Abundances in the Galactic bulge

The metallicity distribution and abundance ratios of the Galactic bulge are reviewed. Issues raised by recent work of different groups, in particular the high metallicity end, the overabundance of alpha-elements in the bulge relative to the thick disc and the measurement of giants versus dwarfs, are discussed. Abundances in the old moderately metal-poor bulge globular clusters are described.

Development of films based on blends of gelatin and poly(vinyl alcohol) cross linked with glutaraldehyde

Both gelatin and poly(vinyl alcohol) (PVA) can be cross linked with glutaraldehyde (GLU). In the case of gelatin, the GLU reacts with each e-NH2 functional group of adjacent lysine residues, while for PVA, the GLU reacts with two adjacent hydroxyl groups, forming acetal bridges. Thus it can be considered possible to cross link adjacent macromolecules of gelatin and PVA using GLU. In this context, the aims of this work were the development of biodegradable films based on blends of gelatin and poly(vinyl alcohol) cross linked with GLU, and the characterization of some of their main physical and functional properties. All the films were produced from film-forming solutions (FFS) containing 2 g macromolecules (PVA + gelatin)/100 g FFS, 25 g glycerol/100 g macromolecules, and 4 g GLU (25% solution)/100 g FFS. The FFS were prepared with two concentrations of PVA (20 or 50 g PVA/100 g macromolecules) and two reaction temperatures: 90 or 55 degrees C, applied for 30 min. The films were obtained after drying (30 degrees C/24 h) and conditioning at 25 degrees C and 58% of relative humidity for 7 days, and were then characterized. The results for the color parameters, mechanical properties, phase transitions and infrared spectra showed that some chemical modifications occurred, principally for the gelatin. However, in general, all the characteristics of the films were either typical of films based on blends of these macromolecules without cross linking, or slightly higher. A greater improvement in the properties of this material was probably not observed due to the crystallinity of the PVA, which has a melting point above 90 degrees C. The presence of microcrystals in the polymer chain probably reduced macromolecular mobility, hindering the reaction. Thus more research is necessary to produce biodegradable films with improved properties. (C) 2011 Elsevier Ltd. All rights reserved.

Physical properties of edible films based on cassava starch as affected by the plasticizer concentration

The aim of this work was to investigate the effect of glycerol contents on physical properties of cassava starch films. The films were prepared from film-forming solutions (FFS) with 2g cassava starch/100g water and 0, 15, 30 and 45g glycerol/100g starch, and were analysed to determine its mechanical properties by tensile tests, the glass-transition temperature (T-g) by differential scanning calorimetry (DSC) and the crystallinity by X-ray diffraction (XRD). The infrared spectra of the films were also recorded. The resistance values of the films decreased, while those of the elasticity increased with an increase in glycerol concentration due to the plasticizer effect of glycerol, which was also observed in DSC curves. The T-g of the films prepared decreased with the glycerol content. However, for samples with 30 and 45g glycerol/100g starch, two T-g curves were observed, probably due to a phase separation phenomenon. According to the XRD diffractograms, the films with 0 and 15gglycerol/100g starch presented an amorphous character, but some tendency to show crystalline peaks were observed for films with 30 and 45g glycerol/100g starch. The results obtained with Fourier transform infrared (FTIR) corroborated these observations. Copyright (C) 2007 John Wiley & Sons, Ltd.

Towards the main sequence: detailed analysis of weak line and post-T Tauri stars

A detailed study was performed for a sample of low-mass pre-main-sequence (PMS) stars, previously identified as weak-line T Tauri stars, which are compared to members of the Tucanae and Horologium Associations. Aiming to verify if there is any pattern of abundances when comparing the young stars at different phases, we selected objects in the range from 1 to 100 Myr, which covers most of PMS evolution. High-resolution optical spectra were acquired at European Southern Observatory and Observatorio do Pico dos Dias. The stellar fundamental parameters effective temperature and gravity were calculated by excitation and ionization equilibria of iron absorption lines. Chemical abundances were obtained via equivalent width calculations and spectral synthesis for 44 per cent of the sample, which shows metallicities within 0.5 dex solar. A classification was developed based on equivalent width of Li I 6708 angstrom and Ha lines and spectral types of the studied stars. This classification allowed a separation of the sample into categories that correspond to different evolutive stages in the PMS. The position of these stars in the Hertzsprung-Russell diagram was also inspected in order to estimate their ages and masses. Among the studied objects, it was verified that our sample actually contains seven weak-line T Tauri stars, three are Classical T Tauri, 12 are Fe/Ge PMS stars and 21 are post-T Tauri or young main-sequence stars. An estimation of circumstellar luminosity was obtained using a disc model to reproduce the observed spectral energy distribution. Most of the stars show low levels of circumstellar emission, corresponding to less than 30 per cent of the total emission.

