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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 235 records · Page 13

Hierarchical Materials from High Information Content Macromolecular Building Blocks: Construction, Dynamic Interventions, and Prediction

Hierarchical materials that exhibit order over multiple length scales are ubiquitous in nature. Because hierarchy gives rise to unique properties and functions, many have sought inspiration from nature when designing and fabricating hierarchical matter. More and more, however, nature’s own high-information content building blocks, proteins, peptides, and peptidomimetics, are being coopted to build hierarchy because the information that determines structure, function, and interfacial interactions can be readily encoded in these versatile macromolecules. Here, we take stock of recent progress in the rational design and characterization of hierarchical materials produced from high-information content blocks with a focus on stimuli-responsive and “smart” architectures. We also review advances in the use of computational simulations and data-driven predictions to shed light on how the side chain chemistry and conformational flexibility of macromolecular blocks drive the emergence of order and the acquisition of hierarchy and also on how ionic, solvent, and surface effects influence the outcomes of assembly. Furthermore, continued progress in the above areas will ultimately usher in an era where an understanding of designed interactions, surface effects, and solution conditions can be harnessed to achieve predictive materials synthesis across scale and drive emergent phenomena in the self-assembly and reconfiguration of high-information content building blocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A designed Copper Histidine-brace enzyme for oxidative depolymerization of polysaccharides as a model of lytic polysaccharide monooxygenase

The “Histidine-brace” (His-brace) copper-binding site, composed of Cu(His) 2 with a backbone amine, is found in metalloproteins with diverse functions. A primary example is lytic polysaccharide monooxygenase (LPMO), a class of enzymes that catalyze the oxidative depolymerization of polysaccharides, providing not only an energy source for native microorganisms but also a route to more effective industrial biomass conversion. Despite its importance, how the Cu His-brace site performs this unique and challenging oxidative depolymerization reaction remains to be understood. To answer this question, we have designed a biosynthetic model of LPMO by incorporating the Cu His-brace motif into azurin, an electron transfer protein. Spectroscopic studies, including ultraviolet-visible (UV–Vis) absorption and electron paramagnetic resonance, confirm copper binding at the designed His-brace site. Moreover, the designed protein is catalytically active towards both cellulose and starch, the native substrates of LPMO, generating degraded oligosaccharides with multiturnovers by C1 oxidation. It also performs oxidative cleavage of the model substrate 4-nitrophenyl-D-glucopyranoside, achieving a turnover number ~9% of that of a native LPMO assayed under identical conditions. This work presents a rationally designed artificial metalloenzyme that acts as a structural and functional mimic of LPMO, which provides a promising system for understanding the role of the Cu His-brace site in LPMO activity and potential application in polysaccharide degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bioexcitons by Design: How Do We Get There?

Biological pigment-protein complexes (PPCs) exhibit a remarkable ability to tune the optical properties of biological excitons (bioexcitons) through specific pigment-protein interactions. While such fine-tuning allows natural systems (e.g., photosynthetic proteins) to carry out their native functions with near-optimal performance, native function itself is often suboptimal for applications such as biofuel production or quantum technology development. Furthermore, this perspective offers a look at near-term prospects for the rational reoptimization of PPC bioexcitons for new functions using site-directed mutagenesis. The primary focus is on the "structure-spectrum" challenge of understanding the relationships between structural features and spectroscopic properties. While recent examples demonstrate that site-directed mutagenesis can be used to tune nearly all key bioexciton parameters (e.g., site energies, inter-pigment couplings, and electronic-vibrational interactions), critical challenges remain before we achieve truly rational design of bioexciton properties.

09 BIOMASS FUELS↗

Integrated lignocellulosic biorefinery for efficient production of furans and photothermal materials

Integrated lignocellulosic biorefineries offer a great potential to valorize all the components in lignocellulose into products, including fuels, chemicals, and materials. However, because of lignocellulose recalcitrance, conversion of bioresources remains a techno-economic challenge for many lignocellulosic biorefineries. In this work, we have proposed a sustainable and profitable biorefinery strategy for lignocellulose fractionation and conversion. In this design, a biphasic solvent consisting of a molten salt hydrate LiCl·4H 2 O and γ-valerolactone (GVL) was initially used for separating hemicellulose from lignocellulose. More interestingly, 100 wt% of biorefinery products from lignin were directly converted to functional photothermal materials by coordinating with Fe 3+ for solar-thermal-electricity conversion. Attributed to this rational design, we report the techno-economic analysis predicts a revenue of 439.3 USD by processing 100 kg of lignocellulosic biomass using the above developed method.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design principles for the ultimate gas deliverable capacity material: nonporous to porous deformations without volume change

