Non-ionic Deep Eutectic Solvents Research Articles

Deep eutectic solvents as green and sustainable diluents in headspace gas chromatography for the determination of trace level genotoxic impurities in pharmaceuticals

Genotoxic impurities (GTIs) are potential carcinogens that need to be controlled down to ppm or lower concentration levels in pharmaceuticals under strict regulations. The static headspace gas chromatography (HS-GC) coupled with electron capture detection (ECD) is an effective approach to monitor halogenated and nitroaromatic genotoxins. Deep eutectic solvents (DESs) possess tunable physico-chemical properties and low vapor pressure for HS-GC methods. In this study, zwitterionic and non-ionic DESs have been used for the first time to develop and validate a sensitive analytical method for the analysis of 24 genotoxins at sub-ppm concentrations. Compared to non-ionic diluents, zwitterionic DESs produced exceptional analytical performance and the betaine : 7 (1,4- butane diol) DES outperformed the betaine : 5 (1,4-butane diol) DES. Limits of detection (LOD) down to the 5-ppb concentration level were achieved in DESs. Wide linear ranges spanning over 5 orders of magnitude (0.005–100 µg g−1) were obtained for most analytes with exceptional sensitivities and high precision. The method accuracy and precision were validated using 3 commercially available drug substances and excellent recoveries were obtained. This study broadens the applicability of HS-GC in the determination of less volatile GTIs by establishing DESs as viable diluent substitutes for organic solvents in routine pharmaceutical analysis.

Deodorization of model biogas by means of novel non-ionic deep eutectic solvent

The paper presents new non-ionic deep eutectic solvent (DES) composed of natural and non-toxic components i.e. guaiacol, camphor and levulinic acid in 1:1:3 molar ratio as a promising absorbent for removal of selected volatile organic compounds (VOCs) including dichloromethane, toluene, hexamethyldisiloxane and propionaldehyde from model biogas. The affi nity of DES for VOCs was determined as vapour-liquid coeffi cients and the results were compared with several well-known DESs based on quaternary ammonium salt as well as n-hexadecane and water. For new DES, the absorption process was carried out under dynamic conditions. The results indicate that non-ionic DES has high affi nity and capacity for VOCs being comparable to n-hexadecane. In addition, absorbed VOCs could be easily desorbed from DES using activated carbon and absorbent could be re-use minimum five times without signifi cant loss of absorption capacity

Efficient absorption of low pressure NH3 by non-ionic phenol-based deep eutectic solvents with multiple acidic sites

In chemical industry, efficient absorption of ammonia (NH3) from industrial exhaust remains a challenge and significant issue for resource utilization and pollution control. Present study proposed a new strategy to design non-ionic deep eutectic solvents (DESs) using phenolic analogues. Several phenol-based DESs with multiple acidic sites were constructed by paring catechol (Cat) or resorcinol (Res) with phenol (PhOH) and investigated as feasible NH3 absorbents from physical property, NH3 absorption performance, and mechanism analysis. Among the as-obtained DESs, Res/PhOH (1:3) demonstrated attractive NH3 absorption capacity at 303.15 K (11.862 mol/kg at 101.3 kPa, and 6.391 mol/kg at 5.0 kPa), surpassing most DESs and ionic liquids (ILs) reported in the literatures. Meanwhile, it displayed good reversibility, satisfactory thermal stability, and high NH3/CO2 selectivity. The mechanism of NH3 absorption was further elucidated using FTIR and NMR spectra, and Quantum chemistry calculation, and inferred as the strong and multiple interaction between NH3 and weakly acidic sites of DESs.

Phenolic-based non-ionic deep eutectic solvent for rapid determination of water soluble neonicotinoid insecticides in tea infusion.

