Mechanistic studies of magnetically recyclable Pd - Fe3O4 heterodimeric nanocrystal-catalyzed organic reactions.

Recently, we have reported several catalytic applications of new Pd - Fe3 O4 heterodimeric nanocrystals as magnetically separable catalysts. Successful applications of the nanocrystals towards various useful organic reactions such as Suzuki, Heck, and Sonogashira coupling reactions, direct C - H arylation, and Wacker oxidation have been recorded. However, detailed mechanistic courses of the reactions have not been delineated, and it was not clear whether these processes proceeded through a homogeneous or heterogeneous mechanism. Here, we report detailed mechanistic investigations of the reactions employing the Pd - Fe3 O4 nanoparticle catalysts. Suzuki coupling and Wacker oxidation reactions were chosen as two representative heterogeneous reactions employing the Pd - Fe3 O4 catalysts, and general kinetic studies, hot filtration tests, and three-phase tests were carried out for the two reactions. The studies showed that the reactions most probably proceed via a solution-phase mechanism.

Magnetically recoverable nanoflake-shaped iron oxide/Pt heterogeneous catalysts and their excellent catalytic performance in the hydrogenation reaction.

In this study, a kind of unique Fe2O3/Pt hybrid consisting of uniform platinum nanoparticles deposited on a nanoflake-shaped Fe2O3 support was prepared by using a solvothermal reaction followed by a heat-induced reduction process. The prepared Fe2O3 sample displays well-defined nanoflake-like morphology; remarkably, there are many specific cavities on its surface. In addition, uniform Pt nanoparticles with narrow size distribution were deposited onto the surface of the preformed flake-like Fe2O3 support to form the Fe2O3/Pt hybrid via a facile heat-induced reduction reaction. Thus, the prepared Fe2O3/Pt hybrid can serve as heterogeneous catalyst over the hydrogenation reaction. Results demonstrated that the specific Fe2O3/Pt heterogeneous catalyst exhibits good catalytic performances, including high conversion, specific selectivity, and excellent recycling durability, over hydrogenation reactions for different substrates. Furthermore, the prepared Fe2O3/Pt heterogeneous catalyst could be easily separated from the product mixture by using a magnet and could be recycled for 10 cycles without catalytic activity loss. In a word, the present synthetic approach is facile, scalable, and reproducible, which can be easily facilitated to prepare other types of noble metals/metal oxide composite systems.

Selective semihydrogenation of alkynes on shape-controlled palladium nanocrystals.

A systematic study on the selective semihydrogenation of alkynes to alkenes on shape-controlled palladium (Pd) nanocrystals was performed. Pd nanocrystals with a cubic shape and thus exposed {100} facets were synthesized in an aqueous solution through the reduction of Na2PdCl4 with L-ascorbic acid in the presence of bromide ions. The Pd nanocubes were tested as catalysts for the semihydrogenation of various alkynes such as 5-decyne, 2-butyne-1,4-diol, and phenylacetylene. For all substrates, the Pd nanocubes exhibited higher alkene selectivity (>90 %) than a commercial Pd/C catalyst (75-90 %), which was attributed to a large adsorption energy of the carbon-carbon triple bond on the {100} facets of the Pd nanocubes. Our approach based on the shape control of Pd nanocrystals offers a simple and effective route to the development of a highly selective catalyst for alkyne semihydrogenation.

Simple synthesis of Pd-Fe3O4 heterodimer nanocrystals and their application as a magnetically recyclable catalyst for Suzuki cross-coupling reactions.

A simple gram-scale synthesis of Pd-Fe(3)O(4) heterodimer nanocrystals was achieved by controlled one-pot thermolysis of a mixture solution composed of iron acetylacetonate, palladium acetylacetonate, oleylamine, and oleic acid. The heterodimer nanocrystals are composed of a 6 nm-sized Pd nanosphere and a 30 nm-sized faceted Fe(3)O(4) nanocrystal and they are soft ferrimagnetic with high saturation magnetization value and low coercivity value. The heterodimer nanocrystals exhibited good activities for various Suzuki coupling reactions. Furthermore, the nanocrystal catalyst could be easily separated from the product mixture by using a magnet and could be recycled 10 times without losing catalytic activity.

Interrupted aortic arch diagnosed with loss of femoral pulse in a patient undergoing patent ductus arteriosus ligation -A case report-.

A 12-year-old boy with ventricular septal defect and patent ductus arteriosus was presented to the operating room. Upon clamping the patent ductus arteriosus, the femoral arterial pressure curve was lost; however, it returned upon unclamping. Upon further dissection, an interrupted aortic arch was found between the left subclavian artery and patent ductus arteriosus. The surgery was discontinued for further evaluation.

Effect of arterial oxygen tension during reperfusion on myocardial recovery in patients undergoing valvular heart surgery.

BACKGROUND: Valvular heart surgery (VHS) utilizing cardiopulmonary bypass (CPB) is inevitably associated with ischemic-reperfusion injury, which is known to depend on oxygen tension during reperfusion. The aim of this study was to evaluate the effect of arterial oxygen tension during reperfusion on myocardial recovery in patients undergoing VHS. METHODS: Fifty-six patients undergoing isolated VHS were randomly exposed to an oxygen fraction of 0.7 (hyperoxic group, n = 28) or 0.5 (normoxic group, n = 28) during reperfusion. All patients received an oxygen fraction of 0.7 during CPB. In the normoxic group, the oxygen fraction was lowered to 0.5 from the last warm cardioplegia administration to 1 minute after aortic unclamping, and was then raised back to 0.7. Hemodynamic data were measured after induction of anesthesia, weaning from CPB, and sternum closure. The frequency of cardiotonic medications used during and after weaning from CPB, and the short-term outcomes during the hospital stay were also assessed. RESULTS: The frequency of vasopressin and milrinone use during weaning from CPB, but not norepinephrine, was significantly less in the normoxic group. The post-operative cardiac enzyme levels and short-term outcomes were not different between the groups. CONCLUSIONS: Normoxic reperfusion from the last cardioplegia administration to 1 minute after aortic unclamping in patients undergoing VHS resulted in significantly less frequent use of vasopressin and inotropics during weaning from CPB than hyperoxic reperfusion, although it did not affect the post-operative myocardial enzyme release or short-term prognosis.