THE COMPTON-THICK SEYFERT 2 NUCLEUS OF NGC 3281: TORUS CONSTRAINTS FROM THE 9.7 mu m SILICATE ABSORPTION

We present mid-infrared (mid-IR) spectra of the Compton-thick Seyfert 2 galaxy NGC 3281, obtained with the Thermal-Region Camera Spectrograph at the Gemini-South telescope. The spectra present a very deep silicate absorption at 9.7 mu m, and [S IV] 10.5 mu m and [Ne II] 12.7 mu m ionic lines, but no evidence of polycyclic aromatic hydrocarbon emission. We find that the nuclear optical extinction is in the range 24 mag <= A(V) <= 83 mag. A temperature T = 300 K was found for the blackbody dust continuum component of the unresolved 65 pc nucleus and the region at 130 pc SE, while the region at 130 pc NW reveals a colder temperature (200 K). We describe the nuclear spectrum of NGC 3281 using a clumpy torus model that suggests that the nucleus of this galaxy hosts a dusty toroidal structure. According to this model, the ratio between the inner and outer radius of the torus in NGC 3281 is R(0)/R(d) = 20, with 14 clouds in the equatorial radius with optical depth of tau(V) = 40 mag. We would be looking in the direction of the torus equatorial radius (i = 60 degrees), which has outer radius of R(0) similar to 11 pc. The column density is N(H) approximate to 1.2 x 10(24) cm(-2) and the iron K alpha equivalent width (approximate to 0.5-1.2 keV) is used to check the torus geometry. Our findings indicate that the X-ray absorbing column density, which classifies NGC 3281 as a Compton-thick source, may also be responsible for the absorption at 9.7 mu m providing strong evidence that the silicate dust responsible for this absorption can be located in the active galactic nucleus torus.

An analysis of the composite stellar population in M32

We obtained long-slit spectra of high signal-to-noise ratio of the galaxy M32 with the Gemini Multi-Object Spectrograph at the Gemini-North telescope. We analysed the integrated spectra by means of full spectral fitting in order to extract the mixture of stellar populations that best represents its composite nature. Three different galactic radii were analysed, from the nuclear region out to 2 arcmin from the centre. This allows us to compare, for the first time, the results of integrated light spectroscopy with those of resolved colour-magnitude diagrams from the literature. As a main result we propose that an ancient and an intermediate-age population co-exist in M32, and that the balance between these two populations change between the nucleus and outside one effective radius (1r(eff)) in the sense that the contribution from the intermediate population is larger at the nuclear region. We retrieve a smaller signal of a young population at all radii whose origin is unclear and may be a contamination from horizontal branch stars, such as the ones identified by Brown et al. in the nuclear region. We compare our metallicity distribution function for a region 1 to 2 arcmin from the centre to the one obtained with photometric data by Grillmair et al. Both distributions are broad, but our spectroscopically derived distribution has a significant component with [Z/Z(circle dot)] <= -1, which is not found by Grillmair et al.

Calculations of vibrational frequencies, Raman activities and degrees of depolarization for complexes involving water, methanol and ethanol

Raman activities and degrees of depolarization are reported for 14 complexes involving methanol, ethanol and water using the MP2/aug-cc-pVDZ model. For ethanol both trans and gauche isomers are considered. The red-shifts of the OH stretching and the blue shifts of the bending tau(CO-OH) mode were analyzed for the proton-donor molecules upon hydrogen bond. The shift of the nu(CO) stretching mode of the alcohol molecules are also analyzed and found to be specific giving characterization of the amphoteric relation, being positive for the proton-acceptor and negative for the proton-donor molecule. (c) 2008 Elsevier B.V. All rights reserved.

