Different coordination modes of an aryl-substituted hydrotris(pyrazolyl) borate ligand in rhodium and iridium complexes

Complexes TptolRh(C2H4)2 (1a) and TptolRh(CH2C(Me)C(Me)CH2) (1b) have been prepared by reaction of KTptol with the appropriate [RhCl(olefin)2]2 dimer (Tptol means hydrotris(3-p-tolylpyrazol-1-yl)borate). The two complexes show a dynamic behaviour that involves exchange between κ2 and κ3 coordination modes of the Tptol ligand. The iridium analogue, TptolIr(CH2C(Me)CHCH2) (2) has also been synthesized, and has been converted into the Ir(III) dinitrogen complex [(κ4-N,N',N'',C-Tptol)Ir(Ph)(N2) (3) by irradiation with UV light under a dinitrogen atmosphere. Compound 3 constitutes a rare example of Ir(III)-N2 complex structurally characterized by X-ray crystallography. Its N2 ligand can be easily substituted by acetonitrile or ethylene upon heating and denticity changes in the Tptol ligand, from κ4-N,N',N'',C (monometallated Tptol, from now on represented as Tptol′) to κ5-N,N′,N″,C,C″ (dimetallated Tp tol ligand, represented as Tptol″) have been observed. When complex 3 is heated in the presence of acetylene, dimerization of the alkyne takes place to yield the enyne complex [(κ5-N,N′,N′′,C,C′-Tp tol)Ir(CH2CHCCH), 7̧ in which the unsaturated organic moiety is bonded to iridium through the carbon-carbon double bond.Ministerio de Educación y Ciencia CTQ2007-62814Consolider-Ingenio 2010 CSD2007-00006Junta de Andalucía FQM-3151, FQM-672CONACYT 22934

The GIRAFFE Inner Bulge Survey (GIBS). I. Survey Description and a kinematical map of the Milky Way bulge

The Galactic bulge is a massive, old component of the Milky Way. It is known to host a bar, and it has recently been demonstrated to have a pronounced boxy/peanut structure in its outer region. Several independent studies suggest the presence of more than one stellar populations in the bulge, with different origins and a relative fraction changing across the bulge area. This is the first of a series of papers presenting the results of the Giraffe Inner Bulge Survey, carried out at the ESO-VLT with the multifibre spectrograph FLAMES. Spectra of ~5000 red clump giants in 24 bulge fields have been obtained at resolution R=6500, in the infrared Calcium triplet wavelength region at 8500 {\AA}. They are used to derive radial velocities and metallicities, based on new calibration specifically devised for this project. Radial velocities for another ~1200 bulge red clump giants, obtained from similar archive data, have been added to the sample. Higher resolution spectra have been obtained for 450 additional stars at latitude b=-3.5, with the aim of investigating chemical abundance patterns variations with longitude, across the inner bulge. In total we present here radial velocities for 6392 RC stars. We derive a radial velocity, and velocity dispersion map of the Milky Way bulge, useful to be compared with similar maps of external bulges, and to infer the expected velocities and dispersion at any line of sight. The K-type giants kinematics is consistent with the cylindrical rotation pattern of M-giants from the BRAVA survey. Our sample enables to extend this result to latitude b=-2, closer to the Galactic plane than probed by previous surveys. Finally, we find strong evidence for a velocity dispersion peak at (0,-1) and (0,-2), possibly indicative of a high density peak in the central 250 pc of the bulgeComment: A&A in pres

Demethylation of oligogalacturonides by FaPE1 in the fruits of the wild strawberry Fragaria vesca triggers metabolic and transcriptional changes associated with defence and development of the fruit

Ectopic expression of the strawberry (Fragariaxananassa) gene FaPE1 encoding pectin methyl esterase produced in the wild species Fragaria vesca partially demethylated oligogalacturonides (OGAs), which conferred partial resistance of ripe fruits to the fungus Botrytis cinerea. Analyses of metabolic and transcriptional changes in the receptacle of the transgenic fruits revealed channelling of metabolites to aspartate and aromatic amino acids as well as phenolics, flavanones, and sesquiterpenoids, which was in parallel with the increased expression of some genes related to plant defence. The results illustrate the changes associated with resistance to B. cinerea in the transgenic F. vesca. These changes were accompanied by a significant decrease in the auxin content of the receptacle of the ripe fruits of transgenic F. vesca, and enhanced expression of some auxin-repressed genes. The role of these OGAs in fruit development was revealed by the larger size of the ripe fruits in transgenic F. vesca. When taken together these results show that in cultivated F. ananassa FaPE1 participates in the de-esterification of pectins and the generation of partially demethylated OGAs, which might reinforce the plant defence system and play an active role in fruit development

