DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Low-temperature formation of pyridine and (iso)quinoline via neutral–neutral reactions

Journal Article · · Nature Astronomy
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5];  [6]; ORCiD logo [7]; ORCiD logo [2]
  1. University of Hawaii at Manoa, Honolulu, HI (United States); University of Hawaii
  2. University of Hawaii at Manoa, Honolulu, HI (United States)
  3. Florida International University, Miami, FL (United States)
  4. Centro Federal de Educação Tecnológica de Minas Gerais, CEFET-MG, Belo Horizonte (Brazil)
  5. Université de Bordeaux, Talence (France)
  6. Université de Bordeaux, Pessac (France)
  7. Chinese Academy of Sciences, Urumqi (China)

Aromatic molecules represent fundamental building blocks in prebiotic chemistry and are contemplated as vital precursors to DNA and RNA nitrogen bases. However, despite the identification of some 300 molecules in extraterrestrial environments, the pathways to pyridine (C5H5N), pyridinyl (C5H4N•), and (iso)quinoline (C9H7N) – the simplest represen-tative of mono and bicyclic aromatic molecule carrying nitrogen – are elusive. Here, we afford compelling evidence on the gas-phase formation of methylene amidogen (H2CN•) and cyanomethyl (H2CCN•) radicals via molecular beam studies and electronic structure calcula-tions. The modeling of the chemistries of Taurus Molecular Cloud (TMC-1) and Titan’s atmosphere contemplates a complex chain of reactions synthesizing pyridine, pyridinyl, and (iso)quinoline from H2CN• and H2CCN• at levels of up to 75%. Furthermore, this study affords unique entry points to precursors of DNA and RNA nitrogen bases in hydrocarbon-rich extraterrestrial environments thus changing the way we think about the origin of prebiotic molecules in our Galaxy.

Research Organization:
University of Hawaii at Manoa, Honolulu, HI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Grant/Contract Number:
FG02-03ER15411
OSTI ID:
2447449
Journal Information:
Nature Astronomy, Journal Name: Nature Astronomy Journal Issue: 7 Vol. 8; ISSN 2397-3366
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

References (65)

