1,611 research outputs found
Iridium complexes bearing a PNP ligand, favoring facile C(sp^3)–H bond cleavage
Hydrogen iodide is lost upon reaction of PNP with IrI_3, where PNP = 2,6-bis-(di-t-butylphosphinomethyl)pyridine to give crystallographically characterized Ir(PNP)*(I)_2, which reacts with H_2 to give Ir(PNP)(H)(I)_2. Ir(PNP)(Cl)_3 is relatively inert towards the intramolecular C–H activation of the tert-butyl's of the PNP ligand
Rhodium complexes bearing tetradentate diamine-bis(phenolate) ligands
Using tetradentate, dianionic ligands, several new rhodium complexes have been prepared. Some of these diamine-bis(phenolate) compounds, are active for C–H activation of benzene. These complexes are air and thermally stable. All four complexes were characterized by X-ray diffraction
Mechanism of efficient anti-Markovnikov olefin hydroarylation catalyzed by homogeneous Ir(III) complexes
The mechanism of the hydroarylation reaction between unactivated olefins (ethylene, propylene, and styrene) and benzene catalyzed by [(R)Ir(μ-acac-O,O,C^3)-(acac-O,O)_2]_2 and [R-Ir(acac-O,O)_2(L)] (R = acetylacetonato, CH_3, CH_2CH_3, Ph, or CH_2CH_2Ph, and L = H_2O or pyridine) Ir(III) complexes was studied by experimental methods. The system is selective for generating the anti-Markovnikov product of linear alkylarenes (61 : 39 for benzene + propylene and 98 : 2 for benzene + styrene). The reaction mechanism was found to follow a rate law with first-order dependence on benzene and catalyst, but a non-linear dependence on olefin. ^(13)C-labelling studies with CH_3^(13)CH_2-Ir-Py showed that reversible β-hydride elimination is facile, but unproductive, giving exclusively saturated alkylarene products. The migration of the ^(13)C-label from the α to β-positions was found to be slower than the C–H activation of benzene (and thus formation of ethane and Ph-d_5-Ir-Py). Kinetic analysis under steady state conditions gave a ratio of the rate constants for CH activation and β-hydride elimination (k_(CH): k_β) of 0.5. The comparable magnitude of these rates suggests a common rate determining transition state/intermediate, which has been shown previously with B3LYP density functional theory (DFT) calculations. Overall, the mechanism of hydroarylation proceeds through a series of pre-equilibrium dissociative steps involving rupture of the dinuclear species or the loss of L from Ph-Ir-L to the solvento, 16-electron species, Ph-Ir(acac-O,O)_2-Sol (where Sol refers to coordinated solvent). This species then undergoes trans to cis isomerization of the acetylacetonato ligand to yield the pseudo octahedral species cis-Ph-Ir-Sol, which is followed by olefin insertion (the regioselective and rate determining step), and then activation of the C–H bond of an incoming benzene to generate the product and regenerate the catalyst
Learning Visual Context by Comparison
Finding diseases from an X-ray image is an important yet highly challenging
task. Current methods for solving this task exploit various characteristics of
the chest X-ray image, but one of the most important characteristics is still
missing: the necessity of comparison between related regions in an image. In
this paper, we present Attend-and-Compare Module (ACM) for capturing the
difference between an object of interest and its corresponding context. We show
that explicit difference modeling can be very helpful in tasks that require
direct comparison between locations from afar. This module can be plugged into
existing deep learning models. For evaluation, we apply our module to three
chest X-ray recognition tasks and COCO object detection & segmentation tasks
and observe consistent improvements across tasks. The code is available at
https://github.com/mk-minchul/attend-and-compare.Comment: ECCV 2020 spotlight pape
VLT/FLAMES-ARGUS observations of stellar wind--ISM cloud interactions in NGC 6357
We present optical/near-IR IFU observations of a gas pillar in the Galactic
HII region NGC 6357 containing the young open star cluster Pismis 24. These
observations have allowed us to examined in detail the gas conditions of the
strong wind-clump interactions taking place on its surface. We identify the
presence of a narrow (~20 km/s) and broad (50-150 km/s) component to the
H_alpha emission line, where the broadest broad component widths are found in a
region that follows the shape of the eastern pillar edge. These connections
have allowed us to firmly associate the broad component with emission from
ionized gas within turbulent mixing layers on the pillar's surface set up by
the shear flows of the O-star winds from the cluster. We discuss the
