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DOE OSTI2024

p14 ARF forms meso-scale assemblies upon phase separation with NPM1

NPM1 is an abundant nucleolar chaperone that, in addition to facilitating ribosome biogenesis, contributes to nucleolar stress responses and tumor suppression through its regulation of the p14 Alternative Reading Frame tumor suppressor protein (p14 ARF ). Oncogenic stress induces p14 ARF to inhibit MDM2, stabilize p53 and arrest the cell cycle. Under non-stress conditions, NPM1 stabilizes p14 ARF in nucleoli, preventing its degradation and blocking p53 activation. However, the mechanisms underlying the regulation of p14 ARF by NPM1 are unclear because the structural features of the p14 ARF -NPM1 complex were elusive. Here we show that p14 ARF assembles into a gel-like meso-scale network upon phase separation with NPM1. This assembly is mediated by intermolecular contacts formed by hydrophobic residues in an α-helix and β-strands within a partially folded N-terminal portion of p14 ARF . These hydrophobic interactions promote phase separation with NPM1, enhance p14 ARF nucleolar partitioning, restrict NPM1 diffusion within condensates and nucleoli, and reduce cellular proliferation. Our structural analysis provides insights into the multifaceted chaperone function of NPM1 in nucleoli by mechanistically linking the nucleolar localization of p14 ARF to its partial folding and meso-scale assembly upon phase separation with NPM1.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2025

Controlling solvation in conducting redox polymers for selective electrochemical separation of nitrate from wastewater

Selective capture of nitrate from wastewater is crucial for ensuring safe drinking water and promoting resource circularity. This study investigated alkylated polyaniline redox polymers as highly-selective electrosorbents to address this challenge. By controlling polymer solvation properties through synthetic functionalization, poly(N-methylaniline) (PNMA) achieves a nitrate uptake of up to 1.38 mmol g −1 -polymer and a separation factor of 7 over chloride. Poly(N-butylaniline) (PNBA) further enhances selectivity, achieving a separation factor beyond 14 due to increased hydrophobicity. The mechanisms underlying this selectivity are investigated using ab initio molecular dynamics (AIMD) and in-situ electrochemical quartz crystal microbalance (EQCM) studies, which reveal that hydrophobicity reduces chloride binding. A technoeconomic analysis indicates that methylation on PANI reduces nitrate removal costs by 50% compared to non-functionalized PANI, due to enhanced selectivity and uptake, and decreased energy consumption. PNMA electrodes demonstrate practical nitrate selectivity over 20 versus chloride in real wastewater, while avoiding sulfate binding. This study highlights the potential of controlling solvation at electroactive polymers to enhance nitrate selectivity, offering a promising design path for redox-mediated electrochemical separations.

chemical engineering↗

DOE OSTI2026

A family portrait of lanmodulin selectivity for enhanced rare-earth separations

Proteins offer a molecular design space to create bespoke ligands for the separation of critical metals like rare earth elements (REs). However, data-intensive approaches to tune metalloprotein selectivity are constrained by the low-throughput nature of existing characterization methods. Here we invented an assay called ‘SpyTag-Catcher Immobilization of Lanmodulin for Assaying Metal-Binding Selectivity’ (SpyCI-LAMBS) to measure metalloprotein selectivity en masse. This 96-format workflow was used to study the selectivity of 621 lanmodulin (LanM) orthologs for 15 REs, revealing eight distinct selectivity profiles based on sequence-to-function analyses. We discovered >200 LanMs with stronger selectivity against low-value LaIII relative to the prototypical LanM. This includes a LanM that can perform a challenging one-stage separation of PrIII from LaIII with up to >99.9 mol% purity and 83% yield. SpyCI-LAMBS is a powerful tool that can rapidly collect high-fidelity selectivity data to inform metal ion separations and machine-learning-assisted metalloprotein design.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2017

Organosolv-Water Cosolvent Phase Separation on Cellulose and its Influence on the Physical Deconstruction of Cellulose: A Molecular Dynamics Analysis

