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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 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Encoding Multilayer Complexity in Anti-Counterfeiting Heterometallic MOF-based Optical Tags

Optical tags provide a way to quickly and unambiguously identify valuable assets. Current tag fluorophore options lack the tunability to allow combined methods of encoding in a single material. Here we report a design strategy to encode multilayer complexity in a family of heterometallic rare-earth metal-organic frameworks based on highly connected nonanuclear clusters. To impart both intricacy and security, a synergistic approach was implemented resulting in both overt (visible) and covert (near infrared, NIR) properties, with concomitant multi-emissive spectra and tunable luminescence lifetimes. Tag authentication is validated with a variety of orthogonal detection methodologies. Importantly, the effect induced by subtle compositional changes on intermetallic energy transfer, and thus on the resulting photophysical properties, is demonstrated. This strategy can be widely implemented to create a large library of highly complex, difficult to counterfeit optical tags.

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

A Semi‐Automated, High‐Throughput Approach for the Synthesis and Identification of Highly Photo‐Cytotoxic Iridium Complexes

Abstract The discovery of new compounds with pharmacological properties is usually a lengthy, laborious and expensive process. Thus, there is increasing interest in developing workflows that allow for the rapid synthesis and evaluation of libraries of compounds with the aim of identifying leads for further drug development. Herein, we apply combinatorial synthesis to build a library of 90 iridium(III) complexes (81 of which are new) over two synthesise‐and‐test cycles, with the aim of identifying potential agents for photodynamic therapy. We demonstrate the power of this approach by identifying highly active complexes that are well‐tolerated in the dark but display very low nM phototoxicity against cancer cells. To build a detailed structure–activity relationship for this class of compounds we have used density functional theory (DFT) calculations to determine some key electronic parameters and study correlations with the experimental data. Finally, we present an optimised semi‐automated synthesise‐and‐test protocol to obtain multiplex data within 72 hours.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ligand‐Directed Actinide Oxo‐Bond Manipulation in Actinyl Thiacalix[4]arene Complexes

Understanding the chemistry of the inert actinide oxo bond in actinyl ions AnO2 2+ is important for controlling actinide behavior in the environment, during separations, and in nuclear waste (An=U, Np, Pu). The thioether calixarene TC4A (4-tert-butyltetrathiacalix[4]arene) binds equatorially to the actinyl cation forming a conical pocket that differentiates the two trans-oxo groups. The 'ate' complexes, [A]2[UO2(TC4A)] (A=[Li(DME)2], HNEt3) and [HNEt3]2[AnO2(TC4A)] (An=U, Np, Pu), enable selective oxo chemistry. Silylation of the UVI oxo groups by bis(trimethylsilyl)pyrazine occurs first at only the unencapsulated exo oxo and only one silylation is needed to enable migration of the endo oxo out of the cone, whereupon a second silylation affords the stable UIV cis-bis(siloxide) [A]2[U(OSiMe3)2(TC4A)]. Calculations confirm that only one silylation event is needed to initiate oxo rearrangement, and that the putative cis dioxo isomer of [UO2(TC4A)]2- would be stable if it could be accessed synthetically, at only 23 kcal.mol-1 in energy above the classical trans dioxo. Calculations for the transuranic cis[AnO2(TC4A)]2- (An=Np, Pu) are at higher energies, 30-35 kcal.mol-1, retaining the U complexes as the more obvious target for a cis-dioxo actinyl ion. The aryloxide (OAr) groups of the macrocycle are essential in stabilizing this as-yet unseen uranyl geometry as further bonding in the TC4A U-OAr groups stabilizes the U=O 'yl' bonds, explaining the stability of the putative cis[UO2(TC4A)]2- in this ligand framework.

Pyrch, Mikaela M↗
DOE OSTI2020

Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

Well-characterized complexes of transplutonium elements are scarce because of the experimental challenges of working with these elements and the rarity of the isotopes. This leads to a lack of structural and spectroscopic data needed to understand the nature of chemical bonds in these compounds. In this work, the synthesis of Cf(DOPO q ) 2 (NO 3 )(py) (DOPO q =2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate; py=pyridine) is reported, in which the nitrate anion is hypothesized to form through the α-radiolysis-induced reaction of pyridine and/or the ligand. Here, computational analysis of the electronic structure of the complex reveals that the Cf III –ligand interactions are largely ionic.

