A kinetic analysis methodology to elucidate the roles of metal, support and solvent for the hydrogenation of 4-phenyl-2-butanone over Pt/TiO<inf>2</inf>

The rate and, more importantly, selectivity (ketone vs aromatic ring) of the hydrogenation of 4-phenyl-2-butanone over a Pt/TiO₂ catalyst have been shown to vary with solvent. In this study, a fundamental kinetic model for this multi-phase reaction has been developed incorporating statistical analysis methods to strengthen the foundations of mechanistically sound kinetic models. A 2-site model was determined to be most appropriate, describing aromatic hydrogenation (postulated to be over a platinum site) and ketone hydrogenation (postulated to be at the platinum–titania interface). Solvent choice has little impact on the ketone hydrogenation rate constant but strongly impacts aromatic hydrogenation due to solvent-catalyst interaction. Reaction selectivity is also correlated to a fitted product adsorption constant parameter. The kinetic analysis method shown has demonstrated the role of solvents in influencing reactant adsorption and reaction selectivity.We acknowledge EPSRC for funding as part of the CASTech grant (EP/G011397/1) and the Department of Employment and Learning for a studentship (IM). NSB was funded by a PhD scholarship from the University of Birmingham. SKW was supported by an Engineering Doctorate Studentship in Formulation Engineering at the University of Birmingham sponsored by the EPSRC (EP/G036713/1) and Johnson Matthey.This is the final version of the article. It was first available from Elsevier via http://dx.doi.org/10.1016/j.jcat.2015.06.00

Effect of solvent on the hydrogenation of 4-phenyl-2-butanone over Pt based catalysts

In part I of this study, experimental data were presented for the hydrogenation of 4-phenyl-2-butanone with a 4% Pt/TiO2 catalyst where the reaction rate and selectivity (ketone vs. aromatic ring) varied with solvent. In this paper, a rigorous kinetic model is presented utilising these data, incorporating statistical analysis methods to strengthen the foundations of mechanistically sound kinetic models. A fundamental kinetic model for the system is presented and a 2-site model was determined to be most appropriate, describing aromatic hydrogenation (postulated to be over a platinum site) and ketone hydrogenation (at the platinum titania interface). Solvent choice has little impact on the ketone hydrogenation rate constant but strongly impacts aromatic hydrogenation due to solvent-catalyst interaction. Reaction selectivity is also correlated to a fitted product adsorption constant parameter. This kinetic analysis method is the first of its kind demonstrating the role of solvents in influencing reactant adsorption and reaction selectivity.We acknowledge EPSRC for funding as part of the CASTech grant (EP/G011397/1) and the Department of Employment and Learning for a studentship (IM). NSB was funded by a PhD scholarship from the University of Birmingham. SKW was supported by an Engineering Doctorate Studentship in Formulation Engineering at the University of Birmingham sponsored by the EPSRC (EP/G036713/1) and Johnson Matthey.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.jcat.2015.06.00

The Effect of Diet Quality and Wing Morph on Male and Female Reproductive Investment in a Nuptial Feeding Ground Cricket

A common approach in the study of life-history trade-off evolution is to manipulate the nutrient content of diets during the life of an individual in order observe how the acquisition of resources influences the relationship between reproduction, lifespan and other life-history parameters such as dispersal. Here, we manipulate the quality of diet that replicate laboratory populations received as a thorough test of how diet quality influences the life-history trade-offs associated with reproductive investment in a nuptial feeding Australian ground cricket (Pteronemobius sp.). In this species, both males and females make significant contributions to the production of offspring, as males provide a nuptial gift by allowing females to chew on a modified tibial spur during copulation and feed directing on their haemolymph. Individuals also have two distinct wing morphs, a short-winged flightless morph and a long-winged morph that has the ability to disperse. By manipulating the quality of diet over seven generations, we found that the reproductive investment of males and females were affected differently by the diet quality treatment and wing morph of the individual. We discuss the broader implications of these findings including the differences in how males and females balance current and future reproductive effort in nuptial feeding insects, the changing nature of sexual selection when diets vary, and how the life-history trade-offs associated with the ability to disperse are expected to differ among populations

Deconstructing Conformal Blocks in 4D CFT

We show how conformal partial waves (or conformal blocks) of spinor/tensor correlators can be related to each other by means of differential operators in four dimensional conformal field theories. We explicitly construct such differential operators for all possible conformal partial waves associated to four-point functions of arbitrary traceless symmetric operators. Our method allows any conformal partial wave to be extracted from a few \u201cseed\u201d correlators, simplifying dramatically the computation needed to bootstrap tensor correlators. \ua9 2015, The Author(s)

Moderate Multiple Parentage and Low Genetic Variation Reduces the Potential for Genetic Incompatibility Avoidance Despite High Risk of Inbreeding

