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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Inverse chirality-induced spin selectivity effect in chiral assemblies of π -conjugated polymers

Coupling of spin and charge currents to structural chirality in non-magnetic materials, known as chirality-induced spin selectivity, is promising for application in spintronic devices at room temperature. Although the chirality-induced spin selectivity effect has been identified in various chiral materials, its Onsager reciprocal process, the inverse chirality-induced spin selectivity effect, remains unexplored. Here we report the observation of the inverse chirality-induced spin selectivity effect in chiral assemblies of π-conjugated polymers. Using spin-pumping techniques, the inverse chirality-induced spin selectivity effect enables quantification of the magnitude of the longitudinal spin-to-charge conversion driven by chirality-induced spin selectivity in different chiral polymers. By widely tuning conductivities and supramolecular chiral structures via a printing method, we found a very long spin relaxation time of up to several nanoseconds parallel to the chiral axis. Furthermore, our demonstration of the inverse chirality-induced spin selectivity effect suggests possibilities for elucidating the puzzling interplay between spin and chirality, and opens a route for spintronic applications using printable chiral assemblies.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Sequence-dependent self-assembly of supramolecular nanofibers in periodic dynamic block copolymers

Block copolymers (BCPs) can spontaneously self-assemble into various nanostructured morphologies which enable their diverse applications in selective membranes, polymer electrolytes, and optoelectronics. To expand the range of nanostructures accessible to block copolymers, we designed dynamic block copolymers (DBCPs) that combine the phase separation of traditional block copolymers with the supramolecular self-assembly of periodic dynamic polymers. We demonstrate that DBCPs synthesized with a periodic block sequence self-assemble into high aspect ratio supramolecular nanofibers with well-ordered PEG and PDMS domains, in contrast to those synthesized with a random sequence which do not form nanofibers but have disordered morphologies. The periodicity of the block sequence ensures regular placement of dynamic bonds along the polymer chain, which enables stacking of the hydrogen bonding units into ordered 1D supramolecular nanofibers and delays the onset of terminal flow by up to 60 °C compared to the random block sequence. The hierarchically assembled supramolecular nanofibers display complex mechanical and thermal phase behavior arising from the interplay between phase separation of the dissimilar polymer backbones and supramolecular interactions between dynamic bonds. Despite identical bulk composition, the periodic DBCPs demonstrate ionic conductivity values over two orders of magnitude higher than their random counterparts due to the formation of well-ordered, interconnected, high aspect ratio ion-transporting PEG domains. In conclusion, these results highlight the potential for DBCPs as an emerging material platform to achieve advanced, self-assembled nanostructured morphologies.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Porous Polymers as Universal Reversal Agents for Heparin Anticoagulants through an Inclusion–Sequestration Mechanism

Heparins are widely used anticoagulants for surgical procedures and extracorporeal therapies. However, all of them have bleeding risks. Protamine sulfate, the only clinically approved antidote for unfractionated heparin (UFH), has adverse effects. Moreover, protamine can only partially neutralize low-molecular-weight heparins (LMWHs) and is not effective for fondaparinux. In this report an inclusion–sequestration strategy for efficient neutralization of heparin anticoagulants by cationic porous supramolecular organic frameworks (SOFs) and porous organic polymers (POPs) is reported. Isothermal titration calorimetric and fluorescence experiments show strong binding affinities of these porous polymers toward heparins, whereas dynamic light scattering and zeta potential analysis confirm that the heparin sequences are adsorbed into the interior of the porous hosts. Activated partial thromboplastin time, anti-FXa, and thromboelastography assays indicate that their neutralization efficacies are higher than or as high as that of protamine for UFH and generally superior to protamine for LMWHs and fondaparinux, which is further confirmed by tail-transection model in mice and ex vivo aPTT or anti-FXa analysis in rats. Acute toxicity evaluations reveal that one of the SOFs displays outstanding biocompatibility. This work suggests that porous polymers can supply safe and rapid reversal of clinically used heparins, as protamine surrogates, providing an improved approach for their neutralization.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Architecture of a catalytically active homotrimeric plant cellulose synthase complex

