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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 559 records · Page 31

Challenges and opportunities for alternative fuels in the maritime sector

Amidst a period of historic transformation, the marine shipping sector faces uncertainty regarding its ability to reliably fuel while remaining compliant with new international environmental regulations and targets. Increasingly stringent environmental standards, and heightened regulatory focus on maritime decarbonization are driving infrastructural and technical development for alternative fuels and mixtures, engine concepts, and operating practices. However, the transition to alternative fueling is highly complex and requires both a global outlook that spans diverse stakeholder demographics and coordination with multiple actors across the value chain. To aid stakeholders involved in decision making and research related to the transition, a scoping study was conducted with the goal of outlining the barriers, uncertainties, and possibilities in the short and long term for the transition. Synthesis of these results provides strategic decision support, technical direction, and a set of R&D priorities for maritime stakeholders and the scientific community.

09 BIOMASS FUELS↗

General formulas for adiabatic invariants in nearly periodic Hamiltonian systems

While it is well known that every nearly periodic Hamiltonian system possesses an adiabatic invariant, extant methods for computing terms in the adiabatic invariant series are inefficient. The most popular method involves the heavy intermediate calculation of a non-unique near-identity coordinate transformation, even though the adiabatic invariant itself is a uniquely defined scalar. Here, a less well-known method, developed by S. Omohundro, avoids calculating intermediate sequences of coordinate transformations but is also inefficient as it involves its own sequence of complex intermediate calculations. In order to improve the efficiency of future calculations of adiabatic invariants, we derive generally applicable, readily computable formulas for the first several terms in the adiabatic invariant series. To demonstrate the utility of these formulas, we apply them to charged-particle dynamics in a strong magnetic field and magnetic field-line dynamics when the field lines are nearly closed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Framework for Extensible, Asynchronous Task Scheduling (FEATS) in Fortran

Most parallel scientific programs contain compiler directives (pragmas) such as those from OpenMP, explicit calls to runtime library procedures such as those implementing the Message Passing Interface (MPI), or compiler-specific language extensions such as those provided by CUDA. By contrast, the recent Fortran standards empower developers to express parallel algorithms without directly referencing lower-level parallel programming models. Fortran’s parallel features place the language within the Partitioned Global Address Space (PGAS) class of programming models. When writing programs that exploit data-parallelism, application developers often find it straightforward to develop custom parallel algorithms. Problems involving complex, heterogeneous, staged calculations, however, pose much greater challenges. Such applications require careful coordination of tasks in a manner that respects dependencies prescribed by a directed acyclic graph. When rolling one’s own solution proves difficult, extending a customizable framework becomes attractive. The paper presents the design, implementation, and use of the Framework for Extensible Asynchronous Task Scheduling (FEATS), which we believe to be the first task-scheduling tool written in modern Fortran. We describe the benefits and compromises associated with choosing Fortran as the implementation language, and we propose ways in which future Fortran standards can best support the use case in this paper.

Richardson, Brad↗

A Micelle Electrolyte Enabled by Fluorinated Ether Additives for Polysulfide Suppression and Li Metal Stabilization in Li-S Battery

The Li-S battery is a promising next-generation technology due to its high theoretical energy density (2600 Wh kg -1 ) and low active material cost. However, poor cycling stability and coulombic efficiency caused by polysulfide dissolution have proven to be major obstacles for a practical Li-S battery implementation. In this work, we develop a novel strategy to suppress polysulfide dissolution using hydrofluoroethers (HFEs) with bi-functional, amphiphlic surfactant-like design: a polar lithiophilic "head" attached to a fluorinated lithiophobic "tail." A unique solvation mechanism is proposed for these solvents whereby dissociated lithium ions are readily coordinated with lithiophilic "head" to induce self-assembly into micelle-like complex structures. Complex formation is verified experimentally by changing the additive structure and concentration using small angle X-ray scattering (SAXS). These HFE-based electrolytes are found to prevent polysulfide dissolution and to have excellent chemical compatibility with lithium metal: Li||Cu stripping/plating tests reveal high coulombic efficiency (>99.5%), modest polarization, and smooth surface morphology of the uniformly deposited lithium. Li-S cells are demonstrated with 1395 mAh g-1 initial capacity and 71.9% retention over 100 cycles at >99.5% efficiency-evidence that the micelle structure of the amphiphilic additives in HFEs can prohibit polysulfide dissolution while enabling facile Li + transport and anode passivation.

