Ketalization of 3-Keto Group of 4-Pregnene-21-ol-3,20-dione and Syntheses of 21-Phenyl-4-pregnene-3,20-dione

20-Ketosteroids react with ethylene glycol in the presence of acids more quickly than the i4-3-keto group. It has been found that the i4-3-keto group of 4-pregnene-21-ol-3,20-dione (I) reacts with ethylene glycol in the presence of pyridine hydrochloriqe and anhydrous sodium sulfate more quickly than the 20-keto group. From the so obtained pregnene-21-ol-3,20-dione-3-ethyleneketal (IV) 21-phenyl-4-pregnene-3,20-dione (VII) was prepared

Mechanism of Hydroxylation of Steroids. Hydroxylation of 16a-Methyl-4-pregnene-21-ol-3,20- dione Acetate with Mucor Griseo-Cyanus

Mucor griseo-cyanus, which introduces an hydroxyl group in the 14-position of several steroids, converts 16a-methyl-4-pregnene- 21-ol-3,20-dione acetate (I) into a monohydrox:yderiva1Jive for which the structure 16a-methyl-4-pregnene-7a,21-diol-3,20-dione (III) has been determined. 16a-Methyl-4-pregnene-21-ol-3,20-dione acetate (I) and 16a- methyl-4-pregnene-7a,21-diol-3,20-dione (III) are transformed by Mucor griseo-cyanus, with a long time of incubation, into a dihydroxyderivative for which the structure 16a-methyl-4-pregnene- 7a,12~,21-triol-3,20-dione triacetate (VI) has been determined. The, 16a-methyl group in compound I inhibits the 14n-hydroxylase of Mucor griseo-cyanus by steric hindrance

Unveiling the population of orphan Gamma Ray Bursts

Gamma Ray Bursts are detectable in the gamma-ray band if their jets are oriented towards the observer. However, for each GRB with a typical theta_jet, there should be ~2/theta_jet^2 bursts whose emission cone is oriented elsewhere in space. These off-axis bursts can be eventually detected when, due to the deceleration of their relativistic jets, the beaming angle becomes comparable to the viewing angle. Orphan Afterglows (OA) should outnumber the current population of bursts detected in the gamma-ray band even if they have not been conclusively observed so far at any frequency. We compute the expected flux of the population of orphan afterglows in the mm, optical and X-ray bands through a population synthesis code of GRBs and the standard afterglow emission model. We estimate the detection rate of OA by on-going and forthcoming surveys. The average duration of OA as transients above a given limiting flux is derived and described with analytical expressions: in general OA should appear as daily transients in optical surveys and as monthly/yearly transients in the mm/radio band. We find that ~ 2 OA yr^-1 could already be detected by Gaia and up to 20 OA yr^-1 could be observed by the ZTF survey. A larger number of 50 OA yr^-1 should be detected by LSST in the optical band. For the X-ray band, ~ 26 OA yr^-1 could be detected by the eROSITA. For the large population of OA detectable by LSST, the X-ray and optical follow up of the light curve (for the brightest cases) and/or the extensive follow up of their emission in the mm and radio band could be the key to disentangle their GRB nature from other extragalactic transients of comparable flux density.Comment: 9 pages, 4 figures, 2 tables. Accepted for publication by Astronomy and Astrophysic

The high-redshift gamma-ray burst GRB140515A

High-redshift gamma-ray bursts have several advantages for the study of the distant universe, providing unique information about the structure and properties of the galaxies in which they exploded. Spectroscopic identification with large ground-based telescopes has improved our knowledge of the class of such distant events. We present the multi-wavelength analysis of the high-$z$ Swift gamma-ray burst GRB140515A ($z = 6.327$). The best estimate of the neutral hydrogen fraction of the intergalactic medium (IGM) towards the burst is $x_{HI} \leq 0.002$. The spectral absorption lines detected for this event are the weakest lines ever observed in gamma-ray burst afterglows, suggesting that GRB140515A exploded in a very low density environment. Its circum-burst medium is characterised by an average extinction (A$_{\rm V} \sim 0.1$) that seems to be typical of $z \ge 6$ events. The observed multi-band light curves are explained either with a very flat injected spectrum ($p = 1.7$) or with a multi-component emission ($p = 2.1$). In the second case a long-lasting central engine activity is needed in order to explain the late time X-ray emission. The possible origin of GRB140515A from a Pop III (or from a Pop II stars with local environment enriched by Pop III) massive star is unlikely.Comment: 10 pages, 8 figures, 5 tables, submitted to Astronomy & Astrophysic