Cellulose is an essential plant cell wall component and represents the most abundant biopolymer on Earth. Supramolecular plant cellulose synthase complexes organize multiple linear glucose polymers into microfibrils as load-bearing wall components. We determined the structure of a poplar cellulose synthase CesA homotrimer that suggests a molecular basis for cellulose microfibril formation. This complex, stabilized by cytosolic plant-conserved regions and helical exchange within the transmembrane segments, forms three channels occupied by nascent cellulose polymers. Secretion steers the polymers toward a common exit point, which could facilitate protofibril formation. CesA’s N-terminal domains assemble into a cytosolic stalk that interacts with a microtubule-tethering protein and may thus be involved in CesA localization. Here, our data suggest how cellulose synthase complexes assemble and provide the molecular basis for plant cell wall engineering.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Protein Assembly by Design

Proteins are nature’s primary building blocks for the construction of sophisticated molecular machines and dynamic materials, ranging from protein complexes such as photosystem II and nitrogenase that drive biogeochemical cycles to cytoskeletal assemblies and muscle fibers for motion. Such natural systems have inspired extensive efforts in the rational design of artificial protein assemblies in the last two decades. As molecular building blocks, proteins are highly complex, in terms of both their three-dimensional structures and chemical compositions. To enable control over the self-assembly of such complex molecules, scientists have devised many creative strategies by combining tools and principles of experimental and computational biophysics, supramolecular chemistry, inorganic chemistry, materials science, and polymer chemistry, among others. Owing to these innovative strategies, what started as a purely structure-building exercise two decades ago has, in short order, led to artificial protein assemblies with unprecedented structures and functions and protein-based materials with unusual properties. Furthermore, our goal in this review is to give an overview of this exciting and highly interdisciplinary area of research, first outlining the design strategies and tools that have been devised for controlling protein self-assembly, then describing the diverse structures of artificial protein assemblies, and finally highlighting the emergent properties and functions of these assemblies.

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

Systematic Evaluation of Counterpoise Correction in Density Functional Theory

A widespread belief persists that the Boys–Bernardi function counterpoise (CP) procedure “overcorrects” supramolecular interaction energies for the effects of basis-set superposition error. To the extent that this is true for correlated wave function methods, it is usually an artifact of low-quality basis sets. The question has not been considered systematically in the context of density functional theory, however, where basis-set convergence is generally less problematic. We present a systematic assessment of the CP procedure for a representative set of functionals and basis sets, considering both benchmark data sets of small dimers and larger supramolecular complexes. The latter include layered composite polymers with ~150 atoms and ligand–protein models with ~300 atoms. Provided that CP correction is used, we find that intermolecular interaction energies of nearly complete-basis quality can be obtained using only double-ζ basis sets. Furthermore, this is less expensive as compared to triple-ζ basis sets without CP correction. CP-corrected interaction energies are less sensitive to the presence of diffuse basis functions as compared to uncorrected energies, which is important because diffuse functions are expensive and often numerically problematic for large systems. Our results upend the conventional wisdom that CP “overcorrects” for basis-set incompleteness. In small basis sets, CP correction is mandatory in order to demonstrate that the results do not rest on error cancellation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Kinetically Controlled Formation of Semi-crystalline Conjugated Polymer Nanostructures

Conjugated polymer (CP) materials that are considered as an attractive choice for various electronic and optoelectronic applications possess highly heterogeneous complex structures that can span several orders of magnitude in length scale. This is due to the intricate coupling effects of weak secondary interactions and entropic forces that determine molecular organization in bulk polymer materials. Understanding the influence of molecular interactions on the emergence and evolution of nano- and microscale structures is of paramount importance to the guided design and development of condensed CP materials. Such understanding is even more critical for the rational design of hierarchical systems away from equilibrium, where weak molecular interactions can guide the system along competing kinetic pathways toward local energy minima and metastable architectures. In this work, we studied a promising concept for accessing various kinetically stabilized semi-crystalline CP nanostructures that are formed in the process of controlled chain-growth Kumada catalyst-transfer polymerization initiated by a small-molecule catalytic species which can exist in equilibrium between free and aggregated states. Specifically, we chose a small-molecule perylenedicarboximide (PDCI) polymerization catalytic initiator which has a strong tendency toward reversible supramolecular assembly–disassembly that can be controlled by temperature. Addition of a thiophene monomer to a solution of the PDCI initiator starts the chain-growth polymerization process, which produces distinct nanoscale semi-crystalline polythiophene structures formed under predominant kinetic control. Furthermore, we demonstrated that, depending on the reaction temperature (which affects the fine balance between the position of PDCI assembly–disassembly equilibrium, rate of polymerization, and solvent–solute interactions for the growing polythiophene chains), a range of kinetically trapped hierarchically organized semi-crystalline CP systems with substantially varying optoelectronic properties could be obtained. In addition to spectroscopic and electron microscopic studies, in order to better reveal the structural aspects of the generated polymer nanoscale systems, we carried out a series of X-ray diffraction and neutron scattering experiments which indicated complex hierarchical organization in these kinetically stabilized CP assembled materials. We expect that this in situ polymerization-based approach can lead to a general way to expand access to various semi-crystalline CP nanostructured materials with broadly tunable electronic and optical properties.

