Selective Reagent Ion Mass Spectrometric Investigations of the Nitroanilines

This paper presents an investigation of proton and charge transfer reactions to 2-, 3- and 4-nitroanilines (C6H6N2O2) involving the reagent ions H3O+·(H2O)n (n=0, 1 and 2) and O2+, respectively, as a function of reduced electric field (60-240 Td), using Selective Reagent Ion-Time-of-Flight-Mass Spectrometry (SRI-ToF-MS). To aid in the interpretation of the H3O+·(H2O)n experimental data, the proton affinities and gas-phase basicities for the three nitroaniline isomers have been determined using density functional theory. These calculations show that proton transfer from both the H3O+ and H3O+·H2O reagent ions to the nitroanilines will be exoergic and hence efficient, with the reactions proceeding at the collisional rate. For proton transfer from H3O+ to the NO2 sites, the exoergicities are 171 kJ mol-1 (1.8 eV), 147 kJ mol-1 (1.5 eV) and 194 kJ mol-1 (2.0 eV) for 2-, 3- and 4-nitroanilines, respectively. Electron transfer from all three of the nitroanilines is also significantly exothermic by approximately 4 eV. Although a substantial transfer of energy occurs during the ion/molecule reactions, the processes are found to predominantly proceed via non-dissociative pathways over a large reduced electric field range. Only at relatively high reduced electric fields (>180 Td) is dissociative proton and charge transfer observed. Differences in fragment product ions and their intensities provide a means to distinguish the isomers, with proton transfer distinguishing 2-nitroaniline (2-NA) from 3- and 4-NA, and charge transfer distinguishing 4-NA from 2- and 3-NA, thereby providing a means to enhance selectivity using SRI-ToF-MS.(VLID)4826158Version of recor

HADES RV Programme with HARPS-N at TNG. VII. Rotation and activity of M-Dwarfs from time-series high-resolution spectroscopy of chromospheric indicators

We aim to investigate the presence of signatures of magnetic cycles and rotation on a sample of 71 early M-dwarfs from the HADES RV programme using high-resolution time-series spectroscopy of the Ca II H & K and Halpha chromospheric activity indicators, the radial velocity series, the parameters of the cross correlation function and the V-band photometry. We used mainly HARPS-N spectra, acquired over four years, and add HARPS spectra from the public ESO database and ASAS photometry light-curves as support data, extending the baseline of the observations of some stars up to 12 years. We provide log(R'hk) measurements for all the stars in the sample, cycle length measurements for 13 stars, rotation periods for 33 stars and we are able to measure the semi-amplitude of the radial velocity signal induced by rotation in 16 stars. We complement our work with previous results and confirm and refine the previously reported relationships between the mean level of chromospheric emission, measured by the log(R'hk), with the rotation period, and with the measured semi-amplitude of the activity induced radial velocity signal for early M-dwarfs. We searched for a possible relation between the measured rotation periods and the lengths of the magnetic cycle, finding a weak correlation between both quantities. Using previous v sin i measurements we estimated the inclinations of the star's poles to the line of sight for all the stars in the sample, and estimate the range of masses of the planets GJ 3998 b and c (2.5 - 4.9 Mearth and 6.3 - 12.5 Mearth), GJ 625 b (2.82 Mearth), GJ 3942 b (7.1 - 10.0 Mearth) and GJ 15A b (3.1 - 3.3 Mearth), assuming their orbits are coplanar with the stellar rotation.Comment: 19 pages, 16 figures, 10 table

Multi-band high resolution spectroscopy rules out the hot Jupiter BD+20 1790b - First data from the GIARPS Commissioning

Context. Stellar activity is currently challenging the detection of young planets via the radial velocity (RV) technique. Aims. We attempt to definitively discriminate the nature of the RV variations for the young active K5 star BD+20 1790, for which visible (VIS) RV measurements show divergent results on the existence of a substellar companion. Methods. We compare VIS data with high precision RVs in the near infrared (NIR) range by using the GIANO - B and IGRINS spectrographs. In addition, we present for the first time simultaneous VIS-NIR observations obtained with GIARPS (GIANO - B and HARPS - N) at Telescopio Nazionale Galileo (TNG). Orbital RVs are achromatic, so the RV amplitude does not change at different wavelengths, while stellar activity induces wavelength-dependent RV variations, which are significantly reduced in the NIR range with respect to the VIS. Results. The NIR radial velocity measurements from GIANO - B and IGRINS show an average amplitude of about one quarter with respect to previously published VIS data, as expected when the RV jitter is due to stellar activity. Coeval multi-band photometry surprisingly shows larger amplitudes in the NIR range, explainable with a mixture of cool and hot spots in the same active region. Conclusions. In this work, the claimed massive planet around BD+20 1790 is ruled out by our data. We exploited the crucial role of multi- wavelength spectroscopy when observing young active stars: thanks to facilities like GIARPS that provide simultaneous observations, this method can reach its maximum potential.Comment: 12 pages, 7 figure

