Chiral Cyclobutane-Containing Cell-Penetrating Peptides as Selective Vectors for Anti-Leishmania Drug Delivery Systems

Two series of new hybrid γ/γ-peptides, γ-CC and γ-CT, formed by (1S,2R)-3-amino2,2,dimethylcyclobutane-1-carboxylic acid joined in alternation to a Nα- functionalized cis- or trans-γ-amino-l-proline derivative, respectively, have been synthesized and evaluated as cell penetrating peptides (CPP) and...

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Detalles Bibliográficos
Autores: Illa, Ona|||0000-0001-7390-4893, Olivares Montia, José Antonio, Gaztelumendi, Nerea|||0000-0002-3837-2956, Martínez-Castro, Laura, Ospina Chavez, Jimena Andrea, Abengozar, María Ángeles, Sciortino, Giuseppe|||0000-0001-9657-1788, Maréchal, Jean-Didier|||0000-0002-8344-9043, Nogués, Carme|||0000-0002-6361-8559, Royo, Miriam|||0000-0001-5292-0819, Rivas, Luis|||0000-0002-2958-3233, Ortuño Mingarro, Rosa María|||0000-0001-7635-7354
Tipo de recurso: artículo
Fecha de publicación:2020
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:233888
Acceso en línea:https://ddd.uab.cat/record/233888
https://dx.doi.org/urn:doi:10.3390/ijms21207502
Access Level:acceso abierto
Palabra clave:Unnatural γ-amino acids
Foldamers
Selective cell-penetrating peptides
Anti-Leishmania
Drug delivery vectors
Descripción
Sumario:Two series of new hybrid γ/γ-peptides, γ-CC and γ-CT, formed by (1S,2R)-3-amino2,2,dimethylcyclobutane-1-carboxylic acid joined in alternation to a Nα- functionalized cis- or trans-γ-amino-l-proline derivative, respectively, have been synthesized and evaluated as cell penetrating peptides (CPP) and as selective vectors for anti-Leishmania drug delivery systems (DDS). They lacked cytotoxicity on the tumoral human cell line HeLa with a moderate cell-uptake on these cells. In contrast, both γ-CC and γ-CT tetradecamers were microbicidal on the protozoan parasite Leishmania beyond 25 µM, with significant intracellular accumulation. They were conjugated to fluorescent doxorubicin (Dox) as a standard drug showing toxicity beyond 1 µM, while free Dox was not toxic. Intracellular accumulation was 2.5 higher than with Dox-TAT conjugate (TAT = transactivator of transcription, taken as a standard CPP). The conformational structure of the conjugates was approached both by circular dichroism spectroscopy and molecular dynamics simulations. Altogether, computational calculations predict that the drug-γ-peptide conjugates adopt conformations that bury the Dox moiety into a cavity of the folded peptide, while the positively charged guanidinium groups face the solvent. The favorable charge/hydrophobicity balance in these CPP improves the solubility of Dox in aqueous media, as well as translocation across cell membranes, making them promising candidates for DDS.