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DOE OSTI2025

Quantifying Groundwater Response and Uncertainty in Beaver‐Influenced Mountainous Floodplains Using Machine Learning‐Based Model Calibration

Abstract Beavers ( Castor canadensis ) alter river corridor hydrology by creating ponds and inundating floodplains, and thereby improving surface water storage. However, the impact of inundation on groundwater, particularly in mountainous alluvial floodplains with permeable gravel/cobble layers overlain by a soil layer, remains uncertain. Numerical modeling across various floodplain structures considers topographic and sediment complexity and multidirectional flow, linking inundation to groundwater response. This study develops a model‐data integration workflow to address uncertainty in groundwater response to beaver‐induced inundations in a mountainous alluvial floodplain in the Upper Colorado River Basin. Uncertain factors include seasonal hydrologic dynamics, hydraulic conductivities, floodplain structures, and meteorological forcings. We employed an ensemble of groundwater models, based on geophysical and hydrologic data, with machine learning‐based calibration using a neural density estimator. This allowed us to quantify the vertical flux from the soil layer to the permeable gravel bed, the down‐valley underflow within the gravel bed, and their ratios. Results show a significant increase in the vertical flux relative to down‐valley underflow, from 2 during dry pond periods to 20 during wet periods, serving as an analogy for conditions without and with beaver ponds. The study highlights the influence of floodplain structure on groundwater storage, water balance, and water quality impacted by beaver ponds. A thick gravel bed layer, with a large down‐valley underflow, minimizes the effect of beaver‐induced inundation on water quality. We emphasize the need for field‐scale measurements of floodplain structure and improved characterization of evapotranspiration changes to reduce uncertainty in groundwater response. Plain Language Summary Beavers change the flow of water in river corridors by creating ponds, expanding wetlands, and flooding floodplains. This increases surface water area, promotes plant growth, and enhances biodiversity. However, the impact of this flooding on groundwater flow is not well understood, especially in mountainous areas with gravel layers where water moves easily beneath soil. In this study, we used numerical modeling to investigate how beaver ponds influence groundwater in a mountainous floodplain of the Upper Colorado River Basin. We adapted a machine learning method to validate our numerical models using multiple field data sets. Our findings show that beaver ponds significantly increase vertical water flow from the soil to the gravel during wet periods, compared to when the ponds are fully drained. The study also highlights the importance of floodplain structure in controlling both water flow in gravel layers along the river direction and vertical flow from the soil to the gravel with the presence of beavers. To reduce uncertainty in groundwater response, we emphasize the need for more field‐scale measurements of floodplain structure, hydraulic properties, and evapotranspiration changes. Key Points Floodplain structures and hydraulic conductivities are important for groundwater response with beaver ponds in mountainous floodplains Large down‐valley underflow in permeability‐stratified floodplains reduces beaver‐induced impacts on groundwater storage and water quality Machine learning‐based model calibration methods are effective for estimating posterior distributions of groundwater model parameters

Wang, Lijing↗

DOE OSTI2025

Conformationally Adaptable Extractant Flexes Strong Lanthanide Reverse-Size Selectivity

Chemical selectivity is traditionally understood in the context of rigid molecular scaffolds with precisely defined local coordination and chemical environments that ultimately facilitate a given transformation of interest. By contrast, nature leverages dynamic structures and strong coupling to enable specific interactions with target species in otherwise complex media. Taking inspiration from nature, we demonstrate unconventional selectivity in the solvent extraction of light over heavy lanthanides using a conformationally flexible ligand called octadecyl acyclopa (ODA). This novel ligand forms pseudocyclic molecular complexes with lanthanide ions at organic/aqueous interfaces, revealed by vibrational sum frequency generation spectroscopy. These complexes are extracted into the organic phase, where femtosecond structural dynamics are probed by two-dimensional infrared spectroscopy and ab initio molecular dynamics simulations to mechanistically frame the macroscopic selectivity trends. We find larger-than-expected structural fluctuations and bond lengths for heavy Ln–ODA complexes that arise from an inability of ODA to contort around the smaller ions to satisfy all would-be bonding interactions, despite forming some individually strong bonds. This finding contrasts with the binding of ODA with lighter lanthanides where, despite individually weaker bonds, collective interactions manifest that minimize structural fluctuations and give rise to enhanced thermodynamic stability. Furthermore, these results point to a new paradigm where conformational dynamics and cumulative bonding interactions can be used to facilitate unconventional chemical transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Resistance to oxyimino-cephalosporins conferred by an alternative mechanism of hydrolysis by the Acinetobacter -derived cephalosporinase-33 (ADC-33), a class C β-lactamase present in carbapenem-resistant Acinetobacter baumannii (CR Ab )

