Attractive Solvent Research Articles

Sodium Copper Chlorophyllin: A Sustainable Bioinspired Catalyst for the Aerobic Oxidative Synthesis of Nitrogen Heterocycles and the Oxidative Cyanation of Tertiary Amines

AbstractA remarkably simple and straightforward protocol has been reported showcasing sodium copper chlorophyllin (SCC) as an eco‐friendly, bioinspired catalyst for the aerobic oxidative synthesis of pharmaceutically prevalent nitrogen‐containing heterocycles, such as benzimidazoles and quinoxalines. This reaction was performed in green solvent water, using the green oxidant, molecular oxygen. SCC displayed exceptional efficiency, congruent with the prevailing metal/non‐metal‐based catalyst regime without requiring additives. The SCC catalyst exhibited excellent recyclability upto three cycles for the benzimidazole synthesis reaction. This benign strategy was successfully applied in synthesizing a bioactive quinoxaline i. e., Tyrphostin AG1296, a promising candidate for melanoma treatment. The catalytic activity of SCC was explored for the synthesis of another privileged moiety i. e., α‐aminonitriles, via the α‐cyanation of tertiary amines under oxidative conditions. This reaction progressed with a mild, easy‐to‐use, convenient cyanide source, such as ethyl cyanoformate, and a green and attractive solvent, such as methanol, precluding acidic media. SCC catalyst was efficiently recycled upto three cycles for the α‐aminonitriles synthesis. Overall, the utility of a biodegradable, robust catalyst such as SCC, eco‐friendly solvents such as water and methanol, green oxidants such as O2, and mild reaction conditions, devoid of acidic additives, renders the present work viable for academic and industrial research.

Improved recyclability of the superbase ionic liquid [MTBNH][AcO] used in the lyocell fiber spinning process

In the research of new solvents for cellulose dissolution for textile fiber production, some ionic liquids offer high dissolving capacities making them attractive solvents for lyocell processes. One especially interesting group is superbase carboxylates. However, despite their excellent pulp dissolving abilities and good spinnability properties in a lyocell process, they have been lacking hydrolytic stability, which hinders their recyclability. In this article, a new type of superbase-based ionic liquid, [MTBNH][AcO], is aimed to provide higher hydrolytic stability than its structural relative predecessors. For evaluation of the hydrolysis behavior of [MTBNH][AcO], we have tested the ionic liquid in two sets of recycling experiments. The “blank-experiments” were applied to investigate hydrolytic behavior without the presence of pulp. These values were compared with the results from spinning trials with pulp. It was found that this new ionic liquid is not only more stable than its predecessor [MTBDH][AcO] in terms of hydrolysis but can also dissolve and spin cellulose at lower temperatures. The spun fibers were tested for their textile-physical properties and their performance was comparable to other lyocell fibers.

Integrative studies of ionic liquid interface layers: bridging experiments, theoretical models and simulations.

Ionic liquids (ILs) are a class of salts existing in the liquid state below 100 °C, possessing low volatility, high thermal stability as well as many highly attractive solvent and electrochemical capabilities, etc., making them highly tunable for a great variety of applications, such as lubricants, electrolytes, and soft functional materials. In many applications, ILs are first either physi- or chemisorbed on a solid surface to successively create more functional materials. The functions of ILs at solid surfaces can differ considerably from those of bulk ILs, mainly due to distinct interfacial layers with tunable structures resulting in new ionic liquid interface layer properties and enhanced performance. Due to an almost infinite number of possible combinations among the cations and anions to form ILs, the diversity of various solid surfaces, as well as different external conditions and stimuli, a detailed molecular-level understanding of their structure-property relationship is of utmost significance for a judicious design of IL-solid interfaces with appropriate properties for task-specific applications. Many experimental techniques, such as atomic force microscopy, surface force apparatus, and so on, have been used for studying the ion structuring of the IL interface layer. Molecular Dynamics simulations have been widely used to investigate the microscopic behavior of the IL interface layer. To interpret and clarify the IL structure and dynamics as well as to predict their properties, it is always beneficial to combine both experiments and simulations as close as possible. In another theoretical model development to bridge the structure and properties of the IL interface layer with performance, thermodynamic prediction & property modeling has been demonstrated as an effective tool to add the properties and function of the studied nanomaterials. Herein, we present recent findings from applying the multiscale triangle "experiment-simulation-thermodynamic modeling" in the studies of ion structuring of ILs in the vicinity of solid surfaces, as well as how it qualitatively and quantitatively correlates to the overall ILs properties, performance, and function. We introduce the most common techniques behind "experiment-simulation-thermodynamic modeling" and how they are applied for studying the IL interface layer structuring, and we highlight the possibilities of the IL interface layer structuring in applications such as lubrication and energy storage.

