Chemoselective Suzuki-Miyaura cross-coupling via kinetic transmetallation

Chemoselective Suzuki-Miyaura cross-coupling generally requires a designed deactivation of one nucleophile towards transmetallation. Here we show that boronic acids can be chemoselectively reacted in the presence of ostensibly equivalently reactive boronic acid pinacol (BPin) esters by kinetic discrimination during transmetallation. Simultaneous electrophile control allows sequential chemoselective cross-couplings in a single operation in the absence of protecting groups

Synthesis of oxindoles and benozfuranones via oxidation of 2-heterocyclic BMIDAs

The synthesis of functionalized oxindoles and benzofuranones via oxidation of 2-BMIDA indoles and benzofurans, respectively, is described. Interconversion of boron species (BMIDAàBF3K) was necessary to enable oxidation and overcome boronic acid stability issues associated with a difficult BMIDA hydrolysis. Overall, a robust process was developed that allowed access to a small library of oxindole and benzofuranone products and facilitated the step-efficient synthesis of biologically-active compounds containing the oxindole pharmacophore

Design of a Direct-Detection Wind and Aerosol Lidar for Mars Orbit

The present knowledge of the Mars atmosphere is greatly limited by a lack of global measurements of winds and aerosols. Hence, measurements of height-resolved wind and aerosol profiles are a priority for new Mars orbiting missions. We have designed a direct-detection lidar (MARLI) to provide global measurements of dust, winds and water ice profiles from Mars orbit. From a 400-km polar orbit, the instrument is designed to provide wind and backscatter measurements with a vertical resolution of 2 km and with resolution of 2 in latitude along track. The instrument uses a single-frequency, seeded Nd:YAG laser that emits 4 mJ pulses at 1064 nm at a 250 Hz pulse rate. The receiver utilizes a 50-cm diameter telescope and a double edge Fabry-Prot etalon as a frequency discriminator to measure the Doppler shift of the aerosol-backscatter profiles. The receiver also includes a polarization-sensitive channel to detect the cross-polarized backscatter profiles from water ice. The receiver uses a sensitive 4 4 pixel HgCdTe avalanche photodiode array as a detector for all signals. Here we describe the measurement concept, instrument design, and calculate its performance for several cases of Mars atmospheric conditions. The calculations show that under a range of atmospheric conditions MARLI is capable of measuring wind speed profiles with random error of 24 m/s within the first three scale heights, enabling vertically resolved mapping of transport processes in this important region of the atmosphere

From bottom-up to top-down control of invertebrate herbivores in a retrogressive chronosequence

In the long-term absence of disturbance, ecosystems often enter a decline or retrogressive phase which leads to reductions in primary productivity, plant biomass, nutrient cycling and foliar quality. However, the consequences of ecosystem retrogression for higher trophic levels such as herbivores and predators, are less clear. Using a post-fire forested island-chronosequence across which retrogression occurs, we provide evidence that nutrient availability strongly controls invertebrate herbivore biomass when predators are few, but that there is a switch from bottom-up to top-down control when predators are common. This trophic flip in herbivore control probably arises because invertebrate predators respond to alternative energy channels from the adjacent aquatic matrix, which were independent of terrestrial plant biomass. Our results suggest that effects of nutrient limitation resulting from ecosystem retrogression on trophic cascades are modified by nutrient-independent variation in predator abundance, and this calls for a more holistic approach to trophic ecology to better understand herbivore effects on plant communities

Synthesis of 2-BMIDA indoles via heteroannulation : applications in drug scaffold and natural product synthesis

G.E.B. thanks the EPSRC and GSK for a PhD studentship. J.W.B.F. thanks the Leverhulme Trust for postdoctoral funding (RPG-2018-362).A Pd-catalyzed heteroannulation approach for the synthesis of C2 borylated indoles is reported. The process allows access to highly functionalized 2-borylated indole scaffolds with complete control of regioselectivity. The utility of the process is demonstrated in the synthesis of borylated sulfa drugs and in the concise synthesis of the Aspidosperma alkaloid Goniomitine.Publisher PDFPeer reviewe

