A new type of doubly silylamido-bridged\ud cyclopentadienyl group 4 metal complexes

Doubly bridged di(silyl-η-amido)cyclopentadienyltitanium and -zirconium complexes and their related cations as the [(PhCH 2)B(C 6F 5) 3] - salts have been isolated (see structure of the Ti derivative). The neutral benzylzirconium complex was a very efficient catalyst in the presence of methylaluminoxane for producing high molecular weight polyethylene and ethylene-1-hexene copolymer

Zirconium and hafnium complexes with (allylsilyl)(η-amidosilyl)-η5-cyclopentadienyl ligands: synthesis, structure and reactivity

The disubstituted cyclopentadiene C5H4(SiMe2Cl)[SiMe2(CH2CH=CH2)] was isolated by reaction of the lithium salt [Li{C5H4SiMe2(CH2CH=CH2)}] with SiMe2Cl2. It was then treated with NH2tBu and LiNH(2,6-Me2C6H3) to give the (aminosilyl)cyclopentadienes C5H4[SiMe2(CH2CH=CH2)][SiMe2(NHR)], which were further deprotonated to their dilithium salts [Li2{1-SiMe2NR-3-SiMe2(CH2CH=CH2)C5H3}] (R = tBu, 2,6-Me2C6H3). Reactions of the metal halides ZrCl4(THF)2 and HfCl4 with these dilithium salts, followed by alkylation of the resulting dichloro complexes, afforded the (η1-amidosilyl)-η5-cyclopentadienyl complexes [M{η5-C5H3(SiMe2-η1-NR)[SiMe2(CH2CH=CH2)]}X2] (R = tBu, 2,6-Me2C6H3; X = Cl, Me, CH2Ph; M = Zr, Hf). Only the bis(iminoacyl) complexes [M{η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}{η2-CR=N(2,6-Me2C6H3)}2] (M = Zr, Hf; R = Me, CH2Ph) could be isolated when the dialkylzirconium and -hafnium complexes were treated with CN(2,6-Me2C6H3); these were slowly transformed into the C–C-coupled diazametallacyclopentene compounds [M{η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}{η1-N(2,6-Me2C6H3)-CR=CR-η1-N(2,6-Me2C6H3)}] (R = Me, CH2Ph, M = Zr; R = Me, M = Hf) when their toluene solutions were heated to 70 °C–80 °C for long periods (2–4 d). The structural characterisation of all of the new compounds is described and the molecular structure of the dimeric dichlorozirconocene [ZrCl(μ-Cl){η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}]2, was determined by X-ray diffraction methods. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005

Sympathetic Control of Circulation in Hypertension and Congestive Heart Failure

Adrenergic overactivity is a common hallmark of both essential hypertension and congestive heart failure. Indirect and direct measures of sympathetic function have clearly shown that sympathetic activation characterizes essential hypertension. This adrenergic overactivity appears to be related to the severity of the hypertensive state, being detectable in its early stages and showing a progressive increase with the severity of the disease. Essential hypertension is also associated with an impaired baroreflex control of vagal activity, whereas baroreceptor modulation of sympathetic nerve traffic remains unaltered, although undergoing a resetting phenomenon. In contrast, secondary hypertension is not associated with an increased adrenergic activity, thus suggesting that an enhancement in efferent sympathetic outflow is a peculiar feature of essential hypertension. Congestive heart failure is a condition also characterized by sympathetic activation, whose degree is proportional to the clinical severity of the disease. This is paralleled by an impairment in arterial baroreceptor modulation of both vagal and sympathetic activity, thus suggesting that the adrenergic overactivity in congestive heart failure is triggered by a reduced afferent restraint on the vasomotor centre. Chronic angiotensin-converting enzyme inhibition reduces the degree of both sympathetic activation and baroreflex dysfunction occurring in heart failure patients, a finding which documents that the neurohumoral abnormalities can be at least partially reversed by pharmacologic treatment