Challenges were raised to established analytical method for monitoring water soluble neonicotinoid insecticide (NEOs) residues in tea infusion. Phenolic-based non-ionic deep eutectic solvent (NIDES) composed by a mixture of DL-menthol and thymol (molar ratio of 1:3) was applied to achieve the determination of selected NEOs. Factors influenced extraction efficiency have been evaluated and molecular dynamics approach was conducted aming to provide a new insight to explain its extraction mechanism. It is found that Boltzmann averaged solvation energy of NEOs was negatively correlated with extraction efficiency. The method validation results indicated good linearities (R2≥0.99), sensitive LOQs (0.05μg L-1), high precisions (RSD<11%) and satisfactory recoveries (57.7%∼98%) at 0.05μg L-1∼100μg L-1. The intake risk of NEOs in tea infusion samples were acceptable which residues in range of 0.1μg L-1∼3.5μg L-1 for thiamethoxam imidacloprid and thiacloprid. This method showed advantages of rapid, green, and easy operation.

Highly Efficient Recovery and Recycling of Cobalt from Spent Lithium-Ion Batteries Using an N-Methylurea-Acetamide Nonionic Deep Eutectic Solvent.

The growing demand for lithium-ion batteries (LiBs) for the electronic and automobile industries combined with the limited availability of key metal components, in particular cobalt, drives the need for efficient methods for the recovery and recycling of these materials from battery waste. Herein, we introduce a novel and efficient approach for the extraction of cobalt, and other metal components, from spent LiBs using a nonionic deep eutectic solvent (ni-DES) comprised of N-methylurea and acetamide under relatively mild conditions. Cobalt could be recovered from lithium cobalt oxide-based LiBs with an extraction efficiency of >97% and used to fabricate new batteries. The N-methylurea was found to act as both a solvent component and a reagent, the mechanism of which was elucidated.

Liquefying Flavonoids with Terpenoids through Deep Eutectic Solvent Formation.

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.

Carbon Dioxide Solubility in Nonionic Deep Eutectic Solvents Containing Phenolic Alcohols.

Deep eutectic solvents (DES) are a new class of green solvents that have shown unique properties in several process applications. This study evaluates nonionic DES containing phenolic alcohols as solvents for carbon dioxide (CO2) capture applications. Potential phenolic alcohols and the molar ratio between DES constituents were preselected for experimental investigations based on the conductor-like screening model for realistic solvation (COSMO-RS). CO2 solubility was experimentally determined in two different DES, namely, L-menthol/thymol in 1:2 molar ratio and thymol/2,6-xylenol in 1:1 molar ratio, at various temperatures and pressures. CO2 solubility in the studied systems was higher than that reported in the literature for ionic DES and ionic liquids. This study demonstrates that nonionic DES containing phenolic alcohols can be excellent, inexpensive, and simple solvents for CO2 capture.

Non-ionic deep eutectic solvents for membrane formation

Deep eutectic solvents (DES) have recently emerged as a new class of inexpensive biodegradable solvents and additives with diverse applications. In this study, a new family of non-ionic deep eutectic solvents (NIDES) is proposed for the first time for membrane preparation. Three types of NIDES, N-methylacetamide-acetamide (DES-1), N-methyl acetamide-N-methyl urea (DES-2), and N-methyl acetamide-N,N′-dimethyl urea (DES-3) were synthesized and used to dissolve polyvinylidene fluoride (PVDF) polymer. The effects of the additive polyvinylpyrrolidone (PVP) and the type of NIDES on the PVDF membrane characteristics, water permeability and bovine serum albumin (BSA) separation were studied. The membranes prepared with DES-1 and 2 wt% PVP exhibited a good water permeate flux (96.82 L/m2.h) and a high BSA separation factor (96.32%). High performance PVDF membranes can thus be efficiently prepared using biodegradable inexpensive NIDES.

