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At least 289 records · Page 16

Electrooxidation of CO on Platinum Nanoparticles Supported on NiO Thin Films

In this paper, we report on a robust experimental model to investigate strong metal–support interactions (SMSI) and their effect on electrocatalytic reactions in the absence and presence of direct contact between the nanoparticles (NPs) and the metal oxide thin film. Specifically, we describe beneficial interactions between Ni 0.9 O thin film supports and PtNPs toward the CO electrooxidation reaction. The metal oxide layer (Ni 0.9 O) is prepared by atomic layer deposition and characterized using X-ray photoelectron spectroscopy (XPS). PtNPs, containing an average of either 55 (Pt 55 ) or 140 (Pt 140 ) atoms, were synthesized using a dendrimer encapsulation method. The results indicate negative shifts of ~100 and ~60 mV of the CO electrooxidation peak potential when Ni 0.9 O thin films are in contact with Pt 55 NPs and Pt 140 NPs, respectively. Additionally, the oxygen evolution reaction (OER) is suppressed only when the PtNPs are in contact with the Ni 0.9 O thin film. Density functional theory (DFT) calculations indicate that both the CO electrooxidation enhancement and suppression of the OER can be attributed to a 1.23 eV decrease of the CO* binding energy and a 0.35 eV increase of the OH* binding energy at a NiO(111)/Pt 55 NP interface compared to isolated Pt 55 NPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating the active site-substrate interplay between x-ray crystal structure and molecular dynamics in chorismate mutase

Designing realistic quantum mechanical (QM) models of enzymes is dependent on reliably discerning and modeling residues, solvents, and cofactors important in crafting the active site microenvironment. Interatomic van der Waals contacts have previously demonstrated usefulness toward designing QM-models, but their measured values (and subsequent residue importance rankings) are expected to be influenceable by subtle changes in protein structure. Using chorismate mutase as a case study, this work examines the differences in ligand-residue interatomic contacts between an x-ray crystal structure and structures from a molecular dynamics simulation. Select structures are further analyzed using symmetry adapted perturbation theory to compute ab initio ligand-residue interaction energies. The findings of this study show that ligand-residue interatomic contacts measured for an x-ray crystal structure are not predictive of active site contacts from a sampling of molecular dynamics frames. In addition, the variability in interatomic contacts among structures is not correlated with variability in interaction energies. However, the results spotlight using interaction energies to characterize and rank residue importance in future computational enzymology workflows.

Chemistry↗

Entropy variations and light ray operators from replica defects

We study the defect operator product expansion (OPE) of displacement operators in free and interacting conformal field theories using replica methods. We show that as n approaches 1 a contact term can emerge when the OPE contains defect operators of twist d - 2. For interacting theories and general states we give evidence that the only possibility is from the defect operator that becomes the stress tensor in the n → 1 limit. This implies that the quantum null energy condition (QNEC) is always saturated for CFTs with a twist gap. As a check, we show independently that in a large class of near vacuum states, the second variation of the entanglement entropy is given by a simple correlation function of averaged null energy operators as studied by Hofman and Maldacena. This suggests that sub-leading terms in the defect OPE are controlled by a defect version of the spin-3 non-local light ray operator and we speculate about the possible origin of such a defect operator. For free theories this contribution condenses to a contact term that leads to violations of QNEC saturation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Modeling Contact Angle vs. Temperature for the Quartz-Water-Decane System

