Search

Diruthenium(II,III) carboxylates Ru2(esp)2Cl (1a), [Ru2(esp)2(H2O)2]BF4 (1b), and Ru2(OAc)4Cl (2) efficiently catalyze the oxygenation of organic sulfides. As noted in a previous work, 1a is active in oxygenation of organic sulfides with tert-butyl hydroperoxide (TBHP) in CH3CN. Reported herein in detail is the oxygenation activity of 1a, 1b, and 2, with the latter being highly selective in oxo-transfer to organic sulfides using TBHP under ambient conditions. Solvent-free oxidation reactions were achieved through dissolving 1a or 1b directly into the substrate with 2 equiv of TBHP, yielding TOF up to 2056 h(-1) with 1b. Also examined are the rate dependence on both catalyst and oxidant concentration for reactions with catalysts 1a and 2. Ru2(OAc)4Cl may be kinetically saturated with TBHP; however, Ru2(esp)2Cl does not display saturation kinetics. By use of a series of para-substituted thioanisoles, linear free-energy relationships were established for both 1a and 2, where the reactivity constants (ρ) are negative and that of 1a is about half that of 2. Given these reactivity data, two plausible reaction pathways were suggested. Density functional theory (DFT) calculation for the model compound Ru2(OAc)4Cl·TBHP, with TBHP on the open axial site, revealed elongation of the O-O bond of TBHP upon coordination.

Objective: To evaluate intraoperative graft patency and identify grafts under risk of early occlusion., Methods: Fifty four patients were submitted to coronary artery bypass surgery and the graft flow was assessed by the Flowmeter (Medtronic Medistim), which utilizes the TTFM method. Three patients had left main disease and 48 had normal or mildly reduced left ventricular function., Results: In hospital mortality was 3.7% (two patients), one for mesenteric thrombosis and one due to cardiogenic chock. Seventeen patients (34%) were submitted to off pump CABG. Arterial Graft flow measures ranged from 8 to 106 ml/min (average 31.14 ml/min), and venous grafts flow ranged from 9 to 149 ml/min (average 50.42 ml/min)., Conclusion: Flowmeter use represents higher safety both for patients and surgeons. Even under legal aspects, the documentation provided by the device can avoid future questionings.

Background: Hot flushes (HFs) and night sweats are frequent complaints among both peri- and postmenopausal women. Beliefs regarding these complaints may vary from one population to another., Objective: To assess HF beliefs and factors related to negative beliefs in a climacteric Hispanic population using the Hot Flush Beliefs Scale (HFBS)., Methods: A total of 1154 healthy women (40-59 years) were assessed with the Menopause Rating Scale (MRS), those presenting HFs were requested to fill out the HFBS and a questionnaire containing socio-demographic data (female and partner)., Results: A total of 646 presented HFs (56%) graded according to the first item of the MRS as mild (28.6%), moderate (33.2%), severe (29.1%) and very severe (9.1%). Mean age of these women was 49.5+/-5.2 years, with 51.9% having 12 or less years of education, 61.5% being postmenopausal and 47.2% living in high altitude. At the moment of the survey 13.9% were on HT, 12.8% on phytoestrogens and 7.1% on psychotropic drugs. Women strongly disagreed in more negatively oriented items of those contained in subscale one (beliefs about self in social context). Contrary to this, women strongly agreed in more negative oriented items contained in subscale two which assesses beliefs about coping with HFs. Women presenting with severe-very severe HFs displayed higher HFBS total and subscale scores indicating a more negative belief regarding HFs. Logistic regression analysis determined that HF severity was related to higher HFBS scores for the total and subscales one and two. Current smoking, higher parity, lower female education, female psychiatric consultation, time since menopause and partner unhealthiness and alcohol consumption were also related to higher HFBS scorings. Postmenopausal status and church attendance were related to lower scores., Conclusion: In this mid-aged Ecuadorian female series negative beliefs regarding HFs were related to the severity of HFs and individual female or partner characteristics. Data provided from clinical research using this tool, alone or in combination with other tests, is warranted., (Copyright 2010 Elsevier Ireland Ltd. All rights reserved.)

We quantified the effects of deforestation, and subsequent cultivation and forest regeneration, on the abundance and composition of mosquito larval habitats, specifically phytotelmata (plant-held waters), in the western Amazon basin. Recently deforested sites were characterized by increased phytotelm density (1.6 phytotelmata/m2) and greater relative abundance of fallen-plant-part phytotelmata (76%) compared to intact forests (0.9 phytotelmata/m2 and 25% fallen plant parts). As a result, the total volume of colonizable phytotelm water was significantly larger in new clearings. Subsequent cultivation of cleared land with mixed crops including pineapple and plantain had similar consequences: phytotelm density (2.2 units/m2) was significantly larger in plantations than in forests due to greater relative abundance of water-filled plant axils (71% vs. 39% in forest). Such axils are the preferred larval habitats for Wyeomyia spp. mosquitoes, which showed a similarly significant increase in production in plantations (0.25 larvae/m2) vs. forests (0.04 larvae/m2). Likewise, Limatus spp. mosquitoes were an order of magnitude more abundant in altered landscapes (especially in recently deforested and cultivated areas) than in mature forest, due to increased abundance of fallen-plant-part phytotelmata, in which they are typically the most common colonists. Because they are potential vectors of pathogens in a region of high endemic and emergent virus activity, increases in local abundance of Limatus spp. and Wyeomyia spp. due to large-scale deforestation and agriculture may influence rates of disease transmission.