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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Radiolytic evaluation of acetohydroxamic acid (AHA) under biphasic (n-dodecane and TBP/DEHBA/DEHiBA) used nuclear fuel reprocessing conditions

Acetohydroxamic acid (AHA) has been proposed as a substitute for uranium(IV) and hydrazine as a plutonium complexant and neptunium reductant for simplified, single-cycle used nuclear fuel reprocessing flowsheets. However, the chemical behavior of AHA in an intense multi-component radiation field is poorly understood, especially under representative biphasic reprocessing solvent system conditions. In response to this critical knowledge gap, this study has investigated the gamma radiolytic integrity of AHA in aqueous nitric solutions in contact with an organic phase, comprising current and future reprocessing ligands (TBP, DEHBA, and DEHiBA) dissolved in n-dodecane diluent. Our data show negligible effect of the organic phase on the radiolytic behavior of AHA compared to complementary single-phase experiments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Vibrational Spectroscopic Monitoring of the Gelation Transition in Nafion Ionomer Dispersions

Infrared and Raman spectroscopy techniques were applied to investigate the drying and aggregation behavior of Nafion ionomer particles dispersed in aqueous solution. Gravimetric measurements aided the identification of gel-phase development within a series of time-resolved spectra that tracked transformations of a dispersion sample during solvent evaporation. A spectral band characteristic of ionomer sidechain end group vibration provided a quantitative probe of the dispersion-to-gel change. For sets of attenuated total reflection Fourier transform infrared (ATR FT-IR) spectra, adherence to Beer's law was attributed to the relatively constant refractive index in the frequency region of hydrated –SO$^{–}_{3}$ group vibrations as fluorocarbon-rich ionomer regions aggregate in forming the structural framework of membranes and thin films. Although vibrational bands associated with ionomer backbone CF 2 stretching vibrations were affected by distortion characteristic of wavelength-dependent refractive index change within a sample, the onset of band distortion signaled gel formation and coincided with ionomer mass % values just below the critical gelation point for Nafion aqueous dispersions. Similar temporal behavior was observed in confocal Raman microscopy experiments that monitored the formation of a thin ionomer film from an individual dispersion droplet. For the ATR FT-IR spectroscopy and confocal Raman microscopy techniques, intensity in the water H–O–H bending vibrational band dropped sharply at the ionomer critical gelation point and displayed a time dependence consistent with changes in water content derived from gravimetric measurements. The reported studies lay groundwork for examining the impact of dispersing solvents and above-ambient temperatures on fluorinated ionomer transformations that influence structural properties of dispersion-cast membranes and thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Expanding manganese(iv) aqueous chemistry: unusually stable water-soluble hexahydrazide clathrochelate complexes

Mn cage complexes are rare, and the ones successfully isolated in the solid state are not stable in water and organic solvents. In this work, we present the first report of mononuclear Mn clathrochelates, in which the encapsulated metal exists in the oxidation state +4. The complexes are extremely stable in the crystalline state and in solutions and show rich redox chemistry.

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

Techno-Economic Analysis and Life Cycle Assessment for the Separation of 2,3-Butanediol from Fermentation Broth Using Liquid–Liquid Extraction

It is energy-intensive to separate dilute 2,3-butanediol (2,3-BDO) (<10 wt %) from the aqueous phase of fermentation broth for sustainable aviation fuel (SAF) using conventional distillation. Liquid–liquid extraction (LLE) using oleyl alcohol as a solvent in a membrane extractor to extract BDO from water can significantly reduce the energy cost and minimize the potential emulsion. In an Aspen Plus model simulation, 95.2% BDO recovery and 97.1% BDO purity have been achieved using this LLE method with solvent recovery and heat integration. Here, the thermal energy cost was estimated to be 4.57 MJ/kg BDO, which is only about 16.8% of the lower heating value (LHV) of the BDO. This method consumes 81% less energy than the cascade distillation and reduces about $0.46/GGE (gasoline gallon equivalent) to the minimal fuel selling price. Meanwhile, the greenhouse gas (GHG) emission is 62% lower than petroleum-based jet fuel production and 34% less than using the cascade distillation.