Innovative approaches are needed to improve the efficiency of oil recovery technologies to meet the growing demands of fossil-fuel based energy consumption. Enhanced oil recovery (EOR) methods such as low-salinity waterflooding and chemically tuned waterflooding aim to optimize the reservoir’s wetting properties, detaching oil globules from rock surfaces and allowing easier oil flow through pore throats. This wetting behavior is commonly quantified by contact angle measurements of the rock-oil-brine interface, which have been thoroughly investigated and theorized for many systems at ambient temperatures and pressures. However, few studies exist for extending contact angle theories away from ambient conditions. In this paper, we model the contact angles of a quartz-water-decane system at elevated temperatures using the surface tension component (STC) approach. Temperature-dependent van der Waals [Lifshitz-van der Waals (LW)] interactions and hydrogen-bonding (acid-base) interactions were calculated and are incorporated into the model for the quartz-water-decane interface. Additionally, the Hough and White procedure was used to create temperature-dependent dielectric functions of quartz, water, and normal decane for calculations of Hamaker coefficients. Hamaker coefficients calculated this way are highly linear with temperature and agree well with Israelachvili’s approximation. The acid-base interactions likely contribute the most to system wettability changes. Resulting contact angles of the quartz-water-decane system shift from water-wet (16°) to slightly water-wet (57.4°) as temperature increases. The model was also successfully verified for the quartz-air-water system. Our results can be used in future studies to determine optimal injected water compositions for specific rock-oil-brine and other systems with consideration of reservoir temperature.

02 PETROLEUM↗

Determination of the Interfacial Energy between Graphene Nanoplatelets and Deuterated or Hydrogenated Polystyrene

The tracer diffusion coefficients of various graphene nanoplatelet-polystyrene (GNP-PS) systems were determined by using dynamic secondary ion mass spectrometry, which provided insights into the interactions within the polymer nanocomposite system. Bilayer films, where one contained trace amounts of deuterated polystyrene (dPS), were produced, and the interdiffusion was measured by detecting the position of the dPS interface. GNPs were placed in both or only one of the two layers. The diffusion coefficient was decreased when GNPs were present in both layers as compared to the samples without GNP, indicating an attractive interaction between GNP and polystyrene. Surprisingly, the coefficient increased relative to the control when GNPs were present only in the PS containing layer, whereas it decreased most strongly when GNP and dPS were present only in the same layer, indicating that an additional preference existed for GNPs and dPS. A significant difference in interfacial energies was measured using contact angle goniometry of PS or dPS droplets on flat GNP layers, confirming the preferential interaction. DFT calculations were used to calculate the interfacial interaction between GNP and dPS or PS, and they showed an attractive potential which was maximal when the PS rings were conformal with the GNP structure. Furthermore, the differential energy between PS and dPS at the GNP interface was in excellent agreement with the measured value. In contrast, contact angle goniometry indicated that the interaction between GNP and poly(methyl methacrylate) (PMMA) was unfavorable, and no difference in interfacial energy between dPMMA and PMMA was observed. Therefore, these techniques can provide a means for determining the relative affinity between GNP and different polymer hosts, which can be an important consideration in the mechanics and adhesion properties of the compounds.

36 MATERIALS SCIENCE↗

High-Vacuum Triboelectric Charging of Space Materials

In the high-vacuum environment of space and the surface of the moon, static electricity on surfaces lacks the atmospheric dissipation mechanisms found on earth. As a result, the ubiquitous triboelectric charging mechanism can lead to high levels of charge on surfaces. This static charge can result in damage to sensitive devices, interfere with communications, and electrostatic levitation of lunar dust. At the NASA Electrostatics and Surface Physics Laboratory (ESPL), we use different apparatuses and techniques to tribo-charge materials in high-vacuum (10-5 torr), including a tribo-robot and a triboelectric regolith-material stage (TRMS). The tribo-robot is used to rub two materials together, and fieldmeters and electrometers can be used to determine how much charge is on the materials. The TRMS is used to drag different materials onto a bed of lunar simulant. This system is used to characterize how materials may interact with lunar dust using fieldmeters, electrometers, and laser scattering. Using these methods, we are building a database of how different space materials charge when contacting each other at high-vacuum, and how materials triboelectrically interact with the lunar surface.

