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At least 181 records · Page 10

Electron Redistributed S-Doped Nickel Iron Phosphides Derived from One-Step Phosphatization of MOFs for Significantly Boosting Electrochemical Water Splitting

Nonprecious transition metal-organic frameworks (MOFs) are one of the most promising precursors for developing electrocatalysts with high porosity and structural rigidity. This study reports the synthesis of high efficiency electrocatalysts based on S-doped NiFeP. MOF-derived S-doped NiFeP structure is synthesized by a one-step phosphorization process with using S-doped MOFs as the precursor, which is more convenient and environment friendly, and also helps retain the samples’ framework. The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance of the NiFeP catalysts can be improved after partially replacing P by S due to the tunable electronic structure. The optimized CCS-NiFeP-10 reaches a current density of 10 mA cm –2 for OER with an overpotential of 201 mV and outperforms most NiFe-based catalysts. The S doping plays an important role in tuning the ΔG values for intermediates formation in Ni atoms to a suitable value and exhibits a pronouncedly improved the OER performance. CCS-NiFeP-20 sample presents excellent HER performance due to the d-band center downshifting from the Fermi level. When the voltage of the electrolytic cell is 1.50 V, a current density of 10 mA cm –2 can be obtained. This strategy paves the way for designing highly active none-noble metal catalysts.

36 MATERIALS SCIENCE↗

Scalable, two–stage, autoinduction of recombinant protein expression in E. coli utilizing phosphate depletion

We report the scalable production of recombinant proteins in Escherichia coli, reliant on tightly controlled autoinduction, triggered by phosphate depletion in the stationary phase. The method, reliant on engineered strains and plasmids, enables improved protein expression across scales. Expression levels using this approach have reached as high as 55% of the total cellular protein. The initial use of the method in instrumented fed–batch fermentations enables cell densities of ~30 gCDW/L and protein titers up to 8.1 ± 0.7 g/L (~270 mg/gCDW). The process has also been adapted to an optimized autoinduction media, enabling routine batch production at culture volumes of 20 μl (384–well plates), 100 μl (96–well plates), 20 ml, and 100 ml. In batch cultures, cell densities routinely reach ~5–7 gCDW/L, offering protein titers above 2 g/L. Here, the methodology has been validated with a set of diverse heterologous proteins and is of general use for the facile optimization of routine protein expression from high throughput screens to fed–batch fermentation.

59 BASIC BIOLOGICAL SCIENCES↗

Solvent effects on extractant conformational energetics in liquid–liquid extraction: a simulation study of molecular solvents and ionic liquids

Extractant design in liquid–liquid extraction (LLE) is a research frontier of metal ion separations that typically focuses on the direct extractant–metal interactions. However, a more detailed understanding of energetic drivers of separations beyond primary metal coordination is often lacking, including the role of solvent in the extractant phase. In this work, we propose a new mechanism for enhancing metal-complexant energetics with nanostructured solvents. Using molecular dynamics simulations with umbrella sampling, we find that the organic solvent can reshape the energetics of the extractant's intramolecular conformational landscape. Here, we calculate free energy profiles of different conformations of a representative bidentate extractant, n-octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphinoxide (CMPO), in four different solvents: dodecane, tributyl phosphate (TBP), and dry and wet ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf 2 N]). By promoting reorganization of the extractant molecule into its binding conformation, our findings reveal how particular solvents can ameliorate this unfavorable step of the metal separation process. In particular, the charge alternating nanodomains formed in ILs substantially reduce the free energy penalty associated with extractant reorganization. Importantly, using alchemical free energy calculations, we find that this stabilization persists even when we explicitly include the extracted cation. These findings provide insight into the energetic drivers of metal ion separations and potentially suggest a new approach to designing effective separations using a molecular-level understanding of solvent effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biomining Critical Elements and Metals

