Engineering Organization of DNA Nano-Chambers through Dimensionally Controlled and Multi-Sequence Encoded Differentiated Bonds
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99 GENERAL AND MISCELLANEOUS↗
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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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One-step lignocellulose depolymerization and saccharification to high sugar yield and less condensed isolated lignin
The cost of sugar production remains a key challenge in future lignocellulosic biorefineries. We demonstrate that ZnBr 2 , an inexpensive inorganic salt, provides nearly theoretical yields of glucose and xylose in one-step from poplar wood at 85 °C and short reaction times at molten salt hydrate (MSH) conditions without an acid. Catalytic depolymerization of the isolated MSH lignin, using a CoS 2 catalyst, yields 17% phenol-like monomers compared to only 1% produced from the acidified MSH lignin. Reductive catalytic fractionation of MSH lignin over Ru/C resulted in two times higher total monomer yield compared to the AMSH lignin. Both the lignin samples were characterized using 2D HSQC NMR and the thioacidolysis method. Thioacidolysis studies reveal 8.4% and 1.8% of β-O-4 linkages in MSH and acidified MSH lignin, respectively. Thermodynamic modeling and 13 C NMR spectroscopy indicate that the effectiveness of this catalyst arises from the strong interaction of the Lewis acidic zinc cation (Zn 2+ ) with the coordinated water molecules resulting in hydrolysis of the metal aquo complex and to the salt-driven increase in the H + activity coefficient. Techno-economic analysis demonstrates that despite being slower, the ZnBr 2 MSH media has cost advantages, compared to conventional hydrolysis and even to the LiBr and ZnBr 2 AMSH, due to the higher quality of lignin.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Homologous acetone carboxylases select Fe(II) or Mn(II) as the catalytic cofactor
The Irving-Williams series refers to the predicted stabilities of transition metal complexes where the observed general stability for divalent first-row transition metal complexes increase across the row. Acetone carboxylases (ACs) use a coordinated divalent metal at their active site in the catalytic conversion of bicarbonate and acetone to form acetoacetate. Highly homologous ACs discriminate among different divalent metals at their active sites such that variations of the enzyme prefer Mn(II) over Fe(II), defying Irving-Williams-predicted behavior. Defining the determinants that promote metal discrimination within the first-row transition metals is of broad fundamental importance in understanding metal-mediated catalysis and metal catalyst design.
59 BASIC BIOLOGICAL SCIENCES↗
Distributed Energy Resource Cybersecurity Framework and Cyber Range Integration
Distributed energy resource (DER) systems feature complex, data-driven communications networks that require careful system coordination and constant vigilance to ensure that grid assets are secure. Because DERs are an important component of the decarbonization strategy, agencies need to secure energy data that could implicate issues of national security if compromised. To help federal energy managers assess, monitor, and manage cybersecurity while achieving decarbonization, the National Renewable Energy Laboratory's (NREL's) Distributed Energy Resource Cybersecurity Framework (DER-CF) offers a comprehensive, web-based assessment tool focusing on cyber governance or policies, technical management, and physical security. The DER-CF currently presents users with a series of pertinent cybersecurity questions that are used to generate a site-specific report and recommendations. This paper outlines a plan to integrate the DER-CF with another key asset-NREL's cyber range-to visualize cybersecurity resilience and compliance and to enhance the usability and accessibility of the DER-CF for federal facility energy managers and planners. This integration will result in a visualization environment to interpret and interact with compliance data. Its development will include regular conversations with stakeholders to assess the effectiveness of these efforts, refine the visualization capability, and ensure its value to our partners.
24 POWER TRANSMISSION AND DISTRIBUTION↗
V2XConnect: Harmonizing the Landscape of Bidirectional Charging Codes, Standards, and Communication Protocols
The utility grid is constantly evolving with new generation sources and diverse loads from backup generators, backup batteries, rooftop photovoltaics (PV), and flexible charging loads. Each of these technologies presents consumers with an opportunity to work with their local utility to promote grid stability, reliability, and affordability. Through a wide range of programs, utilities are incentivizing the use of these resources to benefit the grid. However, especially for devices with inverters that supply power back to the grid, it is important that these assets comply with local grid codes to ensure human safety, power quality, and grid reliability. One of the most promising of these new technologies is the bidirectional electric vehicle (EV) coupled with bidirectional electric vehicle supply equipment (EVSE). This report introduces the technologies that enable bidirectional charging and how these systems operate. It then outlines the necessary interconnection codes and industry standards that govern the operations of grid-tied inverters, including those in bidirectional charging. A key challenge is then outlined from the complex landscape of communication protocols and proprietary systems designed to coordinate these grid assets. Finally, a single gateway solution is proposed to harmonize communications between all assets across an entire site for a cohesive response to grid codes and utility programs that is flexible enough to support a range of market options.
