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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Renewable Schiff-Base Ionic Liquids for Lignocellulosic Biomass Pretreatment

Growing interest in sustainable sources of chemicals and energy from renewable and reliable sources has stimulated the design and synthesis of renewable Schiff-base (iminium) ionic liquids (ILs) to replace fossil-derived ILs. In this study, we report on the synthesis of three unique iminium-acetate ILs from lignin-derived aldehyde for a sustainable “future” lignocellulosic biorefinery. The synthesized ILs contained only imines or imines along with amines in their structure; the ILs with only imines group exhibited better pretreatment efficacy, achieving >89% sugar release. Various analytical and computational tools were employed to understand the pretreatment efficacy of these ILs. This is the first study to demonstrate the ease of synthesis of these renewable ILs, and therefore, opens the door for a new class of “Schiff-base ILs” for further investigation that could also be designed to be task specific.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Experiment K-7-23: Effect of Spaceflight on Level and Function of Immune Cells: Proliferation and Cytokines - Part 2

Lymphocytes from the superficial inguinal lymph nodes of rats flown on the Cosmos 2044 space mission were tested for proliferation in response to polyclonal activators. Cells were cultured with T or B cell mitogens, phorbol ester and calcium ionophore, or T cell mitogen and the lymphokines interleukin-1 (IL-1) or interleukin-2 (IL-2), and assayed for DNA synthesis by (3)H-thymidine incorporation. Lymphocytes also were incubated with concanavalin A (Con A), a T cell mitogen, and tested for IL-2 production. Mitogen-stimulated proliferation of lymphocytes from rats exposed to microgravity was not significantly different from synchronous or vivarium controls. Responses to Con A and IL-2, and Con A and IL-1 likewise were unaffected by space flight. Lymphocytes from all of these groups responded well to phorbol ester and calcium ionophore stimulation. Furthermore, lymph node cells (LNC) from control rats and rats flown on Cosmos 2044 produced similar amounts of IL-2. The results obtained using hindlimb suspended rats were notably different from those of flight and control animals. LNC from suspended rats generally had greater proliferative responses to T cell mitogens than did lymphocytes from other groups. Responsiveness to a B cell mitogen was not enhanced. Con A-stimulated LNC from hindlimb suspended rats also produced more IL-2 than did lymphocytes from the other groups. This difference was statistically significant at both IL-2 induction times tested.

Nash, P. V.↗
NASA NTRS2010

NASA 14 Day Undersea Missions: A Short-Duration Spaceflight Analog for Immune System Dysregulation

BACKGROUND Spaceflight-associated immune dysregulation (SAID) occurs during spaceflight and may represent specific clinical risks for exploration-class missions. An appropriate ground analog for spaceflight-associated immune dysregulation would offer a platform for ground-evaluation of various potential countermeasures. This study evaluated the NASA Undersea Mission Operations ( NEEMO ), consisting of 14 day undersea deployment at the Aquarius station, as an analog for SAID. Sixteen Aquanauts from missions NEEMO-12, 13 and 14 participated in the study. RESULTS Mid-mission alterations leukocyte distribution occurred, including granulocytosis and elevations in central-memory CD8+ T-cells. General T cell function was reduced during NEEMO missions in roughly 50% of subjects. Secreted cytokines profiles were evaluated following whole blood stimulation with CD3/CD28 (T cells) or LPS (monocytes). T cell production of IFNg, IL-5, IL-10, IL-2, TNFa and IL-6 were all reduced before and during the mission. Conversely, monocyte production of TNFa, IL-10, IL-6, IL-1b and IL-8 were elevated during mission, moreso at the MD-14 timepoint. Antibodies to Epstein-Barr virus (EBV) viral capsid antigen and early antigen were increased in approximately 40% of the subjects. Changes in EBV tetramer-positive CD8+ T-cells exhibited a variable pattern. Antibodies against Cytomegalovirus (CMV) were marginally increased during the mission. Herpesvirus reactivation was determined by PCR. EBV viral load was generally elevated at L-6. Higher levels of salivary EBV were found during the NEEMO mission than before and after as well as than the healthy controls. No VZV or CMV was found in any pre, during and after NEEMO mission or control samples. Plasma cortisol was elevated at L-6. CONCLUSION Unfortunately, L-6 may be too near to mission start to be an appropriate baseline measurement. The general immune changes in leukocyte distribution, T cell function, cytokine production, virus specific immunity and viral reactivation are similar to those observed during or following spaceflight. The NEEMO platform may thus have utility for short-duration, ground-based spaceflight-immune research, such as investigations of mechanism or countermeasures validation.