The US government has identified 17 critical elements, including most rare earth elements (REEs), and metals, which are used extensively in consumer electronics as well as military and national security hardware. We are developing techniques for biomining these elements, the process of using microorganisms to extract critical elements from water, ores, and mine waste to fill these needs. Bioextraction is focusing on: 1) building on our first-year successes of identifying microbes that generate exudates that enhance the extraction of multivalent cations, 2) evaluating available phosphate solubilizing microbes to dissolve apatite and monazite, and 3) and biosurfactant producing microbes. Bioaccumulation efforts involves testing microbes that: 1) naturally release complex exudates that contain organic chelating agents, and 2) naturally accumulate or hyperaccumulate (wt-% levels) metals. Results from year one includes proof of concept that biosurfactant producing microorganisms can release REEs from select ores and that release of REEs is increased by the addition of glucose. Molecular results for microorganism profiling proved a population shift after addition of microorganisms. The study will culminate in a proof-of-concept demonstration, manuscripts, and the data needed for scaledup biomining of REEs.

36 MATERIALS SCIENCE↗

Controlled-Environment Agriculture and the Geography of Food, Energy and Water Resilience in the United States

USDA guidelines call for an increase in fruit and vegetable consumption in U.S. households to promote healthier diets. Access to fresh fruits and vegetables are especially lacking in food deserts and food swamps (characterized by a prevalence of food that is highly processed and lacking in nutritional value). Adoption of the recommended healthy diet, which more than doubles the consumption of fruits and vegetables, would have a wide variety of health benefits and would reduce the land footprint of U.S diets. However, adopting a healthy diet would increase phosphate and nitrogen impacts associated with fertilizers and pesticides and would significantly increase freshwater consumption and energy use because of the resource intensity of field cultivation of fruits and vegetables. The majority of these crops are grown in just a few states, including California and Arizona, which are increasingly impacted by climate change. In addition, rural communities are rapidly becoming food deserts, while food produced in these areas is transported long distances to market. In recent years, highly intensified controlled environment (CE) agricultural systems, (i.e., vertical farming) have been developed to provide fresh food closer to consumers. Fruits and vegetables, many of which are amenable to CE culture, occupy a uniquely impactful segment of the food supply-chain, including their value in improving nutrition for vulnerable communities. The objective of this work is to elucidate the location dependency of the energy and water impacts of adoption of distributed CE farming for an important portion of the food system.

controlled environment agriculture↗

In Situ Synthesis of Phosphate-Based CelloMOF as a Promising Separator for Li–Ion Batteries

Nowadays, battery separators play a critical role in determining the sustainability, electrochemical efficiency, and safety of lithium-ion batteries (LIBs). In this contribution, we developed fire-resistant composite membranes called CelloMOF by in situ grafting of metal-organic framework, ZIF-67, onto phosphorylated cellulose nanofibers (P-CNFs) followed by a vacuum filtration process akin to papermaking. The hybrid ZIF-67@P-CNF membrane exhibits superior properties than a polyolefin-based commercial separator (CS) in terms of enhanced thermal and dimensional stability, flame-retardant properties, better surface wettability, and improved electrolyte uptake. Thermal dimensional stability tests revealed that the ZIF-67@P-CNF separator maintained its structure even at 200 °C, whereas CS suffered severe shrinkage, potentially leading to internal short circuits. Combustion tests showed a peak heat release rate (PHRR) of 34.5 W/g and a total heat release (THR) of 1.61 kJ/g for ZIF-67@P-CNF, significantly lower than the PHRR (1111.82 W/g) and THR (40.89 kJ/g) of CS. The composite separator also demonstrated significantly improved wettability, with a contact angle of 32 ± 1.04°, compared to 92 ± 1.07° for CS, highlighting its hydrophilic nature. Electrochemical evaluations in LiFePO 4 /Li half-cells indicated a higher discharge capacity of 149 mA h g -1 at 0.2 C and superior capacity retention of 86% after 50 cycles, outperforming CS (145 mA h g -1 and 84%, respectively). In conclusion, these results underscore the potential of the ZIF-67@P-CNF membrane to advance safe, high-performance LIBs by addressing critical challenges in thermal stability, flame retardancy, and electrolyte compatibility.

