Functional group tolerant hydrogen borrowing C-alkylation

Hydrogen borrowing is an attractive and sustainable strategy for carbon–carbon bond formation that enables alcohols to be used as alkylating reagents in place of alkyl halides. However, despite intensive efforts, limited functional group tolerance is observed in this methodology, which we hypothesize is due to the high temperatures and harsh basic conditions often employed. Here we demonstrate that room temperature and functional group tolerant hydrogen borrowing can be achieved with a simple iridium catalyst in the presence of substoichiometric base without an excess of reagents. Achieving high yields necessitates the application of anaerobic conditions to counteract the oxygen sensitivity of the catalytic iridium hydride intermediate, which otherwise leads to catalyst degradation. Substrates containing heteroatoms capable of complexing the catalyst exhibit limited room temperature reactivity, but the application of moderately higher temperatures enables extension to a broad range of medicinally relevant nitrogen rich heterocycles. These newly developed conditions allow alcohols possessing functional groups that were previously incompatible with hydrogen borrowing reactions to be employed

The influence of CO adsorption on the surface composition of cobalt/palladium alloys

AM is grateful for funding from SASOL Technology UK Ltd (PhD studentship); JG is grateful for the award of a fellowship from the Knut and Alice Wallenberg Foundation. TEJ and AGT acknowledge EPSRC funding of postdoctoral research (EP/E047580/1). The MEIS facility was funded via EPSRC grant EP/E003370/1.Segregation induced by the adsorption of gas phase species can strongly influence the composition of bimetallic surfaces and can therefore play an important role in influencing heterogeneous catalytic reactions. The addition of palladium to cobalt catalysts has been shown to promote Fischer Tropsch catalysis. We investigate the adsorption of CO onto bimetallic CoPd surfaces on Pd{111} using a combination of reflection absorption infrared spectroscopy and medium energy ion scattering. The vibrational frequency of adsorbed CO provides crucial information on the adsorption sites adopted by CO and medium energy ion scattering probes the surface composition before and after CO exposure. We show that cobalt segregation is induced by CO adsorption and rationalise these observations in terms of the strength of adsorption of CO in various surface adsorption sites.PostprintPeer reviewe

New Extinction and Mass Estimates of the Low-mass Companion 1RXS 1609 B with the Magellan AO System: Evidence of an Inclined Dust Disk

We used the Magellan adaptive optics system to image the 11 Myr substellar companion 1RXS 1609 B at the bluest wavelengths to date (z' and Ys). Comparison with synthetic spectra yields a higher temperature than previous studies of $T_\mathrm{eff}=2000\pm100\mathrm{K}$ and significant dust extinction of $A_V=4.5^{+0.5}_{-0.7}$ mag. Mass estimates based on the DUSTY tracks gives 0.012-0.015 Msun, making the companion likely a low-mass brown dwarf surrounded by a dusty disk. Our study suggests that 1RXS 1609 B is one of the 25% of Upper Scorpius low-mass members harboring disks, and it may have formed like a star and not a planet out at 320 AU.Comment: 5 pages, 4 figures; accepted to ApJ

Cryogenic On-Orbit Liquid Depot Storage, Acquisition, and Transfer satellite (COLD-SAT) feasibility study

The Cryogenic On-Orbit Liquid Depot Storage, Acquisition, and Transfer Satellite (COLD-SAT) is an experimental spacecraft launched from an expendable launch vehicle which is designed to investigate the systems and technologies required for efficient, effective, and reliable management of cryogenic fluid in the reduced gravity space environment. The COLD-SAT program will provide the necessary data base and provide low-g proving of fluid and thermal models of cryogenic storage, transfer, and resupply concepts and processes. A conceptual approach was developed and an overview of the results of the 24 month COLD-SAT Phase A feasibility is described which includes: (1) a definition of the technology needs and the accompanying experimental 3 month baseline mission; (2) a description of the experiment subsystem, major features and rationale for satisfaction of primary and secondary experiment requirements using liquid hydrogen as the test fluid; and (3) a presentation of the conceptual design of the COLD-SAT spacecraft subsystems which support the on-orbit experiment with emphasis on areas of greatest challenge

Anaplastic Lymphoma Kinase Spares Organ Growth during Nutrient Restriction in Drosophila

