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1. 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
2. Interstellar glycolamide: A comprehensive rotational study and an astronomical search in Sgr B2(N)

   https://doi.org/10.1051/0004-6361/202038149  

   Sanz-Novo, M. ; Belloche, A. ; Alonso, J. L. ; Kolesniková, L. ; Garrod, R. T. ; Mata, S. ; Müller, H. S. ; Menten, K. M. ; Gong, Y. ( July 2020 , Astronomy & Astrophysics)

   Context. Glycolamide is a glycine isomer and also one of the simplest derivatives of acetamide (e.g., one hydrogen atom is replaced with a hydroxyl group), which is a known interstellar molecule. Aims. In this context, the aim of our work is to provide direct experimental frequencies of the ground vibrational state of glycolamide in the centimeter-, millimeter- and submillimeter-wavelength regions in order to enable its identification in the interstellar medium. Methods. We employed a battery of state-of-the-art rotational spectroscopic techniques in the frequency and time domain to measure the frequencies of glycolamide. We used the spectral line survey named Exploring Molecular Complexity with ALMA (EMoCA), which was performed toward the star forming region Sgr B2(N) with ALMA to search for glycolamide in space. We also searched for glycolamide toward Sgr B2(N) with the Effelsberg radio telescope. The astronomical spectra were analyzed under the local thermodynamic equilibrium approximation. We used the gas-grain chemical kinetics model MAGICKAL to interpret the results of the astronomical observations. Results. About 1500 transitions have been newly assigned up to 460 GHz to the most stable conformer, and a precise set of spectroscopic constants was determined. Spectral features of glycolamide were then searched for in the prominentmore »hot molecular core Sgr B2(N2). We report the nondetection of glycolamide toward this source with an abundance at least six and five times lower than that of acetamide and glycolaldehyde, respectively. Our astrochemical model suggests that glycolamide may be present in this source at a level just below the upper limit, which was derived from the EMoCA survey. We could also not detect the molecule in the region’s extended molecular envelope, which was probed with the Effelsberg telescope. We find an upper limit to its column density that is similar to the column densities obtained earlier for acetamide and glycolaldehyde with the Green Bank Telescope.« less
3. 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
4. Millimeter-wave spectrum of 2-propanimine

   https://doi.org/10.1093/mnras/stad405  

   Zou, Luyao ; Guillemin, Jean-Claude ; Belloche, Arnaud ; Jørgensen, Jes K. ; Margulès, Laurent ; Motiyenko, Roman A. ; Groner, Peter ( February 2023 , Monthly Notices of the Royal Astronomical Society)

   Up to date, only six imines have been detected in the interstellar medium. The 3-carbon imine, 2-propanimine ((CH3)2C = NH), is predicted to be the structural isomer with the lowest energy in the C3H7N group, and appears to be a good candidate for astronomical searches. Unexpectedly, no microwave or millimeter wave spectrum is available for 2-propanimine. In this work, we provide the first high-resolution millimeter wave spectrum of 2-propanimine and its analysis. With the guide of this laboratory measurement, we aim to search for 2-propanimine in two molecule-rich sources Sgr B2(N) and IRAS 16293–2422 using observations from the Atacama Large Millimeter/submillimeter Array (ALMA). Starting from a synthesized sample, we measured the spectrum of 2-propanimine from 50 to 500 GHz, and the ground state lines are successfully assigned and fitted using XIAM and ERHAM programs with the aid of theoretical calculations. The barriers to internal rotation of the two CH3 tops are determined to be 531.956(64) cm−1 and 465.013(26) cm−1 by XIAM. These data are able to provide reliable prediction of transition frequencies for astronomical search. Although a few line matches exist, no confirmed detection of 2-propanimine has been found in the hot molecular core Sgr B2(N1S) and the Class 0 protostar IRAS 16293B.more »Upper-limits of its column density have been derived, and indicate that 2-propanimine is at least 18 times less abundant than methanimine in Sgr B2(N1S), and is at most 50 – 83  per cent of methanimine in IRAS 16293B.

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5. 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