Challenging measurement of the (16)O+(27)Al elastic and inelastic angular distributions up to large angles

The (16)O+(27)Al elastic and inelastic angular distributions have been measured in a broad angular range (13 degrees < theta(lab) < 52 degrees) at about 100 MeV incident energy. The use of the MAGNEX large acceptance magnetic spectrometer and of the ray-reconstruction analysis technique has been crucial in order to provide, in the same experiment, high-resolution energy spectra and cross-section measurements distributed over more than seven orders of magnitude down to hundreds of nb/sr. (C) 2011 Elsevier B.V. All rights reserved.

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd-PSS films were processed using the acid of poly(styrene sulfonate) - H-PSS and neodymium nitrate - Nd(NO(3))(3); the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV-Vis-NIR spectral region presents typical electronic transitions of Nd 3, ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N-O groups in the range of 1400-720 cm(-1), prove the permanence of Nd(NO(3))(x), with x = 1, 2 and/or 3. in the H-PSS matrix. UV-Vis site selective photoluminescence data indicate that the incorporation of Nd 31 introduces a blue shift in PSS emission (325-800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd(3+) reabsorption and energy transfer effects between the PSS matrix and Nd(3+) were also observed. The IR emission of Nd-PSS films at 1076 rim ((4)F(3/2) -> (4)I(11/2)) present constant efficiency, independent on Nd(3+) concentration. The Judd-Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd(3+). Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis, molecular structure and physicochemical properties of bis(3 `-azido-3 `-deoxythymidin-5 `-yl) carbonate

3`-Azido-3`-deoxythymidine (zidovudine, AZT), a synthetic analog of natural nucleoside thymidine, has been used extensively in AIDS treatments. We report here the synthesis. X-ray crystal and molecular structure, NMR, IR and Raman spectra and the thermal behavior of a novel carbonate of AZT [(AZT-O)(2)C=O], prepared by the reaction of zidovudine with carbonyldiimidazole. The carbonate compound, C(21)H(24)N(10)O(9), crystallizes in the tetragonal space group P4(1)2(1)2 with a = b = 15.284(1), c = 21.695(1) angstrom, and Z = 8 molecules per unit cell. It consists of two AZT moieties of closely related conformations which are bridged by a carbonyl group to adopt a folded Z-like shape. (C) 2010 Elsevier B.V. All rights reserved.

Brumadoite, a new copper tellurate hydrate, from Brumado, Bahia, Brazil

Brumadoite, ideally Cu(2)Te(6+)O(4)(OH)(4)center dot 5H(2)O, is a new mineral from Pedra Preta mine, Serra das Eguas, Brumado, Bahia, Brazil. It occurs as microcrystalline aggregates both on and, rarely, pseudomorphous after coarse-grained magnesite, associated with mottramite and quartz. Crystals are platy, subhedral, 1-2 mu m in size. Brumadoite is blue (near RHS 114B), has a pale blue streak and a vitreous lustre. It is transparent to translucent and does not fluoresce. The empirical formula is (Cu(2.90)Pb(0.04)Ca(0.01))(Sigma 2.95) (Te(0.93)(6+)Si(0.05))(Sigma 0.98)O(3.92)(OH)(3.84)center dot 5.24H(2)O. Infrared spectra clearly show both (OH) and H(2)O. Microchemical spot tests using a KI Solution show that brumadoite has tellurium in the 6(+) state. The mineral is monoclinic, P2(1)/m or P2(1). Unit-cell parameters refined from X-ray powder data are a 8.629(2) angstrom, b 5.805(2) angstrom, c 7.654(2) angstrom, beta 103.17(2)degrees, V 373.3(2) angstrom(3), Z = 2. The eight strongest X-ray powder-diffraction lines [d in angstrom, (l),(hkl)] are: 8.432,(100),(100); 3.162,(66),((2) over bar 02); 2.385,(27),(220); 2.291,((1) over bar 12),(22); 1.916,(11),(312); 1.666,(14),((4) over bar 22,114); 1.452,(10), (323, 040); 1.450,(10),(422,403). The name is for the type locality, Brumado, Bahia, Brazil. The new mineral species has been approved by the CNMNC (IMA 2008-028).