Titan's atmosphere and climate: TITAN'S ATMOSPHERE journal March 2017
A Computational Study of the Mechanisms for the Incorporation of a Nitrogen Atom into Polycyclic Aromatic Hydrocarbons in the Titan Haze journal December 2001
A Revised Sensitivity Model for Cassini INMS: Results at Titan journal January 2015
Basic nitrogen-heterocyclic compounds in the Murchison meteorite journal March 1982
Exploring old and new benzene formation pathways in low-pressure premixed flames of aliphatic fuels journal January 2000
Direct dynamics study of the N(4S)+CH3(2A2″) reaction journal June 2015
Extraterrestrial nucleobases in the Murchison meteorite journal June 2008
The carbon isotopic distribution of Murchison amino acids journal December 2004
Investigation of pyridine carboxylic acids in CM2 carbonaceous chondrites: Potential precursor molecules for ancient coenzymes journal July 2014
Ion chemistry and N-containing molecules in Titan's upper atmosphere journal November 2007
Analysis of Titan's neutral upper atmosphere from Cassini Ion Neutral Mass Spectrometer measurements journal April 2009
Titan’s aerosol and stratospheric ice opacities between 18 and 500μm: Vertical and spectral characteristics from Cassini CIRS journal April 2011
Titan aerosol analog absorption features produced from aromatics in the far infrared journal July 2014
The neutral photochemistry of nitriles, amines and imines in the atmosphere of Titan journal February 2015
1D-coupled photochemical model of neutrals, cations and anions in the atmosphere of Titan journal April 2016
Simulating the density of organic species in the atmosphere of Titan with a coupled ion-neutral photochemical model journal May 2019
The photochemical production of aromatics in the atmosphere of Titan journal September 2019
Hydrogen-assisted isomerizations of fulvene to benzene and of larger cyclic aromatic hydrocarbons journal January 2013
Organic chemistry in Titan׳s upper atmosphere and its astrobiological consequences: I. Views towards Cassini plasma spectrometer (CAPS) and ion neutral mass spectrometer (INMS) experiments in space journal May 2015
An Aromatic Universe–A Physical Chemistry Perspective journal April 2021
A Consistent Reduced Network for HCN Chemistry in Early Earth and Titan Atmospheres: Quantum Calculations of Reaction Rate Coefficients journal February 2019
Prediction of Reaction Barriers and Thermochemical Properties with Explicitly Correlated Coupled-Cluster Methods: A Basis Set Assessment journal August 2012
Temperature dependence of the reaction of nitrogen atoms with methyl radicals journal July 1989
Gas-Phase Formation of 1,3,5,7-Cyclooctatetraene (C8H8) through Ring Expansion via the Aromatic 1,3,5-Cyclooctatrien-7-yl Radical (C8H9) Transient journal December 2022
A Combined Crossed Beam and Ab Initio Investigation of the Gas Phase Reaction of Dicarbon Molecules (C 2 ; X 1 Σ g + /a 3 Π u ) with Propene (C 3 H 6 ; X 1 A′): Identification of the Resonantly Stabilized Free Radicals 1- and 3-Vinylpropargyl journal May 2013
A Gaussian-2 Study of Isomeric C 2 H 2 N and C 2 H 2 N + journal April 1999
Penitentes as the origin of the bladed terrain of Tartarus Dorsa on Pluto journal January 2017
On the formation of nitrogen-substituted polycyclic aromatic hydrocarbons (NPAHs) in circumstellar and interstellar environments journal January 2017
Pressure-dependent rate constants for PAH growth: formation of indene and its conversion to naphthalene journal January 2016
Gas-phase synthesis of corannulene – a molecular building block of fullerenes journal January 2021
Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites journal January 2022
Organic compounds in carbonaceous meteorites journal March 2002
Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction journal January 2010
Understanding prebiotic chemistry through the analysis of extraterrestrial amino acids and nucleobases in meteorites journal January 2012
The UMIST database for astrochemistry 2012 journal January 2013
Hydrogenation and dehydrogenation of interstellar PAHs: Spectral characteristics and H 2 formation journal October 2016
Discovery of CH2CHCCH and detection of HCCN, HC4N, CH3CH2CN, and, tentatively, CH3CH2CCH in TMC-1 journal March 2021
A photochemical model of Triton’s atmosphere paired with an uncertainty propagation study journal November 2022
Photodissociation of benzene under collision-free conditions: An ab initio /Rice–Ramsperger–Kassel–Marcus study journal April 2004
Photodissociation dynamics of pyridine journal August 2005
A simple and efficient CCSD(T)-F12 approximation journal December 2007
Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B–Ne, and Al–Ar journal February 2008
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Branching ratios in the N+CH 3 reaction: Formation of the methylene amidogen (H 2 CN) radical journal September 1989
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Coupled cluster theory for high spin, open shell reference wave functions journal October 1993
Laboratory and astronomical identification of cyclopropenylidene, C3H2 journal December 1985
Detection of a new interstellar molecule, H2CN journal May 1994
The Astrobiology of Nucleobases journal July 2003
Variations in the Peak Position of the 6.2 μm Interstellar Emission Feature: A Tracer of N in the Interstellar Polycyclic Aromatic Hydrocarbon Population journal October 2005
Infrared Spectra of Isolated Protonated Polycyclic Aromatic Hydrocarbon Molecules journal October 2009
Large Abundances of Polycyclic Aromatic Hydrocarbons in Titan'S Upper Atmosphere journal June 2013
THE C( 3 P) + NH 3 REACTION IN INTERSTELLAR CHEMISTRY. I. INVESTIGATION OF THE PRODUCT FORMATION CHANNELS journal October 2015
THE C( 3 P) + NH 3 REACTION IN INTERSTELLAR CHEMISTRY. II. LOW TEMPERATURE RATE CONSTANTS AND MODELING OF NH, NH 2 , AND NH 3 ABUNDANCES IN DENSE INTERSTELLAR CLOUDS journal October 2015
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Gas-phase synthesis of benzene via the propargyl radical self-reaction journal May 2021
Gas-phase formation of the resonantly stabilized 1-indenyl (C 9 H 7 ) radical in the interstellar medium journal September 2023
Ultraviolet Spectrometer Observations of Neptune and Triton journal December 1989
Detection of two interstellar polycyclic aromatic hydrocarbons via spectral matched filtering journal March 2021
Complex Organic Interstellar Molecules journal September 2009
New Horizons Observations of the Atmosphere of Pluto journal May 2019
Interstellar Polycyclic Aromatic Hydrocarbon Molecules journal September 2008
The Infrared Spectrum of Protonated Ovalene in Solid Para-Hydrogen and its Possible Contribution to Interstellar Unidentified Infrared Emission journal July 2016
A new Astrobiological Model of the Atmosphere of Titan journal September 2016
Detection Opportunity for Aromatic Signature in Titan’s Aerosols in the 4.1–5.3 μm Range journal July 2018