We explored the potential energy surfaces for adenine synthesis by oligomerizations of HCN or HNC from CBS-QB3 calculations. The pathways have been obtained for the formation of the covalently bound HCN dimer, trimer, tetramer, and pentamer (adenine) by sequential additions of HCN or HNC. The activation energies of the individual oligomerization stages are a few hundred kilojoules per mole, which prevent efficient adenine synthesis in interstellar space or in the atmosphere of Titan. On the other hand, when the oligomerizations start from HCNH+, the activation energies of sequential HCN or HNC additions are significantly reduced. Kinetic analyses results suggest that adenine synthesis by proton-catalyzed oligomerizations cannot occur efficiently in interstellar space or in the atmosphere of Titan, even though some oligomerization stages can occur under the latter condition. Key Words: Prebiotic chemistry—Astrobiology—Chemical evolution—Titan—ISM chemistry. Astrobiology 13, 465–475.
Get full access to this article
View all access options for this article.
References
1.
AdrianiA., DinelliB.M., López-PuertasM., García-ComasM., MoriconiM.L., D'AversaE., FunkeB., CoradiniA.2011. Distribution of HCN in Titan's upper atmosphere from Cassini/VIMS observations at 3 μm. Icarus, 214:584–595.
2.
BaerT., HaseW.L.1996. Unimolecular Reaction Dynamics: Theory and Experiments. Oxford University Press: New York.
3.
BeyerT., SwinehartD.R.1973. Algorithm 448: number of multiply restricted partitions. Commun ACM, 16:379.
4.
BorquezE., CleavesH.J., LazcanoA., MillerS.L.2005. An investigation of prebiotic purine synthesis from the hydrolysis of HCN polymers. Orig Life Evol Biosph, 35:79–90.
5.
DunbarR.C., KlippensteinS.J., HrušákJ., StöckigtD., SchwarzH.1996. Binding energy of Al(C6H6)+ from analysis of radiative association kinetics. J Am Chem Soc, 118:5277–5283.
6.
FerrisJ.P., HaganW.J.Jr.1984. HCN and chemical evolution: the possible role of cyano compounds in prebiotic synthesis. Tetrahedron, 40:1093–1120.
7.
FerrisJ.P., JoshiP.C., EdelsonE.H., LawlessJ.G.1978. HCN: a plausible source of purines, pyrimidines and amino acids on the primitive Earth. J Mol Evol, 11:293–311.
8.
FriedsonA.J., YungY.L.1984. The thermosphere of Titan. J Geophys Res, 89:85–90.
GerlichD., HorningS.1992. Experimental investigation of radiative association processes as related to interstellar chemistry. Chem Rev, 92:1509–1539.
11.
GlaserR., HodgenB., FarrellyD., McKeeE.2007. Adenine synthesis in interstellar space: mechanisms of prebiotic pyrimidine-ring formation of monocyclic HCN-pentamers. Astrobiology, 7:455–470.
12.
HörstS.M., YelleR.V., BuchA., CarrascoN., CernogoraG., DutuitO., QuiricoE., Sciamma-O'BrienE., SmithM.A., SomogyiÁ., SzopaC., ThissenR., VuittonV.2012. Formation of amino acids and nucleotide bases in a Titan atmosphere simulation experiment. Astrobiology, 12:809–817.
13.
HanelR., ConrathB., FlasarF.M., KundeV., MaguireW., PearlJ., PirragliaJ., SamuelsonR., HerathL., AllisonM.1981. Infrared observations of the saturnian system from Voyager 1. Science, 212:192–200.
14.
HenkelC., WilsonT.L., PankoninV.1981. H2CO and CO observations of TMC1. Astron Astrophys, 99:270–273.
15.
HerbstE.1985. An update of and suggested increase in calculated radiative association rate coefficients. Astrophys J, 291:226–229.
16.
HerbstE.2001. The chemistry of interstellar space. Chem Soc Rev, 30:168–176.
17.
HillA., OrgelL.E.2002. Synthesis of adenine from HCN tetramer and ammonium formate. Orig Life Evol Biosph, 32:99–102.
18.
HuebnerW.F., SnyderL.E., BuhlD.1974. HCN radio emission from Comet Kohoutek (1973f)Icarus, 23:580–584.
19.
IrvineW.M.1999. The composition of interstellar molecular clouds. Space Sci Rev, 90:203–218.
20.
KikuchiO., WatanabeT., SatohY., InadomiY.2000. Ab initio GB study of prebiotic synthesis of purine precursors from aqueous hydrogen cyanide: dimerization reaction of HCN in aqueous solution. Theochem, 507:53–62.
21.
KimS.J., GeballeT.R., NollK.S., CourtinR.2005. Clouds, haze, and CH4, CH3D, HCN, and C2H2 in the atmosphere of Titan probed via 3 μm spectroscopy. Icarus, 173:522–532.
LevyM., MillerS.L., BrintonK., BadaJ.L.2000. Prebiotic synthesis of adenine and amino acids under Europa-like conditions. Icarus, 145:609–613.
24.
MarcusR.A., RiceO.K.1951. The kinetics of the recombination of methyl radicals and iodine atoms. J Phys Colloid Chem, 55:894–908.
25.
MillerS.L.1953. A production of amino acids under possible primitive Earth conditions. Science, 117:528–529.
26.