ABSTRACT Antimicrobial resistance inAcinetobacter baumanniiis partly mediated by chromosomal class C β-lactamases, theAcinetobacter-derived cephalosporinases (ADCs). Recently, a growing number of emerging variants were described, expanding this threat. Consistent with other β-lactamases, one of the main areas of variance exists in the Ω-loop region near the site of cephalosporin binding. Interestingly, a common alanine duplication (Adup) is found in this region. Herein, we studied specific Adup variants expressed in a uniformEscherichia coligenetic background that demonstrated high-level resistance to multiple oxyimino-cephalosporins. For ceftolozane and ceftazidime, the Adup ADCs significantly increased levels of resistance (minimum inhibitory concentration [MIC] ≥ 512 µg/mL and MIC ≥ 1,024 µg/mL, respectively). These observations were consistent with the increasedk cat /K M for ceftazidime. For cefiderocol, three Adup variants exhibited increased MICs and increasedk cat /K M for this compound. Timed electrospray ionization mass spectrometry demonstrated stable cephalosporin:ADC adducts with ADC-30 (non-Adup), but not with ADC-33 (Adup), consistent with turnover. The X-ray crystal structure of Adup variant ADC-33 in complex with ceftazidime was determined (1.57 Å resolution) and suggests that increased turnover is facilitated by conformational changes (shift in Tyr221 and orientation of the oxyimino portion of the R1 side chain) and repositioning of water in the active site. These changes appear to favor substrate-assisted catalysis as an alternative mechanism to base-assisted catalysis. These studies also provide unprecedented insight into the mechanism underlying oxyimino-cephalosporin hydrolysis by expanded-spectrum ADC β-lactamases and possibly other class C β-lactamases, which is of critical importance to future drug design. IMPORTANCE The characterization of emergingAcinetobacter-derived cephalosporinase (ADC) variants is necessary to understand the increasing resistance to β-lactam antibiotics inAcinetobacterspp. In this study, cefiderocol retains effectiveness against ADC variants with and without an Ω-loop alanine duplication (Adup). However, the presence of the Adup appears to introduce loop flexibility and structural alterations resulting in increased resistance and steady-state turnover of larger cephalosporins. Further characterization provides unprecedented insight into the mechanism of cephalosporin hydrolysis by ADC β-lactamases and supports a concomitant increase in ADC structural flexibility and cephalosporin affinity that leads to more efficient hydrolysis. In addition, the crystal structure of ADC-33 in complex with ceftazidime is consistent with a substrate-assisted catalysis mechanism. The structural differences in the ADC-33 active site leading to ceftazidime catalysis provide a better understanding of β-lactamase Adup variants and open important opportunities for future drug design and development.

Microbiology↗

DOE OSTI2025

Soft X-ray tomography reveals variations in B. subtilis biofilm structure upon tasA deletion

Bacterial biofilms are complex cell communities within a self-produced extracellular matrix, crucial in various fields but challenging to analyze in 3D. We developed a "biofilm-in-capillary" growth method compatible with full-rotation soft X-ray tomography, enabling high-resolution 3D imaging of bacterial cells and their matrix during biofilm formation. This approach offers 50 nm isotropic spatial resolution, rapid imaging, and quantitative native analysis of biofilm structure. Using Bacillus subtilis biofilms, we detected coherent alignment and chaining of wild-type cells towards the oxygen-rich capillary tip. In contrast, the ΔtasA genetic knock-out showed a loss of cellular orientation and changes in the extracellular matrix. Adding TasA protein to the ΔtasA strain restored matrix density and led to cell assembly compaction, but without the chaining observed in wild-type biofilms. This scalable and transferable approach opens new avenues for examining biofilm structure and function across various species, including mixed biofilms, and response to genetic and environmental factors.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2026

