Reversible melting and equilibrium phase formation of (Bi,Pb)2Sr2Ca2Cu3O10+d

The decomposition and the reformation of the (Bi,Pb)2Sr2Ca2Cu3O10+d (?Bi,Pb(2223)?) phase have been investigated in-situ by means of High-Temperature Neutron Diffraction, both in sintered bulk samples and in Ag-sheathed monofilamentary tapes. Several decomposition experiments were performed at various temperatures and under various annealing atmospheres, under flowing gas as well as in sealed tubes, in order to study the appropriate conditions for Bi,Pb(2223) formation from the melt. The Bi,Pb(2223) phase was found to melt incongruently into (Ca,Sr)2CuO3, (Sr,Ca)14Cu24O41 and a Pb,Bi-rich liquid phase. Phase reformation after melting was successfully obtained both in bulk samples and Ag-sheathed tapes. The possibility of crystallising the Bi,Pb(2223) phase from the melt was found to be extremely sensitive to the temperature and strongly dependent on the Pb losses. The study of the mass losses due to Pb evaporation was complemented by thermogravimetric analysis which proved that Pb losses are responsible for moving away from equilibrium and therefore hinder the reformation of the Bi,Pb(2223) phase from the melt. Thanks to the full pattern profile refinement, a quantitative phase analysis was carried out as a function of time and temperature and the role of the secondary phases was investigated. Lattice distortions and/or transitions were found to occur at high temperature in Bi,Pb(2223), Bi,Pb(2212), (Ca,Sr)2CuO3 and (Sr,Ca)14Cu24O41, due to cation diffusion and stoichiometry changes. The results indicate that it is possible to form the Bi,Pb(2223) phase from a liquid close to equilibrium conditions, like Bi(2212) and Bi(2201), and open new unexplored perspectives for high-quality Ag-sheathed Bi,Pb(2223) tape processing.Comment: 45 pages (including references,figures and captions), 13 figures Submitted to Supercond. Sci. Techno

The local adsorption structure of methylthiolate and butylthiolate on Au(1 1 1): a photoemission core-level shift investigation

Measurements of the core-level shifts in Au 4f photoemission spectra from Au(1 1 1) at different coverages of methylthiolate and butylthiolate are reported. Adsorption leads to two components in addition to that from the bulk, one at lower photoelectron binding energy attributed to surface atoms not bonded to thiolate species, while the second component has a higher binding energy and is attributed to Au atoms bonded to the surface thiolate. The relative intensities of these surface components for the saturation coverage (mainly (√3 × √3)R30°) phases are discussed in terms of different local adsorption sites in a well-ordered surface, and favour adsorption of the thiolate species atop Au adatoms. Alternative interpretations that might be consistent with an Au-adatom-dithiolate model are discussed, particularly in the context of the possible influence of reduced coverage associated with a disordered surface. Marked differences from previously-reported results for longer-chain alkylthiolate layers are highlighted

Sulphur overlayers on the Au(110) surface: LEED and TPD study

The adsorption and desorption of sulphur on the clean reconstructed Au(1 1 0)–(1 × 2) surface has been studied by low energy electron diffraction, Auger electron spectroscopy and temperature programmed desorption. The results obtained show a complex behaviour of the S/Au(1 1 0) system during sulphur desorption at different temperatures. Two structures of the stable ordered sulphur overlayer on the Au(1 1 0) surface, p(4 × 2) and c(4 × 4), were found after annealing the S/Au(1 1 0) system at 630 K and 463 K, respectively. The corresponding sulphur coverage for these overlayers was estimated by AES signal intensity analysis of the Au NOO and S LMM Auger lines to be equal to 0.13 ML and 0.2 ML, respectively. Both sulphur structures appear after removing an excess of sulphur, which mainly desorbs at 358 K as determined from TPD spectra. Furthermore, it was not possible to produce the lower coverage p(4 × 2) sulphur structure by annealing the c(4 × 4) surface. In the case of the p(4 × 2) S overlayer on the Au(1 1 0)–(1 × 2) surface it is proposed that the sulphur is attached to “missing row” sites only. The c(4 × 4) S overlayer arises via desorption of S2 molecules that are formed on the surface due to mobility of sulphur atoms after a prolonged anneal

Chiral recognition in dimerization of adsorbed cysteine observed by scanning tunnelling microscopy

Kühnle A, Linderoth TR, Hammer B, Besenbacher F. Chiral recognition in dimerization of adsorbed cysteine observed by scanning tunnelling microscopy. Nature. 2002;415(6874):891-893.Stereochemistry plays a central role in controlling molecular recognition and interaction: the chemical and biological properties of molecules depend not only on the nature of their constituent atoms but also on how these atoms are positioned in space. Chiral specificity is consequently fundamental in chemical biology and pharmacology(1,2) and has accordingly been widely studied. Advances in scanning probe microscopies now make it possible to probe chiral phenomena at surfaces at the molecular level. These methods have been used to determine the chirality of adsorbed molecules(3-5), and to provide direct evidence for chiral discrimination in molecular interactions(6) and the spontaneous resolution of adsorbates into extended enantiomerically pure overlayers(3,7-9). Here we report scanning tunnelling microscopy studies of cysteine adsorbed to a (110) gold surface, which show that molecular pairs formed from a racemic mixture of this naturally occurring amino acid are exclusively homochiral, and that their binding to the gold surface is associated with local surface restructuring. Density-functional theory(10) calculations indicate that the chiral specificity of the dimer formation process is driven by the optimization of three bonds on each cysteine molecule. These findings thus provide a clear molecular-level illustration of the well known three-point contact model(11,12) for chiral recognition in a simple bimolecular system