RECEIPT AND STORAGE ISSUES AT THE TMI-2 IRRADIATED FUEL STORAGE INSTALLATION

ABSTRACT In less than a year, up to 12 canisters of TMI-2 reactor fuel debris were loaded into each of 28 Dry Storage Containers (DSCs), and placed into interim storage at an Irradiated Spent Fuel Storage Facility (ISFSI) at the Idaho National Engineering and Environmental Laboratory (INEEL). Draining and drying the canisters, loading and welding the DSCs, shipping the DSCs 25 miles, and storing in the ISFSI initially required up to 3 weeks per DSC. Significant time efficiencies were achieved during the early stages, reducing the time to less than one week per DSC. These efficiencies were achieved mostly in canister draining and drying and DSC lid welding, and despite several occurrences that had to be resolved before continuing work. The ISFSI has been operated without issue since, with the exception that license basis monitoring has indicated an unusual pattern of season-and position-dependent hydrogen generation. This paper discusses some of the innovations and storage experiences for the first ISFSI designed for the storage of severely defected fuel. INTRODUCTION In the mid-to late 1980s the TMI-2 debris was packaged, transported to the INEEL, and stored in a water pool. Approximately 340 canisters of debris were removed from water storage, dried four at a time in a separate furnace, packaged into 29 larger steel canisters, and transported to the ISFSI. The TMI-2 ISFSI was the second operated by DOE, the first being the Fort Saint Vrain ISFSI near Denver. Preparation and storage of the TMI-2 fuel presented special challenges. First, the TMI-2 was required to be stored in the ISFSI before May 2001 as part of an INEEL fuel consolidation plan. Only one of the 29 Dry Storage Containers (DSCs) had been stored prior to June 2000. Most of the TMI-2 fuel debris consists of beds of porous chunks, granules, powders, and partial rods and assemblies packed within canisters lined with lightweight concrete, making the debris very difficult to dry. The ISFSI was positioned approximately 25 miles from the water pool where the canisters were stored. Structural considerations limited transport during cold weather and ISFSI loading during high winds. Long, cold winters and high winds are common at the INEEL. This paper describes the means by which these challenges were met and the unplanned occurrences were managed during the shipments. Finally it describes interesting monitoring results from the stored fuel, which suggests that some of the original design assumptions dealing with radiolysis were not realistic

Airborne Measurements of Atmospheric Pressure made Using an IPDA Lidar Operating in the Oxygen A-Band

We report airborne measurements of atmospheric pressure made using an integrated path differential absorption (IPDA) lidar that operates in the oxygen A-band near 765 nm. Remote measurements of atmospheric temperature and pressure are needed for NASA s Active Sensing of CO2 Emissions Over Nights, Days, and Seasons (ASCENDS) mission to measure atmospheric CO2. Accurate measurements of tropospheric CO2 on a global scale are very important in order to better understand its sources and sinks and to improve our predictions of climate change. The goal of ASCENDS is to determine the CO2 dry mixing ratio with lidar measurements from space at a level of ~1 ppm. Analysis to date shows that with current weather models, measurements of both the CO2 column density and the column density of dry air are needed. Since O2 is a stable molecule that uniformly mixed in the atmosphere, measuring O2 absorption in the atmosphere can be used to infer the dry air density. We have developed an airborne (IPDA) lidar for Oxygen, with support from the NASA ESTO IIP program. Our lidar uses DFB-based seed laser diodes, a pulsed modulator, a fiber laser amplifier, and a non-linear crystal to generate wavelength tunable 765 nm laser pulses with a few uJ/pulse energy. The laser pulse rate is 10 KHz, and average transmitted laser power is ~20 mW. Our lidar steps laser pulses across a selected line O2 doublet near 764.7 nm in the Oxygen A-band. The direct detection lidar receiver uses a 20 cm diameter telescope, a Si APD detector in Geiger mode, and a multi-channel scalar to detect and record the time resolved laser backscatter in 40 separate wavelength channels. Subsequent analysis is used to estimate the transmission line shape of the doublet for the laser pulses reflected from the ground. Ground based data analysis allows averaging from 1 to 60 seconds to increase SNR in the transmission line shape of the doublet. Our retrieval algorithm fits the expected O2 lineshapes against the measurements and determines the atmospheric pressure by minimizing the error between the observations and model. We first demonstrated our airborne lidar during flights during summer 2010. We made several improvements and made measurements during the Ascends flights during July 2011. More information about the technique, lidar instrument, airborne measurements, and pressure estimates will be described in the presentation

Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters

Boronic acid solution speciation can be controlled during the Suzuki-Miyaura cross-coupling of haloaryl MIDA boronic esters to enable the formal homologation of boronic acid derivatives. The reaction is contingent upon control of the basic biphase and is thermodynamically driven: temperature control provides highly chemoselective access to either BMIDA adducts at room temperature or BPin products at elevated temperature. Control experiments and solubility analyses have provided some insight into the mechanistic operation of the formal homologation process

Study of Structural and Magnetic Properties of Iron-Rich Mixed Rare-Earth NdDyFe (17-y-x)CoxSiy Compounds

A series of NdDyFe(17-y-x)CoxSiy solid solutions with = 2 and 3 and = 0.5 1.0 and 1.5 were prepared by induction melting stoichiometric amounts of high-purity elements. The postannealed samples consist of two phases belonging to the space groups R3 m and P63 mmc . The lattice parameters and the unit cell volumes were calculated from the refinements of the magnetic and structural unit cells using the FULLPROF version of the Rietveld program. For a fixed content of Co, the maximum Curie temperatures (305 C to 405 C) were observed in samples with = 1 and having two phases, a disordered rhombohedral (DR) structure and a disordered hexagonal (DH) structure. An increase in the Curie temperature of 70 C per atom of cobalt is observed in NdDyFe(17-y-x)CoxSiy with y = 1 and x\u3c 3, suggesting that with a suitable choice of rare earths this DR phase may be a promising candidate for high-energy product permanent magnets. The magnetization versus temperature (M versus T) plots of the solid solutions, which consist of two phases, exhibit only a single magnetic ordering transition temperature