Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites
Abstract
The molecular origins of homochirality on Earth is not understood well, particularly how enantiomerically enriched molecules of astrobiological significance like sugars and amino acids might have been synthesized on icy grains in space preceding their delivery to Earth. Polycyclic aromatic hydrocarbons (PAHs) identified in carbonaceous chondrites could have been processed in molecular clouds by circularly polarized light prior to the depletion of enantiomerically enriched helicenes onto carbonaceous grains resulting in chiral islands. However, the fundamental low temperature reaction mechanisms leading to racemic helicenes are still unknown. Here, by exploiting synchrotron based molecular beam photoionization mass spectrometry combined with electronic structure calculations, we provide compelling testimony on barrierless, low temperature pathways leading to racemates of [5] and [6]helicene. Astrochemical modeling advocates that gas-phase reactions in molecular clouds lead to racemates of helicenes suggesting a pathway for future astronomical observation and providing a fundamental understanding for the origin of homochirality on early Earth.
- Authors:
-
[1];
[2];
[2];
[4];
[6]
- University of Hawaii at Manoa, Honolulu, HI (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Lebedev Physical Institute, Samara (Russia)
- Florida International University (FIU), Miami, FL (United States)
- University of California, Berkeley, CA (United States). Applied Science and Technology; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)
- Chinese Academy of Sciences (CAS), Urumqi (China)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Russian Federation; National Energy Research Scientific Computing Center (NERSC); USDOE
- OSTI Identifier:
- 2325993
- Alternate Identifier(s):
- OSTI ID: 1885468
- Grant/Contract Number:
- AC02-05CH11231; FG02-03ER15411; FG02-04ER15570; 075-15-2021-597
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 24; Journal Issue: 41; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Kaiser, Ralf I., Zhao, Long, Lu, Wenchao, Ahmed, Musahid, Evseev, Mikhail M., Azyazov, Valeriy N., Mebel, Alexander M., Mohamed, Rana K., Fischer, Felix R., and Li, Xiaohu. Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites. United States: N. p., 2022.
Web. doi:10.1039/d2cp03084e.
Kaiser, Ralf I., Zhao, Long, Lu, Wenchao, Ahmed, Musahid, Evseev, Mikhail M., Azyazov, Valeriy N., Mebel, Alexander M., Mohamed, Rana K., Fischer, Felix R., & Li, Xiaohu. Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites. United States. https://doi.org/10.1039/d2cp03084e
Kaiser, Ralf I., Zhao, Long, Lu, Wenchao, Ahmed, Musahid, Evseev, Mikhail M., Azyazov, Valeriy N., Mebel, Alexander M., Mohamed, Rana K., Fischer, Felix R., and Li, Xiaohu. Sat .
"Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites". United States. https://doi.org/10.1039/d2cp03084e. https://www.osti.gov/servlets/purl/2325993.
@article{osti_2325993,
title = {Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites},
author = {Kaiser, Ralf I. and Zhao, Long and Lu, Wenchao and Ahmed, Musahid and Evseev, Mikhail M. and Azyazov, Valeriy N. and Mebel, Alexander M. and Mohamed, Rana K. and Fischer, Felix R. and Li, Xiaohu},
abstractNote = {The molecular origins of homochirality on Earth is not understood well, particularly how enantiomerically enriched molecules of astrobiological significance like sugars and amino acids might have been synthesized on icy grains in space preceding their delivery to Earth. Polycyclic aromatic hydrocarbons (PAHs) identified in carbonaceous chondrites could have been processed in molecular clouds by circularly polarized light prior to the depletion of enantiomerically enriched helicenes onto carbonaceous grains resulting in chiral islands. However, the fundamental low temperature reaction mechanisms leading to racemic helicenes are still unknown. Here, by exploiting synchrotron based molecular beam photoionization mass spectrometry combined with electronic structure calculations, we provide compelling testimony on barrierless, low temperature pathways leading to racemates of [5] and [6]helicene. Astrochemical modeling advocates that gas-phase reactions in molecular clouds lead to racemates of helicenes suggesting a pathway for future astronomical observation and providing a fundamental understanding for the origin of homochirality on early Earth.},
doi = {10.1039/d2cp03084e},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 41,
volume = 24,
place = {United States},
year = {Sat Sep 03 00:00:00 EDT 2022},
month = {Sat Sep 03 00:00:00 EDT 2022}
}
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Works referenced in this record:
Pyrene synthesis in circumstellar envelopes and its role in the formation of 2D nanostructures
journal, March 2018
- Zhao, Long; Kaiser, Ralf I.; Xu, Bo
- Nature Astronomy, Vol. 2, Issue 5
A Combined Experimental and Theoretical Study on the Formation of the Amino Acid Glycine (NH 2 CH 2 COOH) and Its Isomer (CH 3 NHCOOH) in Extraterrestrial Ices
journal, June 2005
- Holtom, Philip D.; Bennett, Chris J.; Osamura, Yoshihiro
- The Astrophysical Journal, Vol. 626, Issue 2
d -Amino acids in molecular evolution in space – Absolute asymmetric photolysis and synthesis of amino acids by circularly polarized light
journal, July 2018
- Sugahara, Haruna; Meinert, Cornelia; Nahon, Laurent
- Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics, Vol. 1866, Issue 7
The molecular universe
journal, July 2013
- Tielens, A. G. G. M.
