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At least 307 records · Page 17

Gated Molecular Diffusion at Liquid–Liquid Interfaces

Abstract The jamming of nanoparticle surfactants (NPSs) at liquid–liquid interface imparts attractive properties to the interfacial assemblies and enables the structuring of liquids. Herein, we report photoresponsive supramolecular microcapsules with jammed NPS assemblies at the oil‐water interface, taking advantage of host–guest molecular recognition. The permeability of the colloidal membrane can be effectively manipulated by switching the NPSs from a jammed state to an unjammed state with a photo trigger, leading to a controlled molecular diffusion and release, affording a versatile platform for the construction of next generation smart microcapsule systems.

Li, Lianshun↗

Sub‐5 Ångstrom Porosity Tuning in Calixarene‐Derived Porous Liquids via Supramolecular Complexation Construction

Abstract Sub‐Ångstrom‐level porosity engineering, which is appealing in gas separations, has been demonstrated in solid carbon, polymer, and framework materials but rarely achieved in the liquid phase. In this work, a gas molecular sieving effect in the liquid phase at sub‐5 Ångstrom scale is created via sophisticated porosity tuning in calixarene‐derived porous liquids (PLs). Type II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents. The chemical structure variation and assembly behavior of the porous host upon PL construction are monitored by spectroscopy‐, X‐ray‐, and neutron‐scattering techniques. The presence of permanent porosity in calixarene‐derived PLs is verified by pressure swing gas uptake, altered CO 2 physisorption behavior, and molecular simulations. Sub‐5 Ångstrom porosity tuning within the PL phase is achieved by introducing bulky substituted groups on the benzene ring of the calixarene host, which then greatly affects the dynamic motion and transport behavior of CO 2 molecules and the Xe uptake performance. The approach being demonstrated in this work represents a promising pathway to tune and leverage the porosity effect for enhanced gas uptake capacity and selectivity in liquid sorbents.

Li, Errui [Department of Chemistry University of T↗

Gated Molecular Diffusion at Liquid–Liquid Interfaces

The jamming of nanoparticle surfactants (NPSs) at liquid-liquid interface imparts attractive properties to the interfacial assemblies and enables the structuring of liquids. Herein, we report photoresponsive supramolecular microcapsules with jammed NPS assemblies at the oil-water interface, taking advantage of host-guest molecular recognition. The permeability of the colloidal membrane can be effectively manipulated by switching the NPSs from a jammed state to an unjammed state with a photo trigger, leading to a controlled molecular diffusion and release, affording a versatile platform for the construction of next generation smart microcapsule systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sub-5 Ångstrom Porosity Tuning in Calixarene-Derived Porous Liquids via Supramolecular Complexation Construction

Sub-Ångstrom-level porosity engineering, which is appealing in gas separations, has been demonstrated in solid carbon, polymer, and framework materials but rarely achieved in the liquid phase. In this work, a gas molecular sieving effect in the liquid phase at sub-5 Ångstrom scale is created via sophisticated porosity tuning in calixarene-derived porous liquids (PLs). Type II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents. The chemical structure variation and assembly behavior of the porous host upon PL construction are monitored by spectroscopy-, X-ray-, and neutron-scattering techniques. The presence of permanent porosity in calixarene-derived PLs is verified by pressure swing gas uptake, altered CO 2 physisorption behavior, and molecular simulations. Sub-5 Ångstrom porosity tuning within the PL phase is achieved by introducing bulky substituted groups on the benzene ring of the calixarene host, which then greatly affects the dynamic motion and transport behavior of CO 2 molecules and the Xe uptake performance. Further, the approach being demonstrated in this work represents a promising pathway to tune and leverage the porosity effect for enhanced gas uptake capacity and selectivity in liquid sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation and coarsening of epitaxially-supported metal nanoclusters

