Molecular Guide for Selecting Green Deep Eutectic Solvents with High Monosaccharide Solubility for Food Applications.

Monosaccharides play a vital role in the human diet due to their interesting biological activity and functional properties. Conventionally, sugars are extracted using volatile organic solvents (VOCs). Deep eutectic solvents (DESs) have recently emerged as a new green alternative to VOCs. Nonetheless, the selection criterion of an appropriate DES for a specific application is a very difficult task due to the designer nature of these solvents and the theoretically infinite number of combinations of their constituents and compositions. This paper presents a framework for screening a large number of DES constituents for monosaccharide extraction application using COSMO-RS. The framework employs the activity coefficients at infinite dilution (γi∞) as a measure of glucose and fructose solubility. Moreover, the toxicity analysis of the constituents is considered to ensure that selected constituents are safe to work with. Finally, the obtained viscosity predictions were used to select DESs that are not transport-limited. To provide more insights into which functional groups are responsible for more effective monosaccharide extraction, a structure-solubility analysis was carried out. Based on an analysis of 212 DES constituents, the top-performing hydrogen bond acceptors were found to be carnitine, betaine, and choline chloride, while the top-performing hydrogen bond donors were oxalic acid, ethanolamine, and citric acid. A research initiative was presented in this paper to develop robust computational frameworks for selecting optimal DESs for a given application to develop an effective DES design strategy that can aid in the development of novel processes using DESs.

Natural deep eutectic solvents for Ultrasonic-Assisted extraction of nutritious date Sugar: Molecular Screening, Experimental, and prediction.

The aim of this study is to develop an environmentally friendly and effective method for the extraction of nutritious date sugar using natural deep eutectic solvents (NADES) and ultrasound-assisted extraction (USAE). The careful design of a suitable NADES-USAE system was systematically supported by COSMO-RS screening, response surface method (RSM) and artificial neural network (ANN). Initially, 26 natural hydrogen bond donors (HBDs) were carefully screened for sugar affinity using COSMO-RS. The best performing HBDs were then used for the synthesis of 5 NADES using choline chloride (ChCl) as HBA. Among the synthesized NADES, the mixture of ChCl, citric acid (CA) and water (1:1:1 with 20 wt% water) resulted in the highest sugar yield of 78.30 ± 3.91 g/100 g, which is superior to conventional solvents such as water (29.92 ± 1.50 g/100 g). Further enhancements using RSM and ANN led to an even higher sugar recovery of 87.81 ± 2.61 g/100 g, at conditions of 30 °C, 45 min, and a solvent to DFP ratio of 40 mL/g. The method NADES-USAE was then compared with conventional hot water extraction (CHWE) (61.36 ± 3.06) and showed 43.1% higher sugar yield. The developed process not only improves the recovery of the nutritious date sugar but also preserves the heat-sensitive bioactive compounds in dates, making it an attractive alternative to CHWE for industrial utilization. Overall, this study shows a promising approach for the extraction of nutritive sugars from dates using environmentally friendly solvents and advanced technology. It also highlights the potential of this approach for valorizing underutilized fruits and preserving their bioactive compounds.

Critical Properties of Ternary Deep Eutectic Solvents Using Group Contribution with Extended Lee-Kesler Mixing Rules.

One of the most commonly used molecular inputs for ionic liquids and deep eutectic solvents (DESs) in the literature are the critical properties and acentric factors, which can be easily determined using the modified Lydersen-Joback-Reid (LJR) method with Lee-Kesler mixing rules. However, the method used in the literature is generally applicable only to binary mixtures of DESs. Nevertheless, ternary DESs are considered to be more interesting and may provide further tailorability for developing task-specific DESs for particular applications. Therefore, in this work, a new framework for estimating the critical properties and the acentric factor of ternary DESs based on their molecular structures is presented by adjusting the framework reported in the literature with an extended version of the Lee-Kesler mixing rules. The presented framework was applied to a data set consisting of 87 ternary DESs with 334 distinct compositions. For validation, the estimated critical properties and acentric factors were used to predict the densities of the ternary DESs. The results showed excellent agreement between the experimental and calculated data, with an average absolute relative deviation (AARD) of 5.203% for ternary DESs and 5.712% for 260 binary DESs (573 compositions). The developed methodology was incorporated into a user-friendly Excel worksheet for computing the critical properties and acentric factors of any ternary or binary DES, which is provided in the Supporting Information. This work promotes the creation of robust, accessible, and user-friendly models capable of predicting the properties of new ternary DESs based on critical properties, thus saving time and resources.

