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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Modulating Solvation Structure in Concentrated Aqueous Organic Redox Flow Battery Electrolyte for Solubility and Transport Enhancement via Polycomplex Ion

Aqueous organic redox flow batteries hold great promise as a technology for creating economical grid energy storage using sustainable materials. Nonetheless, the solubility limit presents a universal barrier for all redox-active organic molecules. In this paper, a new approach is proposed to surpass the solubility limit by manipulating the solvation structure with polycomplex ion additives (PIA). Using poly(3,4-ethylenedioxythiophene) polystyrenesulfonate colloids as one example, its role in dismantling the rigid supramolecular clusters within the highly concentrated 7,8-dihydroxyphenazine-2-sulfonic acid electrolyte is investigated. 1 H and 23 Na NMR spectra and molecular dynamics simulation studies demonstrate that the bipolar structure of the PIA effectively disrupts the aggregations of DHPS and Na + ion in the highly concentrated anolyte, thus rendering a more flexible solvation structure and less restrictive ion transport, leading to substantially improved battery performance of an AORFB cell. The anolyte with PIA achieved 1.6 M and 74.3 Ah L –1 anolyte energy capacity.

25 ENERGY STORAGE↗
DOE OSTI2024

Confinement-induced clustering of H 2 and CO 2 gas molecules in hydrated nanopores

Gas molecule clustering within nanopores holds significance in the fields of nanofluidics, biology, gas adsorption/desorption, and geological gas storage. However, the intricate roles of nanoconfinement and surface chemistry that govern the formation of gas clusters remain inadequately explored. In this study, through free energy calculation in molecular simulations, we systematically compared the tendencies of H 2 and CO 2 molecules to aggregate within hydrated hydrophobic pyrophyllite and hydrophilic gibbsite nanopores. The results indicate that nanoconfinement enhances gas dimer formation in the nanopores, irrespective of surface chemistry. However, surface hydrophilicity prohibits the formation of gas clusters larger than dimers, while large gas clusters form easily in hydrophobic nanopores. Despite H 2 and CO 2 both being non-polar, the larger quadrupole moment of CO 2 leads to a stronger preference for dimer/cluster formation compared to H 2 . Here, our results also indicate that gases prefer to enter the nanopores as individual molecules, but exit the nanopores as dimers/clusters. This investigation provides a mechanistic understanding of gas cluster formation within nanopores, which is relevant to various applications, including geological gas storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Understanding amyloids to prevent biofilm formation in space

There is a pressing need to search for novel approaches to combat biofilm formation, both in space and in medical applications. Many proteins have the ability to form ordered aggregates called amyloids. Amyloids are known to be an important part of biofilms. The use of anti-amyloid drugs is a novel venue for the development of antimicrobial agents. The ultrastructure of the amyloid aggregate shows a high packing of proteins, the second-order structure of which is dominated by β-sheets. The ability to form an amyloid aggregate is especially typical for proteins containing domains (protein fragments) with sufficient lability to arrange themselves in a tight β-sheet structure. Bioinformatics tools allow the prediction of such behavior of proteins in genomic data. We use GeneLab data of microbial populations identified aboard the International Space Station and other spacecraft to look for bacterial species that utilize amyloid aggregation in biofilm formation. We use a combined bioinformatic approach with a relatively high throughput molecular biology assay and biophysical assays to evaluate the anti-amyloid anti-biofilm approach. The significance of the research extends from understanding basic microbial community responses to spaceflight, to biofouling of the built environments in space as well as the long-term health of astronauts. Bioinformatics shows that onboard the ISS, bacterial species produce far more amyloid and prion proteins than are currently verified, hence their role in bacterial ecosystems is largely unknown. As we propose there is a link between amyloid formation in space and biofilm production, this research should lead to new paths for biofilm remediation in space.

