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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 685 records · Page 38

Hybrid biological-chemical strategy for converting polyethylene into a recyclable plastic monomer using engineered Corynebacterium glutamicum

Converting polyethylene (PE) into valuable materials, particularly ones that are better for the environment than the incumbent plastics, not only helps mitigate environmental issues caused by plastic waste but also alleviates the long-standing problem of microbial fermentation competing with food supplies. However, the inherent robustness of PE due to its strong carbon-carbon bonds and high molecular weight necessitates harsh decomposition conditions, resulting in diverse decomposition outcomes that present significant challenges for downstream applications, especially for bioconversion. In this study, we demonstrate a hybrid biological-chemical conversion process for PE, converting its decomposition products, namely short-chain diacids, into a monomer, β-keto-δ-lactone (BKDL), for highly recyclable polydiketoenimine plastics using engineered Corynebacterium glutamicum. Since BKDL synthesis requires a substantial supply of malonyl-CoA, we employed an alternative biosynthesis pathway that leverages C. glutamicum's natural proficiency in amino acid production. We optimized this pathway in vivo by minimizing carbon loss to CO2 and byproducts, improving the transporter system, and maximizing co-factor regeneration. Furthermore, we co-optimized the PE deconstruction process to produce predominantly C4 to C6 diacids and integrated three catabolic pathways into the engineered strain to enhance diacid utilization, maximizing the carbon conversion from PE. Finally, an engineered polyketide synthase was introduced into C. glutamicum to enable BKDL synthesis. This work demonstrates the potential of a chemo-biological hybrid strategy for recycling plastic waste, highlighting its promise in addressing environmental challenges and promoting sustainable materials.

Zhan, Chunjun↗

First-principles study of carbon capture and storage properties of porous MnO 2 octahedral molecular sieve OMS-5

Based on the experimentally determined framework structure of porous MnO 2 octahedral molecular sieve (OMS)-5, we used density functional theory-based calculations to evaluate the effect of Na + cation on pore dimensionality and structural stability, and the interaction between CO 2 and OMS-5. Furthermore, we quantified the formation energy of one CO 2 /unit tunnel and two CO 2 /unit tunnel, and projected the electronic density of states on the OMS-5 framework, CO 2 molecules, and Na+ cations to reveal their individual contributions and bonding nature. Partial charge densities were also calculated to investigate CO 2 adsorption behavior in the OMS-5. Our studies predict the initial stage and driving force for the adsorption of CO 2 in the OMS-5, guiding the OMS material design for carbon capture and storage applications.

36 MATERIALS SCIENCE↗

Machine Learning of In-situ Temperature Reconstruction from Metal-nanoparticle Thermometry on Transmission Electron Microscopy

Utilizing Python programming language and third-party libraries, 2D temperature fields were reconstructed from TEM images demonstratively and a GUI was created. Local temperatures can be fast read on TEM at the nanoscale based on the nanoparticle thermometry. The Artificial Intelligence technique would speed up the in-situ heating TEM research and make real-time in-situ temperature monitoring possible at nanoscale.

42 ENGINEERING↗

NMR of Fully and Partially 13 C-Enriched Biomass Enhances Pendent Group Structural Characterization

Traditional solution-state NMR experiments may either fail or yield unsatisfactory results when employing fully- 13 C-labeled biomass due to complications arising from 13 C– 13 C coupling. Constant-time analogs of HSQC experiments mitigate such issues and deliver enhanced sensitivity. A rarely reported CT-HSQC-TOCSY experiment allows the proton coupling network to deliver much of the same value as the parent experiment on unlabeled or 10–15%- 13 C-labeled biomass polymers but with enhanced sensitivity. In the absence of a viable HMBC analog for long-range correlations, a relayed C–C experiment, i.e., via directly bonded 13 C-labeled networks, enables the reliable assignment of coupled carbons, with the added advantage of correlating the more elusive quaternaries. A C–C-FLOPSY experiment takes advantage of fully- 13 C-labeled materials for mapping extensive carbon networks in the complex polymer mixtures inherent in biomass. Various pendent groups (tricin units, cis- and trans-p-coumarates, and p -hydroxybenzoates) that adorn lignins, and the cis- and trans-ferulates on arabinoxylan polysaccharides, are exquisitely revealed in spectra from isolated lignins or whole-cell-wall materials from maize, sorghum, and poplar.

biopolymers↗

Enhanced Photo-Cross-Linking of Thymines in DNA Holliday Junction-Templated Squaraine Dimers

Programmable self-assembly of dyes using DNA templates to promote exciton delocalization in dye aggregates is gaining considerable interest. New methods to improve the rigidity of the DNA scaffold and thus the stability of the molecular dye aggregates to encourage exciton delocalization are desired. In these dye–DNA constructs, one potential way to increase the stability of the aggregates is to create an additional covalent bond via photo-cross-linking reactions between thymines in the DNA scaffold. Specifically, we report an approach to increase the yield of photo-cross-linking reaction between thymines in the core of a DNA Holliday junction while limiting the damage from UV irradiation to DNA. We investigated the effect of the distance between thymines on the photo-cross-linking reaction yields by using linkers with different lengths to tether the dyes to the DNA templates. By comprehensively evaluating the photo-cross-linking reaction yields of dye–DNA aggregates using linkers with different lengths, we conclude that interstrand thymines tend to photo-cross-link more efficiently with short linkers. A higher cross-linking yield was achieved due to the shorter intermolecular distance between thymines influenced by strong dye–dye interactions. Furthermore, our method establishes the possibility of improving the stability of DNA-scaffolded dye aggregates, thereby expanding their use in exciton-based applications such as light harvesting, nanoscale computing, quantum computing, and optoelectronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent Advances in Nonclassical Crystallization: Fundamentals, Applications, and Challenges