- Reviews of Modern Physics, Vol. 85, Issue 3
Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere
journal, October 2018
- Zhao, Long; Kaiser, Ralf I.; Xu, Bo
- Nature Astronomy, Vol. 2, Issue 12
Beta decay and the origin of biological chirality: New experimental results
journal, January 1984
- House, J.; Rich, A.; Zitzewitz, P. W.
- Origins of Life, Vol. 14, Issue 1-4
Asymmetric photolysis of (RS)-leucine with circularly polarized ultraviolet light
journal, March 1977
- Flores, Jose J.; Bonner, William A.; Massey, Gail A.
- Journal of the American Chemical Society, Vol. 99, Issue 11
Synthesis of a Helical Analogue of Kekulene: A Flexible π-Expanded Helicene with Large Helical Diameter Acting as a Soft Molecular Spring
journal, October 2018
- Nakakuki, Yusuke; Hirose, Takashi; Matsuda, Kenji
- Journal of the American Chemical Society, Vol. 140, Issue 45
A Combined Experimental and Theoretical Study on the Formation of Interstellar Propylene Oxide (CH 3 CHCH 2 O)—A Chiral Molecule
journal, June 2018
- Bergantini, Alexandre; Abplanalp, Matthew J.; Pokhilko, Pavel
- The Astrophysical Journal, Vol. 860, Issue 2
Enantiomeric Excesses Induced in Amino Acids by Ultraviolet Circularly Polarized Light Irradiation of Extraterrestrial ice Analogs: a Possible Source of Asymmetry for Prebiotic Chemistry
journal, May 2014
- Modica, Paola; Meinert, Cornelia; de Marcellus, Pierre
- The Astrophysical Journal, Vol. 788, Issue 1
Stern–Gerlach-Type Separations of Structural and Chiral Isomers by Interstellar Magnets
journal, November 2020
- Stevenson, Cheryl D.; Davis, John P.
- ACS Earth and Space Chemistry, Vol. 4, Issue 12
Magnetars and Magnetic Separation of Chiral Radicals in Interstellar Space: Homochirality
journal, October 2019
- Stevenson, Cheryl D.; Davis, John P.
- The Journal of Physical Chemistry A, Vol. 123, Issue 44
Low temperature formation of naphthalene and its role in the synthesis of PAHs (Polycyclic Aromatic Hydrocarbons) in the interstellar medium
journal, December 2011
- Parker, D. S. N.; Zhang, F.; Kim, Y. S.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 1
Detection of the aromatic molecule benzonitrile ( c -C 6 H 5 CN) in the interstellar medium
journal, January 2018
- McGuire, Brett A.; Burkhardt, Andrew M.; Kalenskii, Sergei
- Science, Vol. 359, Issue 6372
On the Abundance Gradients of Organic Molecules along the TMC‐1 Ridge
journal, May 2000
- Markwick, A. J.; Millar, T. J.; Charnley, S. B.
- The Astrophysical Journal, Vol. 535, Issue 1
Homochirality Originates from the Handedness of Helices
journal, September 2020
- Liu, Shubin
- The Journal of Physical Chemistry Letters, Vol. 11, Issue 20
Ribose and related sugars from ultraviolet irradiation of interstellar ice analogs
journal, April 2016
- Meinert, C.; Myrgorodska, I.; de Marcellus, P.
- Science, Vol. 352, Issue 6282
The UMIST database for astrochemistry 2012
journal, January 2013
- McElroy, D.; Walsh, C.; Markwick, A. J.
