Hemiaminal route for the formation of interstellar glycine: a computational study.

Calculations related to two simple two-step paths (path-I: [Formula: see text] path-II: [Formula: see text]) for the formation of glycine have been discussed. Calculations show that at interstellar conditions these two paths are feasible only in hot cores, not in the cold interstellar clouds (cold core formation is possible only if CH2 = NH, H2O (excess) and CO of path-II, react in a concerted manner). For the laboratory synthesis of glycine, the possibility suggested is via path-I and the reaction being carried out as controlled temperature one-pot synthesis. This study can also be extended to other α-amino acids and possibly enantiomeric excess can be expected. We think this work will not only be able to enrich our future understanding about the formation of amino acids in interstellar medium but also be able to suggest alternative paths for laboratory synthesis of amino acids using either Strecker's or Miller's ingredients. Graphical abstract Using computational calculations, two different reaction paths which go through a hemiaminal (α-hydroxyamine) intermediate have been proposed. It has been proposed that the reaction [Formula: see text] is a thermodynamically favorable reaction path in the laboratory conditions, if carried out as a controlled temperature one-pot synthesis. On the hand, it has been argued that the reaction[Formula: see text] is a feasible reaction path in the interstellar conditions, if it proceeds not via the hemiaminal route, rather in a concerted reaction path.

Possible interstellar formation of glycine through a concerted mechanism: a computational study on the reaction of CH2[double bond, length as m-dash]NH, CO2 and H2.

Glycine being the simplest amino acid and also having significant astrobiological implications, has meant that intensive investigations have been carried out in the past, starting from its detection in the interstellar medium (ISM) to analysis of meteorites and cometary samples and laboratory synthesis, as well as computational studies on the possible reaction paths. In this present work quantum chemical calculations have been performed to investigate the possible interstellar formation of glycine via two different paths; (1) in a two-step process via a dihydroxy carbene intermediate and (2) through a one-step concerted mechanism, starting from reactants like CH2[double bond, length as m-dash]NH, CO, CO2, H2O and H2. For the two reactions representing the carbene route, it was observed that the formation of dihydroxy carbene from either CO + H2O or CO2 + H2 is highly endothermic with large barrier heights, whereas the subsequent step of interaction of this carbene with CH2[double bond, length as m-dash]NH to give glycine is exothermic and the barrier is below the reactants. Based on this observation it is suggested that the formation of glycine via the carbene route is a least favourable or even unfavourable path. On the other hand, the two reactions CH2[double bond, length as m-dash]NH + CO + H2O and CH2[double bond, length as m-dash]NH + CO2 + H2 representing the concerted paths were found to be favourable in leading to the formation of glycine. After an extensive study on the first concerted reaction in our previous work (Phys. Chem. Chem. Phys., 2016, 18, 375-381), in this work a detailed investigation has been carried out for the second concerted reaction, CH2[double bond, length as m-dash]NH + CO2 + H2, which can possibly lead to the interstellar formation of glycine. It was observed that this reaction proceeds through a large barrier and at the same time the transition state shows prominent hydrogen dynamics, indicating a tunnelling possibility for this reaction. Based on these observations the possible formation of glycine via this reaction in hot-cores and in cold interstellar clouds has been proposed. The cold-core possibility of this reaction is argued on the basis of the phenomenon of tunnelling assisted by a van der Waals' complex.

Expanding the applicability of electrostatic potentials to the realm of transition states.

Central to any reaction mechanism study, and sometimes a challenging job, is tracing a transition state in a reaction path. For the first time, electrostatic potentials (ESP) of the reactants were used as guiding tactics to predict whether there is a possibility of any transition state in a reaction surface. The main motive behind this strategy is to see whether the directionality nature of the transition state has something to do with the anisotropic natures of the ESP with their embedded directionalities. Strategically, some atmospherically important, but simple, reactions have been chosen for this study, which heretofore were believed to be barrierless. By carefully analysing the ESP maps of the reactants, regions of possible interactions were located. Using the bilinear interpolation of the 2D grids of the ESP surfaces, search co-ordinates were fine-tuned for a local gradient based approach for the search of a transition state. Out of the three reactions studied in this work, we were able to successfully locate transition states, for the first time, in two cases and the third one still proved to be barrierless. This gives a clear indication that though ESP maps can qualitatively predict the possibility of a transition state; it is not always true that there should definitely be a transition state, as some of the reaction surfaces may genuinely be barrierless. But, nevertheless this strategy definitely has credential to be tested for many more reactions, either new or already established, and may be applied to create the initial search co-ordinates for any well-established transition state search method. Moreover, we have observed that the analysis of the ESP maps of the reactants were very much useful in explaining the nature of interactions existing in those observed transition states and we hope the same can also be extended to any transition state in an electrostatically driven reaction potential energy surface.

Possible interstellar formation of glycine from the reaction of CH2=NH, CO and H2O: catalysis by extra water molecules through the hydrogen relay transport.

"How the fundamental life elements are created in the interstellar medium (ISM)?" is one of the intriguing questions related to the genesis of life. Using computational calculations, we have discussed the reaction of CH2=NH, CO and H2O for the formation of glycine, the simplest life element. This reaction proceeds through a concerted mechanism with reasonably large barriers for the cases with one and two water molecules as reactants. For the two water case we found that the extra water molecule exhibits some catalytic role through the hydrogen transport relay effect and the barrier height is reduced substantially compared to the case with one water molecule. These two cases can be treated as ideal cases for the hot-core formation of the interstellar glycine. With an increasing number of water molecules as the reactants, we found that when the numbers of water molecules are three or more than three, the barrier height reduced so drastically that the transition states were more stable than the reactants. Such a situation gives a clear indication that with excess water molecules as the reactants, this reaction will be feasible even under the low temperature conditions existing in the cold interstellar clouds and the exothermic nature of the reaction will be the driving force.

Reaction between HN and SN: a possible channel for the interstellar formation of N2 and SH in the cold interstellar clouds.

Using computational calculations the potential energy surface (PES) of the reaction between NH and NS has been analysed. The PES of the reaction shows the formation of two very stable species, HNSN and HNNS. Out of these two, HNNS which has the signature N-N linkage was found to be the most stable species in the PES. In view of the highly exothermic nature of the reaction surface, it has been proposed that these two species can possibly be detected in the interstellar space. For the first time it has also been shown that the reaction between the NH and NS can lead to the possible formation of N2via the isomer HNNS, and how the effect of tunnelling can make this reaction very much feasible, even under the extremely low temperature conditions prevailing in the interstellar medium. Based on the already reported results, a similar kind of behaviour for the NH + NO reaction surface has also been proposed. These dissociation reactions leading to the formation of N2 can be considered as potential secondary contributing channels while accounting for the total estimates of N2 in the interstellar medium, and thus HNNS as well as HNNO can be considered as stable reservoir molecules for interstellar N2. Besides the formation of N2, the formation of another astronomically important radical, SH in the cold interstellar clouds, has also been proposed.