Stabilizing Ru-Formyl CO 2 Reduction Intermediates by Formation of Lewis Acid–Base Adducts: A Combined 2DIR and NMR Study

This work demonstrates how the stability of a Ru(II) formyl complex (cis-[Ru(bpy) 2 (CO)(CHO)][PF 6 ]), which is known to decarbonylate to form the metal hydride complex, is greatly enhanced by the addition of a Lewis acidic cation (Li + or Mg 2+ ). Multinuclear NMR is used to measure equilibrium constants of adduct formation, and then ultrafast 2DIR spectroscopy is applied to determine how the electronic structure and local molecular dynamics change upon complexation of the formyl ligand with the Lewis acid. We attribute the stabilization of the complex to the formation of a carbene-like structure where the bond strength between the Ru and the formyl group increases. The change in electronic structure is evidenced by steady-state NMR spectroscopy and DFT calculations. 2DIR measurements further confirm both the complexation of the formyl ligand with the Lewis acid and the change in electronic structure, where changes in vibrational frequency, relaxation kinetics, and a slowdown in the time scale of rotation about the metal-formyl bond are observed in the presence of Lewis acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

M PX 3 van der Waals magnets under pressure ( M = Mn, Ni, V, Fe, Co, Cd; X = S, Se)

van der Waals antiferromagnets with chemical formula MPX 3 (M = V, Mn, Fe, Co, Ni, Cd; X = S, Se) are superb platforms for exploring the fundamental properties of complex chalcogenides, revealing their structure-property relations and unraveling the physics of confinement. Pressure is extremely effective as an external stimulus, able to tune properties and drive new states of matter. In this review, we summarize experimental and theoretical progress to date with special emphasis on the structural, magnetic, and optical properties of the MPX 3 family of materials. Under compression, these compounds host inter-layer sliding and insulator-to-metal transitions accompanied by dramatic volume reduction and spin state collapse, piezochromism, possible polar metal and orbital Mott phases, as well as superconductivity. Some responses are already providing the basis for spintronic, magneto-optic, and thermoelectric devices. We propose that strain may drive similar functionality in these materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Resolving the Electron Plume within a Scanning Electron Microscope

Scanning electron microscopy (SEM), a century-old technique, is today a ubiquitous method of imaging the surface of nanostructures. However, most SEM detectors simply count the number of secondary electrons from a material of interest, and thereby overlook the rich material information contained within them. Here, by simple modifications to a standard SEM tool, we resolve the momentum and energy information on secondary electrons by directly imaging the electron plume generated by the electron beam of the SEM. Leveraging these spectroscopic imaging capabilities, our technique is able to image lateral electric fields across a prototypical silicon p–n junctions and to distinguish differently doped regions, even when buried beyond depths typically accessible by SEM. Intriguingly, the subsurface sensitivity of this technique reveals unexpectedly strong surface band bending within nominally passivated semiconductor structures, providing useful insights for complex layered component designs, in which interfacial dynamics dictate device operation. Further, these capabilities for noninvasive, multimodal probing of complicated electronic components are crucial in today’s electronic manufacturing but is largely inaccessible even with sophisticated techniques. These results show that seemingly simple SEM can be extended to probe complex and useful material properties.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Complexity in the medium-range order of gallium as a polyvalent liquid metal

Simplicity in chemical composition does not always translate into simplicity in the structures and dynamics of liquids and solids. Some elementary liquid metals, such as gallium, show unusual behaviors in thermodynamic and transport properties as a result of their complex atomic structure and dynamics. Here, in this work, we study the real-space atomic correlation function of liquid gallium by neutron scattering. In the pair-distribution function, there exist two kinds of medium-range order (MRO), characterized by oscillations beyond the first nearest neighbors. On the other hand, the first neighbor shell shows only one kind of bond. The two types of MRO are strongly overlapping in space and fluctuating in time. We propose that they are the basis for anomalous behavior of liquid gallium. This view challenges the current view that liquid gallium consists of fluctuating metallic and insulating domains. These findings shed light on the interpretation of similar microscopic anomalies observed in other semimetallic liquids.