Evolutionary Reinforcement of Polymer Networks: A Stepwise-Enhanced Strategy for Ultrarobust Eutectogels.

Gel materials are appealing due to their diverse applications in biomedicine, soft electronics, sensors, and actuators. Nevertheless, the existing synthetic gels are often plagued by feeble network structures and inherent defects associated with solvents, which compromise their mechanical load-bearing capacity and cast persistent doubts about their reliability. Herein, combined with attractive deep eutectic solvent (DES), a stepwise-enhanced strategy is presented to fabricate ultrarobust eutectogels. It focuses on the continuous modulation and optimization of polymer networks through complementary annealing and solvent exchange processes, which drives a progressive increase in both quantity and mass of the interconnected polymer chains at microscopic scale, hence contributing to the evolutionary enhancement of network structure. The resultant eutectogel exhibits superb mechanical properties, including record-breaking strength (31.8MPa), toughness (76.0MJ m-3 ), and Young's modulus (25.6MPa), together with exceptional resistance ability to tear and crack propagation. Moreover, this eutectogel is able to be further programmed through photolithography to in situ create patterned eutectogel for imparting specific functionalities. Enhanced by its broad applicability to various DES combinations, this stepwise-enhanced strategy is poised to serve as a crucial template and methodology for the future development of robust gels.

Highly selective hemin-catalyzed three-component aminoselenation and oxyselenation of alkenes

The highly selective hemin-catalyzed three-component aminoselenation and oxyselenation of alkenes has been developed using various nucleophiles. Remarkably, the use of acetonitrile as a green and attractive solvent in an organic reaction, the use of simple TBHP (tert-butyl hydroperoxide) as a mild oxidant, the use of a biodegradable catalyst, simple workup procedure, and good functional group tolerance (39 examples) are added features to this biomimetic method for the preparation of various difunctionalized organoselenium derivatives. These characteristics demonstrate the scalability of the current strategy for academic research and industrial applications.

Lipase-catalyzed Production of Sugar Esters in Pressurized Fluid Media: A Review

Sugar esters (SE) are amphiphilic compounds containing hydrophilic moieties linked to hydrophobic parent structures with environmental-friendly features regarding non-toxicity, odorless, tasteless, and biodegradability as well as functional, emulsifying, stabilizing, dispersant, and detergent functions. The use of lipases as alternative biocatalysts to the alkaline compounds used industrially to produce SEs introduces interesting points to the process regarding energy consumption reduction, high selectivity, purer products production, and minimization of fossil-based solvents utilization. However, the usual organic solvents required in the reaction are harmful to enzymes, affecting their catalytic capacity. Accordingly, supercritical fluids (SCFs) are interesting options for the enzymatic process, especially carbon dioxide, which reaches such conditions under non-severe circumstances. SCFs have characteristics that make them attractive solvents for SEs production, allowing the manipulation of their properties to increase substrate solubility and reduce mass transfer limitations, intensifying process productivity. However, issues concerning with the strict operating conditions required by lipases and costs linked to project and equipments are shortcomings that must be considered. Therefore, this review gathers the main guidelines and opportunities that drive SEs production through enzymatic catalysis under supercritical conditions, as well as the challenges faced by this technology. Furthermore, technical aspects of properties and characteristics that justify the application of these compounds as well as considerations about how the main process parameters should be managed to enhance the substrates’ conversion are also discussed. Future perspectives indicate that the design of cost-effective bioreactors to improve performance as well as protein engineering to enhance lipases’ stability are points to be explored.

