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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Tuning acidity in silica-overcoated oxides for hydroalkoxylation

Mixed oxides are ubiquitious solid acid catalysts for a number of transformations. Here, the chemistry of mixed oxide interfaces was experimentally probed by constructing model SiO 2 on MO x interfaces using a liquid-phase, stoichiometrically-controlled deposition of tetraethyl orthosilicate (TEOS). Catalytically active Brønsted sites were generated in four series of overcoated SiO 2 on metal oxide materials prepared by depositing TEOS onto Al 2 O 3 , anatase TiO 2 , Nb 2 O 5 , and ZrO 2 . Pyridine DRIFTS studies indicate that the acidity of deposited silanol groups was enhanced by interaction with the metal oxide surface, suggesting that pseudo-bridging silanol type structures were formed. Trimethylphosphine oxide (TMPO) 31 P NMR experiments showed that Brønsted acid strength varied in the overcoated materials, with increasing strength in the following order: SiO 2 /ZrO 2 < SiO 2 /TiO 2 < SiO 2 /Nb 2 O 5 < SiO 2 /Al 2 O 3 . This order correlated with the Lewis acidity and chemical hardness of the underlying metal oxides. The catalytic performance of the materials was evaluated in the liquid-phase hydroalkoxylation of dihydropyran with n-octanol, revealing that activity was highly dependent on SiO 2 loading, which impacted the density of acid sites, and scaled exponentially with Brønsted acid strength, determined by the core metal oxide identity. Brønsted acid strength appears to be the key driver of the materials’ activity, with the highest areal rate of 2.2 mmol / m 2 – h being measured over SiO 2 /Al 2 O 3 . Furthermore, this study shows that SiO 2 -overcoated materials are a systematically tunable class of catalysts that can be applied to acid catalyzed reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Thermodynamics and kinetics of interconversion between platinum nanoparticles and cations in zeolites

In metal-containing zeolites, sintering and redispersion processes exercise control over the identity of metal site structures, but the thermodynamic and kinetic factors that influence these molecular-level processes are not completely understood. Furthermore, we assess the ability of first principles informed free energy models (for supported and unsupported nanoparticles) and kinetic models integrating Ostwald ripening with atom trapping to describe the interconversion between Pt cations and nanoparticles encapsulated in chabazite (CHA) zeolites. Density functional theory-derived thermodynamic phase diagrams show that the interconversion between cations, favored in oxidizing environments, and particles, favored in reducing environments, is fully reversible within a wide range of their respective conditions (temperatures and pressures) for CHA and several other zeolite topologies. Kinetic Monte Carlo simulations of Pt redispersion are consistent with experimentally observed redispersion kinetics of encapsulated Pt nanoparticles in CHA zeolites, and model results suggest the zeolite host imparts additional stability for Pt nanoparticles. We envision our thermodynamic and kinetic models for Pt-CHA are also capable of describing nanoparticle and cation interconversions for other zeolite frameworks under similar conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Understanding the effect of organic coatings on 4-nitrostyrene hydrogenation selectivity over Pt/TiO 2 catalysts

The hydrogenation of 4-nitrostyrene was investigated over Pt/TiO 2 catalysts to understand the effects of different catalyst coatings on product selectivity and reaction rates. This reaction is a much-investigated selectivity probe due to difficulty in controlling reactivity between the nitro and vinyl groups of 4-nitrostyrene, with C=C reduction generally being more favorable. 4-Nitrostyrene hydrogenation reactions were carried out in a batch reactor using uncoated, organothiol coated, phosphonic acid (PA) coated, and ion-conducting polymer (ionomer) coated catalysts. Thiols form dense coatings on Pt surfaces, whereas PAs preferentially accumulate on TiO 2 ; ionomer binding preference is unknown for this type of catalyst. The coating densities of the thiols and PAs were varied to observe the effects of loading on catalytic activity and reaction selectivity relative to the uncoated catalyst. Changes in selectivity were observed for catalysts with all coatings, with thiol coatings shifting selectivity towards the nitro reduction product, 4-vinylaniline (4-VA), and both ionomer and PA coatings shifting towards 4-ethylnitrobenzene, the olefin hydrogenation product. It was observed that selectivity toward 4-VA increased with thiol coating density, where 1,2-benzenedithiol (BDT) coated catalysts exhibited a selectivity of >99%. These changes were attributed to the identity of the adsorption sites blocked by the different coatings: blocking of metal sites via thiols decreased the rate of C=C hydrogenation, whereas blocking of TiO 2 sites by PAs decreased the rate of nitro group hydrogenation. The changes observed for ionomer and PA coatings suggested that ionomers, like PAs, bind preferentially to the metal oxide support rather than the active metal. This work provides new support to the proposal that nitro group hydrogenation preferentially occurs on TiO 2 sites after hydrogen spillover and underscores how selection of ligand functionality can be used to tune catalyst selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