Molecular dynamics investigation of non-ionic deep eutectic solvents

All-atom molecular dynamics simulations have been employed to study deep eutectic solvents (DESs) consisting of thymol or naphthol as hydrogen bond donor (HBD) and menthol as hydrogen bond acceptor (HBA). Radial and spatial distribution functions demonstrate the presence of specific interactions between the components in both systems. The highest percentage of strong H-bond was found in the pair having the phenolic systems as HBD and menthol as HBA. The number of hydrogen bonds formed between various components decreases with an increase in temperature. Self diffusivity of the non-ionic DESs is higher than that of ionic DESs. Liquid – vapor interfaces of all the systems are enriched with HBAs.

Homologue-paired liquids as special non-ionic deep eutectic solvents for efficient absorption of SO2.

Low-viscous homologue-paired liquids (HPLs) are designed and employed as special non-ionic deep eutectic solvents for selective separation of SO2 from CO2 and N2. The HPLs are found to have excellent inherent properties (e.g., low cost, volatility and viscosity), high absorption capacity, fast absorption rate, and moderate Lewis acid-base interaction with SO2. Regeneration experiments are done to show their excellent recyclability, and industrial desulfurization is exemplified in a small column with suitable parameters to show their potential as SO2 absorbents.

Superhydrophobic sponges based on green deep eutectic solvents for spill oil removal from water

The paper described a new method for crude oil-water separation by means of superhydrophobic melamine sponges impregnated by deep eutectic solvents (MS-DES). Due to the numerous potential of two-component DES formation, simple and quick screening of 156 non-ionic deep eutectic solvents using COSMO-RS (Conductor-like Screening Model for Real Solvents) computational model was used. DES which were characterized by high solubility of hydrocarbons and the lowest water solubility were synthesized and embedded on melamine sponges. The new sponges were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), and goniometer. Several parameters affecting the crude oil-water separation (i.e. type and amount of DES, density and porosity of sponges, water contact eagle) were thoroughly studied. In order to studies of MS-DES affinity to the selected groups of crude oil i.e. Saturated, Aromatic, Resins, Asphaltenes (SARA) the thin layer liquid chromatography-flame ionization detection (TLC-FID) was used. The obtained results indicate that the melamine sponges impregnated by DES composed of eucalyptol and menthol in 1:5 molar ratio have high real crude oil absorption capacity in the range of 96.1 – 132.2 g/g and slightly depends on crude oil compositions, superhydrophobic properties (water contact angle 152°), low density of 9.23 mg/cm3, high porosity of 99.39%, and excellent reusability which was almost not changing even after 80 cycles. The outcomes indicate that new MS-DES materials could be excellent alternatives as absorbents for the cleanup of crude oil-polluted water.

Rational design, preparation and characterization of a ternary non-ionic room-temperature deep eutectic solvent derived from urea, acetamide, and sorbitol

Deep eutectic solvents (DESs) have emerged as a new kind of solvent and an excellent alternative to ionic liquids, thanks to its simplicity in preparing and availability of a large number of potential constituents to tune the properties. However, most of the reported DESs are ionic, and to the best of our knowledge, only a few non-ionic DESs are available, which are liquid at room temperature.

Electromembrane extraction using deep eutectic solvents as the liquid membrane

In this work, we investigated for the first time hydrophobic deep eutectic solvents (DES) as supported liquid membrane (SLM) for electromembrane extraction (EME). Camphor, coumarin, DL-menthol, and thymol were used as non-ionic DES components. Different DESs compositions were tested, to study systematically the importance of hydrogen bonding and dispersion/aromatic interactions during mass transfer across the SLM. Unexpectedly, mixtures of coumarin and thymol were highly efficient SLMs, and provided exhaustive or near-exhaustive extraction of non-polar bases, non-polar acids, and polar bases. SLMs with such performance for both bases and acids, in a large polarity window, are not found in current literature. The SLMs were highly aromatic, very strong hydrogen bonding donors, and moderately strong hydrogen bonding acceptors. Aromatic (π type) interactions were apparently very important for transfer of bases, while hydrogen bonding were dominant for acids. EME of six polar basic drugs from plasma, with a coumarin and thymol mixture as SLM, and combined with UHPLC-MS/MS analysis, was evaluated to test the potential for analytical applications. Plasma was diluted 1:1 with phosphate buffer pH 2.0. Calibration curves were linear in the therapeutic ranges (0.970 < R2 < 0.999), recoveries ranged between 47 and 93%, and repeatability was within 1.6–10.7% RSD. The clean-up efficiency was excellent and no matrix effects from plasma were seen. Presence of trace levels of coumarin in the acceptor phase was however found to cause some ion enhancement. Based on the current work, we foresee more research on the use of DES in EME.