Understanding the fundamental limits of gas deliverable capacity in porous materials is of critical importance as it informs whether technical targets (e.g., for on-board vehicular storage) are feasible. High-throughput screening studies of rigid materials, for example, have shown they are not able to achieve the original ARPA-E methane storage targets, yet an interesting question remains: what is the upper limit of deliverable capacity in flexible materials? In this work we develop a statistical adsorption model that specifically probes the limit of deliverable capacity in intrinsically flexible materials. The resulting adsorption thermodynamics indicate that a perfectly designed, intrinsically flexible nanoporous material could achieve higher methane deliverable capacity than the best benchmark systems known to date with little to no total volume change. Density functional theory and grand canonical Monte Carlo simulations identify a known metal–organic framework (MOF) that validates key features of the model. Therefore, this work (1) motivates a continued, extensive effort to rationally design a porous material analogous to the adsorption model and (2) calls for continued discovery of additional high deliverable capacity materials that remain hidden from rigid structure screening studies due to nominal non-porosity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Design of a Highly Stable Single-Ion Conducting Polymer Gel Electrolyte

Single-ion conducting (SIC) polymer electrolytes with a high Li transference number ( t Li + ) have shown the capability to enable enhanced battery performance and safety by avoiding liquid–electrolyte leakage and suppressing Li dendrite formation. However, issues of insufficient ionic conductivity, low electrochemical stability, and poor polymer/electrode interfacial contact have greatly hindered their commercial use. In this work, a Li-containing boron-centered fluorinated SIC polymer gel electrolyte (LiBFSIE) was rationally designed to achieve a high t Li + and high electrochemical stability. Owing to the low dissociation energy of the boron-centered anion and Li + , the as-prepared LiBFSIE exhibited an ionic conductivity of 2 × 10 –4 S/cm at 35 °C, which is exclusively contributed by Li ions owing to a high t Li + of 0.93. Both simulation and experimental approaches were applied to investigate the ion diffusion and concentration gradient in the LiBFSIE and non-cross-linked dual-ion systems. Typical rectangular Li stripping/plating voltage profiles demonstrated the uniform Li deposition assisted by LiBFSIE. The interfacial contact and electrolyte infiltration were further optimized with an in situ UV–vis-initiated polymerization method together with the electrode materials. By virtue of the high electrochemical stability of LiBFSIE, the cells achieved a promising average Coulombic efficiency of 99.95% over 200 cycles, which is higher than that of liquid–electrolyte-based cells. No obvious capacity fading was observed, indicating the long-term stability of LiBFSIE for lithium metal batteries.

36 MATERIALS SCIENCE↗

Theory-guided experimental design in battery materials research

A reliable energy storage ecosystem is imperative for a renewable energy future, and continued research is needed to develop promising rechargeable battery chemistries. To this end, better theoretical and experimental understanding of electrochemical mechanisms and structure-property relationships will allow us to accelerate the development of safer batteries with higher energy densities and longer lifetimes. This Review discusses the interplay between theory and experiment in battery materials research, enabling us to not only uncover hitherto unknown mechanisms but also rationally design more promising electrode and electrolyte materials. We examine specific case studies of theory-guided experimental design in lithium-ion, lithium-metal, sodium-metal, and all-solid-state batteries. We also offer insights into how this framework can be extended to multivalent batteries. To close the loop, we outline recent efforts in coupling machine learning with high-throughput computations and experiments. Last, recommendations for effective collaboration between theorists and experimentalists are provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Density functional theory studies of transition metal carbides and nitrides as electrocatalysts

Transition metal carbides and nitrides are interesting non-precious materials that have been shown to replace or reduce the loading of precious metals for catalyzing several important electrochemical reactions. The purpose of this review is to summarize density functional theory (DFT) studies, describe reaction pathways, identify activity and selectivity descriptors, and present a future outlook in designing carbide and nitride catalysts for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), nitrogen reduction reaction (N 2 RR), CO 2 reduction reaction (CO 2 RR) and alcohol oxidation reactions. Furthermore, this topic is of high interest to scientific communities working in the field of electrocatalysis and this review should provide theoretical guidance for the rational design of improved carbide and nitride electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Bi-Layer Dense/Porous Solid Electrolyte Interphase for Enhanced Lithium-Metal Stability

