High resolution optothermal spectroscopy of pyridine in the S-1 state

The optothermal technique has been utilized to obtain the first high resolution spectrum of pyridine in the region of the S1←S0 electronic transition. Rotational profiles for several vibronic bands (000,6a10,16b206a10,6a20,1210) were measured and found to be severely homogeneously broadened with linewidths of the order of 3–5 GHz, in agreement with previous lifetime measurements. Rotational constants of pyridine in the excited S1 vibronic levels were extracted by a band contour analysis. The values obtained are in good agreement with results from ab initio calculations, also presented here

On the absolute age of the Globular Cluster M92

We present precise and deep optical photometry of the globular M92. Data were collected in three different photometric systems: Sloan Digital Sky Survey (g',r',i',z'; MegaCam@CFHT), Johnson-Kron-Cousins (B, V, I; various ground-based telescopes) and Advanced Camera for Surveys (ACS) Vegamag (F475W, F555W, F814W; Hubble Space Telescope). Special attention was given to the photometric calibration, and the precision of the ground-based data is generally better than 0.01 mag. We computed a new set of {\alpha}-enhanced evolutionary models accounting for the gravitational settling of heavy elements at fixed chemical composition ([{\alpha}/Fe]=+0.3, [Fe/H]=-2.32 dex, Y=0.248). The isochrones -- assuming the same true distance modulus ({\mu}=14.74 mag), the same reddening (E(B-V)=0.025+-0.010 mag), and the same reddening law -- account for the stellar distribution along the main sequence and the red giant branch in different Color-Magnitude Diagrams (i',g'-i' ; i',g'-r' ; i',g'-z' ; I,B-I ; F814W,F475W-F814W). The same outcome applies to the comparison between the predicted Zero-Age-Horizontal-Branch (ZAHB) and the HB stars. We also found a cluster age of 11 +/- 1.5 Gyr, in good agreement with previous estimates. The error budget accounts for uncertainties in the input physics and the photometry. To test the possible occurrence of CNO-enhanced stars, we also computed two sets of {\alpha}- and CNO-enhanced (by a factor of three) models both at fixed total metallicity ([M/H]=-2.10 dex) and at fixed iron abundance. We found that the isochrones based on the former set give the same cluster age (11 +/- 1.5 Gyr) as the canonical {\alpha}-enhanced isochrones. The isochrones based on the latter set also give a similar cluster age (10 +/- 1.5 Gyr). These indings support previous results concerning the weak sensitivity of cluster isochrones to CNO-enhanced chemical mixtures.Comment: This paper makes use of data obtained from the Isaac Newton Group Archive which is maintained as part of the CASU Astronomical Data Centre at the Institute of Astronomy, Cambridge. This research used the facilities of the Canadian Astronomy Data Centre operated by the National Research Council of Canada with the support of the Canadian Space Agenc

On the Delta V_HB_bump parameter in Globular Clusters

We present new empirical estimates of the Delta V_HB_bump parameter for 15 Galactic globular clusters (GGCs) using accurate and homogeneous ground-based optical data. Together with similar evaluations available in the literature, we ended up with a sample of 62 GGCs covering a very broad range in metal content (-2.16<=[M/H]<=-0.58 dex). Adopting the homogeneous metallicity scale provided either by Kraft & Ivans (2004) or by Carretta et al. (2009), we found that the observed Delta V_HB_bump parameters are larger than predicted. In the metal-poor regime ([M/H]<=-1.7, -1.6 dex) 40% of GCs show discrepancies of 2sigma (~0.40 mag) or more. Evolutionary models that account either for alpha- and CNO-enhancement or for helium enhancement do not alleviate the discrepancy between theory and observations. The outcome is the same if we use the new Solar heavy-element mixture. The comparison between alpha- and CNO-enhanced evolutionary models and observations in the Carretta et al. metallicity scale also indicates that observed Delta V_HB_bump parameters, in the metal-rich regime ([M/H]=>0), might be systematically smaller than predicted

In situ Raman analyses of deep-sea hydrothermal and cold seep systems (Gorda Ridge and Hydrate Ridge)

Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 7 (2006): Q05023, doi:10.1029/2005GC001204.The Deep Ocean Raman In Situ Spectrometer (DORISS) instrument was deployed at the Sea Cliff Hydrothermal Field and Hydrate Ridge in July 2004. The first in situ Raman spectra of hydrothermal minerals, fluids, and bacterial mats were obtained. These spectra were analyzed and compared to laboratory Raman measurements of standards and samples collected from the site. Spectra of vent fluid (∼294°C at the orifice) at ∼2700 m depth were collected with noncontact and immersion sampling optics. Compared to spectra of ambient (∼2°C) seawater, the vent fluid spectra show changes in the intensity and positions of the water O-H stretch bands due to the elevated temperature. The sulfate band observed in seawater spectra is reduced in vent fluid spectra as sulfate is removed from vent fluid in the subseafloor. Additional components of hydrothermal fluid are present in concentrations too low to be detected with the current Raman system. A precision underwater positioner (PUP) was used to focus the laser spot on opaque samples such as minerals and bacterial mats. Spectra were obtained of anhydrite from actively venting chimneys, and of barite deposits in hydrothermal crusts. Laboratory analysis of rock samples collected in the vent field also detected the presence of gypsum. Spectra of bacterial mats revealed the presence of elemental sulfur (S8) and the carotenoid beta-carotene. Challenges encountered include strong fluorescence from minerals and organics and insufficient sensitivity of the instrument. The next generation DORISS instrument addresses some of these challenges and holds great potential for use in deep-sea vent environments.Funding was provided by the David & Lucile Packard Foundation

Au25(SCnH2 n+1)18 Clusters in Biomimetic Membranes: Role of Size, Charge, and Transmembrane Potential in Direct Membrane Permeation

Gold nanoclusters and nanoparticles are promising materials for applications in nanomedicine, and therefore, understanding their interaction with cell membranes is of particular importance. A series of neutral and anionic Au25(SCnH2n+1)18 monolayer protected clusters (MPCs) (briefly, Cn0 and Cn- clusters), was embedded into two types of biomimetic membranes supported by mercury electrodes. The first was a dioleoylphosphatidylcholine (DOPC) self-assembled monolayer (SAM), whereas the second was a tethered bilayer lipid membrane (tBLM) obtained by first anchoring a thiolipid monolayer to the mercury surface and then self-assembling a DOPC monolayer on top of it. The diameter of these clusters, from 1.7 to 2.7 nm depending on the thiolate ligand, is smaller than the thickness of biomembranes and biomimetic membranes. Both neutral and anionic Au25(SCnH2n+1)18 MPCs can penetrate the lipid bilayer moiety of the tBLM, without disrupting it; in particular, anionic Au25 clusters require positive transmembrane potentials to do so. Neutral Au25 clusters exchange one electron with mercury in a DOPC SAM, where they can come in contact with the mercury surface, whereas they are prevented from doing so at the tBLM because of their inability to cross the hydrophilic chain separating the lipid bilayer moiety from the mercury surface. The potential of these Au25 clusters to penetrate directly the plasma membrane is particularly convenient for targeted drug delivery. They are highly stable, biocompatible, and catalytic, and their uniform size is of importance in nanomedicine. Moreover, they may induce an efficient energy transfer to 3O2, allowing applications in radiotherapy and antimicrobial activity. \ua

The intrinsic pKa values for phosphatidylcholine, phosphatidylethanolamine, and phosphatidylserine in monolayers deposited on mercury electrodes.

The intrinsic pKa values of the phosphate groups of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) and of the phosphate and carboxyl groups of phosphatidylserine (PS) in self-organized monolayers deposited on a hanging mercury drop electrode were determined by a novel procedure based on measurements of the differential capacity C of this lipid-coated electrode. In view of the Gouy-Chapman theory, plots of 1/C at constant bulk pH and variable KCl concentration against the reciprocal of the calculated diffuse-layer capacity Cd,0 at zero charge exhibit slopes that decrease from an almost unit value to vanishingly low values as the absolute value of the charge density on the lipid increases from zero to approximately 2 microC cm-2. The intrinsic pKa values so determined are 0.5 for PE and 0.8 for PC. The plots of 1/C against 1/Cd,0 for pure PS exhibit slopes that pass from zero to a maximum value and then back to zero as pH is varied from 7.5 to 3, indicating that the charge density of the lipid film passes from slight negative to slight positive values over this pH range. An explanation for this anomalous behavior, which is ascribed to the phosphate group of PS, is provided. Interdispersion of PS and PC molecules in the film decreases the "formal" pKa value of the latter group by about three orders of magnitude