Hua, Chengyun [Oak Ridge National Laboratory (ORNL↗

DOE OSTI2025

Tuning 3-D Nanomaterial Architectures Using Atomic Layer Deposition to Direct Solution Synthesis

The ability to synthesize nanoarchitected materials with tunable geometries provides a means to control their functional properties, with applications in biological, environmental, and energy fields. To this end, various bottom-up and top-down synthesis processes have been developed. However, many of these processes require prepatterning or etching steps, making them challenging to scale-up to complex, nonplanar substrates. Furthermore, the ability to integrate nanomaterials into hierarchical arrays with precise control of feature spacing and orientation remains a challenge. One approach to overcome these patterning challenges is the use of surface modification layers to guide the resulting geometry of nanomaterial architectures grown from the substrate. A powerful strategy to accomplish this is what we will refer to as “surface-directed assembly,” where the resulting geometric parameters (feature size, shape, orientation) are predetermined by the initial surface layer. In particular, the use of Atomic Layer Deposition (ALD) to form a surface layer, followed by solution-based growth processes, has the ability to synthesize architected structures with tunable geometries on complex, nonplanar surfaces. Over the past decade, we have reported a series of studies where surface-directed assembly is used to synthesize ZnO nanowires (NWs) on top of a variety of substrates. In this case, a thin film of ZnO is deposited onto the substrate using ALD, which can guide the NW diameter, spacing, and angular orientation with respect to the substrate by controlling epitaxial relationships. Furthermore, we have shown that by depositing a submonolayer overcoat of a secondary material (e.g., amorphous TiO 2 ), nucleation sites are partially blocked, which can further tune the spacing between nanowires while minimizing changes to their other geometric properties. This approach can be used to generate multilevel hierarchical structures, such as hyperbranched NW arrays with tunable control of each level of hierarchy using ALD. Finally, we have demonstrated that the tunable control of geometric parameters can be scaled-up to curved, nonplanar substrates. This highlights the power of ALD to conformally and uniformly deposit the seed layers on complex substrates with subnanometer precision. To complement these seeded hydrothermal approaches, we expanded this strategy to include conversion chemistry of the initial ALD seed layers. For example, by replacing ZnO with Al 2 O 3 as the seed layer without changing the hydrothermal growth conditions, Al–Zn layered-double hydroxide nanosheets can be formed instead of nanowires. In another example of conversion chemistry, a solution anion-exchange process was used to incorporate sulfur into ALD metal oxide films. In both of these conversion processes, the properties of the initial ALD film enabled tuning of the resulting nanostructure geometry. In this Account, we describe the use of ALD to guide the growth of diverse nanomaterial systems, with tunable control over their geometry and composition. We further show how these approaches can be used to tune functional properties for a range of applications, including superomniphobic surfaces, antibiofouling coatings, and photocatalysis. In conclusion, we conclude with an outlook on how the combination of ALD and solution synthesis can enable future directions in scalable nanomanufacturing to overcome the limitations of traditional top-down and bottom-up approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Holistic Microstructure Control Strategies in Photopolymerization‐Induced Phase Separation of Acrylate Systems

Open porous materials, known for their large surface area and interconnected structures, are essential in various applications, including batteries, ion exchange, catalysis, filtration, and electronic waste recycling. A critical aspect of the functionality of porous membranes is the precise control of pore size and morphology. Photopolymerization-induced phase separation (photo-PIPS) offers a convenient and versatile methods for creating porous structures. However, controlling the porous morphology remains challenging due to the complex interplay between thermodynamics, polymerization kinetics, and monomer structures, which makes it difficult to establish the relationship between processing conditions and resulting morphology in photo-PIPS. Herein, a physics-based phase-field model capable of generating and characterizing the microstructures of porous materials based on both average and localized features is developed. Using the phase-field simulations as test bed, the effects of polarity, light intensity, and curing temperature, as well as the previously unexplored roles of chain transfer agents and substrates, on the morphology of the resulting porous microstructure are investigated. Experiments are performed to verify the results predicted by the simulations. This work lays out a comprehensive guide for designing PIPS-derived porous microstructures and offers practical engineering strategies for tailoring microstructure-level topology and size of pores for application-specific needs.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Toward Multiscale, Multimaterial 3D Printing

