Search NASA⌕ Search

SEARCH · Search NASA

Results for “coordination complex”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 685 records · Page 38

FLORA Equilibrium and Stability Code Archive

FLORA solves, in a 2-D domain (radial and axial dimensions) with a specified azimuthal Fourier mode, for the linearized stability of a long, thin, axisymmetric plasma equilibrium in an applied magnetic field. Before the stability equation is solved, FLORA solves a set of simple equations for pressure balance that specify the equilibrium magnetic field and plasma pressure in the long-thin limit given a simplified description of the magnetic coils. It uses an initial-value method for the linear stability problem in which an equilibrium is given an initial perturbation to its magnetic field, and the temporal behavior of the perturbation is followed. The perturbation has been Fourier expanded in the azimuthal coordinate; each azimuthal mode must be examined separately. The complex partial differential equation of motion for the perturbed radial displacement of the field lines is solved as a coupled system of two real p.d.e.'s and the solution consists of two parts, the real part and the imaginary part. The system is solved by bringing the coupling terms in each equation to the right side and using an iterative technique.

Cohen, Bruce [Lawrence Livermore National Laborato↗

Behavior of solitary waves of coupled nonlinear Schrödinger equations subjected to complex external periodic potentials with odd-$\mathcal{PT}$ symmetry

In this work, we discuss the response of both moving and trapped solitary wave solutions of a two-component nonlinear Schrödinger system in 1 + 1 dimensions to an odd-$\mathcal{PT}$ external periodic complex potential. The dynamical behavior of perturbed solitary waves is explored by conducting numerical simulations of the nonlinear system and using a collective coordinate variational approximation. We present case examples corresponding to choices of parameter values and initial conditions involved therein. The results of the collective coordinate approximation are compared against numerical simulations where we observe qualitatively good agreement between the two. Unlike the case for a single-component solitary wave in a complex periodic $\mathcal{PT}$-symmetric potential, the collective coordinate equations do not have a small oscillation regime, and initially the height of the two components changes in opposite directions often causing instability. We find that the dynamic stability criteria we have used in the one-component case are a good indicator for the onset of dynamic instabilities in the present setup.

97 MATHEMATICS AND COMPUTING↗

Ultra-Compact Transputer-Based Controller for High-Level, Multi-Axis Coordination

The design of machines that rely on arrays of servomotors such as robotic arms, orbital platforms, and combinations of both, imposes a heavy computational burden to coordinate their actions to perform coherent tasks. For example, the robotic equivalent of a person tracing a straight line in space requires enormously complex kinematics calculations, and complexity increases with the number of servo nodes. A new high-level architecture for coordinated servo-machine control enables a practical, distributed transputer alternative to conventional central processor electronics. The solution is inherently scalable, dramatically reduces bulkiness and number of conductor runs throughout the machine, requires only a fraction of the power, and is designed for cooling in a vacuum.

Zenowich, Brian↗

Redox-active dinuclear oxorhenium(V) pyrazolate complexes

Four new structurally similar dinuclear oxorhenium(V) complexes, [{Re(O)X(PPh 3 )} 2 (μ-O)(μ-4-x'-pz) 2 ], where pz = pyrazolate anion, X = X' = Cl (1) and Br (4), X = Cl, X' = Br (2), and X = Br, X' = Cl (3), have been synthesized and characterized. Little variation in spectroscopic features – 1 H NMR, IR, UV–Vis – exists among the four complexes. All complexes possess a bent Re-O-Re core as well as distorted octahedral coordination geometry around the rhenium centers. Finally, a reversible one-electron electrochemical process is observed at approximately 0.84 V vs. Fc + /Fc in all four complexes; however, changing the terminal halide from chloride to bromide slightly destabilizes the oxidized Re(VI) center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pyridine Complexes of Iodobismuthate(III) Anions

