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  1. Context.In recent times, large organic molecules of exceptional complexity have been found in diverse regions of the interstellar medium.

    Aims.In this context, we aim to provide accurate frequencies of the ground vibrational state of two key aliphatic aldehydes,n-butanal and its branched-chain isomer, i-butanal, to enable their eventual detection in the interstellar medium. We also want to test the level of complexity that interstellar chemistry can reach in regions of star formation.

    Methods.We employ a frequency modulation millimeter-wave absorption spectrometer to measure the rotational features ofn- andi-butanal. We analyze the assigned rotational transitions of each rotamer separately using theA-reduced semirigid-rotor Hamiltonian. We use the spectral line survey ReMoCA performed with the Atacama Large Millimeter/submillimeter Array to search forn- andi-butanal toward the star-forming region Sgr B2(N). We also search for both aldehydes toward the molecular cloud G+0.693−0.027 with IRAM 30 m and Yebes 40 m observations. The observational results are compared with computational results from a recent gas-grain astrochemical model.

    Results.Several thousand rotational transitions belonging to the lowest-energy conformers of two distinct linear and branched isomers have been assigned in the laboratory spectra up to 325 GHz. A precise set of the relevant rotational spectroscopic constants has been determined for each structure as a first step toward identifying both molecules in the interstellar medium. We report non-detections ofn-and i-butanal toward both sources, Sgr B2(N1S) and G+0.693-0.027. We find thatn- andi-butanal are at least 2-6 and 6-18 times less abundant than acetaldehyde toward Sgr B2(N1S), respectively, and thatn-butanal is at least 63 times less abundant than acetaldehyde toward G+0.693−0.027. While propanal is not detected toward Sgr B2(N1S) either, with an abundance at least 5–11 lower than that of acetaldehyde, propanal is found to be 7 times less abundant than acetaldehyde in G+0.693−0.027. Comparison with astrochemical models indicates good agreement between observed and simulated abundances (where available). Grain-surface chemistry appears sufficient to reproduce aldehyde ratios in G+0.693−0.027; gas-phase production may play a more active role in Sgr B2(N1S). Model estimates for the larger aldehydes indicate that the observed upper limits may be close to the underlying values.

    Conclusions.Our astronomical results indicate that the family of interstellar aldehydes in the Galactic center region is characterized by a drop of one order of magnitude in abundance at each incrementation in the level of molecular complexity.

     
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  2. 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 of 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. 
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  3. null (Ed.)
    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. 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. 
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  4. null (Ed.)
    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 prominent 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. 
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