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DOE OSTI2021

The Deep Eutectic Solvent Precipitation Synthesis of Metastable Zn 4 V 2 O 9

A precipitation method involving a deep eutectic solvent (DES)–a mixture of hydrogen bond donor and acceptor–is used to synthesize a ternary metal oxide. Without toxic reagents, precipitates consisting of Zn 3 (OH) 2 V 2 O 7 ·nH 2 O and Zn 5 (OH) 6 (CO 3 ) 2 are obtained by simply introducing deionized H 2 O to the DES solution containing dissolved ZnO and V 2 O 5 . Manipulation of the synthetic conditions demonstrates high tunability in the size/morphology of the two-dimensional nanosheets precipitated during the dynamic equilibrium process. According to differential scanning calorimetry and high-temperature powder X-ray diffraction, Zn 3 V 2 O 8 and ZnO obtained by the annealing of the precipitate are intermediates in the reaction pathway toward metastable Zn 4 V 2 O 9 . Intimate mixing of the metal precursors achieved by the precipitation method allows access to the metastable zinc-rich vanadate with unusually rapid heat treatment. Furthermore, the UV–vis and surface photovoltage spectra reveal the presence of sub-band gap states, stemming from the reduced vanadium (V 4+ ) center. Photoelectrochemical measurements confirm weak photoanodic currents for water and methanol oxidation. For the first time, this work shows the synthesis of a metastable oxide with the DES-precipitation route and provides insight into the structure–property relationship of the zinc-rich vanadate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Surface Pb nanoparticle aggregation, coalescence and differential capacitance in a deep eutectic solvent using a simultaneous sample-rotated small angle x-ray scattering and electrochemical methods approach [Surface Pb nanoparticle aggregation, coalescence and differential capacitance in a deep eutectic solvent using a simultaneous grazing transmission small angle x-ray scattering and electrochemical methods approach]

Nanoparticle electrodeposition is a simple and scalable approach to synthesizing supported nanoparticles. Used with a deep eutectic solvent (DES), surface nanoparticles can be assembled and exhibit unique surface charge separation when the DES is adsorbed on the nanoparticle surface. Key to understanding and controlling the assembly and the capacitance is a thorough understanding of surface particle mobility and charge screening, which requires an in-situ approach. In this study, Pb particle formation, size, shape and capacitance are resolved in a 1:2 choline Cl – : urea deep eutectic solvent whilst sweeping the cell potential in the range: 0.2 V to –1.2 V (vs. Ag/AgCl). These system parameters were resolved using a complementary suite of sample-rotated small angle X-ray scattering (SR-SAXS) and electrochemical impedance spectroscopy (EIS), which are presented and discussed in detail. This approach is able to show that both particle and ion transport are impeded in the DES, as aggregation occurs over the course of 6 minutes, and dissolved Pb ions accumulate and remain near the surface after a nucleation pulse is applied. The DES-Pb interactions strongly depend on the cell potential as evidenced by the specific differential capacitance of the Pb deposit, which has a maximum value of 2.5 +/– 0.5 F g –1 at –1.0 V vs. Ag/AgCl. Together, the SR-SAXS-EIS approach is able to characterize the unique nanoparticle capacitance, mobility and ion mobility in a DES and can be used to study a wide range of nanoparticle deposition systems in-situ .

36 MATERIALS SCIENCE↗
DOE OSTI2015

Differential Microscopic Mobility of Components within a Deep Eutectic Solvent

From macroscopic measurements of deep eutectic solvents such as glyceline (1:2 molar ratio of choline chloride to glycerol), the long-range translational diffusion of the larger cation (choline) is known to be slower compared to that of the smaller hydrogen bond donor (glycerol). However, when the diffusion dynamics are analyzed on the subnanometer length scale, we discover that the displacements associated with the localized diffusive motions are actually larger for choline. This counterintuitive diffusive behavior can be understood as follows. The localized diffusive motions confined in the transient cage of neighbor particles, which precede the cage-breaking long-range diffusion jumps, are more spatially constrained for glycerol than for choline because of the stronger hydrogen bonds the former makes with chloride anions. The implications of differential localized mobility of the constituents should be especially important for applications where deep eutectic solvents are confined on the nanometer length scale and their long-range translational diffusion is strongly inhibited (e.g., within microporous media).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent

