TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY AND RAMAN SPECTROELECTROCHEMISTRY OF (CO)(5)W[4,4'-BPY]W(CO)(5), PROBED IN THE VISIBLE AND NEAR-INFRARED

Time-resolved resonance Raman spectroscopy of the lowest energy excited state of the 4,4'-bipyridyl ligand-bridged complex, [(CO)(5)W(L)W(CO5] (1), and Raman spectroscopy of electrochemically reduced 1, both give bands characteristic of the the L(.-) species. This confirms that the ligand L is negatively charged in the lowest energy exicited state which is therefore metal-ligand charge transfer (MLCT) in character. Raman spectra of the radical anion of 1 excited in the far red (800 nm) exhibited a band near 2050 cm(-1) due to a vco symmetric CO stretching mode, compared to the corresponding band at 2070 cm(-1) in the spectrum of the parent, uncharged complex. The lower vco in the reduced complex supports the recent finding by time-resolved IR spectroscopy of a similar frequency decrease for nu(CO) in the longest lived (MLCT) excited state of 1 which was attributed to electron/hole localisation in this state on the IR time scale.

TIME-RESOLVED ABSORPTION, INFRARED, AND RESONANCE RAMAN-SPECTRA OF THE COMPLEXES [RU(X)(R)(CO)(2)(ALPHA-DIIMINE)] (X=HALIDE R=ALKYL) - INFLUENCE OF X ON THE CHARGE-TRANSFER CHARACTER OF THE LOWEST EXCITED-STATE

Nanosecond time-resolved absorption (TA), resonance Raman (TR(3)), and infrared (TRIR) spectra are reported for several complexes [Ru(X)(R)(CO)(2)(alpha-diimine)] (X = Cl, Br, I; R = Me, Et; alpha-diimine = N,N'-diisopropyl-1,4-diaza-1,3-butadiene (iPr-DAB), pyridine-2-carbaldehyde-N-isopropylimine (iPr-PyCa), 2,2'-bipyridine (bpy)). This is the first instance in which the TA, TR(3), and TRIR techniques have been used to probe excited states in the same series of complexes. The TA spectra of the iodide complexes show a transient absorption between 550 and 700 nm, which does not depend on the solvent but shifts to lower energy in the order iPr-DAB > bpy > iPr-PyCa. This band is assigned to an intraligand transition. For the corresponding chloride and bromide complexes this band occurs at higher energy, most probably because of a change of character of the lowest excited state from XLCT to MLCT. The TRIR spectra show an increase in v(CO) (and k(CO)) on promotion to the excited state; however, the shifts Delta v(CO) show a decrease in the order Cl- > Br- > I-. The TR(3) spectra of the excited complexes [Ru(X)(R)(Co)(2)(iPr-DAB)] show v(s)(CN) of the iPr-DAB ligand 50-80 cm(-1) lower in frequency than for the complexes in their ground state. This frequency shift decreases in the order Cl- > Br- > I-, indicating a decrease of CT character of the lowest excited state in this order. However, going from X = Br to I, the effect on Delta v(CO) is much larger than the decrease of Delta v(s)(CN). This different effect on the CO- and CN-stretching frequencies is assigned to a gradual change in character of the lowest excited state from MLCT to XLCT when Cl- is replaced by Br- and I-. This result confirms a similar conclusion derived from previous resonance Raman and emission experiments on these complexes.

THE VLT-FLAMES TARANTULA SURVEY: THE FASTEST ROTATING O-TYPE STAR AND SHORTEST PERIOD LMC PULSAR-REMNANTS OF A SUPERNOVA DISRUPTED BINARY?

We present a spectroscopic analysis of an extremely rapidly rotating late O-type star, VFTS102, observed during a spectroscopic survey of 30 Doradus. VFTS102 has a projected rotational velocity larger than 500 km s(-1) and probably as large as 600 km s-1; as such it would appear to be the most rapidly rotating massive star currently identified. Its radial velocity differs by 40 kms(-1) from the mean for 30 Doradus, suggesting that it is a runaway. VFTS102 lies 12 pc from the X-ray pulsar PSR J0537-6910 in the tail of its X-ray diffuse emission. We suggest that these objects originated from a binary system with the rotational and radial velocities of VFTS102 resulting from mass transfer from the progenitor of PSR J0537-691 and the supernova explosion, respectively.

The carbon abundance in main-sequence B-type stars towards the Galactic anti-centre

Differential carbon abundances (based on the C II doublet at 6580 Angstrom) are presented for eight early type stars, towards the Galactic anti-centre. All the stars have similar atmospheric parameters with effective temperatures in the range 25000-29000 K and surface gravities between log g = 3.9-4.3 dex. The derived photospheric abundances vary by up to 0.6 dex, and with the exception of one star, RLWT-41, the differential abundances are found to be closely correlated with those of nitrogen. This implies that both elements may have been formed by similar mechanisms and that the lack of correlation between the nitrogen and oxygen abundances previously found in this sample is not directly due to CNO-processed core material being mixed to the stellar surface.

The chemical composition towards the galactic anti-centre .2. Differential abundance analyses and distance determinations

In a previous paper we have published observational data for 6 early B-type stars having, galactocentric distances of between 10 and 18 kpc. Using LTE line-blanketed model at mosphere techniques we derived their atmospheric parameters, finding that all our targets had similar effective temperatures and surface gravities. In the following study we additionally include two stars which have been presented previously (Rolleston et al. 1993) and found also to have compatible atmospheric parameters to the original programme stars. The homogeneity of this sample allows quantitative line-by-line differential abundance analyses to be carried out which should reliably detect variations in the chemical compositions of the stellar photospheres. We present differential abundances for eight stars, in either young open clusters or the field, with respect to an arbitrarily chosen standard which shows a normal abundance pattern. Our method of calculating distances from the derived atmospheric parameters means that the relative distance scale should be accurate.