- Astronomy & Astrophysics, Vol. 550
Strain-induced helical chirality in polyaromatic systems
journal, January 2016
- Rickhaus, Michel; Mayor, Marcel; Juríček, Michal
- Chemical Society Reviews, Vol. 45, Issue 6
Low-temperature Formation of Carbonaceous Dust Grains from PAHs
journal, January 2020
- Gavilan Marin, Lisseth; Bejaoui, Salma; Haggmark, Michael
- The Astrophysical Journal, Vol. 889, Issue 2
Assessing the origins of aliphatic amines in the Murchison meteorite from their compound-specific carbon isotopic ratios and enantiomeric composition
journal, September 2014
- Aponte, José C.; Dworkin, Jason P.; Elsila, Jamie E.
- Geochimica et Cosmochimica Acta, Vol. 141
A Spectroscopic View on Cosmic PAH Emission
journal, March 2021
- Peeters, Els; Mackie, Cameron; Candian, Alessandra
- Accounts of Chemical Research, Vol. 54, Issue 8
From Interstellar Amino Acids to Prebiotic Catalytic Peptides: A Review
journal, April 2007
- Brack, André
- Chemistry & Biodiversity, Vol. 4, Issue 4
Asymmetric Autocatalysis of Pyrimidyl Alkanol and Its Application to the Study on the Origin of Homochirality
journal, November 2014
- Soai, Kenso; Kawasaki, Tsuneomi; Matsumoto, Arimasa
- Accounts of Chemical Research, Vol. 47, Issue 12
Low-temperature synthesis of polycyclic aromatic hydrocarbons in Titan’s surface ices and on airless bodies
journal, October 2019
- Abplanalp, Matthew J.; Frigge, Robert; Kaiser, Ralf I.
- Science Advances, Vol. 5, Issue 10
Chiral Molecular Carbon Nanostructures
journal, May 2019
- Fernández-García, Jesús M.; Evans, Paul J.; Filippone, Salvatore
- Accounts of Chemical Research, Vol. 52, Issue 6
Enantiomer excesses of rare and common sugar derivatives in carbonaceous meteorites
journal, May 2016
- Cooper, George; Rios, Andro C.
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 24
Non-racemic amino acids in the Murray and Murchison meteorites
journal, January 2000
- Pizzarello, S.; Cronin, J. R.
- Geochimica et Cosmochimica Acta, Vol. 64, Issue 2
The Helicenes: Potential Carriers of Diffuse Interstellar Bands
journal, January 2021
- Oña-Ruales, Jorge O.; Ruiz-Morales, Yosadara; Alvarez-Ramírez, Fernando
- ACS Earth and Space Chemistry, Vol. 5, Issue 2
Formation of benzene in the interstellar medium
journal, December 2010
- Jones, B. M.; Zhang, F.; Kaiser, R. I.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 2
Photodissociation of benzene under collision-free conditions: An ab initio /Rice–Ramsperger–Kassel–Marcus study
journal, April 2004
- Kislov, V. V.; Nguyen, T. L.; Mebel, A. M.
- The Journal of Chemical Physics, Vol. 120, Issue 15
Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry
journal, January 2013
- Qi, Fei
- Proceedings of the Combustion Institute, Vol. 34, Issue 1
Extended High Circular Polarization in the Orion Massive Star Forming Region: Implications for the Origin of Homochirality in the Solar System
journal, March 2010
- Fukue, Tsubasa; Tamura, Motohide; Kandori, Ryo
- Origins of Life and Evolution of Biospheres, Vol. 40, Issue 3
Gas phase synthesis of [4]-helicene
journal, April 2019
- Zhao, Long; Kaiser, Ralf I.; Xu, Bo
- Nature Communications, Vol. 10, Issue 1
TD-1HNMR Measurements Show Enantioselective Dissociation of Ribose and Glucose in the Presence of H217O
journal, October 2007
- Scorei, Romulus Ion; Cimpoiaşu, Vily Marius; Popa, Radu
- Astrobiology, Vol. 7, Issue 5
Racemic amino acids from the ultraviolet photolysis of interstellar ice analogues
journal, March 2002
- Bernstein, Max P.; Dworkin, Jason P.; Sandford, Scott A.
- Nature, Vol. 416, Issue 6879
Deuterium Fractionation During Amino acid Formation by Photolysis of Interstellar ice Analogs Containing Deuterated Methanol
journal, August 2016
- Oba, Yasuhiro; Takano, Yoshinori; Watanabe, Naoki
- The Astrophysical Journal, Vol. 827, Issue 1
Chirally Sensitive Electron-Induced Molecular Breakup and the Vester-Ulbricht Hypothesis
journal, September 2014
- Dreiling, J. M.; Gay, T. J.
