Inclusion Of Solvent Research Articles

Understanding Na+ Diffusion, Physicochemical Behavior, and Electrochemical Performance of a Gel Polymer Electrolyte.

Gel polymer electrolytes (GPEs) represent a credible alternative to organic liquid electrolytes (LEs) for safer sodium metal batteries. As a compromise between solid polymer electrolytes and LEs, GPEs ensure a good ionic conductivity, improve the electrolyte/electrode interface, and prevent solvent leaks. Herein, a GPE based on acrylate-bifunctionalized polyethylene glycol chains mixed with an ether solvent (TEGDME) and a polyethylene glycol diacrylate (PEG600DA) in a 50/50 wt % ratio was prepared by ultraviolet photopolymerization. Sodium bis(fluorosulfonyl)imide salt (NaFSI) was added at different concentrations to study its interactions with the solvent and/or the cross-linked polymer. Infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and swelling ratio characterizations were combined to determine the physicochemical properties of the GPE. Complementary characterizations including electrochemical impedance spectroscopy, chronopotentiometry, and cyclic voltammetry allowed correlating the physicochemical properties of the GPE to its electrochemical performance. Then, improvements were obtained by careful combination of its components. The cross-linking agent allowed us to obtain a polymer matrix that traps the organic solvent and prevents leakage. Such a solvent inclusion reduces the rigidity of the membrane and lowers its viscosity, offering a room temperature ionic conductivity of 4.8 × 10-4 Ω-1 cm-1. The control of polymer's tortuosity leads to a stable cycling vs sodium metal over several hundred hours without increase of the polarization. Finally, optimization of the salt loading plays a major role in electrostatic cross-linking, leading to an improvement of the mechanical properties of the GPE without reducing its conductivity.

Solvent Effects on the Spin Crossover Properties of Manganese (III) (sal‐N‐1,5,8,12) Complexes

AbstractThe interplay of host‐guest interactions and controlled modulation of spin‐crossover (SCO) behavior is one of the most exploited topics regarding data storage, molecular sensing, and optical technologies. This study examines the effect of solvents on the spin‐crossover (SCO) behavior of manganese(III) complexes [Mn(sal‐N‐1,5,8,12)]I•S (S=CH3OH, C2H5OH, CH3CN) (1) and [Mn(sal‐N‐1,5,8,12)]I3 (2), where (sal‐N‐1,5,8,12)2− is 2,2′‐((1E,13E)‐2,6,9,13‐tetraazatetradeca‐1,13‐diene‐1,14‐diyl)diphenol synthesized by salicylaldehyde and 1,2‐bis(3‐aminopropylamino)ethane. The complexes, crystallizing in orthorhombic or monoclinic systems, exhibit similar supramolecular arrangements with one‐dimensional cationic chains at low temperatures. Magnetic studies reveal that solvent inclusion sharpens the SCO transition and lowers the transition temperature. Specifically, 1⋅CH3OH shows a 13 K thermal hysteresis due to methanol‘s mobility through the channels in the cationic framework. Although the solvent‐free compound was not obtained, compound 2 with a linear I3− anion was synthesized, displaying extensive cation‐anion contacts and a distinct 13 K thermal hysteresis upon heating due to altered intermolecular cooperativity. This emphasizes the significant role of solvent introduction and variation in crystal packing and their impact on the SCO properties.

Breaking Dynamic Behavior in 3D Covalent Organic Framework with Pre-Locked Linker Strategy.

Due to their large surface area and pore volume, three-dimensional covalent organic frameworks (3D COFs) have emerged as competitive porous materials. However, structural dynamic behavior, often observed in imine-linked 3D COFs, could potentially unlock their potential application in gas storage. Herein, we showed how a pre-locked linker strategy introduces breaking dynamic behavior in 3D COFs. A predesigned planar linker-based 3,8-diamino-6-phenylphenanthridine (DPP) was prepared to produce non-dynamic 3D JUC-595, as the benzylideneamine moiety in DPP locked the linker flexibility and restricted the molecular bond rotation of the imine linkages. Upon solvent inclusion and release, the PXRD profile of JUC-595 remained intake, while JUC-594 with a flexible benzidine linker experienced crystal transformation due to framework contraction-expansion. As a result, the activated JUC-595 achieved higher surface areas (754 m2 g-1) than that of JUC-594 (548 m2 g-1). Furthermore, improved CO2 and CH4 storages were also seen in JUC-595 compared with JUC-594. Impressively, JUC-595 recorded a high normalized H2 storage capacity that surpassed other reported high-surface area 3D COFs. This works shows important insights on manipulating the structural properties of 3D COF to tune gas storage performance.