Due to its high theoretical capacity and low electrochemical potential, lithium metal is a highly investigated anode for next-generation high-energy batteries. However, the unstable chemical and topographical heterogeneous surface of lithium gives rise to safety and efficiency concerns that prevent it from being utilized in practical applications. Exposure to electrolyte leads to non-uniform, mixed organic-inorganic solid-electrolyte interphase (SEI) formation, starting a cascading to non-uniform flux distribution, consumption of active materials, and dendrite growth. The SEI is the key feature that will lead to harnessing the capabilities possible with lithium metal. In this work, the formation of a closed-host bi-layer solid electrolyte interphase (SEI) improves the stability of lithium anode. This is successfully realized by forming an interconnected porous LiF-rich artificial SEI in contact with Li metal, and a dense, stable in-situ formed upper layer SEI. The porous layer increases the number of Li/LiF interfaces, which reduces local volume fluctuations and improves Li+ diffusion along these interfaces. Additionally, the tortuous porous structure guides uniform Li+ flux distribution and mechanically suppresses dendrite propagation. The dense upper layer of the SEI accomplishes a closed-host design through reaction with LiNO3 additive and prevents continuous consumption of active materials seen without the additive included in the electrolyte. The duality of a dense top layer with porous bottom layer led to extended cycle life and improved rate performance, evidenced with symmetric cell testing, as well as full cell testing paired with sulfur and LiFePO4 (LFP) cathodes. This work is a good example of a rational design of the SEI, based on comprehensive consideration of various critical factors to improve Li-metal anode stability, and highlights a new pathway to improve cycling and rate performances of Li metal batteries.

25 ENERGY STORAGE↗

Computational analysis of flow in 3D propulsive transition ducts

A numerical analysis of fully three dimensional, statistically steady flows in propulsive transition ducts being considered for use in future aircraft of higher maneuverability is investigated. The purpose of the transition duct is to convert axisymmetric flow from conventional propulsion systems to that of a rectangular geometry of high aspect ratio. In an optimal design, the transition duct would be of minimal length in order to reduce the weight penalty, while the geometrical change would be gradual enough to avoid detrimental flow perturbations. Recent experiments conducted at the Propulsion Aerodynamics Branch have indicated that thrust losses in ducts of superelliptic cross-section can be surprisingly low, even if flow separation occurs near the divergent walls. In order to address the objective of developing a rational design procedure for optimal transition ducts, it is necessary to have available a reliable computational tool for the analysis of flows achieved in a sequence of configurations. Current CFD efforts involving complicated geometries usually must contend with two separate but interactive aspects: namely, grid generation and flow solution. The first two avenues of the present investigation were comprised of suitable grid generation for a class of transition ducts of superelliptic cross-section, and the subsequent application of the flow solver PAB3D to this geometry. The code, PAB3D, was developed as a comprehensive tool for the solution of both internal and external high speed flows. The third avenue of investigation has involved analytical formulations to aid in the understanding of the nature of duct flows, and also to provide a basis of comparison for subsequent numerical solutions. Numerical results to date include the generation of two preliminary grid systems for duct flows, and the initial application of PAB3D to the corresponding geometries, which are of the class tested experimentally.

Sepri, Paavo↗

Unraveling the Effects of Hierarchical Bimodal Microscale Porosity on Thick Electrodes

The thick electrode design is preferential in high-energy lithium-ion batteries (LIBs) systems. However, the sluggish ionic transport in homogeneous porous thick electrodes severely limits the areal capacity at high charging/discharging rates. The hierarchical porous design is a promising approach to mitigate kinetic limitations because it can distribute mass effectively in natural systems. In this study, the effects of bimodal microscale pores are fully investigated in thick electrodes from both architectural and electrochemical perspectives. Notably, by introduction of the bimodal microscale porous structure, the rate capability improves remarkably in thick electrodes with a low porosity (39%). Herein, by combining experimental results with simulations, this work presents a rational design guideline for preparing thick electrodes with a porosity at the commercial level, as well as simultaneous high energy and power densities, which brings new insights into the advanced electrode architecture design in scalable high-energy and high-power energy storage systems for practical applications.

