Homochiral Selectivity in RNA Synthesis: Montmorillonite-catalyzed Quaternary Reactions of D, L-Purine with D, L- Pyrimidine Nucleotides
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Selective adsorption of D, L-ImpA with D, L-ImpU on the platelets of montmorillonite demonstrates an important reaction pathway for the origin of homochirality in RNA synthesis. Our earlier studies have shown that the individual reactions of D, L-ImpA or D, L-ImpU on montmorillonite catalyst produced oligomers which were only partially inhibited by the incorporation of both D- and L-enantiomers. Homochirality in these reactions was largely due to the formation of cyclic dimers that cannot elongate. We investigated the quaternary reactions of D, L-ImpA with D, L-ImpU on montmorillonite. The chain length of these oligomers increased from 9-mer to 11-mer as observed by HPLC, with a concomitant increase in the yield of linear dimers and higher oligomers in the reactions involving D, L-ImpA with D, L-ImpU as compared to the similar reactions carried out with D-enantiomers only. The formation of cyclic dimers of U was completely inhibited in the quaternary reactions. The yield of cyclic dimers of A was reduced from 60% to 10% within the dimer fraction. 12 linear dimers and 3 cyclic dimers were isolated and characterized from the quaternary reaction. The homochirality and regioselectivity of dimers were 64.1% and 71.7%, respectively. Their sequence selectivity was shown by the formation of purine-pyrimidine (54-59%) linkages, followed by purine-purine (29-32%) linkages and pyrimidine-pyrimidine (9-13%) linkages. Of the 16 trimers detected, 10 were homochiral with an overall homochirality of 73-76%. In view of the greater homochirality, sequence- and regio- selectivity, the quaternary reactions on montmorillonite demonstrate an unexpectedly favorable route for the prebiotic synthesis of homochiral RNA compared with the separate reactions of enantiomeric activated mononucleotides.
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The co-oligomerization reaction of activated adenosine and uridine exhibited greater efficiency (up to 74% homochiral selectivity for the trimers) compared with separate reactions.
“The co-oligomerization reaction of activated adenosine and uridine exhibited greater efficiency (up to 74% homochiral selectivity for the trimers) compared with the separate reactions of enantiomeric activated monomers.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [538]
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- Authors
- Joshi, P. C., Aldersley, M. F., & Ferris, J. P.
- Affiliations
- Rensselaer Polytechnic Institute (US)
- Corresponding author
- Ferris, James P.
- ORCID
- Joshi, Prakash C.
- Venue
- Origins of Life and Evolution of Biospheres
- Published
- 2010-08-20
- Volume
- 41
- Issue
- 3
- Pages
- 213-236
- ISSN
- 0169-6149 (ISSN-L)
- 1573-0875
- OpenAlex
- W2077496877
- Cited by
- 32
- References
- 26
- Citations by year
- 2025: 1 · 2024: 1 · 2023: 2 · 2022: 2 · 2021: 1 · 2020: 1 · 2018: 1 · 2017: 1 · 2016: 3 · 2015: 2 · 2014: 3 · 2013: 7 · 2012: 4
- FWCI
- 2.50
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Licence
- Locations
- Origins of Life and Evolution of Biospheres (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Science Foundation (0091892)
- University at Albany
- Division of Chemistry
- Topics
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › RNA and protein synthesis mechanisms
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › DNA and Nucleic Acid Chemistry
- Keywords
- homochirality, RNA synthesis, montmorillonite, clay catalysis, prebiotic synthesis, cyclic dimers, sequence selectivity, regioselectivity, origin of life
- MeSH terms
- Bentonite, Catalysis, Chromatography, High Pressure Liquid, Hydrolysis, Isomerism, Models, Molecular, Phosphorylation, Purine Nucleotides, Pyrimidine Nucleotides, RNA
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