We report a rare family of pyridine-coordinated iodobismuthate(III) salts supported by alkyltriphenylphosphonium and tetraphenylphosphonium cations. Reactions of BiI 3 with Ph 3 PR + I − (R = Me, Et, n Pr, n Bu, Ph) in neat pyridine, followed by crystallization, yield structurally tunable bismuth-halide-pyridine anions dictated by reagent stoichiometry. Combination of BiI 3 and Ph 3 PR + I − in 2:1 ratio produced [Ph 3 PR] 2 [BiI 5 Py], 1 (R = Me, Et, n Pr, Ph), while combination in 1:1 ratio resulted in three compounds: [Ph 3 PR][cis-BiI 4 Py 2 ], 2 (R = n Pr, Ph), [Ph 3 PR][trans-BiI 4 Py 2 ], 3 (R = Me, Et, Ph), and [Ph 3 PR] 2 [transoid-Bi 2 I 8 Py 2 ], 4 (R = Me, Et, n Pr, n Bu, Ph). In many cases, the compounds were isolated as Py or Et 2 O solvates, and in some cases, multiple degrees of solvation or polymorphism were encountered. Hirshfeld analysis of 1–4 showed the major anion–cation/anion/solvent interactions to be H⋯I, H⋯H, and C⋯H. Diffuse reflectance measurements of representative compounds, all of which were yellow-orange to red-orange, revealed bandgaps in the range of 1.9–2.2 eV, where density-of-states KS-DFT calculations attribute the absorption to metal-centered charge transfer within the anionic unit. NLMO and QTAIM analyses further indicate predominantly ionic Bi(III)–I/pyridine bonding with robust inner-sphere coordination that is insensitive to anion speciation.

Bismuth Compounds↗

Structure of the IFNγ receptor complex guides design of biased agonists

The cytokine interferon-γ (IFNγ) is a central coordinator of innate and adaptive immunity, but its highly pleiotropic actions have diminished its prospects for use as an immunotherapeutic agent. Here, we took a structure-based approach to decoupling IFNγ pleiotropy. We engineered an affinity-enhanced variant of the ligand-binding chain of the IFNγ receptor IFNγR1, which enabled us to determine the crystal structure of the complete hexameric (2:2:2) IFNγ–IFNγR1–IFNγR2 signalling complex at 3.25 Å resolution. The structure reveals the mechanism underlying deficits in IFNγ responsiveness in mycobacterial disease syndrome resulting from a T168N mutation in IFNγR2, which impairs assembly of the full signalling complex. The topology of the hexameric complex offers a blueprint for engineering IFNγ variants to tune IFNγ receptor signalling output. Unexpectedly, we found that several partial IFNγ agonists exhibited biased gene-expression profiles. Here, these biased agonists retained the ability to induce upregulation of major histocompatibility complex class I antigen expression, but exhibited impaired induction of programmed death-ligand 1 expression in a wide range of human cancer cell lines, offering a route to decoupling immunostimulatory and immunosuppressive functions of IFNγ for therapeutic applications.

59 BASIC BIOLOGICAL SCIENCES↗

Outer Coordination Sphere Proton Relay Base and Proximity Effects on Hydrogen Oxidation with Iron Electrocatalysts

The intra- and intermolecular deprotonation of [(CpC5F4N)Fe(PEtNR'PEt)H]+ (PEtNR'PEt = (Et2PCH2)2NR') complexes are rate-limiting processes in the electrocatalytic oxidation of hydrogen, and can be mediated by an amine base in the outer coordination sphere (OCS) by facilitating the matching of energy of deprotonation intermediates. A series of complexes with different N-substituents (R' = Me, Et, CH2OMe, CH2N(Ph)Me, and (CH2)nNMe2; n = 1–4) was examined computationally using density functional theory to determine the influence of the identity and proximity of the OCS base on the intramolecular deprotonation. Complexes with an OCS dimethylamino substituent were the most suitably energy matched. The number of carbon atoms between the secondary and OCS nitrogen atoms dictated the strength of the hydrogen bonding interaction and ring strain following deprotonation of the iron hydride. The previously reported [(CpC5F4N)Fe(PEtNR'PEt)H]+ (R' = (CH2)3NMe2) electrocatalyst was predicted to have the most favorable free energy (?G) and free energy of activation (?G‡). To verify the computational results, two of the iron precatalysts, (CpC5F4N)Fe(PEtN(CH2)nNMe2PEt)Cl (n = 2 and 4), were synthesized, and their electrocatalytic activity for the oxidation of hydrogen was determined under an atmosphere of H2 using DABCO as the exogenous base. Maximum turnover frequencies of 270 and 200 s-1 were measured when n = 2 and 4, respectively, validating the computational results.

