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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 901 records · Page 50
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Design of metal-mediated protein assemblies via hydroxamic acid functionalities

The self-assembly of proteins into sophisticated multicomponent assemblies is a hallmark of all living systems and has spawned extensive efforts in the construction of novel synthetic protein architectures with emergent functional properties. Protein assemblies in nature are formed via selective association of multiple protein surfaces through intricate noncovalent protein-protein interactions, a challenging task to accurately replicate in the de novo design of multiprotein systems. In this protocol, we describe the application of metal-coordinating hydroxamate (HA) motifs to direct the metal-mediated assembly of polyhedral protein architectures and 3D crystalline protein frameworks (protein-MOFs). This strategy has been implemented using an asymmetric cytochrome cb562 monomer through selective, concurrent association of Fe 3+ and Zn 2+ ions to form polyhedral cages. Furthermore, the use of ditopic HA linkers as bridging ligands with metal-binding protein nodes has allowed the construction of crystalline 3D protein-MOF lattices. The protocol is divided into two major sections: (1) the development of a Cys-reactive HA molecule for protein derivatization and self-assembly of protein-HA conjugates into polyhedral cages and (2) the synthesis of ditopic HA bridging ligands for the construction of ferritin-based protein-MOFs using symmetric metal-binding protein nodes. Furthermore, protein cages can be analyzed using analytical ultracentrifugation (AUC), transmission electron microscopy (TEM) and single-crystal X-ray diffraction (sc-XRD) techniques. HA-mediated protein-MOFs are formed in sitting-drop vapor diffusion crystallization trays and are probed via sc-XRD and multi-crystal small-angle X-ray scattering (SAXS) measurements. Ligand synthesis, construction of HA-mediated assemblies, and post-assembly analysis as described in this protocol can be performed by a graduate-level researcher within six weeks.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular structural dataset of lignin macromolecule elucidating experimental structural compositions

Abstract Lignin is one of the most abundant biopolymers in nature and has great potential to be transformed into high-value chemicals. However, the limited availability of molecular structure data hinders its potential industrial applications. Herein, we present the Lignin Structural (LGS) Dataset that includes the molecular structure of milled wood lignin focusing on two major monomeric units (coniferyl and syringyl), and the six most common interunit linkages (phenylpropane β-aryl ether, resinol, phenylcoumaran, biphenyl, dibenzodioxocin, and diaryl ether). The dataset constitutes a unique resource that covers a part of lignin’s chemical space characterized by polymer chains with lengths in the range of 3 to 25 monomer units. Structural data were generated using a sequence-controlled polymer generation approach that was calibrated to match experimental lignin properties. The LGS dataset includes 60 K newly generated lignin structures that match with high accuracy (~90%) the experimentally determined structural compositions available in the literature. The LGS dataset is a valuable resource to advance lignin chemistry research, including computational simulation approaches and predictive modelling.

Scientific data↗
DOE OSTI2020

Sorption, solubility and cytotoxicity of novel antibacterial nanofilled dental adhesive resins

Dental adhesives hydrolyze in the mouth. This study investigated the water sorption (SOR), solubility (SOL) and cytotoxicity (CYTO) of experimental adhesives containing nitrogen-doped titanium dioxide nanoparticles (N_TiO 2 ). Specimens (n = 15/group [SOR, SOL]; n = 10/group [CYTO]) of unaltered Clearfil SE Protect (CSP), OptiBond Solo Plus (OSP), Adper Scotchbond (ASB) and experimental adhesives (OSP + 25% or 30% of N_TiO 2 ) were fabricated, desiccated (37 °C) and tested for SOR and SOL according to ISO Specification 4049 (2009). CYTO specimens were UV-sterilized (8 J/cm 2 ) and monomer extracted in growth medium (1, 3 or 7 days). Human pulp cells were isolated and seeded (0.5 × 10 4 ) for MTT assay. SOR and SOL data was analyzed using GLM and SNK (α = 0.05) and CYTO data was analyzed with Kruskal–Wallis and SNK tests (α = 0.05). SOR and SOL values ranged from 25.80 μg/mm 3 (30% N_TiO 2 ) to 28.01 μg/mm 3 (OSP) and 23.88 μg/mm 3 (30% N_TiO 2 ) to 25.39 μg/mm 3 (25% N_TiO 2 ). CYTO results indicated that pulp cells exposed to experimental materials displayed comparable viabilities (p > 0.05) to those of OSP. Experimental materials displayed comparable SOR, SOL and CYTO values (p > 0.05) when compared to unaltered materials. N_TiO 2 incorporation have not adversely impacted SOR, SOL and CYTO properties of unaltered adhesives.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Combined light- and heat-induced shape memory behavior of anthracene-based epoxy elastomers