MillerS.L., CleavesH.J.2007. Prebiotic chemistry on the primitive Earth. Systems Biology: Vol.1: Genomics. RigoutsosI., StephanopoulossG.Oxford University Press: New York, 3–56.
27.
MiyakawaS., CleavesH.J., MillerS.L.2002. The cold origin of life: B. Implications based on pyrimidines and purines produced from frozen ammonium cyanide solutions. Orig Life Evol Biosph, 32:209–218.
28.
MontgomeryJ.A.Jr., FrischM.J., OchterskiJ.W., PeterssonG.A.1999. A complete basis set model chemistry. VI. Use of density functional geometries and frequencies. J Chem Phys, 110:2822–2827.
29.
MorenoR., LellouchE., LaraL.M., CourtinR., Bockelée-MorvanD., HartoghP., RengelM., BiverN., BanaszkiewiczM., GonzálezA.2011. First detection of hydrogen isocyanide (HNC) in Titan's atmosphere. Astron Astrophys, 536:L12.
30.
NgassamV., OrelA.E., Suzor-WeinerA.2005. Ab initio study of the dissociative recombination of HCNH+J Phys Conf Ser, 4:224–228.
31.
OhishiM., IrvineW.M., KaifuN.1992. Molecular abundance variations among and within cold, dark molecular clouds. Astrochemistry of Cosmic PhenomenaIAU Symposium 150SinghP.D.Kluwer Academic Publishers: Dordrecht.
32.
OróJ.1960. Synthesis of adenine from ammonium cyanide. Biochem Biophys Res Commun, 2:407–412.
33.
OróJ.1961. Mechanism of synthesis of adenine from hydrogen cyanide under possible primitive Earth conditions. Nature, 191:1193–1194.
34.
OrgelL.E.2004. Prebiotic chemistry and the origin of the RNA world. Crit Rev Biochem Mol Biol, 39:99–123.
35.
PetrieS., DunbarR.C.2000. Radiative association reactions of Na+, Mg+, and Al+ with abundant interstellar molecules. Variational transition state theory calculations. J Phys Chem A, 104:4480–4488.
36.
PichierriF.2002. Theoretical study of the proton exchange reaction: HCNH++HCN↔HNC+HCNH+Chem Phys Lett, 353:383–388.
37.
PillingS., AndradeD.P.P., NetoA.C., RittnerR., Naves de BritoA.2009. DNA nucleobase synthesis at Titan atmosphere analog by soft X-rays. J Phys Chem A, 113:11161–11166.
38.
RehderD.2010. Chemisty in Space: From Interstellar Matter to the Origin of Life. Wiley-VCH, Weinheim.
39.
RosenstockH.M., WallensteinM.B., WahrhaftigA.L., EyringH.1952. Absolute rate theory for isolated systems and the mass spectra of polyatomic molecules. Proc Natl Acad Sci USA, 38:667–678.
40.
RoyD., NajafianK., von Ragué SchleyerP.2007. Chemical evolution: the mechanism of the formation of adenine under prebiotic conditions. Proc Natl Acad Sci USA, 104:17272–17277.
41.
SanchezR., FerrisJ., OrgelL.E.1966. Conditions for purine synthesis: did prebiotic synthesis occur at low temperatures?Science, 153:72–73.
42.
SanchezR.A., FerbisJ.P., OrgelL.E.1967. Studies in prebiotic synthesis: II. Synthesis of purine precursors and amino acids from aqueous hydrogen cyanide. J Mol Biol, 30:223–253.
43.
SchloerbF.P., KinzelW.M., SwadeD.A., IrvineW.M.1987. Observations of HCN in comet P/Halley. Astron Astrophys, 187:475–480.
44.
SemaniakJ., MinaevB.F., DerkatchA.M., HellbergF., NeauA., RosénS., ThomasR., LarssonM., DanaredH., PaálA., af UgglasM.2001. Dissociative recombination of HCNH+: absolute cross sections and branching ratios. Astrophys J Suppl Ser, 135:275–283.
45.
ShibaY., HiranoT., NagashimaU., IshiiK.1998. Potential energy surfaces and branching ratio of the dissociative recombination reaction HCNH++e-: an ab initio molecular orbital study. J Chem Phys, 108:698–705.
46.
SmithI.W.M., TalbiD., HerbstE.2001. The production of HCN dimer and more complex oligomers in dense interstellar clouds. Astron Astrophys, 369:611–615.
47.
TalbiD., EllingerY.1998. Potential energy surfaces for the electronic dissociative recombination of HCNH+: astrophysical implications on the HCN/HNC abundance ratio. Chem Phys Lett, 288:155–164.
48.
VoetA.B., SchwartzA.W.1983. Prebiotic adenine synthesis from HCN—evidence for a newly discovered major pathway. Bioorg Chem, 12:8–17.
YelleR.V., GriffithC.A.2003. HCN fluorescence on Titan. Icarus, 166:107–115.
51.
YimM.K., ChoeJ.C.2012. Dimerization of HCN in the gas phase: a theoretical mechanistic study. Chem Phys Lett, 538:24–28.
52.
ZiurysL.M., TurnerB.E.1986. HCNH+: a new interstellar molecular ion. Astrophys J, 302:L31–L36.
53.
ZiurysL.M., ApponiA.J., YoderJ.T.1992. Detection of the quadrupole hyperfine structure in HCNH+Astrophys J, 397:L123–L126.
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
