A new alpha,alpha-disubstituted constrained glutamine analogue has been designed to decorate gold nanopartides and to induce a 3(10)-helix when inserted in peptides. Using an efficient "one-pot" asymmetric Schmidt reaction between 4-disubstituted-cydohexanone and hydroxyalkylazides, 1H-azepine-2-oxo-5-amino-5-carboxylic acid was prepared. The main (R) isomer was inserted at the N-terminus in a very short peptide sequence (i.e., PhCO-(R)-Oxo-Azn-L-Ala-Aib-L-AlaNHMe) and a stable 3(10)-helix conformation was obtained, as verified by both NMR experiments and molecular dynamics (MD) simulations. Finally, the presence of the hydroxyl chain at the nitrogen atom of the ring allowed for the preparation of covered chiral gold nanopartides.

1H-Azepine-2-oxo-5-amino-5-carboxylic Acid: A 3(10) Helix Inducer and an Effective Tool for Functionalized Gold Nanoparticles / S. Pellegrino, A. Bonetti, F. Clerici, A. Contini, A. Moretto, R. Soave, M.L. Gelmi. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 80:11(2015 Jun 05), pp. 5507-5516.

1H-Azepine-2-oxo-5-amino-5-carboxylic Acid: A 3(10) Helix Inducer and an Effective Tool for Functionalized Gold Nanoparticles

S. Pellegrino;A. Bonetti;F. Clerici;A. Contini;M.L. Gelmi
2015-06-05

Abstract

A new alpha,alpha-disubstituted constrained glutamine analogue has been designed to decorate gold nanopartides and to induce a 3(10)-helix when inserted in peptides. Using an efficient "one-pot" asymmetric Schmidt reaction between 4-disubstituted-cydohexanone and hydroxyalkylazides, 1H-azepine-2-oxo-5-amino-5-carboxylic acid was prepared. The main (R) isomer was inserted at the N-terminus in a very short peptide sequence (i.e., PhCO-(R)-Oxo-Azn-L-Ala-Aib-L-AlaNHMe) and a stable 3(10)-helix conformation was obtained, as verified by both NMR experiments and molecular dynamics (MD) simulations. Finally, the presence of the hydroxyl chain at the nitrogen atom of the ring allowed for the preparation of covered chiral gold nanopartides.
Asymmetric schmidt reaction; ring expansion reactions; alpha-amino-acids; drug-delivery; hydroxyalkyl azides; secondary structure; molecular-dynamics; optical-absorption; cation-PI; derivates
Settore CHIM/06 - Chimica Organica
Piano Sviluppo Unimi - LINEA B - DOTAZIONE ANNUALE PER ATTIVITA' ISTITUZIONALI
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/289057
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