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1. Laboratory rotational spectroscopy of acrylamide and a search for acrylamide and propionamide toward Sgr B2(N) with ALMA

   https://doi.org/10.1051/0004-6361/202142448  

   Kolesniková, L. ; Belloche, A. ; Koucký, J. ; Alonso, E. R. ; Garrod, R. T. ; Luková, K. ; Menten, K. M. ; Müller, H. S. ; Kania, P. ; Urban, Š. ( March 2022 , Astronomy & Astrophysics)

   Context. Numerous complex organic molecules have been detected in the universe and among them are amides, which are considered as prime models for species containing a peptide linkage. In its backbone, acrylamide (CH 2 CHC(O)NH 2 ) bears not only the peptide bond, but also the vinyl functional group that is a common structural feature in many interstellar compounds. This makes acrylamide an interesting candidate for searches in the interstellar medium. In addition, a tentative detection of the related molecule propionamide (C 2 H 5 C(O)NH 2 ) has been recently claimed toward Sgr B2(N). Aims. The aim of this work is to extend the knowledge of the laboratory rotational spectrum of acrylamide to higher frequencies, which would make it possible to conduct a rigorous search for interstellar signatures of this amide using millimeter wave astronomy. Methods. We measured and analyzed the rotational spectrum of acrylamide between 75 and 480 GHz. We searched for emission of acrylamide in the imaging spectral line survey ReMoCA performed with the Atacama Large Millimeter/submillimeter Array toward Sgr B2(N). We also searched for propionamide in the same source. The astronomical spectra were analyzed under the assumption of local thermodynamic equilibrium. Results. We report accurate laboratorymore »measurements and analyses of thousands of rotational transitions in the ground state and two excited vibrational states of the most stable syn form of acrylamide. In addition, we report an extensive set of rotational transitions for the less stable skew conformer. Tunneling through a low energy barrier between two symmetrically equivalent configurations has been revealed for this higher-energy species. Neither acrylamide nor propionamide were detected toward the two main hot molecular cores of Sgr B2(N). We did not detect propionamide either toward a position located to the east of the main hot core, thereby undermining the recent claim of its interstellar detection toward this position. We find that acrylamide and propionamide are at least 26 and 14 times less abundant, respectively, than acetamide toward the main hot core Sgr B2(N1S), and at least 6 and 3 times less abundant, respectively, than acetamide toward the secondary hot core Sgr B2(N2). Conclusions. A comparison with results of astrochemical kinetics model for related species suggests that acrylamide may be a few hundred times less abundant than acetamide, corresponding to a value that is at least an order of magnitude lower than the observational upper limits. Propionamide may be as little as only a factor of two less abundant than the upper limit derived toward Sgr B2(N1S). Lastly, the spectroscopic data presented in this work will aid future searches of acrylamide in space.« less
2. Millimetre-wave laboratory study of glycinamide and a search for it with ALMA towards Sagittarius B2(N)

   https://doi.org/10.1051/0004-6361/202142350  

   Kisiel, Z. ; Kolesniková, L. ; Belloche, A. ; Guillemin, J.-C. ; Pszczółkowski, L. ; Alonso, E. R. ; Garrod, R. T. ; Białkowska-Jaworska, E. ; León, I. ; Müller, H. S. ; et al ( January 2022 , Astronomy & Astrophysics)

