Radical formation of amino acid precursors in interstellar regions? Ser, Cys and Asp.
It is proposed that the glycine precursor NH(2)CH(2)CN may be synthesised in interstellar dust clouds by the radical combination reactions NH(2)˙ + ˙CH(2)CN → NH(2)CH(2)CN (ΔG = -302 kJ mol(-1)) and/or NH(2)CH(2)˙ + ˙CN → NH(2)CH(2)CN (ΔG = -414 kJ mol(-1)). All calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory. This paper extends that concept to radical/radical coupling reactions to form Ser, Cys and Asp precursor nitriles. The hydrogen abstraction process NH(2)CH(2)CN + HO˙→ NH(2)˙CHCN + H(2)O (ΔG = -130 kJ mol(-1)) is suggested to precede the radical coupling reactions NH(2)˙CHCN + R˙→ NH(2)CHRCN (R˙ = ˙CH(2)OH, ˙CH(2)SH and ˙CH(2)CN) to form nitrile precursors of the amino acids Ser, Cys and Asp. These three reactions are all favourable (ΔG = -240, -227 and -223 kJ mol(-1)). The radical species ˙CH(2)NH(2), ˙CH(2)OH, ˙CH(2)SH and ˙CH(2)CN are shown to be stable for the microsecond timeframe by a combination of theoretical calculations and the experimental mass spectrometric neutralization/reionization procedure.
Knowles
Daniel J
DJ
Department of Chemistry, The University of Adelaide, South Australia, 5005, Australia.
Wang
Tianfang
T
Bowie
John H
JH
D001224:Aspartic Acid / Q000138:chemical synthesis* / Q000737:chemistry; D003545:Cysteine / Q000138:chemical synthesis* / Q000737:chemistry; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D012694:Serine / Q000138:chemical synthesis* / Q000737:chemistry; D013816:Thermodynamics
D009570:Nitriles; D001224:Aspartic Acid; D012694:Serine; D003545:Cysteine