SEARCH · Search NASA

Results for “substrate interactions”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 577 records · Page 32

All sources NASA NTRS DOE OSTI

DOE OSTI2026

Do Flashing and Sealant Materials Need to be Exposed to Extreme Cycling?

In the U.S., over 50% of homes were built before 1980, when minimal building codes existed. The aging of building envelopes can significantly contribute to the air leakage, moisture intrusion, and durability of buildings leading to higher energy demands. Although the durability of building materials and envelope systems has been studied extensively, the durability of specific components like window-wall flashing and sealants remains underexplored. Current standards such as ASTM, NIST, and AAMA primarily focus on durability testing considering the high temperatures only and require sealant testing on anodized aluminum panels, leaving questions about performance in cold or fluctuating temperatures unanswered. Current ASTM and AAMA standards provide guidelines for durability testing but predominantly focus on exposure to higher temperature conditions. It remains unclear how exposure to cold temperatures, or cycles of both hot and cold conditions, affect the durability of these materials. Furthermore, AAMA standards mandate that flashing materials be tested on anodized aluminum panels, which may not reflect real-world applications. Therefore, this initial study aims to explore this concern through testing by constructing two window-wall interface prototypes and applying five different flashing and sealant materials to their joints. These samples were subjected to extreme temperatures, ranging from −34 ℃ (−30 °F) to 50 ℃ (122 °F), over a 28-day period (fourteen cycles of 24 hours), with daily visual inspections to document any signs of deterioration such as wrinkling, distortion, or warping. The study has two main objectives: (1) to determine whether flashing and sealant materials lose their durability and strength when exposed to varying climate conditions, specifically cold climates, and (2) to assess whether the interaction of these materials with different substrates (e.g., lumber, PVC, insulation) affects their durability and strength under varying climate conditions. The findings demonstrate how aging impacts the durability of window-wall systems interfaces, justifying future research that potentially could lead to the development of new testing protocols if significant defects are identified.

Palani, Hevar [ORNL] (ORCID:0000000220211994)↗

NASA NTRS2002

Glycogen synthase kinase 3 phosphorylates kinesin light chains and negatively regulates kinesin-based motility

Membrane-bounded organelles (MBOs) are delivered to different domains in neurons by fast axonal transport. The importance of kinesin for fast antero grade transport is well established, but mechanisms for regulating kinesin-based motility are largely unknown. In this report, we provide biochemical and in vivo evidence that kinesin light chains (KLCs) interact with and are in vivo substrates for glycogen synthase kinase 3 (GSK3). Active GSK3 inhibited anterograde, but not retrograde, transport in squid axoplasm and reduced the amount of kinesin bound to MBOs. Kinesin microtubule binding and microtubule-stimulated ATPase activities were unaffected by GSK3 phosphorylation of KLCs. Active GSK3 was also localized preferentially to regions known to be sites of membrane delivery. These data suggest that GSK3 can regulate fast anterograde axonal transport and targeting of cargos to specific subcellular domains in neurons.

NASA Discipline Neuroscience↗

DOE OSTI2023

Nanodevice, method of making the same, and method of using the same

A nanodevice provides for electric-field control of magnon-QSD interactions. The nanodevice includes a ferroelectric substrate, a ferromagnetic material disposed over the ferroelectric substrate, and a nanodiamond including an ensemble of nitrogen-vacancy (NV) spins, each NV magnetically interfacing with the ferromagnetic material. An electric field is measured by applying a voltage across the ferroelectric substrate and the ferromagnetic material, changing a magnon excitation spectrum of the ferromagnetic material with respect to an electron spin resonance frequency of the ensemble of NV spins, and measuring a relaxation rate of the ensemble of NV spins.