Abstract The development of multi-stimuli-responsive shape memory polymers has received increasing attention because of its scientific and technological significance. In this work, epoxy elastomers with reversible crosslinks are synthesized by polymerizing an anthracene-functionalized epoxy monomer, a diepoxy comonomer, and a dicarboxylic acid curing agent. The synthesized elastomers exhibit active responses to both light and heat enabled by the incorporated anthracene groups. When exposed to 365 nm UV light, additional crosslinking points are created by the photo-induced dimerization of pendant anthracene groups. The formation of the crosslinking points increases modulus and glass transition temperature of the elastomers, allowing for the fixation of a temporary shape at room temperature. The temporary shape remains stable until an external heat stimulus is applied to trigger the scission of the dimerized anthracene, which reduces the modulus and glass transition temperature and allows the elastomers to recover their original shapes. The effects of external stimuli on the thermal and dynamic mechanical properties of the elastomers are investigated experimentally and are correlated with molecular dynamics simulations that reveal the changes of structure and dynamics of the anthracene molecules and flexible chains.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Efficient secretion of a plastic degrading enzyme from the green algae Chlamydomonas reinhardtii

Abstract Plastic pollution has become a global crisis, with microplastics contaminating every environment on the planet, including our food, water, and even our bodies. In response, there is a growing interest in developing plastics that biodegrade naturally, thus avoiding the creation of persistent microplastics. As a mechanism to increase the rate of polyester plastic degradation, we examined the potential of using the green microalgaChlamydomonas reinhardtiifor the expression and secretion of PHL7, an enzyme that breaks down post-consumer polyethylene terephthalate (PET) plastics. We engineeredC. reinhardtiito secrete active PHL7 enzyme and selected strains showing robust expression, by using agar plates containing a polyester polyurethane (PU) dispersion as an efficient screening tool. This method demonstrated the enzyme’s efficacy in degrading ester bond-containing plastics, such as PET and bio-based polyurethanes, and highlights the potential for microalgae to be implemented in environmental biotechnology. The effectiveness of algal-expressed PHL7 in degrading plastics was shown by incubating PET with the supernatant from engineered strains, resulting in substantial plastic degradation, confirmed by mass spectrometry analysis of terephthalic acid formation from PET. Our findings demonstrate the feasibility of polyester plastic recycling using microalgae to produce plastic-degrading enzymes. This eco-friendly approach can support global efforts toward eliminating plastic in our environment, and aligns with the pursuit of low-carbon materials, as these engineered algae can also produce plastic monomer precursors. Finally, this data demonstratesC. reinhardtiicapabilities for recombinant enzyme production and secretion, offering a “green” alternative to traditional industrial enzyme production methods.

Science & Technology - Other Topics↗
DOE OSTI2025

Enzymatic cleavage of model lignin dimers depends on pH, enzyme, and bond type

Lignin is composed of phenylpropanoid monomers linked by ether and carbon-carbon bonds to form a complex heterogeneous structure. Bond-specific studies of lignin-modifying enzymes (LMEs; e.g., laccases and peroxidases) are limited by the polymerization of model lignin substrates and repolymerization of cleavage products. Here we present a high throughput platform to screen LME activities on four tagged model lignin compounds that represent the β-O-4’, β-β’, 5–5’, and 4-O-5’ linkages in lignin. We utilized nanostructure-initiator mass spectrometry (NIMS) and model lignin compounds with tags containing perfluorinated and cationic moieties, which effectively limit polymerization and condensation of the substrates and their degrading products. Sub-microliter sample droplets were printed on the NIMS chip with a novel robotics method. This rapid platform enabled characterization of LMEs across a range of pH 3–10 and relative quantification of modified (typically oxidized), cleaved, and polymerized products. All tested enzymes oxidized the four substrates and cleaved the β-O-4’ and β-β’ substrates to monomeric products. We discovered that the active pH range depended on both the substrate and the enzyme type. This has important applications for biomass conversion to biofuels and bioproducts, where the relative percentages of different bond types in lignin varies depending on feedstock and chemical pretreatment methods.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Biorenewable and circular polydiketoenamine plastics