HPLC-Parallel accelerator and molecular mass spectrometry analysis of 14 C-labeled amino acids

Accelerator mass spectrometry (AMS) is the method of choice for quantitation of low amounts of 14 C-labeled biomolecules. Despite exquisite sensitivity, an important limitation of AMS is its inability to provide structural information about the analyte. This limitation is not critical when the labeled compounds are well-characterized prior to AMS analysis. However, analyte identity is important in other experiments where, for example, a compound is metabolized and the structures of its metabolites are not known. We previously described a moving wire interface that enables direct AMS measurement of liquid sample in the form of discrete drops or HPLC eluent without the need for individual fraction collection, termed liquid sample-AMS (LS-AMS). Here, we now report the coupling of LS-AMS with a molecular mass spectrometer, providing parallel accelerator and molecular mass spectrometry (PAMMS) detection of analytes separated by liquid chromatography. The repeatability of the method was examined by performing repeated injections of 14 C-labeled tryptophan, and relative standard deviations of the 14 C peak areas were ≤10.57% after applying a normalization factor based on a standard. Five 14 C-labeled amino acids were separated and detected to provide simultaneous quantitative AMS and structural MS data, and AMS results were compared with solid sample-AMS (SS-AMS) data using Bland-Altman plots. To demonstrate the utility of the workflow, yeast cells were grown in a medium with 14 C-labeled tryptophan. The cell extracts were analyzed by PAMMS, and 14 C was detected in tryptophan and its metabolite kynurenine.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Unexpected Conformational Behavior of Poly(poly(ethylene glycol) methacrylate)-Poly(propylene carbonate)-Poly(poly(ethylene glycol) methacrylate) (PPEGMA-PPC-PPEGMA) Amphiphilic Block Copolymers in Micellar Solution and at the Air-Water Interface

Self-assemblies (bulk micelles and Langmuir monolayers) of a new amphiphilic block copolymer, poly(poly(ethylene glycol) methacrylate)-poly(propylene carbonate)-poly(poly(ethylene glycol) methacrylate) (PPEGMA-PPC-PPEGMA), were investigated in dilute aqueous solution and at the air-water interface. An important feature that distinguishes PPEGMA-PPC-PPEGMA from conventional linear PEG-based polymer surfactants is that in the hydrophilic PPEGMA block the PEG moieties exist as side chains attached to the poly(methacrylate) (PMA) backbone. This study was performed using three PPEGMA-PPC-PPEGMA samples having an identical PPC molecular weight (5.6 kDa) and different PPEGMA molecular weights (7.3, 2.8 and 2.1 kDa on either side) (named as “G7C6G7”, “G3C5G3”, and “G2C6G2”, respectively). Cryo-TEM images revealed that G2C6G2 micelles form large clusters, whereas G7C6G7 micelles exist as unimers; the behavior of G3C6G3 is intermediate. The average core surface distance between two adjacent G2C6G2 micelles in a cluster was estimated to be only about 3.7 nm, which suggests that in the micelle corona layer only the PEG side chains (but not the PMA backbone) exist as hydrated brush chains. A calculation showed that at the small micelle separation distance observed, the van der Waals attractive forces become significant, and are thus likely responsible for the cluster formation. Steady shear rheometry measurements confirmed that G2C6G2 micelles are indeed only weakly bound in clusters, and these micelle clusters are thus prone to breakup even under mild steady shear. The micelle breakup force estimated from the shear viscosity data is in reasonable agreement with an estimate obtained from the theoretical van der Waals interaction potential. Langmuir monolayers formed at the air-water interface by PPEGMA-PPC-PPEGMA were also characterized; surface pressure-area measurements were performed. Detailed features of the surface pressure-area isotherms further supported that only the PEG side chains are hydrated in the subphase, while the PMA backbone remains unhydrated and situated on the water surface.