Shalaev, Vladimir M.↗

DOE OSTI2019

Role of the Hydrophobic Bridge in the Carbapenemase Activity of Class D β-Lactamases

Class D carbapenemases are enzymes of the utmost clinical importance due to their ability to confer resistance to the last-resort carbapenem antibiotics. We investigated the role of the conserved hydrophobic bridge in the carbapenemase activity of OXA-23, the major carbapenemase of the important pathogen Acinetobacter baumannii . We show that substitution of the bridge residue Phe110 affects resistance to meropenem and doripenem and has little effect on MICs of imipenem. The opposite effect was observed upon substitution of the other bridge residue Met221. Complete disruption of the bridge by the F110A/M221A substitution resulted in a significant loss of affinity for doripenem and meropenem and to a lesser extent for imipenem, which is reflected in the reduced MICs of these antibiotics. In the wild-type OXA-23, the pyrrolidine ring of the meropenem tail forms a hydrophobic interaction with Phe110 of the bridge. Similar interactions would ensue with ring-containing doripenem but not with imipenem, which lacks this ring. Our structural studies showed that this interaction with the meropenem tail is missing in the F110A/M221A mutant. These data explain why disruption of the interaction between the enzyme and the carbapenem substrate impacts the affinity and MICs of meropenem and doripenem to a larger degree than those of imipenem. Our structures also show that the bridge directs the acylated carbapenem into a specific tautomeric conformation. Furthermore, it is not this conformation but rather the stabilizing interaction between the tail of the antibiotic and the hydrophobic bridge that contributes to the carbapenemase activity of class D β-lactamases.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Future directions for active matter on ordered substrates

Active matter is a term encompassing particle-based assemblies with some form of self-propulsion, including certain biological systems as well as synthetic systems such as artificial colloidal swimmers, all of which can exhibit a remarkable variety of new kinds of nonequilibrium phenomena. A wealth of non-active condensed matter systems can be described in terms of a collection of particles coupled to periodic substrates, leading to the emergence of commensurate-incommensurate effects, Mott phases, tribology effects, and pattern formation. It is natural to ask how such phases are modified when the system is active. Here we provide an overview and future directions for studying individual and collectively interacting active matter particles coupled to periodic substrates, where new types of commensuration effects, directional locking, and active phases can occur. Importantly, further directions for exploration include directional locking effects, the realization of active solitons or active defects in incommensurate phases, active Mott phases, active artificial spin ice, active doping transitions, active floating phases, active surface physics, active matter time crystals, and active tribology.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2024

Evidence for autotrophic growth of purple sulfur bacteria using pyrite as electron and sulfur source

ABSTRACT Purple sulfur bacteria (PSB) are capable of anoxygenic photosynthesis via oxidizing reduced sulfur compounds and are considered key drivers of the sulfur cycle in a range of anoxic environments. In this study, we show that Allochromatium vinosum (a PSB species) is capable of autotrophic growth using pyrite as the electron and sulfur source. Comparative growth profile, substrate characterization, and transcriptomic sequencing data provided valuable insight into the molecular mechanisms underlying the bacterial utilization of pyrite and autotrophic growth. Specifically, the pyrite-supported cell cultures (“py”’) demonstrated robust but much slower growth rates and distinct patterns from their sodium sulfide-amended positive controls. Up to ~200-fold upregulation of genes encoding various c - and b -type cytochromes was observed in “py,” pointing to the high relevance of these molecules in scavenging and relaying electrons from pyrite to cytoplasmic metabolisms. Conversely, extensive downregulation of genes related to LH and RC complex components indicates that the electron source may have direct control over the bacterial cells’ photosynthetic activity. In terms of sulfur metabolism, genes encoding periplasmic or membrane-bound proteins (e.g., FccAB and SoxYZ) were largely upregulated, whereas those encoding cytoplasmic proteins (e.g., Dsr and Apr groups) are extensively suppressed. Other notable differentially expressed genes are related to flagella/fimbriae/pilin(+), metal efflux(+), ferrienterochelin(−), and [NiFe] hydrogenases(+). Characterization of the biologically reacted pyrite indicates the presence of polymeric sulfur. These results have, for the first time, put the interplay of PSB and transition metal sulfide chemistry under the spotlight, with the potential to advance multiple fields, including metal and sulfur biogeochemistry, bacterial extracellular electron transfer, and artificial photosynthesis. IMPORTANCE Microbial utilization of solid-phase substrates constitutes a critical area of focus in environmental microbiology, offering valuable insights into microbial metabolic processes and adaptability. Recent advancements in this field have profoundly deepened our knowledge of microbial physiology pertinent to these scenarios and spurred innovations in biosynthesis and energy production. Furthermore, research into interactions between microbes and solid-phase substrates has directly linked microbial activities to the surrounding mineralogical environments, thereby enhancing our understanding of the relevant biogeochemical cycles. Our study represents a significant step forward in this field by demonstrating, for the first time, the autotrophic growth of purple sulfur bacteria using insoluble pyrite (FeS2) as both the electron and sulfur source. The presented comparative growth profiles, substrate characterizations, and transcriptomic sequencing data shed light on the relationships between electron donor types, photosynthetic reaction center activities, and potential extracellular electron transfer in these organisms capable of anoxygenic photosynthesis. Furthermore, the findings of our study may provide new insights into early-Earth biogeochemical evolutions, offering valuable constraints for understanding the environmental conditions and microbial processes that shaped our planet’s history.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2015