Background: Polyandry is widespread throughout the animal kingdom. In the absence of direct benefits of mating with different males, the underlying basis for polyandry is enigmatic because it can carry considerable costs such as elevated exposure to sexual diseases, physical injury or other direct fitness costs. Such costs may be balanced by indirect genetic benefits to the offspring of polyandrous females. We investigated polyandry and patterns of parentage in the spider Stegodyphus lineatus. This species experiences relatively high levels of inbreeding as a result of its spatial population structure, philopatry and limited male mating dispersal. Polyandry may provide an opportunity for post mating inbreeding avoidance that reduces the risk of genetic incompatibilities arising from incestuous matings. However, multiple mating carries direct fitness costs to females suggesting that genetic benefits must be substantial to counter direct costs. Methodology/Principal Findings: Genetic parentage analyses in two populations from Israel and a Greek island, showed mixed-brood parentage in approximately 50 % of the broods. The number of fathers ranged from 1–2 indicating low levels of multiple parentage and there was no evidence for paternity bias in mixed-broods from both populations. Microsatellite loci variation suggested limited genetic variation within populations, especially in the Greek island population. Relatedness estimates among females in the maternal generation and potentially interacting individuals were substantial indicating fullsib and half-sib relationships

Immune-Mobilizing Monoclonal T Cell Receptors Mediate Specific and Rapid Elimination of Hepatitis B-Infected Cells

Background and Aims: Therapies for chronic hepatitis B virus (HBV) infection are urgently needed because of viral integration, persistence of viral antigen expression, inadequate HBV‐specific immune responses, and treatment regimens that require lifelong adherence to suppress the virus. Immune mobilizing monoclonal T Cell receptors against virus (ImmTAV) molecules represent a therapeutic strategy combining an affinity‐enhanced T Cell receptor with an anti‐CD3 T Cell‐activating moiety. This bispecific fusion protein redirects T cells to specifically lyse infected cells expressing the target virus‐derived peptides presented by human leukocyte antigen (HLA). Approach and Results: ImmTAV molecules specific for HLA‐A*02:01‐restricted epitopes from HBV envelope, polymerase, and core antigens were engineered. The ability of ImmTAV‐Env to activate and redirect polyclonal T cells toward cells containing integrated HBV and cells infected with HBV was assessed using cytokine secretion assays and imaging‐based killing assays. Elimination of infected cells was further quantified using a modified fluorescent hybridization of viral RNA assay. Here, we demonstrate that picomolar concentrations of ImmTAV‐Env can redirect T cells from healthy and HBV‐infected donors toward hepatocellular carcinoma (HCC) cells containing integrated HBV DNA resulting in cytokine release, which could be suppressed by the addition of a corticosteroid in vitro. Importantly, ImmTAV‐Env redirection of T cells induced cytolysis of antigen‐positive HCC cells and cells infected with HBV in vitro, causing a reduction of hepatitis B e antigen and specific loss of cells expressing viral RNA. Conclusions: The ImmTAV platform has the potential to enable the elimination of infected cells by redirecting endogenous non‐HBV‐specific T cells, bypassing exhausted HBV‐specific T cells. This represents a promising therapeutic option in the treatment of chronic hepatitis B, with our lead candidate now entering trials

All-mass n-gon integrals in n dimensions

We explore the correspondence between one-loop Feynman integrals and (hyperbolic) simplicial geometry to describe the "all-mass" case: integrals with generic external and internal masses. Specifically, we focus on $n$-particle integrals in exactly $n$ space-time dimensions, as these integrals have particularly nice geometric properties and respect a dual conformal symmetry. In four dimensions, we leverage this geometric connection to give a concise dilogarithmic expression for the all-mass box in terms of the Murakami-Yano formula. In five dimensions, we use a generalized Gauss-Bonnet theorem to derive a similar dilogarithmic expression for the all-mass pentagon. We also use the Schl\"afli formula to write down the symbol of these integrals for all $n$. Finally, we discuss how the geometry behind these formulas depends on space-time signature, and we gather together many results related to these integrals from the mathematics and physics literature.Comment: 49 pages, 8 figure

All You Can Eat: High Performance Capacity and Plasticity in the Common Big-Eared Bat, Micronycteris microtis (Chiroptera: Phyllostomidae)

Ecological specialization and resource partitioning are expected to be particularly high in the species-rich communities of tropical vertebrates, yet many species have broader ecological niches than expected. In Neotropical ecosystems, Neotropical leaf-nosed bats (Phyllostomidae) are one of the most ecologically and functionally diverse vertebrate clades. Resource partitioning in phyllostomids might be achieved through differences in the ability to find and process food. We selected Micronycteris microtis, a very small (5–7 g) animalivorous phyllostomid, to explore whether broad resource use is associated with specific morphological, behavioral and performance traits within the phyllostomid radiation. We documented processing of natural prey and measured bite force in free-ranging M. microtis and other sympatric phyllostomids. We found that M. microtis had a remarkably broad diet for prey size and hardness. For the first time, we also report the consumption of vertebrates (lizards), which makes M. microtis the smallest carnivorous bat reported to date. Compared to other phyllostomids, M. microtis had the highest bite force for its size and cranial shape and high performance plasticity. Bite force and cranial shape appear to have evolved rapidly in the M. microtis lineage. High performance capacity and high efficiency in finding motionless prey might be key traits that allow M. microtis, and perhaps other species, to successfully co-exist with other gleaning bats