Spectrophotometric analysis of GRB afterglow extinction curves with X-shooter

In this work we use gamma-ray burst (GRB) afterglow spectra observed with the VLT/X-shooter spectrograph to measure rest-frame extinction in GRB lines-of-sight by modeling the broadband near-infrared (NIR) to X-ray afterglow spectral energy distributions (SEDs). Our sample consists of nine Swift GRBs, eight of them belonging to the long-duration and one to the short-duration class. Dust is modeled using the average extinction curves of the Milky Way and the two Magellanic Clouds. We derive the rest-frame extinction of the entire sample, which fall in the range $0 \lesssim {\it A}_{\rm V} \lesssim 1.2$. Moreover, the SMC extinction curve is the preferred extinction curve template for the majority of our sample, a result which is in agreement with those commonly observed in GRB lines-of-sights. In one analysed case (GRB 120119A), the common extinction curve templates fail to reproduce the observed extinction. To illustrate the advantage of using the high-quality X-shooter afterglow SEDs over the photometric SEDs, we repeat the modeling using the broadband SEDs with the NIR-to-UV photometric measurements instead of the spectra. The main result is that the spectroscopic data, thanks to a combination of excellent resolution and coverage of the blue part of the SED, are more successful in constraining the extinction curves and therefore the dust properties in GRB hosts with respect to photometric measurements. In all cases but one the extinction curve of one template is preferred over the others. We show that the modeled values of the extinction and the spectral slope, obtained through spectroscopic and photometric SED analysis, can differ significantly for individual events. Finally we stress that, regardless of the resolution of the optical-to-NIR data, the SED modeling gives reliable results only when the fit is performed on a SED covering a broader spectral region.Comment: 17 pages, 7 figures, 4 tables, accepted for publication in Astronomy & Astrophysic

A quiescent galaxy at the position of the long GRB 050219A

Long-duration gamma-ray bursts (LGRBs) are produced by the collapse of very massive stars. Due to the short lifetime of their progenitors, LGRBs pinpoint star-forming galaxies. We present here a multi-band search for the host galaxy of the long dark GRB 050219A within the enhanced Swift/XRT error circle. We used spectroscopic observations acquired with VLT/X-shooter to determine the redshift and star-formation rate of the putative host galaxy. We compared the results with the optical/IR spectral energy distribution obtained with different facilities. Surprisingly, the host galaxy is a old and quiescent early-type galaxy at z = 0.211 characterised by an unprecedentedly low specific star-formation rate. It is the first LGRB host to be also an early-type post-starburst galaxy. This is further evidence that GRBs can explode in all kind of galaxies, with the only requirement being an episode of star-formation.Comment: 11 pages, 10 figures, 3 tables; accepted for publication in Astronomy & Astrophysic

The mysterious optical afterglow spectrum of GRB140506A at z=0.889

Context. Gamma-ray burst (GRBs) afterglows probe sightlines to star-forming regions in distant star-forming galaxies. Here we present a study of the peculiar afterglow spectrum of the z = 0.889 Swift GRB 140506A. Aims. Our aim is to understand the origin of the very unusual properties of the absorption along the line-of-sight. Methods. We analyse spectroscopic observations obtained with the X-shooter spectrograph mounted on the ESO/VLT at two epochs 8.8 h and 33 h after the burst as well as imaging from the GROND instrument. We also present imaging and spectroscopy of the host galaxy obtained with the Magellan telescope. Results. The underlying afterglow appears to be a typical afterglow of a long-duration GRB. However, the material along the line-of- sight has imprinted very unusual features on the spectrum. Firstly, there is a very broad and strong flux drop below 8000 AA (4000 AA in the rest frame), which seems to be variable between the two spectroscopic epochs. We can reproduce the flux-drops both as a giant 2175 AA extinction bump and as an effect of multiple scattering on dust grains in a dense environment. Secondly, we detect absorption lines from excited H i and He i. We also detect molecular absorption from CH+ . Conclusions. We interpret the unusual properties of these spectra as reflecting the presence of three distinct regions along the line-of-sight: the excited He i absorption originates from an H ii-region, whereas the Balmer absorption must originate from an associated photodissociation region. The strong metal line and molecular absorption and the dust extinction must originate from a third, cooler region along the line-of-sight. The presence of (at least) three separate regions is reflected in the fact that the different absorption components have different velocities relative to the systemic redshift of the host galaxy.Comment: 8 pages, 4 figures. Accepted for publications in A&