SummaryDeveloping animals survive periods of starvation by protecting the growth of critical organs at the expense of other tissues. Here, we use Drosophila to explore the as yet unknown mechanisms regulating this privileged tissue growth. As in mammals, we observe in Drosophila that the CNS is more highly spared than other tissues during nutrient restriction (NR). We demonstrate that anaplastic lymphoma kinase (Alk) efficiently protects neural progenitor (neuroblast) growth against reductions in amino acids and insulin-like peptides during NR via two mechanisms. First, Alk suppresses the growth requirement for amino acid sensing via Slimfast/Rheb/TOR complex 1. And second, Alk, rather than insulin-like receptor, primarily activates PI3-kinase. Alk maintains PI3-kinase signaling during NR as its ligand, Jelly belly (Jeb), is constitutively expressed from a glial cell niche surrounding neuroblasts. Together, these findings identify a brain-sparing mechanism that shares some regulatory features with the starvation-resistant growth programs of mammalian tumors.PaperCli

Enhanced Flight Vision Systems Operational Feasibility Study Using Radar and Infrared Sensors

Approach and landing operations during periods of reduced visibility have plagued aircraft pilots since the beginning of aviation. Although techniques are currently available to mitigate some of the visibility conditions, these operations are still ultimately limited by the pilot's ability to "see" required visual landing references (e.g., markings and/or lights of threshold and touchdown zone) and require significant and costly ground infrastructure. Certified Enhanced Flight Vision Systems (EFVS) have shown promise to lift the obscuration veil. They allow the pilot to operate with enhanced vision, in lieu of natural vision, in the visual segment to enable equivalent visual operations (EVO). An aviation standards document was developed with industry and government consensus for using an EFVS for approach, landing, and rollout to a safe taxi speed in visibilities as low as 300 feet runway visual range (RVR). These new standards establish performance, integrity, availability, and safety requirements to operate in this regime without reliance on a pilot's or flight crew's natural vision by use of a fail-operational EFVS. A pilot-in-the-loop high-fidelity motion simulation study was conducted at NASA Langley Research Center to evaluate the operational feasibility, pilot workload, and pilot acceptability of conducting straight-in instrument approaches with published vertical guidance to landing, touchdown, and rollout to a safe taxi speed in visibility as low as 300 feet RVR by use of vision system technologies on a head-up display (HUD) without need or reliance on natural vision. Twelve crews flew various landing and departure scenarios in 1800, 1000, 700, and 300 RVR. This paper details the non-normal results of the study including objective and subjective measures of performance and acceptability. The study validated the operational feasibility of approach and departure operations and success was independent of visibility conditions. Failures were handled within the lateral confines of the runway for all conditions tested. The fail-operational concept with pilot in the loop needs further study

Assessing Dual Sensor Enhanced Flight Vision Systems to Enable Equivalent Visual Operations

Flight deck-based vision system technologies, such as Synthetic Vision (SV) and Enhanced Flight Vision Systems (EFVS), may serve as a revolutionary crew/vehicle interface enabling technologies to meet the challenges of the Next Generation Air Transportation System Equivalent Visual Operations (EVO) concept - that is, the ability to achieve the safety of current-day Visual Flight Rules (VFR) operations and maintain the operational tempos of VFR irrespective of the weather and visibility conditions. One significant challenge lies in the definition of required equipage on the aircraft and on the airport to enable the EVO concept objective. A motion-base simulator experiment was conducted to evaluate the operational feasibility, pilot workload and pilot acceptability of conducting straight-in instrument approaches with published vertical guidance to landing, touchdown, and rollout to a safe taxi speed in visibility as low as 300 ft runway visual range by use of onboard vision system technologies on a Head-Up Display (HUD) without need or reliance on natural vision. Twelve crews evaluated two methods of combining dual sensor (millimeter wave radar and forward looking infrared) EFVS imagery on pilot-flying and pilot-monitoring HUDs as they made approaches to runways with and without touchdown zone and centerline lights. In addition, the impact of adding SV to the dual sensor EFVS imagery on crew flight performance, workload, and situation awareness during extremely low visibility approach and landing operations was assessed. Results indicate that all EFVS concepts flown resulted in excellent approach path tracking and touchdown performance without any workload penalty. Adding SV imagery to EFVS concepts provided situation awareness improvements but no discernible improvements in flight path maintenance

Evolution of the HIV-1 nef gene in HLA-B*57 Positive Elite Suppressors

Elite controllers or suppressors (ES) are HIV-1 infected patients who maintain viral loads of < 50 copies/ml without antiretroviral therapy. CD8+ T cells are thought to play a key role in the control of viral replication and exert selective pressure on gag and nef in HLA-B*57 positive ES. We previously showed evolution in the gag gene of ES which surprisingly was mostly due to synonymous mutations rather than non-synonymous mutation in targeted CTL epitopes. This finding could be the result of structural constraints on Gag, and we therefore examined the less conserved nef gene. We found slow evolution of nef in plasma virus in some ES. This evolution is mostly due to synonymous mutations and occurs at a rate similar to that seen in the gag gene in the same patients. The results provide further evidence of ongoing viral replication in ES and suggest that the nef and gag genes in these patients respond similarly to selective pressure from the host