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

Intra- and Intermolecular Self-Assembly of a 20-nm-Wide Supramolecular Hexagonal Grid.

For the past three decades, the coordination-driven self-assembly of three-dimensional structures has undergone rapid progress; however, parallel efforts to create large discrete two-dimensional architectures-as opposed to polymers-have met with limited success. The synthesis of metallo-supramolecular systems with well-defined shapes and sizes in the range of 10-100 nm remains challenging. Here we report the construction of a series of giant supramolecular hexagonal grids, with diameters on the order of 20 nm and molecular weights greater than 65 kDa, through a combination of intra- and intermolecular metal-mediated self-assembly steps. The hexagonal intermediates and the resulting self-assembled grid architectures were imaged at submolecular resolution by scanning tunnelling microscopy. Characterization (including by scanning tunnelling spectroscopy) enabled the unambiguous atomic-scale determination of fourteen hexagonal grid isomers.

Zhang, Zhe↗
DOE OSTI2022

Medial packing and elastic asymmetry stabilize the double-gyroid in block copolymers

Triply-periodic networks are among the most complex and functionally valuable self-assembled morphologies, yet they form in nearly every class of biological and synthetic soft matter building blocks. In contrast to simpler assembly motifs – spheres, cylinders, layers – networks require molecules to occupy variable local environments, confounding attempts to understand their formation. Here, we examine the double-gyroid network phase by using a geometric formulation of the strong stretching theory of block copolymer melts, a prototypical soft self-assembly system. The theory establishes the direct link between molecular packing, assembly thermodynamics and the medial map, a generic measure of the geometric center of complex shapes. We show that “medial packing” is essential for stability of double-gyroid in strongly-segregated melts, reconciling a long-standing contradiction between infinite- and finite-segregation theories. Additionally, we find a previously unrecognized non-monotonic dependence of network stability on the relative entropic elastic stiffness of matrix-forming to tubular-network forming blocks. The composition window of stable double-gyroid widens for both large and small elastic asymmetry, contradicting intuitive notions that packing frustration is localized to the tubular domains. This study demonstrates the utility of optimized medial tessellations for understanding soft-molecular assembly and packing frustration via an approach that is readily generalizable far beyond gyroids in neat block copolymers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Antifouling strategies for protecting bioelectronic devices

Bioelectronic devices are playing an increasingly important role in many areas of our lives. They power a significant portion of medical diagnostics and are becoming more and more important for delivery of therapeutics and monitoring of chronic symptoms. However, surface fouling phenomena, and especially biofouling in complex biological fluids, restricts the performance of these devices and severely reduces their useful lifespan. In this Research Update, we discuss the main principles and strategies that researchers use to prevent fouling and minimize or remove the foulants from bioelectronic device surfaces. We also survey a variety of antifouling approaches that can enhance device performance.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structural elucidation of polydopamine facilitated by ionic liquid solvation

Minimal understanding of the formation mechanism and structure of polydopamine (pDA) and its natural analogue, eumelanin, impedes the practical application of these versatile polymers and limits our knowledge of the origin of melanoma. The lack of conclusive structural evidence stems from the insolubility of these materials, which has spawned significantly diverse suggestions of pDA's structure in the literature. We discovered that pDA is soluble in certain ionic liquids. Using these ionic liquids (ILs) as solvents, we present an experimental methodology to solvate pDA, enabling us to identify pDA's chemical structure. The resolved pDA structure consists of self-assembled supramolecular aggregates that contribute to the increasing complexity of the polymer. The underlying molecular energetics of pDA solvation and a macroscopic picture of the disruption of the aggregates using IL solvents have been investigated, along with studies of the aggregation mechanism in water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect orders-of-magnitude increase in strength, nevertheless, by varying the polymer we expect to impart other properties such as hydrophobicity, thermal stability and perhaps electrical conductivity. Besides polymers, crosslinkers will include metals and ceramics (e.g., through POSS precursors). Finally, network morphology directs load dissipation, and of approximately 30 different crosslinked oxide aerogels, vanadia, whose structure is fibrous rather than particulate, yields a much stronger (by 4..) material than silica of the same density. It seems imperative to implement control of network morphology, even through templating.