Deconstruction of cellulose is crucial for the chemical conversion of lignocellulose into fuel/bioproduct precursors. Recently, a water-organosolv cosolvent system (THF-water) has been shown to both phase-separate on cellulose surfaces and partially deconstruct Avicel (cellulose) in the absence of acid. Here we employ molecular dynamics simulations to determine whether other common water-organosolv cosolvent systems (acetone, ethanol, and γ-valerolactone) exhibit phase separation at cellulose surface and whether this alters a purely physical cellulose dissociation pathway. Despite finding varied degrees of phase-separation of organosolv on cellulose surfaces, physical dissociation is not enhanced. Interestingly, however, the total amount the median water-cellulose contact lifetimes increases for the cosolvent systems in the order of THF > acetone > ethanol > γ-valerolactone. Together our results indicate two points: a purely physical process for deconstruction of cellulose is unlikely for these cosolvents, and in THF-water, unlike γ-valerolactone- (and some concentrations of acetone and ethanol) water cosolvents, a significant fraction of surface water is slowed. As a result, this slowing may be of importance in enhancing chemical deconstruction of cellulose, as it permits an increase in potential THF-water-cellulose reactions, even while the amount of water near cellulose is decreased.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Selective separation of americium from europium using 2,9-bis(triazine)-1,10-phenanthrolines in ionic liquids: a new twist on an old story

Bis-triazine phenanthrolines have shown great promise for f-block metal separations, attributable to their highly preorganized structure, nitrogen donors, and more enhanced covalent bonding with actinides over lanthanides. However, their limited solubility in traditional solvents remains a technological bottleneck. Here in this paper we report our recent work using a simple 2,9-bis(triazine)-1,10-phenanthroline (Me-BTPhen) dissolved in an ionic liquid (IL), demonstrating the efficacy of IL extraction systems for the selective separation of americium from europium, achieving separation factors in excess of 7500 and selectively removing up to 99% of the americium. Characterization of the coordination environment was performed using a combination of X-ray absorption fine structure spectroscopy (XAFS) and density functional theory (DFT) calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes

Block copolymer electrolytes (BCEs) represent an attractive choice as solid-state ionic conductors for electrochemical technologies used in energy storage and conversion, water treatment, sensors, and data storage and processing. Unlocking the maximum ionic conductivity of BCEs requires an intimate understanding as to how the microphase separated structure influences transport properties. However, elucidating such knowledge remains elusive due to the challenging task of precisely engineering BCEs with a defined structure in bulk materials. In this work, we examined BCEs in a thin film format because it was amenable to attaining BCEs with a desired nanostructure. Specifically, we systematically investigated anion-conducting BCEs with different degrees of connectivity of the ionic domains. For the first time, we demonstrate that increasing terminal defects in the ionic domain from 1 terminal defect per mu m(2) to 20 terminal defects per mu m(2) ( a relatively small amount of defects) decreased ionic conductivity by 67% compared to the maximum value attained. Conversely, maximizing ionic domain connectivity increased the ionic conductivity by two-fold over a non-ordered BCE film. These experiments highlight that microphase separation alone was insufficient for ameliorating ionic conductivity in BCEs. Rather, microphase separation coupled with complete ionic domain connectivity realized BCEs with significantly enhanced ionic conductivity.

Arges, Christopher G. (ORCID:0000000317038323)↗

DOE OSTI2017

Gas separation mechanism of CO 2 selective amidoxime-poly(1-trimethylsilyl-1-propyne) membranes

Polymeric membranes for CO 2 separation have drawn significant attention in academia and industry. We prepared amidoxime-functionalized poly(1-trimethylsilyl-1-propyne) (AO-PTMSP) membranes through hydrosilylation and post-polymerization modification. Compared to neat PTMSP membranes, the AO-PTMSP membranes showed significant enhancements in CO 2 /N 2 gas separation performance (CO 2 permeability ~6000 Barrer; CO 2 /N 2 selectivity 17). This systematic study provides clear guidelines on how to tune the CO 2 -philicity within PTMSP matrices and the effects on gas selectivity. Key parameters for elucidating the gas transport mechanism were discussed based on CO 2 sorption measurements and fractional free volume estimates. The effect of the AO content on CO 2 /N 2 selectivity was further examined by means of density functional theory calculations. Here, both experimental and theoretical data provide consistent results that conclusively show that CO 2 /N 2 separation performance is enhanced by increased CO 2 polymer interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Increased charge transfer state separation via reduced mixed phase interface in polymer solar cells