Lee, Jaewon↗
DOE OSTI2020

A review of spatial Markov models for predicting pre-asymptotic and anomalous transport in porous and fractured media

Heterogeneity across a broad range of scales in geologic porous media often manifests in observations of non-Fickian or anomalous transport. While traditional anomalous transport models can successfully make predictions in certain geological systems, increasing evidence suggests that assumptions relating to independent and identically distributed increments constrain where and when they can be reliably applied. A relatively novel model, the Spatial Markov model (SMM), relaxes the assumption of independence. The SMM belongs to the family of correlated continuous time random walks and has shown promise across a wide range of transport problems relevant to natural porous media. It has been successfully used to model conservative as well as more recently reactive transport in highly complex flows ranging from pore scales to much larger scales of interest in geology and subsurface hydrology. In this review paper we summarize its original development and provide a comprehensive review of its advances and applications as well as lay out a vision for its future development.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Incremental approach for the life-cycle greenhouse gas analysis of carbon capture and utilization

Electro-fuels (e-fuels) are examples of carbon capture and utilization (CCU) hydrocarbon products that are derived from captured carbon dioxide (CO 2 ), while using renewable electricity as the energy feedstock. The environmental impacts of CCU products (e.g., e-fuel) are systematically quantified through life-cycle analysis (LCA). Previous studies evaluating LCA of e-fuels proposed frameworks with an expanded system boundary approach that included the entire supply chain of the production process generating the CO 2 for CCU, in addition to the supply chain of the CCU product. This expanded system boundary approach evaluates two system boundaries, and uses deduction methods to calculate the carbon intensity (CI) of the CCU product (e-fuel). This paper proposes a simpler system boundary using an incremental approach that can calculate identical CI of the CCU product (e-fuel), while avoiding the extensive calculations in the expanded system boundary framework. The proposed incremental approach allocates the burdens of the CO 2 capturing process to the CO 2 feedstock supplying the CCU production process (e.g., e-fuel production). The CI of the captured CO 2 supplied to CCU process is determined by the energy and material requirements for the CO 2 capturing process and transportation to the CCU plant. Thus, the CI of CO 2 supplied to CCU process can be directly linked to the CI of e-fuel without the need to conduct LCA of the preceding process that generates the CO 2 for CCU.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2024

GrainGNN: A dynamic graph neural network for predicting 3D grain microstructure

We propose GrainGNN, a surrogate model for the evolution of polycrystalline grain structure under rapid solidification conditions in metal additive manufacturing. High fidelity simulations of solidification microstructures are typically performed using multicomponent partial differential equations (PDEs) with moving interfaces. The inherent randomness of the PDE initial conditions (grain seeds) necessitates ensemble simulations to predict microstructure statistics, e.g., grain size, aspect ratio, and crystallographic orientation. Here, currently such ensemble simulations are prohibitively expensive and surrogates are necessary.In GrainGNN, we use a dynamic graph to represent interface motion and topological changes due to grain coarsening. We use a reduced representation of the microstructure using hand-crafted features; we combine pattern finding and altering graph algorithms with two neural networks, a classifier (for topological changes) and a regressor (for interface motion). Both networks have an encoder-decoder architecture; the encoder has a multi-layer transformer long-short-term-memory architecture; the decoder is a single layer perceptron.We evaluate GrainGNN by comparing it to high-fidelity phase field simulations for in-distribution and out-of-distribution grain configurations for solidification under laser power bed fusion conditions. GrainGNN results in 80%–90% pointwise accuracy; and nearly identical distributions of scalar quantities of interest (QoI) between phase field and GrainGNN simulations compared using Kolmogorov-Smirnov test. GrainGNN's inference speedup (PyTorch on single x86 CPU) over a high-fidelity phase field simulation (CUDA on a single NVIDIA A100 GPU) is 150×–2000× for 100-initial grain problem. Further, using GrainGNN, we model the formation of 11,600 grains in 220 seconds on a single CPU core.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Anti-symmetric barron functions and their approximation with sums of determinants

A fundamental problem in quantum physics is to encode functions that are completely anti-symmetric under permutations of identical particles. The architecture of neural network models for the electron wave function typically comprises an equivariant component followed by a summation of determinants. The recently introduced Generic Antisymmetric (GA) block is designed to enhance the expressivity of such neural wave functions, and it was found that the 2-layer GA block achieved more accurate energies than the corresponding single-determinant FermiNet architecure, suggesting its promise as a way to improve the expressivity of neural wave functions. In this paper we show how the function expressed by the 2-layer GA block can be decomposed into a sum of determinants. We formalize this result by defining the antisymmetric Barron space as a generalized version of the 2-layer GA block and providing an appromation theorem for this function class. This result can be viewed as a negative result showing that the 2-layer GA block is not more expressive than using multiple determinants.