Biological materials and organisms possess the fundamental ability to self-organize, through which different components are assembled from the molecular level up to hierarchical structures with superior mechanical properties and multifunctionalities. These complex composites inspire material scientists to design new engineered materials by integrating multiple ingredients and structures over a wide range. Additive manufacturing, also known as 3D printing, has advantages with respect to fabricating multiscale and multi-material structures. The need for multifunctional materials is driving 3D printing techniques toward arbitrary 3D architectures with the next level of complexity. In this paper, the aim is to highlight key features of those 3D printing techniques that can produce either multiscale or multimaterial structures, including innovations in printing methods, materials processing approaches, and hardware improvements. Several issues and challenges related to current methods are discussed. Ultimately, the authors also provide their perspective on how to realize the combination of multiscale and multimaterial capabilities in 3D printing processes and future directions based on emerging research.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Dicarbonyl[10,10-dimethyl-5,15-bis(pentafluorophenyl)biladiene]ruthenium(II): discovery of the first ruthenium tetrapyrrole cis -dicarbonyl complex by X-ray and electron diffraction

Dicarbonyl[10,10-dimethyl-5,15-bis(pentafluorophenyl)biladiene]ruthenium(II), [Ru(C 33 H 16 F 10 N 4 )(CO) 2 ] or Ru(CO) 2 [DMBil1], is the first reported ruthenium(II) cis-dicarbonyl tetrapyrrole complex. The neutral complex sports two carbonyls and an oligotetrapyrrolic biladiene ligand. Notably, the biladiene adopts a coordination geometry that is well distorted from square planar and much more closely approximates a seesaw arrangement. Accordingly, Ru(CO) 2 [DMBil1] is not only the first ruthenium cis-dicarbonyl with a tetrapyrrole ligand, but also the first metal biladiene complex in which the tetrapyrrole does not adopt a (pseudo-)square-planar coordination geometry. Ru(CO) 2 [DMBil1] is weakly luminescent, displaying λ em = 552 nm upon excitation at λ ex = 500 nm, supports two reversible 1 e – reductions at –1.45 and –1.73 V (versus Fc + /Fc), and has significant absorption features at 481 and 531 nm, suggesting suitability for photocatalytic and photosensitization applications. While the structure of Ru(CO) 2 [DMBil1] was initially determined by X-ray diffraction, a traditionally acceptable quality structure could not be obtained (despite multiple attempts) because of consistently poor crystal quality. Furthermore, an independent structure obtained from electron diffraction experiments corroborates the structure of this unusual biladiene complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Ultrafast Relaxation of MLCT Excited States in Manganese Tricarbonyl Complexes: Insights from Polarization-Resolved Femtosecond X-ray Absorption Spectroscopy at the Mn and Br K-Edges

Optical absorption features that are often described as metal-to-ligand charge transfer (MLCT) bands underlie the utility of many metal coordination complexes by harnessing the energy of light to drive otherwise inaccessible chemical reactions. Excitation of these bands triggers rapid electronic dynamics that can be challenging to understand, due to complicated potential energy landscapes and highly correlated electronic and nuclear degrees of freedom in metal-containing compounds. The lowest-energy absorption bands in Mn complexes containing alpha-diimine, carbonyl, and halide ligands are particularly interesting, due to the delocalized nature of charge transfer upon excitation. Here, in this study, we report experimental ultrafast dynamics measurements for the series of compounds Mn(CO) 3 ( R bpy)Br ( R bpy = 4,4′-disubstituted-2,2′-bipyridine; R = H, CF 3 , or NO 2 ) using polarization-resolved, femtosecond X-ray absorption spectroscopy (XAS) at both the Mn and Br K edges. The appearance of a new absorption feature in the Br pre-edge spectrum upon optical excitation reveals the instantaneous formation of an electronic hole that is partially localized on the Br atom and has a lifetime that depends on the electron withdrawing character of the R bpy ligand. For two of the complexes (R = H or CF 3 ), a large expansion of the Mn–Br distance results in a rapid redistribution of the hole and a corresponding decrease in anisotropy of the absorption feature within 50 fs, after which the absorption into the hole disappears on a time scale shorter than 300 fs. We observe a different result for the NO 2 substituted compound, for which the Mn–Br bond contracts and the absorption into the Br-centered hole persists beyond the 2 ps time scale of our measurement. The Mn pre-edge spectrum also reveals structural changes for these three complexes, but the new Mn absorption features become evident only after the nuclei respond to the initial excitation, which allows mixing of Mn 3d and 4p orbitals. The combined use of ultrafast Mn and Br K-edge spectroscopy provides unique insight into the ways in which bipyridine substitution alters the excited-state dynamics, including a very different structural response for the most strongly electron withdrawing substituent.