The chemical composition towards the galactic anti-centre .1. Observations and model atmosphere analyses

High resolution spectra of six early B-type main-sequence stars having galactocentric distances of between 10 and 18 kpc are presented. We List the equivalent widths for the metal lines and illustrate their hydrogen and helium line profiles. The stars are analysed using LTE line-blanketed model atmosphere techniques to derive atmospheric parameters and surface chemical compositions. All six stars have similar effective temperatures and surface gravities, allowing a reliable comparison of their metal abundances and distances. Significant variations in the photospheric abundances are evident and are discuss the need for a more detailed line-by-line differential analysis to exactly quantify the differences. This will be presented in a companion paper (Smartt et al. 1996).

A metal deficient early B-type star near the edge of the galactic disk

High resolution spectra of an early B-type star associated with the H II region detected by de Geus et al. (1993) are analysed using LTE model atmosphere techniques to derive stellar atmospheric parameters and a chemical composition. A distance to the star of 8.2 kpc is estimated, placing it near the edge of the galactic disk and closer than the kinematic distance of 20 kpc to the H II region, calculated by de Geus et al. A differential line by line abundance analysis with respect to the spectroscopic standard tau Sco indicates a significant metal depletion, with elements down on average by -0.5 dex.

Dominance of Radiation Pressure in Ion Acceleration with Linearly Polarized Pulses at Intensities of 10(21) W cm(-2)

A novel regime is proposed where, by employing linearly polarized laser pulses at intensities 10(21) W cm(-2) (2 orders of magnitude lower than discussed in previous work [T. Esirkepov et al., Phys. Rev. Lett. 92, 175003 (2004)]), ions are dominantly accelerated from ultrathin foils by the radiation pressure and have monoenergetic spectra. In this regime, ions accelerated from the hole-boring process quickly catch up with the ions accelerated by target normal sheath acceleration, and they then join in a single bunch, undergoing a hybrid light-sail-target normal sheath acceleration. Under an appropriate coupling condition between foil thickness, laser intensity, and pulse duration, laser radiation pressure can be dominant in this hybrid acceleration. Two-dimensional particle-in-cell simulations show that 1.26 GeV quasimonoenergetic C6+ beams are obtained by linearly polarized laser pulses at intensities of 10(21) W cm(-2).

Measurements of energy transport patterns in solid density laser plasma interactions at intensities of 5x10(20) W cm(-2)

K-alpha x-ray emission, extreme ultraviolet emission, and plasma imaging techniques have been used to diagnose energy transport patterns in copper foils ranging in thickness from 5 to 75 mu m for intensities up to 5x10(20) Wcm(-20). The K-alpha emission and shadowgrams both indicate a larger divergence angle than that reported in the literature at lower intensities [R. Stephens , Phys. Rev. E 69, 066414 (2004)]. Foils 5 mu m thick show triple-humped plasma expansion patterns at the back and front surfaces. Hybrid code modeling shows that this can be attributed to an increase in the mean energy of the fast electrons emitted at large radii, which only have sufficient energy to form a plasma in such thin targets.

HIF-2alpha Associated Familial Erythrocytosis Supports the PHD2-HIF2-alpha-VHL Axis as the Major Regulator of Erythropoietin Production

Transcriptionally erythropoietin (Epo) synthesis is tightly regulated by the hypoxia inducible factor (HIF), which is composed of one alpha and one beta subunit that are constitutively expressed. The beta subunit is non-variable, but three different alpha subunits give rise to three isoforms of HIF. The alpha subunit is proteasomally regulated in the presence of oxygen by hydroxylation of the proline in the LXXLAP motif of the oxygen dependent degradation (ODD) domain of HIFalpha, catalysed by members of the prolyl hydroxylase domain (PHD) family of enzymes. This allows the von Hippel Lindau (VHL) protein to associate with the alpha subunit, which is subsequently tagged with ubiquitin and degraded by the proteasome. Any defect in the oxygen sensing pathway that allows the alpha subunit to escape proteasomal regulation leads to elevated expression of HIF target genes.

Recently mutations in both VHL and PHD2 have been identified in a cohort of patients with erythrocytosis, but no mutations were found in the ODD domain of HIF1alpha. Instead, investigation of the homologous region in HIF-2alpha revealed four different mutations, Pro534Leu, Met535Val, Gly537Arg and Gly537Trp in seven individuals/families. Affected individuals presented at a young age with elevated serum Epo. Several individuals have a clinical history of thrombosis, but no evidence of a von Hippel Lindau-like syndrome.

To define how the four mutations relate to the erythrocytosis phenotype functional assays were performed in vitro. Binding of PHD2 to the four HIF-2alpha mutants was impaired to varying degrees, with both the Gly537 mutants showing the greatest reduction. The association of VHL with the hydroxylated Met535Val mutant peptide was similar to wild type HIF- 2alpha, but was decreased in the other three HIF-2alpha mutants. Expression of three HIF- 2alpha target genes, adrenomedullin, NDRG1 and VEGF, was significantly up-regulated in cells stably transfected with the mutants under normoxia compared to wild type HIF-2alpha. Mutations in the ODD domain of HIF-2alpha disrupt proteasomal regulation by reducing the association with PHD2 and hence hydroxylation. Furthermore the binding of VHL is also impaired, even when HIF-2alpha is hydroxylated. Examination of the three-dimensional structure of hydroxylated HIF-1alpha bound to VHL confirms that amino acids close to site of hydroxylation (Pro-531 in isoform 2) are important for this association. These observations, together with recent studies utilising murine models of erythrocytosis, support the PHD2-HIF-2alpha-VHL axis as the major regulator of erythropoietin.