A checkerboard selective absorber with excellent spectral selectivity

A selective absorber with excellent spectral selectivity is proposed and analyzed. The absorber is based on a germanium (Ge) checkerboard on top of a tantalum (Ta) substrate. At wavelengths shorter than the 1.2 μm cutoff, a very high absorption is achieved due to strong cavity resonances in the Ge nanosquares, and their interactions with adjacent nanocavities and the bottom Ta substrate. At longer wavelengths, absorption is greatly suppressed due to destructive interference between the transparent checkerboard layer and the highly reflective Ta substrate. To better describe the superior selectivity of our configuration, a new figure of merit (FOM) is introduced. We observe a FOM value of 0.88 compared to 0.69 for its planar counterpart. We also conduct a thermal analysis to verify the excellent selectivity of our absorber. A high temperature can be achieved and maintained, promising good potential for applications in solar thermophotovoltaic systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

NASA NTRS2005

Electronic Transport through Self Assembled Thiol Molecules: Effect of Monolayer Order, Dynamics and Temperature

We present the charge transport and tunneling conductance of self assembled organic thiol molecules and discuss the influence of order and dynamics in the monolayer on the transport behavior and the effect of temperature. Conjugated thiol molecular wires and organometals such as terpyridine metal complexes provide a new platform for molecular electronic devices and we study their self assembly on Au(111) substrates by the scanning tunneling microscope. Determining the organization of the molecule and the ability to control the nature of its interface with the substrate is important for reliable performance of the molecular electronic devices. By concurrent scanning tunneling microscopy and spectroscopy studies on SAMs formed from oligo (phenelyne ethynelyne) monolayers with and without molecular order, we show that packing and order determine the response of a self assembled monolayer (SAM) to competing interactions. Molecular resolution STM imaging in vacuum shows that the OPES adopt an imcommensurate SAM structure on Au(111) with a rectangular unit cell. Tunneling spectroscopic measurements were performed on the SAM as a function of junction resistance. STS results show that the I-Vs are non linear and asymmetric due to the inherent asymmetry in the molecular structure, with larger currents at negative sample biases. The asymmetry increases with increasing junction resistance due to the asymmetry in the coupling to the leads. This is brought out clearly in the differential conductance, which also shows a gap at the Fermi level. We also studied the effect of order and dynamics in the monolayer on the charge transport and found that competing forces between the electric field, intermolecular interactions, tip-molecule physisorption and substrate-molecule chemisorption impact the transport measurements and its reliability and that the presence of molecular order is very important for reproducible transport measurements. Thus while developing new electronic platforms based on molecules, it is important to have a good control of the molecule-substrate interface, for the devices to perform reliably. While such a control would minimize fluctuations and dynamics in the ensemble, the real challenge is to develop device architectures that are tolerant to fluctuations, since they cannot be totally eliminated in these low dimensional soft systems. Results of temperature dependent STS measurements will also be discussed.