implications of our findings in terms of the broad emission line component that
is increasingly found in extragalactic starburst environments. Although the
broad line widths found here are narrower, we conclude that the mechanisms
producing both must be the same. The difference in line widths may result from
the lower total mechanical wind energy produced by the O stars in Pismis 24
compared to that from a typical young massive star cluster found in a starburst
galaxy. The pillar's edge is also clearly defined by dense (<5000 cm^-3), hot
(>20000 K), and excited (via [NII]/H_a and [SII]/H_a ratios) gas conditions,
implying the presence of a D-type ionization front propagating into the pillar
surface. Although there must be both photoevaporation outflows produced by the
ionization front, and mass-loss through mechanical ablation, we see no evidence
for any significant bulk gas motions on or around the pillar. We postulate that
the evaporated/ablated gas must be rapidly heated before being entrained.Comment: 9 pages, 5 figures (3 colour). Accepted for publication in MNRA
Contribution to understanding the mathematical structure of quantum mechanics
Probabilistic description of results of measurements and its consequences for
understanding quantum mechanics are discussed. It is shown that the basic
mathematical structure of quantum mechanics like the probability amplitudes,
Born rule, commutation and uncertainty relations, probability density current,
momentum operator, rules for including the scalar and vector potentials and
antiparticles can be obtained from the probabilistic description of results of
measurement of the space coordinates and time. Equations of motion of quantum
mechanics, the Klein-Gordon equation, Schrodinger equation and Dirac equation
are obtained from the requirement of the relativistic invariance of the
space-time Fisher information. The limit case of the delta-like probability
densities leads to the Hamilton-Jacobi equation of classical mechanics. Many
particle systems and the postulates of quantum mechanics are also discussed.Comment: 21 page
Shallow water marine sediment bacterial community shifts along a natural CO2 gradient in the Mediterranean Sea off Vulcano, Italy.
The effects of increasing atmospheric CO(2) on ocean ecosystems are a major environmental concern, as rapid shoaling of the carbonate saturation horizon is exposing vast areas of marine sediments to corrosive waters worldwide. Natural CO(2) gradients off Vulcano, Italy, have revealed profound ecosystem changes along rocky shore habitats as carbonate saturation levels decrease, but no investigations have yet been made of the sedimentary habitat. Here, we sampled the upper 2 cm of volcanic sand in three zones, ambient (median pCO(2) 419 μatm, minimum Ω(arag) 3.77), moderately CO(2)-enriched (median pCO(2) 592 μatm, minimum Ω(arag) 2.96), and highly CO(2)-enriched (median pCO(2) 1611 μatm, minimum Ω(arag) 0.35). We tested the hypothesis that increasing levels of seawater pCO(2) would cause significant shifts in sediment bacterial community composition, as shown recently in epilithic biofilms at the study site. In this study, 454 pyrosequencing of the V1 to V3 region of the 16S rRNA gene revealed a shift in community composition with increasing pCO(2). The relative abundances of most of the dominant genera were unaffected by the pCO(2) gradient, although there were significant differences for some 5 % of the genera present (viz. Georgenia, Lutibacter, Photobacterium, Acinetobacter, and Paenibacillus), and Shannon Diversity was greatest in sediments subject to long-term acidification (>100 years). Overall, this supports the view that globally increased ocean pCO(2) will be associated with changes in sediment bacterial community composition but that most of these organisms are resilient. However, further work is required to assess whether these results apply to other types of coastal sediments and whether the changes in relative abundance of bacterial taxa that we observed can significantly alter the biogeochemical functions of marine sediments
Scalable and Stable Ferroelectric Non-Volatile Memory at > 500 C
Non-volatile memory (NVM) devices that reliably operate at temperatures above
300 C are currently non-existent and remains a critically unmet
challenge in the development of high-temperature (T) resilient electronics,
necessary for many emerging, complex computing and sensing in harsh
environments. Ferroelectric AlScN exhibits strong potential for
utilization in NVM devices operating at very high temperatures (> 500
C) given its stable and high remnant polarization (PR) above 100