The chemical enrichment of long gamma-ray bursts nurseries up to z = 2

Aims. We investigate the existence of a metallicity threshold for the production of long gamma-ray bursts (LGRBs). Methods. We used the host galaxies of the Swift/BAT6 sample of LGRBs. We considered the stellar mass, star formation rate (SFR), and metallicity determined from the host galaxy photometry and spectroscopy up to z = 2 and used them to compare the distribution of host galaxies to that of field galaxies in the mass-metallicity and fundamental metallicity relation plane. Results. We find that although LGRBs also form in galaxies with relatively large stellar masses, the large majority of host galaxies have metallicities below log(O=H) ∼ 8:6. The extension to z = 2 results in a good sampling of stellar masses also above Log(M=M) ∼ 9:5 and provides evidence that LGRB host galaxies do not follow the fundamental metallicity relation. As shown by the comparison with dedicated numerical simulations of LGRB host galaxy population, these results are naturally explained by the existence of a mild (∼0:7 Z) threshold for the LGRB formation. The present statistics does not allow us to discriminate between different shapes of the metallicity cutoff, but the relatively high metallicity threshold found in this work is somewhat in disagreement to most of the standard single-star models for LGRB progenitors. © ESO, 201

The chemical enrichment of long gamma-ray bursts nurseries up to z = 2

Aims. We investigate the existence of a metallicity threshold for the production of long gamma-ray bursts (LGRBs). Methods. We used the host galaxies of the Swift/BAT6 sample of LGRBs. We considered the stellar mass, star formation rate (SFR), and metallicity determined from the host galaxy photometry and spectroscopy up to z = 2 and used them to compare the distribution of host galaxies to that of field galaxies in the mass-metallicity and fundamental metallicity relation plane. Results. We find that although LGRBs also form in galaxies with relatively large stellar masses, the large majority of host galaxies have metallicities below log(O=H) ∼ 8:6. The extension to z = 2 results in a good sampling of stellar masses also above Log(M=M) ∼ 9:5 and provides evidence that LGRB host galaxies do not follow the fundamental metallicity relation. As shown by the comparison with dedicated numerical simulations of LGRB host galaxy population, these results are naturally explained by the existence of a mild (∼0:7 Z) threshold for the LGRB formation. The present statistics does not allow us to discriminate between different shapes of the metallicity cutoff, but the relatively high metallicity threshold found in this work is somewhat in disagreement to most of the standard single-star models for LGRB progenitors. © ESO, 201

VLT/X-shooter spectroscopy of massive young stellar objects in the 30 Doradus region of the Large Magellanic Cloud

The process of massive star (M ≥ 8 M⊙) formation is still poorly understood. Observations of massive young stellar objects (MYSOs) are challenging due to their rarity, short formation timescale, large distances, and high circumstellar extinction. Here, we present the results of a spectroscopic analysis of a population of MYSOs in the Large Magellanic Cloud. We took advantage of the spectral resolution and wavelength coverage of X-shooter (300−2500 nm), which is mounted on the European Southern Observatory Very Large Telescope, to detect characteristic spectral features in a dozen MYSO candidates near 30 Doradus, the largest starburst region in the Local Group hosting the most massive stars known. The X-shooter spectra are strongly contaminated by nebular emission. We used a scaling method to subtract the nebular contamination from our objects. We detect Hα, β, [O I] 630.0 nm, Ca II, infrared triplet [Fe II] 1643.5 nm, fluorescent Fe II 1687.8 nm, H2 2121.8 nm, Brγ, and CO bandhead emission in the spectra of multiple candidates. This leads to the spectroscopic confirmation of ten candidates as bona fide MYSOs. We compared our observations with photometric observations from the literature and find all MYSOs to have a strong near-infrared excess. We computed lower limits to the brightness and luminosity of the MYSO candidates, confirming the near-infrared excess and the massive nature of the objects. No clear correlation is seen between the Brγ luminosity and metallicity. Combining our sample with other LMC samples results in a combined detection rate of disk features, such as fluorescent Fe II and CO bandheads, which is consistent with the Galactic rate (40%). Most of our MYSOs show outflow features