Covalent attachment of 3,4,9,10-perylenediimides onto the walls of mesoporous molecular sieves MCM-41 and SBA-15

This work describes the covalent grafting of 3,4,9,10-perylenediimides (PDI), which are fluorescent dyes with very interesting optical properties, onto the walls of mesoporous molecular sieves MCM-41 and SBA-15. The mesoporous materials were first treated with 3-aminopropyltriethoxysilane (APTES) in anhydrous toluene, generating amine-containing surfaces. The amine-containing materials were then reacted with 3,4,9,10-perylenetetracarboxylic dianhydride (PTCA), generating surface-grafted PDI. Infrared spectra of the materials showed that the reaction with amino groups took place at both anhydride ends of the PTCA molecule, resulting in surface attached diimides. No sign of unreacted anhydride groups were found. The new materials, designated as MCMN2PDI and SBAN(2)PDI, presented absorption and emission spectra corresponding to weakly coupled PDI chromophores, in contrast to the strongly coupled rings usually found in solid PDI samples. The materials showed a red fluorescence, which could be observed by the naked eye under UV irradiation or with a fluorescence microscope. The PDI-modified mesoporous materials showed electrical conductivity when pressed into a pellet. The results presented here show that the new materials are potentially useful in the design of nanowires. (C) 2007 Elsevier Inc. All rights reserved.

Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.

Thionicotinamide SAM on Gold: Adsorption Studies and Electroactivity

STM and impedance results of the self-assembled monolayer (SAM) formed with thionicotinamide (TNA) on gold indicate the presence of defects that increase with the immersion time of the electrode in the TNA solution affecting the SAM electroactivity toward the electron transfer reaction of the cytochrome e metalloprotein and [Fe(CN)(6)](4-) and [Ru(NH(3))(6)](3+) complexes. It was observed that this electroactivity was also affected by the pH of the electrolyte solution. SERS and STM data indicate sulfur coordination to the surface with contribution of the NH(2) group. From the dependence of the TNA surface coverage on the temperature and concentration in solution, thermodynamic parameters of adsorption were determined.

Theoretical Characterization of Hydrogen Polyoxides: HOOH, HOOOH, HOOOOH, and HOOO

We have investigated the polyoxides HOOH, HOOOH, HOOOOH, and HOOO employing the CCSD(T) methodology, and the correlation consistent basis sets. For all molecules, we have computed fundamental vibrational frequencies, structural parameters, rotational constants, and rotation-vibration corrections. For HOOOH, we have obtained a good agreement between our results and microwave and infrared spectra measurements, although for the symmetric OO stretch some important differences were found. Heats of formation were computed using atomization energies, and our recommendation is as follows: Delta H degrees(f,298)(HOOOH) = -21.50 kcal/mol and Delta H degrees(f,298)(HOOOOH) = -10.61 kcal/mol. In the case of HOOO, to estimate the heat of formation, we have constructed three isodesmic reactions to cancel high order correlation effects. The results obtained confirmed that the latter effects are very important for HOOO. The new Delta H degrees(f,298)(HOOO) obtained is 5.5 kcal/mol. We have also calculated the zero-point energies of DO and DOOO to correct the experimental lower limit determined for the Delta H degrees(f,298)(HOOO). The Delta(Delta ZPE) decreases the binding energy of HOOO by 0.56 kcal/mol. Employing the latter value, the new experimental lower limit for Delta H degrees(f,298)(HOOO) is 3.07 kcal/mol, just 2.4 kcal/mol lower than our determination. We expect that the fundamental vibrational frequencies and rotational constants determined for HOOOOH and DOOOOD contribute to its identification in the gas phase. The vibrational spectrum of HOOOOH shows some overlapping with that of HOOOH thus indicating that one may encounter some difficulties in its characterization. We discuss the consequences of the thermochemical properties determined in this work, and suggest that the amount of HOOO present in the atmosphere is smaller than that proposed recently in this journal (J. Phys. Chem A 2007, 111, 4727).