Tuning Pd-nanoparticle@MIL-101(Cr) Catalysts for Tandem Reductive Amination.

ABSTRACT: The versatility of MOFs as highly porous Lewis acidic supports for precious metal nanoparticles has been exploited for one-pot tandem reductive amination catalysis. MIL-101(Cr) loaded with Pd nanoparticles ca. 3 nm in size at 0.2-1 wt% has been used to catalyse the reaction of 4'-fluoroacetophenone with benzylamine under 10 bar of H2 to give the secondary amine, 4'-fluoro-α-methyl-N-phenylmethylbenzenemethanamine. For the highest Pd loading, major hydrogenolysis of the secondary amine occurs in a second tandem reaction, but by changing the ratio of Pd to Lewis acidic Cr3+ active sites it is possible to tune the catalytic selectivity to the desired 2° amine product. An empirical kinetic analysis was performed to demonstrate this active site complementarity.

Patient load effects on response time to critical arrhythmias in cardiac telemetry: a randomized trial.

OBJECTIVES: Remotely monitored patients may be at risk for a delayed response to critical arrhythmias if the telemetry watchers who monitor them are subject to an excessive patient load. There are no guidelines or studies regarding the appropriate number of patients that a single watcher may safely and effectively monitor. Our objective was to determine the impact of increasing the number of patients monitored on response time to simulated cardiac arrest. DESIGN: Randomized trial. SETTING: Laboratory-based experiment. SUBJECTS: Forty-two remote telemetry technicians and nurses from cardiac units. INTERVENTIONS: Number of patients monitored in a simulation of cardiac telemetry monitoring work. MEASUREMENTS AND MAIN RESULTS: We carried out a study to compare response times to ventricular fibrillation across five patient loads: 16, 24, 32, 40, and 48 patients. The simulation replicated the work of telemetry watchers using a combination of real recorded patient electrocardiogram signals and a simulated patient experiencing ventricular fibrillation. Study participants were assigned to one of the five patient loads and completed a 4-hour monitoring session, during which they performed tasks-including event documentation and phone calls to report events-similar to real monitoring work. When the simulated patient sustained ventricular fibrillation, the time required to report this arrhythmia was recorded. As patient loads increased, there was a statistically significant increase in response times to the ventricular fibrillation. In addition, frequency of failure to meet a response time goal of less than 20 seconds was significantly higher in the 48-patient condition than in all other conditions. Task performance decreased as patient load increased. CONCLUSIONS: As participants monitored more patients in a laboratory setting, their performance with respect to recognizing critical and noncritical events declined. This study has implications for the design of remote telemetry work and other patient monitoring tasks in critical and intermediate care units.

Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C-C bond formation and alcohol oxidation.

The trivalent metal cations Al(3+) , Cr(3+) , and Fe(3+) were each introduced, together with Sc(3+) , into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe2 O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel-Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe2 O3 nanoparticles were also active Lewis acid species, although less active than Sc(3+) in trimer sites. The incorporation of Fe(3+) into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc(3+) and Fe(3+) . A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.

Improved hydrothermal stability of mesoporous oxides for reactions in the aqueous phase.

A simple and inexpensive approach is used to coat metal oxide surfaces (SBA-15) with thin films of carbon. These carbon films provide improved hydrothermal stability to oxides, such as silica and alumina, which are not otherwise stable at elevated temperatures in the presence of liquid water. Furthermore, the carbon film changes the surface chemistry of the support.