Kumar, Neeraj↗

Structural insight into host plasma membrane association and assembly of HIV-1 matrix protein

Oligomerization of Pr55 Gag is a critical step of the late stage of the HIV life cycle. It has been known that the binding of IP6, an abundant endogenous cyclitol molecule at the MA domain, has been linked to the oligomerization of Pr55 Gag . However, the exact binding site of IP6 on MA remains unknown and the structural details of this interaction are missing. Here, we present three high-resolution crystal structures of the MA domain in complex with IP6 molecules to reveal its binding mode. Additionally, extensive Differential Scanning Fluorimetry analysis combined with cryo- and ambient-temperature X-ray crystallography and GNM-based transfer entropy calculations identify the key residues that participate in IP6 binding. Our data provide novel insights about the multilayered HIV-1 virion assembly process that involves the interplay of IP6 with PIP2, a phosphoinositide essential for the binding of Pr55 Gag to membrane. IP6 and PIP2 have neighboring alternate binding sites within the same highly basic region (residues 18–33). This indicates that IP6 and PIP2 bindings are not mutually exclusive and may play a key role in coordinating virion particles’ membrane localization. Based on our three different IP6-MA complex crystal structures, we propose a new model that involves IP6 coordination of the oligomerization of outer MA and inner CA domain’s 2D layers during assembly and budding.

60 APPLIED LIFE SCIENCES↗

Short- vs . long-range elastic distortion: structural dynamics of a [2 × 2] tetrairon( II ) spin crossover grid complex observed by time-resolved X-Ray crystallography

Spin crossover complexes (SCO) are among the most studied molecular switches due to their potential use in displays, sensors, actuators and memory components. A prerequisite to using these materials is the understanding of the structural changes following the spin transition at out-of-equilibrium conditions. So far, out-of-equilibrium studies in SCO solids have been focused on mononuclear complexes, though a growing number of oligonuclear SCO complexes showing cooperative effects are being reported. Here, we use time-resolved pink Laue crystallography to study the out-of-equilibrium dynamics of a [2 × 2] tetranuclear metallogrid of the form [Fe II 4 L Me 4 ](BF 4 ) 4 ·2MeCN ([L Me ] - = 4-methyl-3,5-bis{6-(2,2'-bipyridyl)}pyrazolate). The out-of-equilibrium spin state switching induced by a ps laser pulse demonstrates that the metallogrid exhibits a multi-step response similar to that reported for mononuclear complexes. Contrary to the mononuclear complexes, the metallogrid shows two types of elastic distortions at different time scales. The first is a short-range distortion that propagates over the entire Fe 4 grid complex during the ps time scale, and it is caused by the rearrangement of the coordination sphere of the photo-switching ion and the constant feedback between strongly linked metal ions. The second is a long-range distortion caused by the anisotropic expansion of the lattice during the ns time scale, observed in mononuclear materials. The structural analysis demonstrates that the long-range prevails over the short-range distortion, inducing the largest deformation of both the entire grid and the coordination sphere of each metal ion. The present study sheds light on the out-of -equilibrium dynamics of a non-cooperative oligonuclear complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chelators and metal complex stability for radiopharmaceutical applications

Abstract Diagnostic and therapeutic nuclear medicine relies heavily on radiometal nuclides. The most widely used and well-known radionuclide is technetium-99m ( 99m Tc), which has dominated diagnostic nuclear medicine since the advent of the 99 Mo/ 99m Tc generator in the 1960s. Since that time, many more radiometals have been developed and incorporated into potential radiopharmaceuticals. One critical aspect of radiometal-containing radiopharmaceuticals is their stability under in vivo conditions. The chelator that is coordinated to the radiometal is a key factor in determining radiometal complex stability. The chelators that have shown the most promise and are under investigation in the development of diagnostic and therapeutic radiopharmaceuticals over the last 5 years are discussed in this review.

