Water-Induced Restructuring of the Surface of a Deep Eutectic Solvent.
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ABSTRACT:
SUBMITTER: Gera R
PROVIDER: S-EPMC8785180 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Deep eutectic solvents (DESs) formed by hydrogen bond donors and acceptors are a promising new class of solvents. Both hydrophilic and hydrophobic binary DESs readily absorb water, making them ternary mixtures, and a small water content is always inevitable under ambient conditions. We present a thorough study of a typical hydrophobic DES formed by a 1:2 mole ratio of tetrabutyl ammonium chloride and decanoic acid, focusing on the effects of a low water content caused by absorbed water vapor, using multinuclear NMR techniques, molecular modeling, and several other physicochemical techniques. Already very low water contents cause dynamic nanoscale phase segregation, reduce solvent viscosity and fragility, increase self-diffusion coefficients and conductivity, and enhance local dynamics. Water interferes with the hydrogen-bonding network between the chloride ions and carboxylic acid groups by solvating them, which enhances carboxylic acid self-correlation and ion pair formation between tetrabutyl ammonium and chloride. Simulations show that the component molar ratio can be varied, with an effect on the internal structure. The water-induced changes in the physical properties are beneficial for most prospective applications but water creates an acidic aqueous nanophase with a high halide ion concentration, which may have chemically adverse effects.
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Project description:The route for the preparation of cellulose nanofiber dispersions from bacterial cellulose using ethylene glycol- or glycerol-based deep eutectic solvents (DES) is demonstrated. Choline chloride was used as a hydrogen bond acceptor and the effect of the combined influence of DES treatment and ultrasound on the thermal and mechanical properties of bacterial cellulose nanofibers (BC-NFs) is demonstrated. It was found that the maximal Young's modulus (9.2 GPa) is achieved for samples prepared using a combination of ethylene glycol-based DES and ultrasound treatment. Samples prepared with glycerol-based DES combined with ultrasound exhibit the maximal strength (132 MPa). Results on the mechanical properties are discussed based on the structural investigations that were performed using FTIR, Raman, WAXD, SEM and AFM measurements, as well as the determination of the degree of polymerization and the density of BC-NF packing during drying with the formation of paper. We propose that the disordering of the BC-NF surface structure along with the preservation of high crystallinity bulk are the key factors leading to the improved mechanical and thermal characteristics of prepared BC-NF-based papers.
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Project description:The use of oxidoreductases (EC1) in non-conventional reaction media has been increasingly explored. In particular, deep eutectic solvents (DESs) have emerged as a novel class of solvents. Herein, an in-depth study of bioreduction with an alcohol dehydrogenase (ADH) in the DES glyceline is presented. The activity and stability of ADH in mixtures of glyceline/water with varying water contents were measured. Furthermore, the thermodynamic water activity and viscosity of mixtures of glyceline/water have been determined. For a better understanding of the observations, molecular dynamics simulations were performed to quantify the molecular flexibility, hydration layer, and intraprotein hydrogen bonds of ADH. The behavior of the enzyme in DESs follows the classic dependence of water activity (aW ) in non-conventional media. At low aW values (<0.2), ADH does not show any activity; at higher aW values, the activity was still lower than that in pure water due to the high viscosities of the DES. These findings could be further explained by increased enzyme flexibility with increasing water content.
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Project description:Oxide perovskites have attracted great interest as materials for energy conversion due to their stability and structural tunability. La-based perovskites of 3d-transition metals have demonstrated excellent activities as electrocatalysts in water oxidation. Herein, we report the synthesis route to La-based perovskites using an environmentally friendly deep eutectic solvent (DES) consisting of choline chloride and malonic acid. The DES route affords phase-pure crystalline materials on a gram scale and results in perovskites with high electrocatalytic activity for oxygen evolution reaction. A convenient, fast, and scalable synthesis proceeds via assisted metathesis at a lower temperature as compared to traditional solid-state methods. Among LaCoO3, LaMn0.5Ni0.5O3, and LaMnO3 perovskites prepared via the DES route, LaCoO3 was established to be the best-performing electrocatalyst for water oxidation in alkaline medium at 0.25 mg cm-2 mass loading. LaCoO3 exhibits current densities of 10, 50, and 100 mA cm-2 at respective overpotentials of approximately 390, 430, and 470 mV, respectively, and features a Tafel slope of 55.8 mV dec-1. The high activity of LaCoO3 as compared to the other prepared perovskites is attributed to the high concentration of oxygen vacancies in the LaCoO3 lattice, as observed by high-resolution transmission electron microscopy. An intrinsically high concentration of O vacancies in the LaCoO3 synthesized via the DES route is ascribed to the reducing atmosphere attained upon thermal decomposition of the DES components. These findings will contribute to the preparation of highly active perovskites for various energy applications.