We report crystals are ubiquitous and play an important role in our daily life. Recent studies on properties and formation of crystals have proven the attachment of particle ranging from ion pairs to well-crystallized nanocrystal is one of the most important ways for crystallization. Compared with the monomer-by-monomer (i.e., atoms, ions, or molecules) addition described in longstanding classical theories, so-called nonclassical crystallization pathways are more complex as the non-specific interaction of variation in system free energy and reaction kinetics. In view of the detailed insights into nonclassical crystallization pathways has broadened the scope of research across various disciplines such as geological events, biomineralization mechanisms, environmental remediation, and the development of functional materials, this paper reviews the current state of the art in nonclassical nucleation (the prenucleation clusters pathway, aggregation pathway, etc.) and growth pathways (oriented attachment and random attachment) based on several spotlights. In addition, the observed specific phenomena on crystallization in the last 10 years as well as recent advancements and achievements made on the synthesis of mesocrystals are also elucidated. With implications and perspectives of nonclassical crystallization researches proposed in this paper, this review aims to summarize research advancement regarding crystallizing systems. Emphasis will be placed on novel insights into nonclassical crystallization of materials, which are expected to provide completely new perspectives on the underlying crystallization mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discovery and Characterization of a Pourbaix-Stable, 1.8 eV Direct Gap Bismuth Manganate Photoanode

Solar-driven oxygen evolution is a critical technology for renewably synthesizing hydrogen- and carbon-containing fuels in solar fuel generators. New photoanode materials are needed to meet efficiency and stability requirements, motivating materials explorations for semiconductors with (i) band-gap energy in the visible spectrum and (ii) stable operation in aqueous electrolyte at the electrochemical potential needed to evolve oxygen from water. Motivated by the oxygen evolution competency of many Mn-based oxides, the existence of several Bi-containing ternary oxide photoanode materials, and the variety of known oxide materials combining these elements with Sm, we explore the Bi-Mn-Sm oxide system for new photoanodes. Through the use of a ferri/ferrocyanide redox couple in high-throughput screening, BiMn 2 O 5 and its alloy with Sm are identified as photoanode materials with a near-ideal optical band gap of 1.8 eV. Using density functional theory-based calculations of the mullite Bi 3+ Mn 3+ Mn 4+ O 5 phase, we identify electronic analogues to the well-known BiVO 4 photoanode and demonstrate excellent Pourbaix stability above the oxygen evolution Nernstian potential from pH 4.5 to 15. Lastly, our suite of experimental and computational characterization indicates that BiMn 2 O 5 is a complex oxide with the necessary optical and chemical properties to be an efficient, stable solar fuel photoanode.

14 SOLAR ENERGY↗

Electrochemical Stability of Metastable Materials

We present a first-principles-based formalism to provide a quantitative measure of the thermodynamic instability and propensity for electrochemical stabilization, passivation, or corrosion of metastable materials in aqueous media. Here, we demonstrate that this formalism can assess the relative Gibbs free energy of candidate materials in aqueous media as well as their decomposition products, combining solid and aqueous phases, as a function of pH and potential. On the basis of benchmarking against 20 stable as well as metastable materials reported in the literature and also our experimental characterization of metastable triclinic-FeVO 4 , we present quantitative estimates for the relative Gibbs free energy and corresponding aqueous regimes where these materials are most likely to be stable, form inert passivating films, or steadily corrode to aqueous species. Furthermore, we show that the structure and composition of the passivating films formed on triclinic-FeVO 4 are also in excellent agreement with the Point Defect Model, as proposed by the corrosion community.

36 MATERIALS SCIENCE↗

Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (˙OH), singlet molecular oxygen ( 1 O 2 *), and triplet excited states of organic compounds ( 3 C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase ˙OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with ˙OH, 1 O 2 *, and 3 C* in cloud droplets and aerosol liquid water. Here, we investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Further, our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.

09 BIOMASS FUELS↗

Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba 3 Ln 2 O 5 Cl 2

Single crystals of a new family of layered lanthanide oxychlorides, Ba 3 Ln 2 O 5 Cl 2 (Ln = Gd–Lu), have been synthesized from a molten barium flux. This family crystallizes in the space group I4/ mmm (No. 139; Z = 2) with lattice parameters a = 4.3384(1)–4.4541(1) Å and c = 24.5108(7)–24.8448(9) Å. Ba 3 Ln 2 O 5 Cl 2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba 2 Ln 2 O 5 formed by corner-connected LnO 5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl 2 . A complete structural study along with bond-valence-sum calculations shows that, for lanthanides larger than gadolinium, the structure becomes unstable. Density functional theory calculations show that the valence-band edge is dominated by oxygen orbitals, whereas the conduction band forms from Ba 5d orbitals. Finally, the synthesis of this family suggests a route to other potential multianion phases.

36 MATERIALS SCIENCE↗

Formation and Characterization of Zein-Based Oleogels

Oleogels are interesting as a result of their ability to hold large amounts of oil in a semi-solid gel structure. In the food industry, oleogels are most often investigated as substitutes for saturated and trans fats. In this work, the lyotropic formation of ethanol/zein/oleic acid gels was observed qualitatively and ternary phase diagrams were constructed to map the observations. The viscoelastic parameters G' and G'' were measured to confirm gel formation as observed in phase diagrams. Ultrasmall X-ray scattering was used to study the microstructural organization of ethanol/zein/oleic acid gels. Furthermore, data suggested that the primary unit or building block for gel network structures was the rod-shaped zein molecule. Ultrasmall X-ray data suggested that zein/oleic acid gels have a highly organized microstructure, possibly the result of zein self-assembly. Zein was considered an effective oleogelator in ethanol/zein/oleic acid systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