25 ENERGY STORAGE↗

Mass and Momentum Transport in Microcavities for Diffusion-Dominant Cell Culture Applications

For the informed design of microfluidic devices, it is important to understand transport phenomena at the microscale. This letter outlines an analytically-driven approach to the design of rectangular microcavities extending perpendicular to a perfusion microchannel for microfluidic cell culture devices. We present equations to estimate the spatial transition from advection- to diffusion-dominant transport inside cavities as a function of the geometry and flow conditions. We also estimate the time required for molecules, such as nutrients or drugs to travel from the microchannel to a given depth into the cavity. These analytical predictions can facilitate the rational design of microfluidic devices to optimize and maintain long-term, physiologically-based culture conditions with low fluid shear stress.

Yew, Alvin G.↗

Inhibition of FOXP3 by stapled alpha-helical peptides dampens regulatory T cell function

Despite continuing advances in the development of novel cellular-, antibody-, and chemotherapeutic-based strategies to enhance immune reactivity, the presence of regulatory T cells (Treg cells) remains a complicating factor for their clinical efficacy. To overcome dosing limitations and off-target effects from antibody-based Treg cell deletional strategies or small molecule drugging, we investigated the ability of hydrocarbon stapled alpha-helical (SAH) peptides to target FOXP3, the master transcription factor regulator of Treg cell development, maintenance, and suppressive function. Using the crystal structure of the FOXP3 homodimer as a guide, we developed SAHs in the likeness of a portion of the native FOXP3 antiparallel coiled-coil homodimerization domain (SAH-FOXP3) to block this key FOXP3 protein-protein interaction (PPI) through molecular mimicry. We describe the design, synthesis, and biochemical evaluation of single- and double-stapled SAHs covering the entire coiled-coil expanse. We show that lead SAH-FOXP3s bind FOXP3, are cell permeable and nontoxic to T cells, induce dose-dependent transcript and protein level alterations of FOXP3 target genes, impede Treg cell function, and lead to Treg cell gene expression changes in vivo consistent with FOXP3 dysfunction. These results demonstrate a proof of concept for rationally designed FOXP3-directed peptide therapeutics that could be used as approaches to amplify endogenous immune responsiveness.

60 APPLIED LIFE SCIENCES↗

Is 3D/2D Passivation a Secret to Success for Polycrystalline Thin-Film Solar Cells?

Three leading thin-film photovoltaic (PV) technologies - cadmium telluride (CdTe), CuIn1-xGaxSe2 (CIGS), and perovskite solar cells (PSCs) - are all polycrystalline, but otherwise appear to have little in common. A comprehensive examination of these technologies, however, reveals a common theme: the formation of two-dimensional (2D) van der Waals materials at three-dimensional (3D) absorber interfaces and grain boundaries. In CdTe, the 2D compound is CdCl2; in CIGS, it is XInSe2 (X= K, Rb, Cs) with X depending on the heavy-alkali post-deposition treatment used; and in lead halide PSCs, PbI2 forms naturally, but many new, more stable, 2D perovskites have also been incorporated. Generally, these 2D interfacial materials are present not by design, but instead have evolved from their 3D counterparts during standard device processing. Here, new data, together with evidence compiled from the literature, are presented to illustrate both the existence of 3D/2D interfaces in CdTe, CIGS, and PSCs, and their correlation with improved passivation and device performance. This suggests that 3D/2D passivation may be a heretofore unappreciated key to successful polycrystalline thin-film PV. Finally, the desired attributes of successful low-dimensional layers are presented with rational design strategies for next generation polycrystalline solar cells.

3D/2D↗

Semiconductor to Topological Insulator Transition Induced by Stress Propagation in Metal Dichalcogenides Core-Shell Lateral Heterostructures

Polymorphic phase transition is an important route for engineering the properties of two-dimensional materials. Heterostructure construction, on the other hand, not only allows the integration of different functionalities for device applications, but also enables the exploration of new physics arising from proximity coupling. Yet, implementing a design that incorporates the advantages of both remains underexplored. Here in this paper, based on comprehensive experimental and theoretical studies of WSe 2 /SnSe 2 core-shell lateral heterostructure, we demonstrate an unexpected H to T' phase transition in transition metal dichalcogenides (TMDs), correlating to a change of materials properties from semiconductor to topological insulator (TI), and propose a novel shell-to-core stress propagation mechanism. This finding offers new insights into TMD phase transition empowered by the rational design of heterostructures. Owing to the superconducting properties of SnSe 2 at low temperatures, the unique TI/superconductor core-shell template is expected to add more arsenals to the ongoing search of Majorana fermions in condensed matter systems.