This mini-review describes developments over the last ~30 years in characterizing the nucleation & growth of epitaxially-supported metal nanoclusters (NCs) or islands during vapor deposition, as well as their post-deposition coarsening. A beyond-mean-field treatment for homogeneous nucleation & growth corrects the deficiencies of traditional treatments in describing, e.g., the island size distribution, but also necessitates consideration of the spatial distribution of islands and their capture zones. We discuss advances in modeling capabilities, including those based upon on an ab-initio level treatment of periphery diffusion kinetics, for description of the non-equilibrium growth shapes of these NCs, focusing on 2D NCs. For post-deposition coarsening of arrays of NCs, there is generally a competition between Ostwald Ripening (OR) and Smoluchowski Ripening (SR). SR is also known as Particle Migration & Coalescence. For 2D NCs in homoepitaxial systems, conventional OR is observed on pristine fcc(111) surfaces, dramatically enhanced OR in the presence of even trace amounts of chalcogens for Cu(111) and Ag(111), and anomalous OR on anisotropic fcc(110) surfaces. The unexpected discovery of SR for fcc(100) homoepitaxial systems prompted extensive analysis of the underlying diffusivities of 2D NCs as a function of size, as well as of NC coalescence dynamics. A comprehensive understanding of these processes is now available. Self-assembly of 3D NCs during deposition, issues related to heterogeneous nucleation, directed assembly, NC growth structure selection, and coarsening are addressed. Finally, for SR of 3D epitaxial NCs, recent insights into the size-dependence of diffusivity are described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

LAN: A Materials Notation for Two-Dimensional Layered Assemblies

Two-dimensional (2D) layered materials offer intriguing possibilities for novel physics and applications. Before any attempt at exploring the materials space in a systematic fashion, or combining insights from theory, computation, and experiment, a formal description of information about an assembly of arbitrary composition is required. Here, we introduce a domain-generic notation that is used to describe the space of 2D layered materials from monolayers to twisted assemblies of arbitrary composition, existent or not yet fabricated. The notation corresponds to a theoretical materials concept of stepwise assembly of layered structures using a sequence of rotation, vertical stacking, and other operations on individual 2D layers. Its scope is demonstrated with several example structures using common single-layer materials as building blocks. This work overall aims to contribute to the systematic codification, capture, and transfer of materials knowledge in the area of 2D layered materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid Molecular Beam Epitaxy for Single-Crystalline Oxide Membranes with Binary Oxide Sacrificial Layers

The advancement in thin-film exfoliation for synthesizing oxide membranes has led to possibilities for creating artificially assembled heterostructures with structurally and chemically incompatible materials. The sacrificial layer method is a promising approach to exfoliate as-grown films from a compatible material system, allowing for their integration with dissimilar materials. Nonetheless, the conventional sacrificial layers often possess an intricate stoichiometry, thereby constraining their practicality and adaptability, particularly when considering techniques such as molecular beam epitaxy (MBE). This is where easy-to-grow binary alkaline-earth-metal oxides with a rock salt crystal structure are useful. These oxides, which include (Mg, Ca, Sr, Ba)O, can be used as a sacrificial layer covering a much broader range of lattice parameters compared to conventional sacrificial layers and are easily dissolvable in deionized water. In this study, we show the epitaxial growth of the single-crystalline perovskite SrTiO 3 (STO) on sacrificial layers consisting of crystalline SrO, BaO, and Ba 1–x Ca x O films, employing a hybrid MBE method. Our results highlight the rapid (≤5 min) dissolution of the sacrificial layer when immersed in deionized water, facilitating the fabrication of millimeter-sized STO membranes. Using high-resolution X-ray diffraction, atomic-force microscopy, scanning transmission electron microscopy, impedance spectroscopy, and scattering-type near-field optical microscopy (SNOM), we demonstrate single-crystalline STO membranes with bulk-like intrinsic dielectric properties. The employment of alkaline earth metal oxides as sacrificial layers is likely to simplify membrane synthesis, particularly with MBE, thus expanding the research and application possibilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ferroelectric phase-transition frustration near a tricritical composition point

Phase transition describes a mutational behavior of matter states at a critical transition temperature or external field. Despite the phase-transition orders are well sorted by classic thermodynamic theory, ambiguous situations interposed between the first- and second-order transitions were exposed one after another. Here, we report discovery of phase-transition frustration near a tricritical composition point in ferroelectric Pb(Zr 1-x Ti x )O 3 . Our multi-scale transmission electron microscopy characterization reveals a number of geometrically frustrated microstructure features such as self-assembled hierarchical domain structure, degeneracy of mesoscale domain tetragonality and decoupled polarization-strain relationship. Associated with deviation from the classic mean-field theory, dielectric critical exponent anomalies and temperature dependent birefringence data unveil that the frustrated transition order stems from intricate competition of short-range polar orders and their decoupling to long-range lattice deformation. With supports from effective Hamiltonian Monte Carlo simulations, our findings point out a potentially universal mechanism to comprehend the abnormal critical phenomena occurring in phase-transition materials.