09 BIOMASS FUELS↗
DOE OSTI2022

Proton-Coupled Electron Transfer in a Ruthenium(II) Bipyrimidine Complex in Its Ground and Excited Electronic States

In this work, proton-coupled electron transfer (PCET) was studied for the ground and excited electronic states of a [Ru(terpy)(bpm)(OH 2 )(PF 6 ) 2 ] complex, Ru-bpm. Cyclic voltammetry measurements show that the Ru(II)-aqua moiety undergoes PCET to form a Ru(IV)-oxo moiety in the anodic region, while the bpm ligand undergoes PCET to form bpmH 2 in the cathodic region. The photophysical behavior of Ru-bpm was studied using steady-state and femtosecond transient UV–vis absorption spectroscopy, coupled with density functional theory (DFT) calculations. The lowest-lying excited state of Ru-bpm is described as a (Ru → bpm) metal-to-ligand charge-transfer (MLCT) state, while the metal-centered (MC) excited state was found computationally to be close in energy to the lowest-energy bright MLCT state (MC state was 0.16 eV above the MLCT state). The excited-state kinetics of Ru-bpm were found via transient absorption spectroscopy to be short-lived and were fit well to a biexponential function with lifetimes $τ_1$ = 4 ps and $τ_2$ = 65 ps in aqueous solution. Kinetic isotope effects of 1.75 ($τ_1$) and 1.61 ($τ_2$) were observed for both decay components, indicating that the solvent plays an important role in the excited-state dynamics of Ru-bpm. Based on the pH-dependent studies and the results from prior studies of similar Ru-complexes, we hypothesize that the 3 MLCT state forms an excited-state hydrogen-bond adduct with the solvent molecules and that this process occurs with a 4 ps lifetime. The formation of such a hydrogen-bond complex is consistent with the electronic density accumulation at the peripheral N atoms of the bpm moiety in the 3 MLCT state. The hydrogen-bonded state 3 MLCT decays to the ground state with a 65 ps lifetime. Such a short lifetime is likely associated with the efficient vibrational energy transfer from the 3 MLCT state to the solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

New Compounds and Phase Selection of Nickel Sulfides via Oxidation State Control in Molten Hydroxides

Molten salts are promising reaction media candidates for the discovery of novel materials; however, they offer little control over oxidation state compared to aqueous solutions. Here, we demonstrated that when two hydroxides are mixed, their melts become fluxes with tunable solubility, which are surprisingly powerful solvents for ternary chalcogenides and offer effective paths for crystal growth to new compounds. We report that precise control of the oxidation state of Ni is achievable in mixed molten LiOH/KOH to grow single crystals of all known ternary K-Ni-S compounds. It is also possible to access several new phases, including a new polytope of β-K 2 Ni 3 S 4 , as well as low-valence KNi 4 S 2 and K 4 Ni 9 S 11 . KNi 4 S 2 is a two-dimensional low-valence nickel-rich sulfide, and β-K 2 Ni 3 S 4 has a hexagonal lattice. Moreover, using KNi 4 S 2 as a template, we obtained a new layered binary Ni 2 S by topotactic deintercalation of K. The new binary Ni 2 S has a van der Waals gap and can function as a new host layer for intercalation chemistry, as demonstrated by the intercalation of LiOH between its layers. The oxidation states of low-valence KNi 4 S 2 and Ni 2 S were studied using X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. Density functional theory calculations showed large antibonding interactions at the Fermi level for both KNi 4 S 2 and Ni 2 S 2 corresponding to the flat-bands with large Ni-d$_{x^2}$$_{y^2}$ character.

