Solvent Screening Research Articles

Expedited Aminoglutarimide C-N Cross-Coupling Enabled by High-Throughput Experimentation.

A simple protocol for the Buchwald-Hartwig cross-coupling of (hetero)aryl halides with unprotected aminoglutarimide to afford diverse cereblon binding motifs is disclosed. The development of this C-N cross-coupling method was enabled by high-throughput combinatory screening of solvents, bases, temperatures, and ligands. Scope studies revealed generality across various heteroaryl and aryl halides with the reaction proceeding under mild conditions. In comparison, this method demonstrated strategic superiority over previously reported approaches, as evidenced by a significant decrease in step count from known syntheses in the patent literature.

Fully Solution‐Processed Polymeric Multilayer Piezoelectric Devices

AbstractThis study demonstrates fully solution‐processed polymeric multilayer piezoelectric devices. The key challenge, the effective control of the redissolution issue that will cause severe electrical shorting and inconsistent piezoelectric output, is overcome by searching for and using a solvent that offers adequate solubility but extremely slow dissolution for the piezoelectric polymer. The solvent screening methodology is established and demonstrated. The process parameters is systematically optimized to maximize the piezoelectric performance of the multilayer devices. The multilayer devices can output a high charge density of 376 µC m−2, even higher than the record charge density of 250 µC m−2 achieved by traditional contact electrification‐based triboelectric nanogenerators operated in ambient air. The crucial factors for increasing device fabrication yield, namely resistance to short circuits and poling‐induced breakdown, are analyzed. The potential of multilayer devices in practical applications is demonstrated using a five‐layer device as a direct power source and energy harvester. More importantly, the process developed here is transferrable for cost‐effective high‐throughput roll‐to‐roll production. This work thus lays the foundation for the mass production of polymeric multilayer piezoelectric devices and paves the way for their future commercialization.

Sustainable Solution Processing Toward High‐Efficiency Organic Solar Cells: A Comprehensive Review of Materials, Strategies, and Applications

AbstractOrganic solar cells (OSCs) have emerged as promising candidates for renewable energy harvesting due to their lightweight, flexible, and low‐cost fabrication potential. The efficiency of OSCs is largely determined by the choice of solvents, which significantly affect the film morphology of the active layers, the intermixed donor‐acceptor domains, and overall device performance. Beginning with an introduction to the importance of solvent selection, the screening and classification of solvents, emphasizing their characteristics and classification based on sustainability, solubility, and other additional considerations are explored. Various non‐halogenated solvents, highlighting commonly used aromatic solvents, biomass‐derived solvents, and water/alcohol‐based solvents are explored. The state‐of‐the‐art donor and acceptor materials, focusing on efficient donor materials such as PM6 and D18, and high‐performing Y‐series acceptors are also presented. Strategies for developing high‐performance OSCs processed using non‐halogenated solvents are examined, including solvent engineering with additive and additive‐free approaches, ternary strategies, and layer‐by‐layer techniques. The fabrication of large‐area devices using non‐halogenated solvents is addressed, focusing on blade‐coating, slot‐coating, and other processing techniques. Finally, this review outlines future research directions in the non‐halogenated solvent processing of OSCs, emphasizing the need for continuous innovation to overcome existing limitations and propel OSC technology toward commercial viability.

Solvent Descriptors Guided Wide‐Temperature Electrolyte Design for High‐Voltage Lithium‐Ion Batteries

AbstractLithium‐ion batteries are increasingly required to operate under harsh conditions, particularly at high temperatures above 55 °C. However, existing electrolytes suffer from inadequate thermal stability and significant interphasial side reactions. Moreover, there is a lack of clear guidelines for developing electrolytes that can withstand high temperatures. Here a solvent screening descriptor is introduced based on dual local softness and dielectric constant. The findings indicate that solvents with moderate dielectric constants and low reactivity are ideal candidates for high‐temperature electrolytes. Among the solvents evaluated, tetraethyl orthosilicate (TEOS) is identified as a suitable option and is utilized to formulate a localized high‐concentration electrolyte (TEOS‐based LHCE). Remarkably, the 1‐Ah LiNi0.8Co0.1Mn0.1||graphite pouch cell utilizing this TEOS‐based LHCE demonstrates 95.8% capacity retention after 300 cycles at 60 °C. Interphasial analysis reveals that the TEOS‐based LHCE promotes the formation of thin, uniform LiF‐rich interphases, effectively suppressing interfacial side reactions at elevated temperatures. This screening strategy not only enhances the understanding of electrolyte performance but also paves the way for high‐throughput screening of electrolytes suitable for wide‐temperature lithium‐ion batteries.