ZIF-67↗

A Unique Case of the “Goldilocks Rule” in Solid-State Electrolytes: Two Are Good, Four Are Too Many

We report the syntheses of two new series of methacrylate monomers with different backbones: ureidopyrimidinone (PU) and boron-substituted urea pyrimidine (U), which enhance both the mechanical and electrochemical properties of the solid-state electrolyte (SSE) while improving the cycle life of lithium iron phosphate (LiFePO 4 , LFP) cathodes. The PU backbone is characterized by four hydrogen bonds (H-bonds), while the U backbone bears only two. Importantly, our research reveals that two H-bonds in these monomers are optimal; in contrast, four are excessive. The exceptional mechanical properties and processability of the SSE with the U series additives, resulting from the optimal H-bonds, were unexpectedly achieved. This leads to the establishment of a “Goldilocks rule” for additive design. The key strategies include: 1) reducing hydrogen-bonding (H-bonding) sites by changing pyrimidinone to pyrimidine and 2) shifting from intermolecular to intramolecular H-bonding and π−π bonding. Furthermore, this reduction in H-bonding also offers significant advantages in processability. The advancement can be extended to electrode fabrication, making the manufacturing of all-solid-state batteries more practical and efficient.

hydrogen bonding↗

Revealing a Hidden Intermediate of Rotatory Catalysis with X-ray Crystallography and Molecular Simulations

The mechanism of rotatory catalysis in ATPhydrolyzing molecular motors remains an unresolved puzzle in biological energy transfer. Notwithstanding the wealth of available biochemical and structural information inferred from years of experiments, knowledge on how the coupling between the chemical and mechanical steps within motors enforces directional rotatory movements remains fragmentary. Even more contentious is to pinpoint the rate-limiting step of a multistep rotation process. Here, using vacuolar or V 1 -type hexameric ATPase as an exemplary rotational motor, we present a model of the complete 4-step conformational cycle involved in rotatory catalysis. First, using Xray crystallography, a new intermediate or “dwell” is identified, which enables the release of an inorganic phosphate (or P i ) after ATP hydrolysis. Using molecular dynamics simulations, this new dwell is placed in a sequence with three other crystal structures to derive a putative cyclic rotation path. Free-energy simulations are employed to estimate the rate of the hexameric protein transformations and delineate allosteric effects that allow new reactant ATP entry only after hydrolysis product exit. An analysis of transfer entropy brings to light how the side-chain-level interactions transcend into larger-scale reorganizations, highlighting the role of the ubiquitous arginine-finger residues in coupling chemical and mechanical information. An inspection of all known rates encompassing the 4-step rotation mechanism implicates the overcoming of the ADP interactions with V 1 -ATPase to be the rate-limiting step of motor action.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Glass-Bonded Monazite Waste Forms for Lanthanide and Actinide Immobilization: From Theoretical Design to Scale-Up Production and Characterization

The development of nuclear waste forms for both existing and future nuclear wastes is critical to ensuring global environmental safety. This study focuses on waste management from molten salt reactors, where fuel exists in a salt form and could be processed in real time for the removal of neutron poisons such as xenon isotopes (e.g., 135 Xe) and rare earth elements (REEs, e.g., 149 Sm). To ensure safe, stable, and long-term disposal in geological repositories, REEs must be incorporated into a durable waste form. Iron-phosphate glasses are a promising candidate due to their low melting points, high chemical durability, and their ability to incorporate high concentrations of REEs. In this study, we successfully prepared iron-phosphate glass waste forms with high Nd loadings (up to 37 mass %) in batch sizes ranging from small (23 g) to large (1600 g). The resulting materials contained up to 75 mass % NdPO 4 , contributing to their mechanical resilience and exceptional chemical durability. These findings highlight the potential of iron-phosphate glasses as high-efficiency, chemically durable waste forms and demonstrate the successful transition from theoretical design to scaled-up production.

amorphous materials↗

Statistical generic design of glass and optimization: Selective review on oxide glasses