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

Scanning Electrochemical Microscopy for Kinetic Investigations in Viscous Deep Eutectic Solvents: Identifying Practical Approach Curves and Deviations from Electron Transfer Models

Determining heterogeneous electrochemical electron transfer (ET) kinetics in electrolytes with a wide range of physical properties is of great interest for achieving high-performance redox flow batteries. Among such electrolytes, concentrated hydrogen-bonded electrolytes (CoHBEs), including deep eutectic solvents (DESs), have recently garnered significant attention. Unfortunately, traditional Tafel analysis using macroelectrodes often encounters issues with mass transfer limitations in CoHBEs with high viscosities, thereby restricting kinetic analysis to a narrow potential window. Here, in this work, we introduce a methodology for evaluating ET kinetics in viscous DES using the scanning electrochemical microscopy (SECM). We first determined practical solutions to SECM tip positioning in ethaline DES, which yield pseudopositive feedback responses. Lattice Boltzmann method (LBM) simulations helped us rationalize the impact of the fluid and concentration fields, as well as tip geometry, tip approach velocity v, and the solvent viscosity ηs, on the shape of the approach curves. In addition to successfully recreating approach curves over a variety of conditions, we found that approaching a conductor ensured a practical point where the normalized tip response (Ni T = 2) converged at L = 0.7 within ∼10% error regardless of tip velocity. With positioning capabilities at hand, we investigated the kinetics of Fe 3+ /Fe 2+ redox couple in aqueous and the ethaline media. The experimental kinetic results were interpreted using the Butler–Volmer (BV) and Marcus–Hush–Chidsey (MHC) models. For ethaline, a nonideal kinetic behavior was observed, potentially attributed to solvent dynamics within DESs or to the interplay of chloride anions in the charge transfer process.

electrodes↗
DOE OSTI2023

Multi-Sourced Collaboration for the Production and Refining of Rare Elements and Critical Metals (Final Technical Report)

The project objective was to develop a feasible and cost-effective method for recovering rare earth elements (REEs) and critical materials (CMs) from coal and coal byproducts, resulting in high-purity individually separated REEs and CMs. The targeted REEs included Y, Pr, Nd, Gd, Dy, and Sm, with a purity of over 99.5%, while the CMs included Co, Mn, Ga, Sr, Li, Ni, Zn, and Ge, with a purity of over 90%. The project aimed to design a prototype facility capable of producing 1-3 tonnes/day of high-purity REO mixes. The work was divided into four designated circuits: 1) REE extraction and concentration, 2) REE separation and purification, 3) RE metal production, and 4) CM production. To achieve these goals, the project involved 11 tasks, including technology reviews, research, process flow diagram development, mass balance estimation, and preliminary technical-economic analysis. The project team included researchers from the University of Kentucky, University of Alabama and Virginia Tech as well as process specialists from Argonne National Laboratory. MP Materials provided technical support regarding rare earth markets and processing while Alliance Coal performed resource assessment. The project included a market analysis for Nd/Pr, Tb, Dy, Gd, Y, Co, Mn, Li, Sr, Ga, Ni, Zn, and Ge. These analyses provided insights into the supply and demand trends as well as historic and future projections of market price relative to purity requirements for these elements. Two coal resources were selected for the project: the West Kentucky No. 13 (Baker) Seam and an undisclosed lignite resource in the Illinois coal basin. The estimated quantities of REEs in these resources were calculated based on production samples and drilling data. It was estimated that there is adequate supply for an operation producing one metric ton daily of higher purity mixed rare earth oxides (MREO) for approximately 20 years at a site located in western Kentucky. In Circuit 1, project data was