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At least 973 records · Page 54

Single- and dual-variant atomic ordering in GaAsP compositionally graded buffers on GaP and Si substrates

Here, we investigate the material properties of GaAsP graded buffers on both GaP and Si substrates in order to determine limitations to dislocation glide in GaAsP. Phase separation is not observed in these GaAsP buffers, but CuPt B atomic ordering is present, and has an impact on the Burgers vector distribution of gliding dislocations. Tellurium surfactant eliminates ordering in GaAsP, allowing control over the glide plane distribution while highlighting the importance of the growth surface and choice of dopant. The impact of single-variant CuPtB ordering of GaAsP buffers grown on GaP substrates is investigated by monitoring the threading dislocation density throughout the buffer in sequential steps. The dislocation density rises steadily throughout the graded buffer, implying that factors other than ordering-induced glide plane switches play a dominant role in the final dislocation density. We observe an increase in surface roughness throughout the buffer and speculate that a dislocation nucleation source on the surface has a low activation energy and may lead to increased threading dislocation density. On Si substrates, the GaAsP buffer displays dual-variant CuPt B ordering rather than single-variant ordering due to the surface step geometry. We discuss how dual-variant ordering leads to a variable glide force, and thus has a different impact on dislocation dynamics than single-variant ordering. Because the III-V on Si nucleation procedure determines the step geometry, it also influences the dislocation dynamics.

36 MATERIALS SCIENCE↗

CO as a substrate and inhibitor of H + reduction for the Mo-, V-, and Fe-nitrogenase isozymes

Three known nitrogenase isozymes, Mo-, V-, and Fe-, catalyze biological reduction of dinitrogen (N 2 ) to ammonia (NH 3 ). All three utilize the same reductive elimination mechanism: an intermediate with two metal-bound hydrides reductively-eliminates hydrogen gas (H 2 ) in a reaction coupled to binding and activation of N 2 . Nonetheless, the three isozymes show dramatically different relative rates of H 2 formation and N 2 reduction, revealing important differences in reactivity with substrates. Carbon monoxide (CO) has been characterized as both an inhibitor and substrate for Mo- and V-nitrogenases, but not for the Fe-nitrogenase. In this work, we present a comparative study of the reactivity of the three isozymes with CO, examining CO both as a substrate and as an inhibitor of proton (H + ) reduction under steady-state conditions. For Mo-nitrogenase, there is neither detectable reduction of CO nor inhibition of H + reduction. Fe- and V-nitrogenase show CO reduction and inhibition of H + reduction that depends on the CO partial pressure. For V-nitrogenase, ethylene (C 2 H 4 ) is the major reduction product with a maximum specific activity of ~7.5 nmol C 2 H 4 /nmol VFe protein/min at 1 atm CO. The major product of CO reduction for Fe-nitrogenase is methane (CH 4 ) with a maximum specific activity of ~4.8 nmol CH 4 /nmol FeFe protein/min at 0.05 atm CO. The rate of CH 4 production by Fe-nitrogenase progressively increases to a maximum at 0.05 atm CO and then declines to ~10% with increasing CO partial pressure up to 1 atm. CO does not inhibit proton reduction in Mo-nitrogenase but shows 16% inhibition for V-nitrogenase and 35% for Fe-nitrogenase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of Human GIVD Cytosolic Phospholipase A2 Reveals Insights into Substrate Recognition

Cytosolic phospholipases A2 (cPLA2s) consist of a family of calcium-sensitive enzymes that function to generate lipid second messengers through hydrolysis of membrane-associated glycerophospholipids. The GIVD cPLA2 (cPLA2δ) is a potential drug target for developing a selective therapeutic agent for the treatment of psoriasis. Here, we present two X-ray structures of human cPLA2δ, capturing an apo state, and in complex with a substrate-like inhibitor. Comparison of the apo and inhibitor-bound structures reveals conformational changes in a flexible cap that allows the substrate to access the relatively buried active site, providing new insight into the mechanism for substrate recognition. The cPLA2δ structure reveals an unexpected second C2 domain that was previously unrecognized from sequence alignments, placing cPLA2δ into the class of membrane-associated proteins that contain a tandem pair of C2 domains. Furthermore, our structures elucidate novel inter-domain interactions and define three potential calcium-binding sites that are likely important for regulation and activation of enzymatic activity. These findings provide novel insights into the molecular mechanisms governing cPLA2's function in signal transduction.