Dholakia, Geetha↗

DOE OSTI2024

The Significance of the 'Insignificant': Non-covalent Interactions in CO 2 Reduction Reactions with 3C-TM (TM=Sc-Zn) Single-Atom Catalysts

With energy shortages and excessive CO 2 emissions driving climate change, converting CO 2 into high-value-added products offers a promising solution for carbon recycling. We investigate CO 2 reduction reactions (CO2RR) catalyzed by 10 single-atom catalysts (SACs), incorporating weak non-covalent interactions, specifically lone pair-π and H-π interactions. The SACs, consisting of transition metals coordinated by three carbon atoms in a defective graphene substrate (3C-TM, TM=Sc-Zn), leverage these interactions to influence the energy fluctuations of intermediates and the limiting potentials of CO 2 RR, without altering the overall reaction pathway. Further, our findings show that SACs based on early transition metals (Sc, Ti, V, Cr) can serve as catalysts for C 1 products, including HCOOH, HCHO, CH 3 OH, and CH 4 , while those based on Fe and Co are suitable for CO formation. Driving force analysis helps bridge theoretical results with experimental observations and propose a modified approach for assessing hydrogen evolution reactions (HER) competition. SACs based on Ni and Cu exhibit moderate HER tolerance, while early transition metals excel in selective CO 2 reduction. We also identify a linear scaling relationship between the free energies of *COOH and *CO. This study offers valuable insights for future experimental studies and large-scale computational screenings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Thermodynamic and NMR analyses of NADPH binding to lipocalin-type prostaglandin D synthase

Lipocalin-type prostaglandin D synthase (L-PGDS) is one of the most abundant proteins in human cerebrospinal fluid (CSF) with dual functions as a prostaglandin D{sub 2} (PGD{sub 2}) synthase and a transporter of lipophilic ligands. Recent studies revealed that L-PGDS plays important roles in protecting against various neuronal diseases induced by reactive oxygen species (ROS). However, the molecular mechanisms of such protective actions of L-PGDS remain unknown. In this study, we conducted thermodynamic and nuclear magnetic resonance (NMR) analyses, and demonstrated that L-PGDS binds to nicotinamide coenzymes, including NADPH, NADP{sup +}, and NADH. Although a hydrophilic ligand is not common for L-PGDS, these ligands, especially NADPH showed specific interaction with L-PGDS at the upper pocket of its ligand-binding cavity with an unusually bifurcated shape. The binding affinity of L-PGDS for NADPH was comparable to that previously reported for NADPH oxidases and NADPH in vitro. These results suggested that L-PGDS potentially attenuates the activities of NADPH oxidases through interaction with NADPH. Given that NADPH is the substrate for NADPH oxidases that play key roles in neuronal cell death by generating excessive ROS, these results imply a novel linkage between L-PGDS and ROS. - Highlights: • Interactions of L-PGDS with nicotinamide coenzymes were studied by ITC and NMR. • The binding affinity of L-PGDS was strongest to NADPH among nicotinamide coenzymes. • NADPH binds to the upper part of L-PGDS ligand-binding cavity. • L-PGDS binds to both lipophilic and hydrophilic ligands. • This study implies a novel linkage between L-PGDS and reactive oxygen species.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2021