Otolski, Christopher J. [Univ. of Kansas, Lawrence↗

DOE OSTI2025

Chemistry and Interfacial Structure Promoting Quasi-van der Waals Epitaxial Growth of WS 2 Nanosheets on Sapphire for Prospective Application in Field-Effect Transistors

How do chemical and structural modifications to the supporting crystal surface affect the subsequent van der Waals (vdW) or quasi(Q)-vdW epitaxial growth of 2D nanocrystals? Developing an atomic-scale picture of such an interfacial system is crucial for understanding its impact on the physical and chemical properties of the supported 2D materials. The elucidation of the interfacial structure and chemistry needed to promote the Q-vdW epitaxial growth of 2D tungsten disulfide (WS 2 ) nanocrystals contributes to the growth mechanism understanding, thus pushing forward the integration of such atomically thin semiconductors toward real field-effect transistor applications. In addition to an atomic-force microscopy top view, we showcase a combination of X-ray techniques for a top-to-bottom investigation of the complexities of the buried interface structures. Furthermore, this approach uses X-ray photoelectron spectroscopy, X-ray standing wave excited X-ray fluorescence, and crystal truncation rod scattering to produce a highly resolved chemical-state-specific 3D atomic map for the extended interface structure of WS 2 /α-Al 2 O 3 (001). Employing these detailed analysis methods, along with density functional theory to further refine the picoscale structure, we demonstrate how two different types of interface engineering during the pregrowth stage lead to significant differences in the chemical and structural modifications to the terminal surface of c-face sapphire, which in turn leads to substantial differences in the submonolayer growth of supported WS 2 2D nanocrystals in terms of lateral domain sizes, epitaxial registry, vdW gaps, and stability.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Electronic Structures of Iron in Oxide Glasses via 1s3p Resonant Inelastic X-ray Scattering

Electronic structures of iron in glasses are essential for unraveling the effect of transition metals on amorphous networks and controlling the electro-optical and transport properties of advanced glasses and amorphous energy-storing materials. The electronic configurations around iron in glasses, however, remain not well understood due to the structural disorders arising from multiple iron species with distinct valence, coordination, and spin states. Here, the first 1s3p resonant inelastic X-ray scattering (RIXS) for oxide glasses identifies hidden electronic configurations for Fe 2+ and Fe 3+ in amorphous networks. The results allow us to quantify the composition-induced evolution of oxygen ligand–field interactions of high-spin Fe 3d states with varying valence and coordination environments in complex glasses. The distinct electronic structures account for the electronic origins of iron-induced changes in the glass properties. The results offer prospects for a simultaneous probing of valence, coordination, and spin states of transition metals in diverse multicomponent oxide glasses and functional amorphous solids via 1s3p RIXS.