59 BASIC BIOLOGICAL SCIENCES↗

Rational design of a carboxylic esterase Rh Est1 based on computational analysis of substrate binding

A new carboxylic esterase RhEst1 which catalyzes the hydrolysis of (S)-(+)-2,2-dimethylcyclopropanecarboxylate (S-DmCpCe), the key chiral building block of cilastatin, was identified and subsequently crystallized in our previous work. Mutant Rh Est 1A147I/V148F/G254A was found to show a 5-fold increase in the catalytic activity. In this work, molecular dynamic simulations were performed to elucidate the molecular determinant of the enzyme activity. Our simulations show that the substrate binds much more strongly in the A147I/V148F/G254A mutant than in wild type, with more hydrogen bonds formed between the substrate and the catalytic triad and the oxyanion hole. The OH group of the catalytic residue Ser101 in the mutant is better positioned to initiate the nucleophilic attack on S-DmCpCe. Interestingly, the "170-179" loop which is involved in shaping the catalytic sites and facilitating the product release shows remarkable dynamic differences in the two systems. Based on the simulation results, six residues were identified as potential "hot-spots" for further experimental testing. Consequently, the G126S and R133L mutants show higher catalytic efficiency as compared with the wild type. In conclusion, this work provides molecular-level insights into the substrate binding mechanism of carboxylic esterase Rh Est1, facilitating future experimental efforts toward developing more efficient Rh Est1 variants for industrial applications.

59 BASIC BIOLOGICAL SCIENCES↗

Spin canting of Ni/CoO/Fe films grown on curved MgO(0 0 1) substrate

Using element-resolved x-ray magnetic circular dichroism (XMCD) and x-ray magnetic linear dichroism (XMLD) measurements, we determined the spin orientations of Ni, CoO and Fe films in Ni/CoO/Fe films grown on a curved MgO(0 0 1) substrate. We find that the vicinal surface of MgO(0 0 1) substrate results in a spin canting towards out-of-plane direction in the Ni and CoO films as a result of the interfacial coupling. The Ni spin canting angle increases monotonically with the vicinal angle in the studied range of 0–17° and the CoO spin canting angle increases more rapidly towards saturation only at a few degrees of the vicinal angle. The uniaxial magnetic anisotropy induced in the Ni layer by the Ni/CoO interfacial coupling is quantitatively determined and is shown to increase monotonically with the vicinal angle. Our result provides a new pathway for tailoring the spin orientation by modifying the substrate surface symmetry in combining with the ferromagnetic/antiferromagnetic interfacial interaction in thin-film based spintronic devices.

36 MATERIALS SCIENCE↗

Thermal stability of Li films on polycrystalline molybdenum substrates

Lithium (Li) coatings on plasma facing components (PFCs) have been proposed as potential solutions to first wall and divertor challenges in tokamak fusion reactors. We report on the thermal behavior of ultrathin pure Li films deposited on polycrystalline substrates of molybdenum (Mo) and a molybdenum alloy (titanium zirconium molybdenum, TZM). These Li films were studied under controlled ultrahigh vacuum (UHV) conditions and thermal stabilities were primarily compared via temperature programmed desorption (TPD) measurements. In addition, on TZM, which is of particular interest, we obtained additional spectroscopic data using Auger electron spectroscopy (AES) and low energy ion scattering (LEIS) to further characterize the film structure and composition. Here, the monolayer of Li in these films in contact with the substrate is bound much stronger than in bulk Li films, and thermally desorbs at much higher temperatures. Interfacial Li on Mo(poly) has a higher thermal stability than that on TZM(poly), where the limiting values for the desorption activation energies, E d , are 3.56 and 2.84 eV, respectively, in the low coverage, high temperature desorption tail. LEIS indicates some clustering or interdiffusion of the Li films on the TZM substrate at 500 K. No appreciable irreversible absorption of Li occurs on Mo or TZM under the conditions of these experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Decoupling the effects of substrate hardness and roughness upon particle adhesion in cold spray

