Unsaturated σ-hydrocarbyl transition-metal complexes. Part 3. Crystal and molecular structure of trans-chlorobis(diethylphenylphosphine)(vinyl)platinum(II)

The molecular structure of trans-[PtCl(CHCH2)(PEt2Ph)2] has been determined by X-ray diffraction methods. The crystals are orthorhombic, space group Pbcn, with a= 10.686(2), b= 13.832(4), c= 16.129(4)Å, and Z= 4. The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R 0.044 for 1 420 diffractometric intensity data. The crystals contain discrete molecules in which the platinum co-ordination is square planar. The Pt–Cl bond vector coincides with a crystallographic diad axis about which the atoms of the vinyl group are disordered. Selected bond lengths (Å) are Pt–Cl 2.398(4), Pt–P 2.295(3), and Pt–C 2.03(2). The Pt–CC angle is 127(2)°. From a survey of the available structural data it is concluded that there is little, if any, back donation from platinum to carbon in platinum–alkenyl linkages.

Secondary structure prediction with support vector machines

Motivation: A new method that uses support vector machines (SVMs) to predict protein secondary structure is described and evaluated. The study is designed to develop a reliable prediction method using an alternative technique and to investigate the applicability of SVMs to this type of bioinformatics problem. Methods: Binary SVMs are trained to discriminate between two structural classes. The binary classifiers are combined in several ways to predict multi-class secondary structure. Results: The average three-state prediction accuracy per protein (Q3) is estimated by cross-validation to be 77.07 ± 0.26% with a segment overlap (Sov) score of 73.32 ± 0.39%. The SVM performs similarly to the 'state-of-the-art' PSIPRED prediction method on a non-homologous test set of 121 proteins despite being trained on substantially fewer examples. A simple consensus of the SVM, PSIPRED and PROFsec achieves significantly higher prediction accuracy than the individual methods. Availability: The SVM classifier is available from the authors. Work is in progress to make the method available on-line and to integrate the SVM predictions into the PSIPRED server.

In vitro antioxidant activity and antigenotoxicity of 5-n-alkylresorcinols

Incubation with 5-n-alkylresorcinols (chain lengths C15:0, C17:0, C19:0, C21:0, and C23:0) increased the self-protection capacity of HT29 human colon cancer cells against DNA damage induced by hydrogen peroxide and genotoxic fecal water samples using comet assay (single-cell gel electrophoresis assay). The alkylresorcinols did not exert potent antioxidant activity in the FRAP (ferric reduction ability of plasma) and DPPH (2,2-diphenyl-1-picrylhydrazyl) radical assays. However they were able to significantly inhibit copper-mediated oxidation of human LDL (low-density lipoprotein) in vitro, and pentadecylresorcinol at 25 micromol/L increased lag time by 65 min. The results show that alkylresorcinols have antigenotoxic and antioxidant activity under in vitro conditions.

Genetic evidence for a predominant role of PI3Kβ catalytic activity in ITAM- and integrin-mediated signaling in platelets.

Phosphatidylinositol 3-kinase (PI3K) isoforms PI3Kbeta and PI3Kgamma are implicated in platelet adhesion, activation, and aggregation, but their relative contribution is still unclear or controversial. Here, we report the first comparative functional analysis of platelets from mice expressing a catalytically inactive form of PI3Kbeta or PI3Kgamma. We demonstrate that both isoforms were similarly required for maximal activation of the small GTPase Rap1b and for complete platelet aggregation upon stimulation of G protein-coupled receptors for adenosine 5'-diphosphate (ADP) or U46619. Their contribution to these events, however, was largely redundant and dispensable. However, PI3Kbeta, but not PI3Kgamma, enzymatic activity was absolutely required for Akt phosphorylation, Rap1 activation, and platelet aggregation downstream of the immunoreceptor tyrosine-based activation motif (ITAM)-bearing receptor glycoprotein VI (GPVI). Moreover, PI3Kbeta was a major essential regulator of platelet adhesion to fibrinogen and of integrin alpha(IIb)beta(3)-mediated spreading. These results provide genetic evidence for a crucial and selective role of PI3Kbeta in signaling through GPVI and integrin alpha(IIb)beta(3).

Impegno nero: Italian intellectuals and the African-American struggle

In the aftermath of the Second World War, Italian intellectuals participated in Italy’s reconstruction with an ideological commitment inspired by the African-American struggle for equal rights in the United States. Drawing on the work of many of the leading figures in postwar Italian culture, including Italo Calvino, Giorgio Caproni, Cesare Pavese, and Elio Vittorini, this essay argues that Italian intellectual impegno—defined as the effort to remake Italian culture and to guide Italian social reform—was united with a significant investment in the African-American cause. The author terms this tendency impegno nero and traces its development in the critical reception of African-American writers including W.E.B. DuBois, Langston Hughes, and Richard Wright. Postwar impegno nero is then contrasted with the treatment of African-American themes under Fascism, when commentators had likewise condemned American racism, but had paradoxically linked their laments for the plight of African Americans with defenses of the racial policies of the Fascist regime. Indeed, Fascist colonialism and anti-Semitism were both justified through references to what Fascist intellectuals believed to be America’s greater injustices. After 1945, in contrast, Italian intellectuals advocated an international, interdependent campaign for justice, symbolizing national reforms by projecting them onto an emblematic America. In this way, impegno nero revived and revised the celebrated "myth of America" that had developed in Italy between the world wars. Advancing a new, postwar myth, Italian intellectuals adopted the African-American struggle in order to reinforce their own efforts in the ongoing struggle for justice in Italy.

