The Critical Role of Water at the Gold-titania Interface in Catalytic CO Oxidation

We provide direct evidence of a water-mediated reaction mechanism for room-temperature CO oxidation over Au/TiO2 catalysts. A hydrogen/deuterium kinetic isotope effect of nearly 2 implicates O-H(D) bond breaking in the rate-determining step. Kinetics and in situ infrared spectroscopy experiments showed that the coverage of weakly adsorbed water on TiO2 largely determines catalyst activity by changing the number of active sites. Density functional theory calculations indicated that proton transfer at the metal-support interface facilitates O2 binding and activation; the resulting Au-OOH species readily reacts with adsorbed Au-CO, yielding Au-COOH. Au-COOH decomposition involves proton transfer to water and was suggested to be rate determining. These results provide a unified explanation to disparate literature results, clearly defining the mechanistic roles of water, support OH groups, and the metal-support interface

NaBr Poisoning of Au/TiO\u3csub\u3e2\u3c/sub\u3e Catalysts: Effects on Kinetics, Poisoning Mechanism, and Estimation of the Number of Catalytic Active Sites

Sodium bromide was used to intentionally poison a commercial Au/TiO2 catalyst with the goals of understanding the nature of halide poisoning and evaluating the number and nature of the catalytic active sites. A series of eight poisoned catalysts were prepared by impregnating the parent catalyst with methanolic solutions of NaBr. Each catalyst was tested with CO oxidation catalysis under differential reactor conditions; O2 reaction orders and Arrhenius activation energies were determined for each material. All of the kinetic data, including a Michaelis−Menten analysis, indicated that the primary effect of adding NaBr was to reduce the number of catalytically active sites. Density functional theory calculations, employed to evaluate likely binding sites for NaBr, showed that NaBr binds more strongly to Au corner and edge atoms than it does to the titania support or to exposed Au face atoms. Infrared spectroscopy of adsorbed CO, along with a Temkin analysis of the data, was also used to evaluate changes to the catalyst upon NaBr deposition. These studies suggested that NaBr addition induces some subtle changes in the coverage dependent properties of CO adsorption, but that these did not substantially impact the CO coverage of the CO binding sites. The experimental and computational results are discussed in terms of possible poisoning mechanisms (siteblocking vs off-site binding and modification); the nature and number of active sites are also discussed in the context of the results

H\u3csub\u3e2\u3c/sub\u3e Oxidation Over Supported Au Nanoparticle Catalysts: Evidence for Heterolytic H\u3csub\u3e2\u3c/sub\u3e Activation at the Metal-Support Interface

Water adsorbed at the metal-support interface (MSI) plays an important role in multiple reactions. Due to its importance in CO preferential oxidation (PrOx), we examined H2 oxidation kinetics in the presence of water over Au/TiO2 and Au/Al2O3 catalysts, reaching the following mechanistic conclusions: (i) O2 activation follows a similar mechanism to that proposed in CO oxidation catalysis; (ii) weakly adsorbed H2O is a strong reaction inhibitor; (iii) fast H2 activation occurs at the MSI, and (iv) H2 activation kinetics are inconsistent with traditional dissociative H2 chemisorption on metals. Density function theory (DFT) calculations using a supported Au nanorod model suggest H2 activation proceeds through a heterolytic dissociation mechanism, resulting in a formal hydride residing on the Au and a proton bound to a surface TiOH group. This potential mechanism was supported by infrared spectroscopy experiments during H2 adsorption on a deuterated Au/TiO2 surface, which showed rapid H-D scrambling with surface hydroxyl groups. DFT calculations suggest that the reaction proceeds largely through proton-mediated pathways and that typical Brønstednsted-Evans Polanyi behavior is broken by introducing weak acid/base sites at the MSI. THe kinetics data were successfully reinterpreted in the context of the heterolytic H2 activation mechanism, tying together the experimental and computational evidence and rationalizing the observed inhibition by physiorbed water on the support as blocking the MSI sites required for heterolytic H2 activation. In addition to providing evidence for the unusual H2 activation mechanism, these results offer additional insight into why water dramatically improves CO PrOx catalysis over Au

Stacked but not Stuck: Unveiling the Role of π→π* Interactions with the Help of the Benzofuran–Formaldehyde Complex