Analysis of Macrostep Interaction via Carbon Diffusion Field in SiC Solution Growth

In the top-seeded solution growth (TSSG) method for SiC, control of macrostep development is crucial for improving the crystal quality. Dislocation conversion phenomena caused by macrosteps with a certain height on the crystal surface can reduce the dislocation density, while over-developed macrosteps bring macroscopic defects such as solvent inclusions. It is experimentally reported that solution flow direction to the step movement has a substantial impact on the macrostep development: parallel solution flow promotes and anti-parallel solution flow suppresses the increase of macrostep height. Our hypothesis is that this macrostep development is governed by the interaction between the macrosteps not by the instability of the density of the atomical steps. In this study, we constructed a computational fluid dynamic model of the boundary layer around macrosteps on the crystal surface, incorporating the solution flow on the boundary layer and consumption of the carbon solute by the macrostep movement quantitatively. The computational simulation reveals that the macrostep with position shift from the center of the adjacent macrosteps moves to the direction of the nearer macrostep under the parallel flow and moves to the farther macrostep under the antiparallel flow. These macrostep movements result in the bunching and debunching of the macrosteps. The mechanisms of macrostep movements demonstrated in this study will be useful for the precise control of macrostep height aiming to the reduction of the dislocation density during SiC solution growth.

Effect of Solution Components on Solvent Inclusion in SiC Solution Growth

Effect of Solution Components on Solvent Inclusion in SiC Solution Growth

Incorporating solvent effects in DFT: insights from cation exchange in faujasites.

Zeolites are versatile materials renowned for their extra-framework cation exchange capabilities, with applications spanning diverse fields, including nuclear waste treatment. While detailed experimental characterization offers valuable insight, density functional theory (DFT) proves particularly adept at investigating ion exchange in zeolites, owing to its atomic and electronic resolution. However, the prevalent occurrence of zeolitic ion exchange in aqueous environments poses a challenge to conventional DFT modeling, traditionally conducted in a vacuum. This study seeks to enhance zeolite modeling by systematically evaluating predictive differences across varying degrees of aqueous solvent inclusion. Specifically focusing on monovalent cation exchange in Na-X zeolites, we explore diverse modeling approaches. These range from simple dehydrated systems (representing bare reference states in vacuum) to more sophisticated models that incorporate aqueous solvent effects through explicit water molecules and/or a dielectric medium. Through comparative analysis of DFT and semi-empirical DFT approaches, along with their validation against experimental results, our findings underscore the necessity to concurrently consider explicit and implicit solvent effects for accurate prediction of zeolitic ionic exchange.

Molecular Probe Embedded Porous Polymer Scaffold as Solid‐State Visual Sensor for Selective and Sequential Sensing of Ultra‐Trace Toxic Heavy Metal Ions in Environmental/Commercial Samples

AbstractThe article reports on the tailor‐made solid‐state optical sensor through controlled imbuement of an amphiphilic probe onto a dual interwoven macro‐/meso‐porous polymer monolithic scaffold for the selective ocular sensing of ultra‐trace toxic heavy metal ions. The structural/surface morphology of the poly(LMC‐co‐TMP) monolith is customized through the stochiometric inclusion of lauryl methacrylate (LMC), trimethyl propanetrimethacrylate (TMP) and porogenic solvents. The riveting sensing performance of the poly(LMC‐co‐TMP) scaffolds for the target ions arises from the built‐in twofold intermingled porous architects that render voluminous surface area and porosity for the embedding of 2‐((1H‐benzoimidazol‐2‐yl)‐4‐butan‐2‐yl)phenol (HBBP), a chromoionophoric probe. The sensor's unique structural and surface properties endure stable ion‐complexation through color transitions from yellow (blank) to a leafy green, peanut brown, and dark blue for Pb2+, Hg2+, and Cd2+, respectively. The sensor imposes high binding affinity for the target ions, with a linear response range of 0–200 ppb for Pb2+/Hg2+ and 0–300 ppb for Cd2+. The detection limit values are 0.46, 0.52, and 0.41 ppb for Pb2+, Hg2+, and Cd2+, respectively. The sensor's hassle‐free on‐field testing in environmental and synthetic samples reveals excellent data reproducibility (Relative Standard Deviation (RSD) ≤1.97%), with pH‐assisted reliable color transitions for eight regenerative trials, with a response time of 45 s.