Impact of 2D–3D Heterointerface on Remote Epitaxial Interaction through Graphene

Remote epitaxy has drawn attention as it offers epitaxy of functional materials that can be released from the substrates with atomic precision, thus enabling production and heterointegration of flexible, transferrable, and stackable freestanding single-crystalline membranes. In addition, the remote interaction of atoms and adatoms through two-dimensional (2D) materials in remote epitaxy allows investigating and utilizing electrical/chemical/physical coupling of bulk (3D) materials via 2D materials (3D-2D-3D coupling). Here, we unveil the respective roles and impacts of the substrate material, graphene, substrate-graphene interface, and epitaxial material for electrostatic coupling of these materials, which governs cohesive ordering and can lead to single-crystal epitaxy in the overlying film. Further, we show that simply coating a graphene layer on wafers does not guarantee successful implementation of remote epitaxy, since atomically precise control of the graphene-coated interface is required, and provide key considerations for maximizing the remote electrostatic interaction between the substrate and adatoms. This was enabled by exploring various material systems and processing conditions, and we demonstrate that the rules of remote epitaxy vary significantly depending on the ionicity of material systems as well as the graphene-substrate interface and the epitaxy environment. The general rule of thumb discovered here enables expanding 3D material libraries that can be stacked in freestanding form.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Structural insight into substrate and product binding in an archaeal mevalonate kinase

Mevalonate kinase (MK) is a key enzyme of the mevalonate pathway, which produces the biosynthetic precursors for steroids, including cholesterol, and isoprenoids, the largest class of natural products. Currently available crystal structures of MK from different organisms depict the enzyme in its unbound, substrate-bound, and inhibitor-bound forms; however, until now no structure has yet been determined of MK bound to its product, 5-phosphomevalonate. Here, we present crystal structures of mevalonate-bound and 5-phosphomevalonate-bound MK from Methanosarcina mazei (MmMK), a methanogenic archaeon. In contrast to the prior structure of a eukaryotic MK bound with mevalonate, we find a striking lack of direct interactions between this archaeal MK and its substrate. Further, these two MmMK structures join the prior structure of the apoenzyme to complete the first suite of structural snapshots that depict unbound, substrate-bound, and product-bound forms of the same MK. With this collection of structures, we now provide additional insight into the catalytic mechanism of this biologically essential enzyme.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Supercharged cellulases show superior thermal stability and enhanced activity towards pretreated biomass and cellulose

Non-productive binding of cellulolytic enzymes to various plant cell wall components, such as lignin and cellulose, necessitates high enzyme loadings to achieve efficient conversion of pretreated lignocellulosic biomass to fermentable sugars. Protein supercharging was previously employed as one of the strategies to reduce non-productive binding to biomass. However, various questions remain unanswered regarding the hydrolysis kinetics of supercharged enzymes towards pretreated biomass substrates and the role played by enzyme interactions with individual cell wall polymers such as cellulose and xylan. In this study, CBM2a (from Thermobifida fusca ) fused with endocellulase Cel5A (from T. fusca ) was used as the model wild-type enzyme and CBM2a was supercharged using Rosetta, to obtain eight variants with net charges spanning -14 to +6. These enzymes were recombinantly expressed in E. coli , purified from cell lysates, and their hydrolytic activities were tested against pretreated biomass substrates (AFEX and EA treated corn stover). Although the wild-type enzyme showed greater activity compared to both negatively and positively supercharged enzymes towards pretreated biomass, thermal denaturation assays identified two negatively supercharged constructs that perform better than the wild-type enzyme (~3 to 4-fold difference in activity) upon thermal deactivation at higher temperatures. To better understand the causal factor of reduced supercharged enzyme activity towards AFEX corn stover, we performed hydrolysis assays on cellulose-I/xylan/pNPC, lignin inhibition assays, and thermal stability assays. Altogether, these assays showed that the negatively supercharged mutants were highly impacted by reduced activity towards xylan whereas the positively supercharged mutants showed dramatically reduced activity towards cellulose and xylan. It was identified that a combination of impaired cellulose binding and lower thermal stability was the cause of reduced hydrolytic activity of positively supercharged enzyme sub-group. Overall, this study demonstrated a systematic approach to investigate the behavior of supercharged enzymes and identified supercharged enzyme constructs that show superior activity at elevated temperatures. Future work will address the impact of parameters such as pH, salt concentration, and assay temperature on the hydrolytic activity and thermal stability of supercharged enzymes.