Investigations into bulk heterojunction organic solar cells have demonstrated that molecular mixing within domains and at interfaces significantly impacts device performance. However, these studies often use broad performance metrics that blur fundamental structure–function mechanisms – in particular the role of the mixed phase in charge generation versus charge extraction. In this work, we present a new analysis based on time-delayed collection field that separately quantifies each fundamental step in the charge generation process. Additionally, we present a novel resonant X-ray scattering analysis to quantify the state of the three-phase nanostructure (phase volumes and their compositions) as it exists in the devices. We find that in a model semicrystalline system, decreasing the mixed phase interface between pure donor and pure acceptor domains has little effect on the efficiency of charge transfer (CT) state formation but instead dramatically increases the efficiency of CT state separation. While charge extraction efficiencies are affected as well, this has only a minor impact on device performance. With both structure and properties quantitatively resolved for the first time on the exact same devices, we determine a simultaneous >99% (anti)correlation between (mixed)pure phase volume and charge separation efficiency, with values fitting well to an exponential saturation model. This result plus our ability to eliminate other possible contributing factors provides strong evidence of a causal relationship that reducing interfacial mixed phases to establish a steep energy gradient between pure phases aids in charge generation and extraction in organic solar cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Entropic selectivity in air separation via a bilayer nanoporous graphene membrane

Membranes represent an energy-efficient technology for air separation, but it is difficult to control the pore size to separate N 2 and O 2 due to their similar kinetic diameters. In this paper we demonstrate by molecular dynamics simulations that a bilayer nanoporous graphene membrane with continuously tunable pore sizes by the offset between the two graphene layers can achieve O 2 /N 2 selectivity of up to 26 with a permeance of over 10 5 GPU (gas permeation unit). We find that entropic selectivity is the main reason behind the high selectivity via the tumbling movement of the skinnier and shorter O 2 molecules entering and passing through the elliptic-cylinder-shaped nanopores of the bilayer membrane. Such motion is absent in the single-layer graphene membrane with pores of similar size and shape which yields an O 2 /N 2 selectivity of only 6 via molecular sieving alone. Hence the bilayer nanoporous graphene membrane provides a novel way to enhance the entropic selectivity for gas separation by controlling both the pore size and the 3D pore shape.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Macromolecular design strategies toward tailoring free volume in glassy polymers for high performance gas separation membranes

The gas separation membrane field has seen exceptional growth since its inception, with extensive research being performed to find novel, high performance polymer membrane materials for application in industrial separations. In this review, we examine recent advances of polymer design strategies to overcome the permeability/selectivity tradeoff relationship and the diminished performance caused by physical aging. We explore fundamental structure–property relationships within current state-of-the-art polymer materials to discern promising routes for continued membrane materials research and development, highlighting promising macromolecular architectures and design strategies providing tailorable polymer free volume for high performance gas separation membranes. Finally, we provide our perspective on encouraging design routes moving forward.

42 ENGINEERING↗

DOE OSTI2020

Squeezing the box: isoreticular contraction of pyrene-based linker in a Zr-based metal–organic framework for Xe/Kr separation

Isoreticular synthesis is a powerful tool to enhance specific attributes of a metal–organic framework (MOF). While the isoreticular expansion of MOF structure are prevalent in the literature, the compression of a topology holds great promise for separations due to the contracted pore apertures and/or cavities. Herein, we report the synthesis, characterization and Xe/Kr separation capability of a new Zr-based MOF, NU-1106, connected by the tetratopic linker 1,3,6,8-pyrene tetracarboxylate, which exhibits a compressed ftw topology compared to the extended ones reported previously. NU-1106 showed selective uptake of Xenon over Krypton, providing the potential for use for separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Adsorption-based membranes for air separation using transition metal oxides