C/cm with demonstrated ferroelectric transition temperature (TC) >
1000 C. Here, we demonstrate an AlScN ferroelectric
diode based NVM device that can reliably operate with clear ferroelectric
switching up to 600 C with distinguishable On and Off states. The
coercive field (EC) from the Pulsed I-V measurements is found to be -5.84 (EC-)
and +5.98 (EC+) (+/- 0.1) MV/cm at room temperature (RT) and found to decrease
with increasing temperature up to 600 C. The devices exhibit high
remnant polarizations (> 100 C/cm) which are stable at high
temperatures. At 500 C, our devices show 1 million read cycles and
stable On-Off ratio above 1 for > 6 hours. Finally, the operating voltages of
our AlScN ferrodiodes are < 15 V at 600 C which is well matched and
compatible with Silicon Carbide (SiC) based high temperature logic technology,
thereby making our demonstration a major step towards commercialization of NVM
integrated high-T computers.Comment: MS and S
Constraints from observations and modeling on atmosphere-surface exchange of mercury in eastern North America
Atmosphere-surface exchange of mercury, although a critical component of its global cycle, is currently poorly constrained. Here we use the GEOS-Chem chemical transport model to interpret atmospheric Hg-0 (gaseous elemental mercury) data collected during the 2013 summer Nitrogen, Oxidants, Mercury and Aerosol Distributions, Sources and Sinks (NOMADSS) aircraft campaign as well as ground-and ship-based observations in terms of their constraints on the atmosphere-surface exchange of Hg-0 over eastern North America. Model-observation comparison suggests that the Northwest Atlantic may be a net source of Hg-0, with high evasion fluxes in summer (our best sensitivity simulation shows an average oceanic Hg-0 flux of 3.3 ng m(-2) h(-1) over the Northwest Atlantic), while the terrestrial ecosystem in the summer of the eastern United States is likely a net sink of Hg-0 (our best sensitivity simulation shows an average terrestrial Hg-0 flux of -0.6 ng m(-2) h(-1) over the eastern United States). The inferred high Hg-0 fluxes from the Northwest Atlantic may result from high wet deposition fluxes of oxidized Hg, which are in turn related to high precipitation rates in this region. We also find that increasing simulated terrestrial fluxes of Hg-0 in spring compared to other seasons can better reproduce observed seasonal variability of Hg-0 concentration at ground-based sites in eastern North America.Peer reviewe
The Impact of Global Warming and Anoxia on Marine Benthic Community Dynamics: an Example from the Toarcian (Early Jurassic)
The Pliensbachian-Toarcian (Early Jurassic) fossil record is an archive of natural data of benthic community response to global warming and marine long-term hypoxia and anoxia. In the early Toarcian mean temperatures increased by the same order of magnitude as that predicted for the near future; laminated, organic-rich, black shales were deposited in many shallow water epicontinental basins; and a biotic crisis occurred in the marine realm, with the extinction of approximately 5% of families and 26% of genera. High-resolution quantitative abundance data of benthic invertebrates were collected from the Cleveland Basin (North Yorkshire, UK), and analysed with multivariate statistical methods to detect how the fauna responded to environmental changes during the early Toarcian. Twelve biofacies were identified. Their changes through time closely resemble the pattern of faunal degradation and recovery observed in modern habitats affected by anoxia. All four successional stages of community structure recorded in modern studies are recognised in the fossil data (i.e. Stage III: climax; II: transitional; I: pioneer; 0: highly disturbed). Two main faunal turnover events occurred: (i) at the onset of anoxia, with the extinction of most benthic species and the survival of a few adapted to thrive in low-oxygen conditions (Stages I to 0) and (ii) in the recovery, when newly evolved species colonized the re-oxygenated soft sediments and the path of recovery did not retrace of pattern of ecological degradation (Stages I to II). The ordination of samples coupled with sedimentological and palaeotemperature proxy data indicate that the onset of anoxia and the extinction horizon coincide with both a rise in temperature and sea level. Our study of how faunal associations co-vary with long and short term sea level and temperature changes has implications for predicting the long-term effects of “dead zones” in modern oceans
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