Chemistry↗

Complex Sources and Impacts on Remediation and Monitoring Approaches - 19058

Remedy selection, implementation, and coordination with tank farm activities for adjacent waste sites need to be facilitated by a technically defensible description of sources and their relative strength and temporal contributions to groundwater contamination. Detailed data describing contaminant source releases are typically not available, so source locations are highly uncertain. Furthermore, data on sources and model parameters are not readily available through direct measurements. Instead, source data are often derived by extrapolation from a few direct and/or indirect measurements, while model parameters are commonly estimated using inverse modeling or calibration methods. Because the conceptual model of sources will influence the mass and timing of the flux of contaminants to groundwater, uncertainty in the source terms should be considered. Even though a best-fit model can often be identified, it may not be the best representation of the sources given the sparse, uncertain nature of the data used for estimating source terms. To support future feasibility studies, a systematic approach is needed for identifying remediation and monitoring activities appropriate under conditions of uncertainty. In this study, an integrated assessment of alternative conceptual model elements has been examined using the B-Complex site in the Hanford Central Plateau to demonstrate how multiple sources in a waste management complex can be described to identify their relative contributions to groundwater. The heterogeneous structure of the system is modeled based on available field information on the lithological data for both the vadose zone and aquifer. The approach includes a simulation assessment and linkages to site data, with an uncertainty analysis applied to evaluate the effects of source term uncertainty on contaminant mass flux to groundwater. An integrated assessment of alternative conceptual model elements was evaluated to identify how parameter uncertainty impacts both temporal and spatial uncertainties associated with vadose zone source terms. Modeling scenarios identify important characteristics of remediation target zones to provide context for how surface barriers, in situ remedies, and water-table treatment zones can be designed to account for source dynamics. Ramifications for remediation and monitoring are discussed within the context of the source term uncertainty. The described approach facilitates systematically addressing alternative conceptual model questions in relation to remediation and monitoring and supports the remedial investigation/ feasibility study process and the remediation strategy development for the Hanford Central Plateau. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Coordinative Entities: Forms of Organizing in Data Intensive Science

Scientific collaboration is a long-standing subject of CSCW scholarship that typically focuses on the development and use of computing systems to facilitate research. The research presented in this article investigates the sociality of science by identifying and describing particular, common forms of organizing that researchers in four different scientific realms employ to conduct work in both local contexts and as part of distributed, global projects. This paper introduces five prototypical forms of organizing we categorize as coordinative entities: the Principal Group, Intermittent Exchange, Sustained Aggregation, Federation, and Facility Organization. Coordinative entities as a categorization help specify, articulate, compare, and trace overlapping and evolving arrangements scientists use to facilitate data intensive research. We use this typology to unpack complexities of data intensive scientific collaboration in four cases, showing how scientists invoke different coordinative entities across three types of research activities: data collection, processing, and analysis. Finally, our contribution scrutinizes the sociality of scientific work to illustrate how these actors engage in relational work within and among diverse, dispersed forms of organizing across project, funding, and disciplinary boundaries.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗

Insights into the excited state dynamics of Fe( ii ) polypyridyl complexes from variable-temperature ultrafast spectroscopy

In order to better define the nature of the nuclear coordinate associated with excited state dynamics in first-row transition metal chromophores, variable-temperature ultrafast time-resolved absorption spectroscopy has been used to determine activation parameters associated with ground state recovery in a series of low-spin Fe( ii ) polypyridyl complexes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Ligand Influence on Indium–Sulfide Cluster Formation and Reactivity