Halo properties and secular evolution in barred galaxies

The halo plays a crucial role in the evolution of barred galaxies. Its near-resonant material absorbs angular momentum emitted from some of the disc particles and helps the bar become stronger. As a result, a bar (oval) forms in the inner parts of the halo of strongly barred disc galaxies. It is thinner in the inner parts (but still considerably fatter than the disc bar) and tends to spherical at larger radii. Its length increases with time, while always staying shorter than the disc bar. It is roughly aligned with the disc bar, which it trails only slightly, and it turns with roughly the same pattern speed. The bi-symmetric component of the halo density continues well outside the halo bar, where it clearly trails behind the disc bar. The length and strength of the disc and halo bars correlate; the former being always much stronger than the latter. If the halo is composed of weakly interacting massive particles, then the formation of the halo bar, by redistributing the matter in the halo and changing its shape, could influence the expected annihilation signal. This is indeed found to be the case if the halo has a core, but not if it has a steep cusp. The formation and evolution of the bar strongly affect the halo orbits. A fraction of them becomes near-resonant, similar to the disc near-resonant orbits at the same resonance, while another fraction becomes chaotic. Finally, a massive and responsive halo makes it harder for a central mass concentration to destroy the disc bar.Comment: 6 pages, 3 figures, to appear in "Island Universes - Structure and Evolution of Disk Galaxies" ed. R. S. de Jon

3D kinematics through the X-shaped Milky Way bulge

Context. It has recently been discovered that the Galactic bulge is X-shaped, with the two southern arms of the X both crossing the lines of sight at l = 0 and | b| > 4, hence producing a double red clump in the bulge color magnitude diagram. Dynamical models predict the formation of X-shaped bulges as extreme cases of boxy-peanut bulges. However, since X-shaped bulges were known to be present only in external galaxies, models have never been compared to 3D kinematical data for individual stars. Aims. We study the orbital motion of Galactic bulge stars in the two arms (overdensities) of the X in the southern hemisphere. The goal is to provide observational constraints to bulge formation models that predict the formation of X-shapes through bar dynamical instabilities. Methods. Radial velocities have been obtained for a sample of 454 bulge giants, roughly equally distributed between the bright and the faint red clump, in a field at (l,b) = (0, −6). Proper motions were derived for all red clump stars in the same field by combining images from two epochs, which were obtained 11 years apart, with WFI at the 2.2 m at La Silla. The observed field contains the globular cluster NGC 6558, whose member stars were used to assess the accuracy of the proper motion measurement. At the same time, as a by-product, we provide the first proper motion measurement of NGC 6558. The proper motions for the spectroscopic subsample are analyzed for a subsample of 352 stars, taking into account the radial velocities and metallicities measured from near-infrared calcium triplet lines. Results. The radial velocity distribution of stars in the bright red clump, which traces the closer overdensity of bulge stars, shows an excess of stars moving towards the Sun. Similarly, an excess of stars receding from the Sun is seen in the far overdensity, which is traced by faint red clump stars. This is explained by the presence of stars on elongated orbits, which are most likely streaming along the arms of the X-shaped bulge. Proper motions for these stars are consistent with qualitative predictions of dynamical models of peanut-shaped bulges. Surprisingly, stars on elongated orbits have preferentially metal-poor (subsolar) metallicities, while the metal rich ones, in both overdensities, are preferentially found in more axisymmetric orbits. The observed proper motion of NGC 6558 has been measured as (μlcos   (b),μb) = (0.30   ±   0.14, −0.43 ± 0.13), with a velocity dispersion of (σlcos(b),σb) = (1.8,1.7) mas/yr. This is the first proper motion measurement for this cluster

α,γ-Peptide nanotube templating of one-dimensional parallel fullerene arrangements

(Figure Presented) The formation and full characterization of single self-assembling α,γ-peptide nanotubes (α,γ-SPNs) is described. The introduction of C60 into cyclic peptides allows the preparation of supramolecular 1D fullerene arrangements induced by peptide nanotube formation under appropriate conditions. © 2009 American Chemical Society.This work was supported by the Spanish Ministry of Education and Science and the ERDF [SAF2007-61015 and Consolider Ingenio 2010 (CSD2007-00006)] and the Xunta de Galicia (GRC2006/ 132, PGIDIT06PXIB209018PR, PGIDIT08CSA047209PR, and R2006/ 124). The work by J.M.V. and J.L.C. was supported by Grants BFU2007- 62382/BMC from the Spanish MEC (J.M.V.) and S-0505/MAT/0283 from the Madrid Regional Government (J.M.V. and J.L.C.). C.R. and R.J.B. thank the Spanish MEC for their FPU Fellowships. We also thank Dr. Carmen Serra (Nanotechnology and Surface Analysis Service at C.A.C.T.I., University of Vigo) for her help with STM. We also thank Dowpharma for their kind gift of ENZA enzymes used in the preparation of D-Boc-γ-Acp-OH.Peer reviewe