Tomasz Zajkowski↗
DOE OSTI2023

Temperature-based reactive flow model for TATB plastic bonded explosives

A new reactive flow model is presented for TATB-based plastic bonded explosives, applicable to shock initiation and detonation problems of differing initial temperature. Temperature disequilibrium is assumed between unreacted explosive, material in the vicinity of compressed defects (called hot spots), and detonation products. The model incorporates temperature-dependent decomposition reaction rates. Arrhenius model parameters were derived from subscale quantum-based molecular dynamics simulations of shock-induced TATB decomposition. Further, a model of detonation carbon aggregation is incorporated, describing the late-time slow release of energy inherent to detonation in TATB-based materials. The predictive ability of the model in the shock initiation regime is tested against recent thin pulse experiments on PBX 9502. Here, the model is found to perform equally well in predicting the size effect curve of ambient, cold, and hot PBX 9502 rate sticks.

Chemistry - Chemical explosives↗
DOE OSTI2020

Self-Assembled Solute Networks in Crowded Electrolyte Solutions and Nanoconfinement of Charged Redoxmer Molecules

Redoxmers are electrochemically active organic molecules storing charge and energy in electrolyte fluids circulating through redox flow batteries (RFBs). Such molecules typically have solvent-repelling cores and solvent-attracting pendant groups introduced to increase solubility in liquid electrolytes. These two features can facilitate nanoscale aggregation of the redoxmer molecules in crowded solutions. In some cases, this aggregation leads to the emergence of continuous networks of solute molecules in contact, and the solution becomes microscopically heterogeneous. In this study, we used small-angle X-ray scattering (SAXS) and molecular dynamics modeling to demonstrate formation of such networks and examine structural factors controlling this self-assembly. We also show that salt ions become excluded from these solute aggregates into small pockets of electrolytes, where these ions strongly associate. This confinement by exclusion is also likely to occur to charged redoxmer molecules in a “sea” of neutral precursors coexisting in the same solution. Here, we demonstrate that the decay lifetime of the confined charged molecules in such solutions can increase several fold compared to dilute solutions. We attribute this behavior to a “microreactor effect” on reverse reactions of the confined species during their decomposition.

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

MCCCS-MN

The MCCCS‒MN (Monte Carlo for Complex Chemical Systems‒Minnesota) software is developed by the Siepmann research group at the University of Minnesota. MCCCS‒MN allows for the simulation of multi-component molecular systems in the canonical, isobaric-isothermal (including constant stress for solids), grand-canonical, semi-grand, and Gibbs (NVT, NPT, and more than two simulation boxes) ensembles. It uses the configurational-bias Monte Carlo method to efficiently sample phase space for linear, branched and cyclic chain molecules, the adiabatic nuclear and electronic sampling Monte Carlo method to treat many-body polarization effects, and the aggregation-volume-bias Monte Carlo algorithm to efficiently sample the spatial distribution of associating molecules. MCCCS-MN employs a molecular representation of the system where force fields contain bonded and non-bonded terms. Funding for the development of MCCCS-MN through grants from the National Science Foundation (simulation of fluid phase equilibria and chromatography) and the Department of Energy (simulation of adsorption equilibria) is gratefully acknowledged.

Siepmann, J.Ilja [University of Minnesota - Twin C↗
NASA NTRS1994

Disintegration of Dust Aggregates in Interstellar Shocks and the Lifetime of Dust Grains in the ISM

Interstellar grains are destroyed by shock waves moving through the ISM. In fact, the destruction of grains may be so effective that it is difficult to explain the observed abundance of dust in the ISM as a steady state between input of grains from stellar sources and destruction of grains in shocks. This is especially a problem for the larger grains. Therefore, the dust grains must be protected in some way. Jones et al. have already considered coatings and the increased post-shock drag effects for low density grains. In molecular clouds and dense clouds, coagulation of grains is an important process, and the largest interstellar grains may indeed be aggregates of smaller grains rather than homogeneous particles. This may provide a means to protect the larger grains, in that, in moderate velocity grain-grain collisions in a shock the aggregates may disintegrate rather than be vaporized. The released small particles are more resilient to shock destruction (except in fast shocks) and may reform larger grains later, recovering the observed size distribution. We have developed a model for the binding forces in grain aggregates and apply this model to the collisions between an aggregate and fast small grains. We discuss the results in the light of statistical collision probabilities and grain life times.