Amid growing concerns over the human health and environmental impacts of plastic waste, the most promising solution would be to build a circular plastics economy where sustainability considerations dictate the full life cycle of plastics use including replacing petrochemicals with biorenewables. Here we show that by incorporating the polyketide triacetic acid lactone (TAL) in polydiketoenamines (PDK) we increase the working temperature of these circular plastics, opening the door wider to applications where circularity is urgently needed. By varying the number of carbons of TAL-derived monomers, both polymer properties and recycling efciency are afected. Simply using glucose as the main carbon source, we engineered a process for producing bioTAL under fed-batch fermentation. Furthermore, a systems analysis of this bioprocess under diferent scenarios quantifes the environmental and economic benefts of PDK plastics and the risks when implemented at an industrial scale, providing opportunities in biorenewable circularity.

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

Depolymerizable and recyclable luminescent polymers with high light-emitting efficiencies

Luminescent polymers are of great interest in a number of photonic technologies, including electroluminescence, bioimaging, medical diagnosis, bio-stimulation and security signage. Incorporating depolymerizability and recyclability into luminescent polymers is pivotal for promoting their sustainability and minimizing their environmental impacts at the end of the product lifecycle, but existing strategies often compromise the light-emitting efficiencies. Here, in this study, we develop a strategy that utilizes cleavable moiety to create depolymerizable and recyclable thermally activated delayed fluorescence (TADF) polymers without compromising their high light-emitting efficiencies. The electroluminescent devices based on the TADF polymers achieved a high external quantum efficiency of up to 15.1 %. The TADF polymers can be depolymerized under either mild acidic or heating conditions, with precise control of the kinetics, and the obtained pure monomers can potentially be isolated and repolymerized for subsequent life applications. This work promotes the end-of-life environmental friendliness and circularity of luminescent materials, paving the way to a sustainable photonic industry. Developing depolymerizable and recyclable polymers with high light-emitting efficiencies is of vital importance for sustainable photonic technologies, but remains challenging. Here the authors design a strategy to develop such polymers based on the use of controllable cleavable moiety.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Critical Enzyme Reactions in Aromatic Catabolism for Microbial Lignin Conversion

The application of microbes to valorize aromatic compounds derived from the abundant plant biopolymer lignin is a rapidly developing area of research that may ultimately enable viable conversion of this recalcitrant and heterogeneous resource to valuable bio-based chemical products. Starting from the three canonical lignin building blocks, which differ in the extent of aromatic ring methoxylation, several common classes of enzymatic reaction occur in the upper pathways of aromatic catabolism to prepare aromatic compounds for assimilation into central carbon metabolism, including aromatic O-demethylation, hydroxylation and decarboxylation. These critical enzymatic steps can often be rate-limiting for efficient biological funnelling of aromatic compounds. Here we review the known enzymatic mechanisms for these reactions that are relevant for aerobic aromatic catabolism of lignin-related monomers, highlighting opportunities at the intersection of biochemistry, enzyme engineering and metabolic engineering for applications in the expanding field of microbial lignin valorization.

aromatic catabolism↗
DOE OSTI2022

Autoprocessing and oxyanion loop reorganization upon GC373 and nirmatrelvir binding of monomeric SARS-CoV-2 main protease catalytic domain

The monomeric catalytic domain (residues 1–199) of SARS-CoV-2 main protease (MPro 1-199 ) fused to 25 amino acids of its flanking nsp4 region mediates its autoprocessing at the nsp4-MPro 1-199 junction. We report the catalytic activity and the dissociation constants of MPro 1-199 and its analogs with the covalent inhibitors GC373 and nirmatrelvir (NMV), and the estimated monomer-dimer equilibrium constants of these complexes. Mass spectrometry indicates the presence of the accumulated adduct of NMV bound to MPro WT and MPro 1-199 and not of GC373. A room temperature crystal structure reveals a native-like fold of the catalytic domain with an unwound oxyanion loop (E state). In contrast, the structure of a covalent complex of the catalytic domain-GC373 or NMV shows an oxyanion loop conformation (E* state) resembling the full-length mature dimer. These results suggest that the E-E* equilibrium modulates autoprocessing of the main protease when converting from a monomeric polyprotein precursor to the mature dimer.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Ultraviolet spectroscopy of pressurized and supercritical carbon dioxide