Ethylene is involved in strawberry fruit ripening in an organ-specific manner

The fruit of the strawberry Fragaria×ananassa has traditionally been classified as non-climacteric because its ripening process is not governed by ethylene. However, previous studies have reported the timely endogenous production of minor amounts of ethylene by the fruit as well as the differential expression of genes of the ethylene synthesis, reception, and signalling pathways during fruit development. Mining of the Fragaria vesca genome allowed for the identification of the two main ethylene biosynthetic genes, 1-aminocyclopropane-1-carboxylic acid (ACC) synthase and ACC oxidase. Their expression pattern during fruit ripening was found to be stage and organ (achene or receptacle) specific. Strawberry plants with altered sensitivity to ethylene could be employed to unravel the role of ethylene in the ripening process of the strawberry fruit. To this end, independent lines of transgenic strawberry plants were generated that overexpress the Arabidopsis etr1-1 mutant ethylene receptor, which is a dominant negative allele, causing diminished sensitivity to ethylene. Genes involved in ethylene perception as well as in its related downstream processes, such as flavonoid biosynthesis, pectin metabolism, and volatile biosynthesis, were differently expressed in two transgenic tissues, the achene and the receptacle. The different transcriptional responsiveness of the achene and the receptacle to ethylene was also revealed by the metabolic profiling of the primary metabolites in these two organs. The free amino acid content was higher in the transgenic lines compared with the control in the mature achene, while glucose and fructose, and citric and malic acids were at lower levels. In the receptacle, the most conspicuous change in the transgenic lines was the depletion of the tricarboxylic acid cycle intermediates at the white stage of development, most probably as a consequence of diminished respiration. The results are discussed in the context of the importance of ethylene during strawberry fruit ripening.Facultad de Ciencias ExactasInstituto de Fisiología Vegeta

Caught in the act: direct detection of Galactic Bars in the buckling phase

The majority of massive disk galaxies, including our own, have stellar bars with vertically thick inner region, known as “boxy/peanut-shaped” (B/P) bulges. The most commonly suggested mechanism for the formation of B/P bulges is a violent vertical “buckling” instability in the bar, something that has been seen in N-body simulations for over 20 years, but never identified in real galaxies. Here, we present the first direct observational evidence for ongoing buckling in two nearby galaxies (NGC 3227 and NGC 4569), including characteristic asymmetric isophotes and (in NGC 4569) stellar kinematic asymmetries that match buckling in simulations. This confirms that the buckling instability takes place and produces B/P bulges in real galaxies. A toy model of bar evolution yields a local fraction of buckling bars consistent with observations if the buckling phase lasts ∼0.5–1 Gyr, in agreement with simulations

Frequency and properties of bars in cluster and field galaxies at intermediate redshifts

We present a study of large-scale bars in field and cluster environments out to redshifts of ~0.8 using a final sample of 945 moderately inclined disk galaxies drawn from the EDisCS project. We characterize bars and their host galaxies and look for relations between the presence of a bar and the properties of the underlying disk. We investigate whether the fraction and properties of bars in clusters are different from their counterparts in the field. The total optical bar fraction in the redshift range z=0.4-0.8 (median z=0.60), averaged over the entire sample, is 25% (20% for strong bars). For the cluster and field subsamples, we measure bar fractions of 24% and 29%, respectively. We find that bars in clusters are on average longer than in the field and preferentially found close to the cluster center, where the bar fraction is somewhat higher (~31%) than at larger distances (~18%). These findings however rely on a relatively small subsample and might be affected by small number statistics. In agreement with local studies, we find that disk-dominated galaxies have a higher optical bar fraction (~45%) than bulge-dominated galaxies (~15%). This result is based on Hubble types and effective radii and does not change with redshift. The latter finding implies that bar formation or dissolution is strongly connected to the emergence of the morphological structure of a disk and is typically accompanied by a transition in the Hubble type. (abridged)Comment: 17 pages, accepted for publication in A&