194 research outputs found
Synthesis and Applications of Rhodacyclopentanones Derived From C-C Bond Activation
Rhodacyclopentanones, an âsp(3)-richâ class of metallacycle, underpin an emerging range of catalytic methodologies for the direct generation of complex scaffolds. This review highlights strategies for accessing rhodacyclopentanones (and related species) by C-C bond activation of cyclobutanones or cyclopropanes. The scope and mechanism of methodologies that exploit these activation modes is outlined
Directed carbonylative (3+1+2) cycloadditions of amino-substituted cyclopropanes and alkynes: reaction development and increased efficiencies using a cationic rhodium system
AbstractUrea-directed carbonylative insertion of Rh(I)-catalysts into one of the two proximal CâC bonds of aminocyclopropanes generates rhodacyclopentanone intermediates. These are trapped by N-tethered alkynes to provide a (3+1+2) cycloaddition protocol that accesses N-heterobicyclic enones. Stoichiometric studies on a series of model rhodacyclopentanone complexes outline key structural features and provide a rationale for the efficacy of urea directing groups. A comprehensive evaluation of cycloaddition scope and a âsecond generationâ cationic Rh(I)-system, which provides enhanced yields and reaction rates for challenging substrates, are presented
Dichotomous mechanistic behaviour in Narasaka-Heck cyclizations: electron rich Pd-catalysts generate iminyl radicals
Pd-catalyzed cyclizations of oxime esters with pendant alkenes undergo ligand controlled mechanistic divergence. Electron deficient phosphines promote aza-Heck cyclization; electron rich systems favour a SET pathway. Mechanistic experiments differentiate the two manifolds.</p
Modular access to substituted azocanes via a rhodium-catalyzed cycloaddition-fragmentation strategy
A short entry to
substituted azocanes by a Rh-catalyzed cycloadditionâfragmentation
process is described. Specifically, exposure of diverse <i>N</i>-cyclopropylacrylamides to phosphine-ligated cationic RhÂ(I) catalyst
systems under a CO atmosphere enables the directed generation of rhodacyclopentanone
intermediates. Subsequent insertion of the alkene component is followed
by fragmentation to give the heterocyclic target. Stereochemical studies
show, for the first time, that alkene insertion into rhodacyclopentanones
can be reversible
LoCuSS: The Sunyaev-Zel'dovich Effect and Weak Lensing Mass Scaling Relation
We present the first weak-lensing-based scaling relation between galaxy
cluster mass, M_wl, and integrated Compton parameter Y_sph. Observations of 18
galaxy clusters at z~0.2 were obtained with the Subaru 8.2-m telescope and the
Sunyaev-Zel'dovich Array. The M_wl-Y_sph scaling relations, measured at
Delta=500, 1000, and 2500 rho_c, are consistent in slope and normalization with
previous results derived under the assumption of hydrostatic equilibrium (HSE).
We find an intrinsic scatter in M_wl at fixed Y_sph of 20%, larger than both
previous measurements of M_HSE-Y_sph scatter as well as the scatter in true
mass at fixed Y_sph found in simulations. Moreover, the scatter in our
lensing-based scaling relations is morphology dependent, with 30-40% larger
M_wl for undisturbed compared to disturbed clusters at the same Y_sph at r_500.
Further examination suggests that the segregation may be explained by the
inability of our spherical lens models to faithfully describe the
three-dimensional structure of the clusters, in particular, the structure along
the line-of-sight. We find that the ellipticity of the brightest cluster
galaxy, a proxy for halo orientation, correlates well with the offset in mass
from the mean scaling relation, which supports this picture. This provides
empirical evidence that line-of-sight projection effects are an important
systematic uncertainty in lensing-based scaling relations.Comment: Accepted versio
Survival of patients with newly diagnosed high-grade myeloid neoplasms who do not meet standard trial eligibility
Few patients with cancer, including those with acute myeloid leukemia and high-grade myeloid neoplasms, participate in clinical trials. Broadening standard eligibility criteria may increase clinical trial participation. In this retrospective single-center analysis, we identified 442 consecutive newly diagnosed patients from 2014 to 2016. Patients were considered eligible if they had performance status 0-2, normal renal and hepatic function, no recent solid tumor, left ventricular ejection fraction (EF) â„ 50%, and no history of congestive heart failure (CHF) or myocardial infarction (MI); ineligible patients failed to meet one or more of these criteria. We included 372 patients who received chemotherapy. Ineligible patients represented 40% of the population and had a 1-79-fold greater risk of death (95% CI 1.37, 2.33) than eligible patients. Very few patients had cardiac co-morbidities, including 2% with low EF, 4% with prior CHF, and 5% with prior MI. In multivariable analysis, ineligibility was associated with decreased survival [HR 1-44 (95% CI 1-07, 1-93)]. Allogeneic transplantation, performed in 150 patients (40%), was associated with improved survival [HR 0-66, 95% CI (0-48, 0-91)]. Therefore, standard eligibility characteristics identify a patient population with improved survival. Further treatment options are needed for patients considered ineligible for clinical trials
"We have no voice for that" : Land Rights, Power, and Gender in Rural Sierra Leone
Acknowledgements I wish to thank the participants in the Gender and Land Governance Conference at Utrecht University in January 2013 for helpful comments and suggestions. Funding I would like to thank the Faculty of Management at Radboud University Nijmegen for funding the six months of fieldwork on which this article is based.Peer reviewedPostprin
LSST: from Science Drivers to Reference Design and Anticipated Data Products
(Abridged) We describe here the most ambitious survey currently planned in
the optical, the Large Synoptic Survey Telescope (LSST). A vast array of