42 ENGINEERING↗

Naturally ornate RNA-only complexes revealed by cryo-EM

The structures of natural RNAs remain poorly characterized and may hold numerous surprises. Here we report three-dimensional structures of three large ornate bacterial RNAs using cryo-electron microscopy (cryo-EM). GOLLD (Giant, Ornate, Lake- and Lactobacillales-Derived), ROOL (Rumen-Originating, Ornate, Large) and OLE (Ornate Large Extremophilic) RNAs form homo-oligomeric complexes whose stoichiometries are retained at lower concentrations than measured in cells. OLE RNA forms a dimeric complex with long co-axial pipes spanning two monomers. Both GOLLD and ROOL form distinct RNA-only multimeric nanocages with diameters larger than the ribosome, each empty except for a disordered loop. Extensive intramolecular and intermolecular A-minor interactions, kissing loops, an unusual A–A helix and other interactions stabilize the three complexes. Sequence covariation analysis of these large RNAs reveals evolutionary conservation of intermolecular interactions, supporting the biological importance of large, ornate RNA quaternary structures that can assemble without any involvement of proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Imidazole-graphyne: a new 2D carbon nitride with a direct bandgap and strong IR refraction

Six-membered rings are common building blocks of many carbon structures. Recent studies have shown that penta-graphene composed of five-membered carbon rings have properties very different from that of graphene. This has motivated the search for new carbon structures. Among this is cp-graphyne, composed of carbon pentagons and bridged by acetylenic linkers. However, the bandgap of cp-graphyne, like that of graphene, is zero, making it unsuitable for applications in electronics. Herein, we show that a new two-dimensional (2D) carbon nitride structure formed by assembling the five-membered imidazole molecules with acetylenic linker can overcome this limitation. Named ID-GY, this new material not only has a direct band gap of 1.10 eV, but it is dynamically and mechanically stable and can withstand temperatures up to 1200 K. In addition, due to its porous and anisotropic geometry, the Young's modulus of ID-GY along the diagonal direction is lower than that of most 2D materials reported previously. Equally important, ID-GY exhibits strong refraction near infrared (IR) and has potential for applications in nanoelectronics and optical devices. These results, based on density functional theory, can stimulate experimental studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shockwave dissipation by interface-dominated porous structures

The advent of additive manufacturing (AM) has enabled topological control of structures at the micrometer scale, transforming the properties of polymers for a variety of applications. Examples include tailored mechanical responses, acoustic properties, and thermal properties. Porous polymer materials are a class of materials used for shock and blast mitigation, yet they frequently possess a lack of structural order and are largely developed and evaluated via trial-and-error. Here, we demonstrate control of shockwave dissipation through interface-dominated structures prepared by AM using 2-photon polymerization. A fractal structure with voids, or free surfaces, arranged less than 100 μm apart, allows for rarefaction interactions on the timescale of the shockwave loading. Simulations and dynamic x-ray phase contrast imaging experiments show that fractal structures with interfaces assembled within a “critical” volume reduce shockwave stress and wave velocity by over an order of magnitude within the first unit cell.

36 MATERIALS SCIENCE↗

Programmable exploration of magnetic states in Lieb-kagome interpolated lattices

We investigate a hybrid modeling framework in which a quantum annealer is used to simulate magnetic interactions in molecular qubit lattices inspired by experimentally realizable systems. Using phthalocyanine assemblies as a structurally constrained prototype, we model a continuous deformation from a Lieb to a kagome lattice, revealing frustration-driven disorder and magnetic field-induced reordering in the spin structure. Here, the goal is to show how a quantum annealer can operate as a physically instantiated, programmable platform to emulate experimentally relevant lattice deformations and produce observables in a manner analogous to an experimental measurement, enabling the characterization of magnetic arrangements beyond the reach of current molecular architectures. This surrogate modeling approach offers a pathway to explore and iteratively design tunable magnetic states in synthetic materials. The synthetic design, structural characterization, and quantum simulation framework established here defines a modular and scalable paradigm for probing the limits of engineered matter across chemistry, condensed matter, and quantum information science.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Horizontal gene transfer of the Mer operon is associated with large effects on the transcriptome and increased tolerance to mercury in nitrogen-fixing bacteria