Solvent Regeneration Methods for Combined Dearomatization, Desulfurization, and Denitrogenation of Fuels Using Deep Eutectic Solvents.

Deep eutectic solvents (DESs) can be used as potential solvents for various applications. However, their recovery depends on both economic and environmental considerations. In this study, the possibilities for the recovery of methyl triphenyl phosphonium bromide/triethylene glycol (MTPPB/TEG 1:4) after the application of combined dearomatization, desulfurization, and denitrogenation of fuels are investigated. The DES was first prepared and characterized for its density, viscosity, and water content. Then, the single-stage liquid-liquid extraction was conducted in addition to testing the repetitive use of the DES. After that, two regeneration methods were studied: the stripping method (with n-heptane) and the washing method (with distilled water or diethyl ether). In addition, a parametric study was conducted to optimize the regeneration methods. The results showed that washing the used DES with distilled water was significantly more effective than stripping the DES with n-heptane. In terms of quinoline reduction, distilled water reduced the quinoline content in the DES from 3.2 to 2.1 wt %, while n-heptane showed a minor reduction in the quinoline content (3.2 to 3 wt %). It was also found that a much more effective recovery could be achieved by (i) increasing the DES-to-regeneration solvent mass ratio and (ii) increasing the number of wash cycles. Furthermore, the regeneration temperature did not have a significant effect on the recyclability of the DES. The results demonstrated that the regenerated DES was as effective in extraction as a fresh batch of DES.

Predicting the Surface Tension of Deep Eutectic Solvents Using Artificial Neural Networks.

Studies on deep eutectic solvents (DESs), a new class of "green" solvents, are attracting increasing attention from researchers, as evidenced by the rapidly growing number of publications in the literature. One of the main advantages of DESs is that they are tailor-made solvents, and therefore, the number of potential DESs is extremely large. It is essential to have computational methods capable of predicting the physicochemical properties of DESs, which are needed in many industrial applications and research. Surface tension is one of the most important properties required in many applications. In this work, we report a relatively generalized artificial neural network (ANN) for predicting the surface tension of DESs. The database used can be considered comprehensive because it contains 1571 data points from 133 different DES mixtures in 520 compositions prepared from 18 ions and 63 hydrogen bond donors in a temperature range of 277-425 K. The ANN model uses molecular parameter inputs derived from the conductor-like screening model for real solvents (S σ-profiles). The training and testing results show that the best performing ANN architecture consisted of two hidden layers with 15 neurons each (9-15-15-1). The proposed ANN was excellent in predicting the surface tension of DESs, as R 2 values of 0.986 and 0.977 were obtained for training and testing, respectively, with an overall average absolute relative deviation of 2.20%. The proposed models represent an initiative to promote the development of robust models capable of predicting the properties of DESs based only on molecular parameters, leading to savings in investigation time and resources.

Deep Eutectic Solvent Assisted Dispersion of Carbon Nanotubes in Water.