Designing a single glass composition for a multidimensional property space is challenging, and the difficulty increases with the number of design criteria. Traditionally, the task is accomplished using multiple statistical models that describe the relationships between composition (C) and property (P) values, i.e., C-P models. Recently, the structure (S)-property (P) statistical modeling has emerged as a complementary approach. The S-P modeling approach has also been shown to be a preferred method for modeling glass properties, particularly when a small data set is available, such as in single-component studies, or when strong nonlinearities exist between composition and properties. The combined model package, C-S-P, implements the concept of generic glass design, i.e., designing glass for performance by first selecting a specific or optimized set of glass network structural groups using S-P models and then transferring the designed structures (genes) to a particular composition using C-S models. This article reviews a set of supporting cases from the previous C-S-P modeling studies of phosphate, silicate, and borosilicate glasses, which are relevant for many critical commercial applications. The methodology for developing the statistical C-S-P database is presented, enabling the application of P?S?C to achieve a generic glass design and optimization, targeting multiple design criteria for both performance and processing properties simultaneously.

Network structure↗

Binding mechanism and binding free energy of amino acids and citrate to hydroxyapatite surfaces as a function of crystallographic facet, pH, and electrolytes

Hydroxyapatite (HAP) is the major mineral phase in bone and teeth. The interaction of individual amino acids and citrate ions with different crystallographic HAP surfaces has remained uncertain for decades, creating a knowledge gap to rationally design interactions with peptides, proteins, and drugs. In this contribution, we quantify the binding mechanisms and binding free energies of the 20 end-capped natural amino acids and citrate ions on the basal (001) and prismatic (010)/(020) planes of hydroxyapatite at pH values of 7 and 5 for the first time at the molecular scale. We utilized over 1500 steered molecular dynamics simulations with highly accurate potentials that reproduce surface and hydration energies of (hkl) hydroxyapatite surfaces at different pH values. Charged residues demonstrate a much higher affinity to HAP than charge-neutral species due to the formation of superficial ion pairs and ease of penetration into layers of water molecules on the mineral surface. Binding free energies range from 0 to -60 kJ/mol and were determined with ~10% uncertainty. The highest affinity was found for citrate, followed by Asp(-) and Glu(-), and followed after a gap by Arg(+), Lys(+), as well as by His(+) at pH 5. The (hkl)-specific area density of calcium ions, the protonation state of phosphate ions, and subsurface directional order of the ions in HAP lead to surface-specific binding patterns. Amino acids without ionic side groups exhibit weak binding, between -3 and 0 kJ/mol, due to difficulties to penetrate the first layer of water molecules on the apatite surfaces. We explain recognition processes that remained elusive in experiments, in prior simulations, discuss agreement with available data, and reconcile conflicting interpretations. In conclusion, the findings can serve as useful input for the design of peptides, proteins, and drug molecules for the modification of bone and teeth-related materials, as well as control of apatite mineralization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-situ synchrotron X-ray diffraction of hydroxyapatite-zirconia composite during conventional and flash sintering

Here, we conducted in-situ X-ray diffraction to study the crystalline phase evolution in hydroxyapatite-zirconia composites during both conventional and flash sintering processes. Additionally, we examined the thermal history and microstructure of the composite under these sintering conditions. Despite both sintering methods reaching similar average temperatures, they yielded distinct results in terms of crystalline phase composition and microstructure. In the flash sintered samples, we observed a complete transformation of hydroxyapatite into α- tricalcium phosphate and a complete tetragonal to cubic phase transition in zirconia. Conversely, the conventionally sintered samples remained practically stable. Notably, the flash sintered samples exhibited needle-like microstructures, which were absent in their conventionally sintered counterparts. This divergence suggests that the application of an electric field plays a role in generating athermal effects during the sintering of hydroxyapatite-zirconia composites.

36 MATERIALS SCIENCE↗

Generation of Pseudomonas putida KT2440 Strains with Efficient Utilization of Xylose and Galactose via Adaptive Laboratory Evolution