Tailoring eco-friendly siloxane-based electrolytes for high-performance lithium–sulfur batteries

Lithium–sulfur batteries (LSBs), with their ultra-high theoretical energy density (2600 Wh kg−1), are considered one of the most attractive high-energy batteries. However, the “shuttling effect” of polysulfides and the uncontrolled growth of lithium (Li) dendrites pose significant challenges to the practical implementation of LSBs. Herein, a lightweight and eco-friendly diethoxydimethylsilane (DEMS) is chosen as a multi-functional solvent for LSBs. The low polarity of DEMS promotes the “solid–solid” conversion of sulfurized polyacrylonitrile (SPAN) during charge–discharge processes, eliminating the shuttle effect of polysulfides. Moreover, the DEMS-based electrolyte enables highly reversible Li plating/stripping processes across a wide temperature range spanning from −20 to 60 °C. As a result, the Li/SPAN batteries using the DEMS electrolyte exhibit excellent cyclic stability at 0.2 C with retainable capacities of 524.4 mAh/g after 200 cycles, 598.8 mAh/g after 100 cycles, and 318.6 mAh/g after 50 cycles at 26, 60 and −20 °C, respectively. This study aims to identify low-cost and highly stable electrolytes through solvent screening to enhance the electrochemical performance of LSBs.

Green and efficient extraction of an anticaner agent N-methylsansalvamide using ultrasound-assisted deep eutectic solvents from mycelia of strain Frusarium sp. R1

N-methylsansalvamide (SA), one of cyclic pentadepsipeptides produced by several Fusarium strains, is a promising therapeutic agent for the treatment of cancer disease. In order to make sufficient amount of SA for drug development, a green and efficient extraction process of SA from the mycelia of strain Fusarium sp. R1 using deep eutectic solvent-assisted ultrasound extraction (DES-UAE) was firstly achieved in this work. Solvent screening results indicated that choline chloride-acetic acid (ChCl-Aa) was shown to be the best DES for SA extraction. Through single-factor trials, Plackett-Burman design (PBD) and BoxBehnken design (BBD) experiments, the optimal conditions for DES-UAE with the highest SA yield of 58.2 ± 1.1 mg/g were obtained as follows: ChCl-Aa ratio of 1:2.0 (M/M), water content of 16.4 %, liquid-solid ratio of 37:1 (mL/g), ultrasonic power of 175 W for 47.4 min at 46.3 °C. Compared to conventional extraction approaches, DES-UAE exhibited better SA yield since it caused more serious damage to the surface of mycelia powder on basis of scanning electron microscopy (SEM) analysis. Furthermore, molecular interaction studies suggested that SA has a variety of interactions with ChCl-Aa, including hydrogen and electrovalent bonds as well as van der Waals forces. Finally, the recovery rate of SA reached up to 99.5 % when the ratio of distilled water and DES extracts was 15:1 (V/V). These findings provide the way for large-scale production of SA.

Solvent screening for the purification of monoterpenoids by countercurrent and centrifugal partition chromatography

AbstractBACKGROUNDCountercurrent chromatography (CCC) and centrifugal partition chromatography (CPC) are efficient techniques to purify terpenoids from essential oils. These methods require suitable solvent systems for the partition between the two immiscible liquid phases. In this study, using the analytical shake‐flask method, we measured the partition coefficients of three model monoterpenoids, namely carvone, eucalyptol and thymol, in 11 biphasic solvent systems, at 298.2 K. Moreover, the predictive COSMO‐RS model was applied to represent the partition coefficients of data measured in this work and retrieved from the literature, the liquid–liquid equilibrium (LLE) data of three solvent families suitable for CCC/CPC separations (i.e., Arizona, Modified Arizona and Green Arizona) and the solute's partition coefficients in the three solvent families.RESULTSThe partition coefficients obtained for thymol and eucalyptol are the first partition data available in the literature. The obtained root mean square deviations (RMSDs) between the experimental and predicted partition coefficients (log basis) varied between 0.28 and 0.49. For LLE, RMSDs of 0.040 and 0.048 were achieved for the Arizona and Green Arizona families, respectively.CONCLUSIONThe predictive COSMO‐RS model describes the monoterpenoid partition coefficients and the LLE data of the solvent families well. The most favorable solvent systems to perform the separations were identified, showing that systems with low and intermediate‐to‐low polarities are the most promising options for separating the selected monoterpenoids from their natural matrices by CCC/CPC techniques. © 2024 Society of Chemical Industry (SCI).