Dominik, C.↗
DOE OSTI2022

Ionic Liquid Facilitated Solvent‐Phase Polymerization of Ultrasmooth Coatings of Polycatecholamines

Mussel-inspired polycatecholamine coatings and films have proven to be versatile materials for surface modification. However, the progress of chemically modified coatings with tailored properties has been slow due to the lack of definitive evidence of their polymeric structure. Polycatecholamines form aggregates during polymerization, and their formation mechanism has been a subject of debate owing to their insolubility in traditional molecular solvents. Exploiting the capability of ionic liquids (ILs) to exhibit strong electrostatic interactions, herein, the first solution-phase polymerization approach is reported to achieve polymerization of four catecholamines – dopamine (DA), norepinephrine (NE), L-3,4-dihydroxyphenylalanine (L-DOPA), and adrenaline (AD). Kinetic control over the polymerization process in the solution phase enabled it to follow the process with 1 H NMR spectroscopy, revealing the formation of structural features of resulting complex heterogeneous and soluble polymers. The polymers are both covalent and associative in nature. Solution phase polymerization prevented the formation of large aggregates in the solution, thus facilitating the formation of coatings that are ultra-smooth and have root mean square roughness of the order of sub-nm to nm scale.

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

Why Does Oriented Attachment Produce Low-Dimensional Structures?

Oriented attachment is a nonclassical crystal growth mechanism that frequently leads to the formation of low-dimensional nanocrystals, such as nanowires or nanoplates, as well as intricately branched nanocrystals. This chapter discusses several experimentally observed instances of such structures, as well as theoretical efforts to understand them. Recent molecular-dynamics simulation studies in our group aimed at understanding how oriented attachment could promote the aggregation of Ag nanoplates to produce two-dimensional sheets are highlighted. Here, the mechanism found in this study may extend to other systems for which lowdimensional crystal growth occurs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

O-GlcNAc forces an α-synuclein amyloid strain with notably diminished seeding and pathology

Amyloid-forming proteins such α-synuclein and tau, which are implicated in Alzheimer’s and Parkinson’s disease, can form different fibril structures or strains with distinct toxic properties, seeding activities and pathology. Understanding the determinants contributing to the formation of different amyloid features could open new avenues for developing disease-specific diagnostics and therapies. Here we report that O-GlcNAc modification of α-synuclein monomers results in the formation of amyloid fibril with distinct core structure, as revealed by cryogenic electron microscopy, and diminished seeding activity in seeding-based neuronal and rodent models of Parkinson’s disease. Although the mechanisms underpinning the seeding neutralization activity of the O-GlcNAc-modified fibrils remain unclear, our in vitro mechanistic studies indicate that heat shock proteins interactions with O-GlcNAc fibril inhibit their seeding activity, suggesting that the O-GlcNAc modification may alter the interactome of the α-synuclein fibrils in ways that lead to reduce seeding activity in vivo. Our results show that posttranslational modifications, such as O-GlcNAc modification, of α-synuclein are key determinants of α-synuclein amyloid strains and pathogenicity.

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

Associative polymers with controlled sticker placement: How reversible bond distribution and density govern polymer dynamics

Associative polymers with precisely arranged stickers offer opportunities to program material properties with molecular precision. Yet, it remains unclear how the placement and fraction of stickers dictate structure, dynamics, and macroscopic properties. By developing a model unentangled polymer system with hydrogen-bonding stickers, we show that randomly distributed stickers neither form clusters nor change flow properties, whereas stickers placed at chain ends drive nanocluster formation even at low concentrations. Adding more end stickers produces a rubbery plateau spanning eight decades in frequency with two distinct relaxation timescales, in contrast to the single plateau predicted by the classic sticky Rouse model. These results demonstrate that sticker distribution dictates whether associative polymers undergo nanocluster formation or microphase separation, while substantial alterations in dynamics and viscoelasticity require both sticker aggregation and thermomechanical stability of associated domains. Our findings resolve a longstanding debate on associative polymer dynamics and provide molecular design rules for programmable soft materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Variable-Temperature Scattering and Spectroscopy Characterizations for Temperature-Dependent Solution Assembly of PffBT4T-Based Conjugated Polymers