tert-Butylsilylcyclopentadienyl Group 4 metal complexes

New Group 4 metal t-butyldimethylsilylcyclopentadienyl complexes [MCpCp′Cl2] (Cp=η5-C5H5; Cp′=η5-C5H4SiMe2tBu; M=Ti 4, Zr 5, Hf 6) were prepared by reaction of 1 equiv. of the lithium (2) and thallium (3) salts of t-butyldimethylsilylcyclopentadiene 1 with the monocyclopentadienyl complexes [MCpCl3·DME] (M=Zr, Hf) and [TiCpCl3], respectively. A similar reaction using ZrCl4(THF)2 and HfCl4 with 2 equiv. of the lithium salt 2 gave the symmetric [MCp′2Cl2] ( M=Zr 7, Hf 8) metallocenes. Alkylation of these compounds with 2 equiv. of MgRCl (R=Me, CH2Ph) and Li(CH2CMe2Ph) afforded the dialkyl complexes [MCpCp′R2] (R=Me, M=Zr 9, Hf 10; R=CH2Ph, M=Ti 11, Zr 12, Hf 13), [ZrCp′2(CH2Ph)2] 14 and [ZrCpCp′(CH2CMe2Ph)2] 17. A Similar reaction of 5 with 1 equiv. of Mg(CH2Ph)Cl gave the monobenzyl compound [ZrCpCp′Cl(CH2Ph)] (15). Hydrolysis of 15 with a stoichiometric amount of water afforded the dinuclear μ-oxo compound [(ZrCpCp′Cl)2(μ-O)] (16). All of the new complexes reported were characterized by elemental analysis and 1H and 13C NMR spectroscopy and the molecular structures of 4 and 16 were determined by X-ray diffraction methods. Ethylene polymerization activities were measured for compounds 4–7.Financial support of our work by MCyT (project MAT2001-1309) is gratefully acknowledged. R.W. and C.R. are grateful to DFG, MEC and Repsol S.A. for fellowships

MytiBase: a knowledgebase of mussel (M. galloprovincialis) transcribed sequences

<p>Abstract</p> <p>Background</p> <p>Although Bivalves are among the most studied marine organisms due to their ecological role, economic importance and use in pollution biomonitoring, very little information is available on the genome sequences of mussels. This study reports the functional analysis of a large-scale Expressed Sequence Tag (EST) sequencing from different tissues of <it>Mytilus galloprovincialis </it>(the Mediterranean mussel) challenged with toxic pollutants, temperature and potentially pathogenic bacteria.</p> <p>Results</p> <p>We have constructed and sequenced seventeen cDNA libraries from different Mediterranean mussel tissues: gills, digestive gland, foot, anterior and posterior adductor muscle, mantle and haemocytes. A total of 24,939 clones were sequenced from these libraries generating 18,788 high-quality ESTs which were assembled into 2,446 overlapping clusters and 4,666 singletons resulting in a total of 7,112 non-redundant sequences. In particular, a high-quality normalized cDNA library (Nor01) was constructed as determined by the high rate of gene discovery (65.6%). Bioinformatic screening of the non-redundant <it>M. galloprovincialis </it>sequences identified 159 microsatellite-containing ESTs. Clusters, consensuses, related similarities and gene ontology searches have been organized in a dedicated, searchable database <url>http://mussel.cribi.unipd.it</url>.</p> <p>Conclusion</p> <p>We defined the first species-specific catalogue of <it>M. galloprovincialis </it>ESTs including 7,112 unique transcribed sequences. Putative microsatellite markers were identified. This annotated catalogue represents a valuable platform for expression studies, marker validation and genetic linkage analysis for investigations in the biology of Mediterranean mussels.</p

The chemical evolution of Omega Centauri's progenitor system

Chemical evolution models are presented for the anomalous globular cluster Omega Centauri. After demonstrating that the chemical features of Omega Cen can not be reproduced in the framework of the closed-box self-enrichment scenario, we discuss a model in which this cluster is the remnant of a dwarf spheroidal galaxy evolved in isolation and then swallowed by the Milky Way. Both infall of primordial matter and metal-enriched gas outflows have to be considered in order to reproduce the stellar metallicity distribution function, the age-metallicity relation and several abundance ratios. Yet, as long as an ordinary stellar mass function and standard stellar yields are assumed, we fail by far to get the enormous helium enhancement required to explain the blue main sequence (and, perhaps, the extreme horizontal branch) stellar data. Rotating models of massive stars producing stellar winds with large helium excesses at low metallicities have been put forward as promising candidates to solve the `helium enigma' of Omega Cen (Maeder & Meynet, 2006, A&A, 448, L37). However, we show that for any reasonable choice of the initial mass function the helium-to-metal enrichment of the integrated stellar population is unavoidably much lower than 70 and conclude that the issue of the helium enhancement in Omega Cen still waits for a satisfactory explanation. We briefly speculate upon possible solutions.Comment: 11 pages, 9 figures; accepted for publication in MNRA