   Context. Glycinamide (NH 2 CH 2 C(O)NH 2 ) is considered to be one of the possible precursors of the simplest amino acid, glycine. Its only rotational spectrum reported so far has been in the centimetre-wave region on a laser-ablation generated supersonic expansion sample. Aims. The aim of this work is to extend the laboratory spectrum of glycinamide to the millimetre (mm) wave region to support searches for this molecule in the interstellar medium and to perform the first check for its presence in the high-mass star forming region Sagittarius B2(N). Methods. Glycinamide was synthesised chemically and was studied with broadband rotational spectroscopy in the 90–329 GHz region with the sample in slow flow at 50°C. Tunnelling across a low-energy barrier between two symmetry equivalent configurations of the molecule resulted in splitting of each vibrational state and many perturbations in associated rotational energy levels, requiring careful coupled state fits for each vibrational doublet. We searched for emission of glycinamide in the imaging spectral line survey ReMoCA performed with the Atacama Large Millimetre/submillimetre Array towards Sgr B2(N). The astronomical spectra were analysed under the assumption of local thermodynamic equilibrium. Results. We report the first analysis of the mm-wave rotational spectrum ofmore »glycinamide, resulting in fitting – to experimental measurement accuracy – of over 1200 assigned and measured transition frequencies for the ground-state tunnelling doublet and of many lines for tunnelling doublets for two singly excited vibrational states. We also determine the precise vibrational separation in each doublet. We did not detect emission from glycinamide in the hot molecular core Sgr B2(N1S). We derived a column density upper limit of 1.5 × 10 16 cm −2 , which implies that glycinamide is at least seven times less abundant than aminoacetonitrile and 1.8 times less abundant than urea in this source. A comparison with results of astrochemical kinetics models for species related to glycinamide suggests that its abundance may be at least one order of magnitude below the upper limit obtained towards Sgr B2(N1S). This means that glycinamide emission in this source likely lies well below the spectral confusion limit in the frequency range covered by the ReMoCA survey. Conclusions. Thanks to the spectroscopic data provided by this study, the search for glycinamide in the interstellar medium can continue on a firm basis. Targetting sources with a lower level of spectral confusion, such as the Galactic Center shocked region G+0.693-0.027, may be a promising avenue.« less
3. Rotational spectroscopic study and astronomical search for propiolamide in Sgr B2(N)

   https://doi.org/10.1051/0004-6361/202040211  

   Alonso, E. R. ; Kolesniková, L. ; Belloche, A. ; Mata, S. ; Garrod, R. T. ; Jabri, A. ; León, I. ; Guillemin, J.-C. ; Müller, H. S. ; Menten, K. M. ; et al ( March 2021 , Astronomy & Astrophysics)

   Context. For all the amides detected in the interstellar medium (ISM), the corresponding nitriles or isonitriles have also been detected in the ISM, some of which have relatively high abundances. Among the abundant nitriles for which the corresponding amide has not yet been detected is cyanoacetylene (HCCCN), whose amide counterpart is propiolamide (HCCC(O)NH 2 ). Aims. With the aim of supporting searches for this amide in the ISM, we provide a complete rotational study of propiolamide from 6 to 440 GHz. Methods. Time-domain Fourier transform microwave spectroscopy under supersonic expansion conditions between 6 and 18 GHz was used to accurately measure and analyze ground-state rotational transitions with resolved hyperfine structure arising from nuclear quadrupole coupling interactions of the 14 N nucleus. We combined this technique with the frequency-domain room-temperature millimeter wave and submillimeter wave spectroscopies from 75 to 440 GHz in order to record and assign the rotational spectra in the ground state and in the low-lying excited vibrational states. We used the ReMoCA spectral line survey performed with the Atacama Large Millimeter/submillimeter Array toward the star-forming region Sgr B2(N) to search for propiolamide. Results. We identified and measured more than 5500 distinct frequency lines of propiolamide in the laboratory.more »These lines were fitted using an effective semi-rigid rotor Hamiltonian with nuclear quadrupole coupling interactions taken into consideration. We obtained accurate sets of spectroscopic parameters for the ground state and the three low-lying excited vibrational states. We report the nondetection of propiolamide toward the hot cores Sgr B2(N1S) and Sgr B2(N2). We find that propiolamide is at least 50 and 13 times less abundant than acetamide in Sgr B2(N1S) and Sgr B2(N2), respectively, indicating that the abundance difference between both amides is more pronounced by at least a factor of 8 and 2, respectively, than for their corresponding nitriles. Conclusions. Although propiolamide has yet to be included in astrochemical modeling networks, the observed upper limit to the ratio of propiolamide to acetamide seems consistent with the ratios of related species as determined from past simulations. The comprehensive spectroscopic data presented in this paper will aid future astronomical searches.« less
4. Interstellar detection and chemical modeling of iso-propanol and its normal isomer

   https://doi.org/10.1051/0004-6361/202243575  

   Belloche, A. ; Garrod, R. T. ; Zingsheim, O. ; Müller, H. S. ; Menten, K. M. ( June 2022 , Astronomy & Astrophysics)