Atomistic simulations of polysaccharide materials for insights into their crystal structure, nanostructure, and dissolution mechanism

AbstractCrystalline polysaccharides are abundant in nature and can be transformed into highly functional materials. However, the molecular basis for the formation of higher-order structures remains unclear. Computer simulation is an advanced tool for modeling macromolecular structures, and the atomistic simulations provide valuable information on the crystalline polysaccharides. Fiber deformation, crystalline transition, and novel nanostructures of cellulose were characterized through molecular dynamics simulations and density functional theory calculations of models of molecular chain sheets extracted from the crystal structure of the cellulose polymorphs. Extended ensemble molecular dynamics simulations were applied to analyze the artificial crystal structure of non-natural amylose analog polysaccharides, revealing the hexagonal packing of double helices through the self-assembly of molecular chains dispersed in aqueous solution. Dissolution simulations of the cellulose and chitin crystalline fibers revealed that the anions of ionic liquids, with their solvation power, played a key role in the cleavage of intermolecular hydrogen bonds in the crystal structure, whereas the cations contributed to irreversible molecular chain dispersion. The good correlation between the actual solubility of polysaccharides and the predicted number of intermolecular hydrogen bonds prompted the development of a platform that combined simulations and machine learning for high-throughput screening of solvents for cellulose and chitin.

Exploring the mechanisms of benzanilide crystal growth and morphology: Crystal surface structure, solvent diffusion and solvent-interface interactions

Flaky crystals are fragile, rendering them unsuitable for various applications including use, processing, storage and transportation. This work investigates the growth and morphology regulation mechanisms of flaky crystals using benzanilide as a model material. Initially, block-like crystals are prepared by solvent screening and cooling crystallization with its morphology greatly improved. Subsequently, growth kinetics of (111), (1–10) and (020) faces are established with crystal growth experiments. The crystal growth of (001) face is also determined to follow a two-dimensional nucleation model with the microscopic surface analysis using atomic force microscopy. The changes of the surface integration resistance and the growth step height are regarded as kinetic mechanisms of the growth behavior and crystal morphology modulation by solvent and supersaturation. Finally, the molecular mechanism of the modulation of the solvent in crystal morphology is revealed base on crystal surface structure analysis and molecular dynamics simulations. The weak solvent-interface polar interactions facilitate the incorporation of benzanilide molecules into the weak polarity (001) face, leading to the surface roughening and increased crystal thickness when employing strongly polar solvents such as acetonitrile. Unlike the former, the relatively weak hydrogen bonding interactions between solvents and strong polarity (020) face, and the higher diffusion ability of molecules promote the rapid growth and disappearance of (020) face in ethanol and acetonitrile with strong hydrogen bond formation ability. This study can contribute to a deeper understanding of the solvent effect on crystal morphology and provide guidance for optimizing crystallization conditions to obtain shape-tailored crystal products.

Mechanistic and thermodynamic studies on directing group-assisted copper-catalyzed α-C(sp2)−H amination of aryl amines with alkylamines

In mechanistic, three possible pathways of α-C(sp[2])−H functionalization amination of picolinamide with morpholine catalyzed by Cu(OAc)2/O2 in p-xylene were studied. Through theoretical calculations, it was found that the pathway involving the radical-cation intermediates produced by the subsequent single electron transfer (SET) was proved to be the most favorable. Then, we also discussed the solvation and substituent effects of three key steps, including N − H bond deprotonation, C − N bond formation rate-determining step and C − H bond deprotonation step, so as to fully understand the mechanism of directing group-assisted copper-catalyzed α-C − H functionalization of aniline and the screening of substrates and solvents. In thermodynamic, the SET process plays a crucial role in the entire catalytic cycle. Therefore, we further studied the reduction potential (Ered) values of Cu(II) radical-cation intermediates involved in the SET process, reflecting the occurrence trend of SET from the thermodynamic point of view, and studied the substituent effects and structure-activity relationships on Ered values of Cu(II) complexes derivatives formed by different Cu(Ⅱ) catalysts, different directing groups, different alkylamines and aromatic amines substrates. It is also found that there are many quantitative structure-activity relationships between Ered and the singly occupied molecular orbital (SOMO) energy, Hammett substituent constant σ+ and other structural parameters.

