Synthesis, Characterization, and Density Functional Theory Investigation of the Solid-State [UO 2 Cl 4 (H 2 O)] 2– Complex
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Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO 2 Reduction
The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO 2 to higher energy products. However, the mechanism of proton transfer in these systems is poorly understood. Herein, we present a series of cobalt complexes with varying pendant secondary and tertiary amines in the ligand framework with the aim of disentangling the roles of the first and second coordination spheres in CO 2 reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO 2 , and the number of pendant secondary amines, respectively. Density functional theory studies explain the experimentally observed trends and indicate that pendant secondary amines do not directly transfer protons to CO 2 , but instead bind acid molecules from solution. Taken together, these results suggest a mechanism in which noncooperative pendant amines facilitate a hydrogen-bonding network that enables direct proton transfer from acid to the activated CO 2 substrate.
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Ligand-Functionalized Polymer Membranes for Selective Ion Separations
Selective ion separations are central to technologies spanning water purification, resource recovery, and clean energy. Conventional polymer membranes, which rely on steric hindrance or Donnan exclusion, struggle to discriminate between chemically similar ions in high-ionic-strength environments. Ligand-functionalized membranes offer a transformative strategy by embedding molecular recognition directly into polymer matrices, enabling selective complexation and transport. Here, this Viewpoint highlights the structure–function relationships underlying ligand-mediated ion separation, emphasizing the interplay of dehydration penalties, ligand coordination, and nanoscale confinement. We discuss design principles, denticity, donor identity, rigidity, and spatial organization, alongside the permeability–selectivity trade-off, multicomponent effects, and stability challenges. Finally, we outline emerging strategies, from bioinspired ligands to computationally guided design, that chart a path toward next-generation membranes for precise and energy-efficient ion separations.
ions↗
Room temperature crystal field splitting of curium resolved by circularly polarized luminescence spectroscopy
Coordination of Cm(III) with a chiral decadentate ligand N,N,N',N'-tetrakis[(6-carboxypyridin-2-yl)methyl]-1,2-diaminocyclohexane (tpadac) generated complexes with strong luminescence allowing for the unprecedented measurement of well-resolved Cm(III) circularly polarized luminescence spectra. Quantitative resolution of the electronic structure of the [Cm(tpadac)][K] complexes was achieved at room temperature, highlighting the strength of the combination of luminescence and circularly polarized luminescence spectroscopies to unravel the fundamental electronic structure of Cm(III). These results are a clear demonstration that these spectroscopies are powerful yet simple tools for the fundamental understanding of electronic structure, which opens the door to future investigations of other Cm(III) complexes in geometries relevant to nuclear applications, and even other 5f-elements.
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Influence of Heat Treatments in H 2 and Ar on the E 1 center in β -Gs 2 O 3
In this report the influence of heat treating n-type bulk β-Ga 2 O 3 in hydrogen (H2) and argon (Ar) gases on the presence of the defect level commonly labeled as E 1 was studied. Fourier transform-infrared spectroscopy confirms that hydrogen (H) is incorporated into β-Ga 2 O 3 during H 2 annealing at 900 °C. Deep-level transient spectroscopy measurements reveal that the concentration of the E 1 level is promoted by the introduction of H, in contrast to what is observed in samples heat-treated in an Ar flow. We further find the E 1 level to be stable against heat treatments at 650 K, both with and without an applied reverse-bias voltage. Potential candidates for the defect origin of E 1 are investigated using hybrid-functional calculations, and three types of defect complexes involving H are found to exhibit charge-state transition levels compatible with E 1 , including substitutional H at one of the threefold coordinated O sites, Ga-substitutional shallow donor impurities passivated by H, and certain configurations of singly hydrogenated Ga–O divacancies. Among these types, only the latter exhibit H binding energies that are consistent with the observed thermal stability of E 1 .