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

An Allyl Uranium(IV) Sandwich Complex: Are ϕ Bonding Interactions Possible?

Abstract A method to explore head‐to‐head ϕ back‐bonding from uranium f‐orbitals into allyl π* orbitals has been pursued. Anionic allyl groups were coordinated to uranium with tethered anilide ligands, then the products were investigated by using NMR spectroscopy, single‐crystal XRD, and theoretical methods. The (allyl)silylanilide ligand, N ‐((dimethyl)prop‐2‐enylsilyl)‐2,6‐diisopropylaniline (LH), was used as either the fully protonated, singly deprotonated, or doubly deprotonated form, thereby highlighting the stability and versatility of the silylanilide motif. A free, neutral allyl group was observed in UI 2 (L1) 2 ( 1 ), which was synthesized by using the mono‐deprotonated ligand [K][ N ‐((dimethyl)prop‐2‐enyl)silyl)‐2,6‐diisopropylanilide] (L1). The desired homoleptic sandwich complex U[L2] 2 ( 2 ) was prepared from all three ligand precursors, but the most consistent results came from using the dipotassium salt of the doubly deprotonated ligand [K] 2 [ N ‐((dimethyl)propenidesilyl)‐2,6‐diisopropylanilide] (L2). This allyl‐based sandwich complex was studied by using theoretical techniques with supporting experimental spectroscopy to investigate the potential for phi (ϕ) back‐bonding. The bonding between U IV and the allyl fragments is best described as ligand‐to‐metal electron donation from a two carbon fragment‐localized electron density into empty f‐orbitals.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Neptunyl Pyrrophen Complexes: Exploring Schiff Base Chemistry with Multidentate Acyclic Ligands and Transuranics

Here we report the synthesis, structure, and characterization of two novel neptunyl complexes (NpO 2 L1 and NpO 2 L2) constructed from phenylene-substituted benzyl ester bis(pyrrole)phenylenediamine (named “pyrrophen”) ligands. In both cases, the neptunium center exists in the +6 oxidation state,. As our specific interest is in exploring the chemistry of neptunium compounds containing the linear neptunyl ion (NpO 2 2+ ) through equatorially coordinating the metal by multidentate organic ligands, we have identified the differences that are likely to cause discrepancy between the two complexes by examining the ions and their coordinative environments through single-crystal X-ray crystallography, diffuse reflectance, and Raman spectroscopy. This is the first time pyrrophen has been utilized in Np chemistry and demonstrates a new platform to study 5 f electron participation and coordination.

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

Enhanced Nanostructure Dynamics on Au(111) with Adsorbed Sulfur due to Au–S Complex Formation

Chemisorbed species can enhance the fluxional dynamics of nanostructured metal surfaces which has implications for applications such as catalysis. Scanning tunneling microscopy studies at room temperature reveal that the presence of adsorbed sulfur (S) greatly enhances the decay rate of 2D Au islands in the vicinity of extended step edges on Au(111). This enhancement is already significant at S coverages, θS, of a few hundredths of a monolayer (ML), and is most pronounced for 0.1–0.3 ML where the decay rate is increased by a factor of around 30. For θ S close to saturation at about 0.6 ML, sulfur induces pitting and reconstruction of the entire surface, and Au islands are stabilized. Enhanced coarsening at lower θS is attributed to the formation and diffusion across terraces of Au–S complexes, particularly AuS 2 and Au4S 4 , with some lesser contribution from Au3S4. This picture is supported by density functional theory analysis of complex formation energies and diffusion barriers.