Kim, Yong-Hyun [Seoul National Univ. (Korea, Repub↗

DOE OSTI2024

SEC ‐ SAXS / MC Ensemble Structural Studies of the Microtubule Binding Protein Cdt1 Show Monomeric, Folded‐Over Conformations

ABSTRACT Cdt1 is a mixed folded protein critical for DNA replication licensing and it also has a “moonlighting” role at the kinetochore via direct binding to microtubules and the Ndc80 complex. However, it is unknown how the structure and conformations of Cdt1 could allow it to participate in these multiple, unique sets of protein complexes. While robust methods exist to study entirely folded or unfolded proteins, structure–function studies of combined, mixed folded/disordered proteins remain challenging. In this work, we employ orthogonal biophysical and computational techniques to provide structural characterization of mitosis‐competent human Cdt1. Thermal stability analyses shows that both folded winged helix domains1 are unstable. CD and NMR show that the N‐terminal and linker regions are intrinsically disordered. DLS shows that Cdt1 is monomeric and polydisperse, while SEC‐MALS confirms that it is monomeric at high concentrations, but without any apparent inter‐molecular self‐association. SEC‐SAXS enabled computational modeling of the protein structures. Using the program SASSIE, we performed rigid body Monte Carlo simulations to generate a conformational ensemble of structures. We observe that neither fully extended nor extremely compact Cdt1 conformations are consistent with SAXS. The best‐fit models have the N‐terminal and linker disordered regions extended into the solution and the two folded domains close to each other in apparent “folded over” conformations. We hypothesize the best‐fit Cdt1 conformations could be consistent with a function as a scaffold protein that may be sterically blocked without binding partners. Our study also provides a template for combining experimental and computational techniques to study mixed‐folded proteins.

Cell Biology↗

DOE OSTI2025

Structural Evolution of Mixed-Addenda Keggin Polyoxometalate Anions with Atom-by-Atom Substitution

Polyoxometalates (POMs) are molecular metal oxides with distinctive electronic properties that make them promising materials for applications in energy, sensors, and memory devices. One of the most promising methods of tuning the stability, photochromic, redox, and electron-spin properties of POMs is through the substitution of the metal “addenda” atoms that, along with oxygen, constitute their cage-like structures. Because traditional synthesis methods typically produce a distribution of POMs, the isolation and characterization of multimetallic POMs with predetermined stoichiometry remains challenging. The presence of multiple energetically accessible isomers further complicates the experimental characterization and theoretical modeling of multimetallic POMs. Herein, we leverage the distinguishing mass-selection capabilities of ion soft landing to prepare stoichiometrically selected Keggin PMo x W 12-x O 40 3- (x = 0 – 6, 8, 10, and 12) POMs on self-assembled monolayer surfaces free of the solvent molecules and counterions that often confound characterization of complex species at interfaces. The structures of the supported POMs are characterized with atom-by-atom precision using in situ infrared (IR) reflection absorption spectroscopy complemented by detailed density functional theory calculations. Our joint experimental and theoretical results reveal an almost linear shift in the positions of the IR bands towards lower wavenumbers with an increase in the number of lighter molybdenum atoms compared to heavier W atoms in PMoxW 12-x O 40 3- . The theoretical calculations also indicate that numerous isomeric structures may be populated at the experimental conditions and, consequently, contribute to the overall IR spectra. In conclusion, our findings indicate that in addition to the number of substituted addenda atoms and the presence of multiple isomeric structures, interactions with the surface play an important role in determining the IR spectra and structure of supported bimetallic POMs.

Prabhakaran, Venkateshkumar [Pacific Northwest Nat↗

DOE OSTI2025

Structures of TGF-β with betaglycan and signaling receptors reveal mechanisms of complex assembly and signaling

Abstract Betaglycan (BG) is a transmembrane co-receptor of the transforming growth factor-β (TGF-β) family of signaling ligands. It is essential for embryonic development, tissue homeostasis and fertility in adults. It functions by enabling binding of the three TGF-β isoforms to their signaling receptors and is additionally required for inhibin A (InhA) activity. Despite its requirement for the functions of TGF-βs and InhA in vivo, structural information explaining BG ligand selectivity and its mechanism of action is lacking. Here, we determine the structure of TGF-β bound both to BG and the signaling receptors, TGFBR1 and TGFBR2. We identify key regions responsible for ligand engagement, which has revealed binding interfaces that differ from those described for the closely related co-receptor of the TGF-β family, endoglin, thus demonstrating remarkable evolutionary adaptation to enable ligand selectivity. Finally, we provide a structural explanation for the hand-off mechanism underlying TGF-β signal potentiation.

Science & Technology - Other Topics↗