Abundant Z-cyanomethanimine in the interstellar medium: paving the way to the synthesis of adenine

We report the first detection in the interstellar medium of the Z-isomer of cyanomethanimine (HNCHCN), an HCN dimer proposed as precursor of adenine. We identified six transitions of Z-cyanomethanimine, along with five transitions of E-cyanomethanimine, using IRAM 30m observations towards the Galactic Center quiescent molecular cloud G+0.693. The Z-isomer has a column density of (2.0$\pm$0.6)$\times$10$^{14}$ cm$^{-2}$ and an abundance of 1.5$\times$10$^{-9}$. The relative abundance ratio between the isomers is [Z/E]$\sim$6. This value cannot be explained by the two chemical formation routes previously proposed (gas-phase and grain surface), which predicts abundances ratios between 0.9 and 1.5. The observed [Z/E] ratio is in good agreement with thermodynamic equilibrium at the gas kinetic temperature (130$-$210 K). Since isomerization is not possible in the ISM, the two species may be formed at high temperature. New chemical models, including surface chemistry on dust grains and gas-phase reactions, should be explored to explain our findings. Whatever the formation mechanism, the high abundance of Z-HNCHCN shows that precursors of adenine are efficiently formed in the ISM.Comment: Accepted in Monthly Notices of the Royal Astronomical Society Letter

Complex organic molecules in the Galactic Centre: the N-bearing family

We present an unbiased spectral line survey toward the Galactic Centre (GC) quiescent giant molecular cloud (QGMC), G+0.693 using the GBT and IRAM 30$\,$ telescopes. Our study highlights an extremely rich organic inventory of abundant amounts of nitrogen (N)-bearing species in a source without signatures of star formation. We report the detection of 17 N-bearing species in this source, of which 8 are complex organic molecules (COMs). A comparison of the derived abundances relative to H$_2$ is made across various galactic and extragalactic environments. We conclude that the unique chemistry in this source is likely to be dominated by low-velocity shocks with X-rays/cosmic rays also playing an important role in the chemistry. Like previous findings obtained for O-bearing molecules, our results for N-bearing species suggest a more efficient hydrogenation of these species on dust grains in G+0.693 than in hot cores in the Galactic disk, as a consequence of the low dust temperatures coupled with energetic processing by X-ray/cosmic ray radiation in the GC.Comment: 24 pages, 23 figures, 7 tables, accepted for publication in MNRA

Disentangling the excitation conditions of the dense gas in M17 SW

We probe the chemical and energetic conditions in dense gas created by radiative feedback through observations of multiple CO, HCN and HCO$^+$ transitions toward the dense core of M17 SW. We used the dual band receiver GREAT on board the SOFIA airborne telescope to obtain maps of the $J=16-15$, $J=12-11$, and $J=11-10$ transitions of $^{12}$CO. We compare these maps with corresponding APEX and IRAM 30m telescope data for low- and mid-$J$ CO, HCN and HCO$^+$ emission lines, including maps of the HCN $J=8-7$ and HCO$^+$ $J=9-8$ transitions. The excitation conditions of $^{12}$CO, HCO$^+$ and HCN are estimated with a two-phase non-LTE radiative transfer model of the line spectral energy distributions (LSEDs) at four selected positions. The energy balance at these positions is also studied. We obtained extensive LSEDs for the CO, HCN and HCO$^+$ molecules toward M17 SW. The LSED shape, particularly the high-$J$ tail of the CO lines observed with SOFIA/GREAT, is distinctive for the underlying excitation conditions. The critical magnetic field criterion implies that the cold cloudlets at two positions are partially controlled by processes that create and dissipate internal motions. Supersonic but sub-Alfv\'enic velocities in the cold component at most selected positions indicates that internal motions are likely MHD waves. Magnetic pressure dominates thermal pressure in both gas components at all selected positions, assuming random orientation of the magnetic field. The magnetic pressure of a constant magnetic field throughout all the gas phases can support the total internal pressure of the cold components, but it cannot support the internal pressure of the warm components. If the magnetic field scales as $B \propto n^{2/3}$, then the evolution of the cold cloudlets at two selected positions, and the warm cloudlets at all selected positions, will be determined by ambipolar diffusion.Comment: 26 pages, 13 figures, A&A accepte