33 ADVANCED PROPULSION SYSTEMS↗
Application of a numerically generated orthogonal coordinate system to the solution of inviscid axisymmetric supersonic flow over blunt bodies
A numerically generated orthogonal coordinate system (with the body surface and shock wave as opposite boundaries) was applied with a time asymptotic method to obtain steady flow solutions for axisymmetric inviscid flow over several blunt bodies including spheres, paraboloids, ellipsoids, hyperboloids, hemisphere cylinders, spherically blunted cones, and a body with a concavity in the stagnation region. Comparisons with experimental data and with the results of other computational methods are discussed. The numerically generated orthogonal coordinate system is described and applications of the method to complex body shapes, particularly those with concave regions, are discussed.
Hamilton, H. H., II↗
A transport equation for eddy viscosity
A transport equation for eddy viscosity is proposed for wall bounded turbulent flows. The proposed model reduces to a quasi-homogeneous form far from surfaces. Near to a surface, the nonhomogeneous effect of the wall is modeled by an elliptic relaxation model. All the model terms are expressed in local variables and are coordinate independent; the model is intended to be used in complex flows. Turbulent channel flow and turbulent boundary layer flows with/without pressure gradient are calculated using the present model. Comparisons between model calculations and direct numerical simulation or experimental data show good agreement.
Durbin, P. A.↗
Maven Observations of Electron-Induced Whistler Mode Waves in the Martian Magnetosphere
We report on narrowband electromagnetic waves at frequencies between the local electron cyclotron and lower hybrid frequencies observed by the Mars Atmosphere and Volatile EvolutioN (MAVEN) spacecraft in the Martian induced magnetosphere. The peaked electric field wave spectra below the electron cyclotron frequency were first observed by Phobos-2 in the Martian magnetosphere, but the lack of magnetic field wave data prevented definitive identification of the wave mode and their generation mechanisms remain unclear. Analysis of electric and magnetic field wave spectra obtained by MAVEN demonstrates that the observed narrowband waves have properties consistent with the whistler mode. Linear growth rates computed from the measured electron velocity distributions suggest that these whistler mode waves can be generated by cyclotron resonance with anisotropic electrons. Large electron anisotropy in the Martian magnetosphere is caused by absorption of parallel electrons by the collisional atmosphere. The narrowband whistler mode waves and anisotropic electrons are observed on both open and closed field lines and have similar spatial distributions in MSO and planetary coordinates. Some of the waves on closed field lines exhibit complex frequency-time structures such as discrete elements of rising tones and two bands above and below half the electron cyclotron frequency. These MAVEN observations indicate that whistler mode waves driven by anisotropic electrons, which are commonly observed in intrinsic magnetospheres and at unmagnetized airless bodies, are also present at Mars. The wave-induced electron precipitation into the Martian atmosphere should be evaluated in future studies.
martian↗
Kamodo’s Model-Agnostic Satellite Flythrough: Lowering the Utilization Barrier for Heliophysics Model Outputs
Heliophysics model outputs are increasingly accessible, but typically are not usable by the majority of the community unless directly collaborating with the relevant model developers. Prohibitive factors include complex file output formats, cryptic metadata, unspecified and often customized coordinate systems, and non-linear coordinate grids. Some pockets of progress exist, giving interfaces to various simulation outputs, but only for a small set of outputs and typically not with open-source, freely available packages. Additionally, the increasing array of tools built upon these sporadic interfaces are typically model-specific. We present Kamodo’s model-agnostic satellite flythrough capabilities as the solution to the utilization barrier for heliophysics model outputs. Developed at the Community Coordinated Modeling Center, these flythrough capabilities are built in Python upon a network of model-agnostic interfaces developed in collaboration with model developers, providing interpolation results the community can trust. Kamodo’s flythrough capabilities present the user with a growing variety of flythrough tools based upon a rapidly expanding library of heliophysics model outputs in several domains, currently including a variety of Ionosphere-Thermosphere-Mesosphere and global magnetosphere model outputs. Each capability is designed to be easily accessible via simplistic model-agnostic syntax, with the entire package freely available in the cloud on Github. Here, we describe the tools developed, include several sample applications for common science questions, demonstrate interoperability with selected packages, and summarize ongoing developments.