Crucian, B. E.↗
NASA NTRS2013

Plasma Cytokine Concentrations Indicate In-vivo Hormonal Regulation of Immunity is Altered During Long-Duration Spaceflight

Background: Aspects of immune system dysregulation associated with long‐duration spaceflight have yet to be fully characterized, and may represent a clinical risk to crewmembers during deep space missions. Plasma cytokine concentration may serve as an indicator of in vivo physiological changes or immune system mobilization. Methods: The plasma concentrations of 22 cytokines were monitored in 28 astronauts during long‐duration spaceflight onboard the International Space Station. Blood samples were collected three times before flight, 3‐5 times during flight (depending on mission duration), at landing and 30 days post‐landing. Analysis was performed by bead array immunoassay. Results: With few exceptions, minimal detectable mean plasma levels (<10 pg/ml) were observed at baseline (launch minus 180) for innate inflammatory cytokines or adaptive regulatory cytokines, however IL‐1ra and several chemokines were constitutively present. An increase in the plasma concentration IL‐8, IL‐1ra, Tpo, CCL4, CXCL5, TNF(alpha), GM‐CSF and VEGF was observed associated with spaceflight. Significant post‐flight increases were observed for IL‐6 and CCL2. No significant alterations were observed during or following spaceflight for adaptive/T‐regulatory cytokines (IL‐2, IFN(gamma), IL‐17, IL4, IL‐5, IL‐10). Conclusions: This pattern of cytokine dysregulation suggests multiple physiological adaptations persist during flight, including inflammation, leukocyte recruitment, angiogenesis and thrombocyte regulation.

Crician, Brian E.↗
DOE OSTI2025

CO 2 in Ionene–Ionic Liquid Composite Membranes

Abstract Ionene – ionic liquid (IL) composites are promising materials for CO 2 separation, yet a molecular‐level understanding of their structure and its impact on CO 2 speciation, solubility, rotation, and diffusivity remains unclear. Herein, using multimodal nuclear magnetic resonance (NMR), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), atomic force microscopy (AFM), and molecular dynamics (MD) simulations, we reveal that the composites contain IL‐rich domains extending across hundreds of nanometres within the ionene matrix, and these bicontinuous domains span the entire membrane depth. CO 2 also absorbs into the ionene matrix, with the distribution between two CO 2 species varying with temperature and time. The rotational correlation times of these two species are on the timescale of 0.1 and 1 ns, respectively. As IL content increases, the ionic domains expand, resulting in higher CO 2 solubility due to enhanced molecular dynamics and increased free volume in both ionene backbones and IL‐rich regions. Although CO 2 diffusion in the membranes is an order of magnitude slower than in bulk IL, the activation energy for CO 2 diffusion remains comparable. Ionene‐IL composites represent a promising platform for designing CO 2 separation membranes, offering enhanced CO 2 diffusion and selectivity through IL‐rich domains, and increased CO 2 solubility and mechanical integrity from the ionene matrix.

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

Influence of the Anions on the Interaction Energy between Water and Ionic Liquids

It is essential to understand the interaction energy between water and ionic liquids (ILs) in search of ILs for dehumidification applications. In this paper, the intermolecular interaction energy between water and 1-ethyl-3-methylimidazolium ([EMIM])-based ILs was investigated. The vapor-liquid equilibrium data were first measured for solutions of [EMIM][BF 4 ], [EMIM][N(CN) 2 ], [EMIM][CF 3 SO 3 ], and [EMIM][CH 3 SO 3 ] with water molar fractions of 8–95 % at temperatures of 303–343 K. The IL-IL and water-IL intermolecular interaction energies were determined by using the correlated non-random two-liquid model. The results revealed that fluorine atoms in anions reduce the attraction energy between IL and water, and thus, decrease the water affinity.