There are two stages of particle adhesion relevant to cold spray: adhesion of the first layer to the substrate, followed by inter-particle adhesion during subsequent deposition. In this work we study the second of these, in which particles strike a previously-deposited layer that is roughened and hardened by prior particle impacts. Specifically, we decouple the effects of surface roughness and hardness on particle adhesion for copper-on-copper impacts. We measure changes to the critical velocity, V cr , in single particle impacts produced by the Laser Induced Particle Impact Test on several surfaces including a cold sprayed surface and a polished version of that surface. We find that increases in both substrate roughness and hardness suppress particle adhesion to higher velocities, indeed in rather equal proportion by ∼10–15% each. This suggests that there is a higher V cr associated with coating build-up (particle-particle bonding) that is overall ∼30% higher than V cr for particle-substrate adhesion.

36 MATERIALS SCIENCE↗

Quantitative soil zymography: Mechanisms, processes of substrate and enzyme diffusion in porous media

Soil membrane zymography enables 2D mapping of enzyme activities on the surface of soil samples. The method is according to diffusion of components of enzymatically-mediated reactions to/from membrane, and, hence, reflects the distribution of enzyme activities at the intact soil surface. Zymography has been already successfully implemented in numerous soil ecology applications. Here we identify two methodological aspects for further improvement and expansion of the method at micro and macro scales: first, accounting for the area of contact between the soil surface and the zymography membranes and, second, accounting for diffusion effects during the zymography procedure. We tested three methods, namely, laser-scanning, staining with a fluorescent product (e.g. MUF: 4-methylumbelliferone), and X-ray computed micro-tomography, for assessing the area of the soil surface in contact with the membranes. We quantified diffusion of MUF, enzymes and substrate between the substrate-saturated membrane and soil as well as diffusion processes during membrane zymography via HP2 software. Diffusion of the substrate from the membrane and of the MUF-product to the membrane was detected, while there were no clear evidence of enzyme diffusion to/in the membrane. According to the model simulations, the enzyme activities detected via 2D zymography probably represent only a small portion, about 20%, of the actual reactions within the soil volume that is in both direct contact and in hydrological contact with zymography membranes. This is a result of omnidirectional diffusion of reaction products. The membrane contact with the soil surface estimated by three methods ranged from 3.4 to 36.5% further signifying that only a fraction of enzymes activity is detectable in a course of 2D soil zymography.

59 BASIC BIOLOGICAL SCIENCES↗

Analysis of current-driven oscillatory dynamics of single-layer homoepitaxial islands on crystalline conducting substrates

Here we report results of a systematic study on the complex oscillatory current-driven dynamics of single-layer homoepitaxial islands on crystalline substrate surfaces and the dependence of this driven dynamical behavior on important physical parameters, including island size, substrate surface orientation, and direction of externally applied electric field. The analysis is based on a nonlinear model of driven island edge morphological evolution that accounts for curvature-driven edge diffusion, edge electromigration, and edge diffusional anisotropy. Using a linear theory of island edge morphological stability, we calculate a critical island size at which the island’s equilibrium edge shape becomes unstable, which sets a lower bound for the onset of time-periodic oscillatory dynamical response. Using direct dynamical simulations, we study the edge morphological dynamics of current-driven single-layer islands at larger-than-critical size, and determine the actual island size at which the migrating islands undergo a transition from steady to time-periodic asymptotic states through a subcritical Hopf bifurcation. At the highest symmetry of diffusional anisotropy examined, on {111} surfaces of face-centered cubic crystalline substrates, we find that more complex stable oscillatory states can be reached through period-doubling bifurcation at island sizes larger than those at the Hopf points. We characterize in detail the island morphology and dynamical response at the stable time-periodic asymptotic states, determine the range of stability of these oscillatory states terminated by island breakup, and explain the morphological features of the stable oscillating islands on the basis of linear stability theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Differential contribution of key metabolic substrates and cellular oxygen in HIF signalling