   Context. The detection of a branched alkyl molecule in the high-mass star forming protocluster Sagittarius (Sgr) B2(N) permitted by the advent of the Atacama Large Millimeter/submillimeter Array (ALMA) revealed a new dimension of interstellar chemistry. Astrochemical simulations subsequently predicted that beyond a certain degree of molecular complexity, branched molecules could even dominate over their straight-chain isomers. Aims. More generally, we aim to probe further the presence in the interstellar medium of complex organic molecules with the capacity to exhibit both a normal and iso form, via the attachment of a functional group to either a primary or secondary carbon atom. Methods. We used the imaging spectral line survey ReMoCA performed with ALMA at high angular resolution and the results of a recent spectroscopic study of propanol to search for the iso and normal isomers of this molecule in the hot molecular core Sgr B2(N2). We analyzed the interferometric spectra under the assumption of local thermodynamical equilibrium. We expanded the network of the astrochemical model MAGICKAL to explore the formation routes of propanol and put the observational results in a broader astrochemical context. Results. We report the first interstellar detection of iso-propanol, ¿-C 3 H 7 OH, toward a position ofmore »Sgr B2(N2) that shows narrow linewidths. We also report the first secure detection of the normal isomer of propanol, n-C 3 H 7 OH, in a hot core. Iso-propanol is found to be nearly as abundant as normal-propanol, with an abundance ratio of 0.6 which is similar to the ratio of 0.4 that we obtained previously for iso- and normal-propyl cyanide in Sgr B2(N2) at lower angular resolution with our previous ALMA survey, EMoCA. The observational results are in good agreement with the outcomes of our astrochemical models, which indicate that the OH-radical addition to propylene in dust-grain ice mantles, driven by water photodissociation, can produce appropriate quantities of normal- and iso-propanol. The normal-to-iso ratio in Sgr B2(N2) may be a direct inheritance of the branching ratio of this reaction process. Conclusions. The detection of normal- and iso-propanol and their ratio indicate that the modest preference for the normal form of propyl cyanide determined previously may be a more general feature among similarly sized interstellar molecules. Detecting other pairs of interstellar organic molecules with a functional group attached either to a primary or secondary carbon may help in pinning down the processes that dominate in setting their normal-to-iso ratios. Butanol and its isomers would be the next obvious candidates in the alcohol family, but their detection in hot cores will be challenging.« less
5. CH ₃ -Terminated Carbon Chains in the GOTHAM Survey of TMC-1: Evidence of Interstellar CH ₃ C ₇ N

   https://doi.org/10.3847/1538-4357/ac3238  

   Siebert, Mark A. ; Lee, Kin Long ; Remijan, Anthony J. ; Burkhardt, Andrew M. ; Loomis, Ryan A. ; McCarthy, Michael C. ; McGuire, Brett A. ( January 2022 , The Astrophysical Journal)

   Abstract We report a systematic study of all known methyl carbon chains toward TMC-1 using the second data release of the GOTHAM survey, as well as a search for larger species. Using Markov Chain Monte Carlo simulations and spectral line stacking of over 30 rotational transitions, we report statistically significant emission from methylcyanotriacetylene (CH 3 C 7 N) at a confidence level of 4.6 σ , and use it to derive a column density of ∼10 11 cm −2 . We also searched for the related species, methyltetraacetylene (CH 3 C 8 H), and place upper limits on the column density of this molecule. By carrying out the above statistical analyses for all other previously detected methyl-terminated carbon chains that have emission lines in our survey, we assess the abundances, excitation conditions, and formation chemistry of methylpolyynes (CH 3 C 2 n H) and methylcyanopolyynes (CH 3 C 2 n -1 N) in TMC-1, and compare those with predictions from a chemical model. Based on our observed trends in column density and relative populations of the A and E nuclear spin isomers, we find that the methylpolyyne and methylcyanopolyyne families exhibit stark differences from one another, pointing to separate interstellarmore »formation pathways, which is confirmed through gas–grain chemical modeling with nautilus .« less