obtained from a pilot heap leach and REE concentration facility. It was concluded that the existing circuit, which generated a MREO concentrate, two types of CM mixed products, and Li- and Sr-containing waters, would be suitable feed for circuits 2-4. Data from the first-of-its-kind coal coarse refuse heap leach pilot pad played a crucial role in estimating reliable elemental concentrations of the pregnant leaching solution (PLS). The average total REE concentration in the PLS was found to be 28.6 ppm. In Circuit 2, several concepts were explored including a novel process referred to as solvent-assisted chromatography (SAC). This concept involved a novel columnar reactor that incorporated multiple mixer/settlers, thereby enabling the operation of counter-flowing aqueous and organic phases. Unfortunately, due to project time constraints, a complete fundamental modeling analysis could not be completed to fully evaluate the technology. Molten salt electrowinning was considered as an alternative for circuit 3 following circuit 2 purification circuit utilizing the novel SAC process. A mass and energy balance of Nd reduction to metal in a fluoride containing molten salt electrolyte was conducted. Comparisons were made with the current state of Asian molten salt electrorefining, and potential improvements in siphoning rare earth metals (REM) from the reactor were presented. A cost estimate was performed for the production of 1 tonne per day, which yielded a total of $2.29 million for the nine electrowinning (EW) cells required. The selected option for circuits 2 and 3 was a plasma distillation process, which initially separates rare earth elements (REEs) from other elements. This is followed by selective electrowinning in various ionic liquids. The selection was made on the basis of thermodynamic modeling and experimental data previously published by a project partner. The combination offers an innovative approach to integrated refining and RE metal production. For Circuit 4, an extensive literature review was conducted for the processing of the CMs. The ultimate decision was to utilize a combined plasma and ionic liquid process as well to produce individual high-purity concentrates of Zn, Ni, Co, Mn, and Mg. A separate flowsheet for Li and Sr was recommended, which would yield carbonates of these elements. Due to the lack of suitable experimental data at this time, a process recommendation could not be provided but several methods have been proposed for consideration. Lastly, a techno-economic analysis (TEA) was conducted to assess the effectiveness of the proposed process for further investigation. The TEA results revealed a capital expense (CapEx) of $737 million and an annual operational expense (OpEx) of $220 million. Due to the selected elements, the hypothetical heap leach pad can produce 1 metric tonne per day of REO equivalent, but a conscious decision was made to only treat targeted REEs, resulting in the production of 0.4 metric tonne of REM. An estimated annual revenue of $90.87 million was projected based on standard market pricing information provided by the funding agency. During the TEA, ten different modules were evaluated for costing purposes. The precipitation circuit was identified as the largest single operational expense, followed by the Mg/Mn process due to the amount of treated metal. In terms of capital expenditures, the heap leach process incurred the highest cost, followed by the Mg/Mn process. The scalability of the plasma process is a crucial consideration since the reactors cannot be scaled beyond the largest demonstrated size due to their reliance on surface area of the slag and vapor phase. The purity estimate for the REEs are generally 98%±2% to produce a metal. The purity level being lower than the project objective was due to the lack of specific experimental data needed to tighten the tolerance of the estimates. Based on literature and previous experience, the CMs are estimated as follows; Ga (95%+, metal), Sr (95%+, carbonate), Li (95%+, carbonate), Ni (98%±2%, metal), Zn (95%+, metal sponge), Ge (95%+, metal), Co (98%±2%, metal), and Mn (98%±2%, metal).

