Combined experimental and computational investigations of rhodium-catalysed C-H functionalisation of pyrazoles with alkenes

Detailed experimental and computational studies have been carried out on the oxidative coupling of the alkenes C(2)H(3)Y (Y=CO(2)Me (a), Ph (b), C(O)Me (c)) with 3-aryl-5-R-pyrazoles (R=Me (1 a), Ph (1 b), CF(3) (1 c)) using a [Rh(MeCN)(3)Cp*][PF(6)](2)/Cu(OAc)(2)⋅H(2)O catalyst system. In the reaction of methyl acrylate with 1 a, up to five products (2 aa–6 aa) were formed, including the trans monovinyl product, either complexed within a novel Cu(I) dimer (2 aa) or as the free species (3 aa), and a divinyl species (6 aa); both 3 aa and 6 aa underwent cyclisation by an aza-Michael reaction to give fused heterocycles 4 aa and 5 aa, respectively. With styrene, only trans mono- and divinylation products were observed, whereas with methyl vinyl ketone, a stronger Michael acceptor, only cyclised oxidative coupling products were formed. Density functional theory calculations were performed to characterise the different migratory insertion and β-H transfer steps implicated in the reactions of 1 a with methyl acrylate and styrene. The calculations showed a clear kinetic preference for 2,1-insertion and the formation of trans vinyl products, consistent with the experimental results

Characterization of between-group inequality of longevity in European Union countries

Comparisons of differential survival by country are useful in many domains. In the area of public policy, they help policymakers and analysts assess how much various groups benefit from public programs, such as social security and health care. In financial markets and especially for actuaries, they are important for designing annuities and life insurance products. This paper presents a method for clustering information about differential mortality by country. The approach is then used to group mortality surfaces for European Union (EU) countries. The aim of this paper is to measure between-group inequality in mortality experience in EU countries through a range of mortality indicators. Additionally, the indicators permit the characterization of each group. It is important to take into account characteristics such as sex; therefore, this study differentiates between males and females in order to detect whether their patterns and characterizations are different. It is concluded that there are clear differences in mortality between the east and west of the EU that are more important than the traditional south-north division, with a significant disadvantage for Eastern Europe, and especially for males in Baltic countries. We find that the mortality indicators have evolved in all countries in such a way that the gap between groups has been maintained, both in terms of the differences in mortality levels and variability

Planck Low Frequency Instrument: Beam Patterns

The Low Frequency Instrument on board the ESA Planck satellite is coupled to the Planck 1.5 meter off-axis dual reflector telescope by an array of 27 corrugated feed horns operating at 30, 44, 70, and 100 GHz. We briefly present here a detailed study of the optical interface devoted to optimize the angular resolution (10 arcmin at 100 GHz as a goal) and at the same time to minimize all the systematics coming from the sidelobes of the radiation pattern. Through optical simulations, we provide shapes, locations on the sky, angular resolutions, and polarization properties of each beam.Comment: On behalf of the Planck collaboration. 3 pages, 1 figure. Article published in the Proceedings of the 2K1BC Experimental Cosmology at millimetre wavelength

Renal health after long-term exposure to tenofovir disoproxil fumarate (TDF) in HIV/HBV positive adults in Ghana

Objectives: The study assessed markers of renal health in HIV/HBV co-infected patients receiving TDF- containing antiretroviral therapy in Ghana. Methods: Urinary protein-to-creatinine ratio (uPCR) and albumin-to-protein ratio (uAPR) were measured cross-sectionally after a median of four years of TDF. At this time, alongside extensive laboratory testing, patients underwent evaluation of liver stiffness and blood pressure. The estimated glomerular filtration rate (eGFR) was measured longitudinally before and during TDF therapy. Results: Among 101 participants (66% women, median age 44 years, median CD4 count 572 cells/mm 3 ) 21% and 17% had detectable HIV-1 RNA and HBV DNA, respectively. Overall 35% showed hypertension, 6% diabetes, 7% liver stiffness indicative of cirrhosis, and 18% urinary excretion of Schistosoma antigen. Tubular proteinuria occurred in 16% of patients and was independently predicted by female gender and hypertension. The eGFR declined by median 1.8 ml/min/year during TDF exposure (IQR −4.4, −0.0); more pronounced declines ( ≥5 ml/min/year) occurred in 22% of patients and were associated with receiv-ing ritonavir-boosted lopinavir rather than efavirenz. HBV DNA, HBeAg, transaminases, and liver stiffness were not predictive of renal function abnormalities. Conclusions: The findings mandate improved diagnosis and management of hypertension and suggest targeted laboratory monitoring of patients receiving TDF alongside a booster in sub-Saharan Africa

