Homochiral oligopeptides via surface recognition and enantiomeric cross impediment in the polymerization of racemic phenylalanine N‐carboxyanhydride crystals suspended in water
Abstract
As part of our program on the search of possible prebiotic routes for the formation of oligopeptides of homochiral sequence (isotactic) from racemic precursors in aqueous environment, we report the polymerization of racemic crystals of phenylalanine N-carboxyanhydrides, enantioselectively tagged with five deuterium atoms, suspended in water containing various amine initiators. Racemic mixtures of isotactic oligopeptides, comprising up to 25 repeat units of the same handedness, as the dominant component for each length, were observed in a MALDI-TOF mass spectrometry analysis. The racemic mixtures of the peptides could be desymmetrized by initiating the polymerization reaction with water-soluble methyl esters of either enantiopure alpha-amino acids or dipeptides. A three-step mechanism is proposed to account for these results: (i) Surface recognition of the chiral initiator by the chiral sites present at specific faces of the crystal; (ii) Oligopeptide elongation at the polymer/crystal interface; and (iii) Self-assembly of the short isotactic peptides into racemic antiparallel beta-sheets as templates followed by cross-enantiomeric impediment in the growth of enantiomeric chains at the peptide beta-sheet/crystal interface.
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The stereoselectivity of the oligomerization reaction is strongly enhanced under conditions for which β-sheet aggregates are initially present or emerge during the reaction process.
“These authors found that the stereoselectivity of the oligomerization reaction is strongly enhanced under conditions for which b-sheet aggregates are initially present 549 or emerge during the reaction process.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [549]
These supramolecular aggregates serve as templates in the propagation step of chain elongation leading to long peptides and copeptides with a significant bias towards homochirality.
“These supramolecular aggregates serve as templates in the propagation step of chain elongation leading to long peptides and copeptides with a significant bias towards homochirality.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [549]
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Self-citation
- Authors
- Nery, J. G., Eliash, R., Bolbach, G., Weissbuch, I., & Lahav, M.
- Affiliations
- Weizmann Institute of Science (IL)
- Corresponding author
- Lahav, Meir
- ORCID
- Lahav, Meir
- Venue
- Chirality
- Publisher
- Wiley
- Published
- 2007-03-12
- Volume
- 19
- Issue
- 8
- Pages
- 612-624
- ISSN
- 0899-0042 (ISSN-L)
- 1520-636X
- OpenAlex
- W2080759069
- Cited by
- 18
- References
- 42
- Citations by year
- 2024: 1 · 2023: 1 · 2022: 1 · 2012: 3
- FWCI
- 2.00
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Chirality (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Chemical Synthesis and Analysis
- Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
- Keywords
- racemic crystals, surface recognition, deuterium labeling, peptide self-assembly, antiparallel beta-sheet, polymerization mechanism, aqueous polymerization
- MeSH terms
- Anhydrides, Crystallization, Microscopy, Electron, Scanning, Models, Molecular, Oligopeptides, Peptides, Phenylalanine, Solutions, Stereoisomerism, Water, Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
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