25 ENERGY STORAGE↗

Enabling Interconnected Science Workflows through an Adapter Approach

The INTERSECT Software framework project aims to create an open federated library that connects, coordinates, and controls systems in the scientific domain. It features the Adapter, a flexible and extensible interface inspired by the Adapter design pattern in object-oriented programming. By utilizing Adapters, the INTERSECT SDK enables effective communication and coordination within a diverse ecosystem of systems. This adaptability facilitates the execution of complex operations within the framework, promoting collaboration and efficient workflow management in scientific research. Additionally, the generalizability of Adapters and their patterns enhances their utility in other scientific software projects and challenges.

McGaha, Jesse↗

Excited State Covalency, Dynamics, and Photochemistry of Square Planar Ni-Thiolate Complexes Revealed by Ultrafast X-ray Absorption

Highly covalent Ni bis(dithiolene) and related complexes provide an ideal platform for investigating the effects of metal–ligand orbital hybridization on excited state character and dynamics. In particular, we focus on the ligand field excited states that dominate the photophysics of first-row transition metal complexes. Here, we investigate if they can be significantly delocalized off the metal center, possibly yielding photochemical reactivity more similar to charge transfer excited states than metal-centered ligand field excited states. Here [Ni(mpo) 2 ] (mpo = 2-mercaptopyridine- N-oxide) provides a representative example for the larger chemical class and is an active electro- and photo-catalyst for proton reduction. A detailed characterization of the excited state electronic structure, dynamics, and photochemistry of [Ni(mpo) 2 ] is presented based on ultrafast transient X- ray absorption spectroscopy at the Ni and S 1s core absorption K-edges. By comparing the ultrafast Ni K-edge absorption to ab initio calculations, we identify an excited state relaxation mechanism where an initial ligand-to-metal charge transfer excitation results in both excited state electron transfer (generating a catalytically relevant reduced photoproduct [Ni(mpo) 2 ] − ) and relaxation to a pseudo-tetrahedral triplet ligand field excited state. From the ultrafast S K-edge absorption, the ligand field excited state is found to be highly delocalized onto the thiolate ligands and a tetrahedral structural distortion is shown to substantially influence the degree of delocalization. The results identify a significant structural coordinate to target when aiming to control the excited state covalency in square planar complexes.

Lim, Hyeongtaek [SLAC National Accelerator Laborat↗

Mechanisms of Zn removal from water by amorphous geopolymer: Molecular-level insights from X-ray absorption spectroscopy, isotope fractionation, and surface complexation modeling

Porous geopolymers have attracted widespread attention as promising heavy metal adsorbents that can be synthesized from aluminosilicate solid wastes. However, the precise microstructural evidence for adsorbed heavy metals on geopolymers remains unclear due to the insensitivity of conventional characterization techniques on minerals with amorphous structure and surface disorder. Batch adsorption and column experiments coupled with X-ray absorption spectroscopy (XAS), Zn stable isotope, and surface complexation model (SCM) were employed to reveal the Zn removal mechanisms with coal fly ash porous geopolymer (CFAPG) at a molecular scale. The macroscopic kinetic and isothermal adsorption of Zn on CFAPG were well described by the pseudo-second-order model and Bi_Langmuir equation, respectively, indicating the presence of abundant heterogeneous active sites on the CFAPG surface. Further, two types of active sites on the CFAPG surface were identified by XAS coupled with Zn isotopes in batch experiments at pH <= 6.0: one is pH-dependent and associated with tetrahedral zinc coordi-nation, and the other is pH-insensitive and associated with octahedral zinc coordination; these sites were confirmed by the bidentate SCM as the variable charge site (surface complexation, >S-OH) and the permanent negative charge site (cation exchange, >X - ), respectively. Furthermore, the important contribution of surface co -precipitation besides surface complexation and cation exchange to the Zn adsorption on CFAPG was identified by XAS coupled with SCM in a flow-through column experiment at pH >6.0. These investigations provide a systemic understanding of the Zn adsorption mechanisms on CFAPG and an SCM reference for the application and prediction of geopolymers in heavy metal-contaminated water remediations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coordination Chemistry as a Universal Strategy for a Controlled Perovskite Crystallization