science will be enabled by a single wide-deep-fast sky survey, and LSST will
have unique survey capability in the faint time domain. The LSST design is
driven by four main science themes: probing dark energy and dark matter, taking
an inventory of the Solar System, exploring the transient optical sky, and
mapping the Milky Way. LSST will be a wide-field ground-based system sited at
Cerro Pach\'{o}n in northern Chile. The telescope will have an 8.4 m (6.5 m
effective) primary mirror, a 9.6 deg field of view, and a 3.2 Gigapixel
camera. The standard observing sequence will consist of pairs of 15-second
exposures in a given field, with two such visits in each pointing in a given
night. With these repeats, the LSST system is capable of imaging about 10,000
square degrees of sky in a single filter in three nights. The typical 5
point-source depth in a single visit in will be (AB). The
project is in the construction phase and will begin regular survey operations
by 2022. The survey area will be contained within 30,000 deg with
, and will be imaged multiple times in six bands, ,
covering the wavelength range 320--1050 nm. About 90\% of the observing time
will be devoted to a deep-wide-fast survey mode which will uniformly observe a
18,000 deg region about 800 times (summed over all six bands) during the
anticipated 10 years of operations, and yield a coadded map to . The
remaining 10\% of the observing time will be allocated to projects such as a
Very Deep and Fast time domain survey. The goal is to make LSST data products,
including a relational database of about 32 trillion observations of 40 billion
objects, available to the public and scientists around the world.Comment: 57 pages, 32 color figures, version with high-resolution figures
available from https://www.lsst.org/overvie
Using ecological and field survey data to establish a national list of the wild bee pollinators of crops
The importance of wild bees for crop pollination is well established, but less is known about which species contribute to service delivery to inform agricultural management, monitoring and conservation. Using sites in Great Britain as a case study, we use a novel qualitative approach combining ecological information and field survey data to establish a national list of crop pollinating bees for four economically important crops (apple, field bean, oilseed rape and strawberry). A traits data base was used to establish potential pollinators, and combined with field data to identify both dominant crop flower visiting bee species and other species that could be important crop pollinators, but which are not presently sampled in large numbers on crops flowers. Whilst we found evidence that a small number of common, generalist species make a disproportionate contribution to flower visits, many more species were identified as potential pollinators, including rare and specialist species. Furthermore, we found evidence of substantial variation in the bee communities of different crops. Establishing a national list of crop pollinators is important for practitioners and policy makers, allowing targeted management approaches for improved ecosystem services, conservation and species monitoring. Data can be used to make recommendations about how pollinator diversity could be promoted in agricultural landscapes. Our results suggest agri-environment schemes need to support a higher diversity of species than at present, notably of solitary bees. Management would also benefit from targeting specific species to enhance crop pollination services to particular crops. Whilst our study is focused upon Great Britain, our methodology can easily be applied to other countries, crops and groups of pollinating insects.LH was funded by NERC QMEE CDT. EJB was funded by a BBSRC Ph.D. studentship under grant BB/F016581/1. LB was was supported by the Scholarship Program of the German Federal Environmental Foundation (Deutsche Bundesstiftung Umwelt, DBU, AZ 20014/302). AJC was funded by the BBSRC and Syngenta UK as part of a case award Ph.D. (grant no. 1518739). AE was funded by the Swiss National Science Foundation (grant number 405940-115642). DG and A-MK were funded by grant PCIN2014-145-C02-02 (MinECo; EcoFruit project BiodivERsA-FACCE2014-74). MG was supported by Establishing a UK Pollinator Monitoring and Research Partnership (PMRP) a collaborative project funded by Defra, the Welsh and Scottish Governments, JNCC and project partnersâ. GAdG was funded via research projects BO-11-011.01-051 and BO-43-011.06-007, commissioned by the Dutch Ministry of Agriculture, Nature and Food Quality. DK was funded by the Dutch Ministry of Economic Affairs (BO-11-011.01-011). AK-H was funded by the NKFIH project (FK123813), the Bolyai JĂĄnos Fellowship of the MTA, the ĂNKP-19-4-SZIE-3 New National Excellence Program of the Ministry for Innovation and Technology, and together with RF by the Hungarian Scientific Research Fund OTKA 101940. MM was funded by Waitrose & Partners, Fruition PO, and the University of Worcester. MM was funded by grant INIA-RTA2013-00139-C03-01 (MinECo and FEDER). BBP and RFS were funded by the UK Natural Environment Research Council as part of Wessex BESS (ref. NE/J014680/1). NJV was funded by the Walloon Region (Belgium) Direction gĂ©nĂ©rale opĂ©rationnelle de lâAgriculture, des Ressources naturelles et de lâEnvironnement (DGO3) for the "ModĂšle permaculturel" project on biodiversity in micro-farms, FNRS/FWO joint programme EOS â Excellence Of Science CliPS: Climate change and its impact on Pollination Services (project 30947854)". CW was funded by the Deutsche Forschungsgemeinschaft (DFG) (Project number 405945293). BW was funded by the Natural Environment Research Council (NERC) under research programme NE/N018125/1 ASSIST â Achieving Sustainable Agricultural Systems www.assist.ceh.ac.uk. TB and TO are supported by BBSRC, NERC, ESRC and the Scottish Government under the Global Food Security Programme (Grant BB/R00580X/1)
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