Joseph Toth↗

Effect of Solvent Composition on Non-DLVO Forces and Oriented Attachment of Zinc Oxide Nanoparticles

Oriented attachment (OA) occurs when nanoparticles in solution align their crystallographic axes prior to colliding and subsequently fuse into single crystals. Traditional colloidal theories such as DLVO provide a framework for evaluating OA but fail to capture key particle interactions due to the atomistic details of both the crystal structure and the interfacial solution structure. Using zinc oxide as a model system, we investigated the effect of the solvent on short-ranged and long-ranged particle interactions and the resulting OA mechanism. In situ TEM imaging showed that ZnO nanocrystals in toluene undergo long-range attraction comparable to 1kT at separations of 10 nm and 3kT near particle contact. These observations were rationalized by considering non-DLVO interactions, namely dipole-dipole forces and torques between the polar ZnO nanocrystals. Langevin dynamics simulations showed stronger interactions in toluene compared to methanol solvents, consistent with the experimental results. Concurrently, we performed atomic force microscopy measurements using ZnO-coated probes for the short-ranged interaction. Our data provided valuable insights into another type of non-DLVO interaction, namely the repulsive solvation force. Specifically, the solvation force was stronger in water compared to ethanol and methanol, due to the stronger hydrogen bonding and denser packing of water molecules at the interface. In conclusion, our results highlight the importance of non-DLVO forces in a general framework for understanding and predicting particle aggregation and attachment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resonant difference-frequency atomic force ultrasonic microscope

A scanning probe microscope and methodology called resonant difference-frequency atomic force ultrasonic microscopy (RDF-AFUM), employs an ultrasonic wave launched from the bottom of a sample while the cantilever of an atomic force microscope, driven at a frequency differing from the ultrasonic frequency by one of the contact resonance frequencies of the cantilever, engages the sample top surface. The nonlinear mixing of the oscillating cantilever and the ultrasonic wave in the region defined by the cantilever tip-sample surface interaction force generates difference-frequency oscillations at the cantilever contact resonance. The resonance-enhanced difference-frequency signals are used to create images of nanoscale near-surface and subsurface features.

Cantrell, John H.↗

HOSS: an implementation of the combined finite-discrete element method

Nearly thirty years since its inception, the combined finite-discrete element method (FDEM) has made remarkable strides in becoming a mainstream analysis tool within the field of Computational Mechanics. FDEM was developed to effectively “bridge the gap” between two disparate Computational Mechanics approaches known as the finite and discrete element meth-ods. At Los Alamos National Laboratory (LANL) researchers developed the Hybrid Optimization Software Suite (HOSS) as a hybrid multi-physics platform, based on FDEM, for the simulation of solid material behavior complemented with the latest technological enhancements for full fluid–solid interaction. Furthermore, in HOSS, several newly developed FDEM algorithms have been implemented that yield more accurate material deformation formulations, inter-particle interaction solvers, and fracture and fragmentation solutions. Additionally, an explicit computational fluid dynamics solver and a novel fluid–solid interaction algorithms have been fully integrated (as opposed to coupled) into the HOSS’ solid mechanical solver, allowing for the study of an even wider range of problems. Advancements such as this are leading HOSS to become a tool of choice for multi-physics problems. Finally, HOSS has been successfully applied by a myriad of researchers for analysis in rock mechanics, oil and gas industries, engineering application (structural, mechanical and biomedical engineering), mining, blast loading, high velocity impact, as well as seismic and acoustic analysis. This paper intends to summarize the latest development and application efforts for HOSS.

58 GEOSCIENCES↗

On the interaction of ultrasound with cracks: Applications to fatigue crack growth

Partial contact of two rough fatigue crack surfaces leads to transmission and diffraction of an acoustic signal at those contacts. Recent experimental and theoretical efforts to understand and quantify such contact in greater detail are discussed. The objective is to develop an understanding of the closure phenomenon and its application to the interpretation of fatigue data, in particular the R-ratio, spike overload/underload and threshold effects on crack propagation.