Abstract Carbon dioxide (CO 2 ) is prevalent in planetary atmospheres and sees use in a variety of industrial applications. Despite its ubiquitous nature, its photochemistry remains poorly understood. In this work we explore the density dependence of pressurized and supercritical CO 2 electronic absorption spectra by vacuum ultraviolet spectroscopy over the wavelength range 1455-2000 Å. We show that the lowest absorption band transition energy is unaffected by a density increase up to and beyond the thermodynamic critical point (137 bar, 308 K). However, the diffuse vibrational structure inherent to the spectrum gradually decreases in magnitude. This effect cannot be explained solely by collisional broadening and/or dimerization. We suggest that at high densities close proximity of neighboring CO 2 molecules with a variety of orientations perturbs the multiple monomer electronic state potential energy surfaces, facilitating coupling between binding and dissociative states. We estimate a critical radius of ~4.1 Å necessary to cause such perturbations.

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

Ab initio molecular dynamics free energy study of enhanced copper (II) dimerization on mineral surfaces

Understanding the adsorption of isolated metal cations from water on to mineral surfaces is critical for toxic waste retention and cleanup in the environment. Heterogeneous nucleation of metal oxyhydroxides and other minerals on material surfaces is key to crystal growth and dissolution. The link connecting these two areas, namely cation dimerization and polymerization, is far less understood. In this work we apply ab initio molecular dynamics calculations to examine the coordination structure of hydroxide-bridged Cu(II) dimers, and the free energy changes associated with Cu(II) dimerization on silica surfaces. The dimer dissociation pathway involves sequential breaking of two Cu 2+ -OH – bonds, yielding three local minima in the free energy profiles associated with 0-2 OH – bridges between the metal cations, and requires the design of a (to our knowledge) novel reaction coordinate for the simulations. Cu(II) adsorbed on silica surfaces are found to exhibit stronger tendency towards dimerization than when residing in water. Cluster-plus-implicit-solvent methods yield incorrect trends if OH – hydration is not correctly depicted. The predicted free energy landscapes are consistent with fast equilibrium times (seconds) among adsorbed structures, and favor Cu 2+ dimer formation on silica surfaces over monomer adsorption.

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

Improving AlphaFold2-based protein tertiary structure prediction with MULTICOM in CASP15

Since the 14th Critical Assessment of Techniques for Protein Structure Prediction (CASP14), AlphaFold2 has become the standard method for protein tertiary structure prediction. One remaining challenge is to further improve its prediction. We developed a new version of the MULTICOM system to sample diverse multiple sequence alignments (MSAs) and structural templates to improve the input for AlphaFold2 to generate structural models. The models are then ranked by both the pairwise model similarity and AlphaFold2 self-reported model quality score. The top ranked models are refined by a novel structure alignment-based refinement method powered by Foldseek. Moreover, for a monomer target that is a subunit of a protein assembly (complex), MULTICOM integrates tertiary and quaternary structure predictions to account for tertiary structural changes induced by protein-protein interaction. The system participated in the tertiary structure prediction in 2022 CASP15 experiment. Our server predictor MULTICOM_refine ranked 3rd among 47 CASP15 server predictors and our human predictor MULTICOM ranked 7th among all 132 human and server predictors. The average GDT-TS score and TM-score of the first structural models that MULTICOM_refine predicted for 94 CASP15 domains are ~0.80 and ~0.92, 9.6% and 8.2% higher than ~0.73 and 0.85 of the standard AlphaFold2 predictor respectively.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Analyses of circular solutions for advanced plastics waste recycling

A circular plastics economy can leverage the lightweight, strong and durable characteristics of macromolecular materials, while simultaneously reducing the negative environmental impacts associated with polymer waste. Advanced recycling technologies provide an opportunity to valorize plastics waste and extend the lifespan of these materials by converting waste into new monomers, polymers or specialty chemicals. Although many advanced technologies appear promising, assessments of economic and environmental sustainability are often not conducted in a standardized fashion and neglect factors such as plastics waste transportation, sorting and pretreatment. These shortcomings can lead to inaccurate or misleading predictions, reduce opportunities for optimization and limit industrial relevance. In this Review, we highlight select industrial case studies to underscore the notable consequences of underestimating the complexity of real-life consumer plastics waste. In addition, the current challenges associated with the assessment of the industrial viability of laboratory-scale processes are explored. Here, by discussing relevant analysis frameworks and system boundaries, along with potential analytical pitfalls, future research will be guided beyond chemical considerations and toward impactful circular solutions.

