On the importance of steady-state isotopic techniques for the investigation of the mechanism of the reverse water-gas-shift reaction

The formation and reactivity of surface intermediates in the reverse water-gas-shift reaction on a Pt/CeO2 catalyst are critically dependent on the reaction conditions so that conclusionsregarding the reaction mechanism cannot be inferred using ex operando conditions.

Electron collisions with Fe-peak elements: Forbidden transitions between the low lying valence states 3d6, 3d54s, and 3d54p of Fe III:

Effective collision strengths are presented for the Fe-peak element Fe III at electron temperatures (Te in degrees Kelvin) in the range 2 × 103 to 1 × 106. Forbidden transitions results are given between the 3d6, 3d54s, and the 3d54p manifolds applicable to the modeling of laboratory and astrophysical plasmas.

BRCA1 and c-Myc Associate to Transcriptionally Repress Psoriasin, a DNA Damage-Inducible Gene

Evidence is accumulating to suggest that some of the diverse functions associated with BRCA1 may relate to its ability to transcriptionally regulate key downstream target genes. Here, we identify S100A7 (psoriasin), S100A8, and S100A9, members of the S100A family of calcium-binding proteins, as novel BRCA1-repressed targets. We show that functional BRCA1 is required for repression of these family members and that a BRCA1 disease–associated mutation abrogates BRCA1-mediated repression of psoriasin. Furthermore, we show that BRCA1 and c-Myc form a complex on the psoriasin promoter and that BRCA1-mediated repression of psoriasin is dependent on functional c-Myc. Finally, we show that psoriasin expression is induced by the topoisomerase IIA poison, etoposide, in the absence of functional BRCA1 and increased psoriasin expression enhances cellular sensitivity to this chemotherapeutic agent. Therefore, we identified a novel transcriptional mechanism that is likely to contribute to BRCA1-mediated resistance to etoposide.

Bimetallic effects in the liquid phase hydrogenation of 2-butanone

A series of bimetallic Ru-containing monometallic and bimetallic catalysts were prepared and tested for their activity for the hydrogenation of 2-butanone to 2-butanol at 30 °C and 3 bar H2. RuPt bimetallic catalysts were the most active for the reaction, with a ratio of 5 wt% Ru:1 wt% Pt on activated carbon (AC) found to be optimum. The activity of this bimetallic catalyst was more than double that of the sum of the activities of the monometallic Ru and Pt catalysts, providing evidence of a “bimetallic” effect. Structural analysis of the bimetallic catalysts revealed that they consisted of clusters of particles of the order of 1–2 nm. Extended X-ray absorption fine structure analysis showed that there were two types of particle on the surface of the bimetallic RuPt catalyst, specifically monometallic Ru and bimetallic RuPt particles. For the bimetallic particles, it was possible to fit the data with a model in which a Ru core of 1.1 nm is enclosed by two Pt-rich layers, the outer layer containing only 13 at% Ru. Pretreatment of the monometallic and bimetallic catalysts in hydrogen had a significant effect on the activity. Both the bimetallic and monometallic Ru-based catalysts showed a trend of decreasing activity with increasing temperature of prereduction in hydrogen. This loss of activity was almost fully reversible by exposure of the catalysts to air after reduction. The changing activity with exposure to different gas phase environments could not be attributed to changes in particle size or surface composition. It is proposed that the introduction of hydrogen results in a gradual smoothing of the surface and loss of defect sites; this process being reversible on introduction of air. These defect sites are particularly important for the dissociative adsorption of hydrogen, potentially the rate-determining step in this reaction.

Three primary kinetic characteristics observed in a pulse-response TAP experiment

The state-by-state transient screening approach based on a pulse-response thin-zone TAP experiment is further developed whereby single-pulse kinetic tests are treated as small perturbations to catalyst compositions and analyzed using integral method of moments. Results on three primary kinetic characteristics, termed basic kinetic coefficients, are presented. These three coefficients were introduced as main observables from experimentally measured TAP-responses in a kinetic-model-free manner. Each was analytically determined from moments of responses with no assumption about the detailed kinetic model. In this paper, the inverse question of how well these coefficients represent the time evolution of the observed responses is addressed. Sets of three basic kinetic coefficients are calculated from model and experimental responses and these calculated values are used to generate 3-coefficient curves in a kinetic-model-free manner. The comparison of these 3-coefficient curves with original responses shows that three basic kinetic coefficients can be sufficient to describe the observed kinetics of exit flow time dependencies with no assumption regarding the detailed kinetic model.

Risk adjustment for hospital use using social security data: cross sectional small area analysis

Objectives: To identify demographic and socioeconomic determinants of need for acute hospital treatment at small area level. To establish whether there is a relation between poverty and use of inpatient services. To devise a risk adjustment formula for distributing public funds for hospital services using, as far as possible, variables that can be updated between censuses. Design: Cross sectional analysis. Spatial interactive modelling was used to quantify the proximity of the population to health service facilities. Two stage weighted least squares regression was used to model use against supply of hospital and community services and a wide range of potential needs drivers including health, socioeconomic census variables, uptake of income support and family credit, and religious denomination. Setting: Northern Ireland. Main outcome measure: Intensity of use of inpatient services. Results: After endogeneity of supply and use was taken into account, a statistical model was produced that predicted use based on five variables: income support, family credit, elderly people living alone, all ages standardised mortality ratio, and low birth weight. The main effect of the formula produced is to move resources from urban to rural areas. Conclusions: This work has produced a population risk adjustment formula for acute hospital treatment in which four of the five variables can be updated annually rather than relying on census derived data. Inclusion of the social security data makes a substantial difference to the model and to the results produced by the formula.

Kassinakinin S: A novel histamine-releasing heptadecapeptide from frog (Kassina senegalensis) skin secretion

Amphibian defensive skin secretions remain a largely untapped resource for the peptide biochemist with an interest in the identification, structural characterization, and precursor cDNA cloning of novel bioactive peptides. Here we report the isolation, structural characterization, functional profiling, and nucleotide sequence of precursor cDNA of a novel histamine-releasing heptadecapeptide, FIPVTLLALHKIKEKLN-amide, from the defensive skin secretion of the African running frog, Kassina senegalensis. This peptide was found to be a potent histamine secretagogue (EC[5][0]=6 µM; maximal release = 25 µM) in a rat peritoneal mast cell model system and was accordingly named kassinakinin S. The open-reading frame of the cDNA encoding prepro-kassinakinin S was found to consist of 71 amino acid residues containing a single copy of kassinakinin S and its glycyl residue amide donor at the C-terminus. Kassinakinin S can thus be added to the growing list of amphibian skin bioactive peptide prototypes.