Buck, O.↗

The interaction of gold with gallium arsenide

Gold and gold-based alloys, commonly used as solar-cell contact materials, are known to react readily with gallium arsenide. Experiments designed to identify the mechanisms involved in these GaAs-metal interactions have yielded several interesting results. It is shown that the reaction of GaAs with gold takes place via a dissociative diffusion process. It is shown further that the GaAs-metal reaction rate is controlled to a very great extent by the condition of the free surface of the contact metal, an interesting example of which is the previously unexplained increase in the reaction rate that has been observed for samples annealed in a vacuum environment as compared to those annealed in a gaseous ambient. A number of other hard-to-explain observations, such as the low-temperature formation of voids in the gold lattice and crystallite growth on the gold surface, are also explained by invoking this mechanism.

Weizer, Victor G.↗

Electron tunneling through covalent and noncovalent pathways in proteins

A model is presented for electron tunneling in proteins which allows the donor-acceptor interaction to be mediated by the covalent bonds between amino acids and noncovalent contacts between amino acid chains. The important tunneling pathways are predicted to include mostly bonded groups with less favorable nonbonded interactions being important when the through bond pathway is prohibitively long. In some cases, vibrational motion of nonbonded groups along the tunneling pathway strongly influences the temperature dependence of the rate. Quantitative estimates for the sizes of these noncovalent interactions are made and their role in protein mediated electron transport is discussed.

Beratan, David N.↗

Morphology and the Strength of Intermolecular Contact in Protein Crystals

The strengths of intermolecular contacts (macrobonds) in four lysozyme crystals were estimated based on the strengths of individual intermolecular interatomic interaction pairs. The periodic bond chain of these macrobonds accounts for the morphology of protein crystals as shown previously. Further in this paper, the surface area of contact, polar coordinate representation of contact site, Coulombic contribution on the macrobond strength, and the surface energy of the crystal have been evaluated. Comparing location of intermolecular contacts in different polymorphic crystal modifications, we show that these contacts can form a wide variety of patches on the molecular surface. The patches are located practically everywhere on this surface except for the concave active site. The contacts frequently include water molecules, with specific intermolecular hydrogen-bonds on the background of non-specific attractive interactions. The strengths of macrobonds are also compared to those of other protein complex systems. Making use of the contact strengths and taking into account bond hydration we also estimated crystal-water interfacial energies for different crystal faces.

Matsuura, Yoshiki↗

Can classical DEM simultaneously capture compressibility and flowability of milled biomass?

Accurate prediction of the rheological behavior of biomass is essential for the design and operation of hoppers, feeders, and storage systems in biorefineries. This study examines whether the classical, coarse-grained discrete element method (DEM) formulation can simultaneously reproduce the compressibility and flowability of milled herbaceous biomass, using Miscanthus × giganteus as a representative material. The model represents particles as rigid spheres interacting through Hertz-Mindlin elastic-frictional contacts augmented with an area-dependent cohesion term. Laboratory cyclic compression and wedge-shaped hopper discharge experiments were used as calibration benchmarks. Although the model can independently reproduce each behavior by appropriately tuning particle Young's modulus E and cohesion energy density k, an extensive parametric investigation comprising more than 600 simulations reveals that the optimal parameter regions for compression and hopper flow are distinct and non-overlapping in (E, k) space. Surrogate surface analysis further shows that the corresponding objective-function valleys exhibit similar trends but are approximately parallel and spatially offset, precluding a unified calibration within the explored domain. Sensitivity analysis indicates that compressibility is governed predominantly by stiffness and cohesion, whereas the slope of the mass flow rate-opening relation in hopper discharge is primarily controlled by tangential friction. Extensions incorporating particle size distribution and clumped-sphere representations do not eliminate the incompatibility. These results systematically reveal, for the first time, the structural limitation of simplified DEM formulations in representing biomass rheological behavior, underscoring the necessity for models incorporating additional physical mechanisms, such as particle deformability or enhanced interlocking, to achieve unified predictive capability for biomass handling behavior.