While Pseudomonas putida KT2440 has great potential for biomass-converting processes, its inability to utilize the biomass abundant sugars xylose and galactose has limited its applications. Here, in this study, we utilized Adaptive Laboratory Evolution (ALE) to optimize engineered KT2440 with heterologous expression of xylD encoding xylonate dehydratase from Caulobacter crescentus and galETKM encoding UDP-glucose 4-epimerase, galactose-1-phosphate uridylyltransferase, galactokinase, and galactose-1-epimerase from Escherichia coli K-12 MG1655. Poor starting strain growth (<0.1 h –1 or none) was evolutionarily optimized to rates of up to 0.25 h –1 on xylose and 0.52 h –1 on galactose. Whole-genome sequencing, transcriptomic analysis, and growth screens revealed significant roles of kguT encoding a 2-ketogluconate operon repressor and 2-ketogluconate transporter, and gtsABCD encoding an ATP-binding cassette (ABC) sugar transporting system in xylose and galactose growth conditions, respectively. Finally, we expressed the heterologous indigoidine production pathway in the evolved and unevolved engineered strains and successfully produced 3.2 g/L and 2.2 g/L from 10 g/L of either xylose or galactose in the evolved strains whereas the unevolved strains did not produce any detectable product. Thus, the generated KT2440 strains have the potential for broad application as optimized platform chassis to develop efficient microorganism-based biomass-utilizing bioprocesses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiscale Evaluation of Acetohydroxamic Acid (AHA) Radiolysis Under Used Nuclear Fuel Reprocessing Solvent System Conditions

Acetohydroxamic acid (AHA) has been proposed as an alternative agent for the selective separation of plutonium and neptunium from co-extracted uranium during the reprocessing of used nuclear fuel. However, the fundamental radiolytic behavior of this molecule under envisioned process conditions – i.e., acidic biphasic solvent systems – is not sufficiently understood to support process applications. Here we present a systematic irradiation study (steady-state gamma and time-resolved pulsed electron) into the radiolytic integrity of AHA and formation of degradation products in aqueous nitric acid (HNO3) solutions (0.2 M) in presence and absence of an organic phase, comprising current (tri-butyl phosphate - TBP) and future (N,N-di-(2-ethylhexyl)butyramide - DEHBA and di-2-ethylhexylisobutyramide - DEHiBA) reprocessing ligands dissolved in n-dodecane diluent. Experimental data are complimented by predictive multiscale model calculations for the elucidation of underpinning mechanisms.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Glass transition temperature studies of planetary ball milled glasses: Accessing the rapidly cooled glassy state in Na 4 P 2 S 7-x O x , 0 ≤ x ≤ 7, Oxy-thio phosphate glasses

This paper details the very first in-depth study of the glass transition temperature (T g ) for planetary balled milled (PBM) Na 4 P 2 S 7-x O x (NaPSO), where 0 ≤ x ≤ 7, glasses. For 0 ≤ x ≤ 5, fully amorphous, homogeneous, and chemically reacted compositions can be prepared. For samples with 5 < x ≤ 7, partially amorphous but fully chemically reacted glass-ceramics can be produced. The reproducible, thermally cyclable onset T g and the onset crystallization temperature, T c , were investigated as a function of the composition and of the short-range order (SRO) structures of the glasses. Additionally, we examined the extreme sub-T g exothermic relaxations present due to the high energy milling processing and correspondingly high effective quenching rate. Using a differential scanning calorimeter (DSC) and scanning from well below the onset T g , the glasses are observed to relax exothermally below T g . The integrated relaxation enthalpy, ΔH rel , is ~ 0 for the x = 2 glass, but is significantly exothermic for lower and higher values of x. Once the high fictive state of these glasses has been erased by scanning to above the T g , but below the T c of the glass, the DSC scans of the glasses recover normal behavior for a normally cooled glass without any relaxation exotherm. The T g s of these glasses remain relatively constant for 0 ≤ x ≤ 3, but for glasses with 3 < x ≤ 5, T g increases sharply following the combined effects of the phosphate chain length increasing caused by the formation of bridging oxygens and the increasing concentration of more charge dense non-bridging oxygens (NBOs). For x > 5, both T g and Tc decrease sharply, becoming nearly identical at x = 7 where glass formation essentially ceases. For smaller values of x, T c increases with both chain length and the structural complexity of the composition but decreases sharply for glass-ceramics of x > 5.