Centennial variations in sunspot number, open solar flux and streamer belt width: 3. Modelling

From the variation of near-Earth interplanetary conditions, reconstructed for the mid-19th century to the present day using historic geomagnetic activity observations, Lockwood and Owens [2014] have suggested that Earth remains within a broadened streamer belt during solar cycles when the Open Solar Flux (OSF) is low. From this they propose that the Earth was immersed in almost constant slow solar wind during the Maunder minimum (c. 1650-1710). In this paper, we extend continuity modelling of the OSF to predict the streamer belt width using both group sunspot numbers and corrected international sunspot numbers to quantify the emergence rate of new OSF. The results support the idea that the solar wind at Earth was persistently slow during the Maunder minimum because the streamer belt was broad.

Azide monoliths as convenient flow reactors for efficient Curtius rearrangement reactions

The preparation and use of an azide-containing monolithic reactor is described for use in a flow chemistry device and in particular for conducting Curtius rearrangement reactions via acid chloride inputs.

Sea level extremes at the coasts of China

Hourly sea level records from 1954 to 2012 at 20 tide gauges at and adjacent to the Chinese coasts are used to analyze extremes in sea level and in tidal residual. Tides and tropical cyclones determine the spatial distribution of sea level maxima. Tidal residual maxima are predominantly determined by tropical cyclones. The 50 year return level is found to be sensitive to the number of extreme events used in the estimation. This is caused by the small number of tropical cyclone events happening each year which lead to other local storm events included thus significantly affecting the estimates. Significant increase in sea level extremes is found with trends in the range between 2.0 and 14.1 mm yr−1. The trends are primarily driven by changes in median sea level but also linked with increases in tidal amplitudes at three stations. Tropical cyclones cause significant interannual variations in the extremes. The interannual variability in the sea level extremes is also influenced by the changes in median sea level at the north and by the 18.6 year nodal cycle at the South China Sea. Neither of PDO and ENSO is found to be an indicator of changes in the size of extremes, but ENSO appears to regulate the number of tropical cyclones that reach the Chinese coasts. Global mean atmospheric temperature appears to be a good descriptor of the interannual variability of tidal residual extremes induced by tropical cyclones but the trend in global temperature is inconsistent with the lack of trend in the residuals.

Speleothems as sensitive recorders of volcanic eruptions - the Bronze Age Minoan eruption recorded in a stalagmite from Turkey

Mounting evidence exists that variations in sulphur content in stalagmites are closely linked to changes in volcanic or anthropogenic atmospheric sulphur. The strong dependency of sulphur on soil pH and ecosystem storage, however, can result in a delay of several years to decades in the registration of volcanic eruptions and anthropogenic emissions by stalagmites. Here we present synchrotron-radiation based trace element analysis performed on a precisely-dated section of a stalagmite from Sofular Cave in Northern Turkey. As this section covers the time interval of the intensively studied Minoan volcanic eruption between 1600 and 1650 BC, we can test whether this vigorous eruption can be traced in a stalagmite. Of all measured trace elements, only bromine shows a clear short-lived peak at 1621±251621±25 BC, whereas sulphur and molybdenum show peaks later at 1617±251617±25 and 1589±251589±25 respectively. We suggest that all trace element peaks are related to the Minoan eruption, whereas the observed phasing of bromine, molybdenum and sulphur is related to differences in their retention rates in the soil above Sofular Cave. For the first time, we can show that bromine appears to be an ideal volcanic tracer in stalagmites, as it is a prominent volatile component in volcanic eruptions, can be easily leached in soils and rapidly transferred from the atmosphere through the soil and bedrock into the cave and stalagmite respectively. Highly resolved oxygen and carbon isotope profiles indicate that the Minoan eruption had no detectable climatic and environmental impact in Northern Turkey.

Sparta and the English Republic

In 1659-60, James Harrington and Henry Stubbe, two republican authors, engaged in a bad-tempered pamphlet debate about the constitution of classical Sparta. This took place in the context of political collapse after the fall of the Cromwellian Protectorate, as republicans desperately attempted to devise safeguards which could prevent the return of monarchy. Questions of constitutional form were not always at the forefront of 1650s English republicanism, but Harrington’s ideal constitution of ‘Oceana’ brought these questions to the fore in 1659’s discussions. Sparta formed a key plank of the ‘ancient prudence’ which supported Harrington’s theory, and like Stubbe he drew on Nicolaus Cragius’ De Republica Lacedaemoniorum (1593) for evidence, and was attracted to some of the more apparently ‘aristocratic’ elements of the Spartan constitution. However, classical texts and modern scholarly authority, such as Cragius’, were not the only ingredients in the English version of the ‘classical republican’ tradition; sixteenth- and seventeenth-century political thinkers and current exigencies also shaped Harrington and Stubbe’s arguments. Both Harrington and Stubbe ended up challenging the scholarly and ancient consensus that Sparta was an aristocracy or mixed polity, Harrington reinterpreting it to assimilate it to ‘democracy’, and Stubbe attempting to rehabilitate a model of benign ‘oligarchy’.