Single Crystal Growth of Synthetic Sulfide- and Phosphide-Based Minerals for Physical Measurements

In this work, we review recent advances in the use of high-temperature solution growth that allow for the growth of single crystalline samples of synthetic minerals. We outline how low-melting binary or ternary solutions are attractive solvents for solution growth and provide examples of the growth of bismuthinite (Bi2S3), galena (PbS) and parkerite (Ni3Bi2S2). We then focus on the Rh-S, Pd-S and Ni-P phase spaces to discuss how the low-melting regions near transition metal-main group eutectic compositions make excellent solvents for crystal growth of several binary and ternary minerals containing both high melting and volatile elements as well as for the discovery of new materials. We end by discussing the growth of synthetic canfieldite (Ag8SnS6) and argyrodite (Ag8GeS6) from Ag2S–Sn-S-based solutions.

Hemin-catalyzed controlled oxidative cyanation of secondary amine for the synthesis of α-aminonitriles and α-iminonitriles

We report an efficient and controlled oxidative cyanation approach for the synthesis of α-aminonitriles and α-iminonitriles in MeOH using Hemin (1 mol %) as a nontoxic and natural catalyst under room temperature. This work is the first report on the incorporation of a natural iron porphyrin complex as a redox catalyst for the oxidation of secondary amines. The significant features of this biomimetic strategy for the preparation of α-aminonitriles and α-iminonitriles include the use of MeOH as green and attractive solvent in an organic reaction, the use of ethyl cyanoformate as a benign cyanide source due to its mild conditions, environmentally friendly, the use of a biodegradable catalyst, no moisture sensitivity, simple workup procedure, and controllable, which all together make the current method attractive for academic research as well as industrial applications.

Deep Eutectic Solvent as Green Solvent in Extraction of Biological Macromolecules: A Review

Greater awareness of environmental sustainability has driven many industries to transition from using synthetic organic solvents to greener solvents in their manufacturing. Deep eutectic solvents (DESs) have emerged as a highly promising category of green solvents with well-demonstrated and wide-ranging applications, including their use as a solvent in extraction of small-molecule bioactive compounds for food and pharmaceutical applications. The use of DES as an extraction solvent of biological macromolecules, on the other hand, has not been as extensively studied. Thereby, the feasibility of employing DES for biomacromolecule extraction has not been well elucidated. To bridge this gap, this review provides an overview of DES with an emphasis on its unique physicochemical properties that make it an attractive green solvent (e.g., non-toxicity, biodegradability, ease of preparation, renewable, tailorable properties). Recent advances in DES extraction of three classes of biomacromolecules—i.e., proteins, carbohydrates, and lipids—were discussed and future research needs were identified. The importance of DES’s properties—particularly its viscosity, polarity, molar ratio of DES components, and water addition—on the DES extraction’s performance were discussed. Not unlike the findings from DES extraction of bioactive small molecules, DES extraction of biomacromolecules was concluded to be generally superior to extraction using synthetic organic solvents.

Flow-through strategy to fractionate lignin from eucalyptus with formic acid/hydrochloric solution under mild conditions

Formic acid is an attractive solvent for the fractionation of lignocellulose for the production of biomaterials and chemicals, while the operation conducted in a batch manner is not conducive to mass transfer in separation process. In this research, eucalyptus was fractionated with formic acid/hydrochloric solution in a flow-through reactor at 95 °C, and the structural characteristics and the composition of fractionated lignin in different stages were investigated. Results showed that the fractionation efficiency was notably improved with a flow-through reactor, as evidenced by the low solid residue yield of 49.5% and the lignin removal rate of 79.4% as compared to the batch manner. During the fractionation process, the dissolution rate of lignin decreased gradually, and the obtained lignin samples showed low molecular weight (<3000), good uniformity (<2), and high thermal stability. The structure analysis showed that β-O-4, β-β, and β-5 linkages in lignin were degraded to varying degrees with increased time, and the degradation of G units was more severe than S ones.