Changes in availability and utilisation of O{sub 2} and metabolic substrates are common in ischemia and cancer. We examined effects of substrate deprivation on HIF signalling in PC12 cells exposed to different atmospheric O{sub 2}. Upon 2–4 h moderate hypoxia, HIF-α protein levels were dictated by the availability of glutamine and glucose, essential for deep cell deoxygenation and glycolytic ATP flux. Nuclear accumulation of HIF-1α dramatically decreased upon inhibition of glutaminolysis or glutamine deprivation. Elevation of HIF-2α levels was transcription-independent and associated with the activation of Akt and Erk1/2. Upon 2 h anoxia, HIF-2α levels strongly correlated with cellular ATP, produced exclusively via glycolysis. Without glucose, HIF signalling was suppressed, giving way to other regulators of cell adaptation to energy crisis, e.g. AMPK. Consequently, viability of cells deprived of O{sub 2} and glucose decreased upon inhibition of AMPK with dorsomorphin. The capacity of cells to accumulate HIF-2α decreased after 24 h glucose deprivation. This effect, associated with increased AMPKα phosphorylation, was sensitive to dorsomorphin. In chronically hypoxic cells, glutamine played no major role in HIF-2α accumulation, which became mainly glucose-dependent. Overall, the availability of O{sub 2} and metabolic substrates intricately regulates HIF signalling by affecting cell oxygenation, ATP levels and pathways involved in production of HIF-α. - Highlights: • Gln and Glc regulate HIF levels in hypoxic cells by maintaining low O{sub 2} and high ATP. • HIF-α levels under anoxia correlate with cellular ATP and critically depend on Glc. • Gln and Glc modulate activity of Akt, Erk and AMPK, regulating HIF production. • HIF signalling is differentially inhibited by prolonged Glc and Gln deprivation. • Unlike Glc, Gln plays no major role in HIF signalling in chronically hypoxic cells.

60 APPLIED LIFE SCIENCES↗

Assessing the impact of substrate-level enzyme regulations limiting ethanol titer in Clostridium thermocellum using a core kinetic model

Clostridium thermocellum is a promising candidate for consolidated bioprocessing because it can directly ferment cellulose to ethanol. Despite significant efforts, achieved yields and titers fall below industrially relevant targets. This implies that there still exist unknown enzymatic, regulatory, and/or possibly thermodynamic bottlenecks that can throttle back metabolic flow. By (i) elucidating internal metabolic fluxes in wild-type C. thermocellum grown on cellobiose via 13 C-metabolic flux analysis ( 13 C-MFA), (ii) parameterizing a core kinetic model, and (iii) subsequently deploying an ensemble-docking workflow for discovering substrate-level regulations, this paper aims to reveal some of these factors and expand our knowledgebase governing C. thermocellum metabolism. Generated 13 C labeling data were used with 13 C-MFA to generate a wild-type flux distribution for the metabolic network. Notably, flux elucidation through MFA alluded to serine generation via the mercaptopyruvate pathway. Using the elucidated flux distributions in conjunction with batch fermentation process yield data for various mutant strains, we constructed a kinetic model of C. thermocellum core metabolism (i.e. k-ctherm138). Subsequently, we used the parameterized kinetic model to explore the effect of removing substrate-level regulations on ethanol yield and titer. Upon exploring all possible simultaneous (up to four) regulation removals we identified combinations that lead to many-fold model predicted improvement in ethanol titer. In addition, by coupling a systematic method for identifying putative competitive inhibitory mechanisms using K-FIT kinetic parameterization with the ensemble-docking workflow, we flagged 67 putative substrate-level inhibition mechanisms across central carbon metabolism supported by both kinetic formalism and docking analysis.

59 BASIC BIOLOGICAL SCIENCES↗

Structures of Pseudomonas aeruginosa LpxA Reveal the Basis for Its Substrate Selectivity