Leventis, Nicholas↗
DOE OSTI2024

Developmental assembly of multi-component polymer systems through interconnected synthetic gene networks in vitro

Abstract Living cells regulate the dynamics of developmental events through interconnected signaling systems that activate and deactivate inert precursors. This suggests that similarly, synthetic biomaterials could be designed to develop over time by using chemical reaction networks to regulate the availability of assembling components. Here we demonstrate how the sequential activation or deactivation of distinct DNA building blocks can be modularly coordinated to form distinct populations of self-assembling polymers using a transcriptional signaling cascade of synthetic genes. Our building blocks are DNA tiles that polymerize into nanotubes, and whose assembly can be controlled by RNA molecules produced by synthetic genes that target the tile interaction domains. To achieve different RNA production rates, we use a strategy based on promoter “nicking” and strand displacement. By changing the way the genes are cascaded and the RNA levels, we demonstrate that we can obtain spatially and temporally different outcomes in nanotube assembly, including random DNA polymers, block polymers, and as well as distinct autonomous formation and dissolution of distinct polymer populations. Our work demonstrates a way to construct autonomous supramolecular materials whose properties depend on the timing of molecular instructions for self-assembly, and can be immediately extended to a variety of other nucleic acid circuits and assemblies.

Science & Technology - Other Topics↗
DOE OSTI2020

Disulfonated Poly(arylene ether sulfone) Random Copolymers Containing Hierarchical Iptycene Units for Proton Exchange Membranes

Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30–50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

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

Supramolecular Arene‐Perfluoroarene Assembly Enhances Photoiniferter Polymerization Kinetics

Ultra-high-molecular-weight (UHMW, >106 Da) polymers have unique thermomechanical properties due to their large number of physical entanglements. Producing UHMW styrenic polymers is challenging because of their prohibitively slow homopolymerization kinetics. In this report, we show that alternating photoiniferter copolymerization between methoxy-functionalized styrenic monomers and pentafluorostyrene can circumvent this limitation under conditions where arene–perfluoroarene (AP) interactions contribute to favorable monomer association and accelerate copolymerization. Increasing methoxy substitution on the styrene arene ring leads to pronounced rate enhancements that correlate with electronic complementarity between the styrenic comonomers. Density functional theory calculations reveal increasingly favorable AP interaction energies across the series, consistent with monomer association contributing to faster propagation. The result is up to 2000% enhancement in propagation rate in copolymerizations compared to styrene homopolymerization. Despite these rate enhancements, the resulting materials retain broadly similar glass-transition temperatures and network-like thermomechanical behavior, with only modest softening across the series. Here, we then leverage the approach to produce UHMW trialkoxystyrene copolymers bearing sterically encumbered pendants, which are ultrasoft (Young's modulus of 8 kPa) and highly extensible (560%). These results establish that designed supramolecular association between styrenics is a powerful tool for controlling reactivity in radical polymerization and generating otherwise difficult-to-obtain materials.

Marquez, Joshua D. [University of Florida, Gainesv↗
DOE OSTI2025

Sub‐5 Ångstrom Porosity Tuning in Calixarene‐Derived Porous Liquids via Supramolecular Complexation Construction

Abstract Sub‐Ångstrom‐level porosity engineering, which is appealing in gas separations, has been demonstrated in solid carbon, polymer, and framework materials but rarely achieved in the liquid phase. In this work, a gas molecular sieving effect in the liquid phase at sub‐5 Ångstrom scale is created via sophisticated porosity tuning in calixarene‐derived porous liquids (PLs). Type II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents. The chemical structure variation and assembly behavior of the porous host upon PL construction are monitored by spectroscopy‐, X‐ray‐, and neutron‐scattering techniques. The presence of permanent porosity in calixarene‐derived PLs is verified by pressure swing gas uptake, altered CO 2 physisorption behavior, and molecular simulations. Sub‐5 Ångstrom porosity tuning within the PL phase is achieved by introducing bulky substituted groups on the benzene ring of the calixarene host, which then greatly affects the dynamic motion and transport behavior of CO 2 molecules and the Xe uptake performance. The approach being demonstrated in this work represents a promising pathway to tune and leverage the porosity effect for enhanced gas uptake capacity and selectivity in liquid sorbents.

Li, Errui [Department of Chemistry University of T↗