Radiative and mechanical feedback into the molecular gas of NGC 253

Starburst galaxies are undergoing intense periods of star formation. Understanding the heating and cooling mechanisms in these galaxies can give us insight to the driving mechanisms that fuel the starburst. Molecular emission lines play a crucial role in the cooling of the excited gas. With SPIRE on the Herschel Space Observatory we have observed the rich molecular spectrum towards the central region of NGC 253. CO transitions from J=4-3 to 13-12 are observed and together with low-J line fluxes from ground based observations, these lines trace the excitation of CO. By studying the CO excitation ladder and comparing the intensities to models, we investigate whether the gas is excited by UV radiation, X-rays, cosmic rays, or turbulent heating. Comparing the $^{12}$CO and $^{13}$CO observations to large velocity gradient models and PDR models we find three main ISM phases. We estimate the density, temperature,and masses of these ISM phases. By adding $^{13}$CO, HCN, and HNC line intensities, we are able to constrain these degeneracies and determine the heating sources. The first ISM phase responsible for the low-J CO lines is excited by PDRs, but the second and third phases, responsible for the mid to high-J CO transitions, require an additional heating source. We find three possible combinations of models that can reproduce our observed molecular emission. Although we cannot determine which of these are preferable, we can conclude that mechanical heating is necessary to reproduce the observed molecular emission and cosmic ray heating is a negligible heating source. We then estimate the mass of each ISM phase; $6\times 10^7$ M$_\odot$ for phase 1 (low-J CO lines), $3\times 10^7$ M$_\odot$ for phase 2 (mid-J CO lines), and $9\times 10^6$ M$_\odot$ for phase 3 (high-J CO lines) for a total system mass of $1\times10^{8}$ M$_\odot$

AQME: Automated quantum mechanical environments for researchers and educators

AQME, automated quantum mechanical environments, is a free and open-source Python package for the rapid deployment of automated workflows using cheminformatics and quantum chemistry. AQME workflows integrate tasks performed across multiple computational chemistry packages and data formats, preserving all computational protocols, data, and metadata for machine and human users to access and reuse. AQME has a modular structure of independent modules that can be implemented in any sequence, allowing the users to use all or only the desired parts of the program. The code has been developed for researchers with basic familiarity with the Python programming language. The CSEARCH module interfaces to molecular mechanics and semi-empirical QM (SQM) conformer generation tools (e.g., RDKit and Conformer–Rotamer Ensemble Sampling Tool, CREST) starting from various initial structure formats. The CMIN module enables geometry refinement with SQM and neural network potentials, such as ANI. The QPREP module interfaces with multiple QM programs, such as Gaussian, ORCA, and PySCF. The QCORR module processes QM results, storing structural, energetic, and property data while also enabling automated error handling (i.e., convergence errors, wrong number of imaginary frequencies, isomerization, etc.) and job resubmission. The QDESCP module provides easy access to QM ensemble-averaged molecular descriptors and computed properties, such as NMR spectra. Overall, AQME provides automated, transparent, and reproducible workflows to produce, analyze and archive computational chemistry results. SMILES inputs can be used, and many aspects of tedious human manipulation can be avoided. Installation and execution on Windows, macOS, and Linux platforms have been tested, and the code has been developed to support access through Jupyter Notebooks, the command line, and job submission (e.g., Slurm) scripts. Examples of pre-configured workflows are available in various formats, and hands-on video tutorials illustrate their use

Genetic Admixture Analysis in the Population of Tacuarembó Uruguay Using Alu Insertions

Tacuarembó is a department located in the northeastern of Uruguay, whose population is the result of several migration waves from Europe and Near East as well as Africans and Afro-descents mostly from Brazil, these waves settled on the territory of various Native ethnic groups (Charrúa, Minuán, and Guaraní). In the past, this population has been the focus of genetic studies showing this tri-hybrid origin, with greater contributions of Natives and Africans than other Uruguayan regions. In this paper we aim to analyzeAluinsertions (A25, ACE, APOA1, B65, D1, F13B, PV92, TPA25) in order to provide valuable information for ancestrality and genetic differentiation (GD), and to compare with previous studies on Tacuarembó population as well as toAlufrequencies in other Uruguayan populations.The European contribution withAluand classical markers (CM) was almost equal to a previous study using 22 classical markers (63% vs 65%) while African contribution was higher(30% vs15% respectively), and the Native Americans contribution shows an important difference 7% inAluvs20%. There are no significant differences between Tacuarembó and Montevideo in GD, but there are significant differences between Tacuarembó and Basques descendants from Trinidad. Our results support the previous findings obtained with classical markers that demonstrate the tri-hybrid composition of the Tacuarembó population, correlated with the historic records. Finally,Aluinsertions provides interesting information in light of the admixture process in the Uruguayan population