The solution structure of conjugated polymers (CPs) from which the films are cast is critical for tailoring the thin-film morphology thus device performance. Here, we used multimodal variable-temperature scattering and spectroscopy tools to fully quantify the solution assembly of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-dialkyl-2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PffBT4T) polymers with varying side-chain lengths at different assembly temperatures. The conformational and aggregation behaviors for PffBT4T-based CPs were found to be very sensitive to both temperature and side chain length using ultraviolet–visible (UV–vis) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and small-angle neutron scattering (SANS). We found that with slightly increasing side chain length from 2-octyldodecyl (C8C12) to 2-nonyltridecyl (C9C13), PffBT4T-based CPs show a significant decrease in aggregation-to-dissolved chain transition temperature (10 °C), degree of aggregation, enthalpy change of aggregation, and size of the aggregates in solution. At room temperature, PffBT4T polymer strongly aggregated to form fabric structure with the film thickness of a few nanometers in thickness and hundreds of nanometers in length, as probed by atomic force microscopy (AFM), transmission electronic microscopy (TEM), and dynamic light scattering (DLS). At the elevated temperature above the aggregation-to-dissolved chain transition temperature, PffBT4T is fully dissolved and adopts a semiflexible coil conformation with the persistence length of 3.1 nm for PffBT4T-C8C12 and a slightly increased persistence length of 3.4 nm for PffBT4T-C9C13, according to temperature-dependent SANS measurements. Longer side chains of PffBT4T-C9C13 also lead to less aggregation enthalpy gain compared with PffBT4T-C8C12. This work provides a solution structure manipulating strategy of CPs and thus will inspire the molecular design and processing protocols of CPs toward higher performance electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Influence of substituents on the vectorial difference static dipole upon excitation in synthetic bacteriochlorins

Organic dye aggregates have been shown to exhibit exciton delocalization in natural and synthetic systems. Such dye aggregates show promise in the emerging area of quantum information science (QIS). We believe that the difference static dipole (Δd) is an essential dye parameter in the development of molecular QIS systems. However, a foundational understanding of the structural factors influencing Δd remains elusive. Bacteriochlorins play a vital role in photosynthesis due to their exceptional photophysical properties. Therefore, bacteriochlorins are particularly suitable dyes for the construction of aggregate systems for QIS. Synthetic bacteriochlorins further offer stability and tunability via chemical modifications. Here, the influence of substituents on the Δd of monomeric (non-aggregated) dyes was investigated via density functional theory (DFT) and time-dependent (TD-)DFT in a set of 5-methoxybacteriochlorins progressively substituted with ethynyl, phenyl, and phenylethynyl substituents at the 3,13- and 3,13,15-positions of the macrocycle. Symmetrically substituted 5-methoxybacteriochlorins were shown to have the largest Δd. The increase in Δd in the series of dyes was largely due to changes in orientation of the static dipole upon excitation rather than large changes in magnitude. In addition, the transition dipole (μ) and the angle between Δd and μ (ζ) were calculated. Three 5-methoxybacteriochlorins with high predicted Δd and μ were synthesized and characterized spectroscopically. The trend in Δd values empirically determined using the solvatochromic Stokes shift method was comparable with the DFT calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The Influence of Alkyl Spacers and Molecular Weight on the Charge Transport and Storage Properties of Oxy‐Bithiophene‐Based Conjugated Polymers

Abstract Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy‐bithiophene‐based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field‐effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non‐polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.

