Nickel-Catalyzed Mizoroki-Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products

Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel-catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, whereas the appropriate base suppressed alkene isomerization of the product. Although aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that, by using triethylsilyl trifluoromethanesulfonate, we can effect a counterion exchange of the catalytic nickel complex, such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity.National Institute of General Medical Sciences (U.S.) (NIGMS (GM62755))National Institutes of Health (U.S.) (NIH Postdoctoral Fellowship)National Science Foundation (U.S.) (NSF Graduate Research Fellowship

Magnetism and half-metallicity at the O surfaces of ceramic oxides

The occurence of spin-polarization at ZrO$_{2}$, Al$_{2}$O$_{3}$ and MgO surfaces is proved by means of \textit{ab-initio} calculations within the density functional theory. Large spin moments, as high as 1.56 $\mu_B$, develop at O-ended polar terminations, transforming the non-magnetic insulator into a half-metal. The magnetic moments mainly reside in the surface oxygen atoms and their origin is related to the existence of $2p$ holes of well-defined spin polarization at the valence band of the ionic oxide. The direct relation between magnetization and local loss of donor charge makes possible to extend the magnetization mechanism beyond surface properties

Star Formation in Disk Galaxies. I. Formation and Evolution of Giant Molecular Clouds via Gravitational Instability and Cloud Collisions

We investigate the formation and evolution of giant molecular clouds (GMCs) in a Milky-Way-like disk galaxy with a flat rotation curve. We perform a series of 3D adaptive mesh refinement (AMR) numerical simulations that follow both the global evolution on scales of ~20kpc and resolve down to scales ~<10pc with a multiphase atomic interstellar medium (ISM). In this first study, we omit star formation and feedback, and focus on the processes of gravitational instability and cloud collisions and interactions. We define clouds as regions with n_H>=100cm^-3 and track the evolution of individual clouds as they orbit through the galaxy from their birth to their eventual destruction via merger or via destructive collision with another cloud. After ~140Myr a large fraction of the gas in the disk has fragmented into clouds with masses ~10^6 Msun and a mass spectrum similar to that of Galactic GMCs. The disk settles into a quasi steady state in which gravitational scattering of clouds keeps the disk near the threshold of global gravitational instability. The cloud collision time is found to be a small fraction, ~1/5, of the orbital time, and this is an efficient mechanism to inject turbulence into the clouds. This helps to keep clouds only moderately gravitationally bound, with virial parameters of order unity. Many other observed GMC properties, such as mass surface density, angular momentum, velocity dispersion, and vertical distribution, can be accounted for in this simple model with no stellar feedback.Comment: 21 pages ApJ format, including 16 figures, accepted to Ap

Value co-creation in the delivery of outcome-based contracts for business-to-business service

Working paperThis study introduces the concept of outcome-based contracting (OBC) as the mechanism for firms to focus on delivering value-in-use, and as the driver for value co-creation as the firm would need to jointly deliver outcomes with the customer. The paper analyses two OBC-type contracts between the UK Ministry of Defence and two of its industrial partners. We find that in delivering to outcomes and achieving value-in-use, the state-dependent nature of value in usage „pushes back‟ into the organization, requiring the firm to re-evaluate the way they are structured to receive changes from customer state-dependencies so as to deliver a better service. Our analysis presents seven generic attributes of value co-creation (AVCs) essential for the capability to deliver value-in-use. These are behavioral alignment, process alignment, congruence in customer expectations, congruence in firm expectations, empowerment and perceived control, behavioral transformation, and complementary competencies. The attributes discovered through qualitative data were matched with previous academic literature and operationalized and a measurement instrument was developed. The instrument was then validated by performing an exploratory and second order confirmatory factor analysis.This research was made possible through the joint funding of the Engineering & Physical Science Research Council (UK) and BAE Systems on the Support Service Solutions: Strategy & Transition (S4T) project consortium led by the University of Cambridge. The authors gratefully acknowledge the staff of BAE Systems and MBDA as well as members of the ADAPT IPT, 16th Regiment, ATTAC IPT, MoD and the RAF who have all contributed substantially towards this research

A comparative DFT study of electronic properties of 2H-, 4H- and 6H-SiC(0001) and SiC(000-1) clean surfaces: Significance of the surface Stark effect

Electric field, uniform within the slab, emerging due to Fermi level pinning at its both sides is analyzed using DFT simulations of the SiC surface slabs of different thickness. It is shown that for thicker slab the field is nonuniform and this fact is related to the surface state charge. Using the electron density and potential profiles it is proved that for high precision simulations it is necessary to take into account enough number of the Si-C layers. We show that using 12 diatomic layers leads to satisfactory results. It is also demonstrated that the change of the opposite side slab termination, both by different type of atoms or by their location, can be used to adjust electric field within the slab, creating a tool for simulation of surface properties, depending on the doping in the bulk of semiconductor. Using these simulations it was found that, depending on the electric field, the energy of the surface states changes in a different way than energy of the bulk states. This criterion can be used to distinguish Shockley and Tamm surface states. The electronic properties, i.e. energy and type of surface states of the three clean surfaces: 2H-, 4H-, 6H-SiC(0001), and SiC($000 \bar{1}$) are analyzed and compared using field dependent DFT simulations.Comment: 18 pages, 10 figures, 4 table

Follow-up monitoring in a cat with leishmaniosis and coinfections with Hepatozoon felis and ‘Candidatus Mycoplasma haemominutum’

Case summary A 6-year-old female neutered domestic shorthair cat from Cyprus was presented with multiple ulcerated skin nodules. Cytology and histopathology of the lesions revealed granulomatous dermatitis with intracytoplasmic organisms, consistent with amastigotes of Leishmania species. Biochemistry identified a mild hyperproteinaemia. Blood extraction and PCR detected Leishmania species, Hepatozoon species and ‘Candidatus Mycoplasma haemominutum’ (CMhm) DNA. Subsequent sequencing identified Hepatozoon felis. Additionally, the rRNA internal transcribed spacer 1 locus of Leishmania infantum was partially sequenced and phylogeny showed it to cluster with species derived from dogs in Italy and Uzbekistan, and a human in France. Allopurinol treatment was administered for 6 months. Clinical signs resolved in the second month of treatment with no deterioration 8 months post-treatment cessation. Quantitative PCR and ELISA were used to monitor L infantum blood DNA and antibody levels. The cat had high L infantum DNA levels pretreatment that gradually declined during treatment but increased 8 months post-treatment cessation. Similarly, ELISA revealed high levels of antibodies pretreatment, which gradually declined during treatment and increased slightly 8 months post-treatment cessation. The cat remained PCR positive for CMhm and Hepatozoon species throughout the study. There was no clinical evidence of relapse 24 months post-treatment. Relevance and novel information To our knowledge, this is the first clinical report of a cat with leishmaniosis with H felis and CMhm coinfections. The high L infantum DNA levels post-treatment cessation might indicate that although the lesions had resolved, prolonged or an alternative treatment could have been considere