36 MATERIALS SCIENCE↗
Ratchet, swivel, tilt and roll: a complete description of subunit rotation in the ribosome
Protein synthesis by the ribosome requires large-scale rearrangements of the ‘small’ subunit (SSU; ~1 MDa), including inter- and intra-subunit rotational motions. However, with nearly 2000 structures of ribosomes and ribosomal subunits now publicly available, it is exceedingly difficult to design experiments based on analysis of all known rotation states. To overcome this, we developed an approach where the orientation of each SSU head and body is described in terms of three angular coordinates (rotation, tilt and tilt direction) and a single translation. By considering the entire RCSB PDB database, we describe 1208 fully-assembled ribosome complexes and 334 isolated small subunits, which span >50 species. This reveals aspects of subunit rearrangements that are universal, and others that are organism/domain-specific. For example, we show that tilt-like rearrangements of the SSU body (i.e. ‘rolling’) are pervasive in both prokaryotic and eukaryotic (cytosolic and mitochondrial) ribosomes. As another example, domain orientations associated with frameshifting in bacteria are similar to those found in eukaryotic ribosomes. Together, this study establishes a common foundation with which structural, simulation, single-molecule and biochemical efforts can more precisely interrogate the dynamics of this prototypical molecular machine.
59 BASIC BIOLOGICAL SCIENCES↗
Aqua(pentahydrogennitrilotris(methylenephosphonato))lithium hydrate [Li(H{sub 2}O)(N(CH{sub 2}PO{sub 3}){sub 3}H{sub 5})] • H{sub 2}O: Synthesis and structure
Aqua(pentahydrogennitrilotris(methylenephosphonato))lithium hydrate is a linear coordination polymer. Its crystal structure is described in space group P{sup –}1, Z = 2; a = 5.5732(2), b = 7.0106(2), and c = 16.9010(5) Å; α = 97.515(2)°, β = 94.551(2)°, and γ = 95.123(2)°. The tetrahedral coordination of the Li atom includes two oxygen atoms of a phosphonate ligand, one oxygen atom of another phosphonate ligand, and a water molecule. Complex formation is accompanied by closing of the eight-membered Li–O–P–C–N–C–P–O chelate ring. Polymeric chains run along the [100] direction. The chains are connected by hydrogen bonds.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Evaluating the performance of the immersed boundary method within the grey zone for improved weather forecasts in the HRRR model
Improved performance of the High Resolution Rapid Refresh (HRRR) weather forecast in regions of complex terrain is a primary goal of the second Wind Forecasting Improvement Project (WFIP2). The HRRR forecast uses the Weather Research and Forecasting (WRF) model at a horizontal resolution of 3 km and includes an experimental nest over the WFIP2 study area with 750 m horizontal resolution. At these resolutions the complex terrain of the WFIP2 study area, the Columbia River Gorge, is well resolved and can include steep terrain slopes. The terrain-following coordinate system used by the WRF model is susceptible to numerical instabilities as model resolution and resolved terrain slopes increase. The immersed boundary method (IBM) has been shown to reduce these instabilities at very high resolutions (roughly 10 m or less), and thus use of IBM is desirable for high resolution simulations over the WFIP2 study area. However, accuracy of the IBM appears to degrade with coarser grid resolution and the sensitivities of IBMs to grid resolution are not well understood. In this report, we work to understand the accuracy and performance of the IBM at coarser resolutions with the goal of developing an IBM for use in the grey zone, or the intermediate scales between mesoscale and large-eddy simulation. Here, several existing immersed boundary algorithms from the literature are implemented into WRF, along with a new implementation developed during this project. The IBM algorithms for the atmospheric boundary layer are evaluated within the WRF model for a range of grid resolutions. While the strong performance of IBMs at high-resolution is confirmed, important model sensitivities are also revealed. Particular focus is placed on IBM performance at intermediate grid resolutions, which to this point has not been studied in the atmospheric modeling literature.
54 ENVIRONMENTAL SCIENCES↗
First-generation college student forges ahead, now key to Lab's mission
Fatima Woody was just 17 and a student at Pojoaque Valley High School when she first started her career as a Los Alamos Neutron Science Center receptionist. Now she's in a crucial role that keeps plutonium pit production and other mission processes operating with as little interruption as possible. Over nearly four decades, Fatima has gradually advanced from her initial positions as a receptionist and administrative secretary to become a computer technician, then a computer system professional who specializes in project management. Today, she coordinates the workflow for nearly two dozen deployed information technology technicians who keep the computer systems and networks operating at the high-tech complex that houses the Lab's Plutonium Facility.