Measurement of the K_L \to \pi\mu\nu form factor parameters with the KLOE detector

Using 328 pb^{-1}of data collected at DAFNE corresponding to $\sim$ 1.8 million $K_L\to \pi\mu\nu$ decays, we have measured the $K_{\mu 3}$ form factor parameters. The structure of the $K-\pi$ vector-current provides information about the dynamics of the strong interaction; its knowledge is necessary for evaluation of the phase-space integral required for measuring the CKM matrix element $V_{us}$ and for testing lepton universality in kaon decays. Using a new parametrization for the vector and scalar form factors, we find $\lambda_+$=\pt(25.7\pm 0.6),-3, and $\lambda_0$=\pt(14.0\pm 2.1),-3,. Our result for $\lambda_0$, together with recent lattice calculations of $f_\pi$, $f_K$ and $f(0)$, satisfies the Callan-Trieman relatio

Stellar mass-loss, rotation and the chemical enrichment of early type galaxies

We present a comparison between the [Ca,C,N/Fe]-mass relations observed in local spheroids and the results of a chemical evolution model which already successfully reproduces the [Mg/Fe]-mass and the [Fe/H]-mass relations in these systems. We find that the [Ca/Fe]-mass relation is naturally explained by such a model without any additional assumption. In particular, the observed under-abundance of Ca with respect to Mg can be attributed to the different contributions from supernovae Type Ia and supernovae Type II to the nucleosynthesis of these two elements. For C and N, we consider new stellar yields that take into account stellar mass loss and rotation. These yields have been shown to successfully reproduce the C and N abundances in Milky Way metal-poor stars. The use of these new stellar yields produces a good agreement between the chemical evolution model predictions and the integrated stellar population observations for C. In the case of N, the inclusion of fast rotators and stellar mass-loss nucleosynthesis prescriptions improves our predictions for the slope of the [N/Fe] vs. sigma relation, but a zero point discrepancy of 0.3 dex remains. This work demonstrates that current stellar yields are unable to simultaneously reproduce the large mean stellar [] ratios inferred from integrated spectra of elliptical galaxies and the low N abundance measured in the gas of high redshift spheroids from absorption lines. However, it seems reasonable to suggest that there may be uncertainties in either the inferred stellar or gas-phase N abundances at the level of 0.3 dex. (abriged)Comment: 13 pages, 5 figures, MNRAS in pres

Dark sectors 2016 Workshop: community report

This report, based on the Dark Sectors workshop at SLAC in April 2016, summarizes the scientific importance of searches for dark sector dark matter and forces at masses beneath the weak-scale, the status of this broad international field, the important milestones motivating future exploration, and promising experimental opportunities to reach these milestones over the next 5-10 years

Missense mutations in Desmocollin-2 N-terminus, associated with arrhythmogenic right ventricular cardiomyopathy, affect intracellular localization of desmocollin-2 in vitro

<p>Abstract</p> <p>Background</p> <p>Mutations in genes encoding desmosomal proteins have been reported to cause arrhythmogenic right ventricular cardiomyopathy (ARVC), an autosomal dominant disease characterised by progressive myocardial atrophy with fibro-fatty replacement.</p> <p>We screened 54 ARVC probands for mutations in desmocollin-2 (<it>DSC2</it>), the only desmocollin isoform expressed in cardiac tissue.</p> <p>Methods</p> <p>Mutation screening was performed by denaturing high-performance liquid chromatography and direct sequencing.</p> <p>To evaluate the pathogenic potentials of the <it>DSC2 </it>mutations detected in patients affected with ARVC, full-length wild-type and mutated cDNAs were cloned in eukaryotic expression vectors to obtain a fusion protein with green fluorescence protein (GFP); constructs were transfected in neonatal rat cardiomyocytes and in HL-1 cells.</p> <p>Results</p> <p>We identified two heterozygous mutations (c.304G>A (p.E102K) and c.1034T>C (p.I345T)) in two probands and in four family members. The two mutations p.E102K and p.I345T map to the N-terminal region, relevant to adhesive interactions.</p> <p>In vitro functional studies demonstrated that, unlike wild-type DSC2, the two N-terminal mutants are predominantly localised in the cytoplasm.</p> <p>Conclusion</p> <p>The two missense mutations in the N-terminal domain affect the normal localisation of DSC2, thus suggesting the potential pathogenic effect of the reported mutations. Identification of additional DSC2 mutations associated with ARVC may result in increased diagnostic accuracy with implications for genetic counseling.</p