Deep Eutectic Solvents (DESs) are emerging as a promising medium for many chemical processes. They can be used to observe specific properties required for nanomaterials' applications. Controlled CO2 adsorption requires disaggregation of carbon nanotubes into smaller bundles which can be accomplished by dispersing them in aqueous DES system. In this study, response surface methodology (RSM) was adopted to examine the impacts of three important factors on the dispersion of single walled carbon nanotubes (SWNTs) in Choline Chloride-Glycerol (ChCl-Gly) DES; (i) ChCl-Gly (mass% in water), (ii) sonication energy input (J/mL), and (iii) SWNTs' concentration (mg/L). The net negative surface charge of ChCl-Gly, a "green solvent," provided superior dispersion of inherently negatively charged SWNTs in water via electrostatic repulsion. The impacts of the dispersion factors were quantified by the average aggregate diameter (nm) and polydispersity (polydispersity index, PDI) of SWNTs in aqueous-DES systems. Models were developed, experimentally verified, and statistically validated to map the impacts of these factors and to obtain optimized dispersions. The optimized dispersions, characterized by the small (<100 nm) and uniform (<0.1 PDI) SWNTs' aggregates, were achieved at lower sonication energy costs which can have promising implications across many nano-manufacturing fields. The dispersion/aggregation mechanism was proposed using COSMO-RS (based on equilibrium thermodynamics and quantum chemistry) modeling of ChCl-Gly and zeta potential measurements of SWNTs. This understanding will help create optimally sustainable and economically feasible DES-nanomaterial dispersions.

Polyethylene glycol-based deep eutectic solvents as a novel agent for natural gas sweetening.

Deep eutectic solvents (DESs) have received significant attention as potential extracting agents in recent years due to their favorable characteristics including low cost, easy preparation and environmentally safe starting materials. Experimentally screening for highly efficient DESs meeting various requirements for natural gas sweetening remains a challenging task. Thus, an extensive database of estimated Henry's law constants (Hi) and solubilities (xi) of CO2 in 170 different DESs at 25°C has been constructed using the COSMO-RS method to select potential DESs. Based on the COSMO-RS study, three DESs, namely tetrabutylammonium bromide (TBAB)+polyethylene glycol (PEG-8) (on a molar basis 1:4), TBAB+octanoic acid (OCT) (1:4), and methyltriphenylphosphonium bromide (MTPB)+PEG-8 (1:10), were chosen for further experimentation up to 2 bar at 25°C using a vapor-liquid equilibria (VLE) apparatus. Reliable thermophysical properties were determined experimentally, and a detailed equilibrium-based model was developed for one of the glycol-based DESs (i.e., TBAB+PEG-8 (1:4)). This information is an essential prerequisite for carrying out process simulations of natural gas sweetening plants using ASPEN PLUS. The simulation results for the proposed DES were compared to those of monoethylene glycol (MEG). Here, we find that the aqueous TBAB+PEG-8 (1:4) solvent shows ~60% lower total energy consumption and higher CO2 removal when compared to those using the MEG solvent.

Computational investigation of the microstructural characteristics and physical properties of glycerol-based deep eutectic solvents.

Recently, there has been significant interest in the possibility of using deep eutectic solvents (DESs) as novel green media and alternatives to conventional solvents and ionic liquids (ILs) in many applications. Due to their attractive properties, such as their biodegradability, low cost, easy preparation, and nontoxicity, DESs appear to be very promising solvents for use in the field of green chemistry. This computational study investigated six glycerol-based DESs: DES1 (glycerol:methyl triphenyl phosphonium bromide), DES2 (glycerol:benzyl triphenyl phosphonium chloride), DES3 (glycerol:allyl triphenyl phosphonium bromide), DES4 (glycerol:choline chloride), DES5 (glycerol:N,N-diethylethanolammonium chloride), and DES6 (glycerol:tetra-n-butylammonium bromide). The chemical structures and combination mechanisms as well as the sigma profiles and sigma potentials of the studied DESs were explored in detail. Moreover, density, viscosity, vapor pressure, and IR analytical data were predicted and compared with the corresponding experimental values reported in the literature for these DESs. To achieve these goals, the conductor-like screening model for realistic solvents (COSMO-RS) and the Amsterdam Density Functional (ADF) software package were used. The predicted results were found to be in good agreement with the corresponding experimental values reported in the literature. Further theoretical investigations are needed to confirm the experimental results-regarding both properties and applications-reported for these DESs.