Here, many applications of deep eutectic solvents (DES) rely on exploitation of their unique yet complex liquid structures. Due to the ionic nature of the DES components, their diffuse structures are perturbed in the presence of a charged surface. We hypothesize that it is possible to perturb the bulk DES structure far (> 100 nm) from a curved, charged surface with mesoscopic dimensions. We performed in situ, synchrotron-based ultra-small angle X-ray scattering (USAXS) experiments to study the solvent distribution near the surface of charged mesoporous silica particles (MPS) (≈ 0.5 µm in diameter) suspended in both water and a common type of DES (1:2 choline Cl-:ethylene glycol). A careful USAXS analysis reveals that the perturbation of electron density distribution within the DES extends ≈ 1 μm beyond the particle surface, and that this perturbation can be manipulated by the addition of salt ions (AgCl). The concentration of the pore-filling fluid is greatly reduced in the DES. Notably, we extracted the real-space structures of these fluctuations from the USAXS data using a simulated annealing approach that does not require a priori knowledge about the scattering form factor, and can be generalized to a wide range of complex small-angle scattering problems.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Insights into the Solvation Characteristics of Zwitterionic Deep Eutectic Solvents Using Multiple Polarity Scales

Deep eutectic solvents (DESs) formed by mixing zwitterionic hydrogen bond acceptors (HBAs) with diol- and organic acid-based hydrogen bond donors (HBDs) are popular sustainable solvents. In addition to possessing an amphiphilic character, zwitterionic DESs offer unique solvation properties, unlike those composed of halide-containing HBAs. While all other popular classes of DESs have been investigated, no study has attempted to characterize the solvation characteristics of zwitterionic DESs. In this study, the solvation properties of betaine [Bet]-, sulfobetaine-, and l-carnitine [l-Car]-based DESs were thoroughly investigated for the first time using solvatochromic dye methods and inverse gas chromatography (IGC). Herein, the Nile red polarity scale revealed that DESs composed of organic acids were generally more polar than diol-based DESs. Kamlet–Taft solvent parameters revealed that glycerol-based DESs offered exceptionally high hydrogen bond donating ability compared to those composed of 1,4-butane diol and triethylene glycol. The Abraham solvation parameter model revealed hydrogen bond basicity to be the most dominant interaction, and it was generally higher for diol-based HBDs compared to organic acid-based HBDs. Additionally, sulfobetaine HBAs possessing longer alkyl chains generally offered higher dispersive-type interactions and hydrogen bond basicity compared to [Bet] and [l-Car] salts. This is the first study to combine and compare results from solvatochromic dye methods and IGC in an attempt to comprehensively explain and predict the solvation characteristics of zwitterionic DESs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Combining High-Throughput Experiments and Active Learning to Characterize Deep Eutectic Solvents

The high tunability of deep eutectic solvents (DESs) stems from the ease of changing their precursors and relative compositions. However, measuring the physicochemical properties across large composition and temperature ranges, necessary to properly design target-specific DESs, is tedious and error-prone and represents a bottleneck in the advancement and scalability of DES-based applications. As such, active learning (AL) methodologies based on Gaussian processes (GPs) were developed in this work to minimize the experimental effort necessary to characterize DESs. Owing to its importance for large-scale applications, the reduction of DES viscosity through the addition of a low-molecular-weight solvent was explored as a case study. A high-throughput experimental screening was initially performed on nine different ternary DESs. Then, GPs were successfully trained to predict DES viscosity from its composition and temperature, showcasing the ability of these stochastic, nonparametric models to accurately describe the physicochemical properties of complex mixtures. Finally, the ability of GPs to provide estimates of their own uncertainty was leveraged through an AL framework to minimize the number of data points necessary to obtain accurate viscosity modes. This led to a significant reduction in data requirements, with many systems requiring only five independent viscosity data points to be properly described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Reactive capture and electrochemical conversion of CO 2 with ionic liquids and deep eutectic solvents

Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture and conversion (RCC) of CO 2 due to their wide electrochemical stability window, low volatility, and high CO 2 solubility. There is environmental and economic interest in the direct utilization of the captured CO 2 using electrified and modular processes that forgo the thermal- or pressure-swing regeneration steps to concentrate CO 2 , eliminating the need to compress, transport, or store the gas. The conventional electrochemical conversion of CO 2 with aqueous electrolytes presents limited CO 2 solubility and high energy requirement to achieve industrially relevant products. Additionally, aqueous systems have competitive hydrogen evolution. In the past decade, there has been significant progress toward the design of ILs and DESs, and their composites to separate CO 2 from dilute streams. In parallel, but not necessarily in synergy, there have been studies focused on a few select ILs and DESs for electrochemical reduction of CO 2 , often diluting them with aqueous or non-aqueous solvents. The resulting electrode–electrolyte interfaces present a complex speciation for RCC. In this review, we describe how the ILs and DESs are tuned for RCC and specifically address the CO 2 chemisorption and electroreduction mechanisms. Critical bulk and interfacial properties of ILs and DESs are discussed in the context of RCC, and the potential of these electrolytes are presented through a techno-economic evaluation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Adsorptive behavior of poly (vinylidene fluoride) membranes for the recovery of lignin-derived hydrophobic deep eutectic solvents

Abstract Recently, membrane technology has gained significant traction as an energy-efficient alternative to traditional thermal processes for solvent recovery. Deep eutectic solvents (DESs) have emerged as sustainable alternatives to conventional organic solvents, yet a systematic methodology for selecting compatible membrane materials for their recovery remains underdeveloped. This study established a predictive framework for membrane material selection in hydrophobic DES applications using Hansen Solubility Parameters (HSP) with inverted criteria targeting materials with relative energy difference (RED) values greater than 1.0. Flat sheet membranes were fabricated via the non-solvent induced phase separation (NIPS) technique. Four NIPS fabricated polymer membranes were evaluated: polysulfone, cellulose acetate, polyvinylidene fluoride (PVDF) fabricated with polyethylene glycol (PEG) as a pore-forming agent, and polybenzimidazole (PBI). The HSP approach successfully predicted membrane-solvent compatibility, with polysulfone (RED = 0.6) and cellulose acetate (RED = 0.9) dissolving completely within 24 h, while PVDF (RED = 1.9) and PBI (RED = 1.1) maintained structural integrity throughout a 7-day exposure period. Furthermore, PVDF demonstrated superior performance with minimal weight gain (3.0%), hydrophobic surface characteristics (122° water contact angle), and enhanced mechanical properties following DES exposure. Comprehensive chemical and morphological characterization confirmed PVDF’s chemical stability and revealed a surface-selective interaction mechanism involving simultaneous PEG (pore-forming agent) extraction and DES component adsorption. Adsorption kinetics followed pseudo-first-order behavior with reversible characteristics, best described by the Temkin isotherm model (R² = 0.9987). PVDF membranes-maintained separation functionality with average lignin rejection (75.2 ± 7.69%) and demonstrated filtration permeability of 2.0 ± 0.34 LMH/bar. This methodology provides a rational approach for membrane selection in emerging solvent systems, contributing to the advancement of sustainable separation technologies for DES-based biomass processing applications.

Science & Technology - Other Topics↗
DOE OSTI2026

Diol-enhanced natural deep eutectic solvents for efficient poplar pretreatment

Natural deep eutectic solvents (NDESs) are promising biomass pretreatment media, but their industrial application is often hindered by high viscosity. To address this limitation, diol-enhanced ternary DESs (TDESs) were prepared by incorporating 1,4-butanediol (1,4-BDO) or ethylene glycol (EG) into a choline chloride (ChCl) and 3,4-dihydroxybenzoic acid (DHBA) system. The applied TDESs maintained a liquid state at room temperature and had significantly reduced viscosity compared to the binary DES (BDES). In addition, the applied diols increased lignin solubility and suppressed lignin condensation by intercepting reactive carbocation intermediates. As a result, the recovered lignins from diol-induced TDES pretreatments showed better preservation of β-O-4 linkages and reduced condensation, improving their potential for downstream valorization. The diol-assisted DES systems showed a synergistic effect from the reduced viscosity, enhanced lignin solubility, and suppression of unwanted condensation, resulting in more effective biomass pretreatment performance, including the enhanced delignification and higher enzymatic digestibility compared to BDES. The 1,4-BDO-enhanced DES was also successfully applied to DHBA-enriched transgenic poplar, highlighting its potential for the processing of engineered biomass feedstocks.