Partial Viscosity Decoupling of Solute Solvation, Rotation, and Translation Dynamics in Lauric Acid/Menthol Deep Eutectic Solvent: Modulation of Dynamic Heterogeneity with Length Scale.

Deep eutectic solvents (DESs) are new-generation media that can be fine-tuned to have desired properties circumventing economic and environmental issues. Typically, these are ionic, and only recently, nonionic DESs, having interesting properties, are being explored. In this report, we examined the structure and dynamics of a nonionic lauric acid/menthol (LA/Men) DES through steady-state emission, solvation dynamics, time-resolved fluorescence anisotropy, and translational diffusion dynamics. The zero shift in the emission spectra of coumarin 153 (a solvatochromic dye) as a function of the excitation wavelength suggests that LA/Men DES is spatially homogenous. Decoupling (p = 0.63) of the average solvation time, ⟨τs⟩, from medium viscosity suggests the presence of mild dynamic heterogeneity in the system. Rotational time, ⟨τr⟩, which reflects the nature of the first solvation shell, shows little decoupling (p = 0.81), suggesting it to be fairly dynamically homogeneous at a shorter length scale. An Arrhenius-type analysis also proves that rotation is mainly controlled by medium viscosity. Translational diffusion time, ⟨τD⟩, which provides information at a larger length scale, is strongly decoupled from medium viscosity (p = 0.29). This indicates that at a larger length scale, the DES is quite dynamically heterogeneous. The slow component of solvation time, which is believed to originate at a larger length scale, correlates well with the translational diffusion timescale having similar activation energies. This suggests that their origin is same. Expectedly, for the long component of solvation time, the decoupling is quite strong (p = 0.30). Overall, our result demonstrates the structure and dynamics of the nonionic LA/Men DES, and the existence of length scale-dependent heterogeneity has been proposed.

Assessing the Location of Ionic and Molecular Solutes in a Molecularly Heterogeneous and Nonionic Deep Eutectic Solvent.

Deep eutectic solvents (DES) are emerging sustainable designer solvents viewed as greener and better alternatives to ionic liquids. Nonionic DESs possess unique properties such as viscosity and hydrophobicity that make them desirable in microextraction applications such as oil-spill remediation. This work builds upon a nonionic DES, NMA–LA DES, previously designed by our group. The NMA–LA DES presents a rich nanoscopic morphology that could be used to allocate solutes of different polarities. In this work, the possibility of solvating different solutes within the nanoscopically heterogeneous molecular structure of the NMA–LA DES is investigated using ionic and molecular solutes. In particular, the localized vibrational transitions in these solutes are used as reporters of the DES molecular structure via vibrational spectroscopy. The FTIR and 2DIR data suggest that the ionic solute is confined in a polar and continuous domain formed by NMA, clearly sensing the direct effect of the change in NMA concentration. In the case of the molecular nonionic and polar solute, the data indicates that the solute resides in the interface between the polar and nonpolar domains. Finally, the results for the nonpolar and nonionic solute (W(CO)6) are unexpected and less conclusive. Contrary to its polarity, the data suggest that the W(CO)6 resides within the NMA polar domain of the DES, probably by inducing a domain restructuring in the solvent. However, the data are not conclusive enough to discard the possibility that the restructuring comprises not only the polar domain but also the interface. Overall, our results demonstrate that the NMA–LA DES has nanoscopic domains with affinity to particular molecular properties, such as polarity. Thus, the presented results have a direct implication to separation science.

