Heterochirality Restricts the Self-Assembly of Phenylalanine Dipeptides Capped with Highly Aromatic Groups

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Data de publicació
2020Autor/a
Gil, Ana M.
Mayans, Enric
Jiménez, Ana I.
Puiggalí, Jordi
Alemán, Carlos
Citació recomanada
Gil, Ana M.;
Casanovas Salas, Jordi;
Mayans, Enric;
Jiménez, Ana I.;
Puiggalí, Jordi;
Alemán, Carlos;
.
(2020)
.
Heterochirality Restricts the Self-Assembly of Phenylalanine Dipeptides Capped with Highly Aromatic Groups.
Journal of Physical Chemistry B, 2020, vol. 124, núm. 28, p. 5913-5918.
https://doi.org/10.1021/acs.jpcb.0c04513.
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The influence of stereochemistry on the self-assembly of phenylalanine (Phe) dipeptides bearing aromatic fluorenyl groups at both the N- and C-termini (Fmoc, OFm) has been investigated. For this purpose, Fmoc–d-Phe–l-Phe–OFm and Fmoc–l-Phe–l-Phe–OFm have been examined considering a wide variety of solvents, which differ in dielectric constant and volatility. Results reveal that replacement of l-Phe by d-Phe has a major impact on the self-assembly propensities, restricting drastically the structural diversity and polymorphism shown by the homochiral dipeptide. Thus, the analogous heterochiral dipeptide shows a great propensity to form micro/nanofibers, independently of the environmental conditions. Theoretical calculations revealed that the stability of antiparallel disposition is much higher (a factor of ca. 15) for Fmoc–d-Phe–l-Phe–OFm than that for Fmoc–l-Phe–l-Phe–OFm, which has been attributed to the hydrophobic core formed in the former. Overall, results suggest that control of the backbone chirality is a potent and versatile strategy to drive and finely tune the self-assembly propensities of highly aromatic peptides.