Software↗
Defining Collaborative Control Interactions Using Systems Theory
Human teams collaborate by establishing roles, changing functional authorities, maintaining team cognition, coordinating, and mutually helping one another close control loops. These complex inter-actions are inspiring novel concepts to improve human-machine and multi-machine collaboration. However, these new systems face engineering gaps in modeling, analysis, design, and assurance. As such, few have been fielded in safety-critical domains like aerospace. To analyze safety, this paper introduces a system-theoretic framework to describe interactions that are—or are planned to be—used in multi-controller systems. It outlines a taxonomy of seven structural dimensions that influence controller interactions and nine dynamics observed in collaborative control that are defined using Systems Theory. An analyzed set of 101 controller interactions in aerospace systems demonstrates how to apply the framework and that designers are trying to create more sophisticated systems. This framework provides the foundation to extend system-theoretic hazard analysis techniques to systematically find collabora-tive-control causal factors.
Human machine teaming↗
Megawatt Scale Charging System Architecture
The paper presents a novel and futuristic architecture for a megawatt charging system (MCS) capable of charging light, medium, and heavy-duty vehicles. The station architecture consists of multiport systems with each multiport interfacing the grid, EV, PV, and energy storage system through an intermediate DC bus. The station being a “system of systems” requires a complex software layer with intelligence, control, and communication for effective coordination and utilization of the power electronic interfaces and the assets. The paper elaborates on the station architecture and the associated software layer used for control and coordination. Additionally, the paper provides an approach to utilize hardware-in-the-loop (HIL) capabilities to validate such architectures.
Krishna Moorthy, Radha↗
CO 2 Hydrogenation and Formic Acid Dehydrogenation Using Ir Catalysts with Amide-Based Ligands
In this work, a series of Ir catalysts bearing amide-based ligands generated by a deprotonated amide moiety was prepared with the hypotheses that the strong electron-donating ability of the coordinated anionic nitrogen atom and the proton-responsive OH group near the metal center will improve the catalytic activity for CO 2 hydrogenation and formic acid (FA) dehydrogenation. The effects of the modifications of the ligand architecture on the catalytic activity were investigated for CO 2 hydrogenation at ambient conditions (25 °C with 0.1 MPa H 2 /CO 2 (v/v = 1/1)) and under slightly harsher conditions (50 °C with 1.0 MPa H 2 /CO 2 ) in basic aqueous solutions together with deuterium kinetic isotope effects (KIEs) with selected catalysts. Cp*Ir( L12 )(H 2 O)HSO 4 ( L12 = 6-hydroxy- N -phenylpicolinamidate) that has an anionic coordinating N atom and an OH group in the second coordination sphere, exhibits a turnover frequency (TOF) of 198 h –1 based on the initial 1 h of reaction. This TOF which, to the best of our knowledge, is the highest value ever reported under ambient conditions in basic aqueous solutions. However, Cp*Ir( L10 )(H 2 O)HSO 4 ( L10 = (4-hydroxy- N -methylpicolinamidate) performs better in long-term CO 2 hydrogenation (up to a TON of 14 700 with [Ir] = 10 μM after 348 h and the final formate concentration of 0.643 M with [Ir] = 250 μM) at ambient conditions. Further, the catalytic activity for FA dehydrogenation was examined under three different conditions (pH 1.6, 2.3, and 3.5). The Cp*Ir( L12 )(H 2 O)HSO 4 complex in any of these conditions is less active compared to the picolinamidate catalysts without ortho -OH, owing to its instability. The complex without OH group, Cp*Ir( L8 )(H 2 O)HSO 4 ( L8 = N -phenyl-picolinamidate), exhibits a high TOF (up to 118 000 h -1 ) at 60 °C. Theoretical calculations were performed to examine the catalytic mechanism, and a step-by-step mechanism has been proposed for both CO 2 hydrogenation and FA dehydrogenation reactions. Density functional theory calculations of [Cp*Ir( L3 )(H 2 O)]HSO 4 ( L3 = picolinamidate) and the X-ray structure of the [Cp*Ir( L7 )(H)]·H 2 O ( L7 = N -methylpicolinamidate) complex imply a pH-dependent conformational change from N , N coordination to N , O coordination upon lowering the pH of the aqueous solution.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Spectroscopic and Electronic Structure Study of ETHE1: Elucidating the Factors Influencing Sulfur Oxidation and Oxygenation in Mononuclear Nonheme Iron Enzymes
