8 research outputs found

    Best Practices to Diversify Chemistry Faculty

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    Many academic institutions have looked at various ways to make their faculty a more diverse and inclusive group of people that better reflect the demographic swath of their current and future student bodies. This is even more so important in chemistry departments, where there has long been a discussion on the “leaky pipeline” for women and underrepresented groups. The work presented here examines programs and policies at various departments aimed at increasing the diversity of their faculty applicant pool, and compares them against the reception of the general scientific community by way of applicant demographics and the use of a survey instrument designed to ascertain the advertisement language that lends to a more diverse applicant pool. The combination of these results is then used to generate a list of best practices that administrations and academic search committees can use to improve their ability to attract diverse talent

    Base-Free Transfer Hydrogenation of Ketones Using Cp*Ir(pyridinesulfonamide)Cl Precatalysts

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    <i>N</i>-(2-(Pyridin-2-yl)­ethyl)­benzenesulfonamide derivatives and 1,1,1-trifluoro-<i>N</i>-(2-(pyridin-2-yl)­ethyl)­methane­sulfonamide (<b>1</b>–<b>4</b>), along with three-legged piano stool Cp*Ir<sup>III</sup>Cl complexes (<b>5</b>–<b>11</b>) (Cp* = pentamethyl­cyclopentadienyl) bearing pyridinesulfonamide ligands with varying electronic parameters, were synthesized. These ligands and air-stable complexes were characterized by <sup>1</sup>H and <sup>13</sup>C­{<sup>1</sup>H} NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Precatalysts, <b>5</b>–<b>11</b>, were assessed for transfer hydrogenation of aryl, diaryl, dialkyl, linear, cycloaliphatic, and α,β-unsaturated ketones, diones, β-ketoesters, and a biomass-derived substrate with 2-propanol, using 1 mol % precatalyst. Catalysis was also efficient using a 0.1 mol % loading. Remarkably, all catalysis experiments can be conducted in air without dried and degassed substrates, and basic additives and halide abstractors are not required for high activity in transfer hydrogenation. Control experiments and a mercury poisoning experiment support a homogeneous catalyzed pathway. Overall, the fastest reactions are observed using electron-poor substrates and precatalysts bearing electron-rich ligands

    Synthesis and Characterization of Iridium(I) and Iridium(III) Complexes Containing Dialkylbiphenylphosphines

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    The synthesis and characterization of iridium complexes containing the PCy<sub>2</sub>biPh ligand (PCy<sub>2</sub>biPh = 2-(dicyclohexylphosphino)­biphenyl), is described. Chloride abstraction from (COD)­Ir­(PCy<sub>2</sub>biPh)­Cl with Na­(BAr<sub>F</sub>)<sub>4</sub> affords [(COD)­Ir­(PCy<sub>2</sub>biPh)]­[B­(Ar<sub>F</sub>)<sub>4</sub>] (<b>1</b>, Ar<sub>F</sub> = 3,5-bis­(trifluoromethyl)­phenyl). Heating <b>1</b> in benzene results in dehydrogenation of one of the cyclohexyl groups on the phosphine ligand with COD serving as the hydrogen acceptor, leading to the new complex <b>2</b>, with benzene coordinated in an η<sup>6</sup> fashion to the metal center. Complex <b>1</b> reacts with H<sub>2</sub> to produce the Ir­(III) dihydride complex [(PCy<sub>2</sub>biPh)­IrH<sub>2</sub>]­[B­(Ar<sub>F</sub>)<sub>4</sub>] (<b>3</b>). Initial studies of transfer dehydrogenation and attempts at benzene hydrogenation using <b>1</b> and <b>3</b> are described

    Synthesis and Characterization of Iridium(I) and Iridium(III) Complexes Containing Dialkylbiphenylphosphines

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    The synthesis and characterization of iridium complexes containing the PCy<sub>2</sub>biPh ligand (PCy<sub>2</sub>biPh = 2-(dicyclohexylphosphino)­biphenyl), is described. Chloride abstraction from (COD)­Ir­(PCy<sub>2</sub>biPh)­Cl with Na­(BAr<sub>F</sub>)<sub>4</sub> affords [(COD)­Ir­(PCy<sub>2</sub>biPh)]­[B­(Ar<sub>F</sub>)<sub>4</sub>] (<b>1</b>, Ar<sub>F</sub> = 3,5-bis­(trifluoromethyl)­phenyl). Heating <b>1</b> in benzene results in dehydrogenation of one of the cyclohexyl groups on the phosphine ligand with COD serving as the hydrogen acceptor, leading to the new complex <b>2</b>, with benzene coordinated in an η<sup>6</sup> fashion to the metal center. Complex <b>1</b> reacts with H<sub>2</sub> to produce the Ir­(III) dihydride complex [(PCy<sub>2</sub>biPh)­IrH<sub>2</sub>]­[B­(Ar<sub>F</sub>)<sub>4</sub>] (<b>3</b>). Initial studies of transfer dehydrogenation and attempts at benzene hydrogenation using <b>1</b> and <b>3</b> are described

    BOugie or stylet in patients UnderGoing Intubation Emergently (BOUGIE): protocol and statistical analysis plan for a randomised clinical trial

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    Introduction Intubation-related complications are less frequent when intubation is successful on the first attempt. The rate of first attempt success in the emergency department (ED) and intensive care unit (ICU) is typically less than 90%. The bougie, a semirigid introducer that can be placed into the trachea to facilitate a Seldinger-like technique of tracheal intubation and is typically reserved for difficult or failed intubations, might improve first attempt success. Evidence supporting its use, however, is from a single academic ED with frequent bougie use. Validation of these findings is needed before widespread implementation.Methods and analysis The BOugie or stylet in patients Undergoing Intubation Emergently trial is a prospective, multicentre, non-blinded randomised trial being conducted in six EDs and six ICUs in the USA. The trial plans to enrol 1106 critically ill adults undergoing orotracheal intubation. Eligible patients are randomised 1:1 for the use of a bougie or use of an endotracheal tube with stylet for the first intubation attempt. The primary outcome is successful intubation on the first attempt. The secondary outcome is severe hypoxaemia, defined as an oxygen saturation less than 80% between induction until 2 min after completion of intubation. Enrolment began on 29 April 2019 and is expected to be completed in 2021.Ethics and dissemination The trial protocol was approved with waiver of informed consent by the Central Institutional Review Board at Vanderbilt University Medical Center or the local institutional review board at an enrolling site. The results will be submitted for publication in a peer-reviewed journal and presented at scientific conferences.Trial registration number ClinicalTrials.gov Registry (NCT03928925)

    Effect of Antiplatelet Therapy on Survival and Organ Support–Free Days in Critically Ill Patients With COVID-19

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