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

Response of Pseudomonas putida to Complex, Aromatic-Rich Fractions from Biomass

There is strong interest in the valorization of lignin to produce valuable products; however, its structural complexity has been a conversion bottleneck. Chemical pretreatment liberates lignin-derived soluble fractions that may be upgraded by bioconversion. Here, cholinium ionic liquid pretreatment of sorghum produced soluble, aromatic-rich fractions that were converted by Pseudomonas putida (P. putida), a promising host for aromatic bioconversion. Growth studies and mutational analysis demonstrated that P. putida growth on these fractions was dependent on aromatic monomers but unknown factors also contributed. Proteomic and metabolomic analyses indicated that these unknown factors were amino acids and residual ionic liquid; the oligomeric aromatic fraction derived from lignin was not converted. A cholinium catabolic pathway was identified, and the deletion of the pathway stopped the ability of P. putida to grow on cholinium ionic liquid. This work demonstrates that aromatic-rich fractions obtained through pretreatment contain multiple substrates; conversion strategies should account for this complexity.

09 BIOMASS FUELS↗
DOE OSTI2023

A Straightforward Access to Cyclic (Alkyl)(amino)carbene Copper (I) Complexes

Here, the synthesis and characterization of cyclic (alkyl)(amino)carbene, bicyclic (alkyl)(amino)carbene and cyclic (amino)(barrelene)carbene copper (I) complexes is reported. These complexes are obtained via a scalable, versatile, green, and cost/user-friendly strategy.

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

Structural Trends and Vibrational Analysis of N,N,N′,N′−Tetramethylmalonamide Complexes Across the Lanthanide Series

Fundamental understanding of coordination chemistry across the lanthanide series is essential for explaining chemical behavior of rare-earth metals in complex liquid-liquid extraction processes, which in turn affects the distribution ratios and efficacy of separations as a whole. In this work, we explore the structural trends between the lanthanides and a neutral N,N,N',N'-tetramethylmalonamide (TMMA) ligand within four isolated families of solid-state compounds: Ln(trans-TMMA) 2 (NO 3 ) 3 Ln=La-Nd, Sm; Ln(cis-TMMA) 2 (NO 3 ) 3 Ln=Eu-Tb, Er; [Ln(TMMA) 3 (NO 3 ) 2 ][Ln(TMMA)(NO 3 ) 4 ] Ln=Dy-Tm; Ln(Κ 2 -TMMA)(iPrOH)(NO 3 ) 3 and Ln(Κ 1 -TMMA)(Κ 2 -TMMA)(NO 3 ) 3 Ln=Yb, Lu. Moving across the lanthanide series, we note the formation of both discrete charge-neutral complexes, as well as charged molecular anion-cation pairs, with variations in spatial ligand arrangement, coordination numbers, and ligand denticities. IR and Raman spectroscopy paired with DFT frequency calculations were used for an in-depth investigation of vibrational modes unique to each structural family. The collection of isolated model compounds was also discussed in the context of liquid-liquid separations based on reported distribution ratios from malonamide extraction.

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

Spatial and temporal variation in forest transpiration across a forested boreal peatland complex

Transpiration is a globally important component of evapotranspiration. Careful upscaling of transpiration from point measurements is thus crucial for quantifying water and energy fluxes. In spatially heterogeneous landscapes common across the boreal biome, upscaled transpiration estimates are difficult to determine due to variation in local environmental conditions (e.g., basal area, soil moisture, permafrost). Here, we sought to determine stand-level attributes that influence transpiration scalars for a forested boreal peatland complex consisting of sparsely treed wetlands and densely treed permafrost plateaus as land cover types. The objectives were to quantify spatial and temporal variability in stand-level transpiration, and to identify sources of uncertainty when scaling point measurements to the stand-level. Using heat ratio method sap flow sensors, we determined sap velocity for black spruce and tamarack for 2-week periods during peak growing season in 2013, 2017 and 2018. We found greater basal area, drier soils, and the presence of permafrost increased daily sap velocity in individual trees, suggesting that local environmental conditions are important in dictating sap velocity. When sap velocity was scaled to stand-level transpiration using gridded 20 × 20 m resolution data across the ~10 ha Scotty Creek ForestGEO plot, we observed significant differences in daily plot transpiration among years (0.17–0.30 mm), and across land cover types. Daily transpiration was lowest in grid-cells with sparsely treed wetlands compared to grid-cells with well-drained and densely treed permafrost plateaus, where daily transpiration reached 0.80 mm, or 30% of the daily evapotranspiration. When transpiration scalars (i.e., sap velocity) were not specific to the different land cover types (i.e., permafrost plateaus and wetlands), scaled stand-level transpiration was overestimated by 42%. To quantify the relative contribution of tree transpiration to ecosystem evapotranspiration, we recommend that sampling designs stratify across local environmental conditions to accurately represent variation associated with land cover types, especially with different hydrological functioning as encountered in rapidly thawing boreal peatland complexes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Incorporating the Role(s) of Human Actors in Complex System Design for Safety and Security