36 MATERIALS SCIENCE↗

Modeling of transverse stimulated Raman scattering in KDP/DKDP in large-aperture plates suitable for polarization control

Transverse stimulated Raman scattering (TSRS) in potassium dihydrogen phosphate (KDP) and deuterated potassium dihydrogen phosphate (DKDP) plates for large-aperture, inertial confinement fusion (ICF)-class laser systems is a well-recognized limitation giving rise to parasitic energy conversion and laser-induced damage. The onset of TSRS is manifested in plates exposed to the ultraviolet section of the beam. TSRS amplification is a coherent process that grows exponentially and is distributed nonuniformly in the crystal and at the crystal surfaces. To understand the growth and spatial distribution of TSRS energy in various configurations, a modeling approach has been developed to simulate the operational conditions relevant to ICF-class laser systems. Specific aspects explored in this work include (i) the behavior of TSRS in large-aperture crystal plates suitable for third-harmonic generation and use as wave plates for polarization control in current-generation ICF-class laser system configurations; (ii) methods, and their limitations, of TSRS suppression and (iii) optimal geometries to guide future designs.

47 OTHER INSTRUMENTATION↗

Psilocybin: crystal structure solutions enable phase analysis of prior art and recently patented examples

Psilocybin {systematic name: 3-[2-(dimethylamino)ethyl]-1 H -indol-4-yl dihydrogen phosphate} is a zwitterionic tryptamine natural product found in numerous species of fungi known for their psychoactive properties. Following its structural elucidation and chemical synthesis in 1959, purified synthetic psilocybin has been evaluated in clinical trials and has shown promise in the treatment of various mental health disorders. In a recent process-scale crystallization investigation, three crystalline forms of psilocybin were repeatedly observed: Hydrate A, Polymorph A, and Polymorph B. The crystal structure for Hydrate A was solved previously by single-crystal X-ray diffraction. This article presents new crystal structure solutions for the two anhydrates, Polymorphs A and B, based on Rietveld refinement using laboratory and synchrotron X-ray diffraction data, and density functional theory (DFT) calculations. Utilizing the three solved structures, an investigation was conducted via Rietveld method (RM) based quantitative phase analysis (QPA) to estimate the contribution of the three different forms in powder X-ray diffraction (PXRD) patterns provided by different sources of bulk psilocybin produced between 1963 and 2021. Over the last 57 years, each of these samples quantitatively reflect one or more of the hydrate and anhydrate polymorphs. In addition to quantitatively evaluating the composition of each sample, this article evaluates correlations between the crystal forms present, corresponding process methods, sample age, and storage conditions. Furthermore, revision is recommended on characterizations in recently granted patents that include descriptions of crystalline psilocybin inappropriately reported as a single-phase `isostructural variant.' Rietveld refinement demonstrated that the claimed material was composed of approximately 81% Polymorph A and 19% Polymorph B, both of which have been identified in historical samples. In this article, we show conclusively that all published data can be explained in terms of three well-defined forms of psilocybin and that no additional forms are needed to explain the diffraction patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Third Harmonic Generator Optics Loop Transportation and Handling

The National Ignition Facility (NIF) uses crystal optics made from Potassium Di-Hydrogen Phosphate (KDP) for frequency conversion, changing the fundamental wavelength of 1053 nm to the third harmonic at 351 nm. The crystal optics are manufactured at a vendor and shipped to Lawrence Livermore National Laboratory (LLNL) where they are measured, mitigated, cleaned, coated, and placed into line replaceable units (LRUs) in the Optics Processing Facility (OPF) clean room and transported to the NIF where they are stored under Nitrogen purge until they are installed in the beamline. The KDP crystal optics are sensitive to humidity and temperature, so they are stored under Nitrogen purge providing a clean and dry environment. The sensitivity to the environment and the brittle nature of the crystals makes transportation and handling (T&H) challenging. Coupled with challenges in holding the crystal optics in the LRU to not distort the optic, there is a balance between T&H and fixturing the optic in the laser system. The purpose of the LRU is to make the optics interchangeable allowing for a relatively quick interchange. Kinematic mounts and ceramic frames aid in making this possible. Optics in the NIF that are frequently changed out have an established recycle loop. The loop for an optic can be complex depending on the amount of processing and rework necessary. Some optics can’t be reconditioned so they are replaced with new optics.

47 OTHER INSTRUMENTATION↗