Superoxide Ion: Generation and Chemical Implications.

Superoxide ion (O2(•-)) is of great significance as a radical species implicated in diverse chemical and biological systems. However, the chemistry knowledge of O2(•-) is rather scarce. In addition, numerous studies on O2(•-) were conducted within the latter half of the 20th century. Therefore, the current advancement in technology and instrumentation will certainly provide better insights into mechanisms and products of O2(•-) reactions and thus will result in new findings. This review emphasizes the state-of-the-art research on O2(•-) so as to enable researchers to venture into future research. It comprises the main characteristics of O2(•-) followed by generation methods. The reaction types of O2(•-) are reviewed, and its potential applications including the destruction of hazardous chemicals, synthesis of organic compounds, and many other applications are highlighted. The O2(•-) environmental chemistry is also discussed. The detection methods of O2(•-) are categorized and elaborated. Special attention is given to the feasibility of using ionic liquids as media for O2(•-), addressing the latest progress of generation and applications. The effect of electrodes on the O2(•-) electrochemical generation is reviewed. Finally, some remarks and future perspectives are concluded.

RETRACTED: Neoteric FT-IR investigation on the functional groups of phosphonium-based deep eutectic solvents.

Deep eutectic solvents (DESs) are novel solvent media that are currently under investigation as an alternative to ionic liquids and conventional solvents. The physical properties of DESs as well as their mild environmental footprint and potentially critical industrial application necessitate understanding the interaction of functional groups on both the salt and hydrogen bond donor (HBD). In this study, four DESs were prepared by mixing triethylenglycol, diethylenglycol, ethylenglycol, and glycerol as HBDs with methyltriphenylphosphonium bromide as a salt at a molar ratio of 1:4. Fourier transform infrared spectroscopy was conducted to highlight the chemical structure and mechanism of the combination of the four DESs. New spectra illustrating the combination of the functional groups of the HBDs and salt were observed and interpreted. This study is the first to investigate the properties of neoteric phosphonium-based DESs.

Assessment of cytotoxicity and toxicity for phosphonium-based deep eutectic solvents.

In this work, the cytotoxicity and toxicity of phosphonium-based deep eutectic solvents (DESs) with three hydrogen bond donors, namely glycerine, ethylene glycol, and triethylene glycol were investigated. The cytotoxicity effect was tested using brine shrimp (Artemia salina). The toxicity was investigated using the two Gram positive bacteria Bacillus subtilis and Staphylococcus aureus, and two Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The cytotoxicity of tested DESs was much higher than that of their individual components, indicating their toxicological behavior was different. It was also found that there was toxic effect on the studied bacteria, indicating their potential application as anti-bacterial agents. To the best of our knowledge, this is the first time the cytotoxicity and toxicity of phosphonium-based DESs were studied.

Are deep eutectic solvents benign or toxic?

In continuation of investigation for environmentally benign protocol for new solvents termed deep eutectic solvents (DESs), it is herein reported results concerning the toxicity and cytotoxicity of choline chloride (ChCl) based DESs with four hydrogen bond donors including glycerine, ethylene glycol, triethylene glycol and urea. The toxicity was investigated using two Gram positive bacteria Bacillus subtilis and Staphylococcus aureus, and two Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The cytotoxicity effect was tested using the Artemia salina leach. It was found that there was no toxic effect for the tested DESs on all of the studied bacteria confirming their benign effects on these bacteria. Nevertheless, it was found that the cytotoxicity of DESs was much higher than their individual components (e.g. glycerine, ChCl) indicating that their toxicological behavior is different. For our best knowledge this is the first time that toxicity and cytotoxicity of DESs were studied. The toxicity and cytotoxicity of DESs varied depending on the structure of components. Careful usage of the terms non-toxicity and biodegradability must be considered. More investigation on this matter is required.

Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production.

An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751).