Abstract Background Mercury (Hg) is highly toxic and has the potential to cause severe health problems for humans and foraging animals when transported into edible plant parts. Soil rhizobia that form symbiosis with legumes may possess mechanisms to prevent heavy metal translocation from roots to shoots in plants by exporting metals from nodules or compartmentalizing metal ions inside nodules. Horizontal gene transfer has potential to confer immediate de novo adaptations to stress. We used comparative genomics of high quality de novo assemblies to identify structural differences in the genomes of nitrogen-fixing rhizobia that were isolated from a mercury (Hg) mine site that show high variation in their tolerance to Hg. Results Our analyses identified multiple structurally conserved merA homologs in the genomes of Sinorhizobium medicae and Rhizobium leguminosarum but only the strains that possessed a Mer operon exhibited 10-fold increased tolerance to Hg. RNAseq analysis revealed nearly all genes in the Mer operon were significantly up-regulated in response to Hg stress in free-living conditions and in nodules. In both free-living and nodule environments, we found the Hg-tolerant strains with a Mer operon exhibited the fewest number of differentially expressed genes (DEGs) in the genome, indicating a rapid and efficient detoxification of Hg from the cells that reduced general stress responses to the Hg-treatment. Expression changes in S. medicae while in bacteroids showed that both rhizobia strain and host-plant tolerance affected the number of DEGs. Aside from Mer operon genes, nif genes which are involved in nitrogenase activity in S. medicae showed significant up-regulation in the most Hg-tolerant strain while inside the most Hg-accumulating host-plant. Transfer of a plasmid containing the Mer operon from the most tolerant strain to low-tolerant strains resulted in an immediate increase in Hg tolerance, indicating that the Mer operon is able to confer hyper tolerance to Hg. Conclusions Mer operons have not been previously reported in nitrogen-fixing rhizobia. This study demonstrates a pivotal role of the Mer operon in effective mercury detoxification and hypertolerance in nitrogen-fixing rhizobia. This finding has major implications not only for soil bioremediation, but also host plants growing in mercury contaminated soils.

59 BASIC BIOLOGICAL SCIENCES↗

Small and mighty: adaptation of superphylum Patescibacteria to groundwater environment drives their genome simplicity

The newly defined superphylum Patescibacteria such as Parcubacteria (OD1) and Microgenomates (OP11) has been found to be prevalent in groundwater, sediment, lake, and other aquifer environments. Recently increasing attention has been paid to this diverse superphylum including > 20 candidate phyla (a large part of the candidate phylum radiation, CPR) because it refreshed our view of the tree of life. However, adaptive traits contributing to its prevalence are still not well known. Results Here, we investigated the genomic features and metabolic pathways of Patescibacteria in groundwater through genome-resolved metagenomics analysis of >600 Gbp sequence data. We observed that, while the members of Patescibacteria have reduced genomes (~ 1 Mbp) exclusively, functions essential to growth and reproduction such as genetic information processing were retained. Surprisingly, they have sharply reduced redundant and nonessential functions, including specific metabolic activities and stress response systems. The Patescibacteria have ultra-small cells and simplified membrane structures, including flagellar assembly, transporters, and two-component systems. Despite the lack of CRISPR viral defense, the bacteria may evade predation through deletion of common membrane phage receptors and other alternative strategies, which may explain the low representation of prophage proteins in their genomes and lack of CRISPR. By establishing the linkages between bacterial features and the groundwater environmental conditions, our results provide important insights into the functions and evolution of this CPR group.

59 BASIC BIOLOGICAL SCIENCES↗

Integration of computer vision system to track the alignment SRF cavities into the test cryostat for PIP-II at Fermilab

PIP-II cryomodules use a computer vision system (H-BCAMs system) to monitor the alignment of SRF cavities and focusing lenses during assembly, testing, and operation. This contribution details the integration of the H-BCAMs into the Spoke Test Cryostat (STC) at Fermilab, which is utilized for cold testing SRF cavities prior to their integration into the string assembly. Thermal and structural finite element analyses were employed to estimate the cavities’ deformations, to be validated during cold testing in the STC using H-BCAMs. Notably, this marks the first instance of H-BCAMs integration into a cryostat and operation within a cryogenic environment.