Molecularly Heterogeneous Structure of a Nonionic Deep Eutectic Solvent Composed of N-Methylacetamide and Lauric Acid.

Deep eutectic solvents (DES) are a new class of designer solvents with a wide range of possible applications. DESs are typically made from an ionic compound and a hydrogen bond donor, but lately DESs made of nonionic compounds with interesting properties have started to appear. This study focuses on describing the structure, dynamics, and interactions of a nonionic DES composed of N-methylacetamide (NMA) and lauric acid (LA). Linear IR and time-resolved IR experiments show that LA-NMA DES is the result of hydrogen bond interaction between the two molecular components, though the interaction energy is only favored by ∼1 kJ/mol with respect to the pure components. The IR experiments also reveal the presence of molecular heterogeneities produced by the nanosegregation of polar and nonpolar domains formed by N-methylacetamide and lauric acid, respectively. In addition, it is observed that the hydrogen bond interaction between components occurs at the interface of the two distinct polarity domains. The proposed molecular picture is also supported by the observation of nanodomains with the approximate size of two lauric acids via small-angle X-ray scattering.

Polymer synthesis in non-ionic deep eutectic solvents

Acetamide- and urea-derivative based non-ionic deep eutectic solvents in polymer synthesis.

Phenolic hydrogen bond donors in the formation of non-ionic deep eutectic solvents: the quest for type V DES.

Mixtures of non-ionic compounds have been reported as DES but most are just ideal mixtures. In the thymol-menthol system, an abnormal strong interaction was identified stemming from the acidity difference of the phenolic and aliphatic hydroxyl groups. This type of interaction is found to be the key to prepare non-ionic DES, that may be classified as type V.

Synthesis-Free Phase-Selective Gelator for Oil-Spill Remediation.

A new deep eutectic solvent (DES) was developed as a phase-selective gelator for oil-spill remediation. The newly designed nonionic DES is based on a combination of an amide (N-methylacetamide) and a long chain carboxylic acid (lauric acid) and does not require any synthetic procedure besides mixing. Our studies show that the DES works as gelator by forming a gel between lauric acid and the hydrocarbon, whereas the amide serves to form the DES and dissolves in water during the gelation process. In addition, the DES material has gelation properties comparable to those considered as state-of-the-art. Overall, the newly developed material shows a promising future in oil recovery methodologies.

Dynamics of a PEG based non-ionic deep eutectic solvent: Temperature dependence

Temperature dependent dynamics of a polyethylene glycol based non-ionic deep eutectic solvent (DES) has been investigated via both dielectric relaxation spectroscopic (DRS), and time-resolved fluorescence (TRF) Stokes shift and anisotropy measurements. The composition of the DES considered is as follows: w[fCH3CONH2+(1−f)NH2CONH2]+(1−w)PEG, where w represents the weight fraction and f represents the mole fraction. In this investigation we have kept w fixed at 0.67 and f fixed at 0.6. Both DR and TRF measurements have been carried out within the temperature range, 308≤T(K)≤333. DRS measurements have been performed within the frequency window, 0.2 ≤ ν/GHz ≤ 50. TRF measurements employ coumarin 153 (C153), a fluorescent probe molecule, as a local reporter. Interestingly, the estimated static dielectric constant (ε0) for this DES is considerably large, even higher than the ε0 value of polar solvents like, dimethyl formamide and acetonitrile. Measured DR spectra require four relaxation processes, spread over sub-10 ps to nanosecond time regime, to adequately describe the detected DR dynamics of this DES. Surprisingly, this non-ionic DES possesses a nanosecond relaxation component similar to that in ionic acetamide DESs. The presence of this slow relaxation component is further supported by the corresponding dynamic fluorescence Stokes shifts measurements. Both DR and dynamic fluorescence anisotropy data reveal substantial fractional viscosity dependence for solute rotation in this DES.