Palladium-catalyzed allylation and deacylative allylation of 3-acetyl-2-oxindoles with allylic alcohols

The Pd-catalyzed allylation of 3-acetyl-2-oxindoles with allyl alcohol is performed using 3 mol% of Pd(dba)2, rac-BINAP and BINOL phosphoric acid as catalytic mixture. This procedure allows the in situ synthesis of 3-allyl-2-oxindole by adding Triton B to the reaction mixture. The deacylative allylation of 3-acetyl-3-methyl-2-oxindoles with allylic alcohols is carried out with 3 mol% of Pd(OAc)2, dppp and 1.5 equiv. of LiOtBu as base affording the corresponding 3,3-disubstituted 2-oxindoles in good yields. Both methodologies can be combined for the preparation of unsymmetrical 3,3-diallylated 2-oxindoles such as compound 7. The DaA must be carried out in the absence of oxygen in order to avoid the competitive formation of 3-alkyl-3-hydroxy-2-indoles. The later compounds can be easily obtained by deacylative oxidation of 3-alkylated 3-acetyl-2-oxindoles with LiOEt at rt under air.We gratefully acknowledge financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEO2009/039 and PROMETEOII/2014/017) and the University of Alicante. A. O.-M. thanks MINECO for a predoctoral fellowship

The effects of spatial resolution on Integral Field Spectrograph surveys at different redshifts. The CALIFA perspective

Over the past decade, 3D optical spectroscopy has become the preferred tool for understanding the properties of galaxies and is now increasingly used to carry out galaxy surveys. Low redshift surveys include SAURON, DiskMass, ATLAS3D, PINGS and VENGA. At redshifts above 0.7, surveys such as MASSIV, SINS, GLACE, and IMAGES have targeted the most luminous galaxies to study mainly their kinematic properties. The on-going CALIFA survey ($z\sim0.02$) is the first of a series of upcoming Integral Field Spectroscopy (IFS) surveys with large samples representative of the entire population of galaxies. Others include SAMI and MaNGA at lower redshift and the upcoming KMOS surveys at higher redshift. Given the importance of spatial scales in IFS surveys, the study of the effects of spatial resolution on the recovered parameters becomes important. We explore the capability of the CALIFA survey and a hypothetical higher redshift survey to reproduce the properties of a sample of objects observed with better spatial resolution at lower redshift. Using a sample of PINGS galaxies, we simulate observations at different redshifts. We then study the behaviour of different parameters as the spatial resolution degrades with increasing redshift.Comment: 20 pages, 16 figures. Accepted for publication in A&

The folding of a metallopeptide

We have applied solid-phase synthesis methods for the construction of tris(bipyridyl) peptidic ligands that coordinate Fe(II) ions with high affinity and fold into stable mononuclear metallopeptides. The main factors influencing the folding pathway and chiral control of the peptidic ligands around the metal ions have been studied both by experimental techniques (CD, UV-vis and NMR) and molecular modeling tools. Amongst the numerous molecular variables that have been studied, this study clearly illustrates how the chirality of a given set of aminoacids (proline in this case) of the peptide dictates the chirality of the metal center of the resulting metallopeptide. Moreover, the relatively hydrophobic peptidic models used in this work show that the most stable structures present reduced solvent contacts and, in counterpart, stabilize the cis configuration of the proline residuesWe are thankful for the support given by the Spanish grants SAF2013-41943-R, CTQ2012-31341, CTQ2011-23336 and CTQ2013-49317-EXP; the ERDF and the European Research Council (Advanced Grant 340055); the Xunta de Galicia grants GRC2013-041 and PGIDIT08CSA-047209PR and the Generalitat de Catalunya grant 2009SGR68. Support of COST Action CM1105 is kindly acknowledged. G.R. thanks the INL for his PhD fellowshipS

The O3N2 and N2 abundance indicators revisited: improved calibrations based on CALIFA and Te-based literature data