The most efficient and stable perovskite solar cells (PSCs) are made from complex mixture of precursors, which are practically always dissolved in combinations of the volatile (and toxic) N, N-Dimethylformamide (DMF), and the non-volatile (and green) dimethyl sulfoxide (DMSO) solvents. Typically, to then form a thin film, an extreme oversaturation of the perovskite precursor is initiated to trigger nucleation sites, e.g. by vacuum, an airstream or a so-called antisolvent. Unfortunately, most such oversaturation triggers do not expel the lingering (and highly coordinating) DMSO, which is highly coordinating, from the thin films; this detrimentally affects long-term stability. Here, for the first time, we introduce (the green) dimethyl sulfide (DMS) as a novel nucleation trigger for perovskite films combining, uniquely, high coordination and high vapor pressure. More precisely, DMS coordinates more strongly than all currently used solvents, hence replacing them, including DMSO, effectively during film formation. Crucially, DMS also has among the highest vapor pressures reported in literature, thus effectively leaving the thin film shortly after formation. This gives DMS a universal scope: DMS replaces other solvents by coordinating more strongly and removes itself once the film formation is finished. To demonstrate this novel coordination chemistry approach, we process MAPbI 3 PSCs, typically dissolved in hard-to-remove (and green) DMSO achieving 21.6% efficiency, among the highest reported efficiencies for this system. To confirm the universality of our strategy, we tested DMS for FAPbI 3 as another composition, which showed higher efficiency of 23.5% compared to 20.9% for fabricated device with CB. Finally, this work provides a universal strategy to control perovskite crystallization using coordination chemistry heralding the revival of perovskite compositions with pure DMSO, such as MAPbI 3 .

36 MATERIALS SCIENCE↗

Trifluoromethylated Phenanthroline Ligands Reduce Excited-State Distortion in Homoleptic Copper(I) Complexes

Herein, we report the synthesis and excited-state dynamics for a series of homoleptic copper(I) trifluoromethylated phenanthroline complexes with two, three, and four trifluoromethyl functional groups. Our analysis of the steady-state absorbance and emission, transient-absorption spectroscopy, and electronic-structure-theory calculations results enable in-depth analysis of the pseudo-Jahn–Teller distortion inhibition from increased steric hindrance of the trifluoromethyl functional group relative to the prototypical dimethyl phenanthroline complex. Surprisingly, our results demonstrate that the greatest degree of pseudo-Jahn–Teller distortion inhibition is achieved with trifluoromethylation of only the 2 and 9 positions by an unusual combination of steric hindrance and stabilization of a nondistorted 1 MLCT manifold observed by transient kinetic lifetimes and optimized excited-state structures. The intersystem-crossing (ISC) lifetime for the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex is 69 ps, while the triplet excited-state lifetime and emission quantum yield are 106 ns and 4 × 10 –3 , respectively. Further trifluoromethylation of the phenanthroline yields a greater σ bond inductive withdrawing force on the phenanthroline nitrogens, ultimately resulting in weaker coordination to the copper. Last, the surprising success of the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex by adjusting both ligand sterics and electronic properties outlines a new strategy for developing long-lived Cu(I) charge-transfer complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalytic properties of a novel ruthenium( ii ) terpyridine-based complex towards CO 2 reduction