Enantiomer separation of 2-halomandelic acids via diastereomeric salt formation with chiral N-substituted 2-amino-2-phenylethanols.

Chiral N-substituted secondary 1,2-aminoalcohols have been developed for the enantioseparation of ortho-halomandelic acids (o-X-MAs) via diastereomeric salt formation. Two structural isomers, N-methyl-2-amino-1,2-diphenylethanol and N-benzyl-2-amino-2-phenylethanol, showed high separation abilities for o-X-MAs (X = Cl, Br, I). The chiral recognition mechanism was elucidated by crystallographic analysis of the less-soluble salts. The substituents on the nitrogen atom of the resolving agents and the inclusion of the crystallization solvent stabilized the salt and enhanced their separation ability.

Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions.

We present results from explicit-solvent coarse-grained molecular dynamics (MD) simulations of fully charged, salt-free, and unentangled polyelectrolytes in semidilute solutions. The inclusion of a polar solvent in the model allows for a more physical representation of these solutions at concentrations, where the assumptions of a continuum dielectric medium and screened hydrodynamics break down. The collective dynamic structure factor of polyelectrolytes, S(q,t), showed that at [Formula: see text], where [Formula: see text] is the polyelectrolyte peak in the structure factor S(q) and [Formula: see text] is the correlation length, the relaxation time obtained from fits to stretched exponential was [Formula: see text], which describes unscreened Zimm-like dynamics. This is in contrast to implicit-solvent simulations using a Langevin thermostat where [Formula: see text]. At [Formula: see text], a crossover region was observed that eventually transitions to another inflection point [Formula: see text] at length scales larger than [Formula: see text] for both implicit- and explicit-solvent simulations. The simulation results were also compared to scaling predictions for correlation length, [Formula: see text], specific viscosity, [Formula: see text], and diffusion coefficient, [Formula: see text], where [Formula: see text] is the polyelectrolyte concentration. The scaling prediction for [Formula: see text] holds; however, deviations from the predictions for [Formula: see text] and D were observed for systems at higher [Formula: see text], which are in qualitative agreements with recent experimental results. This study highlights the importance of explicit-solvent effects in molecular dynamics simulations, particularly in semidilute solutions, for a better understanding of polyelectrolyte solution behavior.

Phase-Resolved Electrochemiluminescence with a Single Luminophore.

Multiphase chemical systems are greatly different than bulk solutions, as they provide a unique environment for reactions to proceed and have unique physicochemical properties. Thus, new tools need to be developed to gain a more detailed understanding of these systems. Here, we use electrogenerated chemiluminescence (ECL) to elucidate phase boundaries precisely and comprehensively between aqueous droplets and an organic continuous phase owing to ECL's unprecedented spatial resolution (a few micrometers) confined at the electrode surface. Phase-resolved mapping was accomplished by selecting a luminophore that is soluble in both phases while selecting two coreactants that are exclusively soluble in one phase or the other. This type of system allows us to map the complex liquid|electrode and the liquid|liquid interfaces in a multiphase system. We show that electrical connectivity is not conserved throughout solvent inclusions, which result from neighboring droplet coalescence, indicating an unexpected initial lack of electronic communication. These results have great importance to energy storage and conversion devices and wearable/implantable sensors, which are dominated by complex, multiphase environments.

A Study of the Bisphosphonic Derivatives from the Pudovik Reaction of Dialkyl α-Oxophosphonates and >P(O)H Reagents: X-ray Structure and Bioactivity.