The 1:1 benzofuran–formaldehyde complex has been chosen as model system for analyzing π→π* interactions in supramolecular organizations involving heteroaromatic rings and carbonyl groups. A joint “rotational spectroscopy–quantum chemistry” strategy unveiled the dominant role of π→π* interactions in tuning the intermolecular interactions of such adduct. The exploration of the intermolecular potential energy surface led to the identification of 14 low-energy minima, with 4 stacked isomers being more stable than those linked by hydrogen bond or lone-pair→π interactions. All energy minima are separated by loose transition states, thus suggesting an effective relaxation to the global minimum under the experimental conditions. This expectation has been confirmed by the experimental detection of only one species, which was unambiguously assigned owing to the computation of accurate spectroscopic parameters and the characterization of 11 isotopologues. The large number of isotopic species opened the way to the determination of the first semi-experimental equilibrium structure for a molecular complex of such a dimension

The planarity of the stickface motion in the field hockey hit

The field hockey hit is an important but poorly understood stroke. This study investigated the planarity of the stickface motion during the downswing, in order to better characterise the kinematics and to assess the suitability of planar pendulum models for simulating the hit. Thirteen experienced female field hockey players were filmed executing hits with a single approach step, and the kinematics of the centre of the stickface were measured. A method was developed for identifying how far back from impact the stickface motion was planar. Orthogonal least-squares regression was used to determine best-fit planes for sections of the stickface path of varying length, each of which ended at impact, and these sections were considered planar if the mean residual between the stickface path and the fitted plane was less than 0.25% of the distance traveled by the stickface during that period. On average the stickface motion was planar for the last 83±12% of its downswing path, with the length of the planar section ranging from 1.85 m to 2.70 m. The suitability of a planar model for the stickface motion was supported, but further investigation of the stick and arm kinematics is warranted

The planarity of the stickface motion in the field hockey hit

The field hockey hit is an important but poorly understood stroke. This study investigated the planarity of the stickface motion during the downswing, in order to better characterise the kinematics and to assess the suitability of planar pendulum models for simulating the hit. Thirteen experienced female field hockey players were filmed executing hits with a single approach step, and the kinematics of the centre of the stickface were measured. A method was developed for identifying how far back from impact the stickface motion was planar. Orthogonal least-squares regression was used to determine best-fit planes for sections of the stickface path of varying length, each of which ended at impact, and these sections were considered planar if the mean residual between the stickface path and the fitted plane was less than 0.25% of the distance traveled by the stickface during that period. On average the stickface motion was planar for the last 83±12% of its downswing path, with the length of the planar section ranging from 1.85 m to 2.70 m. The suitability of a planar model for the stickface motion was supported, but further investigation of the stick and arm kinematics is warranted

Search for corannulene (C20H10) in the Red Rectangle

Polycyclic Aromatic Hydrocarbons (PAHs) are widely accepted as the carriers of the Aromatic Infrared Bands (AIBs), but an unambiguous identification of any specific interstellar PAH is still missing. For polar PAHs, pure rotational transitions can be used as spectral fingerprints for identification. Combining dedicated experiments, detailed simulations and observations, we explore d the mm wavelength domain to search for specific rotational transitions of corannulene (C20H10). We performed high-resolution spectroscopic measurements and a simulation of the emission spectrum of ultraviolet-excited C20H10 in the environment of the Red Rectangle (RR), calculating its synthetic rotational spectrum. Based on these results, we conducted a first observational campaign at the IRAM 30-m telescope towards this source to search for several high-J rotational transitions of C20H10. The laboratory detection of the J = 112 ← 111 transition of corannulene showed that no centrifugal splitting is present up to this line. Observations with the IRAM 30-m telescope towards the RR do not show any corannulene emission at any of the observed frequencies, down to a rms noise level of Tmb= 8 mK for the J =135 → 134 transition at 137.615 GHz. Comparing the noise level with the synthetic spectrum, we are able to estimate an upper limit to the fraction of carbon locked in corannulene of about 1.0 × 10−5 relative to the total abundance of carbon in PAHs. The sensitivity achieved in this work shows that radio spectroscopy can be a powerful tool to search for polar PAHs. We compare this upper limit with models for the PAH size distribution, emphasizing that small PAHs are much less abundant than predicted. We show that this cannot be explained by destruction but is more likely related to the chemistry of their formation in the environment of the R

