Racemic β‐Sheets as Templates for the Generation of Homochiral (Isotactic) Peptides from Aqueous Solutions of (RS)‐Valine or ‐Leucine N‐Carboxy‐ anhydrides: Relevance to Biochirogenesis
Abstract
As part of our program on biochirogenesis of homochiral peptides from racemic precursors, we report the feasibility of obtaining peptides with homochiral sequences composed of up to 25 residues of the same handedness in the polymerization of racemic valine or leucine N‐carboxyanhydrides in aqueous solutions, as initiated by amines. The composition of the oligopeptides was determined by MALDI‐TOF mass spectrometry, and the sequences of some of the heterochiral diastereoisomers were studied by MALDI‐TOF MS/MS performed on samples in which the S enantiomers of the monomer were tagged with deuterium atoms. The process comprises several steps: 1) a Markov mechanism of asymmetric induction in the early stages of the polymerization yields libraries of racemic oligopeptides enriched with isotactic diastereoisomers, together with oligopeptide sequences containing enantiomeric blocks of homochiral residues; 2) the short peptides self‐assemble into racemic colloidal architectures that serve as regio‐enantioselective templates in the ensuing process of chain elongation; 3) homochiral residues of the amino acids located at the periphery of these colloidal aggregates exert efficient enantioselection, which results in the formation of long isotactic oligopeptides. The final diastereoisomeric distribution of the peptides depends upon the composition of the templates, which is determined by the concentration of the initiator. The racemic mixtures of isotactic peptides can be desymmetrized by using enantiopure methyl esters of α‐amino acids as initiators.
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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 [551]
Racemic mixtures of isotactic peptides are desymmetrized by adding chiral initiators or by biasing the initial enantiomer composition.
“Racemic mixtures of isotactic peptides are desymmetrized by adding chiral initiators 551 or by biasing the initial enantiomer composition.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [551]
Large enhancement of the homochiral content was detected, notably for the oligomerization of rac-Val NCA in the presence of 5% of an initiator.
“Large enhancement of the homochiral content was detected, notably for the oligomerization of rac-Val NCA in the presence of 5% of an initiator (Fig. 22).”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [551]
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 [551]
Stereoselective polymerization of rac-Val N-carboxyanhydride occurs in the presence of n-butylamine as the initiator.
“Stereoselective polymerization of rac-Val N-carboxyanhydride in the presence of 5 mol% (square) or 25 mol% (diamond) of n-butylamine as the initiator.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [551]
Cites
Nery, J. G., Eliash, R., Bolbach, G., Weissbuch, I., & Lahav, M. (2007) · Chirality · doi:10.1002/chir.20363 · Cited by 18 · see citing works
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Prebiotic Systems Chemistry: New Perspectives for the Origins of Life
Ruiz-Mirazo, K., Briones, C., & de la Escosura, A. (2014) · Chemical Reviews · doi:10.1021/cr2004844 · Cited by 930 · see citing works
Crystalline Architectures as Templates of Relevance to the Origins of Homochirality
Weissbuch, I., & Lahav, M. (2011) · Chemical Reviews · doi:10.1021/cr1002479 · Cited by 284 · see citing works
Self-citationPossible chemical and physical scenarios towards biological homochirality
Sallembien, Q., Bouteiller, L., Crassous, J., & Raynal, M. (2022) · Chemical Society Reviews · doi:10.1039/d1cs01179k · Cited by 186 · see citing works
- Authors
- Rubinstein, I., Clodic, G., Bolbach, G., Weissbuch, I., & Lahav, M.
- Affiliations
- Weizmann Institute of Science (IL)
- Institut de Biologie Paris-Seine (FR)
- Venue
- Chemistry – A European Journal
- Publisher
- Wiley
- Published
- 2008-12
- Volume
- 14
- Issue
- 35
- Pages
- 10999-11009
- ISSN
- 0947-6539 (ISSN-L)
- 1521-3765
- OpenAlex
- W1977974923
- Cited by
- 19
- References
- 1
- Citations by year
- 2023: 1 · 2022: 1 · 2021: 1 · 2017: 1 · 2013: 2 · 2012: 3
- FWCI
- 1.94
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Chemistry - A European Journal (publishedVersion)
- PubMed (publishedVersion)
- HAL (submittedVersion)
- Funders
- Weizmann Institute of Science
- Israel Science Foundation
- 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
- asymmetric induction, colloidal templates, enantioselectivity, desymmetrization
- MeSH terms
- Anhydrides, Leucine, Peptides, Solutions, Stereoisomerism, Valine, Water, Protein Structure, Secondary, Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
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