3,4-dihydroxybenzoic acid↗
DOE OSTI2020

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 1 H 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Deep Eutectic Solvents: A Review of Fundamentals and Applications

Deep eutectic solvents (DESs) are an emerging class of mixtures characterized by significant depressions in melting points compared to those of the neat constituent components. These green materials are promising for applications as inexpensive ’designer’ solvents exhibiting a host of tunable physicochemical properties. Here, a detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in this class of solvents. Complex hydrogen bonding behavior is postulated as the root cause of their melt-ing point depressions and physicochemical properties; to understand these hydrogen bonded networks, it is imperative to study these systems as dynamic entities using both simulations and experiments. This review emphasizes recent research efforts in order to elucidate the next steps needed to develop a fundamental framework for understanding DESs. It covers recent developments in DES research, frames outstanding scientific questions, and identifies gainful research thrusts that would advance the field towards predictive models and fundamental understanding of these solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Analysis of persistent contaminants and personal care products by dispersive liquid-liquid microextraction using hydrophobic magnetic deep eutectic solvents

Here, in this work, hydrophobic magnetic deep eutectic solvents (HMDESs) were used in the development of a simple and rapid dispersive liquid-liquid microextraction (DLLME) approach coupled to high performance liquid chromatography with UV detection (HPLC-UV) for the determination of ten organic contaminants including five polycyclic aromatic hydrocarbons, four UV filters, and a pesticide from water at trace levels. The HMDESs were prepared by mixing a hydrogen bond acceptor, metal halide salt, and hydrogen bond donor in suitable molar ratios. Two HMDESs, 2 tetraoctylammonium bromide ([N 8888 + ][Br - ]): cobalt chloride (CoCl 2 ): 4 octanoic acid (OA) and 3 trioctylphosphine oxide (TOPO): neodymium chloride (NdCl 3 ): 3 OA, offered the highest analyte extraction efficiency overall and were chosen as suitable solvents for validation of the microextraction method. Under optimized extraction conditions, the method required 30 µL of HMDES as extraction solvent, acetone (87.5 µL) as disperser solvent, a NaCl concentration of 30% (w/v), and an extraction time of 120 s at 20°C. Enrichment factors of the analytes ranged from 44.6 for 3-(4-methylbenzylindene) camphor to 66.0 for 2-ethylhexyl-4-(dimethyl)aminobenzoate. The method provided low limits of detection (LODs) ranging from 0.5 to 4.5 µg L -1 , and acceptable precision, with RSD values lower than 9.6%. Furthermore, the validated method was successfully applied for tap and lake water analysis, resulting in relative recoveries of spiked samples ranging between 94.7 and 119.2%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Thermodynamic Water Activity Explains the Unusual Electrochemical Stability of Aqueous Deep Eutectic Solvents

The presence of water in nonaqueous deep eutectic solvent (DES) electrolytes has been debated in recent years, with efforts ranging from its complete removal to willful addition. It was shown that controlled amounts of water can be beneficial, as it not only enhances the physicochemical properties of these electrolytes but also has no significant detrimental effects on their electrochemical stability. Despite these advantages, there is still limited understanding of how water interacts with DES systems at the molecular level. This study examines the water activity in ethylene glycol and glycerol, as well as their binary mixtures with choline chloride to form the DESs ethaline and glyceline, respectively. In this work, we show that the high electrochemical stability of glyceline is related to its lower water activity compared to ethaline and can be attributed to the robust H-bonding network formed by the three hydroxyl groups of glycerol. Its 3D H-bond network effectively integrates water molecules within its solvent structure, reducing degradation and maintaining stability at higher water contents. The deviations from the ideal Raoult's law behavior are reflected in the water activity and activity coefficients, which highlight the intricate H-bond interactions within DES-water mixtures. Water acts like a lubricant within the more viscous DES mixtures without being detrimental to their electrochemical performance. The presented results emphasize the necessity of customizing DES-water compositions to enhance their performance as electrolytes, especially in flow battery applications where electrochemical stability, ionic conductivity, and fluidity are of utmost importance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Characterization and Catalytic Transfer Hydrogenolysis of Deep Eutectic Solvent Extracted Sorghum Lignin to Phenolic Compounds