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Direct Extraction of Lanthanide Oxides and Nitrates in Tributyl Phosphate

This work investigated the dissolution rate of lanthanide oxides and nitrates in a 30 vol % TBP-n-paraffin solvent (pre-equilibrated with various nitric acid concentrations) using visible (Vis) spectroscopy over time. Some dissolution mechanics were observed, such as an aqueous layer forming, considerably longer dissolution times for the heavier lanthanides (hours) vs. the lighter lanthanides (minutes), and the impacts of mixing lanthanide oxides or nitrates during dissolution. Neodymium, samarium, holmium, and erbium were selected due to their unique spectroscopic signatures and to represent the lighter (neodymium and samarium) and heavier (holmium and erbium) lanthanides. Even though europium does not have a strong absorbance in the range studied, europium was used in some instances to also represent the lighter lanthanides. Cerium oxide was used to representant dissolution of tetravalent lanthanides.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Bridging the time scale in exascale computing of chemical systems (Final Technical Report)

This report summarizes the work carried out with support of the United States Department of Energy under Award DE-SC0019441. The theme of this project was to develop and apply methods that allowed for the acceleration of atomistic calculations, particularly in challenging areas such as multiphase systems, electrified interfaces, uncertainty estimation, and applications requiring chemical accuracy, which tend to be applications where simulation time is severely bottlenecked by the computational time requirements. Much of the focus was on the application of emerging machine-learning methodologies, although a wide range of methodologies were employed. This report has two major sections. The first focuses on the methodological advances themselves. Within this part, we report a number of major advances, a few examples of which are described here. We report the first machine-learning scheme for the acceleration of electronically grand-canonical calculations (that is, those applicable to electrochemistry). We report new methods of performing transfer learning, in which physics-based priors can be used to provide predictions, often with uncertainty estimates, of images well outside of training sets; we also offer ways to fine-tune these transfer-learning models. We provide a new systematic means to generate and apply minimal training data sets to very large (10,000’s of atoms) systems, with only small training sets appropriate for electronic structure. We developed new methodologies to integrate surface vibrations into surface adsorption calculations. We made advances to the applicability of diffusion Monte Carlo methods to allow (learned) force prediction, finite-size error correction, and force-free means of searching for transition states. We integrated machine-learned atomistic predictions into mechanism generation codes. Additionally, we released new software including AmpTorch, a modernized version of our original atomistic machine-learning code Amp. The second part of this report focuses on the scientific applications that accompanied, and were often enabled by, the methodological advances described earlier. A few examples follow, but full details are in the individual chapters of the report. For example, we developed a general theory of phonon-induced friction on molecular adsorbates. We showed fundamentally how solvent influences the adsorption and desorption process and how it differs from the processes typically involved at the solid–gas interface, making aqueous-phase and electrocatalysis different from traditional thermocatalysis. We examined how metal–insulator and magnetic transitions can be probed, and accelerated exciton dynamics via Frenkel Hamiltonian parameters. We showed that the nearsighted force-training approach, developed within this project, can predict both the stability and reactivity of large nanoparticles, and can also lead to insights on catalyst coverage on binding energies and entropies. These applied studies, which generally integrated with our method development, allowed us to push forward the theoretical understanding of several reaction classes.

08 HYDROGEN↗
DOE OSTI2021

Rate-Based Absorption Modeling for Postcombustion CO 2 Capture with Additively Manufactured Structured Packing

Carbon capture using amine-based solvents in an absorption process is a leading candidate for reducing greenhouse gas emissions in industrial flue gas streams. To reduce operating costs and associated parasitic energy of these processes, process intensification utilizing additively manufactured structured packing has emerged as a new technology to manage exothermic reactions during absorption while improving CO 2 capture. A rate-based model framework has been developed for these novel packings that incorporates the mass and heat transfer phenomena for amine-based absorption of CO 2 . The rate-based model framework is first benchmarked using available solubility data and pilot plant data for aqueous monoethanolamine. The model validation shows accurate prediction of both CO 2 equilibrium partial pressures and ion speciation for solubility data as well as CO 2 capture, temperature profile, and solvent composition for pilot plant data in the absorption column. The model framework is then applied toward predicting the CO 2 capture performance of additively manufactured structured packing. Simulations agree with experimental data in predicting the CO 2 capture and the capture performance increase due to cooling within the structured packing device. Finally, advantages of this rate-based model framework are the utilization of correlations that may predict mass transfer and heat transfer coefficients of the packing based on the geometric properties of the device and the implementation of the model framework in open-source programming.

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

Redox-homogeneous, gel electrolyte-embedded high-mass-loading cathodes for high-energy lithium metal batteries

Lithium metal batteries have higher theoretical energy than their Li-ion counterparts, where graphite is used at the anode. However, one of the main stumbling blocks in developing practical Li metal batteries is the lack of cathodes with high-mass-loading capable of delivering highly reversible redox reactions. To overcome this issue, here we report an electrode structure that incorporates a UV-cured non-aqueous gel electrolyte and a cathode where the LiNi 0.8 Co 0.1 Mn 0.1 O 2 active material is contained in an electron-conductive matrix produced via simultaneous electrospinning and electrospraying. This peculiar structure prevents the solvent-drying-triggered non-uniform distribution of electrode components and shortens the time for cell aging while improving the overall redox homogeneity. Moreover, the electron-conductive matrix eliminates the use of the metal current collector. When a cathode with a mass loading of 60 mg cm -2 is coupled with a 100 µm thick Li metal electrode using additional non-aqueous fluorinated electrolyte solution in lab-scale pouch cell configuration, a specific energy and energy density of 321 Wh kg -1 and 772 Wh L -1 (based on the total mass of the cell), respectively, can be delivered in the initial cycle at 0.1 C (i.e., 1.2 mA cm -2 ) and 25 °C.