36 MATERIALS SCIENCE↗

A Pyrrole Modified 3,4‐Propylenedioxythiophene Conjugated Polymer as Hole Transport Layer for Efficient and Stable Perovskite Solar Cells

Despite the outstanding electric properties and cost-effectiveness of poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives, their performance as hole transport layer (HTL) materials in conventional perovskite solar cells (PSCs) has lagged behind that of widely used spirobifluorene-based molecules or poly(triaryl amine). This gap is mainly from their poor solubility and energy alignment mismatch. In this work, the design and synthesis of a pyrrole-modified HTL (PPr) based on 3,4-propylenedioxythiophene (ProDOT) are presented for efficient and stable PSCs. As a result of the superior defects passivation ability, excellent contact with perovskite, enhanced hole extraction, and high hydrophobicity, the unencapsulated PPr-based PSCs showed the peak PCE of 21.49% and outstanding moisture stability (over 4000 h). This work highlights the potential application of ProDOT-based materials as HTL for PSCs and underscores the importance of the rational design of PEDOT and its derivatives.

14 SOLAR ENERGY↗

Drug discovery efforts at George Mason University

With over 39,000 students, and research expenditures in excess of $200 million, George Mason University (GMU) is the largest R1 (Carnegie Classification of very high research activity) university in Virginia. Mason scientists have been involved in the discovery and development of novel diagnostics and therapeutics in areas as diverse as infectious diseases and cancer. Below are highlights of the efforts being led by Mason researchers in the drug discovery arena. To enable targeted cellular delivery, and non-biomedical applications, Veneziano and colleagues have developed a synthesis strategy that enables the design of self-assembling DNA nanoparticles (DNA origami) with prescribed shape and size in the 10 to 100 nm range. The nanoparticles can be loaded with molecules of interest such as drugs, proteins and peptides, and are a promising new addition to the drug delivery platforms currently in use. The investigators also recently used the DNA origami nanoparticles to fine tune the spatial presentation of immunogens to study the impact on B cell activation. These studies are an important step towards the rational design of vaccines for a variety of infectious agents. To elucidate the parameters for optimizing the delivery efficiency of lipid nanoparticles (LNPs), Buschmann, Paige and colleagues have devised methods for predicting and experimentally validating the pKa of LNPs based on the structure of the ionizable lipids used to formulate the LNPs. These studies may pave the way for the development of new LNP delivery vehicles that have reduced systemic distribution and improved endosomal release of their cargo post administration. To better understand protein-protein interactions and identify potential drug targets that disrupt such interactions, Luchini and colleagues have developed a methodology that identifies contact points between proteins using small molecule dyes. The dye molecules noncovalently bind to the accessible surfaces of a protein complex with very high affinity, but are excluded from contact regions. When the complex is denatured and digested with trypsin, the exposed regions covered by the dye do not get cleaved by the enzyme, whereas the contact points are digested. The resulting fragments can then be identified using mass spectrometry. The data generated can serve as the basis for designing small molecules and peptides that can disrupt the formation of protein complexes involved in disease processes. For example, using peptides based on the interleukin 1 receptor accessory protein (IL-1RAcP), Luchini, Liotta, Paige and colleagues disrupted the formation of IL-1/IL-R/IL-1RAcP complex and demonstrated that the inhibition of complex formation reduced the inflammatory response to IL-1B. Working on the discovery of novel antimicrobial agents, Bishop, van Hoek and colleagues have discovered a number of antimicrobial peptides from reptiles and other species. DRGN-1, is a synthetic peptide based on a histone H1-derived peptide that they had identified from Komodo Dragon plasma. DRGN-1 was shown to disrupt bacterial biofilms and promote wound healing in an animal model. The peptide, along with others, is being developed and tested in preclinical studies. Other research by van Hoek and colleagues focuses on in silico antimicrobial peptide discovery, screening of small molecules for antibacterial properties, as well as assessment of diffusible signal factors (DFS) as future therapeutics. The above examples provide insight into the cutting-edge studies undertaken by GMU scientists to develop novel methodologies and platform technologies important to drug discovery.

59 BASIC BIOLOGICAL SCIENCES↗