The electrocatalytic properties of Ru complexes are of great technological interest given their potential application in reactions such water splitting and CO 2 reduction. In this work, a novel terpyridine-based Ru(II) complex, [RuCl(trpy)(acpy)], trpy = 2,2':6',2"-terpyridine, acpy - = 2-pyridylacetate was synthesized and its spectroscopic, electrochemical and catalytic properties were explored in detail. In dry acetonitrile, the complex exhibits two reduction peaks at -1.95 V and -2.20 V vs. Fc/Fc + , attributed to consecutive 1 e - reduction. Under CO 2 atmosphere, a catalytic wave is observed (E onset = 2.1 V vs. Fc/Fc + ), with CO as the main reduction product. Bulk electrolysis reveals a turnover number (TON) of 12 (k obs = 1.5 s -1 ). In the presence of 1% water, an improvement in the catalytic activity is observed (TON CO = 21 and k obs = 2.0 s -1 ) and, additionally, formate was also detected (TON HCOO = 7). Spectroelectrochemical experiments allowed the identification of a metallocarboxylate (Ru–COO - ) intermediate under anhydrous conditions, while in water, the partial labilization of the acpy- ligand was observed in the course of the catalytic cycle. The experimental data was combined with DFT calculations, allowing the proposal of a catalytic cycle. Here the results establish important relationships between selectivity, ligand structure and reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal Ion Fluxes Controlling Amphibian Fertilization

Mammalian oocytes undergo major changes in zinc content and localization to be fertilized, the most striking being the rapid exocytosis of over 10 billion zinc ions in what are known as zinc sparks. Here, we report that fertilization of amphibian Xenopus laevis eggs also initiates a zinc spark that progresses across the cell surface in coordination with dynamic calcium waves. This zinc exocytosis is accompanied by a newly recognized loss of intracellular manganese. Synchrotron-based X-ray fluorescence and analytical electron microscopy reveal that zinc and manganese are sequestered in a system of cortical granules that are abundant at the animal pole. Through electron-nuclear double-resonance studies, we rule out Mn2+ complexation with phosphate or nitrogenous ligands in intact eggs, but the data are consistent with a carboxylate coordination environment. Our observations suggest that zinc and manganese fluxes are a conserved feature of fertilization in vertebrates and that they function as part of a physiological block to polyspermy.

Seeler, John F.↗

Lanthanide-dependent alcohol dehydrogenases require an essential aspartate residue for metal coordination and enzymatic function

The lanthanide elements (Ln 3+ ), those with atomic numbers 57–63 (excluding promethium, Pm 3+ ), form a cofactor complex with pyrroloquinoline quinone (PQQ) in bacterial XoxF methanol dehydrogenases (MDHs) and ExaF ethanol dehydrogenases (EDHs), expanding the range of biological elements and opening novel areas of metabolism and ecology. Other MDHs, known as MxaFIs, are related in sequence and structure to these proteins, yet they instead possess a Ca 2+ -PQQ cofactor. An important missing piece of the Ln 3+ puzzle is defining what features distinguish enzymes that use Ln 3+ -PQQ cofactors from those that do not. In this work, using XoxF1 MDH from the model methylotrophic bacterium Methylorubrum extorquens AM1, we investigated the functional importance of a proposed lanthanide-coordinating aspartate residue. We report two crystal structures of XoxF1, one with and another without PQQ, both with La 3+ bound in the active-site region and coordinated by Asp 320 . Using constructs to produce either recombinant XoxF1 or its D320A variant, we show that Asp 320 is needed for in vivo catalytic function, in vitro activity, and La 3+ coordination. XoxF1 and XoxF1 D320A, when produced in the absence of La 3+ , coordinated Ca 2+ but exhibited little or no catalytic activity. We also generated the parallel substitution in ExaF to produce ExaF D319S and found that this variant loses the capacity for efficient ethanol oxidation with La 3+ . These results provide evidence that a Ln 3+ -coordinating aspartate is essential for the enzymatic functions of XoxF MDHs and ExaF EDHs, supporting the notion that sequences of these enzymes, and the genes that encode them, are markers for Ln 3+ metabolism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactions of Np(VI) and Pu(VI) with Phenanthroline Result in Bending the [NpVIO2]2+ Unit and a Reduced Pu(V) Species