The use of IFS is since recently allowing to measure the emission line fluxes of an increasingly large number of star-forming galaxies both locally and at high redshift. The main goal of this study is to review the most widely used empirical oxygen calibrations, O3N2 and N2, by using new direct abundance measurements. We pay special attention to the expected uncertainty of these calibrations as a function of the index value or abundance derived and the presence of possible systematic offsets. This is possible thanks to the analysis of the most ambitious compilation of Te-based HII regions to date. This new dataset compiles the Te-based abundances of 603 HII regions extracted from the literature but also includes new measurements from the CALIFA survey. Besides providing new and improved empirical calibrations for the gas abundance, we also present here a comparison between our revisited calibrations with a total of 3423 additional CALIFA HII complexes with abundances derived using the ONS calibration by Pilyugin et al. (2010). The combined analysis of Te-based and ONS abundances allows us to derive their most accurate calibration to date for both the O3N2 and N2 single-ratio indicators, in terms of all statistical significance, quality and coverage of the space of parameters. In particular, we infer that these indicators show shallower abundance dependencies and statistically-significant offsets compared to those of Pettini and Pagel (2004), Nagao et al. (2006) and P\'erez-Montero and Contini (2009). The O3N2 and N2 indicators can be empirically applied to derive oxygen abundances calibrations from either direct abundance determinations with random errors of 0.18 and 0.16, respectively, or from indirect ones (but based on a large amount of data) reaching an average precision of 0.08 and 0.09 dex (random) and 0.02 and 0.08 dex (systematic; compared to the direct estimations),respectively.Comment: 12 pages, 5 figures, accepted for publication in A&

SSDSS IV MaNGA - Properties of AGN host galaxies

We present here the characterization of the main properties of a sample of 98 AGN host galaxies, both type-II and type-I, in comparison with those of about 2700 non-active galaxies observed by the MaNGA survey. We found that AGN hosts are morphologically early-type or early-spirals. For a given morphology AGN hosts are, in average, more massive, more compact, more central peaked and rather pressurethan rotational-supported systems. We confirm previous results indicating that AGN hosts are located in the intermediate/transition region between star-forming and non-star-forming galaxies (i.e., the so-called green valley), both in the ColorMagnitude and the star formation main sequence diagrams. Taking into account their relative distribution in terms of the stellar metallicity and oxygen gas abundance and a rough estimation of their molecular gas content, we consider that these galaxies are in the process of halting/quenching the star formation, in an actual transition between both groups. The analysis of the radial distributions of the starformation rate, specific star-formation rate, and molecular gas density shows that the quenching happens from inside-out involving both a decrease of the efficiency of the star formation and a deficit of molecular gas. All the intermediate data-products used to derive the results of our analysis are distributed in a database including the spatial distribution and average properties of the stellar populations and ionized gas, published as a Sloan Digital Sky Survey Value Added Catalog being part of the 14th Data Release: http://www.sdss.org/dr14/manga/manga-data/manga-pipe3d-value-added-catalog/Comment: 48 pages, 14 figures, in press in RMxA

Stellar Population gradients in galaxy discs from the CALIFA survey

While studies of gas-phase metallicity gradients in disc galaxies are common, very little has been done in the acquisition of stellar abundance gradients in the same regions. We present here a comparative study of the stellar metallicity and age distributions in a sample of 62 nearly face-on, spiral galaxies with and without bars, using data from the CALIFA survey. We measure the slopes of the gradients and study their relation with other properties of the galaxies. We find that the mean stellar age and metallicity gradients in the disc are shallow and negative. Furthermore, when normalized to the effective radius of the disc, the slope of the stellar population gradients does not correlate with the mass or with the morphological type of the galaxies. Contrary to this, the values of both age and metallicity at $\sim$2.5 scale-lengths correlate with the central velocity dispersion in a similar manner to the central values of the bulges, although bulges show, on average, older ages and higher metallicities than the discs. One of the goals of the present paper is to test the theoretical prediction that non-linear coupling between the bar and the spiral arms is an efficient mechanism for producing radial migrations across significant distances within discs. The process of radial migration should flatten the stellar metallicity gradient with time and, therefore, we would expect flatter stellar metallicity gradients in barred galaxies. However, we do not find any difference in the metallicity or age gradients in galaxies with without bars. We discuss possible scenarios that can lead to this absence of difference.Comment: 24 pages, 17 figures, accepted for publication in A&