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

High-throughput measurements of CO 2 permeance and solubility in ionic liquid reveal a synergistic role of ionic interactions and void fractions

The factors that govern CO 2 solubility in ionic liquids (ILs) are of great interest for the development of new materials for CO 2 capture and utilization. The cationic functional group (i.e., imidazolium, pyrrolidinium, pyridinium, etc.), alkyl chain length of cation, degree of fluorination of anion, anion size, and the void fraction in IL are known to influence CO 2 solubility. However, a comprehensive explanation of how these factors collectively affect CO 2 solubility has not been developed yet. This knowledge gap is largely attributed to the lack of CO 2 solubility data for IL structures other than imidazolium based ILs. We report here an automated high-throughput (HT) setup for the measurement of CO 2 solubility in room-temperature ILs (RTILs) combining six different anions and nine different cations for a total of 19 different specific ranges of RTILs. The HT setup first dispenses up to 200 µL of RTILs in a 96-well microtiter plate and then utilizes a robotic arm to measure cyclic voltammogram (CV) in each well using maneuverable Ag electrodes. The Cottrell analysis of the CO 2 reduction CV peak provides a direct measurement of CO 2 permeance in RTILs, which yields Henry’s constant from the estimated diffusion coefficient of CO 2 . Henry’s constants thus obtained are in very good agreement with those reported earlier. The measured CO 2 permeance and Henry’s constant of all RTILs seem to follow a first-order dependence on void fraction and a second-order dependence on electrostatic interaction between anion and cation of IL, with some synergistic dependence on the product of a void fraction and electrostatic interaction, making them two important descriptors for the design of novel ILs.

CO2 Solubility↗
DOE OSTI2021

Ionic liquid-water mixtures enhance pretreatment and anaerobic digestion of agave bagasse

Agave bagasse (AB), a byproduct of tequila production, is a waste generated in large quantities and an emerging alternative for biofuels production. Nevertheless, the use of lignocellulosic biomass for this purpose requires a pretreatment that maximizes its degradation and utilization. Although there are several pretreatment types, using ionic liquids (IL) has become attractive due to its ability to dissolve the lignocellulosic biomass under mild conditions of time and temperature. As a drawback are the high cost of IL's and their high viscosity; thus mixing them with water is a way to overcome these hindrances. This work aimed to evaluate the effect of pretreatment with three diluted ILs on the A. tequilana bagasse structure and sugars production, as well as the potential of the enzymatic hydrolysate to produce methane in batch mode. The evaluated ILs were: 1-ethyl-3-methylimidazolium acetate [Emim][OAc], choline lysinate [Ch][Lys] and ethanolamine acetate [EOA][OAc]. The results showed that the IL with the best performance was [Ch][Lys], which not only offered the highest yields of sugar production (0.57 ± 0.03 g total sugars / g bagasse) but also, it is possible to use it at 30 % in a mix with water obtaining similar yields as with pure IL. Enzymatic hydrolysis of IL pretreated AB achieved 50.7 kg sugars and 49.3 kg of sugars for 90 %-[Ch][Lys] and 30 %-[Ch][Lys], respectively per 100 kg of untreated biomass. The enzymatic hydrolysate from the 30 %-[Ch][Lys] pretreated AB was able to achieve 0.28 L CH4/g CODfed, demonstrating that both sugar and methane yields are maintained when pure or 30 %-[Ch][Lys] are used for pretreatment, representing a step forward towards process feasibility.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Impact of Ionic Liquid on Lithium Ion Battery with a Solid Poly(Ionic Liquid) Pentablock Terpolymer as Electrolyte and Separator