Despite decades of actinyl chemistry, genuinely bent actinyl structures remain rare beyond uranium. We report the first crystallographic characterization of a bent neptunyl(VI) complex, NpO 2 Cl 2 (phen) 2, along with a linear plutonyl species that, unexpectedly, adopts the +V oxidation state. Coordination of two 1,10-phenanthroline ligands to NpO 2 2+ enforces pronounced bending of the O yl –Np–O yl unit to 162° through steric clashes with the axial phenathroline ligand, representing the sharpest angle reported for any neptunyl(VI) complex. In contrast, synthesis with PuO 2 2+ produces a reduced linear Pu(V) species, PuO 2 Cl(phen) 2, underscoring the redox lability and the reluctance of plutonium to distort. Raman and IR spectra yield the first experimental stretching and interaction force constants for plutonyl(V). Comparison with values for plutonyl(VI) and bent and linear uranyl(VI) and neptunyl(VI) compounds shows that reduction perturbs the actinyl bond more than bending within one oxidation state. Electrochemical and spectroscopic studies clarify phenanthroline binding to Pu(VI) and the system’s reactivity. Quantum chemical calculations indicate that bending is energetically favored in the U–Np–Pu series, but the stabilization energy decreases as the actinide atomic number increases. NBO and QTAIM analyses reveal systematic trends: increasing 5f occupancy and decreasing An–O yl bond covalency from U to Pu. These results demonstrate that ligand-induced bending in neptunyl(VI) species is not only electronically feasible but also synthetically achievable, though plutonyl(VI) is constrained by redox reactivity. This work expands the frontier of nonlinear actinyl chemistry and illuminates how structure, oxidation state, and electronic configuration interrelate across the actinyl series.

actinides↗

Unexpected Roles of Triethanolamine in the Photochemical Reduction of CO 2 to Formate by Ruthenium Complexes

We show a series of 4,4'-dimethyl-2,2'-bipyridyl ruthenium complexes with carbonyl ligands were prepared and studied using a combination of electrochemical and spectroscopic methods with infrared detection to provide structural information on reaction intermediates in the photochemical reduction of CO 2 to formate in acetonitrile (CH 3 CN). An unsaturated 5-coordinate intermediate was characterized, and the hydride-transfer step to CO 2 from a singly reduced metal-hydride complex was observed with kinetic resolution. While triethanolamine (TEOA) was expected to act as a proton acceptor to ensure the sacrificial behavior of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as an electron donor, time-resolved infrared measurements revealed that about 90% of the photogenerated one-electron reduced complexes undergo unproductive back electron transfer. Furthermore, TEOA showed the ability to capture CO 2 from CH 3 CN solutions to form a zwitterionic alkylcarbonate adduct and was actively engaged in key catalytic steps such as metal-hydride formation, hydride transfer to CO 2 to form the bound formate intermediate, and dissociation of formate ion product. Collectively, the data provide an overview of the transient intermediates of Ru(II) carbonyl complexes and emphasize the importance of considering the participation of TEOA when investigating and proposing catalytic pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning aminopolycarboxylate chelators for efficient complexation of trivalent actinides

The complexation of trivalent lanthanides and minor actinides (Am 3+ , Cm 3+ , and Cf 3+ ) by the acyclic aminopolycarboxylate chelators 6,6'-((ethane-1,2-diylbis–((carboxymethyl)azanediyl))bis–(methylene))dipicolinic acid (H 4 octapa) and 6,6'-((((4-(1-(2-(2-(2-hydroxyethoxy)ethoxy)ethyl)-1H-1,2,3-triazol-4-yl)pyridine-2,6-diyl)bis–(methylene))bis–((carboxymethyl)azanediyl))bis–(methylene)) dipicolinic acid (H 4 pypa-peg) were studied using potentiometry, spectroscopy, competitive complexation liquid–liquid extraction, and ab initio molecular dynamics simulations. Two studied reagents are strong multidentate chelators, well-suited for applications seeking radiometal coordination for in-vivo delivery and f-element isolation. The previously reported H 4 octapa forms a compact coordination packet, while H 4 pypa-peg is less sterically constrained due to the presence of central pyridine ring. The solubility of H 4 octapa is limited in a non-complexing high ionic strength perchlorate media. However, the introduction of a polyethylene glycol group in H 4 pypa-peg increased the solubility without influencing its ability to complex the lanthanides and minor actinides in solution.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