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Dynamics and Control of Flexible Space Vehicles
The purpose of this report is twofold: (1) to survey the established analytic procedures for the simulation of controlled flexible space vehicles, and (2) to develop in detail methods that employ a combination of discrete and distributed ("modal") coordinates, i.e., the hybrid-coordinate methods. Analytic procedures are described in three categories: (1) discrete-coordinate methods, (2) hybrid-coordinate methods, and (3) vehicle normal-coordinate methods. Each of these approaches is described and analyzed for its advantages and disadvantages, and each is found to have an area of applicability. The hybrid-coordinate method combines the efficiency of the vehicle normal-coordinate method with the versatility of the discrete-coordinate method, and appears to have the widest range of practical application. The results in this report have practical utility in two areas: (1) complex digital computer simulation of flexible space vehicles of arbitrary configuration subject to realistic control laws, and (2) preliminary control system design based on transfer functions for linearized models of dynamics and control laws.
Likins, P. W.↗
Three-dimensional multigrid Navier-Stokes computations for turbomachinery applications
The fully three-dimensional, time-dependent compressible Navier-Stokes equations in cylindrical coordinates are presently used, in conjunction with the multistage Runge-Kutta numerical integration scheme for solution of the governing flow equations, to simulate complex flowfields within turbomechanical components whose pertinent effects encompass those of viscosity, compressibility, blade rotation, and tip clearance. Computed results are presented for selected cascades, emphasizing the code's capabilities in the accurate prediction of such features as airfoil loadings, exit flow angles, shocks, and secondary flows. Computations for several test cases have been performed on a Cray-YMP, using nearly 90,000 grid points.
Subramanian, S. V.↗
Teams and teamwork at NASA Langley Research Center
The recent reorganization and shift to managing total quality at the NASA Langley Research Center (LaRC) has placed an increasing emphasis on teams and teamwork in accomplishing day-to-day work activities and long-term projects. The purpose of this research was to review the nature of teams and teamwork at LaRC. Models of team performance and teamwork guided the gathering of information. Current and former team members served as participants; their collective experience reflected membership in over 200 teams at LaRC. The participants responded to a survey of open-ended questions which assessed various aspects of teams and teamwork. The participants also met in a workshop to clarify and elaborate on their responses. The work accomplished by the teams ranged from high-level managerial decision making (e.g., developing plans for LaRC reorganization) to creating scientific proposals (e.g., describing spaceflight projects to be designed, sold, and built). Teams typically had nine members who remained together for six months. Member turnover was around 20 percent; this turnover was attributed to heavy loads of other work assignments and little formal recognition and reward for team membership. Team members usually shared a common and valued goal, but there was not a clear standard (except delivery of a document) for knowing when the goal was achieved. However, members viewed their teams as successful. A major factor in team success was the setting of explicit a priori rules for communication. Task interdependencies between members were not complex (e.g., sharing of meeting notes and ideas about issues), except between members of scientific teams (i.e., reliance on the expertise of others). Thus, coordination of activities usually involved scheduling and attendance of team meetings. The team leader was designated by the team's sponsor. This leader usually shared power and responsibilities with other members, such that team members established their own operating procedures for decision making. Sponsors followed a hands-off policy during team operations, but they approved and reviewed team products. Most teams, particularly high-level decision-making teams, had little or no authority to carry out their decisions. Team members had few interpersonal conflicts. They monitored each other respectfully about meeting deadlines. Feedback and backup behaviors were seen as desirable aspects of teamwork, wanted by the members, and done appropriately.
Dickinson, Terry L.↗
Low Cost Mission Operations Workshop
The presentations given at the Low Cost (Space) Mission Operations (LCMO) Workshop are outlined. The LCMO concepts are covered in four introductory sections: Definition of Mission Operations (OPS); Mission Operations (MOS) Elements; The Operations Concept; and Mission Operations for Two Classes of Missions (operationally simple and complex). Individual presentations cover the following topics: Science Data Processing and Analysis; Mis sion Design, Planning, and Sequencing; Data Transport and Delivery, and Mission Coordination and Engineering Analysis. A list of panelists who participated in the conference is included along with a listing of the contact persons for obtaining more information concerning LCMO at JPL. The presentation of this document is in outline and graphic form.