In this work, we use computational modeling to examine the viability of adsorption-based pore-flow membranes for separating gases when a purely size-based separation strategy is ineffective. Using molecular dynamics simulations of O 2 and N 2 , we model permeation through a nanoporous graphene membrane. Permeation is assumed to follow a five-step adsorption-based pathway, with desorption being the rate-limiting step. Using this model, we observe increased selectivity between O 2 and N 2 , resulting from increased adsorption energy differences. We explore the limits of this strategy, providing an initial set of constraints that need to be satisfied to allow for selectivity. Finally, we provide a preliminary exploration of some transition metal oxides that appear to satisfy those conditions. Using density functional theory calculations, we confirm that these oxides possess adsorption energies needed to operate as adsorption-based pore-flow membranes. These adsorption energies provide a suitable motivation to examine adsorption-based pore-flow membranes as a viable option for air separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Supramolecular assemblies of polybenzimidazole and aromatic polycarboxylic acids with superior mechanical and H 2 /CO 2 separation properties

Aromatic polycarboxylic acids complex with imidazoles, forming supramolecular assemblies. Herein, we demonstrate that polybenzimidazole (PBI) can be augmented by aromatic polycarboxylic acids, including phthalic acid (PA), trimesic acid (TMA), and pyromellitic acid (PMA), and the resulting supramolecular assemblies exhibit attractive H 2 /CO 2 separation performance for precombustion carbon capture. The acid doping decreases the free volume and gas permeability but increases H 2 /CO 2 selectivity, which can be correlated with the molar ratio of the protons to PBI repeating units in the assemblies. Increasing the temperature decreases the H 2 /CO 2 selectivity because of weakened interactions. When challenged with model gas mixtures, a supramolecular assembly based on TMA shows H 2 /CO 2 separation properties superior to state-of-the-art materials and above Robeson's upper bound. Furthermore, this study elucidates the fruitful harnessing of dynamic non-covalent bonds to design robust and highly selective membranes for industrial gas separations.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Tuneable phase behaviour and glass transition via polymerization-induced phase separation in crosslinked step-growth polymers

We report once limited to chain-growth polymerizations, fine control over polymerization-induced phase separation (PIPS) has recently been demonstrated in rubber-toughened thermoset materials formed through step-growth polymerizations. The domain length scales of these thermoset materials can be elegantly tuned by utilizing a binary mixture of curing agents (CAs) that individually yield disparate morphologies. Importantly, varying the composition of the binary mixture affects characteristics of the materials such as glass transition temperature and tensile behavior. Here, we establish a full phase diagram of PIPS in a rubber-toughened epoxy system tuned by a binary CA mixture to provide a robust framework of phase behaviour. X-Ray scattering in situ and post-PIPS is employed to elucidate the PIPS mechanism whereby an initial polymerization-induced compositional fluctuation causes nanoscale phase separation of rubber and epoxy components prior to local chain crosslinking and potential macrophase separation. We further demonstrate the universality of this approach by alternatively employing binary epoxy or binary rubber mixtures to achieve broad variations in morphology and glass transitions.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Precisely segmented PEEK–ionene + ionic liquid composite membranes for CO 2 separation

Ionenes, polymers with ionic groups incorporated directly within the backbone are a highly versatile class of materials, although they have received much less attention than polyelectrolytes which have ionic groups pendant from the polymer backbone. By designing ionenes that incorporate robust properties of poly(ether ether ketone) (PEEK), we have achieved new imidazolium-containing PEEK–ionene architectures that create opportunities for enhanced CO 2 separation membranes. To achieve these materials, an new imidazole-functionalized PEEK oligomer (ImK(EEK) 2 KIm) was synthesized through facile and straightforward routes. This molecule was then polymerized via condensation reactions with two different aromatic (α,α'-dibromo-p-xylene) and aliphatic (dibromohexyl containing-bis(imidazolium)hexane dibromide salt) comonomers and exchanged with bistriflimide ([Tf 2 N]) anion to obtain two unique PEEK–ionenes containing distinct PEEK and ionic segments: p([ImK(EEK) 2 Im-p-xyl][Tf 2 N] 2 ) and p([ImK(EEK) 2 (ImC 6 ) 3 ][Tf 2 N] 4 ). While the neat PEEK–ionenes exhibited high molecular weight but were not able to form high-quality films, adding stoichiometric amounts of “free” IL (1-methyl-3-butylimidazolium bistriflimide, [C 4 mIm][Tf 2 N]), greatly improved the flexibility and processability of the resultant membranes. Further, the structure–property relationships of bulk PEEK–ionenes and corresponding composites were extensively characterized by different analytical techniques (thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, and solid-state NMR). In conclusion, the gas separation properties were investigated, with the PEEK–ionenes + IL composites exhibiting CO 2 permeabilities of 14–94 barrer and good CO 2 /N 2 permselectivities of 26–35, indicating that new designs of segmented ionenes and composites with ILs a promising material design strategy for developing gas separation membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Picolinate-based acyclic ligand for rare earth element extraction and separation