In this work, a ternary blend solid polymer electrolyte (SPE) consisting of a poly(ionic liquid) (PIL) multiblock polymer, lithium salt, and ionic liquid (IL) was investigated with the goal of understanding the influence of IL concentration on ion transport mechanisms and electrochemical stability. The physical, transport, mechanical, morphological, and electrochemical properties of the ternary blend SPE were systematically investigated as a function of IL concentration (r = [IL]/[PIL] mole ratio between 0.1 and 0.7). The results indicate that with increasing IL concentration, the continuous conductive domain increases along with the polymer chain segmental mobility, as well as facilitate ionic conductivity, while the mechanical modulus exhibits a percolation threshold (from 52.17 MPa to 0.55 MPa at r = 0.2 to 0.3). Surprisingly, at higher IL concentrations, there is a reduction in the lithium cation mobility (i.e., 9.3 × 10-12 m2 s-1 versus 3.8 × 10-12 m2 s-1 for r = 0.2 versus r = 0.5, respectively) as evidenced by pulsed-field gradient nuclear magnetic resonance (PFG-NMR), which coincides with an increased overpotential (i.e., 50 mV versus 150 mV for r = 0.2 versus r = 0.5, respectively) evidenced by lithium metal stripping and plating. This work provides valuable insights into the impact of IL on lithium ion conducting PIL block polymers, which may enable the design of new SPEs with both high ionic conductivity and improved stability for the future lithium ion batteries.

Chen, Tzu-Ling↗
DOE OSTI2023

Atomic Level Interactions and Suprastructural Configuration of Plant Cell Wall Polymers in Dialkylimidazolium Ionic Liquids

Ionic liquids (ILs) have been widely investigated for the pretreatment and deconstruction of lignocellulosic feedstocks. However, the modes of interaction between IL-anions and cations, and plant cell wall polymers, namely, cellulose, hemicellulose, and lignin, as well as the resulting ultrastructural changes are still unclear. In this study, we investigated the atomic level and suprastructural interactions of microcrystalline cellulose, birch wood xylan, and organosolv lignin with 1,3-dialkylimidazolium ILs having varying sizes of carboxylate anions. Analysis by 13 C NMR spectroscopy indicated that cellulose and lignin exhibited stronger hydrogen bonding with acetate ions than with formate ions, as evidenced by greater chemical shift changes. Small-angle X-ray scattering analysis showed that while both cellulose and xylan adopted a single-stranded conformation in acetate-ILs, twice as many acetate ions were bound to one anhydroglucose unit than to an anhydroxylose unit. Further, we also determined that a minimum of seven representative carbohydrate units must interact with an anion for that IL to effectively dissolve cellulose or xylan. Lignin is associated as groups of four polymer molecules in formate-ILs and dispersed as single molecules in acetate-ILs, which indicates that it is highly soluble in the latter. In summary, our study demonstrated that 1,3-dialkylimidazolium acetates displayed stronger binding interactions with cellulose and lignin, as compared to formates, and thus have superior potential to fractionate these polymers from lignocellulosic feedstocks.

13C NMR↗
DOE OSTI2024

Key Experimental Considerations When Evaluating Functional Ionic Liquids for Combined Capture and Electrochemical Conversion of CO 2

Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO 2 (ECO 2 R) due to their role in the double-layer structure formation and increased CO 2 availability at the electrode surface, which reduces the voltage requirement. However, not all ILs are the same, considering the purity and degree of the functionality of the IL. Further, there are critical experimental factors that impact the evaluation of ILs for ECO 2 R including the reference electrode, working electrode construction, cosolvent selection, cell geometry, and whether the electrochemical cell is a single compartment or a divided cell. Here, we describe improved synthesis methods of imidazolium cyanopyrrolide IL for electrochemical studies in consideration of precursor composition and reaction time. We explored how IL with cosolvents (i.e. acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) affects conductivity, CO 2 mass transport, and ECO 2 R activation overpotential together with the effects of electrode materials (Sn, Ag, Au, and glassy carbon). Acetonitrile was found to be the best solvent for lowering the onset potential and increasing the catalytic current density for the production of CO owing to the enhanced ion mobility in combination with the silver electrode. Further, the ECO 2 R activity of molecular catalysts Ni(cyclam)Cl 2 and iron tetraphenylsulfonato porphyrin (FeTPPS) on the carbon cloth electrode maintained high Faradaic efficiencies for CO in the presence of the IL. This study presents best practices for examining nontraditional multifunctional electrolytes amenable to integrated CO 2 capture and conversion technologies for homogeneous and heterogeneous ECO 2 R.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Molecular-Level Insights into the Influence of Ionic Liquids on the Structure and Dynamics of Neutral and Charged Polyimides

We use all-atom molecular dynamics simulations to investigate how increasing ionic functionalization influences polyimide (PI) behavior in ionic liquid (IL) solvation environments. Here, we examine three polymer systems with varying charge densities: a neutral polyimide [N−PI] containing imidazole rings and progressively introduce charge through quaternization to create singly [C−PI] + and doubly charged [C−2PI] 2+ variants across a wide range of IL concentration (0−90 wt %). Through comprehensive structural, mechanical, and electrostatic analyses, we reveal that polymer charge density plays a central role in shaping IL organization and interaction with the polymer matrix. At low IL content, charged systems exhibit strong electrostatic complexation, leading to chain compaction, localized ESP environments, and elevated dielectric constants. As IL concentration increases, the effect of the different polymer charge states becomes less significant. Notably, an intermediate composition regime at approximately 50 wt % IL is associated with changes in IL-rich domain connectivity and overall system behavior across all three PI systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High-Throughput Screening and Accurate Prediction of Ionic Liquid Viscosities Using Interpretable Machine Learning

Ionic liquids (ILs) are a novel group of green solvents with great promise for various industrial applications, including carbon capture and lignocellulosic biomass deconstruction. However, the use of ILs at the industrial scale remains challenging due to their high viscosities at ambient temperatures. To develop ILs with lower viscosities, a systematic study of their quantitative structure–property relationship (QSPR) is desirable. Here, we developed four machine learning (ML) models to predict viscosity at various temperature and pressure ranges, trained over a wide range of ILs consisting of various cationic and anionic families. ML methods including two-factor polynomial regression (two-factor PR), support vector regression (SVR), feed-forward neural networks (FFNN), and categorical boosting (CATBoost) were developed based on features that have proven useful in previous ML studies: COSMO-RS (conductor-like screening model for real solvents)-derived surface screening charge densities (sigma profiles). FFNN and CATBoost were the most accurate in predicting IL viscosities with lower average absolute relative deviation and higher R2 values on the test set. Tanimoto similarity scores were calculated to characterize the chemical space and structural similarity of the investigated ions. Furthermore, SHapley Additive exPlanation (SHAP) analysis was employed to interpret the ML results. Temperature, the polar area of ILs, and the nonpolar regions of ions are key features that influence the viscosity predictions. Importantly, the IL viscosity prediction here is the most accurate reported to date.

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

Marine Toxicity, Biodegradability, and Rolling-Sliding Tribological Performance of Ionic Liquid-Enhanced Environmentally-Acceptable Lubricants for Tidal Turbomachinery