Source record↗
Integrated Data Modeling and Simulation on the Joint Polar Satellite System Program
The Joint Polar Satellite System is a modern, large-scale, complex, multi-mission aerospace program, and presents a variety of design, testing and operational challenges due to: (1) System Scope: multi-mission coordination, role, responsibility and accountability challenges stemming from porous/ill-defined system and organizational boundaries (including foreign policy interactions) (2) Degree of Concurrency: design, implementation, integration, verification and operation occurring simultaneously, at multiple scales in the system hierarchy (3) Multi-Decadal Lifecycle: technical obsolesce, reliability and sustainment concerns, including those related to organizational and industrial base. Additionally, these systems tend to become embedded in the broader societal infrastructure, resulting in new system stakeholders with perhaps different preferences (4) Barriers to Effective Communications: process and cultural issues that emerge due to geographic dispersion and as one spans boundaries including gov./contractor, NASA/Other USG, and international relationships.
Roberts, Christopher J.↗
Selective CO 2 Reduction by Bis(bipyridine)cobalt(II) Catalysts: The Role of Pendant Pyridine as a Proton Acceptor
Electrochemical CO 2 reduction reaction (CO 2 RR) catalyzed by molecular earth-abundant metal catalysts is a promising strategy to convert CO 2 into value-added products. One recent trend in this field has been focusing on the rational design of catalysts by incorporating redox-active ligands and modifying the secondary coordination sphere (SCS) to achieve efficient and selective CO 2 RR. Herein, we report a series of Co bis(bipyridine) catalysts featuring various dangling groups, such as pyridine, tertiary amine, or butyl, in the secondary coordination sphere (Co-PyMe, Co-Py, Co-PrN, and Co-Bu). Efficient, selective electrocatalytic CO 2 RR was achieved by the complexes after the generation of triply reduced intermediate consisting of a Co I center and a dianionic ligand, producing CO as the major product and trace amount of H 2 . Strong correlations with the identity of dangling groups and turnover frequency (TOF) have been observed, in which Co-PyMe displayed the highest TOF (1086 s –1 in MeCN/H 2 O). Mechanistic studies indicated that the acceleration of CO 2 RR with pyridine-functionalized catalysts were derived from the protonation of pyridine dangling groups which participated as weak acids in the H-bonding network with exogenous proton sources, stabilizing CO 2 -bound intermediates and facilitating proton transfer. In addition, precatalytic CO 2 binding and activation at the third reduction (−2.1 V) was revealed by CV and SEC-IR studies. The resultant doubly reduced CO-bound species acted as a trapping state which inhibited CO 2 RR electrocatalysis. Regeneration of active species was accessed via reductive dissociation of CO at a more negative potential. In conclusion, this study highlights the combined effects of redox-active ligands and pyridine/pyridinium as SCS groups on CO 2 RR catalysis and provides design principles for future development of CO 2 RR catalysts utilizing pyridine/pyridiniums as SCS functional groups to fine-tune the catalytic activity.
CO2 reduction↗
Deep Learning Coordinate-Free Quantum Chemistry
Computing quantum chemical properties of small molecules and polymers can provide insights valuable to physicists, chemists and biologists when designing new materials, catalysts, biological probes and drugs. Deep learning can compute quantum chemical properties accurately in a fraction of the time required by commonly used methods such as density functional theory (DFT). However, many of these deep learning architectures require energy minimized molecular geometries as input, which is also computationally expensive, and decreasing the reproducibility and throughput of these methods. In this study, we demonstrate that accurate quantum chemical computations can be performed without optimized geometries by operating in the coordinate-free domain using deep learning on graph encodings. Furthermore, we also find that the choice of graph-encoding architecture substantially affects the performance of these methods. The Wave architecture outperforms graph convolution architectures, particularly on complex molecules. Furthermore, the structures of these graph encoding architectures provide an opportunity to probe an important, outstanding question in quantum mechanics: What types of quantum chemical properties can be represented by local-variable models? We find that Wave, a local-variable model, is more accurately calculates quantum chemical properties. Graph convolutional architectures require global variables, and are not as effective as as Wave. We anticipate that coordinate-free, deep-learning models of quantum chemistry will become valuable tools in chemistry and biology, enabling researchers to rapidly screen chemical databases or identify new molecules using automated, de-novo design algorithms.