Critical assessment of structure-based approaches to improve protein resistance in aqueous ionic liquids by enzyme-wide saturation mutagenesis

Ionic liquids (IL) and aqueous ionic liquids (aIL) are attractive (co-)solvents for green industrial processes involving biocatalysts, but often reduce enzyme activity. Experimental and computational methods are applied to predict favorable substitution sites and, most often, subsequent site-directed surface charge modifications are introduced to enhance enzyme resistance towards aIL. However, almost no studies evaluate the prediction precision with random mutagenesis or the application of simple data-driven filtering processes. Here, we systematically and rigorously evaluated the performance of 22 previously described structure-based approaches to increase enzyme resistance to aIL based on an experimental complete site-saturation mutagenesis library of Bacillus subtilis Lipase A (BsLipA) screened against four aIL. We show that, surprisingly, most of the approaches yield low gain-in-precision (GiP) values, particularly for predicting relevant positions: 14 approaches perform worse than random mutagenesis. Encouragingly, exploiting experimental information on the thermostability of BsLipA or structural weak spots of BsLipA predicted by rigidity theory yields GiP = 3.03 and 2.39 for relevant variants and GiP = 1.61 and 1.41 for relevant positions. Combining five simple-to-compute physicochemical and evolutionary properties substantially increases the precision of predicting relevant variants and positions, yielding GiP = 3.35 and 1.29. Finally, combining these properties with predictions of structural weak spots identified by rigidity theory additionally improves GiP for relevant variants up to 4-fold to ∼10 and sustains or increases GiP for relevant positions, resulting in a prediction precision of ∼90% compared to ∼9% in random mutagenesis. This combination should be applicable to other enzyme systems for guiding protein engineering approaches towards improved aIL resistance.

Role of the Solvation Shell Structure and Dynamics on K‐Ion and Li‐Ion Transport in Mixed Carbonate Electrolytes

AbstractEthylene and diethyl carbonates (EC : DEC) have been attractive solvents for Li‐ion electrolytes because these can exhibit a good ionic conductivity and stable electrochemical performance. However, in the contemporary K‐ion electrolytes, KPF6 presents a limited solubility of ∼0.6 M in EC : DEC (volume ratio 1 : 1), which restricts its performance. Here, the molecular basis for these distinct solvation behaviors is clarified by combining experimental attenuated total reflectance‐infrared spectroscopy and electrochemical impedance spectroscopy measurements with molecular dynamics simulations, revealing the distinct roles of EC and DEC solvents on the solubility, ionic conductivity, and solvation shell structures of KPF6 and LiPF6 salts in EC : DEC mixtures. In turn, these insights have enabled the formulation of a new K‐ion electrolyte with EC : DEC volume ratio of 1.5 that exhibits significantly increased KPF6 solubility (∼0.9 M) and ionic conductivity, reaching 13.99 mS cm−1 at 25 °C.

New Solvents for CO2 and H2S Removal from Gaseous Streams

Acid gas removal from gaseous streams such as flue gas, natural gas and biogas is mainly performed by chemical absorption with amines, but the process is highly energy intensive and can generate emissions of harmful compounds to the atmosphere. Considering the emerging interest in carbon capture, mainly associated with increasing environmental concerns, there is much current effort to develop innovative solvents able to lower the energy and environmental impact of the acid gas removal processes. To be competitive, the new blends must show a CO2 uptake capacity comparable to the one of the traditional MEA benchmark solution. In this work, a review of the state of the art of attractive solvents alternative to the traditional MEA amine blend for acid gas removal is presented. These novel solvents are classified into three main classes: biphasic blends—involving the formation of two liquid phases, water-lean solvents and green solvents. For each solvent, the peculiar features, the level of technological development and the main expected pros and cons are discussed. At the end, a summary on the most promising perspectives and on the major limitations is provided.