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Project description:Graphene electrodes and deep eutectic solvents (DESs) are two emerging material systems that have individually shown highly promising properties in electrochemical applications. To date, however, it has not been tested whether the combination of graphene and DESs can yield synergistic effects in electrochemistry. We therefore study the electrochemical behavior of a defined graphene monolayer of centimeter-scale, which was produced by chemical vapor deposition and transferred onto insulating SiO2/Si supports, in the common DES choline chloride/ethylene glycol (12CE) under typical electrochemical conditions. We measure the graphene potential window in 12CE and estimate the apparent electron transfer kinetics of an outer-sphere redox couple. We further explore the applicability of the 12CE electrolyte to fabricate nanostructured metal (Zn) and metalloid (Ge) hybrids with graphene by electrodeposition. By comparing our graphene electrodes with common bulk glassy carbon electrodes, a key finding we make is that the two-dimensional nature of the graphene electrodes has a clear impact on DES-based electrochemistry. Thereby, we provide a first framework toward rational optimization of graphene-DES systems for electrochemical applications.
| S-EPMC7496728 | biostudies-literature
Project description:The increased use of deep eutectic solvents (DESs) in recent years has been significant and provides new approaches to sample collection and preparation. At the same time, the use of these new solvents to prepare samples can present challenges for subsequent analyses. Common analytical approaches, such as fluorescent labeling, may not be compatible with the solvents. In this work, we explore how effective three traditional fluorescent labels can be at derivatizing amino acids in the most common DESs, formed from choline chloride and ethylene glycol. We demonstrate that the unique solvent characteristics of the DESs still allow for two of the fluorophores, fluorescein isothiocyanate and 5-carboxyfluorescein succinimidyl ester, to effectively label amino acids. Initial optimizations of the reaction conditions demonstrate that we can effectively label both d- and l-amino acids, in solution with concentrations of amino acids down to 4 μM. Capillary electrophoretic separations following this preparation can detect as little as 50 nM. This is possible without removal of any DES from the sample matrix. These results represent the first complete fluorescent labeling reaction in a DES and subsequent capillary electrophoretic separation of the analytes.
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Project description:Feathers, an industrial by-product, are a valuable source of keratin that could be used, for example, in the preparation of films for biomedical and packaging applications. However, the utilisation of feather keratin requires scalable processes to convert feathers into a feasible keratin stream. This paper shows how deep eutectic solvent (DES) fractionated feathers could be converted into strong films. In the DES fractionation process, two keratin fractions with different molecular weights were obtained. The films made of the high molecular weight keratin fraction had better mechanical properties and stability against moisture than the films made of the low molecular weight keratin fraction. The strength properties were further improved by cross-linking the keratin with diglycidyl ether enabling the formation of a uniform keratin network, whereas glutaraldehyde did not show a clear cross-linking effect. These keratin films could be used, for example, in food packaging or medical applications such as wound care.
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Project description:The formation of deep eutectic solvents (DES) is tied to negative deviations to ideality caused by the establishment of stronger interactions in the mixture than in the pure DES precursors. This work tested thymol and menthol as hydrogen bond donors when combined with different flavonoids. Negative deviations from ideality were observed upon mixing thymol with either flavone or flavanone, two parent flavonoids that only have hydrogen bond acceptor (HBA) groups, thus forming non-ionic DES (Type V). On the other hand, the menthol systems with the same compounds generally showed positive deviations from ideality. That was also the case with the mixtures containing the more complex hydroxylated flavonoid, hesperetin, which resulted in positive deviations when mixed with either thymol or menthol. COSMO-RS successfully predicted the behavior of the solid-liquid phase diagram of the studied systems, allowing for evaluation of the impact of the different contributions to the intermolecular interactions, and proving to be a good tool for the design of DES.
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Project description:The exploitation and use of alternative synthetic methods, in the face of classical procedures that do not conform to the ethics of green chemistry, represent an ever-present problem in the pharmaceutical industry. The procedures for the synthesis of benzimidazoles have become a focus in synthetic organic chemistry, as they are building blocks of strong interest for the development of compounds with pharmacological activity. Various benzimidazole derivatives exhibit important activities such as antimicrobial, antiviral, anti-inflammatory, and analgesic activities, and some of the already synthesized compounds have found very strong applications in medicine praxis. Here we report a selective and sustainable method for the synthesis of 1,2-disubstituted or 2-substituted benzimidazoles, starting from o-phenylenediamine in the presence of different aldehydes. The use of deep eutectic solvent (DES), both as reaction medium and reagent without any external solvent, provides advantages in terms of yields as well as in the work up procedure of the reaction.
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Project description:Traditional coupling of ligands for gold wet etching makes large-scale applications problematic. Deep eutectic solvents (DESs) are a new class of environment-friendly solvents, which could possibly overcome the shortcomings. In this work, the effect of water content on the Au anodic process in DES ethaline was investigated by combining linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Meanwhile, we employed atomic force microscopy (AFM) to image the evolution of the surface morphology of the Au electrode during its dissolution and passivation process. The obtained AFM data help to explain the observations about the effect of water content on the Au anodic process from the microscopic perspective. High water contents make the occurrence of anodic dissolution of gold at higher potential, but enhances the rate of the electron transfer and gold dissolution. AFM results reveal the occurrence of massive exfoliation, which confirms that the gold dissolution reaction is more violent in ethaline with higher water contents. In addition, AFM results illustrate that the passive film and its average roughness could be tailored by changing the water content of ethaline.
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