09 BIOMASS FUELS↗

Emerged Metallicity in Molecular Ferromagnetic Wires

Supramolecular engineering bridges molecular assembly with macromolecular charge-transfer salts, promising the design to construct supramolecular architectures that integrate cooperative properties difficult or impossible to find in conventional lattices. Here, we report the crystal engineering design and kinetic growth of one-dimensional supramolecular wires composed of bis(ethylenedithio)tetrathiafulvalene (ET + ) cation and polymeric Cu[N(CN) 2 ] 2 – anion. A bulk ferromagnetic order is discovered for filling up the gap where strong ferromagnetism is missing in such ET molecule-based charge-transfer salts. Metallicity is induced by electric current from the semiconducting wire, which is attributed to strain effect by tuning its close molecular contact. This structural feature is evidenced through the combination of various mechanistic spectroscopic studies. Further, electric dipole is established from the close molecular contacts and is suggestive to stabilize ferromagnetic spin interaction through anions bridging spin sites. The breakthrough shown here provides a pathway to explore low-dimensional supramolecular materials exhibiting strong electron correlation, metallicity, and ferromagnetism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Engineering of Nanoscale Heterogeneous Transition Metal Dichalcogenide–Au Interfaces

Engineering the transition metal dichalcogenide (TMD)–metal interface is critical for the development of two-dimensional semiconductor devices. By directly probing the electronic structures of WS 2 –Au and WSe 2 –Au interfaces with high spatial resolution, we delineate nanoscale heterogeneities in the composite systems that give rise to local Schottky barrier height modulations. Photoelectron spectroscopy reveals large variations (>100 meV) in TMD work function and binding energies for the occupied electronic states. Characterization of the composite systems with electron backscatter diffraction and scanning tunneling microscopy leads us to attribute these heterogeneities to differing crystallite orientations in the Au contact, suggesting an inherent role of the metal microstructure in contact formation. Here we then leverage our understanding to develop straightforward Au processing techniques to form TMD–Au interfaces with reduced heterogeneity. Our findings illustrate the sensitivity of TMDs’ electronic properties to metal contact microstructure and the viability of tuning the interface through contact engineering.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Engineering an efficient and bright split Corynactis californica green fluorescent protein

Split green fluorescent protein (GFP) has been used in a panoply of cellular biology applications to study protein translocation, monitor protein solubility and aggregation, detect protein–protein interactions, enhance protein crystallization, and even map neuron contacts. Recent work shows the utility of split fluorescent proteins for large scale labeling of proteins in cells using CRISPR, but sets of efficient split fluorescent proteins that do not cross-react are needed for multiplexing experiments. We present a new monomeric split green fluorescent protein (ccGFP) engineered from a tetrameric GFP found in Corynactis californica, a bright red colonial anthozoan similar to sea anemones and scleractinian stony corals. Split ccGFP from C. californica complements up to threefold faster compared to the original Aequorea victoria split GFP and enable multiplexed labeling with existing A. victoria split YFP and CFP.

59 BASIC BIOLOGICAL SCIENCES↗

Structure determination of the HgcAB complex using metagenome sequence data: insights into microbial mercury methylation

Bacteria and archaea possessing the hgcAB gene pair methylate inorganic mercury (Hg) to form highly toxic methylmercury. HgcA consists of a corrinoid binding domain and a transmembrane domain, and HgcB is a dicluster ferredoxin. However, their detailed structure and function have not been thoroughly characterized. We modeled the HgcAB complex by combining metagenome sequence data mining, coevolution analysis, and Rosetta structure calculations. In addition, we overexpressed HgcA and HgcB in Escherichia coli, confirmed spectroscopically that they bind cobalamin and [4Fe-4S] clusters, respectively, and incorporated these cofactors into the structural model. Surprisingly, the two domains of HgcA do not interact with each other, but HgcB forms extensive contacts with both domains. The model suggests that conserved cysteines in HgcB are involved in shuttling HgII, methylmercury, or both. These findings refine our understanding of the mechanism of Hg methylation and expand the known repertoire of corrinoid methyltransferases in nature.

59 BASIC BIOLOGICAL SCIENCES↗