Deep eutectic solvent (DES) is intrinsically cheaper than many ionic liquids (ILs) due to low precursor cost, simple synthesis, and improved recyclability. Meanwhile, DES can be as effective as ILs toward dissolving lignin from plant materials. However, the lignin depolymerization mechanism in DES, the structural and chemical properties of DES-extracted lignin (DES-EL), and the possible valorization pathways of DES-EL toward value-added products were not well understood. This paper aims to characterize the lignin streams from DES (1:2 choline chloride:lactic acid) treated sorghum and further upgrade the extracted lignin to phenolic compounds. As revealed by HSQC, 13 C, and 31 P NMR analysis, DES cleaved nearly all ether linkages in native lignin, resulting in significant size reduction. We further catalytically upgraded DES-EL to phenolic compounds via catalytic transfer hydrogenolysis in the presence of isopropyl alcohol. Among the three tested catalysts (Ru/C, Pd/C, and Pt/C), Ru/C proved the most effective in deconstructing DES-EL, with oil, char, and gas yields of 36.3, 46.4, 17.3 wt %, respectively. Major lignin monomeric products in the oil were phenol, 4-ethylphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-propylphenol, and 4-hydroxy-benzenepropanoic acid. Finally, this study provides a mechanistic understanding of lignin depolymerization in DES and demonstrates a possible way to catalytic upgrading of DES-EL to low molecular weight phenolic compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Utilization of deep eutectic solvent as a degumming protocol for Apocynum venetum bast

Deep eutectic solvent (DES) pretreatment coupled with alkaline degumming on Apocynum venetum bast was studied for developing an eco-friendly and effective degumming method. Here, a 1:2 mixture of choline chloride and urea was used in a microwave-assisted DES pretreatment optimized to 60 min and 110 °C. The impact of the deep eutectic solvent pretreatment on the properties of produced semi-degummed and refined dry fibers were assessed by examining the fiber chemical composition, surface microstructure, cellulose crystallinity, degree of polymerization, and fiber thermal properties. The combined DES and alkaline degumming treatment effectively removed the gummy matter including hemicellulose and lignin from the A. venetum bast, providing a smooth and clean fiber surface. This combined DES and alkaline degumming treatment also shows the ability to extract amorphous cellulose, leading to an increase of fiber crystallinity and a decrease of the average cellulose molecular weight. The thermal stability of the fibers was improved significantly after the degumming treatment. The refined dry fibers produced by this combined DES-alkaline treatment exhibited comparable chemical and physical properties (e.g. residual gum content, fiber length, fiber fineness, breaking tenacity) compared with traditionally alkali degumming method. These results revealed that DES is a practical and feasible pretreatment protocol for A. venetum bast degumming.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Tuning the Properties of Lignin‐Derived Deep Eutectic Solvents for Biomass Processing

Lignin-derived deep eutectic solvents (DESs) have been investigated as sustainable green media for biomass processing. However, the properties and processability of DESs have not been fully understood with the chemical structures of their constituents for biomass fractionation. Here, in this article, the properties of the phenolic DESs are discussed with different numbers of functional groups, such as –OCH 3 and –CHO in their hydrogen bond donor (HBD) structures. The formation of DES is significantly related to the hydrogen bond between its constituents, identified by nuclear magnetic resonance (NMR) analysis and density functional theory calculation (DFT). Lower viscosity and net basicity of DES are achieved with fewer –OCH 3 on HBD structures, resulting in enhanced processability and fractionation efficiency. The thermal stability of the DES is also influenced by the –OCH 3 and –CHO of HBD, as indicated by its onset temperature. The recyclability of the phenolic DES is confirmed by the fractionation performance of the recycled DES. Understanding the structural impacts of DES constituents on the properties and performance is crucial for designing solvents in biorefinery applications.

