusing methods such as the performance optimizing injection sequence (POISe) method. It is further demonstrated that both halves of the sandwich are needed, since the beneficial effect is clearly much smaller when only one plug is present. A drawback of the method is that some of the late-eluting peaks are slightly adversely affected by the presence of the sandwich liquid in the case where 127 μm i.d. tubing was used. The mechanism for this peak deterioration effect is at present still unclear but only occurs under gradient conditions and is clearly linked to the size of the sandwich plugs (the smaller the plugs, the smaller the adverse effect) and the internal diameter of the tubing used between the injection valve and the column.

Exotic dynamics of bimolecular reaction–diffusion fronts in immiscible systems

Dynamics of bimolecular A+B→C reaction-diffusion (RD) fronts have been well characterized in miscible systems. We study here their properties when reactants A and B are initially dissolved in two immiscible solvents put in contact. Neglecting any convective effects, we show that bimolecular RD fronts developing in such immiscible systems upon transfer from the reactants from one phase to the other can change directions up to four times, contrary to miscible systems where only two changes of direction are possible. Further, the conditions for which two local maxima in the reaction rate can exist are identified.

Advances on Cellulose Manufacture in Biphasic Reaction Media.

Cellulose is produced industrially by the kraft and sulfite processes. The evolution of these technologies in biorefineries is driven by the need to obtain greater added value through the efficient use of raw materials and energy. In this field, organosolv technologies (and within them, those using liquid phases made up of water and one partly miscible organic solvent, known as "biphasic fractionation" in reference to the number of liquid phases) represent an alternative that is receiving increasing interest. This study considers basic aspects of the composition of lignocellulosic materials, describes the fundamentals of industrial cellulose pulp production processes, introduces the organosolv methods, and comprehensively reviews published results on organosolv fractionation based on the use of media containing water and an immiscible solvent (1-butanol, 1-pentanol or 2-methyltetrahydrofuran). Special attention is devoted to aspects related to cellulose recovery and fractionation selectivity, measured through the amount and composition of the treated solids.

How hydrogen bond donor acceptor ratio and water content impact heterogeneity in microstructure and dynamics of N,N-diisooctylacetamide and decanol based hydrophobic deep eutectic solvent

Recently hydrophobic deep eutectic solvents (HDESs) have emerged as a potential green alternative media for the extraction of compounds from aqueous environment, and their increased importance as water immiscible solvent has attracted researchers to gain more insights into this domain. The present study employs atomistic molecular dynamics simulations to elucidate the microscopic structural organization, dynamics, and crucial interactions in N,N-diisooctylacetamide (DOA) plus decanol (DEO) based HDES at different mole ratios of the hydrogen bond donor (HBD) and acceptor (HBA). The analysis of simulated X-ray and neutron scattering structure functions reveals a nanoscale heterogeneous structural organization in the HDES at all compositions. The genesis for this heterogeneity can be derived from the polarity alternation peaks of partial structure functions in the low-q region. Polarity ordering in DOA:DEO (1:2) HDES is observed at longer length-scales in comparison to that in DOA:DEO (1:1) and DOA:DEO (2:1) HDESs. Moreover, the liquid morphologies are portrayed by nano-polar domains ingrained into the apolar environment depicting polar and apolar self-segregation. The analysis of angle-resolved radial distribution functions suggests that the microstructures of these HDESs are dominated by a strong DEO-DEO and DEO-DOA hydrogen bonding interactions. Slower decay of the hydrogen bond autocorrelation function corresponding to DOA-DEO suggests stronger hydrogen bonding in DOA-DEO than DEO-DEO. The translational mobility of both the components decreases as the DOA concentration increases. The DEO molecules exhibit faster diffusion in bulk HDES than the DOA molecules. A small water content in the HDES leads to slightly enhanced segregation of polar and apolar environments in the HDESs. We observe that water molecules interfere with the hydrogen bonding network of DOA and DEO by establishing hydrogen bond with them, thereby reducing the strength of DEO-DEO and DOA-DEO hydrogen bond interactions. The hydration also causes slightly faster hydrogen bond relaxation dynamics, indicating the weakening of hydrogen bond interactions between the constituent species of the HDESs.

Metal-Organic Framework Nanoparticles with Universal Dispersibility through Crown Ether Surface Coordination for Phase-Transfer Catalysis and Separation Membranes.

Dispersing metal-organic framework (MOF) solids in stable colloids is crucial for their availability and processibility. Herein, we report a crown ether surface coordination approach for functionalizing the surface-exposed metal sites of MOF particles with amphiphilic carboxylated crown ether (CEC). The surface-bound crown ethers significantly improve MOF solvation without compromising the accessible voids. We demonstrate that CEC-coated MOFs exhibit exceptional colloidal dispersibility and stability in 11 distinct solvents and six polymer matrices with a wide range of polarities. The MOF-CEC can be instantaneously suspended in immiscible two-phase solvents as an effective phase-transfer catalyst and can form various uniform membranes with enhanced adsorption and separation performance, illustrating the effectiveness of crown ether coating.