Abrahamsen, Nilin↗
DOE OSTI2026

Hourglass control in staggered-grid hydrodynamics using virtual element stabilization techniques

Numerical simulations using the staggered-grid hydrodynamics (SGH) discretization suffer from hourglass instabilities. In this work, we develop a stabilization method to suppress the hourglass instabilities using techniques from the virtual element method (VEM). The stiffness matrix of the VEM consists of two terms: the consistency matrix which is rank deficient and the stability matrix. Here, we first show that in two dimensions and on general polygons, the stiffness matrix of the SGH is identical to the consistency matrix of the linear VEM for both the diffusion equation and the linear elasticity equation. These analyses explain the origin of the hourglass instabilities of the SGH discretization method, and establish a theoretical foundation for our proposed stabilization method by augmenting the stiffness matrix of the SGH discretization using the VEM stability matrix. Then, we present numerical examples using Lagrangian SGH simulations. The numerical experiments demonstrate that the proposed VEM stabilization method is effective at eliminating hourglass modes in the SGH discretization.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Using electron channeling contrast imaging to inform and improve the growth of high-efficiency GaAs solar cells on nanopatterned GaAs substrates

Patterned substrates provide opportunities for reducing the cost of high-efficiency III-V devices by incorporating mechanically weak layers beneficial for substrate reuse (e.g. by spalling). In this work, the functionality of electron channeling contrast imaging (ECCI) as a tool to efficiently understand and mitigate defect formation is exemplified by developing a process in which high-quality III-V material can be grown on nanopatterned GaAs substrates. Reactive ion etching used in the patterning process was found to damage the GaAs substrate surface, leading to the formation of stacking faults in the epitaxial material as observed by ECCI. Etching the patterned substrates in a 1 NH4OH: 1 H2O2: 50 DI H2O solution for 10 s prior to growth removed the substrate surface damage and stacking faults were no longer present. Growth of solar cell device structures initially produced samples with many macroscale flaws creating shunts in the devices, which complicated the assessment of material quality by device measurements. However, ECCI revealed that the epitaxial material surrounding macroscale flaws was free from any crystallographic defects such as stacking faults and threading dislocations. With this knowledge, we focused on refining the patterning process to eliminate the macroscale flaws. Solar cells were then grown on the improved nanopatterned substrates and exhibited device structures with defect densities less than 5 x 105 cm -2 and average conversion efficiency of 24.8%, nearly identical to devices grown on unpatterned epi-ready substrates (25.0%).

14 SOLAR ENERGY↗
DOE OSTI2023

Photoelectrochemical and Photovoltaic Performance of As-deposited Ink-based CuInS 2 Heterojunction Thin Film

In this report, we demonstrate low-temperature ink-based fabrication of CuInS 2 -based photoelectrodes for hydrogen production capable of producing photocurrent densities as high as 8.8mA.cm -2 . In this process, molecular ink made of metal chlorides and thiourea dissolved in methanol was spin coated onto Mo-coated soda lime glass substrates. Samples were then placed on a hot plate (sample surface temperature: 250°C) to induce CuInS 2 formation and remove the solvent and by-products. No further processing, such as high temperature sulfurization, was performed. Further, the CuInS 2 films were then integrated as photocathode for hydrogen evolution by photoelectrodeposition of Pt nanoparticles. Photocurrent density of 0.4mA.cm -2 at 0V vs. RHE was detected from such electrodes. However, samples coated with CdS/ZnO/ITO overlayers forming heterojunction prior to Pt deposition exhibited significant improvement of the photocurrent density, reaching 8.8mA.cm -2 at 0V vs. RHE, highlighting the improved charge transfer by the p-n junction formed at the CuInS 2 /CdS interface. The charge transfer resistance of the CuInS 2 /CdS/ZnO/ITO-Pt photoelectrode was almost 5 times lower than that of the CuInS 2 -Pt photoelectrode as revealed by electrochemical impedance spectroscopy analysis. In addition, the onset potential was shifted by ca. 0.45V toward the anodic direction, reaching 0.75V vs. RHE. Solar cell made of identical structure (Mo/CuInS 2 /CdS/ZnO/ITO) showed power conversion efficiency of 2.1% with short-circuit photocurrent density and open circuit voltage of 7.4mA.cm -2 and 820mV, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Harvest legacies and climate change interact to shape forest structure and biomass through time