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29Si solid state NMR and Ti K-edge XAFS pre-edge spectroscopy reveal complex behavior of Ti in silicate melts
Abstract An understanding of the mechanisms of Ti is incorporation into silicate glasses and melts is critical for the field of petrology. Trace-element thermobarometry, high-field-strength element partitioning, and the physical properties of magmas are all be influenced by Ti incorporation into glasses and changes therein in response to changes in composition and temperature. In this study, we combine 29 Si solid state NMR and Ti K -edge XAFS spectroscopy to investigate how Ti is incorporated into quenched Na-silicate glasses, and the influence of Ti on the structure of silicate species in these glasses. 29 Si NMR shows that in both Ti-bearing Na 2 O•4SiO 2 (NS4) and Na 2 O•8SiO 2 (NS8) glasses, increasing the amount of Ti in the melt results in a shift of Si Q 4 peak in the 29 Si NMR spectra reflecting Ti nearest neighbors for Si in Q 4 speciation. The Ti XAFS results from NS8 glass indicate that Ti is primarily incorporated in [5]-fold coordination. At higher Ti content, there is a shift of the XAFS pre-edge feature suggesting mixing of [4]-fold Ti into the spectra. Combined, the 29 Si NMR and XAFS pre-edge data are consistent with Ti incorporation as isolated [5] Ti atoms and the formation of [5] Ti clusters at relatively low Ti concentrations, with no evidence for Ti–Na interactions as suggested by previous studies. As the Ti content increases, the Ti atoms begin to occupy 4-fold coordinated sites interacting primarily with Si in Q 4 speciation (no significant Na– [4] Ti bonding). The internal consistency of these two techniques provides a uniquely complete snapshot of the complexity of Ti incorporation in silicate melts and underlies the importance of understanding Ti incorporation mechanisms in natural magmatic systems.
Ackerson, Michael R.↗
Bulk Glassy GeTe 2 : A Missing Member of the Tetrahedral GeX 2 Family and a Precursor for the Next Generation of Phase-Change Materials
Vitreous germanium disulfide GeS 2 and diselenide GeSe 2 belong to canonical chalcogenide glasses extensively studied over the past half century. Their high-temperature orthorhombic polymorphs are congruently melting compounds, and the tetrahedral crystal and glass structure is largely preserved in the melt. In contrast, the ditelluride counterpart is absent in the Ge-Te phase diagram, which shows only a single compound, monotelluride GeTe. Phase-change materials based on GeTe have become a technologically important class of solids, and their structure and properties are also widely studied. Surprisingly, very scarce information is available for alloys having GeTe 2 stoichiometry. Using a fast quenching procedure in silica capillaries, high-energy X-ray diffraction, and Raman spectroscopy supported by first-principles simulations, we show that bulk glassy GeTe 2 differs substantially from the lighter GeX 2 members, revealing 46% of trigonal germanium, 31% of three-fold coordinated tellurium, and only 20% of edge-sharing tetrahedra or pyramids. The fraction of homopolar Ge-Ge bonds is low; however, the population of dominant Te-Te dimers and Te n oligomers, n <= 10, appears to be significant. The complex structural and chemical topology of g-GeTe 2 is directly related to the thermodynamic metastability of germanium ditelluride, schematically represented by the following reaction: GeTe 2 $\rightleftarrows$ GeTe + Te. Disproportionation is complete above liquidus in the temperature range of semiconductor-metal transition, and the dense metallic GeTe 2 liquid, mostly consisting of five-fold coordinated Ge species, exhibits high fluidity, strong fragility (m = 99 ± 5), and presumably a fast structural transformation rate combined with low atomic mobility in the vicinity of the glass transition temperature, favorable for reliable long-term data retention in nonvolatile memories. The observed and predicted characteristic features make GeTe 2 a promising precursor for the next generation of phase-change materials, especially coupled with additional metal doping, depolymerizing the tetrahedral interconnected glass network and accelerating (sub)nanosecond crystallization.
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