ETHE1 is a member of a growing subclass of nonheme Fe enzymes that catalyzes transformations of sulfur-containing substrates without a cofactor. ETHE1 dioxygenates glutathione persulfide (GSSH) to glutathione (GSH) and sulfite in a reaction which is similar to that of cysteine dioxygenase (CDO), but with monodentate (vs bidentate) substrate coordination and a 2-His/1-Asp (vs 3-His) ligand set. In this study, we demonstrate that GSS– binds directly to the iron active site, causing coordination unsaturation to prime the site for O 2 activation. Nitrosyl complexes without and with GSSH were generated and spectroscopically characterized as unreactive analogues for the invoked ferric superoxide intermediate. New spectral features from persulfide binding to the Fe III include the appearance of a low-energy Fe III ligand field transition, an energy shift of a NO– to Fe III CT transition, and two new GSS– to Fe III CT transitions. Time-dependent density functional theory calculations were used to simulate the experimental spectra to determine the persulfide orientation. Correlation of these spectral features with those of monodentate cysteine binding in isopenicillin N synthase (IPNS) shows that the persulfide is a poorer donor but still results in an equivalent frontier molecular orbital for reactivity. The ETHE1 persulfide dioxygenation reaction coordinate was calculated, and while the initial steps are similar to the reaction coordinate of CDO, an additional hydrolysis step is required in ETHE1 to break the S–S bond. Unlike ETHE1 and CDO, which both oxygenate sulfur, IPNS oxidizes sulfur through an initial H atom abstraction. Thus, factors that determine oxygenase vs oxidase reactivity were evaluated. In general, sulfur oxygenation is thermodynamically favored and has a lower barrier for reactivity. Furthermore, in IPNS, second-sphere residues in the active site pocket constrain the substrate, raising the barrier for sulfur oxygenation relative to oxidation via H atom abstraction.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structural and Spectroscopic Characterization of Plutonium and Other Tetravalent Metals Complexed to a Keggin Ion
Here, we report the isolation of the first plutonium(IV) complex with a Keggin ion chelator: Cs 20 [Pu(PW 11 O 39 ) 2 ] 2 ·13H 2 O. Single crystal XRD and solid-state UV–vis absorbance analysis demonstrate the stabilization of Pu 4+ by the Keggin ligand. The unit cell contains two [Pu(PW 11 O 39 ) 2 ] 10– complexes (Pu(PW 11 ) 2 ) bridged by Cs + . Raman and 31 P NMR spectra of Pu(PW 11 ) 2 are consistent with the analogous Zr 4+ , Hf 4+ , Ce 4+ , and Th 4+ complexes. The Pu–O bond distances at the two Pu sites are 2.35(3) and 2.34(3) Å, matching the value extrapolated from the bonding trend built with the other 8-coordinated tetravalent cations. However, the long-range arrangement of the Pu(PW 11 ) 2 complexes within the lattice is unique in the series of M IV (PW 11 ) 2 compounds: pairs of Pu(PW 11 ) 2 are organized perpendicular to each other. Based on solution-state UV–visible absorbance, small-angle X-ray scattering (SAXS), and 31 P NMR, the tetravalent cations quantitatively form the 1:2 species in solution ([Pu(PW 11 O 39 ) 2 ] 10– (aq) ) and no 1:1 species ([Pu(PW 11 O 39 )(H 2 O) x ] 3– (aq) ). Finally, a linear correlation exists between the metal–oxygen distances in the M IV (PW 11 ) 2 compounds and the corresponding metal dioxides, allowing for extrapolation for Pa 4+ , Am 4+ , and Bk 4+ . The results indicate that our microscale POM approach represents a viable pathway to probe properties of rare actinide ions in discrete molecules, beyond the traditional oxide extended solids.