State of the climate in 2013

In 2013, the vast majority of the monitored climate variables reported here maintained trends established in recent decades. ENSO was in a neutral state during the entire year, remaining mostly on the cool side of neutral with modest impacts on regional weather patterns around the world. This follows several years dominated by the effects of either La Niña or El Niño events. According to several independent analyses, 2013 was again among the 10 warmest years on record at the global scale, both at the Earths surface and through the troposphere. Some regions in the Southern Hemisphere had record or near-record high temperatures for the year. Australia observed its hottest year on record, while Argentina and New Zealand reported their second and third hottest years, respectively. In Antarctica, Amundsen-Scott South Pole Station reported its highest annual temperature since records began in 1957. At the opposite pole, the Arctic observed its seventh warmest year since records began in the early 20th century. At 20-m depth, record high temperatures were measured at some permafrost stations on the North Slope of Alaska and in the Brooks Range. In the Northern Hemisphere extratropics, anomalous meridional atmospheric circulation occurred throughout much of the year, leading to marked regional extremes of both temperature and precipitation. Cold temperature anomalies during winter across Eurasia were followed by warm spring temperature anomalies, which were linked to a new record low Eurasian snow cover extent in May. Minimum sea ice extent in the Arctic was the sixth lowest since satellite observations began in 1979. Including 2013, all seven lowest extents on record have occurred in the past seven years. Antarctica, on the other hand, had above-average sea ice extent throughout 2013, with 116 days of new daily high extent records, including a new daily maximum sea ice area of 19.57 million km2 reached on 1 October. ENSO-neutral conditions in the eastern central Pacific Ocean and a negative Pacific decadal oscillation pattern in the North Pacific had the largest impacts on the global sea surface temperature in 2013. The North Pacific reached a historic high temperature in 2013 and on balance the globally-averaged sea surface temperature was among the 10 highest on record. Overall, the salt content in nearsurface ocean waters increased while in intermediate waters it decreased. Global mean sea level continued to rise during 2013, on pace with a trend of 3.2 mm yr-1 over the past two decades. A portion of this trend (0.5 mm yr-1) has been attributed to natural variability associated with the Pacific decadal oscillation as well as to ongoing contributions from the melting of glaciers and ice sheets and ocean warming. Global tropical cyclone frequency during 2013 was slightly above average with a total of 94 storms, although the North Atlantic Basin had its quietest hurricane season since 1994. In the Western North Pacific Basin, Super Typhoon Haiyan, the deadliest tropical cyclone of 2013, had 1-minute sustained winds estimated to be 170 kt (87.5 m s-1) on 7 November, the highest wind speed ever assigned to a tropical cyclone. High storm surge was also associated with Haiyan as it made landfall over the central Philippines, an area where sea level is currently at historic highs, increasing by 200 mm since 1970. In the atmosphere, carbon dioxide, methane, and nitrous oxide all continued to increase in 2013. As in previous years, each of these major greenhouse gases once again reached historic high concentrations. In the Arctic, carbon dioxide and methane increased at the same rate as the global increase. These increases are likely due to export from lower latitudes rather than a consequence of increases in Arctic sources, such as thawing permafrost. At Mauna Loa, Hawaii, for the first time since measurements began in 1958, the daily average mixing ratio of carbon dioxide exceeded 400 ppm on 9 May. The state of these variables, along with dozens of others, and the 2013 climate conditions of regions around the world are discussed in further detail in this 24th edition of the State of the Climate series. © 2014, American Meteorological Society. All rights reserved

Effects of Anacetrapib in Patients with Atherosclerotic Vascular Disease

BACKGROUND: Patients with atherosclerotic vascular disease remain at high risk for cardiovascular events despite effective statin-based treatment of low-density lipoprotein (LDL) cholesterol levels. The inhibition of cholesteryl ester transfer protein (CETP) by anacetrapib reduces LDL cholesterol levels and increases high-density lipoprotein (HDL) cholesterol levels. However, trials of other CETP inhibitors have shown neutral or adverse effects on cardiovascular outcomes. METHODS: We conducted a randomized, double-blind, placebo-controlled trial involving 30,449 adults with atherosclerotic vascular disease who were receiving intensive atorvastatin therapy and who had a mean LDL cholesterol level of 61 mg per deciliter (1.58 mmol per liter), a mean non-HDL cholesterol level of 92 mg per deciliter (2.38 mmol per liter), and a mean HDL cholesterol level of 40 mg per deciliter (1.03 mmol per liter). The patients were assigned to receive either 100 mg of anacetrapib once daily (15,225 patients) or matching placebo (15,224 patients). The primary outcome was the first major coronary event, a composite of coronary death, myocardial infarction, or coronary revascularization. RESULTS: During the median follow-up period of 4.1 years, the primary outcome occurred in significantly fewer patients in the anacetrapib group than in the placebo group (1640 of 15,225 patients [10.8%] vs. 1803 of 15,224 patients [11.8%]; rate ratio, 0.91; 95% confidence interval, 0.85 to 0.97; P=0.004). The relative difference in risk was similar across multiple prespecified subgroups. At the trial midpoint, the mean level of HDL cholesterol was higher by 43 mg per deciliter (1.12 mmol per liter) in the anacetrapib group than in the placebo group (a relative difference of 104%), and the mean level of non-HDL cholesterol was lower by 17 mg per deciliter (0.44 mmol per liter), a relative difference of -18%. There were no significant between-group differences in the risk of death, cancer, or other serious adverse events. CONCLUSIONS: Among patients with atherosclerotic vascular disease who were receiving intensive statin therapy, the use of anacetrapib resulted in a lower incidence of major coronary events than the use of placebo. (Funded by Merck and others; Current Controlled Trials number, ISRCTN48678192 ; ClinicalTrials.gov number, NCT01252953 ; and EudraCT number, 2010-023467-18 .)