ezAlign

The ezAlign is aimed at clustering coarse grain simulation to find common or uncommon occurrences and convert coarse (CG) grained coordinate and topology files to atomistic formats. We use a PointNet based approach to map individual frames of simulation to points in a latent space. These points are then clustered using a variety of clustering methods. Clusters are analyzed to associate them with states in the simulation. Frames can be chosen from these clusters based on proximity to cluster centers. ezAlign takes CG coordinate and topology files and converts and outputs their corresponding atomistic formats using an alignment and relaxation procedure. ezAlign is designed to convert complex, solvated biological systems including lipid membranes with drug-like molecules using GROMACS. A GROMACS checkpoint (.cpt) file is also outputted to enable continuation simulations that retain the equilibrated atomic velocities. Independent atomistic coordinates and topologies for every molecule must already be included in ezAlign/files. A number of commonly simulated biological molecules are currently provided.

Bennett, WilliamF.↗

Multi-Ion Complexes and Competition from Bulky BArF – Anions for Chloride Binding in Ion Pairing Conditions

Cationic charges have long been used to enhance anion binding. Embedding charge introduces strong ion pairing for target anions but also for off-target ions, ultimately generating a mixture of multi-ion species that are hard to identify and quantify. While many sidestep this problem using polar solvents and weakly coordinating ions, these approaches exclude a substantial cross-section of conditions found in applications spanning recognition, assembly, separations, templation, and catalysis. To confront this complexity, we study the binding of an anion to a cationic receptor featuring low shape complementarity in a low-polarity solvent to maximize ionic interactions. We prepared the receptor as a salt of the weakly coordinating tetrakis­[3,5-bis­(trifluoromethyl)­phenyl]­borate (BArF – ) anion and studied the binding of small chloride (Cl – ) and medium-sized iodide (I – ) anions. Surprisingly, the use of the bulky BArF – anion does not suppress ion pairing interactions, with 65% of the receptor being paired at 0.5 mM in dichloromethane. We observe multi-ion receptor-Cl – complexes (2:1, 1:1, 1:2), reinforcing the complexity that emerges when working in low-polarity media. Here, we reveal the dependence of affinity on anion charge density and size and that bulky BArF – counteranions compete for chloride binding. These studies reveal the noninnocence of BArF – anions and strategies to quantify multi-ion species.

Ion pairing↗

Programmable hydrogels by combining persistent and transient dynamic bonds

Out-of-equilibrium chemistry is currently being applied to polymer systems to mimic the autonomous behavior of biological materials. In this study, hydrogels with self-healing properties were developed that combine persistent crosslinks from dynamic metal-ligand coordination with transient crosslinks from dynamic anhydride bonds. Polymers containing terpyridine ligands and carboxylic acid groups were synthesized and crosslinked with divalent metal ions (Fe 2+ , Ni 2+ , Co 2+ , Zn 2+ , Cu 2+ ). The coordination bonds from terpyridine–metal coordination impart persistent stability, while transient anhydrides formed on treatment with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) temporarily increase crosslink density. Distinct behaviors are observed depending on the choice of metal, with Ni 2+ forming robust, stable networks; Zn 2+ creating moderately dynamic gels; and Cu 2+ yielding highly dynamic, soft materials. Treatment with EDC increased storage moduli significantly, with transient effects lasting up to 280 min depending on the metal ion. Self-healing experiments demonstrated independent contributions from metal coordination and transient anhydrides, enabling recovery of stress and strain under varying conditions. Additionally, complex and reversible 2D stiffness patterns were generated by spatially controlled EDC treatment of Zn 2+ and Cu 2+ hydrogel films, demonstrating programmability and reusability.

Rajawasam, Chamoni W. H. [Miami University, Oxford↗