Discovering universal statistical laws of complex networks

Different network models have been suggested for the topology underlying complex interactions in natural systems. These models are aimed at replicating specific statistical features encountered in real-world networks. However, it is rarely considered to which degree the results obtained for one particular network class can be extrapolated to real-world networks. We address this issue by comparing different classical and more recently developed network models with respect to their generalisation power, which we identify with large structural variability and absence of constraints imposed by the construction scheme. After having identified the most variable networks, we address the issue of which constraints are common to all network classes and are thus suitable candidates for being generic statistical laws of complex networks. In fact, we find that generic, not model-related dependencies between different network characteristics do exist. This allows, for instance, to infer global features from local ones using regression models trained on networks with high generalisation power. Our results confirm and extend previous findings regarding the synchronisation properties of neural networks. Our method seems especially relevant for large networks, which are difficult to map completely, like the neural networks in the brain. The structure of such large networks cannot be fully sampled with the present technology. Our approach provides a method to estimate global properties of under-sampled networks with good approximation. Finally, we demonstrate on three different data sets (C. elegans' neuronal network, R. prowazekii's metabolic network, and a network of synonyms extracted from Roget's Thesaurus) that real-world networks have statistical relations compatible with those obtained using regression models

Genetic Studies of Sulfadiazine-resistant and Methionine-requiring \u3cem\u3eNeisseria\u3c/em\u3e Isolated From Clinical Material

Deoxyribonucleate (DNA) preparations were extracted from Neisseria meningitidis (four isolates from spinal fluid and blood) and N. gonorrhoeae strains, all of which were resistant to sulfadiazine upon primary isolation. These DNA preparations, together with others from in vitro mutants of N. meningitidis and N. perflava, were examined in transformation tests by using as recipient a drug-susceptible strain of N. meningitidis (Ne 15 Sul-s Met+) which was able to grow in a methionine-free defined medium. The sulfadiazine resistance typical of each donor was introduced into the uniform constitution of this recipient. Production of p-aminobenzoic acid was not significantly altered thereby. Transformants elicited by DNA from the N. meningitidis clinical isolates were resistant to at least 200 μg of sulfadiazine/ml, and did not show a requirement for methionine (Sul-r Met+). DNA from six strains of N. gonorrhoeae, which were isolated during the period of therapeutic use of sulfonamides, conveyed lower degrees of resistance and, invariably, a concurrent methionine requirement (Sul-r/Met−). The requirement of these transformants, and that of in vitro mutants selected on sulfadiazine-agar, was satisfied by methionine, but not by vitamin B12, homocysteine, cystathionine, homoserine, or cysteine. Sul-r Met+ and Sul-r/Met− loci could coexist in the same genome, but were segregated during transformation. On the other hand, the dual Sul-r/Met− properties were not separated by recombination, but were eliminated together. DNA from various Sul-r/Met− clones tested against recipients having nonidentical Sul-r/Met− mutant sites yielded Sul-s Met+ transformants. The met locus involved is genetically complex, and will be a valuable tool for studies of genetic fine structure of members of Neisseria, and of genetic homology between species

Thermodynamic Behavior of a Model Covalent Material Described by the Environment-Dependent Interatomic Potential

Using molecular dynamics simulations we study the thermodynamic behavior of a single-component covalent material described by the recently proposed Environment-Dependent Interatomic Potential (EDIP). The parameterization of EDIP for silicon exhibits a range of unusual properties typically found in more complex materials, such as the existence of two structurally distinct disordered phases, a density decrease upon melting of the low-temperature amorphous phase, and negative thermal expansion coefficients for both the crystal (at high temperatures) and the amorphous phase (at all temperatures). Structural differences between the two disordered phases also lead to a first-order transition between them, which suggests the existence of a second critical point, as is believed to exist for amorphous forms of frozen water. For EDIP-Si, however, the unusual behavior is associated not only with the open nature of tetrahedral bonding but also with a competition between four-fold (covalent) and five-fold (metallic) coordination. The unusual behavior of the model and its unique ability to simulation the liquid/amorphous transition on molecular-dynamics time scales make it a suitable prototype for fundamental studies of anomalous thermodynamics in disordeered systems.Comment: 48 pages (double-spaced), 13 figure