09 BIOMASS FUELS↗

DOE OSTI2019

Theoretical Model Study of Interplay of Coulomb Interaction and Electron-Phonon Interaction in the Thermal Properties of Monolayer Graphene

We propose here a tight-binding (TB) model Hamiltonian for monolayer graphene-on-substrate describing the nearest-neighbor-hopping, on-site Coulomb interaction on the sub-lattices and the electron-phonon interaction under the high-frequency limit of phonon vibration. Applying Lang-Firsov canonical transformation, the electron and phonon systems are decoupled in the atomic Hamiltonian, such that the effective Coulomb interaction and effective nearest-neighbor-hopping integral respectively appear as U-tilde =U−2t{sub 1}λ and t-tilde {sub 1}=t{sub 1}e{sup ((−t{sub 1}λ)/(ω{sub 0}))}, where U, t{sub 1}, λ and ω{sub 0} are respectively Coulomb energy, nearest-neighbor-hopping integral, electron-phonon (e-ph) coupling and phonon frequency. The effective Coulomb interaction in the Hamiltonian is considered within mean-field approximation. The Hamiltonian is solved by Zubarev’s Green’s function technique. The temperature-dependent electronic entropy and specific heat are calculated from the free energy of graphene system and are computed numerically. The temperature-dependent electronic specific heat exhibits a charge gap peak at room temperature arising due to the effect of Coulomb interaction and electron-phonon interaction. The evolution of these peaks in specific heat is investigated by varying the model parameters of the system.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2017

Sequence of Silicon Monolayer Structures Grown on a Ru Surface: from a Herringbone Structure to Silicene

Silicon-based two-dimensional (2D) materials are uniquely suited for integration in Si-based electronics. Silicene, an analogue of graphene, was recently fabricated on several substrates and was used to make a field-effect transistor. Here, we report that when Ru(0001) is used as a substrate, a range of distinct monolayer silicon structures forms, evolving toward silicene with increasing Si coverage. Low Si coverage produces a herringbone structure, a hitherto undiscovered 2D phase of silicon. With increasing Si coverage, herringbone elbows evolve into silicene-like honeycomb stripes under tension, resulting in a herringbone-honeycomb 2D superlattice. At even higher coverage, the honeycomb stripes widen and merge coherently to form silicene in registry with the substrate. Scanning tunneling microscopy (STM) was used to image the structures. The structural stability and electronic properties of the Si 2D structures, the interaction between the Si 2D structures and the Ru substrate, and the evolution of the distinct monolayer Si structures were elucidated by density functional theory (DFT) calculations. This work paves the way for further investigations of monolayer Si structures, the corresponding growth mechanisms, and possible functionalization by impurities.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Interaction Between Graphene-Coated SiC Single Crystal and Liquid Copper

The wettability of graphene-coated SiC single crystal (C{sub Gn}/SiC{sup sc}) by liquid Cu (99.99%) was investigated by a sessile drop method in vacuum conditions at temperature of 1100 °C. The graphene layer was produced via a chemical vapor deposition routine using 4H-SiC single crystal cut out from 6″ wafer. A dispensed drop technique combined with a non-contact heating of a couple of materials was applied. The Cu drop was squeezed from a graphite capillary and deposited on the substrate directly in a vacuum chamber. The first Cu drop did not wet the C{sub Gn}/SiC{sup sc} substrate and showed a lack of adhesion to the substrate: the falling Cu drop only touched the substrate forming a contact angle of θ{sub 0} = 121° and then immediately rolled like a ball along the substrate surface. After settling near the edge of the substrate in about 0.15 s, the Cu drop formed an asymmetric shape with the right and left contact angles of different values (θ{sub R} = 86° and θ{sub L} = 70°, respectively), while in the next 30 min, θ{sub R} and θ{sub L} achieved the same final value of ~ 52°. The second Cu drop was put down on the displacement path of the first drop, and immediately after the deposition, it also did not wet the substrate (θ = 123°). This drop kept symmetry and the primary position, but its wetting behavior was unusual: both θ{sub R} and θ{sub L} decreased in 17 min to the value of 23° and next, they increased to a final value of 65°. Visual observations revealed a presence of ~ 2.5-mm-thick interfacial phase layer reactively formed under the second drop. Scanning electron microscopy (SEM) investigations revealed the presence of carbon-enriched precipitates on the top surface of the first Cu drop. These precipitates were identified by the Raman spectroscopy as double-layer graphene. The Raman spectrum taken from the substrate far from the drop revealed the presence of graphene, while that obtained from the first drop displacement path exhibited a decreased intensity of 2D peak. The results of SEM investigations and Raman spectroscopy studies suggest that the presence of graphene layer on the SiC substrate suppresses but does not completely prevent chemical interaction between liquid Cu drop and SiC. Both chemical degradation (etching) and mechanical degradation of the graphene layer during drop rolling due to high adhesion of the Cu drop to the SiC substrate are responsible for mass transfer through the 2nd drop/substrate interface that in turn results in significant changes of structure and chemistry of the drop and the interface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2021