An indium–sulfide tetramer ([InMe 2 (SSiMe 3 )] 4 ), which contains reactive silyl and methyl groups, is shown to be an isolable intermediate in cluster synthesis. The reactive groups allow it to act as a synthon in the formation of multinuclear indium–sulfide architectures, evidenced by the crystallization of a coordination polymer ([In 20 S 14 Me 32 (4,4’-bpy) 5 ·5CH 2 Cl 2 ] n ) utilizing In 10 S 7 clusters as nodes. The reaction between trimethylindium (InMe 3 ) and bis­(trimethylsilyl)­sulfide (S­(SiMe 3 ) 2 ) is explored with and without the presence of a ligating bipyridine. In both cases, a sulfide-indium adduct is formed, which slowly converts into a multimetallic complex. Here, the ligand 2,2’-bipyridine (2,2’-bpy) is coordinated to InMe 3 to form the adduct InMe 3 (bpy), which upon addition of sulfide, eliminates tetramethylsilane (TMS) and binds two additional InMe 3 moieties (InMe 2 (bpy)­(μ 3 -SSiMe 3 )­(InMe 3 ) 2 ). When reacted neatly without bipyridine, InMe 3 and S­(SiMe 3 ) 2 form the adduct InMe 3 (S­(SiMe 3 ) 2 ), which subsequently eliminates TMS and intermolecularly associates to yield [InMe 2 (SSiMe 3 )] 4 . Although stable in an inert atmosphere, [InMe 2 (SSiMe 3 )] 4 undergoes facile hydrolysis to yield [InMeS] n when exposed to air. The effect of ligand addition (4,4’-bipyridine (4,4’-bpy)) to [InMe 2 (SSiMe 3 )] 4 is then examined. In every case, it is shown that the presence of the bpy ligand has a profound influence on the resulting structure, as shown by the unexpected formation of a trimer and In 10 S 7 cluster network.

Bell, Colby Seth [Argonne National Laboratory (ANL↗

Iron Carbonyl Complexes of [2.2.2]Hericene as a Rigid Tris(1,3-diene) Ligand

Hericene is an unusual hexaolefin consisting of three 1,3-diene units located on a rigid bicyclo [2.2.2]octane framework that restricts the geometrical relationships of metal atoms bonded to these olefinic units. In order to explore possible effects of this rigidity limiting metal–metal interaction in polynuclear derivatives possibly stabilizing coordinatively unsaturated species, the structures and energetics of the hericene iron carbonyl complexes (hericene)Fem(CO)n (m = 1, n = 3; m = 2, n = 6, 5; m = 3, n = 9, 8) have been investigated by density functional theory. The lowest-energy (hericene)Fem(CO)3m (m = 1, 2, 3) structures have the cavities of the hericene ligand filled with a single Fe(CO)3 moiety bonded to a 1,3-diolefin unit. Such species have been synthesized by the reaction of Fe2(CO)9 with hericene. For the (hericene)Fe2(CO)5 system, the lowest energy structures are singlet structures with an Fe(CO)3 unit bonded to a 1,3-diene unit in one hericene cavity and an Fe(CO)2 unit in another hericene cavity bonded to three C=C double bonds from two 1,3-diene units. Higher energy (hericene)Fe2(CO)5 structures include a structure in which a single hericene cavity contains a Fe2(CO)4(µ-CO) moiety with each iron atom bonded to a 1,3-diene unit. In addition, both singlet and triplet (hericene)Fe2(CO)5 structures are found in which an Fe(CO)3 moiety and an Fe(CO)2 moiety located in separate hericene cavities are each bonded to a 1,3-diene unit. The lowest-energy (hericene)Fe3(CO)8 structures have two hericene cavities containing Fe(CO)3 moieties fully bonded to 1,3-diene units and a third hericene cavity containing an Fe(CO)2 moiety fully bonded to a 1,3-diene unit.