New hydroxy-methylenebisphosphonic derivatives were prepared with different P-functions. The outcome of the reaction of α-oxophosphonates (YC(O)P(O)(OR)2) and dialkyl phosphites or diarylphosphine oxides depended on the Y substituent of the oxo-compound, the nature of the P-reagent and the amount of the diethylamine catalyst. Starting from dimethyl α-oxoethylphosphonate, in the presence of 5% of diethylamine, the corresponding Pudovik adduct was the single product. While using 40% of the catalyst, the rearranged species with the >P(O)-O-CH-P(O)< skeleton was the exclusive component. A similar reaction of α-oxobenzylphosphonate followed the rearrangement protocol. X-ray crystallography revealed not only the spatial structures of the three products, but also an intricate pattern evolving from the interplay of slight chemical differences, solvent inclusion and disorder as well as H-bridge patterns, which invite further investigation. In vitro activity of the compounds was assessed on different tumor cell cultures using end-point-type cell tetrazolium-based measurements. These structure-activity studies revealed a cytostatic effect for four rearranged derivatives containing aromatic units. One of them had a pronounced effect on MDA-MB 231 and Ebc-1 cells, showing IC50 = 37.8 and 25.9 µM, respectively.

Effects of oyster mushroom, Lentinus sajor-caju on growth, gut histology and haematology of Clarias gariepinus

There is need to reduce usage of antibiotics in favor of prebiotics and phytogenic in aquafeed production. The study evaluated effects of mushroom on growth, gut histology and haematological variables of Clarias gariepinus. Five treatment feeds were made to vary in inclusion of solvent extracted oyster mushrooms, Lentinus sajor-caju as follows: Feed 1, 0%; Feed 2, 4%; Feed 3, 8%; Feed 4, 12% and Feed 5, 16%. The diets were made isonitrogenous (42%) and isolipidic (6.0%). The growth performances, gut histology and haematological profile of the fish were estimated using standard procedures. The essential amino acid (EAA) contents of the mushroom and feeds were analyzed following standard methods. Ingredients were mixed according to proportions, preconditioned and steam pelleted. African catfish of average weight 9.48g were stocked in three replicates 20liter aquarium, at 113.76g/aquarium and fed with the experimental diets for 90days. Results showed that mushroom had good array of EAA especially lysine (7%). The haematobiochemical parameters and growth of the catfish were best at 8% mushroom extract inclusion. Histological sections showed significant increase in length and width of the mucosal fold microvilli as mushroom extract inclusion increased up to 8%. Similarly, red blood cell counts, packed cell volume, hemoglobin and total white blood cell counts of the catfish increased up to 8%. Fish fed Feed 3 had the best specific growth rate (3.00±0.06% day-1), food conversion ratio (1.54±0.01), weight gain, (128.67±0.02g) and protein conversion ratio of 0.3±0.04. Catfish fed with higher than 8% inclusion of mushroom had reduced growth rates, hemato-biochemical and histological parameters. This may be probably due to the high polysaccharides and beta-glucans present in mushroom. Thus, mushroom extracts should be included in catfish feed but not beyond 8%.

Influence of the Inclusion of Propylene Carbonate Electrolyte Solvent on the Microstructure and Thermal and Mechanical Stability of Poly(l-lactic acid) and Poly(vinylidene fluoride-co-hexafluoropropylene) Battery Separator Membranes.

The influence of the inclusion of the organic solvent propylene carbonate (PC) in microporous membranes based on poly(l-lactic acid) (PLLA) and poly(vinylidene fluoride-co-hexafluoropropylene) P(VDF-HFP) has been studied based on its relevance for the application of those separator membranes in lithium-ion batteries. The membranes have been produced through solvent casting and characterized with respect to the swelling ratio originated by the uptake of the organic solvent. The organic solvent uptake affects the porous microstructure and crystalline phase of both membrane types. The organic solvent uptake amount affects the crystal size of the membranes as a consequence of the interaction between the solvent and the polymer, since the presence of the solvent modifies the melting process of the polymer crystals due to a freezing temperature depression effect. It is also shown that the organic solvent partially penetrates into the amorphous phase of the polymer, leading to a mechanical plasticizing effect. Thus, the interaction between the organic solvent and the porous membrane is essential to properly tailor membrane properties, which in turn will affect lithium-ion battery performance.