The rare earth elements (REEs) play an important role in many modern technologies, particularly those relevant to clean energy. Despite their increasing importance, obtaining them in elementally pure forms suitable for downstream applications is challenging due to their similar chemical properties. This problem has impeded efforts to efficiently and selectively extract them from end-of-life materials and electronic waste. Here, we report a cost-efficient acyclic picolinate-based chelator H 4 aapa. The REE stability constants (log K ML ) of this chelator were measured via pH potentiometric and UV-Visible spectrophotometric titrations, revealing it to preferably bind light over heavy REEs like many recently reported 18-membered macrocycles. Its REE complexes were characterized by X-ray crystallography and NMR spectroscopy, demonstrating that this chelator can attain different conformations. The unique properties of aapa were subsequently used to separate REEs via the dissolution of insoluble REE oxalate mixtures. This dissolution-based separation led to large separation factors, the most significant being that for the Ce 3+ /Lu 3+ pair (38.6) at pH 4. Leveraging the strong REE binding affinity of aapa, we further demonstrated this chelator can leach REEs from authentic end-of-life materials in the form of magnet waste and autocatalyst smelting (autocat) slag. With this approach, exposure of these materials to a 20 mM solution of aapa at neutral pH generates a metal-containing solution enriched in Nd 3+ and Dy 3+ by 56.9 wt% and 3.0 wt%, marking a 4-fold improvement over the use of 4 M HNO 3 .

Gao, Yangyang [University of California, Santa Bar↗

DOE OSTI2024

MUSE adaptive-optics spectroscopy confirms dual active galactic nuclei and strongly lensed systems at sub-arcsec separation

The novel Gaia multi peak (GMP) technique has proven to be able to successfully select dual and lensed active galactic nuclei (AGN) candidates at sub-arcsecond separations. Both populations are important because dual AGN represent one of the central, still largely untested, predictions of ΛCDM cosmology, and compact lensed AGN allow us to probe the central regions of the lensing galaxies. In this work, we present high-spatial-resolution spectroscopy of 12 GMP-selected systems. We used the adaptive-optics assisted integral-field spectrograph MUSE at the VLT to resolve each system and investigate the nature of each component. All targets show the presence of two components confirming the GMP selection. We classify 4 targets as dual AGN, 3 as lensed quasar candidates, and 5 as a chance alignment of a star and an AGN. With separations ranging from 0.30″ to 0.86″, these dual and lensed systems are among the most compact systems discovered to date at z > 0.5. This is the largest sample of distant dual AGN with sub-arcsecond separations ever presented in a single paper.

Scialpi, M. (ORCID:0009000651004986)↗

DOE OSTI2018

A tunable path-separated electron interferometer with an amplitude-dividing grating beamsplitter

We demonstrate a tunable path-separated electron interferometer using a single amplitude-dividing beamsplitter to prepare multiple spatially isolated, coherent electron probe beams. We place four electrostatic bi-prisms in the optical column of a scanning transmission electron microscope (STEM) to achieve path separations of up to 25 μ m, the largest demonstrated within amplitude-division electron interferometers while maintaining fringe visibility of the directly observed interference fringes at the detector. We characterize the fringe visibility of this setup over a range of path separations and perform STEM holography to reconstruct the full object wave of a fabricated Si ramp test phase object. We report a quantitative object-wave measurement in this configuration and confirm with an independent off-axis electron holography measurement. This experimental design can potentially be applied to high-resolution phase imaging and fundamental physics experiments, such as an exploration of the electron wave packet coherence length and the Aharonov-Bohm effect.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