- Physical Review Letters, Vol. 113, Issue 11
Chirality Amplified: Long, Discrete Helicene Nanoribbons
journal, December 2020
- Xiao, Xiao; Pedersen, Stephan K.; Aranda, Daniel
- Journal of the American Chemical Society, Vol. 143, Issue 2
UV photolysis, organic molecules in young disks, and the origin of meteoritic amino acids
journal, April 2011
- Throop, Henry B.
- Icarus, Vol. 212, Issue 2
Chiroptical Properties of Symmetric Double, Triple, and Multiple Helicenes
journal, January 2021
- Mori, Tadashi
- Chemical Reviews, Vol. 121, Issue 4
Crossed beam reaction of cyano radicals with hydrocarbon molecules. I. Chemical dynamics of cyanobenzene (C6H5CN; X 1A1) and perdeutero cyanobenzene (C6D5CN; X 1A1) formation from reaction of CN(X 2Σ+) with benzene C6H6(X 1A1g), and d6-benzene C6D6(X 1A1g)
journal, October 1999
- Balucani, N.; Asvany, O.; Chang, A. H. H.
- The Journal of Chemical Physics, Vol. 111, Issue 16
Gaussian-3 theory using coupled cluster energies
journal, November 1999
- Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C.
- Chemical Physics Letters, Vol. 314, Issue 1-2
Carbonaceous Chondrite Meteorites: the Chronicle of a Potential Evolutionary Path between Stars and Life
journal, January 2017
- Pizzarello, Sandra; Shock, Everett
- Origins of Life and Evolution of Biospheres, Vol. 47, Issue 3
Enrichment of the amino acid L-isovaline by aqueous alteration on CI and CM meteorite parent bodies
journal, March 2009
- Glavin, D. P.; Dworkin, J. P.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 14
The Formation of Nitriles in Hydrocarbon-Rich Atmospheres of Planets and Their Satellites: Laboratory Investigations by the Crossed Molecular Beam Technique
journal, September 2001
- Kaiser, Ralf I.; Balucani, Nadia
- Accounts of Chemical Research, Vol. 34, Issue 9
The Search for Chiral Asymmetry as a Potential Biosignature in our Solar System
journal, November 2019
- Glavin, Daniel P.; Burton, Aaron S.; Elsila, Jamie E.
- Chemical Reviews, Vol. 120, Issue 11
Isotopic evidence for extraterrestrial non- racemic amino acids in the Murchison meteorite
journal, September 1997
- Engel, M. H.; Macko, S. A.
- Nature, Vol. 389, Issue 6648
Detection of two interstellar polycyclic aromatic hydrocarbons via spectral matched filtering
journal, March 2021
- McGuire, Brett A.; Loomis, Ryan A.; Burkhardt, Andrew M.
- Science, Vol. 371, Issue 6535
A Detailed Study of the Amino Acids Produced from the Vacuum UV Irradiation of Interstellar Ice Analogs
journal, January 2008
- Nuevo, Michel; Auger, Geneviève; Blanot, Didier
- Origins of Life and Evolution of Biospheres, Vol. 38, Issue 1
On the Formation of Dipeptides in Interstellar Model ices
journal, February 2013
- Kaiser, R. I.; Stockton, A. M.; Kim, Y. S.
- The Astrophysical Journal, Vol. 765, Issue 2
Gaussian-3 (G3) theory for molecules containing first and second-row atoms
journal, November 1998
- Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C.
- The Journal of Chemical Physics, Vol. 109, Issue 18
Gaussian-3 theory using density functional geometries and zero-point energies
journal, April 1999
- Baboul, Anwar G.; Curtiss, Larry A.; Redfern, Paul C.
- The Journal of Chemical Physics, Vol. 110, Issue 16
A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase
journal, January 2020
- Zhao, Long; Kaiser, Ralf I.; Xu, Bo
- Angewandte Chemie International Edition, Vol. 59, Issue 10
Extraterrestrial prebiotic molecules: photochemistry vs. radiation chemistry of interstellar ices
journal, January 2019
- Arumainayagam, Chris R.; Garrod, Robin T.; Boyer, Michael C.
- Chemical Society Reviews, Vol. 48, Issue 8