Characterization of membrane wetting phenomenon by ionic liquid via ultrasonic time-domain reflectometry (UTDR)

Ionic liquids (ILs) are becoming attractive solvents or catalysts in many industries, thus energy-efficient membrane-based technologies for the purification and concentration of ILs are gaining attention. Membrane wetting by ILs is recognised as the major challenge in membrane processes, but limited information is available. In this study, the dynamics of wetting of commercial hydrophobic polytetrafluoroethylene (PTFE) membranes by a water-immiscible IL, trihexyl(tetradecyl)phosphonium (THTDP), was characterized by an online and non-destructive technique – ultrasonic time-domain reflectometry (UTDR). In the UTDR analysis, information such as resistance of membrane to IL penetration, duration and rate of wetting process can be deduced from the changes in arrival time and amplitude of reflected peak from the IL/pore-air interface, i.e., pores in pristine hydrophobic membrane are completely-filled with air until IL penetration that displaces the pore-air. The UTDR analysis was further supported by offline and destructive methods typically used to characterize membrane such as Fourier-transform infrared spectroscopy (FTIR), contact angle (CA), liquid entry pressure (LEP) and field emission scanning electron microscopy (FESEM). Through the abovementioned analyses, it was concluded that the commercial hydrophobic PTFE membranes exhibited poor anti-wetting properties against concentrated THTDP IL due to chemical affinity between IL and membrane.

Novel deep eutectic solvent made from sulfonic acid with acetamide, an ATR-IR characterization of different mole compositions and physicochemical properties of 1:6 mol ratios with electrodeposition of copper

Interest in DES is leveling up with increasing need for providing additional knowledge on their behavior and comparability with other type of solvents. In- addition cheap and environmental safe DES are emerging as attractive solvents in many applications. A novel deep eutectic solvent was made by simple mixing different mole ratios of sulfonic acid with acetamide. The effect of mole ratio on the interaction between the DES components was observed by ATR-IR with gradual color changes of formed DES. At 1 to 2 mol ratio respectively a different vibrational interactions is recorded. The least viscose DES of sulfonic acid with acetamide (1:6) shows temperature dependents of conductivity, viscosity and density with similar behaviors of other DESs. The cyclovolatammograms of 1:6 mol ratio of DES or its copper sulfate solution were measured and indicate a one-step reduction and oxidation of copper (Cu+2 to Cu0). Less than 75 nm copper was electrodeposited from its solution in DES with round particles on zinc substrate. DES and its solution with Copper sulfate was investigated by UV-visible spectroscopy suggested an Oh coordination of Cu2+ to DES.

Pyrolysis of ionic liquid pretreated lignite: Effect of 1-butyl-3-methylimidazolium methyl sulfate pretreatment on kinetic and thermodynamic parameters of lignite

ABSTRACT In this work, the effect of ionic liquid (IL) pretreatment on the pyrolytic behavior of lignite was analyzed by examining reactivity, kinetic, and thermodynamic parameters. Pretreatment of lignite with 1-butyl-3-methylimidazolium methyl sulfate ([Bmim][MeSO4]) was carried out at 150°C and 30 min followed by thermal analysis under an inert environment, at a constant ramp rate of 20°C/min. Ten Coats–Redfern (CR) models were applied to the TGA data to evaluate kinetic and thermodynamic parameters. IL-treated lignite increased volatile matter from 46.39% to 57.81% and reduced ash from 21.71% to 8.50%. DTG profiles indicated that [Bmim][MeSO4] accelerated the thermal degradation of lignite by breaking the hydrogen bonding structure of coal, which was statistically confirmed by a higher average rate of thermal degradation, mean relative reactivity (Rm), pyrolysis factor (PF), and lower activation energy (Eα) than untreated lignite. This study shows that [Bmim][MeSO4] could be an attractive eco-friendly pretreatment solvent for the thermochemical conversion of lignite.

