Thermoelectric properties of Co, Ir, and Os-Doped FeSi Alloys: Evidence for Strong Electron-Phonon Coupling

The effects of various transition metal dopants on the electrical and thermal transport properties of Fe1-xMxSi alloys (M= Co, Ir, Os) are reported. The maximum thermoelectric figure of merit ZTmax is improved from 0.007 at 60 K for pure FeSi to ZT = 0.08 at 100 K for 4% Ir doping. A comparison of the thermal conductivity data among Os, Ir and Co doped alloys indicates strong electron-phonon coupling in this compound. Because of this interaction, the common approximation of dividing the total thermal conductivity into independent electronic and lattice components ({\kappa}Total = {\kappa}electronic + {\kappa}lattice) fails for these alloys. The effects of grain size on thermoelectric properties of Fe0.96Ir0.04Si alloys are also reported. The thermal conductivity can be lowered by about 50% with little or no effect on the electrical resistivity or Seebeck coefficient. This results in ZTmax = 0.125 at 100 K, still about a factor of five too low for solid-state refrigeration applications

Stereocontrolled enantioselective total synthesis of the [2+2] quadrigemine alkaloids.

A unified strategy for enantioselective total synthesis of all stereoisomers of the 2+2 family of quadrigemine alkaloids is reported. In this approach, two enantioselective intramolecular Heck reactions are carried out at the same time on precursors fashioned in four steps from either meso- or (+)-chimonanthine to form the two critical quaternary carbons of the peripheral cyclotryptamine rings of these products. Useful levels of catalyst control are realized in either desymmetrizing a meso precursor or controlling diastereoselectivity in elaborating C2-symmetic intermediates. None of the synthetic quadrigemines are identical with alkaloids isolated previously and referred to as quadrigemines A and E. In addition, we report improvements in our previous total syntheses of (+)- or (-)-quadrigemine C that shortened the synthetic sequence to 10 steps and provided these products in 2.2% overall yield from tryptamine

Toward a Symphony of Reactivity: Cascades Involving Catalysis and Sigmatropic Rearrangements

Catalysis and synthesis are intimately linked in modern organic chemistry. The synthesis of complex molecules is an ever evolving area of science. In many regards, the inherent beauty associated with a synthetic sequence can be linked to a certain combination of the creativity with which a sequence is designed and the overall efficiency with which the ultimate process is performed. In synthesis, as in other endeavors, beauty is very much in the eyes of the beholder.† It is with this in mind that we will attempt to review an area of synthesis that has fascinated us and that we find extraordinarily beautiful, namely the combination of catalysis and sigmatropic rearrangements in consecutive and cascade sequences

Regional data exchange to improve care for veterans after non-VA hospitalization: a randomized controlled trial

BACKGROUND: Coordination of care, especially after a patient experiences an acute care event, is a challenge for many health systems. Event notification is a form of health information exchange (HIE) which has the potential to support care coordination by alerting primary care providers when a patient experiences an acute care event. While promising, there exists little evidence on the impact of event notification in support of reengagement into primary care. The objectives of this study are to 1) examine the effectiveness of event notification on health outcomes for older adults who experience acute care events, and 2) compare approaches to how providers respond to event notifications. METHODS: In a cluster randomized trial conducted across two medical centers within the U.S. Veterans Health Administration (VHA) system, we plan to enroll older patients (≥ 65 years of age) who utilize both VHA and non-VHA providers. Patients will be enrolled into one of three arms: 1) usual care; 2) event notifications only; or 3) event notifications plus a care transitions intervention. In the event notification arms, following a non-VHA acute care encounter, an HIE-based intervention will send an event notification to VHA providers. Patients in the event notification plus care transitions arm will also receive 30 days of care transition support from a social worker. The primary outcome measure is 90-day readmission rate. Secondary outcomes will be high risk medication discrepancies as well as care transitions processes within the VHA health system. Qualitative assessments of the intervention will inform VHA system-wide implementation. DISCUSSION: While HIE has been evaluated in other contexts, little evidence exists on HIE-enabled event notification interventions. Furthermore, this trial offers the opportunity to examine the use of event notifications that trigger a care transitions intervention to further support coordination of care. TRIAL REGISTRATION: ClinicalTrials.gov NCT02689076. "Regional Data Exchange to Improve Care for Veterans After Non-VA Hospitalization." Registered 23 February 2016

Non-Carbonyl-Stabilized Metallocarbenoids in Synthesis: The Development of a Tandem Rhodium-Catalyzed Bamford−Stevens/Thermal Aliphatic Claisen Rearrangement Sequence

A tandem rhodium-catalyzed Bamford−Stevens/Claisen rearrangement is presented. The tandem reaction uses Eschenmoser hydrazones for the in situ generation of non-carbonyl-stabilized diazo alkanes, which are presumably intercepted by Rh(II) catalysts to induce a 1,2-hydride migration. This sequence provides high levels of stereocontrol for the generation of simple acyclic (Z)-enol ethers. These enol ethers undergo either thermal or Lewis acid accelerated Claisen rearrangements to provide products of high diastereopurity. Also presented are cascade reactions, wherein a third chemical step occurs after the initial tandem sequence (i.e., Bamford−Stevens/Claisen/ene and Bamford−Stevens/Claisen/Cope)

Visualization of electrochemical reactions in battery materials with X-ray microscopy and mapping

Unlocking the full performance capabilities of battery materials will require a thorough understanding of the underlying electrochemical mechanisms at a variety of length scales. A broad arsenal of X-ray microscopy and mapping techniques is now available to probe these processes down to the nanoscale. The tunable nature of X-ray sources allows for the extraction of chemical states through spectromicroscopy. The addition of phase contrast imaging can retrieve the complex-valued refraction of the material, giving an even more nuanced chemical picture. Tomography and coherent Bragg diffraction imaging provide a reconstructed three-dimensional volume of the specimen, as well as internal strain information from the latter. Many recent insights into battery materials have been achieved through the creative use of these, and similar, methods. Experiments performed while the battery is being actively cycled reveal behavior that differs significantly from what is observed at equilibrium and metastable conditions. Planned improvements to X-ray source brightness and coherence will extend these techniques by alleviating the current trade-off in time, chemical, and spatial resolutio

Large-scale discovery of enhancers from human heart tissue.

Development and function of the human heart depend on the dynamic control of tissue-specific gene expression by distant-acting transcriptional enhancers. To generate an accurate genome-wide map of human heart enhancers, we used an epigenomic enhancer discovery approach and identified ∼6,200 candidate enhancer sequences directly from fetal and adult human heart tissue. Consistent with their predicted function, these elements were markedly enriched near genes implicated in heart development, function and disease. To further validate their in vivo enhancer activity, we tested 65 of these human sequences in a transgenic mouse enhancer assay and observed that 43 (66%) drove reproducible reporter gene expression in the heart. These results support the discovery of a genome-wide set of noncoding sequences highly enriched in human heart enhancers that is likely to facilitate downstream studies of the role of enhancers in development and pathological conditions of the heart

A Diastereodivergent Synthetic Strategy for the Syntheses of Communesin F and Perophoramidine

An efficient, unified, and stereodivergent approach toward communesin F and perophoramidine was examined. The C(3) all-carbon quaternary center of an oxindole was smoothly constructed by base-promoted indolone-malonate alkylation chemistry. The complementary relative stereochemistry of the crucial vicinal quaternary centers found in communesin F and perophoramidine was selectively installed by substrate-controlled decarboxylative allylic alkylations