In Gram-negative bacteria, the first step of lipid A biosynthesis is catalyzed by UDP-N-acetylglucosamine acyltransferase (LpxA) through the transfer of a R-3-hydroxyacyl chain from the acyl carrier protein (ACP) to the 3-hydroxyl group of UDP-GlcNAc. Previous studies suggest that LpxA is a critical determinant of the acyl chain length found in lipid A, which varies among species of bacteria. In Escherichia coli and Leptospira interrogans, LpxA prefers to incorporate longer R-3-hydroxyacyl chains (C14 and C12, respectively), whereas in Pseudomonas aeruginosa, the enzyme is selective for R-3-hydroxydecanoyl, a 10-hydrocarbon long acyl chain. We now report three P. aeruginosa LpxA crystal structures: apo protein, substrate complex with UDP-GlcNAc, and product complex with UDP-3-O-(R-3-hydroxydecanoyl)-GlcNAc. A comparison between the apo form and complexes identifies key residues that position UDP-GlcNAc appropriately for catalysis and supports the role of catalytic His121 in activating the UDP-GlcNAc 3-hydroxyl group for nucleophilic attack during the reaction. Here, the product-complex structure, for the first time, offers structural insights into how Met169 serves to constrain the length of the acyl chain and thus functions as the so-called hydrocarbon ruler. Furthermore, compared with ortholog LpxA structures, the purported oxyanion hole, formed by the backbone amide group of Gly139, displays a different conformation in P. aeruginosa LpxA, which suggests flexibility of this structural feature important for catalysis and the potential need for substrate-induced conformational change in catalysis. Taken together, the three structures provide valuable insights into P. aeruginosa LpxA catalysis and substrate specificity as well as templates for future inhibitor discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Substrate Promotes Productive Gas Binding in the α-Ketoglutarate-Dependent Oxygenase FIH

The Fe 2+ /α-ketoglutarate (αKG)-dependent oxygenases use molecular oxygen to conduct a wide variety of reactions with important biological implications, such as DNA base excision repair, histone demethylation, and the cellular hypoxia response. These enzymes follow a sequential mechanism in which O 2 binds and reacts after the primary substrate binds, making those structural factors that promote productive O 2 binding central to their chemistry. A large challenge in this field is to identify strategies that engender productive turnover. Factor inhibiting HIF (FIH) is a Fe 2+ /αKG-dependent oxygenase that forms part of the O 2 sensing machinery in human cells by hydroxylating the C-terminal transactivation domain (CTAD) found within the HIF-1α protein. In this work, the structure of FIH was determined with the O 2 analogue NO bound to Fe, offering the first direct insight into the gas binding geometry in this enzyme. Through a combination of density functional theory calculations, {FeNO} 7 electron paramagnetic resonance spectroscopy, and ultraviolet–visible absorption spectroscopy, we demonstrate that CTAD binding stimulates O 2 reactivity by altering the orientation of the bound gas molecule. Although unliganded FIH binds NO with moderate affinity, the bound gas can adopt either of two orientations with similar stability; upon CTAD binding, NO adopts a single preferred orientation that is appropriate for supporting oxidative decarboxylation. Combined with other studies of related enzymes, our data suggest that substrate-induced reorientation of bound O 2 is the mechanism utilized by the αKG oxygenases to tightly couple O 2 activation to substrate hydroxylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Mutation and Substrate Binding on the Stability of Cytochrome P450 BM3 Variants

Cytochrome P450 BM3 is a heme-containing enzyme from Bacillus megaterium that displays high monooxygenase activity and has a self-sufficient electron transfer system in the full-length enzyme. Its potential synthetic applications drive protein engineering efforts to produce variants capable of oxidizing nonnative substrates such as pharmaceuticals and aromatic pollutants. However, promiscuous P450 BM3 mutants often exhibit lower stability, thereby hindering their industrial application. This study demonstrated that the heme domain R47L/F87V/L188Q/E267V/F81I pentuple mutant (PM) is destabilized because of the disruption of hydrophobic contacts and salt bridge interactions. This was directly observed from crystal structures of PM in the presence and absence of ligands (palmitic acid and metyrapone). The instability of the tertiary structure and heme environment of substrate-free PM was confirmed by pulse proteolysis and circular dichroism, respectively. Binding of the inhibitor, metyrapone, significantly stabilized PM, but the presence of the native substrate, palmitic acid, had no effect. On the basis of high-temperature molecular dynamics simulations, the lid domain, β-sheet 1, and Cys ligand loop (a β-bulge segment connected to the heme) are the most labile regions and, thus, potential sites for stabilizing mutations. Possible approaches to stabilization include improvement of hydrophobic packing interactions in the lid domain and introduction of new salt bridges into β-sheet 1 and the heme region. An understanding of the molecular factors behind the loss of stability of P450 BM3 variants therefore expedites site-directed mutagenesis studies aimed at developing thermostability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design of Planarizing Growth Conditions on Unpolished and Faceted (100)-Oriented GaAs Substrates Using Hydride Vapor Phase Epitaxy