Environmentally acceptable lubricants (EALs) are increasingly being recognized in many fields including waterpower, hydraulics, water transport, agricultural machinery, offshore wind turbines, etc. Specifically, high-performance EALs are demanded for tidal turbomachinery to ensure high efficiency and reliability and avoid the significant risk of direct contamination of the marine ecosystem upon leaks. Here we report a new development of ionic liquid (IL)-enhanced EALs for tidal energy. One short-chain phosphonium phosphate and one short-chain ammonium phosphate ILs were used as the candidate additives and the IL-containing EALs demonstrated significantly improved lubricating performance, much lower toxicity, and increased biodegradability compared with commercial baselines. Specifically, in a rolling-sliding test simulating the operation of a model tidal turbine gearbox bearing, an EAL containing the ILs at a 0.5 wt % concentration demonstrated 40% lower friction, 45% less wear loss, substantially reduced rolling contact fatigue-induced surface damage, and one order of magnitude lower vibration noise compared with a commercial gear oil. In an EPA standard toxicity test, 90 and 70% survival of marine biota was observed when exposed to an EAL containing 5 wt % of the short-chain phosphonium phosphate and ammonium phosphate ILs, respectively, while the selected commercial gear oil and bioderived additive killed all marine biota. In a standard biodegradability test, 2 wt % addition of the phosphonium phosphate IL not only retained the EAL’s ready biodegradability but further boosted the oil decomposition from a range of 60–80% to a higher level of 80–95%. Conversely, adding the commercial bioderived additive downgraded the EAL from readily to inherently biodegradable. Furthermore, this work offers scientific insights for development of ILs as potential EAL additives for marine energy and broader applications.

additives↗
DOE OSTI2025

Machine learning-enabled discovery of ionic liquid–solvent electrolytes exhibiting high ionic conductivity

Ionic liquids (ILs), which are a class of materials with versatile nature and growing popularity, are facing impediments toward widespread usage as electrolytes due to various factors such as low ionic conductivity, high viscosity, high market price etc. One of the ways these limitations can be addressed is by mixing ILs with a molecular solvent. In a combinatorial sense, there exists an immense number of specific IL–solvent combinations. An exhaustive experimental or even simulation-based investigation of the chemical space spanned by such combinations can be extremely time-consuming, expensive, and nearly impossible. An alternative approach is to employ machine learning-based models developed from available databases. Although there exists prior literature that integrates machine learning to investigate mixtures of specific solvents with ILs, these models lack generalization necessitating development of a large number of ML models to handle various solvents. To remedy this shortcoming, as a part of designing green electrolytes with high ionic conductivity that can have potential applications in next-generation batteries and solar cells, this work aims to develop a unified machine learning model to predict ionic conductivity of any IL–solvent mixture system. In this regard, three models, namely, Random Forest, extreme gradient boosting (XGBoost), and artificial neural network (ANN) were formulated using the NIST ILThermo database. The dataset contained 549 unique ionic liquids from 16 cation families and 81 unique solvents, representing a total of 23 712 datapoints. SHAPLEY additive explanation (SHAP) method was used to assess the impact of various features on model prediction and their significance was compared with literature to gain physical insight about the model behavior. Finally, using the developed models, approximately 2.5 million IL–solvent mixtures at five different compositions were screened at room temperature. The high-throughput screening yielded nearly 19 000 IL–solvent mixtures for which ionic conductivity was found to exceed the ionic conductivity of conventional Li-ion battery electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2024

Molecular dynamics simulations of uranyl and plutonyl cations in a task-specific ionic liquid

Ionic liquids (ILs) are a unique class of solvents with potential applications in advanced separation technologies relevant to the nuclear industry. ILs are salts with low melting points and a wide range of tunable physical properties, such as viscosity, hydrophobiciy, conductivity, and liquidus range. ILs have negligible vapor pressure, are often non-flammable, and can have high thermal stability and a wide electrochemical window, making them attractive for use in separations processes relevant to the nuclear industry. Metal salts generally have a low solubility in ILs; however, by incorporating new functional groups into the IL cation or anion that promote complexation with the metal, the solubility can be greatly increased. One such task-specific ionic liquid (TSIL) is 1-carboxy-N, N, N-trimethylglycine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf 2 N]). Water, which is detrimental for electrochemical separations, is a common impurity in ILs and can coordinate with actinyl cations, particularly in ILs containing only weakly coordinating components. Understanding the behavior of actinides in TSIL/water mixtures on a molecular level is vital for designing improved separations processes. Classical molecular dynamics simulations of uranyl(VI) and plutonyl(VI) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf 2 N]) with deprotonated Hbet (betaine) and water have been performed to understand the coordination and dynamics of the actinyl cations. We find that betaine is a much stronger ligand than water and prefers to coordinate the metal in a bidentate manner. Potential of mean force simulations yield a relative free energy for betaine coordination of approximately -120 to -90 kJ/mol in mixtures with water. As the amount of betaine coordinated to the actinide increases, the diffusion coefficient of the actinyl cation decreases. Moreover, the betaine ligand is able to bridge between two metal centers, resulting in dimeric complexes with actinide–actinide distances of ~5 Å. Potential of mean force simulations show that these structures are stable, with relative free energies of up to -40 kJ/mol. The crystal structure for [(UO 2 ) 2 (bet) 6 (H 2 O) 2 ][Tf 2 N] 4 shows that the betaine bridges between two uranium atoms to form dimeric complexes similar to those found in our simulations.