The O3N2 and N2 abundance indicators revisited: improved calibrations based on CALIFA and T e-based literature data

Astronomy and Astrophysics 559 (2013): A114 reproduced with permission from Astronomy and AstrophysicsThe use of integral field spectroscopy is since recently allowing to measure the emission line fluxes of an increasingly large number of star-forming galaxies, both locally and at high redshift. Many studies have used these fluxes to derive the gas-phase metallicity of the galaxies by applying the so-called strong-line methods. However, the metallicity indicators that these datasets use were empirically calibrated using few direct abundance data points (Te-based measurements). Furthermore, a precise determination of the prediction intervals of these indicators is commonly lacking in these calibrations. Such limitations might lead to systematic errors in determining the gas-phase metallicity, especially at high redshift, which might have a strong impact on our understanding of the chemical evolution of the Universe. The main goal of this study is to review the most widely used empirical oxygen calibrations, O3N2 and N2, by using newdirect abundance measurements. We pay special attention to (1) the expected uncertainty of these calibrations as a function of the index value or abundance derived and (2) the presence of possible systematic offsets. This is possible thanks to the analysis of the most ambitious compilation of Te-based H ii regions to date. This new dataset compiles the Te-based abundances of 603 H ii regions extracted from the literature but also includes new measurements from the CALIFA survey. Besides providing new and improved empirical calibrations for the gas abundance, we also present a comparison between our revisited calibrations with a total of 3423 additional CALIFA H ii complexes with abundances derived using the ONS calibration from the literature. The combined analysis of T e-based and ONS abundances allows us to derive their most accurate calibration to date for both the O3N2 and N2 single-ratio indicators, in terms of all statistical significance, quality, and coverage of the parameters space. In particular, we infer that these indicators show shallower abundance dependencies and statistically significant offsets compared to others'. The O3N2 and N2 indicators can be empirically applied to derive oxygen abundances calibrations from either direct abundance determinations with random errors of 0.18 and 0.16, respectively, or from indirect ones (but based on a large amount of data), reaching an average precision of 0.08 and 0.09 dex (random) and 0.02 and 0.08 dex (systematic; compared to the direct estimations), respectivelyR.A. Marino is funded by the Spanish program of International Campus of Excellence Moncloa (CEI). D. Mast thank the Plan Nacional de Investigación y Desarrollo funding programs, AYA2012-31935 of the Spanish Ministerio de Economía y Competitividad, for the support given to this project. S.F.S thanks the the Ramón y Cajal project RyC-2011-07590 of the spanish Ministerio de Economía y Competitividad, for the support giving to this project. F.F.R.O. acknowledges the Mexican National Council for Science and Technology (CONACYT) for financial support under the program Estancias Postdoctorales y Sabáticas al Extranjero para la Consolidación de Grupos de Investigación, 2010-2012. We acknowledge financial support for the ESTALLIDOS collaboration by the Spanish Ministerio de Ciencia e Innovación under grant AYA2010- 21887-C04-03. BG-L also acknowledges support from the Spanish Ministerio de Economía y Competitividad (MINECO) under grant AYA2012- 39408-C02-02. J.F.-B. acknowledges financial support from the Ramón y Cajal Program and grant AYA2010-21322-C03-02 from the Spanish Ministry of Economy and Competitiveness (MINECO), as well as to the DAGAL network from the People’s Program (Marie Curie Actions) of the European Union’s Seventh Framework Program FP7/2007-2013/ under REA grant agreement number PITN-GA-2011-289313. CK has been funded by project AYA2010-21887 from the Spanish PNAYA. P.P. acknowledges support by the Fundação para a Ciência e a Tecnologia (FCT) under project FCOMP-01-0124-FEDER-029170 (Reference FCT PTDC/FIS-AST/3214/2012), funded by FCT-MEC (PIDDAC) and FEDER (COMPETE). R.M.G.D. and R.G.B. also acknowledge support from the Spanish Ministerio de Economía y Competitividad (MINECO) under grant AyA2010-15081. V.S., L.G., and A.M.M. acknowledge financial support from the Fundação para a Ciência e a Tecnologia (FCT) under program Ciência 2008 and the research grant PTDC/CTE-AST/112582/200

The Mass-Metallicity relation explored with CALIFA: I. Is there a dependence on the star formation rate?

