Radical-assisted pathways for the prebiotic formation of nucleobases
from plausible precursors
Abstract
The perplexity of how the building blocks of life formed from simple and
abundantly-available precursors on early earth has baffled scientific
community for centuries. In order to get a clearer picture, the present
study proposes and investigates plausible ammonia-assisted, free radical
pathways for nucleobase formation from starting precursors such as
cyanoacetaldehyde, urea, cyanoacetylene and cyanamide. Particularly,
density functional theory is used to obtain optimized geometries and
zero-point vibrational energy corrected electronic energies of
reactants, transition states, intermediates and products along the
reaction pathways in the gas phase at B3LYP/6–311G(d,p) level, as well
as in the water (dielectric constant of 78.3) and ammonia (dielectric
constant of 22.4) using the IEFPCM framework. Our proposed mechanisms
are characterized by a smaller number of precursors and relatively lower
barriers compared to previously reported reactions with other prebiotic
precursors [1-3]. Features such as barrier-less formation of
imidazole intermediate and favorable contribution of prebiotic enolate
chemistry highlight the plausibility of the presently proposed pathways.
The pathways are most suitable to environments like prebiotic earth (for
purine formation) and present-day Titan (for purine and pyrimidine
formation) where radical reactions are rendered feasible by continuous
influx of UV and cosmic radiations. Overall, our analysis proposes
kinetically accessible routes to nucleobases formation, and will
hopefully contribute towards understanding the relevance of these
precursors in prebiotic reactions. References: Jeilani, Y. A. Williams,
P. N. Walton, S., Nguyen, M. T. (2016) Phys. Chem. Chem. Phys.,18,
20177-20188. Jeilani, Y. A. Fearce, C. and Nguyen, M. T. (2015) Phys.
Chem. Chem. Phys.,17, 24294-24303. Nguyen, H. T. Jeilani, Y. A., Hung,
H. M. and Nguyen, M. T. (2015) J. Phys. Chem. A, 119, 8871-8883.