and nuclear chemistry↗
X-ray and molecular dynamics study of the temperature-dependent structure of molten NaF-ZrF 4
The local atomic structure of NaF-ZrF 4 (53–47 mol%) molten system and its evolution with temperature are examined with x-ray scattering measurements which are then used to validate the quality of ab initio and neural network-based molecular dynamics (NNMD) calculations in the temperature range 515–700°C. The machine-learning enhanced NNMD calculations offer improved efficiency while maintaining accuracy at higher distances compared to ab initio calculations. Looking at the evolution of the pair distribution function with increasing temperature, a fundamental change in the liquid structure within the selected temperature range, accompanied by a slight decrease in overall correlation is revealed. NNMD calculations indicate the coexistence of three different fluorozirconate complexes: [ZrF 6 ] 2– , [ZrF 7 ] 3– , and [ZrF 8 ] 4– , with a shift in the dominant coordination state from the 7-coordinated Zr cation toward a 6-coordinated cation with increasing temperature. The study also highlights the metastability of different local coordination structures, with frequent interconversions between the 6- and 7-coordinate states. Analysis of the Zr-F-Zr angular distribution function reveals the presence of both “edge-sharing” and “corner-sharing” fluorozirconate complexes with specific bond angles and distances in accord with previous studies, while the next-nearest-neighbor cation-cation correlations demonstrate a clear preference for unlike cations as nearest-neighbor pairs, emphasizing nonrandom arrangement. Finally, these findings contribute to a comprehensive understanding of the complex local structure of the molten salt, providing insights into temperature-dependent preferences and correlations within the molten system.
36 MATERIALS SCIENCE↗
Phosphoryl-Ligand Adducts of Rare Earth-TriNOx Complexes: Systematic Studies and Implications for Separations Chemistry
Phosphoryl ligands of the general formula O$=$PR 3 (R = Me, OMe, Et, $^n$Bu, Ph, $^i$Pr, NMe 2 ) were coordinated to [Nd(TriNOx)] (TriNOx 3– = ([(2-$^t$BuNO)C 6 H 4 CH 2 ] 3 N) 3– ), and the resulting complexes were characterized. Solution equilibrium constants for each complex were determined, demonstrating a large range for phosphoryl ligands’ Lewis basicity. Thermogravimetric analyses provided evidence for the qualitative thermodynamic preference of phosphoryl ligands for [Nd(TriNOx)] over the dysprosium analogue. Here, these findings were exploited for the separation of binary mixtures of neodymium/dysrosium and lanthanum/neodymium. Implementation of phosphoryl ligands in the TriNOx separation system expands its scope and demonstrates a fundamentally different mode for separating rare-earth cations based on adducts with neutral donors.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Research to Confront Climate Change Complexity: Intersectionality, Integration, and Innovative Governance
Abstract Climate impacts increasingly unfold in interlinked systems of people, nature, and infrastructure. The cascading consequences are revealing sometimes surprising connections across sectors and regions, and prospects for climate responses also depend on complex, difficult‐to‐understand interactions. In this commentary, we build on the innovations of the United States Fifth National Climate Assessment to suggest a framework for understanding and responding to complex climate challenges. This approach involves: (a) integration of disciplines and expertise to understand how intersectionality shapes complex climate impacts and the wide‐ranging effects of climate responses, (b) collaborations among diverse knowledge holders to improve responses and better encompass intersectionality, and (c) sustained experimentation with and learning about governance approaches capable of handling the complexity of climate change. Together, these three pillars underscore that usability of climate‐relevant knowledge requires transdisciplinary coordination of research and practice. We outline actionable steps for climate research to incorporate intersectionality, integration, and innovative governance, as is increasingly necessary for confronting climate complexity and sustaining equitable, ideally vibrant climate futures.
54 ENVIRONMENTAL SCIENCES↗
Beyond Duality: Rationalizing Repulsive Coulomb Barriers in Host–Guest Cyclodextrin–Dodecaborate Complexes
The repulsive Coulomb barrier (RCB), an intrinsic potential energy barrier along electron detachment or charge-separation coordinates in multiply charged anions (MCAs), provides dynamic stability to MCAs whose electronic and thermodynamic stabilities are largely dictated by strong internal Coulomb repulsions. Spectroscopic and theoretical characterizations of the RCB have been focused on isolated MCAs. In this work, we extend the RCB investigation beyond the previous scope by including noncovalent host–guest cyclodextrin-closo-dodecaborate dianionic complexes χCD·B 12 X 12 2– (χ = α, β, γ; X = H, F–I). Here, photodechment photoelectron spectroscopy reveals the existence of two distinctly different RCBs, derived from detaching electrons from the guest dianions (RCB 1 ) or ionizing the host neutrals (RCB 2 ), respectively, with the latter being substantially smaller than the former. In conclusion, theoretical calculations support the duality of RCBs in these complexes and further exhibit highly anisotropic nature of the RCBs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