25 ENERGY STORAGE↗
DOE OSTI2020

Influence of TMAO as co-solvent on the gelation of silica-PNIPAm core-shell nanogels at intermediate volume fractions

We study the structure and dynamics of poly(N-isopropylacrylamide) (PNIPAm) core-shell nanogels dispersed in aqueous trimethylamine N-oxide (TMAO) solutions by means of smallangle X-ray scattering and X-ray photon correlation spectroscopy (XPCS). Upon increasing the temperature above the lower critical solution temperature of PNIPAm at 33°C, a colloidal gel is formed as identified by an increase of I(q) at small q as well as a slowing down of sample dynamics by various orders of magnitude. With increasing TMAO concentration the gelation transition shifts linearly to lower temperatures. Above a TMAO concentration of approximately 0.40 mol/L corresponding to a 1:1 ratio of TMAO and NIPAm groups, collapsed PNIPAm states are found for all temperatures without any gelation transition. This suggests that reduction of PNIPAm-water hydrogen bonds due to the presence of TMAO results in a stabilisation of the collapsed PNIPAm state and suppresses gelation of the nanogel.

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

The Role of Protons and Hydrides in the Catalytic Hydrogenolysis of Guaiacol at the Ruthenium Nanoparticle-water Interface

The mechanistic roles of free hydronium ions, surface hydrides, and interfacial protons during guaiacol hydrodeoxygenation (HDO) on ruthenium nanoparticles are established. As guaiacol adsorbs on Ru, it loses its strong aromaticity and undergoes a rapid H-shift from its hydroxyl to meta carbons (in relation to its hydroxyl group), leading enol and keto surface isomers to exist in chemical equilibrium. HDO occurs via a hydridic H-adatom (H*) attack to the enol, followed by a kinetically relevant C-O bond rupture step, during which water shuttles the hydroxyl proton, enabling its intramolecular attack to the methoxy, evolving a high charged [Ru(s)-(C6H5O-)…(H+)…OCH3]† transition state. The competing HYD begins with a rapid H* attack to the keto, before a second, kinetically relevant H* attack, without proton involvement. Water, despite shifting the thermodynamics towards the more polar surface keto, promotes HDO to a much greater extent than HYD, because of its dual catalytic roles—it mobilizes hydroxyl proton (Brønsted acid) to cleave the strong C-O bond, synchronizing with the Ru metal surface (base) function that stabilizes the resulting [Ru(s)-(C6H5O-)…(H+)…OCH3]† transition state, and the water layers solvate this charged transition state, further reducing its free energy. Free hydronium ions do catalyze a separate homogeneous enol-keto isomerization, but this reaction is kinetically unrelated to HDO catalysis. This mechanistic picture explains the strong effects of polar protic solvent in hydrodeoxygenation, highlighting (i) the requirements of surface hydrides and interfacial protons acting in tandem to complete a HDO turnover and (ii) the cooperative role of protic solvent and metal surface in breaking the aromaticity and stabilizing charged reactive precursors and transition states.

Shangguan, Junnan↗
DOE OSTI2022

Solvation Thermodynamics of Solutes in Water and Ionic Liquids Using the Multiscale Solvation-Layer Interface Condition Continuum Model

We report molecular assembly processes are generally driven by thermodynamic properties in solutions. Atomistic modeling can be very helpful in designing and understanding complex systems, except that bulk solvent is very inefficient to treat explicitly as discrete molecules. The SLIC/CDC multiscale model combines continuum solvent electrostatics based on the solvent layer interface condition (SLIC) with statistical thermodynamic models for hydrogen bonding and nonpolar modes: cavity formation, dispersion interactions, combinatorial mixing (CDC). The SLIC/CDC model predicts Gibbs energies of solvation for a database of 500 solutes in water with average accuracy better than 1 kcal/mol both for experimental measurements and for explicit-solvent molecular dynamics simulations. The separate SLIC/CDC energy mode values agree quantitatively with those computed from explicit-solvent molecular dynamics. The SLIC/SASA multiscale model combines the SLIC continuum electrostatic model with the solvent accessible surface area (SASA) nonpolar energy mode. The SLIC/SASA model predicts Gibbs energies of solvation with better than 1.4 kcal/mol average accuracy in aqueous systems and better than 1.6 kcal/mol average accuracy in ionic liquids. Both models predict solvation entropies, and are the first implicit-solvation models capable of predicting solvation heat capacities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Origin of Proteolytic Stability of Peptide-Brush Polymers as Globular Proteomimetics