43 PARTICLE ACCELERATORS↗

Solar Steam on Demand

INTRODUCTION: This Report summarizes the research and development project performed by Sunvapor and the subrecipient National Renewable Energy Laboratory (NREL) during the period of 10/01/2018-9/30/2021. The work was aimed at the economic integration of solar steam with an industrial process, and in particular, the advantages that a novel type of thermal energy storage and collector design could bring to the system. The completed work includes experimental research on the storage material, design of the collector, engineering of a complete solar steam plant, and economic analysis. The plant was, in the end, not constructed, due to COVID-19 impacts to the project host. PURPOSE: The purpose of the project was to test the hypothesis that a levelized cost of heat (LCOH) of 2¢/kWh delivered to a steam-consuming process, including energy discharged from storage, could be feasibly achieved. PROJECT OBJECTIVES: For Budget Period 1 our objectives were to engineer a prototype industrial solar steam generation system, and design and test a Latent Heat Energy Storage (LHES) lab-scale system. For Budget Period 2 our objectives were to construct and test the solar steam prototype plant, and to build and factory-test a full LHES module. For Budget Period 3 our objective was to integrate the storage module with the solar steam generator, show successful long duration energy tests of the combined system, and use the results to project the LCOH of delivered steam to a second-generation plant. PROJECT OUTCOMES: Various phase change materials (PCMs) for the LHES were tested for compatibility with industrial steam uses as measured by phase change temperature, stability of latent heat of fusion, and their corrosive effects on steel (the heat exchanger material). Two of these materials (sodium formate and sodium/ potassium) showed potential to meet the technical criteria. The estimated cost of a complete LHES module with these materials did not meet economic targets. The developmental collector design builds from previous work to exploit the potential cost advantages of a spaceframe of lumber construction. Design improvements were achieved in assembly efficiency and structural performance. A complete engineering package was completed for the solar steam system without storage that included the developmental as well as commercial arrays. The plant was permitted for construction. The storage CAPEX for a reference plant was estimate to be greater than $\$ 57$/kWh. The LCOH of the system without storage and with developmental collectors of lumber construction was projected to be 2¢/kWh, assuming a FCR of 8.2% over thirty years. PROJECT MILESTONES: The Milestones fully achieved in the first Budget Period includes obtaining a Letter of Intent from an industrial steam-consuming project host, issuance of a construction permit, and corrosion resistance. The Milestone that was partly achieved was the degradation in the latent heat of fusion. Milestones associated with Budget Periods 2 and 3, related to the construction and operation of the plant were not achieved as a result of the host shutting down the plant due to COVID-19 impacts. CONCLUSIONS: Sunvapor was able to secure an agreement with a host to build a fully engineered and permitted solar steam plant that met the host’s economic goals. As a basis for comparison, the solar field design was comprised of eight commercial collector arrays and one developmental Green Parabolic Trough Collector (GPTC) array. The projected LCOH with a solar field entirely populated with a second generation GPTC met the goal of 2¢/kWh. The experimental program concerning the PCM indicated the feasibility of meeting their technical requirements for industrial steam uses. The cost of the complete LHES exceeded its $\$ 14$/kWh target, and therefore the inclusion of LHES could not be economically justified. Due to COVID-19 impacts on the host, the solar steam plant was not constructed.

14 SOLAR ENERGY↗

GAMSOR: Gamma Source Preparation and DIF3D Flux Solution (Rev. 2)

Nuclear reactors that rely upon the fission reaction have two modes of thermal energy deposition in the reactor system: neutron absorption and gamma absorption. The gamma rays are typically generated by neutron capture reactions or during the fission process which means the primary driver of energy production is of course the neutron interaction. In conventional reactor physics methods, the gamma heating component is ignored such that the gamma absorption is forced to occur at the gamma emission site. For experimental reactor systems like EBR-II and FFTF, the placement of structural pins and assemblies internal to the core leads to problems with power heating predictions because there is no fission power source internal to the assembly to dictate a spatial distribution of the power.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

MQXFA Series Magnet Production Specification: US HL-LHC Accelerator Upgrade Project

The purpose of this document is to define the specifications for the structure fabrication and assembly of MQXFA series magnets to be used by the US High-Luminosity LHC Accelerator Upgrade Project (AUP). Magnets fabricated according to these specifications are expected to allow MQXFA magnets to meet the MQXFA Functional Requirements Specification. These specifications for the fabrication of MQXFA series magnets are based on the R&D performed by the US LHC Accelerator Research Program (LARP) and the development performed by AUP, in collaboration with CERN, through fabrication and test of pre-series coils and magnets.

43 PARTICLE ACCELERATORS↗