Numerical Modeling of the Cellular Structure Formation Process in SiC Solution Growth for Suppression of Solvent Inclusions

Numerical Modeling of the Cellular Structure Formation Process in SiC Solution Growth for Suppression of Solvent Inclusions

Effect of solvent inclusion on the structures and solid-state fluorescence of coordination compounds of naphthalimide derivatives and metal halides

Abstract The structural characteristics and solid-state fluorescence of coordination compounds formed between the fluorophore N-((3-pyridyl)methyl)-1,8-naphthalimide (3-pn) and a range of divalent metal halides, were investigated. Six new crystal structures, of the formula ML 2 X 2.solv, were obtained through the combination of the organic ligand L = 3-pn with the divalent metal halides CoX2 (X = Cl− or Br−) or ZnX2 (X = Cl− or Br−) in different solvents. It was found that solvent molecules are incorporated into all the structures, and that the same complex can incorporate different solvent molecules. The conformation of the complex molecule is determined by the solvent molecule incorporated into the structure. The fluorescence intensity is affected by the identity of the metal and halido ligand in the complex molecule, while the identity of the solvent molecule and the metal ion affects the emission wavelength. Thus, the solvent of crystallisation impacts on the solid-state fluorescence of the compounds, hence the same complex can be made to fluoresce at different wavelengths depending on the solvent of crystallisation.

AIE activity, mechanochromic property and solvent inclusion of two β-diketones with tetraphenylethylene unit

Highly twisted molecular conformation easily leads to the loose molecular packing and big voids, which are desirable for mechanochromism and solvent inclusion. Here, TPE-BF and TPE-BT with highly twisted molecular conformation were designed and synthesized by α-substitution of two β-diketonates. TPE-BF and TPE-BT show similar aggregation-induced emission activity, but different mechanochromism. Subsequently, the corresponding internal mechanism are analyzed and discussed in-depth by XRD, DSC, fluorescence lifetime, crystal analysis and theoretical calculation. Compared with crystal TPE-BF, crystal TPE-BT exhibits more obvious mechanochromism (red shift of 12 nm) before/after grinding, which is attributed to EtOAc inclusion and different intermolecular interactions and stacking. Furthermore, wavelength shifts of TPE-BF and TPE-BT do not exceed 35 nm after phase transition from crystalline state to amorphous state. Obviously, highly twisted molecular conformations fail to bring about high-contrast mechanochromism (wavelength shift above 100 nm), whose reason should be the suppressed intermolecular π-π interactions and overlap before/after grinding. Combined with previous research results of our laboratory, the luminogens forming solvent inclusion generally have twisted molecular conformation, and similar structural fragment with solvent molecule, which will provide a potential design strategy for selective solvent inclusion.

Obtaining a Water-soluble Form of Hydrophobic Indolelocarbazole Derivative Using Solubilizer Complex

Introduction. LHS-1269 is an indolocarbazole derivative with high antitumor activity. Due to the hydrophobic properties of the active substance, the use of organic co-solvents – dimethyl sulfoxide (DMSO) and ethanol – is required to obtain an injectable dosage form (DP). However, the inclusion of organic solvents in the composition of the DF carries a potential risk of side effects as a result of the use of the drug.Aim. Selection of auxiliary substances for obtaining an aqueous solution of hydrophobic indolecarbazole derivative, which allows minimizing the concentration of organic solvents in the composition of DF.Materials and methods. The object of the study is the active substance LHS-1269 series 010320, produced in the Chemical Synthesis Laboratory of the N. N. Blokhin National Medical Research Center of Oncology. The following auxiliary substances were used to obtain model compositions: Kollidon® 17 PF, Kollisolv® PEG-400, Kolliphor® P 188, Montanox™ 20, DMSO (p.a.), ethanol 95 % (standardized according to pharmacopoeia quality standard ФС.2.2.0019.18 of The State Pharmacopoeia of the Russian Federation). Analytical scales OHAUS Analytical Plus AP 100S and laboratory scales AND DL-120 were used for weighing LHS-1269 and auxiliary substances. The dissolution and mixing of the components was carried out on an IKA® C-MAG HS 4 magnetic stirrer.Results and discussion. In the course of the study, 2 groups of model compositions were obtained and estimated, comprising a complex of two or more auxiliary substances as a solubilizer. The first group of formulations contained DMSO at a concentration of 5 % and ethanol at concentrations from 0 to 15 %. The compositions of the second group included DMSO from 0 to 4 %. As a result, it was found that the addition of 5 % Kolliphor® P 188 to the composition of the solution reduces the content of ethanol to 5 %. In this case, with further decrease in ethanol, turbidity of the solution and precipitation are observed. Reducing the concentration of DMSO in the DF to 2 % was achieved by using a combination of 20 % ethanol and solubilizer complex – Kollidon® 17 (20 %), Kollisolv® PEG-400 (20 %) and Kolliphor® P 188 (5 %). In this case, the total dissolution of the active substance without DMSO was observed when compensating for the organic solvent by introducing additional auxiliary substances – Montanox™ 20 (5 %) and benzene (2 %).Conclusion. As a result of the research, the compositions of the auxiliary substances of solubilizers are selected, allowing to obtain an aqueous solution of the hydrophobic compound LHS-1269 with a minimum concentration of organic solvents.