Peptide-brush polymers (PBPs), wherein every side-chain of the polymers is peptidic, represent a new class of proteomimetic with unusually high proteolytic resistance while maintaining bioactivity. Here, we sought to determine the origin of this behavior and to assess its generality via a combined theory and experimental approach. A series of PBPs with various polymer backbone structures were prepared and examined for their proteolytic stability and bioactivity. We discovered that an increase in the hydrophobicity of the polymer backbones is predictive of an elevation in proteolytic stability of the side-chain peptides. Computer simulations, together with small-angle X-ray scattering (SAXS) analysis, revealed globular morphologies for these polymers, in which pendant peptides condense around hydrophobic synthetic polymer backbones driven by the hydrophobic effect. As the hydrophobicity of the polymer backbones increases, the extent of solvent exposure of peptide cleavage sites decreases, reducing their accessibility to proteolytic enzymes. This study provides insight into the important factors driving PBP aqueous-phase structures to behave as globular, synthetic polymer-based proteomimetics.

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

n-Butanol or isobutanol as a value-added fuel additive to inhibit microbial degradation of stored gasoline

Biofouling of gasoline can occur during fuel storage caused by bacteria and fungi that form a biofilm at a fuel/water interface and that produce organic acids and sulfides. Fuel additives are applied to gasoline to prevent biofouling but are relatively expensive, are not always effective against biofilms, and do not contribute to the combustibility of gasoline. Bio-isobutanol is an approved, certified advanced biofuel and is added up to 16% ( v/v ) in gasoline blends “iBut16”; n-butanol blends are currently under review. Microorganisms are inhibited by n-butanol or isobutanol when the aqueous concentration reaches >2-3% (w/ v ). We determined that n-butanol partitions into the aqueous phase of a model gasoline/water system reaching concentrations of 42 g/L and up to 48 g/L from gasoline blends at 10% and 24% ( v/v ), respectively. Likewise, isobutanol blended in gasoline at 10% and 24% ( v/v ) partitioned into an aqueous phase at 45 g/L and 53 g/L, respectively. Several bacterial and fungal strains that originate from fuel storage tanks, or are known to be solvent tolerant, were evaluated for their potential growth in a range of n- and isobutanol concentrations. Growth rates for all strains tested were reduced by 40–100% relative to untreated controls in n- and isobutanol concentrations of 1.5 and 2.0% ( v/v ). No observable growth occurred for any of the microorganisms in solvent concentrations at 3.0% ( v/v ). T amphiphilic and chaotropic properties of n- or isobutanol help them inhibit microbial growth and could serve as effective biocides during fuel storage as well as being valuable fuel additives.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Brush-modified fluorescent organic nanoparticles by ATRP with rigidity-regulated emission

Organic nanoparticles provide exceptional intraparticle tailorability, enabling the incorporation of functional molecules for diverse applications. In this study, we present the synthesis and characterization of fluorescent organic nanoparticles (FoNPs) with encapsulated aggregation-induced emission (AIE) luminogens with emission properties regulated by particle rigidity. Atom transfer radical polymerization (ATRP) was employed in dispersed media to develop various fluorescence colors tuned by precise control over particle rigidity. Comprehensive analyses revealed that increased particle rigidity significantly enhanced photoluminescence, achieving quantum yields of up to 22% in selected solvents. The high chain-end fidelity facilitated the grafting of hydrophilic polymer brushes from surfaces of FoNPs used as macroinitiators, enabling their dispersion in aqueous media while maintaining bright fluorescence. These findings highlight the potential of rigidity-regulated FoNPs as versatile platforms for advanced material applications, particularly in fluorescent waterborne films and aqueous-phase sensing systems.

Yin, Rongguan [Carnegie Mellon Univ., Pittsburgh, ↗