Metal-organic frameworks (MOFs) bring new life to hydrogen-bonding organocatalysts in confined spaces

Hydrogen-bonding organocatalysis has emerged as a promising biomimetic alternative to Lewis acid catalysis. Urea, thiourea and squaramide moieties represent the most common hydrogen-bond donors used for the preparation of these catalysts. However, their significant tendency to undergo self-quenching (self-aggregation) often decreases their solubility and reactivity. Recently, scientists have found a promising way around this problem by immobilizing the hydrogen-bonding organocatalysts on metal–organic frameworks (MOFs). Along with advantageous modular synthesis and recycling properties, the tunable porosity and topology of MOFs also allows fast mass transport and/or interactions with substrates. Herein, we highlight the existing examples dealing with the fabrication and testing of hydrogen-bonding organocatalyst-containing MOFs, providing also our vision for further advances in this area. The results derived from these studies will likely serve as inspiration for the future development of superior hydrogen-bonding organocatalysts to accomplish in confined spaces chemical transformations that are either slow or unaffordable under standard homogeneous conditions

The prion 2018 round tables (I): the structure of PrP Sc

Understanding the structure of PrPSc is without doubt a sine qua non to understand not only PrPSc propagation, but also critical features of that process such as the strain phenomenon and transmission barriers. While elucidation of the PrPSc structure has been full of difficulties, we now have a large amount of structural information that allows us to begin to understand it. This commentary article summarizes a round table that took place within the Prion 2018 meeting held in Santiago de Compostela to discuss the state of the art in this matter. Two alternative models of PrPSc exist: the PIRIBS and the 4-rung β-solenoid models. Both of them have relevant features. The 4-rung β-solenoid model agrees with experimental constraints of brain derived PrPSc obtained from cryo-EM and X-ray fiber diffraction studies. Furthermore, it allows facile accommodation of the bulky glycans that decorate brain-derived PrPSc. On the other hand, the infectious PrP23-144 amyloid exhibits a PIRIBS architecture. Perhaps, both types of structure co-exist.Supported by grants BFU2013-48436-C2-1-P and BFU2017- 86692-P from the Spanish Ministries of Economy and Competitiveness and Science, Innovation and Universities, respectively, to JRR and grant 201600029 from the Alberta Prion Research Institute to HW. This work was also supported in part by the Intramural Research Program of the NIAID (BC) and by the National Institute of Health grants R01 NS045585 (IVB), P01 AI106705 (WKS), R01 NS083687 (WKS) and R01 NS103848 (WKS)S

Comparing [CII], HI, and CO dynamics of nearby galaxies

The HI and CO components of the interstellar medium (ISM) are usually used to derive the dynamical mass M_dyn of nearby galaxies. Both components become too faint to be used as a tracer in observations of high-redshift galaxies. In those cases, the 158 $\mu$m line of atomic carbon [CII] may be the only way to derive M_dyn. As the distribution and kinematics of the ISM tracer affects the determination of M_dyn, it is important to quantify the relative distributions of HI, CO and [CII]. HI and CO are well-characterised observationally, however, for [CII] only very few measurements exist. Here we compare observations of CO, HI, and [CII] emission of a sample of nearby galaxies, drawn from the HERACLES, THINGS and KINGFISH surveys. We find that within R_25, the average [CII] exponential radial profile is slightly shallower than that of the CO, but much steeper than the HI distribution. This is also reflected in the integrated spectrum ("global profile"), where the [CII] spectrum looks more like that of the CO than that of the HI. For one galaxy, a spectrally resolved comparison of integrated spectra was possible; other comparisons were limited by the intrinsic line-widths of the galaxies and the coarse velocity resolution of the [CII] data. Using high-spectral-resolution SOFIA [CII] data of a number of star forming regions in two nearby galaxies, we find that their [CII] linewidths agree better with those of the CO than the HI. As the radial extent of a given ISM tracer is a key input in deriving M_dyn from spatially unresolved data, we conclude that the relevant length-scale to use in determining M_dyn based on [CII] data, is that of the well-characterised CO distribution. This length scale is similar to that of the optical disk.Comment: Accepted for publication in the Astronomical Journa