We present the results on the study of the global and local M-Z relation based on the first data available from the CALIFA survey (150 galaxies). This survey provides integral field spectroscopy of the complete optical extent of each galaxy (up to 2-3 effective radii), with enough resolution to separate individual HII regions and/or aggregations. Nearly $\sim$3000 individual HII regions have been detected. The spectra cover the wavelength range between [OII]3727 and [SII]6731, with a sufficient signal-to-noise to derive the oxygen abundance and star-formation rate associated with each region. In addition, we have computed the integrated and spatially resolved stellar masses (and surface densities), based on SDSS photometric data. We explore the relations between the stellar mass, oxygen abundance and star-formation rate using this dataset. We derive a tight relation between the integrated stellar mass and the gas-phase abundance, with a dispersion smaller than the one already reported in the literature ($\sigma_{\Delta{\rm log(O/H)}}=$0.07 dex). Indeed, this dispersion is only slightly larger than the typical error derived for our oxygen abundances. However, we do not find any secondary relation with the star-formation rate, other than the one induced due to the primary relation of this quantity with the stellar mass. We confirm the result using the $\sim$3000 individual HII regions, for the corresponding local relations. Our results agree with the scenario in which gas recycling in galaxies, both locally and globally, is much faster than other typical timescales, like that of gas accretion by inflow and/or metal loss due to outflows. In essence, late-type/disk dominated galaxies seem to be in a quasi-steady situation, with a behavior similar to the one expected from an instantaneous recycling/closed-box model.Comment: 19 Pages, 8 figures, Accepted for Publishing in Astronomy and Astrophysics (A&A

CALIFA, the Calar Alto Legacy Integral Field Area survey: I. Survey presentation

We present here the Calar Alto Legacy Integral Field Area (CALIFA) survey, which has been designed to provide a first step in this direction.We summarize the survey goals and design, including sample selection and observational strategy.We also showcase the data taken during the first observing runs (June/July 2010) and outline the reduction pipeline, quality control schemes and general characteristics of the reduced data. This survey is obtaining spatially resolved spectroscopic information of a diameter selected sample of $\sim600$ galaxies in the Local Universe (0.005< z <0.03). CALIFA has been designed to allow the building of two-dimensional maps of the following quantities: (a) stellar populations: ages and metallicities; (b) ionized gas: distribution, excitation mechanism and chemical abundances; and (c) kinematic properties: both from stellar and ionized gas components. CALIFA uses the PPAK Integral Field Unit (IFU), with a hexagonal field-of-view of \sim1.3\sq\arcmin', with a 100% covering factor by adopting a three-pointing dithering scheme. The optical wavelength range is covered from 3700 to 7000 {\AA}, using two overlapping setups (V500 and V1200), with different resolutions: R\sim850 and R\sim1650, respectively. CALIFA is a legacy survey, intended for the community. The reduced data will be released, once the quality has been guaranteed. The analyzed data fulfill the expectations of the original observing proposal, on the basis of a set of quality checks and exploratory analysis. We conclude from this first look at the data that CALIFA will be an important resource for archaeological studies of galaxies in the Local Universe.Comment: 32 pages, 29 figures, Accepted for publishing in Astronomy and Astrophysic

The templated growth of a chiral transition metal chalcogenide

We demonstrate that an intrinsically chiral, high Miller index surface of an achiral metal can be used to template the enantioselective growth of chiral transition metal chalcogenide films. Specifically, Cu(643)R can be used as a template for the enantioselective growth of a chiral copper telluride alloy surface. Beyond a critical alloy thickness the chiral influence of the Cu(643)R surface diminishes and an achiral surface forms. Our work demonstrates a new method of producing chiral transition metal chalcogenide surfaces, with potential applications in the study of structurally chiral topological insulators