Forest structural change driven by climate trends has been observed worldwide and is expected to increase in the future. Management of forest structure has been an important tool for mitigating the impacts of climate change but forest structure may shift independently of management goals as it interacts with climate change. Here, we investigated the long-term impacts of harvest-based management strategies on structure and resistance to climate-induced biomass loss using a process-based ecosystem model for a midwestern USA hardwood forest. We identified aboveground biomass loss events and compared the cumulative number of these events following a five-year period of active management under four management strategies and two climate change scenarios. Management legacy had the clearest impact on climate-driven biomass loss over the mid-term (∼25 years) with the shelterwood scenario experiencing no loss events during this period. However, by the end of the century legacy effects faded and climate change severity became the driver of differences as greater warming scenarios experienced twice the loss events, and end-of-century loss events were 3–10 times more frequent than mid-century events. We found that while structure was distinct among harvest scenarios through the mid-century, differences were negligible by the end-of-century; identical to when management correlated with loss event frequency. Here, we found that loss events were preceded by a drop in precipitation two years prior, while no specific forest structure preceded a loss event. However, the structures preceding a biomass loss event were distinct across different legacies, implying additional influences of past management.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Thin film growth effects on electrical conductivity in entropy stabilized oxides

Entropy stabilization has garnered significant attention as a new approach to designing novel materials. Much of the work in this area has focused on bulk ceramic processing, leaving entropy-stabilized thin films relatively under-explored. Following an extensive multi-variable investigation of polycrystalline (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O thin films deposited via pulsed laser deposition (PLD), it is shown here that substrate temperature and deposition pressure have strong and repeatable effects on film texture and lattice parameter. Further analysis shows that films deposited at lower temperatures and under lower oxygen chamber pressure are 40x less electrically resistive than otherwise identical films grown at higher temperature and pressure. Annealing these films in an oxygen-rich environment increases their electrical resistivity to match that of the films grown at higher temperatures and pressures. Because of this, the electric conductivity is hypothesized to be the result of polaron hopping mediated by transition metal valence changes which compensate for oxygen off-stoichiometry.

36 MATERIALS SCIENCE↗
DOE OSTI2026

How alkyl branching shapes structure in imidazolium and pyrrolidinium NTf 2 ionic liquids

High-energy X-ray scattering experiments and molecular dynamics (MD) simulations were carried out on ionic liquids (ILs) consisting of 1-alkyl-3-methylimidazolium and 1-alkyl-1-methylpyrrolidinium cations. These cations were paired with bis(trifluoromethylsulfonyl)amide anions and identical alkyl tails were used for both cationic species. The goal of this work is to investigate how the nanoscale structure of the ionic liquid changes with the length and with the degree of branching of the alkyl tail, for ILs having a common anion. We investigate spatial correlations in the intermolecular region, focusing on the intrinsic charge-charge interactions that characterize all ionic liquids, as well as the nanoscale domain segregation that is present in IL species with significant nonpolar components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Physical structure of constitutional isomers influences antiproliferation activity of thiosemicarbazone-alkylthiocarbamate copper complexes