Uso y prescripción de cannabis medicinal por reumatólogos en Argentina

El uso y prescripción del cannabis y sus derivados en Reumatología está aún en discusión. La ley de cannabis fue sancionada hace casi 3 años, aunque la reglamentación recién está comenzando. El objetivo de este estudio fue conocer la forma en que el reumatólogo se posiciona frente al uso de cannabis en el marco de su práctica médica. A través de una encuesta realizada durante el Congreso Argentino de Reumatología 2019 se recabó la opinión de 314 médicos que respondieron preguntas acerca del uso, recomendaciones y posturas respecto a la indicación y uso de cannabinoides en su práctica diaria

Placental thrombosis in acute phase abortions during experimental Toxoplasma gondii infection in sheep

43 p.After oral administration of ewes during mid gestation with 2000 freshly prepared sporulated oocysts of T. gondii isolate M4, abortions occurred between days 7 and 11 in 91.6% of pregnant and infected ewes. Afterwards, a further infection was carried out at late gestation in another group of sheep with 500 sporulated oocysts. Abortions happened again between days 9 and 11 post infection (pi) in 58.3% of the infected ewes. Classically, abortions in natural and experimental ovine toxoplasmosis usually occur one month after infection. Few experimental studies have reported the so-called acute phase abortions as early as 7 to 14 days after oral inoculation of oocysts, and pyrexia was proposed to be responsible for abortion, although the underline mechanism was not elucidated. In the present study, all placentas analysed from ewes suffering acute phase abortions showed infarcts and thrombosis in the caruncullar villi of the placentomes and ischemic lesions (periventricular leukomalacia) in the brain of some foetuses. The parasite was identified by PCR in samples from some placentomes of only one sheep, and no antigen was detected by immunohistochemical labelling. These findings suggest that the vascular lesions found in the placenta, and the consequent hypoxic damage to the foetus, could be associated to the occurrence of acute phase abortions. Although the pathogenesis of these lesions remains to be determined, the infectious dose or virulence of the isolate may play a role in their developmentS

The HADES RV Programme with HARPS-N@TNG II. Data treatment and simulations

The distribution of exoplanets around low-mass stars is still not well understood. Such stars, however, present an excellent opportunity of reaching down to the rocky and habitable planet domains. The number of current detections used for statistical purposes is still quite modest and different surveys, using both photometry and precise radial velocities, are searching for planets around M dwarfs. Our HARPS-N red dwarf exoplanet survey is aimed at the detection of new planets around a sample of 78 selected stars, together with the subsequent characterization of their activity properties. Here we investigate the survey performance and strategy. From 2700 observed spectra, we compare the radial velocity determinations of the HARPS-N DRS pipeline and the HARPS-TERRA code, we calculate the mean activity jitter level, we evaluate the planet detection expectations, and we address the general question of how to define the strategy of spectroscopic surveys in order to be most efficient in the detection of planets. We find that the HARPS-TERRA radial velocities show less scatter and we calculate a mean activity jitter of 2.3 m/s for our sample. For a general radial velocity survey with limited observing time, the number of observations per star is key for the detection efficiency. In the case of an early M-type target sample, we conclude that approximately 50 observations per star with exposure times of 900 s and precisions of about 1 m/s maximizes the number of planet detections

The GAPS programme at TNG XXII. The GIARPS view of the extended helium atmosphere of HD189733 b accounting for stellar activity

Exoplanets orbiting very close to their host star are strongly irradiated. This can lead the upper atmospheric layers to expand and evaporate into space. The metastable helium (HeI) triplet at 1083.3nm has recently been shown to be a powerful diagnostic to probe extended and escaping exoplanetary atmosphere. We perform high-resolution transmission spectroscopy of the transiting hot Jupiter HD189733b with the GIARPS (GIANO-B + HARPS-N) observing mode of the Telescopio Nazionale Galileo, taking advantage of the simultaneous optical+near infrared spectral coverage to detect HeI in the planet's extended atmosphere and to gauge the impact of stellar magnetic activity on the planetary absorption signal. Observations were performed during five transit events of HD189733b. By comparison of the in- and out-of-transit GIANO-B observations we compute high-resolution transmission spectra, on which we perform equivalent width measurements and light-curves analyses to gauge the excess in-transit absorption in the HeI triplet. We detect an absorption signal during all five transits. The mean in-transit absorption depth amounts to 0.75+/-0.03%. We detect night-to-night variations in the HeI absorption signal likely due to the transit events occurring in presence of stellar surface inhomogeneities. We evaluate the impact of stellar-activity pseudo-signals on the true planetary absorption using a comparative analysis of the HeI and the H$\alpha$ lines. We interpret the time-series of the HeI absorption lines in the three nights not affected by stellar contamination -exhibiting a mean in-transit absorption depth of 0.77+/-0.04%- using a 3-d atmospheric code. Our simulations suggest that the helium layers only fill part of the Roche lobe. Observations can be explained with a thermosphere heated to $\sim$12000 K, expanding up to $\sim$1.2 planetary radii, and losing $\sim$1 g/s of metastable helium.Comment: 17 pages, 17 figures, accepted for publication in A&