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

Development of Ionic Liquid-Additized, GF-5/6 Compatible Low-Viscosity Oils for Automotive Engine and Rear Axle Lubrication for 4% Improved Fuel Economy

This joint project among ORNL, GM, and DRO successfully developed ionic liquid-additized low viscosity lubricants, SAE 0W-12 and 70W-80, for both IC engine and rear axle lubrication, respectively, and demonstrated combined vehicle fuel economy improvement (FEI). Phosphonium-alkylphosphate ILs have been found to be the most effective among the candidates in protecting surface damage from both sliding wear and rolling contact fatigue, and optimal IL concentrations have been determined. The IL’s impact on three-way catalyst seems to be significantly less adverse than the conventional ZDDP. Oil formulations were optimized for both energy efficiency and wear protection. Tribological bench testing of the IL-additized low-viscosity oils showed at least 40% lower boundary friction, more than 60% lower elastohydrodynamic friction, and greater than 50% less wear compared with commercial baselines. IL-additized lubricants have demonstrated FEI by 9.9% in engine dynamometer tests under extreme conditions and 6.9% increased power output in gear rig tests. Prototype IL-additized engine oil and rear axle fluid exhibited combined FEI of 1.39% and 3.24% benchmarked against the state-of-the-art baselines in vehicle testing of fresh oils under the Federal Test Procedure (FTP) city cycle and Highway Fuel Economy Driving Schedule (HWFET), respectively. Used oil analysis suggested that the IL-additized low-viscosity oils produced less wear than the commercial baselines. The gained fundamental understanding and demonstrated FEI in this work pave the way for future development and implementation of the ionic liquid technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Factors that influence the activity of biomass-degrading enzymes in the presence of ionic liquids—a review

Ionic liquids (ILs) are seen as a more sustainable alternative to volatile organic solvents that are accelerating innovations in many industries such as energy storage, separations, and bioprocessing. The ability to effectively deconstruct lignocellulosic biomass is a significant hurdle in the biorefining/bioprocessing industry and presents limitations towards the commercial production of bioproducts (such as biofuels, biomaterials, etc. ). Certain ILs have been shown to promote effective lignin removal, cellulose recovery, and sugar yields from various biomass feedstocks such as corn stover, wheat straw, sugarcane bagasse, sorghum, switchgrass, miscanthus, poplar, pine, eucalyptus, and certain mixtures of municipal solid waste. However, these improvements are often counteracted by the limited biocompatibility of ILs, which results in an IL-induced reduction in enzyme activity and stability—an important downstream step in the conversion of biomass to biofuels/bioproducts. As a result, significant efforts have been made to discover and engineer compatible enzyme-IL systems and to improve our understanding on the effect that these ILs have on these systems. This review seeks to examine the impact of ionic liquids on enzymes involved in lignocellulosic biomass deconstruction, with a specific focus on their relevance in the context of pretreatment. Beyond presenting an overview of the ionic liquid pretreatment landscape, we outline the main factors that influence enzyme activity and stability in the presence of ILs This data is consolidated and analyzed to apply this body of knowledge towards new innovations that could lead to improvements in the processing of biomass to biofuels and bioproducts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