Combined in Silico and in Vitro Approaches To Uncover the Oxidation and Schiff Base Reaction of Baicalein as an Inhibitor of Amyloid Protein Aggregation.

Schiff bases autoxidation computational chemistry quinones transition states

Journal

Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783

Informations de publication

Date de publication:
19 Feb 2022
Historique:
received: 26 11 2021
pubmed: 7 1 2022
medline: 24 2 2022
entrez: 6 1 2022
Statut: ppublish

Résumé

The oxidized form of baicalein (BA) leads to covalent binding with human amyloid proteins. Such adducts hamper the aggregation and deposition of fibrils. A novel reaction of BA with pentylamine (PA) as a model for the lysine side chain is described. This is the first study addressing the atomistic details of a Schiff base reaction with the trihydroxylated moiety of BA. Nuclear magnetic resonance and mass spectrometry approaches clearly indicate the formation of dehydrobaicalein in solution as well as its condensation with PA under aerobic conditions, yielding regioselectively C6-substituted products. The combined results suggest initial ion pair formation between BA and PA, followed by a redox chain reaction: the initiation by oxygen/air; an o-quinone-based chain involving oxidation and reduction steps; and extra off-chain formation of a doubly oxidized product. These mechanistic details support the anti-amyloid activity of BA and endorse its trihydroxyphenyl moiety as a pharmacophore for drug-design studies.

Identifiants

pubmed: 34989442
doi: 10.1002/chem.202104240
doi:

Substances chimiques

Amyloidogenic Proteins 0
Flavanones 0
Protein Aggregates 0
Schiff Bases 0
baicalein 49QAH60606

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

e202104240

Subventions

Organisme : Fundação para a Ciência e a Tecnologia
ID : UIDB/50006/2020
Organisme : Fundação para a Ciência e a Tecnologia
ID : CEECIND/02017/2018

Informations de copyright

© 2022 Wiley-VCH GmbH.

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Auteurs

Natércia F Brás (NF)

LAQV, REQUIMTE Departamento de Química e Bioquímica Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007, Porto, Portugal.
Department Chemie, Ludwig-Maximilians-Universität Muenchen, 81377, Muenchen, Germany.

Salavat S Ashirbaev (SS)

Department Chemie, Ludwig-Maximilians-Universität Muenchen, 81377, Muenchen, Germany.

Hendrik Zipse (H)

Department Chemie, Ludwig-Maximilians-Universität Muenchen, 81377, Muenchen, Germany.

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