Predicting CO2 equilibrium solubility in various amine-CO2 systems using an artificial neural network model

Three proposed reaction mechanisms can occur in an amine-CO2 system: either zwitterionic or termolecular mechanisms for primary/secondary amines and base-catalyzed hydration for tertiary amines. The intricacy of this system hinders the construction of a general model for all types of amines. This study attempts to build an artificial neural network model that predicts the equilibrium solubility of any nonblended aqueous amine-CO2 system under given operating conditions, regardless of the reaction mechanism. This is a novel approach that has not yet been reported. The amines were characterized using molecular descriptors derived from COSMO theory through density functional theory calculations to incorporate molecular structures as model features. Our model achieved performance metrics (R2) of 0.9645 and 0.9481 for the training and validation sets, respectively. For unfamiliar amines that were absent in both the training and validation sets, our model achieved an R2 of 0.8601. Model benchmarking was performed using a previously established thermodynamic model. Interpretations of the model are also provided based on the chosen features. This study also offers exploratory insight into how the molecular structure and operating conditions affect the CO2 equilibrium solubility in amines. The model developed in this study has the potential to reduce the solvent screening time in determining appropriate amines for larger-scale applications.

Process-driven solvent screening for efficient extractive distillation using interpolative rational functions

When designing extractive distillation processes, using selectivity and capacity at infinite dilution alone is hard to identify the real optimal solvent with minimal process cost. To overcome this problem, a new process-driven solvent screening approach is developed. As simple and reliable surrogate models, rational functions (algebraic fractions such that the numerator and the denominator are polynomials) and multivariate polynomials (a subset of rational functions) are trained to interpolate vapor–liquid equilibria with thermodynamic consistency. The surrogate models can directly be embedded into superstructure-based extractive distillation process design to obtain optimal solutions within a few seconds. This enables to evaluate the real process performance of numerous solvents efficiently. Incorporating the accelerated process design strategy, a multi-level solvent screening framework is proposed and exemplified for the separation of a close-boiling mixture ethylbenzene/styrene. The solvent C2H2Br4 ultimately enables a cost reduction of 27.9 % compared to the industrially used benchmark solvent sulfolane.

Biphasic Furfural Oxidation with Hydrogen Peroxide: Process-Level Solvent Screening and Solvent Effect on Catalytic Activity

Biphasic Furfural Oxidation with Hydrogen Peroxide: Process-Level Solvent Screening and Solvent Effect on Catalytic Activity

Conceptual design of furfural extraction, oxidative upgrading and product recovery: COSMO-RS-based process-level solvent screening

Liquid phase oxidation of furfural using hydrogen peroxide offers a promising route for bio-based C4 furanones and diacids; however, only dilute water-based process designs have been previously suggested that have limited techno-economic potential. In this study, a conceptual process design is presented, where aqueous furfural is extracted using an organic solvent, coupled with peroxide oxidation and product recovery in the presence of the solvent. To address the problem of solvent selection, the COSMO-RS-based solvent screening framework is applied, where quantum mechanics-based thermodynamics are utilized in pinch-based process models. About 2500 solvent candidates were identified as feasible. Focusing on a set of 400 solvent candidates revealed energy consumption values (Qreb,tot/ṁprod recov) between approximately 2 MWh/tonne and 33 MWh/tonne, signifying the potential of the solvent-based process in outperforming the reference aqueous process (49.4 MWh/tonne). The study provides potential solvent candidates and future directions to consider in more costly computational and experimental efforts.