Here we performed a design of experiments (DoE) analysis to determine the effect of various growth parameters on in situ planarizing overgrowth of rough substrates using hydride vapor phase epitaxy (HVPE). We used two types of rough (100)-oriented GaAs substrates to compare the effect of the initial morphology on the epitaxial growth behavior: an irregular, as-cut surface resultant from cutting the wafer from a GaAs boule and a regularly faceted surface produced by controlled spalling. The DoE analysis identified trends in the overgrowth behavior with changing growth conditions, and we used these trends to design favorable planarization growth conditions for each surface type. These favorable conditions enabled full planarization of a spalled surface with >2.5 um facet height within 10.8 min of growth. The root mean squared (RMS) surface roughness of the resulting (100) surface was 24.5 nm over a 286 um x 215 um area. Our results show that planarization growth by HVPE is a promising technique to enable device growth directly on rough substrates, and the trends revealed through DoE analysis indicate a path toward further optimization of planarization growth conditions for as-cut and spalled surfaces.

14 SOLAR ENERGY↗

Substrate-Mediated Evaporation and Stochastic Evolution of Supported Au Nanoparticles

Here, we use in situ transmission electron microscopy with automated tracking to study supported gold nanoparticles (NPs) during high-temperature vacuum annealing. The average mass loss per NP is governed by a flat, nearly size-independent substrate-mediated evaporation profile. On top of this mean shrinkage, individual NPs show significant fluctuations in apparent growth or shrinkage, and NP volume follows a random-walk-like trajectory. To rationalize both the ensemble-mean behavior and the particle-resolved variability, we develop a self-consistent theory that couples substrate-mediated evaporation to collective 2D Ostwald-type mass exchange through a shared adatom field, described in terms of a renormalized screening length and background concentration. In the experimentally relevant regime, the theory predicts an approximately size-independent mean shrinkage rate and clarifies how net mass loss suppresses classical coarsening. Superimposed on this deterministic drift, we quantify stochastic volume trajectories and capture their fluctuation spectrum with a minimal Langevin description consistent with intermittent adatom attachment and detachment events. In addition, we characterize the lateral diffusive motion of NPs, which is responsible for their coalescence. Altogether, our results highlight that stochasticity is intrinsic at the nanoscale and that predicting the evolution of supported NPs at early and intermediate times requires a unified framework combining substrate-mediated evaporation, collective mass exchange, and stochastic fluctuations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Two-Dimensional Titanium Carbide (MXene) as Surface-Enhanced Raman Scattering Substrate

Here, noble metal (gold or silver) nanoparticles or patterned films are typically used as substrates for surface-enhanced Raman spectroscopy (SERS). Two-dimensional (2D) carbides and nitrides (MXenes) exhibit unique electronic and optical properties, including metallic conductivity and plasmon resonance in the visible or near-infrared range, making them promising candidates for a wide variety of applications. Herein, we show that 2D titanium carbide, Ti 3 C 2 T x , enhances Raman signal from organic dyes on a substrate and in solution. As a proof of concept, MXene SERS substrates were manufactured by spray-coating and used to detect several common dyes, with calculated enhancement factors reaching ~10 6 . Titanium carbide MXene demonstrates SERS effect in aqueous colloidal solutions, suggesting the potential for biomedical or environmental applications, where MXene can selectively enhance positively charged molecules.

36 MATERIALS SCIENCE↗

A Single Layer of MoS 2 Activates Gold for Room Temperature CO Oxidation on an Inert Silica Substrate

Here, we demonstrate the facile deposition of catalytically active stable Au nanoparticles on single-layer MoS 2 , on an inert oxide substrate (SiO 2 ). Unlike a gold surface, adsorption of CO on these gold particles proceeds even at room temperature. Subsequent exposure to oxygen leads to CO 2 formation and desorption along a reaction pathway described, in detail, by density functional theory. The barrier to CO oxidation, along this pathway, is less than 300 meV, corroborating the facile nature of the CO oxidation reactions in this system. X-ray photoelectron spectroscopy directly reveals that the carbon monoxide, adsorbed on Au nanoparticles on single-layer MoS 2 , can be repeatedly titrated off the substrate by exposure to oxygen. Comparison of computational results assuming a defect-laden and pristine MoS 2 substrate suggest that the pristine single-layer material may be superior in supporting this reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