Yu, Hang [Department of Physics and Centre for Pro↗
DOE OSTI2026

Disentangling cation effects on ion mobility and structure in ionic liquid electrolytes

Ionic liquids (ILs) are low-temperature molten salts, where ion transport is primarily governed by ion–ion interactions. Yet, the impact of organic IL cations on critical electrolyte properties such as ion dissociation and overall transport behavior in lithium-salt-doped ILs remains poorly understood. Moreover, despite their critical role in designing IL-based electrolytes for energy storage applications, ion–ion interactions and ion-specific transport under an applied electrical potential are seldom quantified, largely due to the unique experimental and computational challenges involved. Herein, we compare transport properties obtained using 1 H, 7 Li, and 19 F pulsed-field gradient nuclear magnetic resonance (NMR) and electrophoretic NMR (eNMR) with those measured by electrochemical impedance spectroscopy. Non-equilibrium molecular dynamics (MD) simulations and eNMR confirm the presence of negatively charged [Li(TFSI) n ] (1−n) aggregates that migrate towards the positive electrode, resulting in negative lithium transference numbers. Equilibrium MD simulations reveal a vehicular Li ion transport mechanism facilitated by long-lived aggregates with Li + cations strongly bound to multiple TFSI − anions. Finally, we observe an inverse relationship between the apparent charge of the TFSI − anion in the neat IL, which is dictated by the IL cation, and Li + transport in the salt-doped systems. This highlights the opportunity to tune electrolyte performance by tailoring cation chemistry.

Li-ion batteries↗
DOE OSTI2024

The Influence of Alkyl Spacers and Molecular Weight on the Charge Transport and Storage Properties of Oxy‐Bithiophene‐Based Conjugated Polymers

Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy-bithiophene-based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field-effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non-polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.

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

Giant Concentric Metallosupramolecule with Aggregation-Induced Phosphorescent Emission

Fluorescent metallo-supramolecules have received considerable attention due to their precisely-controlled dimensions as well as the tunable photophysical and photochemical properties. However, phosphorescent analogues are still rare, and limited to small structures with low-temperature phosphorescence. In this work, we report the self-assembly and photophysical studies of a giant, discrete metallo-supramolecular concentric hexagon functionalized with six alkynylplatinum(II) bzimpy moieties. With a size larger than 10 nm and molecular weight higher than 26,000 Da, the assembled terpyridine-based supramolecule displayed phosphorescent emission at room temperature. Moreover, the supramolecule exhibited enhanced aggregation-induced phosphorescent emission compared to the ligand by tuning the aggregation states through intermolecular interactions, and significant enhancement of emission to CO 2 gas.

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

Precision Loading and Delivery of Molecular Cargo by Size-Controlled Coacervation of Gold Nanoparticles Functionalized with Elastin-like Peptides

Thermoresponsive elastin-like peptides (ELPs) have been extensively investigated in biotechnology and medicine, but little attention has been paid to the process by which coacervation causes ELP-decorated particles to aggregate. Here, using gold nanoparticles (AuNPs) functionalized with a cysteine-terminated 96-repeat of the VPGVG sequence (V96-Cys), we show that the size of the clusters that reversibly form above the ELP transition temperature can be finely controlled in the 250 to 930 nm range by specifying the concentration of free V96-Cys in solution and using AuNPs of different sizes. We further find that the localized surface plasmon resonance peak of the embedded AuNPs progressively red-shifts with cluster size, likely due to an increase in particle–particle contacts. We exploit this fine control over size to homogeneously load precise amounts of the dye Nile Red and the antibiotic Tetracycline into clusters of different hydrodynamic diameters and deliver cargos near-quantitatively by deconstructing the aggregates below the ELP transition temperature. Beyond establishing a key role for free ELPs in the agglomeration of ELP-functionalized particles, our results provide a path for the thermally controlled delivery of precise quantities of molecular cargo. This capability might prove useful in combination photothermal therapies and theranostic applications, and to trigger spatially and temporally uniform responses from biological, electronic, or optical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