Luo, Jinfeng↗

Preclinical Risk Evaluation of Normal Tissue Injury With Novel Radiosensitizers

Genotoxic damage induced by radiation triggers a highly coordinated DNA damage response, and molecular inhibitors of key nodes within this complex response network can profoundly enhance the antitumor efficacy of radiation. This is especially true for drugs targeting the catalytic subunit of DNA-dependent protein kinase, which is a core component of the nonhomologous end-joining DNA repair pathway, and ataxia telangiectasia mutated, which coordinates cell cycle arrest, apoptosis, and DNA repair functionalities after radiation exposure. Unlike the more modest in vitro radiosensitizing effects seen with classic sensitizing agents such as cisplatin, 5-fluorouracil, or taxanes, DNA-dependent protein kinase or ataxia telangiectasia mutated inhibitors provide much more robust sensitizing effects in vitro, as might be anticipated from targeting these key DNA repair modulators. However, patients with homozygous inactivating mutations of ataxia telangiectasia mutated or mice with homozygous defects in DNA-dependent protein kinase (severe combined immunodeficiency) have profoundly enhanced acute normal tissue radiation reactions. Therefore, there is significant potential that the combination of small molecule inhibitors of these kinases with radiation could cause similar dose-limiting acute normal tissue toxicities. Similarly, although less understood, inhibition of these DNA repair response pathways could markedly increase the risk of late radiation toxicities. Because these potent radiosensitizers could be highly useful to improve local control of otherwise radiation-resistant tumors, understanding the potential for elevated risks of radiation injury is essential for optimizing therapeutic ratio and developing safe and informative clinical trials. In this review, we will discuss 2 straightforward models to assess the potential for enhanced mucosal toxicity in the oral cavity and small intestine established in our laboratories. We also will discuss similar strategies for evaluating potential drug–radiation interactions with regard to increased risks of debilitating late effects.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Controlled environment agriculture: An opportunity to strengthen interagency research collaboration in the US government

Challenges facing food production and agricultural systems are increasingly interconnected with economic, security, health, and equity issues, among others. Threats such as extreme weather, economic volatility, and shrinking water resources and arable land, influence our ability to maintain a safe and resilient food supply. One promising solution to these threats is controlled environment agriculture (CEA). In many cases, CEA can drastically reduce the amount of water and land used in crop production while increasing productivity. Operations may be established in nearly any environment and harvests can take place year-round, supporting food system resiliency and sustainability. CEA sits at the nexus of a number of disciplines and industries, making it well suited for transdisciplinary and multi-institutional research coordination. Herein, authors from multiple US government agencies present CEA as a case study in improving cross-agency research collaboration. The federal government houses a range of scientific expertise and research capabilities, positioning scientists to lead national and global efforts in transdisciplinary, interagency approaches to complex challenges. Navigating cross-agency collaboration can be a challenge, especially coordinating across different scientific disciplines, geographic locations, and funding mechanisms. To enhance multiagency efforts, collaborators could prioritize (i) organizing personnel and resources, (ii) enhancing existing multiagency collaborations, and (iii) focusing on further opportunities for coordination. Adopting these approaches could enable federal researchers to reinforce and advance academic and industry efforts to address current CEA challenges while solidifying the United States as a leader in this arena.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

A Coordinated Mineralogical and Oxygen Isotopic Study of Refractory Ca-Al-Rich Inclusions

Refractory Ca-Al-rich inclusions (CAIs) in primitive chondritic meteorites represent the oldest solids that formed in our Solar System. Coordinated analyses using multiple ion and electron-beam techniques are vital to fully understand complex nebular and asteroidal processes that CAIs may have experienced in the context of the formation and early evolution of our Solar System. We report the results of a coordinated mineralogical and oxygen isotopic study of unique grossite bearing CAIs from reduced CV (Vigarano type) carbonaceous chondrites using transmission electron microscopy and secondary ion mass spectrometry. Grossite (CaAl 4 O 7 ) occurs in cores of nodules in fine grained CAIs that likely represent aggregates of nebular condensates. In many occurrences, grossite has been partially replaced by hercynite [(Fe,Mg,Zn)Al 2 O 4 ], which displays complex microstructures and compositions, and magnetite nanoparticles. This grossite alteration likely occurred via crystallographically controlled metasomatic reactions with Zn, Fe-rich aqueous fluids on the parent asteroid. The constituent phases of grossite bearing CAIs show heterogeneous oxygen isotopic compositions . That is, grossite and perovskite are 16 O poor and melilite is variably 16 O-depleted in contrast to solar like, 16 O-rich hibonite and spinel. The observed oxygen isotopic distribution is interpreted as a result of mineralogically controlled oxygen isotopic exchange with an 16 O-poor fluid on the parent asteroid. Collectively, we conclude that the presence of limited fluids played an important role in preferential alteration of grossite to hercynite and magnetite and various degrees of 16 O depletion in grossite, perovskite, and melilite during thermal metamorphism on the CV chondrite parent asteroid.

Jangmi Han↗