Analysis of the High-Pressure High-Temperature (HPHT) growth of single crystal diamond

A multi-scale, computational model is developed to describe the growth characteristics of single-crystal diamond in the High-Pressure, High-Temperature (HPHT) process. This model is the first to connect phase-change kinetics governing crystal growth to the continuum transport of carbon through the growth cell. Results show the importance of convective transport driven by buoyant flow in the metallic solvent, which increases the growth rate by nearly an order of magnitude over that obtained under diffusion alone. Parametric studies show how crystal growth may be kinetically-limited or transport-limited, depending on the value of the macroscopic kinetic coefficient. Estimating this kinetic coefficient from growth experiments yields a phase-change Damköhler number of unity, indicating a mixed regime where phase-change kinetics and transport are comparable and strongly coupled in this system. Mechanisms responsible for slowing growth as the crystal size increases are explained. Supersaturation inhomogeneities along the facets of larger crystals are predicted, which may be relevant to solvent inclusion formation during growth.

Tautomeric Equilibrium in 1-Benzamidoisoquinoline Derivatives.

In this study, the tautomeric equilibrium of a sequence of 1-benzamidoisoquinoline derivatives was investigated with the tools of NMR spectroscopy and computational chemistry. The equilibrium between different tautomers in these systems could be controlled via the substitution effect, and the relative content of the amide form varied from 74% for the strong electron-donating NMe2 substituent to 38% for the strong electron-accepting NO2 group in the phenyl ring. In contrast to the previously investigated 2-phenacylquinoline derivatives, the most stable and thus most abundant tautomer in the 1-benzamidoisoquinoline series except the two most electron-accepting substituents was an amide. The intramolecular hydrogen bond present in the enol tautomer competed with the intermolecular hydrogen bonds created with the solvent molecules and thus was not a sufficient factor to favor this tautomer in the mixture. Although routinely computational studies of tautomeric equilibrium are performed within the continuum solvent models, it is proven here that the inclusion of the explicit solvent is mandatory in order to reproduce the experimental tendencies observed for this type of system, facilitating strong intermolecular hydrogen bonds.

Improvement of surface morphology by optimizing the growth conditions in solution growth of SiC single crystal

In this study, 4H-SiC single crystal with 2-inch diameter was grown from Si-Cr-C ternary solution with Al addition and the surface morphology of specimen was improved through optimizing the growth conditions. The results suggested that the SiC single crystal grown at 0.1 MPa of He gas exhibits a relatively stable growth process with hexagonal shape and the growth rate is about 152 μm/h due to the appropriate thermal field distribution near the growth interface. In addition, the appearance of polycrystalline SiC precipitated around the seed crystal and the formation of solvent inclusions in the grown crystal could be significantly suppressed by using specially designed seed holder wrapped by BN cap. However, some pore or void defects can still be clearly observed in the grown crystal and possible improved ways aimed at reducing or eliminating pore defects are briefly summarized and the detailed research will be further discussed in the next step of our work.