A series of hybrid thiosemicarbazone-alkylthiocarbamate copper complexes with similar electronic environments but distinct physical structures have been prepared, characterized, and evaluated for antiproliferation activity. The complexes include the constitutional isomers (1-phenylpropane-1-imine-(O-ethylthiocarbamato)-2-one-(N-methylthiosemicarbazonato))copper(II) (CuL 1 ) and (1-phenylpropane-1-one-(N-methylthiosemicarbazonato)-2-imine-(O-ethylthiocarbamato))copper(II) (CuL 2 ) along with (1-propane-1-imine-(O-ethylthiocarbamato)-2-one-(N-methylthiosemicarbazonato))copper(II) (CuL 3 ). Complexes CuL 1 and CuL 2 differ in the positions of the pendent thiosemicarbazone (TSC) and alkylthiocarbamate (ATC) moieties on the 1-phenylpropane backbone. Complex CuL 3 employs a propane backbone with the TSC in the 2-position as in CuL 1 . The isomer pair CuL 1 and CuL 2 have equivalent electronic environments with indistinguishable Cu II/I potentials (E 1/2 = -0.86 V vs. ferrocenium/ferrocene) and electron paramagnetic resonance (EPR) spectra (g ∥ = 2.26, g ⊥ = 2.08). The electronic structure of CuL 3 has a similar E 1/2 of -0.84 V and identical EPR parameters to CuL 1, 2 . Single crystal X-ray diffraction studies confirm a consistent donor environment with no substantial variation in the Cusingle bondN or Cusingle bondS bond distances and angles between the complexes. The antiproliferation activities of the CuL 1–3 were evaluated against the lung adenocarcinoma cell line (A549) and nonmalignant lung fibroblast cell line (IMR-90) using the MTT assay. CuL 1 had the highest A549 activity ( A549 EC 50 = 0.065 μM) and selectivity ( IMR-90 EC 50 / A549 EC 50 = 20). The constitutional isomer CuL 2 displayed decreased A549 activity (0.18 μM) and selectivity (10.6). The complex CuL 3 displayed activity (0.009 μM) similar to CuL 1 but with a lack of selectivity (1.0). Cellular copper loading determined by ICP-MS was consistent with the activity and selectivity trends. The complexes CuL 1–3 did not induce reactive oxygen species (ROS) generation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Calcitonin Receptor N-Glycosylation Enhances Peptide Hormone Affinity by Controlling Receptor Dynamics

The class B G protein-coupled receptor (GPCR) calcitonin receptor (CTR) is a drug target for osteoporosis and diabetes. N-glycosylation of asparagine 130 in its extracellular domain (ECD) enhances calcitonin hormone affinity with the proximal GlcNAc residue mediating this effect through an unknown mechanism. Here, we present two crystal structures of salmon calcitonin-bound, GlcNAc-bearing CTR ECD at 1.78 and 2.85 Å resolutions and analyze the mechanism of the glycan effect. The N130 GlcNAc does not contact the hormone. Surprisingly, the structures are nearly identical to a structure of hormone-bound, N-glycan-free ECD, which suggested that the GlcNAc might affect CTR dynamics not observed in the static crystallographic snapshots. Hydrogen-deuterium exchange mass spectrometry and molecular dynamics simulations revealed that glycosylation stabilized a β-sheet adjacent to the N130 GlcNAc and the N-terminal α-helix near the peptide-binding site while increasing flexibility of the peptide-binding site turret loop. These changes due to N-glycosylation increased the ligand on-rate and decreased its off-rate. The glycan effect extended to RAMP-CTR amylin receptor complexes and was also conserved in the related CGRP receptor. These results reveal that N-glycosylation can modulate GPCR function by altering receptor dynamics.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Molecular-field-theory fits to magnetic susceptibilities of antiferromagnetic GdCu 2 Si 2 , CuO, LiCrO 2 , and α-CaCr 2 O 4 single crystals below their Néel temperatures

A recently-developed molecular field theory (MFT) has been used to fit single-crystal magnetic susceptibility χ versus temperature T data below the respective antiferromagnetic ordering temperature T N for a variety of collinear and coplanar noncollinear Heisenberg antiferromagnets. The spins in the system are assumed to interact by Heisenberg exchange and to be identical and crystallographically equivalent. The fitting parameters for χ(T ) of collinear antiferromagnets are measurable quantities: the Weiss temperature θ p in the Curie-Weiss law, TN, χ(T N ), and the spin S. For coplanar noncollinear helix and cycloid structures, an additional fitting parameter is the turn angle between layers of ferromagnetically-aligned spins. Here MFT fits to anisotropic χ(T) data from the literature for single crystals of the collinear antiferromagnets GdCu 2 Si 2 and CuO and the noncollinear antiferromagnets LiCrO 2 with a 120° cycloidal structure and α-CaCr 2 O 4 with a 120° helical structure below their respective N´eel temperatures are presented. The MFT fit to the anisotropic χ(T ≤ T N ) data for CuO is poor, whereas the fits to the data for GdCu 2 Si 2 , LiCrO 2 , and α-CaCr 2 O 4 are quite good. The poor fit for CuO is attributed to the influence of strong quantum fluctuations associated with the small Cu spin and the quasi-one-dimensional magnetism that are not taken into account by the MFT. The magnetic contribution to the zero-field heat capacity of the collinear antiferromagnet GdNiGe 3 at T ≤ T N is also fitted by the MFT.

36 MATERIALS SCIENCE↗