Fowler-Nordheim-like local injection of photoelectrons from a silicon tip

Tunneling between a photo-excited p-type silicon tip and a gold surface is studied as a function of tip bias, tip/sample distance and light intensity. In order to extend the range of application of future spin injection experiments, the measurements are carried out under nitrogen gas at room temperature. It is found that while tunneling of valence band electrons is described by a standard process between the semiconductor valence band and the metal, the tunneling of photoelectrons obeys a Fowler-Nordheim-like process directly from the conduction band. In the latter case, the bias dependence of the photocurrent as a function of distance is in agreement with theoretical predictions which include image charge effects. Quantitative analysis of the bias dependence of the dark and photocurrent spectra gives reasonable values for the distance, and for the tip and metal work functions. For small distances image charge effects induce a vanishing of the barrier and the bias dependence of the photocurrent is exponential. In common with many works on field emission, fluctuations in the tunneling currents are observed. These are mainly attributed to changes in the prefactor for the tunneling photocurrent, which we suggest is caused by an electric-field-induced modification of the thickness of the natural oxide layer covering the tip apex.Comment: 12 pages, 11 figures. Submitted to Phys. Rev.

Highly selective and solvent-dependent reduction of Nitrobenzene to N-phenylhydroxylamine, azoxybenzene, and aniline catalyzed by phosphino-modified polymer immobilized ionic liquid-stabilized AuNPs

Gold nanoparticles stabilized by phosphine-decorated polymer immobilized ionic liquids (AuNP@PPh2-PIILP) is an extremely efficient multiproduct selective catalyst for the sodium borohydride-mediated reduction of nitrobenzene giving N-phenylhydroxylamine, azoxybenzene, or aniline as the sole product under mild conditions and a very low catalyst loading. The use of a single nanoparticle-based catalyst for the partial and complete reduction of nitroarenes to afford three different products with exceptionally high selectivities is unprecedented. Under optimum conditions, thermodynamically unfavorable N-phenylhydroxylamine can be obtained as the sole product in near quantitative yield in water, whereas a change in reaction solvent to ethanol results in a dramatic switch in selectivity to afford azoxybenzene. The key to obtaining such a high selectivity for N-phenylhydroxylamine is the use of a nitrogen atmosphere at room temperature as reactions conducted under an inert atmosphere occur via the direct pathway and are essentially irreversible, while reactions in air afford significant amounts of azoxy-based products by virtue of competing condensation due to reversible formation of N-phenylhydroxylamine. Ultimately, aniline can also be obtained quantitatively and selectively by adjusting the reaction temperature and time accordingly. Introduction of PEG onto the polyionic liquid resulted in a dramatic improvement in catalyst efficiency such that N-phenylhydroxylamine could be obtained with a turnover number (TON) of 100 000 (turnover frequency (TOF) of 73 000 h–1, with >99% selectivity), azoxybenzene with a TON of 55 000 (TOF of 37 000 h–1 with 100% selectivity), and aniline with a TON of 500 000 (TOF of 62 500 h–1, with 100% selectivity). As the combination of ionic liquid and phosphine is required to achieve high activity and selectivity, further studies are currently underway to explore whether interfacial electronic effects influence adsorption and thereby selectivity and whether channeling of the substrate by the electrostatic potential around the AuNPs is responsible for the high activity. This is the first report of a AuNP-based system that can selectively reduce nitroarenes to either of two synthetically important intermediates as well as aniline and, in this regard, is an exciting discovery that will form the basis to develop a continuous flow process enabling facile scale-up

Counter-Insurgency Campaigning

21 cm; 189 ha

Chronic extra-aortic balloon counterpulsation: First-in-human pilot study in end-stage heart failure

Background: Some patients continue to have significant heart failure symptoms despite optimal medical therapy. Methods: We describe a first-in-human experience with an implantable non–blood-contacting extra-ascending aortic counterpulsation heart assist system (C-Pulse) in 5 end-stage heart failure patients, aged 54 to 73 years. Results: All patients improved by 1 NYHA class and improvements in invasive hemodynamics were documented in 3 patients. Three of 5 patients (60%) had infectious complications. Two patients were explanted at 5 and 7 weeks, respectively, as a result of mediastinal infection related to the implant procedure. One patient was successfully transplanted at 1 month and 1 remained hemodynamically improved on the device at 6 months but suffered infective complications. The device and protocol have been modified as a result of this pilot study with a further multicenter safety study underway. Conclusions: Although feasibility of this device is suggested by this pilot study, safety and efficacy will need to be examined in a larger cohort with longer follow-up