High-throughput computational screening for optimal solvents in methyl 2-hydroxyisobutyrate-water separation

In the semiconductor industry, the efficacy of methyl 2-hydroxyisobutyrate (HBM) as a photoresist thinner is crucial but often compromised by water contamination. Additionally, the manufacturing process tends to form an azeotrope with water, rendering traditional distillation methods inefficient for purification. This study introduces a novel computational screening approach to identify optimal solvents for the liquid-liquid extraction of HBM, offering a sustainable alternative to conventional distillation. Our three-step sequential screening protocol utilizes molecular dynamics simulations to evaluate intermolecular interaction energy, partition coefficient, and environmental, health, and safety (EHS) parameters. Initially, a comprehensive database of 4919 solvents was screened using molecular dynamics simulations to assess interaction energies and partition coefficients. Solvents that met these energy criteria were further evaluated for their EHS profiles. This process identified seven solvents that optimize extraction efficiency while adhering to stringent environmental and safety standards. Our approach not only enhances the purity and performance of HBM in semiconductor manufacturing but also presents a green, cost-effective solution for other industrial chemical processes requiring refined solvent selection.

Kinetic evaluation of Azadirichtin and related phytoconstituents extraction from Azadirachtaindica (neem) and Melia azedarach (chinaberry) seeds using ultrasound assisted extraction and maceration

The comparative extraction of total phenolic compounds from A. indica and M. azedarach seed powder using two different methodologies is evaluated. The solvent screening was done using soxhlet extraction for six different solvents and methanol had the maximum extraction capacity for both seed powder. Extraction of total phenolic compounds from A. indica and M. azedarach seed powder was done using maceration and ultrasound. The kinetics and extraction mechanism was evaluated using popular three empirical and five semi-empirical models along with scanning electron micrograph analysis. The rate constants showed an enhancement in extraction kinetics of about 4.5 fold for M. azedarach and 7.8 fold for A. indica seeds using ultrasound. Based on model evaluation, extraction using maceration for both seeds follows inter-particle diffusion as the rate-limiting step with non-swelling behaviour. Whereas, in the case of ultrasound, the dependence of rate is on the diffusion of solute within the solid and the solid surface to the solvent. In addition, HPLC and GC-MS analysis suggested differences in the composition of extracts and some important phytochemicals were extracted in larger quantities using ultrasound as compared to maceration.

First-Principles Modeling of the Absorption Spectrum of Crystal Violet in Solution: The Importance of Environmentally Driven Symmetry Breaking.

Theoretical spectroscopy plays a crucial role in understanding the properties of the materials and molecules. One of the most promising methods for computing optical spectra of chromophores embedded in complex environments from the first principles is the cumulant approach, where both (generally anharmonic) vibrational degrees of freedom and environmental interactions are explicitly accounted for. In this work, we verify the capabilities of the cumulant approach in describing the effect of complex environmental interactions on linear absorption spectra by studying Crystal Violet (CV) in different solvents. The experimental absorption spectrum of CV strongly depends on the nature of the solvent, indicating strong coupling to the condensed-phase environment. We demonstrate that these changes in absorption line shape are driven by an increased splitting between absorption bands of two low-lying excited states that is caused by a breaking of the D3 symmetry of the molecule and that in polar solvents, this symmetry breaking is mainly driven by electrostatic interactions with the condensed-phase environment rather than distortion of the structure of the molecule, in contrast with conclusions reached in a number of previous studies. Our results reveal the importance of explicitly including a counterion in the calculations in nonpolar solvents due to electrostatic interactions between CV and the ion. In polar solvents, these interactions are strongly reduced due to solvent screening effects, thus minimizing the symmetry breaking. Computed spectra in methanol are found to be in reasonable agreement with the experiment, demonstrating the strengths of the outlined approach in modeling strong environmental interactions.

Modeling Study on Heat Capacity, Viscosity, and Density of Ionic Liquid–Organic Solvent–Organic Solvent Ternary Mixtures via Machine Learning