Aqueous ionic liquids redistribute local enzyme stability via long-range perturbation pathways

Ionic liquids (IL) and aqueous ionic liquids (aIL) are attractive (co–)solvents for biocatalysis due to their unique properties. On the other hand, the incubation of enzymes in IL or aIL often reduces enzyme activity. Recent studies proposed various aIL-induced effects to explain the reduction, classified as direct effects, e.g., local dehydration or competitive inhibition, and indirect effects, e.g., structural perturbations or disturbed catalytic site integrity. However, the molecular origin of indirect effects has largely remained elusive. Here we show by multi-μs long molecular dynamics simulations, free energy computations, and rigidity analyses that aIL favorably interact with specific residues of Bacillus subtilis Lipase A (BsLipA) and modify the local structural stability of this model enzyme by inducing long-range perturbations of noncovalent interactions. The perturbations percolate over neighboring residues and eventually affect the catalytic site and the buried protein core. Validation against a complete experimental site saturation mutagenesis library of BsLipA (3620 variants) reveals that the residues of the perturbation pathways are distinguished sequence positions where substitutions highly likely yield significantly improved residual activity. Our results demonstrate that identifying these perturbation pathways and specific IL ion-residue interactions there effectively predicts focused variant libraries with improved aIL tolerance.

Deep eutectic solvents in separations: Methods of preparation, polarity, and applications in extractions and capillary electrochromatography

Deep eutectic solvents (DESs) have emerged as alternatives to conventional organic solvents and ionic liquids (ILs). Their tunable and designer physio-chemical properties, low cost, and ease of preparation make them attractive solvent systems for use in extractions and additives to chromatographic separations. However, due to the diverse range of hydrogen bond acceptors and donors that comprise DESs, choosing the appropriate solvent for separations can be challenging. This review discusses all methods of DES preparation and details their advantages and disadvantages. Since polarity is an important aspect in their use in separations, the classification of DESs based on the betaine dye and nile red scales as well as Kamlet-Taft parameters is also discussed. Finally, a summary of applications of DESs in various extraction processes (phenolics, fuels, metals, proteins, carbohydrates), solid-phase extraction, solid-phase microextraction, as well as capillary electrochromatography is provided.

Synergistic effect of dual Brønsted acidic deep eutectic solvents for oxidative desulfurization of diesel fuel

Deep eutectic solvents (DESs) are generally used as attractive solvents or extractants rather than catalysts in the field of synthesis and separation. Herein, dual Brønsted acidic DESs were prepared by mixing sulfonated quaternary ammonium and oxalic acid as extractants and catalysts for deep oxidative desulfurization. Compared to the DESs with single acidic group, the dual acidic DESs exhibited much higher catalytic activity likely due to the synergistic effect. The 1H NMR study indicated that the weak interaction between DES and sulfur compounds led to a low extraction capacity. However, the sulfur removal could reach 97.7% under optimized reaction conditions. Density functional theory (DFT) calculations demonstrated that sulfonic group and carboxylic group are of equal importance to desulfurization performance. Further, the desulfurization efficiency was also strongly affected by the viscosity of DESs. Here, we put forward a new strategy that the reaction time could be sharply shortened to 40 min and 100 min by adding low viscous acetonitrile and polyethylene glycol into DES to form mixing reaction system, respectively.

Development of a novel cellulose solvent based on pyrrolidinium hydroxide and reliable solubility analysis.

Cellulose processing remains a challenge as it is insoluble in water and common organic solvents. Ionic liquids (ILs) are organic salts with a melting point below 100 °C and are known for their excellent solvent properties. Unlike common organic solvents, which can form toxic or flammable vapours due to their high volatility, ILs can be considered as more environmentally friendly due to their negligible vapour pressure and flame retardant properties. We found that N-butyl-N-methylpyrrolidinium hydroxide enables rapid dissolution of up to 20 wt% Avicel® cellulose at 25 °C in aqueous solution (50 wt% water), making it the first pyrrolidinium-based salt capable of dissolving cellulose. Furthermore, solubility studies are currently carried out mainly with the naked eye, microscopy or spectroscopy. The former is a subjective method because it depends on the observer, and particles at the micro-level cannot be seen with the human eye. Microscopic and spectroscopic analyses are suitable for the verification of solubility; however, the acquisition costs of the instruments are high, and sample preparation is time-consuming. We propose that turbidity is a suitable measure for solubility, and investigated a simple and fast method to evaluate cellulose solubility in aqueous N-butyl-N-methylpyrrolidinium hydroxide by employing a turbidimeter which was compared with microscopy and ocular (eye) observation. In this study, we have not only found a promising new solvent for cellulose processing, but also offer a reliable solubility analysis.