Nickel–Sulfonate Mode of Substrate Binding for Forward and Reverse Reactions of Methyl-SCoM Reductase Suggest a Radical Mechanism Involving Long-Range Electron Transfer

Methyl-coenzyme M reductase (MCR) catalyzes both the synthesis and the anaerobic oxidation of methane (AOM). Its catalytic site contains Ni at the core of cofactor F 430 . The Ni ion, in its low-valent Ni(I) state, lights the fuse leading to homolysis of the C–S bond of methyl-coenzyme M (methyl-SCoM) to generate a methyl radical, which abstracts a hydrogen atom from coenzyme B (HSCoB) to generate methane and the mixed disulfide CoMSSCoB. Direct reversal of this reaction activates methane to initiate anaerobic methane oxidation. On the basis of the crystal structures, which reveal a Ni–thiol interaction between Ni(II)–MCR and inhibitor CoMSH, a Ni(I)–thioether complex with substrate methyl-SCoM has been transposed to canonical MCR mechanisms. Similarly, a Ni(I)–disulfide with CoMSSCoB is proposed for the reverse reaction. However, this Ni(I)–sulfur interaction poses a conundrum for the proposed hydrogen-atom abstraction reaction because the >6 Å distance between the thiol group of SCoB and the thiol of SCoM observed in the structures appears to be too long for such a reaction. The spectroscopic, kinetic, structural, and computational studies described here establish that both methyl-SCoM and CoMSSCoB bind to the active Ni(I) state of MCR through their sulfonate groups, forming a hexacoordinate Ni(I)–N/O complex, not Ni(I)–S. These studies rule out direct Ni(I)–sulfur interactions in both substrate-bound states. As a solution to the mechanistic conundrum, we propose that both the forward and the reverse MCR reactions emanate through long-range electron transfer from the Ni(I)–sulfonate complexes with methyl-SCoM and CoMSSCoB, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Development of tight-binding based GW algorithm and its computational implementation for graphene

Graphene has been a hot subject of research in the last decade as it holds a promise for various applications. One interesting issue is whether or not graphene should be classified into a strongly or weakly correlated system, as the optical properties may change upon several factors, such as the substrate, voltage bias, adatoms, etc. As the Coulomb repulsive interactions among electrons can generate the correlation effects that may modify the single-particle spectra (density of states) and the two-particle spectra (optical conductivity) of graphene, we aim to explore such interactions in this study. The understanding of such correlation effects is important because eventually they play an important role in inducing the effective attractive interactions between electrons and holes that bind them into excitons. We do this study theoretically by developing a GW method implemented on the basis of the tight-binding (TB) model Hamiltonian. Unlike the well-known GW method developed within density functional theory (DFT) framework, our TB-based GW implementation may serve as an alternative technique suitable for systems which Hamiltonian is to be constructed through a tight-binding based or similar models. This study includes theoretical formulation of the Green’s function G, the renormalized interaction function W from random phase approximation (RPA), and the corresponding self energy derived from Feynman diagrams, as well as the development of the algorithm to compute those quantities. As an evaluation of the method, we perform calculations of the density of states and the optical conductivity of graphene, and analyze the results.

77 NANOSCIENCE AND NANOTECHNOLOGY↗