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

Year in review 2006: Critical Care – paediatrics

In 2006, paediatric intensive care-related subjects were discussed in a number of papers published in various journals, including Critical Care. Because they focused on the cardiovascular system and its support, we summarize them here. In particular, these papers highlighted the management of refractory septic shock, extracorporeal support, outcome markers in sepsis, and outcome after cardiac arrest

Highly Regioselective Indoline Synthesis under Nickel/Photoredox Dual Catalysis

Nickel/photoredox catalysis is used to synthesize indolines in one step from iodoacetanilides and alkenes. Very high regioselectivity for 3-substituted indoline products is obtained for both aliphatic and styrenyl olefins. Mechanistic investigations indicate that oxidation to Ni(III) is necessary to perform the difficult C–N bond-forming reductive elimination, producing a Ni(I) complex, which in turn is reduced to Ni(0). This process serves to further demonstrate the utility of photoredox catalysts as controlled single electron transfer agents in multioxidation state nickel catalysis.National Institute of General Medical Sciences (U.S.) (GM63755

Investigating Atomic Details of the CaF2_2(111) Surface with a qPlus Sensor

The (111) surface of CaF$_2$ has been intensively studied with large-amplitude frequency-modulation atomic force microscopy and atomic contrast formation is now well understood. It has been shown that the apparent contrast patterns obtained with a polar tip strongly depend on the tip terminating ion and three sub-lattices of anions and cations can be imaged. Here, we study the details of atomic contrast formation on CaF$_2$(111) with small-amplitude force microscopy utilizing the qPlus sensor that has been shown to provide utmost resolution at high scanning stability. Step edges resulting from cleaving crystals in-situ in the ultra-high vacuum appear as very sharp structures and on flat terraces, the atomic corrugation is seen in high clarity even for large area scans. The atomic structure is also not lost when scanning across triple layer step edges. High resolution scans of small surface areas yield contrast features of anion- and cation sub-lattices with unprecedented resolution. These contrast patterns are related to previously reported theoretical results.Comment: 18 pages, 9 Figures, presented at 7th Int Conf Noncontact AFM Seattle, USA Sep 12-15 2004, accepted for publication in Nanotechnology, http://www.iop.or

The changing GMC population in galaxy interactions

This is the final version. Available from OUP via the DOI in this recordWith the advent of modern observational efforts providing extensive giant molecular cloud catalogues, understanding the evolution of such clouds in a galactic context is of prime importance. While numerous previous numerical and theoretical works have focused on the cloud properties in isolated discs, few have looked into the cloud population in an interacting disc system. We present results of the first study investigating the evolution of the cloud population in galaxy experiencing an M51-like tidal fly-by using numerical simulations including star formation, interstellar medium cooling, and stellar feedback. We see the cloud population shift to large unbound clouds in the wake of the companion passage, with the largest clouds appearing as fleeting short-lived agglomerations of smaller clouds within the tidal spiral arms, brought together by large-scale streaming motions. These are then sheared apart as they leave the protection of the spiral arms. Clouds appear to lead diverse lives, even within similar environments, with some being born from gas shocked by filaments streaming into the spiral arms, and others from effectively isolated smaller colliding pairs. Overall, this cloud population produces a shallower mass function than the disc in isolation, especially in the arms compared to the inter-arm regions. Direct comparisons to M51 observations show similarities between cloud populations, though models tailored to the mass and orbital models of M51 appear necessary to precisely reproduce the cloud population

9~GHz measurement of squeezed light by interfacing silicon photonics and integrated electronics

Photonic quantum technology can be enhanced by monolithic fabrication of both the underpinning quantum hardware and the corresponding electronics for classical readout and control. Together, this enables miniaturisation and mass-manufacture of small quantum devices---such as quantum communication nodes, quantum sensors and sources of randomness---and promises the precision and scale of fabrication required to assemble useful quantum computers. Here we combine CMOS compatible silicon and germanium-on-silicon nano-photonics with silicon-germanium integrated amplification electronics to improve performance of on-chip homodyne detection of quantum light. We observe a 3 dB bandwidth of 1.7 GHz, shot-noise limited performance beyond 9 GHz and minaturise the required footprint to 0.84 mm. We use the device to observe quantum squeezed light, from 100 MHz to 9 GHz, generated in a lithium niobate waveguide. This demonstrates that an all-integrated approach yields faster homodyne detectors for quantum technology than has been achieved to-date and opens the way to full-stack integration of photonic quantum devices.Comment: Nat. Photonics (2020

Study of Drain Injected Breakdown Mechanisms in AlGaN/GaN-on-SiC HEMTs

Breakdown mechanism in 0.25- μm gate length AlGaN/GaN-on-SiC iron doped high electron mobility transistors (HEMTs) with background carbon is investigated through the drain current injection technique. The measurement results reveal that it can be divided into two distinct stages according to the gate voltage levels. The first stage of the measured drain injected breakdown is mainly due to the initiation of the punchthrough process under the gate, and the second stage of breakdown is associated with the potential barrier between the unintentionally doped (UID) GaN and the Fe doped p-type GaN buffer layer which also has a higher carbon density. The electroluminescence (EL) results suggest that the first stage shows uniform punchthrough current flow, but localized leakage current flow associated with a snapback breakdown mechanism replaces the uniform punchthrough current flow and dominates the second stage. A 2D-TCAD simulation has been implemented and shows the current paths under uniform flow conditions

The Global Evolution of Giant Molecular Clouds II: The Role of Accretion

We present virial models for the global evolution of giant molecular clouds. Focusing on the presence of an accretion flow, and accounting for the amount of mass, momentum, and energy supplied by accretion and star formation feedback, we are able to follow the growth, evolution, and dispersal of individual giant molecular clouds. Our model clouds reproduce the scaling relations observed in both galactic and extragalactic clouds. We find that accretion and star formation contribute contribute roughly equal amounts of turbulent kinetic energy over the lifetime of the cloud. Clouds attain virial equilibrium and grow in such a way as to maintain roughly constant surface densities, with typical surface densities of order 50 - 200 Msun pc^-2, in good agreement with observations of giant molecular clouds in the Milky Way and nearby external galaxies. We find that as clouds grow, their velocity dispersion and radius must also increase, implying that the linewidth-size relation constitutes an age sequence. Lastly, we compare our models to observations of giant molecular clouds and associated young star clusters in the LMC and find good agreement between our model clouds and the observed relationship between H ii regions, young star clusters, and giant molecular clouds.Comment: 23 Pages, 9 Figures. Accepted to Ap