Catalog for the ESPRESSO blind radial velocity exoplanet survey

One of the main scientific drivers for ESPRESSO,\'Echelle SPectrograph, is the detection and characterization of Earth-class exoplanets. With this goal in mind, the ESPRESSO Guaranteed Time Observations (GTO) Catalog identifies the best target stars for a blind search for the radial velocity (RV) signals caused by Earth-class exoplanets. Using the most complete stellar catalogs available, we screened for the most suitable G, K, and M dwarf stars for the detection of Earth-class exoplanets with ESPRESSO. For most of the stars, we then gathered high-resolution spectra from new observations or from archival data. We used these spectra to spectroscopically investigate the existence of any stellar binaries, both bound or background stars. We derived the activity level using chromospheric activity indexes using $log(R'_{HK})$, as well as the projected rotational velocity $\textit{v sin i}$. For the cases where planet companions are already known, we also looked at the possibility that additional planets may exist in the host's habitable zone using dynamical arguments. We estimated the spectroscopic contamination level, $\textit{v sin i}$, activity, stellar parameters and chemical abundances for 249 of the most promising targets. Using these data, we selected 45 stars that match our criteria for detectability of a planet like Earth. The stars presented and discussed in this paper constitute the ESPRESSO GTO catalog for the RV blind search for Earth-class planets. They can also be used for any other work requiring a detailed spectroscopic characterization of stars in the solar neighborhood.Comment: Corrected a typo in references. Corrected typo in table B.

HADES RV Programme with HARPS-N at TNG XIII. A sub-Neptune around the M dwarf GJ 720 A

Context. The high number of super-Earth and Earth-like planets in the habitable zone (HZ) detected around M-dwarf stars in the last years has revealed these stellar objects to be the key for planetary radial velocity (RV) searches. Aims. Using the HARPS-N spectrograph within The HArps-n red Dwarf Exoplanet Survey (HADES) we reach the precision needed to detect small planets with a few Earth masses using the RV technique. Methods. We obtained 138 HARPS-N RV measurements between 2013 May and 2020 September of GJ 720 A, classified as an M0.5V star located at a distance of 15.56 pc. To characterize the stellar variability and to discern the periodic variation due to the Keplerian signals from those related to stellar activity, the HARPS-N spectroscopic activity indicators and the simultaneous photometric observations were analyzed. The combined analysis of HARPS-N RVs and activity indicators let us to address the nature of the periodic signals. The final model and the orbital planetary parameters were obtained by fitting simultaneously the stellar variability and the Keplerian signal using a Gaussian process regression and following a Bayesian criterion. Results. The HARPS-N RV periodic signals around 40 d and 100 d have counterparts at the same frequencies in HARPS-N activity indicators and photometric light curves. Then we attribute these periodicities to stellar activity the former period being likely associated with the stellar rotation. GJ 720 A shows the most significant signal at 19.466$\pm$0.005 d with no counterparts in any stellar activity indices. We hence ascribe this RV signal, having a semiamplitude of 4.72$\pm$0.27 m/s , to the presence of a sub-Neptune mass planet. The planet GJ 720 Ab has a minimum mass of 13.64$\pm$0.79 M$_{\oplus}$, it is in circular orbit at 0.119$\pm$0.002 AU from its parent star, and lies inside the inner boundary of the HZ around its parent star

HADES RV Programme with HARPS-N at TNG XII. The abundance signature of M dwarf stars with planets

Most of our current knowledge on planet formation is still based on the analysis of main-sequence, solar-type stars. Conversely, detailed chemical studies of large samples of M-dwarf planet hosts are still missing. We develop for the first time a methodology to determine stellar abundances of elements others than iron for M dwarf stars from high-resolution, optical spectra. Our methodology is based on the use of principal component analysis and sparse Bayesian's methods. We made use of a set of M dwarfs orbiting around an FGK primary with known abundances to train our methods. We applied our methods to derive stellar metalliticies and abundances of a large sample of M dwarfs observed within the framework of current radial velocity surveys. We then used a sample of nearby FGK stars to cross-validate our technique by comparing the derived abundance trends in the M dwarf sample with those found on the FGK stars. The metallicity distribution of the different subsamples shows that M dwarfs hosting giant planets show a planet-metallicity correlation as well as a correlation with the stellar mass. M dwarfs hosting low-mass planets do not seem to follow the planet-metallicity correlation. We also found that the frequency of low-mass planets does not depend on the mass of the stellar host. These results seem in agreement with previous works. However, we note that for giant planet hosts our metallicities predict a weaker planet metallicity correlation but a stronger mass-dependency than photometric values. We show, for the first time, that there seems to be no differences in the abundance distribution of elements different from iron between M dwarfs with and without known planets. Our data shows that low-mass stars with planets follow the same metallicity, mass, and abundance trends than their FGK counterparts.Comment: Accepted for publication by Astronomy & Astrophysic