Physicochemical properties of ionic liquids (ILs) are essential in solvent screening and process design. However, due to their vast diversity, acquiring IL properties through experimentation alone is both time-consuming and costly. For this reason, the creation of prediction models that can accurately forecast the characteristics of IL and its mixtures is crucial to their application. This study proposes a model for predicting the three important parameters of the IL-organic solvent–organic solvent ternary system: density, viscosity, and heat capacity. The model incorporates group contribution (GC) and machine learning (ML) methods. A link between variables such as temperature, pressure, and molecular structure is established by the model. We gathered 2775 viscosity, 6515 density, and 1057 heat capacity data points to compare the prediction accuracy of three machine learning methods, namely, artificial neural networks (ANNs), extreme gradient boosting (XGBoost), and light gradient boosting machine (LightGBM). As can be observed from the findings, the ANN model produced the best results out of the three GC-based ML methods, even though all three produced dependable predictions. For heat capacity, the mean absolute error (MAE) of the ANN model is 1.7320 and the squared correlation coefficient (R2) is 0.9929. Regarding viscosity, the MAE of the ANN model is 0.0225 and the R2 is 0.9973. For density, the MAE of the ANN model is 7.3760 and the R2 is 0.9943. The Shapley additive explanatory (SHAP) approach was applied to the study to comprehend the significance of each feature in the prediction findings. The analysis results indicated that the R-CH3 group of the ILs, followed by the imidazolium (Im) group, had the highest impact on the heat capacity property of the ternary system. On the other hand, the Im group and the R-H group of ILs had the most effects on viscosity. In terms of density, the Im group of the ILs had the greatest effect on the ternary system, followed by the molar fraction of the organic solvent.

Natural deep eutectic solvent-ultrasound for the extraction of flavonoids from Fructus aurantii: Theoretical screening, experimental and mechanism

To reduce the environmental pollution caused by organic solvents and improve the extraction efficiency, a green and high-effective natural deep eutectic solvent (NADES) was screened out and prepared for the extraction of flavonoids from Fructus aurantii based on the COMOS-RS and experimental verification. The results showed the results of theoretical screening and experimental verification were consistent, and Ch-Lea was the best extraction solvent, which further proved the COMOS-RS was an efficient tool for the solvent screening. Then, the extraction conditions were investigated. The optimum extraction conditions were as follows: molar ratio (1:2), water content (30%), solid–liquid ratio (1/60 g/g) and extraction time (15 min), yet the extraction temperature and power did not significantly affect the extraction yield. Under the optimal extraction condition, the extraction yield of flavonoids was 122.68 mg/g. Compared with the traditional extraction solvents (methanol and ethanol), Ch-Lea has a higher extraction yield. And the green assessment was conducted based on Eco-Scale methodology, which results indicated the Ch-Lea was more environmentally friendly than methanol and ethanol. Meanwhile, the Ch-Lea has good reusability, and the extraction yields from four reuses were 122.68 mg/g, 125.13 mg/g, 122.56 mg/g and 105.63 mg/g, respectively. Moreover, the extraction mechanism was delved into using molecular dynamics (MD) simulation and reduced density gradient (RDG) analysis. The hydrogen bond interaction, particularly the O-H bonds, between Ch-Lea and the naringin molecule emerged as the primary force driving the extraction process. In summary, Ch-Lea is a green, economical, and highly effective solvent, making it a promising candidate for flavonoid extraction from Fructus aurantii. Its potential as an alternative to traditional extraction solvents further underscores its value.

A new phase-change solvent composed of diethylenetriamine, n-butanol and water for CO2 capture

In this work, a new phase-change solvent composed of diethylenetriamine (DETA)/n-butanol/water is reported for CO2 capture. Screening of the absorption solvents, and the performance of absorption, desorption, and cyclic capacity are comprehensively investigated. The experimental results show that 30 wt% DETA/water systems exhibit excellent absorption performance. Accordingly, 30 wt% DETA/n-butanol/H2O system is used as a phase-change solvent for CO2 capture. The DETA/n-butanol/H2O mixture with mass ratio 3:4:3 shows better absorption performance compared to others of 3:1:6, 3:2:5, 3:3:4, 3:4:3, 3:5:2, and 3:6:1, and the equilibrium CO2 loading reaches up to 3.70 mol·kg−1 at 60 min, 313.15 K and 101 kPa. The 3:4:3 DETA/n-butanol/H2O system displays low heat duty with a relative heat duty of 61.4 %, and outstanding cyclic capacity (CC). CC increases by 47.6 % compared to the widely used 30 wt% aqueous monoethanolamine (MEA) solution. Finally, 13C NMR is used to determine the species before and after CO2 absorption. The mechanism of the phase transition is analyzed according to the species polarity which is estimated using Gaussian 09 W program.