The Planck Low Frequency Instrument

The Low Frequency Instrument (LFI) of the "Planck Surveyor" ESA mission will perform high-resolution imaging of the Cosmic Microwave Background anisotropies at four frequencies in the 30-100 GHz range. We review the LFI main scientific objectives, the current status of the instrument design and the on-going effort to develop software simulations of the LFI observations. In particular we discuss the design status of the PLANCK telescope, which is critical for reaching adequate effective angular resolution.Comment: 10 pages, Latex (use epsfig.sty); 4 Postscript figures; Astrophys. Lett & Comm, in press. Proc. of the Conference: "The Cosmic Microwave Background and the Planck Mission", Santander, Spain, 22-25 June 199

Studying the evolution in time of bimetallic nanoparticles morphology by Cyclic Voltammetry

Over the last decades, bimetallic nanosized systems have attracted more and more interest thanks to their novel optical, catalytic, magnetic, and sensing properties, often different from the ones of their monometallic counterparts. Studies directed towards the size, shape, composition, and functionalization of the bimetallic nanoparticles are optimized to design sophisticated materials for the intended applications. Considering these facts, it is important to evaluate not only the type and the quantity of the two metals involved, but also their morphological distribution (e.g. alloy or core-shell). Characterization techniques normally used to investigate bimetallic systems are HR-TEM and EXAFS, very expensive and not so easily accessible. Recently, electrochemistry has been employed as alternative or complementary, low-cost, efficient technique with very promising results, allowing the discrimination between alloyed and perfect or defective core-shell systems after their synthesis. A further achievement is the possibility to follow step by step the formation morphology of these nanomaterials during their synthetic procedure. In the present work, we present a study on Au-Pt bimetallic nanoparticles, in form of alloy or core-shell. Cyclovoltammetry (CV) is used as a fast, low-cost and simple screening technique to distinguish the general composition of the sample and to understand the evolution in time of the systems morphology during their synthesis. An additional advantage is the possibility to conduct the study of the material simply in liquid form, without the need of using solid supports, as normally required by other characterization techniques. Interesting results are obtained for Au-based bimetallic samples, gaining information in accordance with TEM images and EXAFS spectra. This fact moves the interest towards the study of other bimetallic systems, to be used in catalytic, electrocatalytic and electroanalytical applications

Bioelectrochemical Nitrogen fixation (e-BNF): Electro-stimulation of enriched biofilm communities drives autotrophic nitrogen and carbon fixation

A new approach to microbial electrosynthesis is proposed, aimed at producing whole biomass from N2 and inorganic carbon, by electrostimulation of complex microbial communities. On a carbon-based conductor under constant polarization ( 120.7\u202fV vs SHE), an electroactive biofilm was enriched with autotrophic nitrogen fixing microorganims and led to biomass synthesis at higher amounts (up to 18 fold), as compared to controls kept at open circuit (OC). After 110\u202fdays, the electron transfer had increased by 30-fold, as compared to abiotic conditions. Metagenomics evidenced Nif genes associated with autotrophs (both Archaea and Bacteria) only in polarized biofilms, but not in OC. With this first proof of concept experiment, we propose to call this promising field \u2018bioelectrochemical nitrogen fixation\u2019 (e-BNF): a possible way to \u2018power\u2019 biological nitrogen fixation, organic carbon storage and soil fertility against desertification, and possibly a new tool to study the development of early prokaryotic life in extreme environments