Traditional systems engineering demonstrates the importance of customer needs in scoping and defining design requirements; yet, in practice, other human stakeholders are often absent from early lifecycle phases. Human factors are often omitted in practice when evaluating and down-selecting design options due to constraints such as time, money, access to user populations, or difficulty in proving system robustness through the inclusion of human behaviors. Advances in systems engineering increasingly include non-technical influences into the design, deployment, operations, and maintenance of interacting components to achieve common performance objectives. Furthermore, such advances highlight the need to better account for the various roles of human actors to achieve desired performance outcomes in complex systems. Many of these efforts seek to infuse lessons and concepts from human factors (enhanced decision-making through Crew Resource Management), systems safety (Rasmussen's “drift toward danger”) and organization science (Giddens' recurrent human acts leading to emergent behaviors) into systems engineering to better understand how socio-technical interactions impact emergent system performance. Safety and security are examples of complex system performance outcomes that are directly impacted by varying roles of human actors. Using security performance of high consequence facilities as a representative use case, this article will outline the System Context Lenses to understand how to include various roles of human actors into systems engineering design. Several exemplar applications of this organizing lenses will be summarized and used to highlight more generalized insights for the broader systems engineering community.

42 ENGINEERING↗
DOE OSTI2025

Governance and Resilience: A Holistic Approach to Systems Security in Complex and Chaotic Environments

Here, a systems governance approach emphasizes a holistic perspective that identifies and navigates the interdependencies and conflicts between security and operational needs. Governance is defined as a collection of metasystems that provide the necessary constraints and processes to support, steer, adapt, transform, and sustain a system (Keating et al. 2022). Utilizing the Cynefin framework, which distinguishes between simple, complicated, complex, and chaotic environments (Snowden and Boone 2007), the article highlights the challenges faced by nuclear power plants in predatory contexts and the importance of integrating security objectives into governance frameworks. By incorporating security as a fundamental aspect of governance, the article underscores its significance for persistence, adaptation, and transformation in the face of uncertainty. Additionally, it introduces key heuristics of systems security, such as the importance of context, knowledge‐based decision‐making, and organization‐specific sociological factors (Williams and Caskey 2024). Ultimately, this work provides valuable insights into enhancing resilient operations in complex environments by reinforcing the connection between effective governance and security in systems engineering.

Caskey, Susan A. [Sandia National Laboratories (SN↗
DOE OSTI2023

Ground and excited electronic structures of electride and alkalide units: The cases of Metal-Tren, -Azacryptand, and -TriPip222 complexes

A systematic electronic structure analysis was conducted for M(L) n molecular electrides and their corresponding alkalide units M(L) n @M' (M/M' = Na, K; L = Tren, Azacryptand, TriPip222; n = 1, 2). All complexes belong to the “superalkali” category due to their low ionization potentials. The saturated molecular electrides display M+(L) n - form with a greatly diffuse quasispherical electron cloud. They were identified as “superatoms” considering the contours of populating atomic-type molecular orbitals. The observed superatomic Aufbau order of M(Tren) 2 is 1S, 1P, 1D, 1F, 2S, 2P, and 1G and it is consistent with those of M(Azacryptand) and M(TriPip222) up to the analyzed 1F level. Their excitation energies decrease gradually moving from M(Tren) 2 to M(Azacryptand) and to M(TriPip222). The studied alkalide complexes carry [M(L) n ] + @M' - ionic structure and their dissociation energies vary in the sequence of K(L) n @Na > Na(L) n @Na > K(L) n @K > Na(L) n @K. Similar to molecular electrides, the anions of alkalide units occupy electrons in diffuse Rydberg-like orbitals. In this work, excited states of [M(L) n @M'] 0/+/- and their trends are also analyzed.