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

Mechanically robust and reprocessable imine exchange networks from modular polyester pre-polymers

Covalent adaptable networks (CANs) containing reversible cross-links impart recyclability to thermoset materials without sacrificing their desirable properties (e.g. high tensile strength and solvent resistance). In addition to thermal recycling, the sustainability of these materials may be further improved by incorporating bio-sourced monomers or by enabling alternate end-of-life fates, such as biodegradation or recovery of starting materials. The alternating ring-opening copolymerisation of epoxides and cyclic anhydrides permits the modular synthesis of polyester pre-polymers that can then be cross-linked to form dynamic imine-linked networks. In this work, we report the synthesis and characterisation of five imine exchange polyester CANs with varied cross-linking densities and pre-polymer architectures. While the materials exhibit characteristic thermoset properties at service temperatures, differences in pre-polymer architecture produce distinct dynamic mechanical effects at elevated temperatures. The networks may be thermally reprocessed with full recovery of their tensile strengths and cross-linking densities, dissociated to pre-polymer, or hydrolytically degraded.

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

Metal–organic framework (MOF) materials as polymerization catalysts: a review and recent advances

Synthetic polymers are ubiquitous across both the industrial and consumer segments of the world economy. Catalysts enable rapid, efficient, selective, and even stereoselective, formation of desired polymers from any of a host of candidate monomers. While numerous molecular catalysts have been shown to be effective for these reactions, separation of the catalysts from reaction products is typically difficult – a potentially problematic complication that suggests instead the use of heterogeneous catalysts. Many of the most effective heterogeneous catalysts, however, comprise supported collections of reaction centres that are decidedly nonuniform in their composition, siting, and activity. Nonuniformity complicates atomic-scale evaluation of the basis for catalytic activity and thus impedes scientific hypothesis-driven understanding and development of superior catalysts. In view of the fundamental desirability of structural and chemical uniformity at the meso, nano, and even atomic scale, crystallographically well-defined, high-porosity metal–organic frameworks (MOFs) have attracted attention as model catalysts and/or catalyst-supports for a wide variety of chemical transformations. In the realm of synthetic polymers, catalyst-functionalized MOFs have been studied for reactions ranging from coordination-mediated polymerization of ethylene to visible-light initiated radical polymerizations. Nevertheless, many polymerization reactions remain to be explored – and, no doubt, will be explored, given the remarkable structural and compositional diversity of attainable MOFs. Noteworthy emerging studies include work directed toward more sophisticated catalytic schemes such as polymer templating using MOF pore architectures and tandem copolymerizations using MOF-supported reaction centres. Finally, it is appropriate to recognize that MOFs themselves are synthetic polymers – albeit, uncoventional ones.

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

On the mechanism of soot nucleation. II. E-bridge formation at the PAH bay

A recently proposed mechanism of soot nucleation based upon the formation of a rotationally-activated dimer in the collision of an aromatic molecule and a radical leading to a stable, doubly-bonded E-bridge between them, rooted in the existence of a five-membered ring on the molecule edge, has been further investigated with a focus on the 5-6 E-bridge forming in the reaction of a PAH cyclopenta group with a bay site of another PAH. As a prototype reaction of this kind, we examined the reaction between 4-phenanthrenyl and acenaphthylene and, to project these results to larger aromatic structures, we also explored the size effect of the E-bridge forming reactions by computing the 1-naphthyl + acenaphthylene system and comparing these results with the prior results for pyrenyl + acepyrene. The two systems have been studied through high-level G3(MP2,CC)//B3LYP/6-311G(d,p) ab initio calculations of their potential energy surfaces combined with the RRKM/Master Equation calculations of reaction rate constants. With PAH monomers of similar sizes involved, the formation of E-bridge structures at the bay radical sites appeared to be faster and lead to increased nucleation rates as compared to the zigzag-forming ones. Furthermore, a model combining both the bay and zigzag rotationally-induced formation of E-bridges successfully reaches the level of nucleation fluxes comparable to those of the irreversible pyrene dimerization, thus affirming the rotationally-activated dimerization as a feasible mechanism for soot particle nucleation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