Ryu, Jiae [State University of New York (SUNY), Sy↗
DOE OSTI2025

Temperature-Dependent Molecular Diffusional Properties in Deep Eutectic Solvents and Eutectogels

Eutectogels (ETGs) prepared from deep eutectic solvents (DESs), a gelator, and water have many uses in separations, catalysis, and energy storage systems. In these applications, temperature-dependent molecular diffusional properties and intermolecular interactions play a critical role in their function. Diffusional properties of Alexa Fluor 633 and ATTO 647N were measured across a range of temperatures in choline chloride:2glycerol DESs comprised of one molar equivalent of choline chloride and two molar equivalents of glycerol (also known as glyceline) as well as ETGs made from this DES, a xanthan gum gelator, and 10% w/w water or 20% w/w water. Fluorescence recovery after photobleaching (FRAP) was employed to evaluate potential changes in molecular diffusion within DESs and ETGs from 20 to 100 °C. Surprisingly, the ETGs have a larger sample viscosity but also exhibit faster molecular diffusion when compared to the dry DES. This is attributed to macroscopic properties of the ETGs (e.g., pores, three-dimensional structure). The FRAP data also show an irreversible temperature-dependent decrease in the diffusion coefficient of both fluorophores in the ETGs. This is consistent with differential scanning calorimetry data of the ETG, which shows a shift to a more negative glass transition temperature (−36 °C to −47 °C) after the first cooling/heating cycle. Raman data reveal no detectable changes in the intermolecular interactions in either the DESs or ETGs as a function of temperature or water content. Finally, the findings on temperature- and water-dependent diffusional properties of DESs and ETGs provide a foundation for optimizing the use of these materials across various applications, particularly where repeated heating/cooling cycles may be used.

alcohols↗
DOE OSTI2026

Nanodomain Formation and Temperature-Dependent Diffusion in Deep Eutectic Solvents Revealed by Single-Molecule Tracking

Deep eutectic solvents (DESs) are typically regarded as homogeneous liquids; however, recent work shows that many exhibit nanoscale structural heterogeneity. Most studies attribute these nanoscale features to short-range chemical interactions. It is still unclear whether a long-range physical mechanism also plays a role. Here, in this study, we examined the nanoscale structure in two hydrophobic DESs, 1:3 tetrabutylammonium bromide: l-menthol (DES-butyl) and 1:3 tetraoctylammonium bromide: l-menthol (DES-octyl). The notation 1:3 represents the molar ratio of the hydrogen bond acceptors to hydrogen bond donors used in the synthesis of the DESs. Single-molecule tracking (SMT) coupled with maximum entropy method (MEM) analysis was used to measure the number of diffusion populations of a dilute concentration of an added fluorescent probe. The presence of more than one population of diffusion coefficients indicates the existence of multiple local environments for the fluorescent probe (i.e., nanoscale structures in the DES). DES-butyl showed a relatively narrow diffusion coefficient distribution centered at 0.55 μm 2 /s, whereas DES-octyl displayed two distinct diffusing populations at 20 °C, with diffusion coefficients of 0.12 μm 2 /s and 0.53 μm 2 /s for the slow and fast populations, respectively. As DES-octyl was heated, the slow-diffusing population steadily diminished and disappeared above ∼30 °C, indicating that the nanodomains present at lower temperatures collapse as the liquid becomes more thermodynamically mixed. This temperature-dependent homogenization is consistent with a physical mechanism of nanostructure formation, for example, liquid–liquid phase separation (LLPS), wherein the structure is not driven solely by specific chemical interactions. The SMT-MEM results suggest that a long-range physical mechanism is the most plausible origin of the measured nanoscale structure in DES-octyl.

Opare-Addo, Jemima [Ames Laboratory (AMES), Ames, ↗