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

Coordination Stoichiometry Effects on the Binding Hierarchy of Histamine and Imidazole–M 2+ Complexes

Histidine–M 2+ coordination bonds are a recognized bond motif in biogenic materials with high hardness and extensibility, which has led to growing interest in their use in soft materials for mechanical function. However, the effect of different metal ions on the stability of the coordination complex remains poorly understood, complicating their implementation in metal-coordinated polymer materials. Herein, rheology experiments and density functional theory calculations are used to characterize the stability of coordination complexes and establish the binding hierarchy of histamine and imidazole with Ni 2+ , Cu 2+ , and Zn 2+ . It is found that the binding hierarchy is driven by the specific affinity of the metal ions to different coordination states, which can be macroscopically tuned by changing the metal-to-ligand stoichiometry of the metal-coordinated network. These findings facilitate the rational selection of metal ions for optimizing the mechanical properties of metal-coordinated materials.

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

A Minkowski difference-based advancing front packing technique for generating convex noncircular particles in complex domains

In this work, a Minkowski difference-based advancing front approach is proposed to generate convex and non-circular particles in a predefined computational domain. Two specific algorithms are developed to handle the contact conformity of generated particles with the boundaries of the computational domain. The first, called the open form, is used to handle the smooth contact of generated particles with (external) boundaries, while the other, called the closed form, is proposed to handle the internal boundaries of a computational domain with a complex cavity. The Gilbert-Johnson-Keerthi (GJK) method is used to efficiently solve the contact detection between the newly generated particle at the front and existing particles. Furthermore, the problem of one-sided particle lifting, which can cause some defects in the packing structure in existing advancing front methods during packing generation, is highlighted and an effective solution is developed. Several examples of increasing complexity are used to demonstrate the efficiency and applicability of the proposed packing generation approach. The numerical results show that the generated packing is not only more uniform, but also achieves a higher packing density than existing advancing front methods.

42 ENGINEERING↗
DOE OSTI2021

Crystal structures of inhibitor complexes of M‐PMV protease with visible flap loops

Abstract Mason‐Pfizer monkey virus protease (PR) was crystallized in complex with two pepstatin‐based inhibitors in P 1 space group. In both crystal structures, the extended flap loops that lock the inhibitor/substrate over the active site, are visible in the electron density either completely or with only small gaps, providing the first observation of the conformation of the flap loops in dimeric complex form of this retropepsin. The H‐bond network in the active site (with D26N mutation) differs from that reported for the P 2 1 crystal structures and is similar to a rarely occurring system in HIV‐1 PR.

Wosicki, Stanislaw↗
DOE OSTI2023

Structural characterization of an intrinsically disordered protein complex using integrated small-angle neutron scattering and computing

Characterizing structural ensembles of intrinsically disordered proteins (IDPs) and intrinsically disordered regions (IDRs) of proteins is essential for studying structure–function relationships. Due to the different neutron scattering lengths of hydrogen and deuterium, selective labeling and contrast matching in small-angle neutron scattering (SANS) becomes an effective tool to study dynamic structures of disordered systems. However, experimental timescales typically capture measurements averaged over multiple conformations, leaving complex SANS data for disentanglement. We hereby demonstrate an integrated method to elucidate the structural ensemble of a complex formed by two IDRs. We use data from both full contrast and contrast matching with residue-specific deuterium labeling SANS experiments, microsecond all-atom molecular dynamics (MD) simulations with four molecular mechanics force fields, and an autoencoder-based deep learning (DL) algorithm. From our combined approach, we show that selective deuteration provides additional information that helps characterize structural ensembles. We find that among the four force fields, a99SB-disp and CHARMM36m show the strongest agreement with SANS and NMR experiments. In addition, our DL algorithm not only complements conventional structural analysis methods but also successfully differentiates NMR and MD structures which are indistinguishable on the free energy surface. Finally, we present an ensemble that describes experimental SANS and NMR data better than MD ensembles generated by one single force field and reveal three clusters of distinct conformations. Our results demonstrate a new integrated approach for characterizing structural ensembles of IDPs.

59 BASIC BIOLOGICAL SCIENCES↗