Click on Click: Click-Flavone Glycosides Encapsulated in Click-Functionalised Polymersomes for Glioblastoma Therapy

In this study, three new 3,7-dihydroxyflavone (<b>1</b>) derivatives with different sugars were designed and synthesised by click chemistry. Click chemistry requires the previously modification of building blocks with azide and alkyne groups and therefore, the 3,7-dihydroxyflavone (<b...

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Main Authors: Nuno M. Saraiva, Ana Alves, Ana Isabel Barbosa, Andreia Marinho, Salette Reis, Marta Correia-da-Silva, Paulo C. Costa
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Pharmaceutics
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Online Access:https://www.mdpi.com/1999-4923/17/6/771
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author Nuno M. Saraiva
Ana Alves
Ana Isabel Barbosa
Andreia Marinho
Salette Reis
Marta Correia-da-Silva
Paulo C. Costa
author_facet Nuno M. Saraiva
Ana Alves
Ana Isabel Barbosa
Andreia Marinho
Salette Reis
Marta Correia-da-Silva
Paulo C. Costa
author_sort Nuno M. Saraiva
collection DOAJ
description In this study, three new 3,7-dihydroxyflavone (<b>1</b>) derivatives with different sugars were designed and synthesised by click chemistry. Click chemistry requires the previously modification of building blocks with azide and alkyne groups and therefore, the 3,7-dihydroxyflavone (<b>1</b>) was first converted in 3,7-(prop-2-yn-yloxy)flavone (<b>2</b>) and acetobromo-<i>α</i>-D-glucose (<b>3</b>) was converted into 2,3,4,6-tetra-O-acetyl-<i>β</i>-glucopyranosyl azide (<b>4</b>). Subsequently, a click reaction was performed via copper-catalysed cycloaddition (CuAAC) between <b>2</b> and <b>4,</b> as well as between <b>2</b> and 2-acetamido-3,4,6-tetra-O-acetyl-2-deoxy-<i>β</i>-D-glucopyranosyl (<b>AG931</b>) and, <b>2</b> and commercial 2-azidoethyl 2,3,4,6-tetra-O-acetyl-<i>β</i>-D-glucopyranosyl (<b>AG358</b>), resulting in three distinct disubstituted flavone glycosides (<b>5a</b>–<b>5c</b>). Biological assays performed on L929 fibroblast cell lines and human glioblastoma astrocytoma U-251 cell lines indicated cytocompatibility with fibroblasts and reduced metabolic activity of GBM cells in the presence of compound <b>5b</b> and <b>5c</b>. To enhance therapeutic effect, improve local drug delivery, and overcome solubility issues of these high molecular weight compounds, the synthesised compounds were encapsulated in polymeric particles (polymersomes, PMs) composed of polylactic acid-polyethylene glycol (PEG-PLA) functionalized, once more by click chemistry, with 0.1 mol% transferrin mimetic (T7—HRPYIAH) peptide. The PMs were prepared by solvent displacement and exhibited stability over 100 days, encapsulation efficiency of 39–93%, and mean size diameters of 120–180 nm. The toxicity assays of the PMs on the U-251 cell line showed a significant decrease in metabolic activity, supporting the potential of this delivery system against GBM. Among the PMs tested, the flavone <b>5c</b>-based PM demonstrated the highest efficacy.
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spelling doaj-art-11ef7eabbaee4a9ab5c0e014d37ed2582025-08-20T03:27:39ZengMDPI AGPharmaceutics1999-49232025-06-0117677110.3390/pharmaceutics17060771Click on Click: Click-Flavone Glycosides Encapsulated in Click-Functionalised Polymersomes for Glioblastoma TherapyNuno M. Saraiva0Ana Alves1Ana Isabel Barbosa2Andreia Marinho3Salette Reis4Marta Correia-da-Silva5Paulo C. Costa6LQOF—Laboratory of Organic and Pharmaceutical Chemistry, Department of Chemical Sciences, Faculty of Pharmacy, University of Porto, Rua Jorge de Viterbo Ferreira 228, 4050-313 Porto, PortugalUCIBIO—Applied Molecular Biosciences Unit, MedTech-Laboratory of Pharmaceutical Technology, Faculty of Pharmacy, University of Porto, Rua Jorge de Viterbo Ferreira 228, 4050-313 Porto, PortugalLAQV-REQUIMTE—Associated Laboratory for Green Chemistry, Network of Chemistry and Technology, Department of Chemical Sciences, Faculty of Pharmacy, University of Porto, Rua Viterbo Ferreira 228, 4050-313 Porto, PortugalLAQV-REQUIMTE—Associated Laboratory for Green Chemistry, Network of Chemistry and Technology, Department of Chemical Sciences, Faculty of Pharmacy, University of Porto, Rua Viterbo Ferreira 228, 4050-313 Porto, PortugalLAQV-REQUIMTE—Associated Laboratory for Green Chemistry, Network of Chemistry and Technology, Department of Chemical Sciences, Faculty of Pharmacy, University of Porto, Rua Viterbo Ferreira 228, 4050-313 Porto, PortugalLQOF—Laboratory of Organic and Pharmaceutical Chemistry, Department of Chemical Sciences, Faculty of Pharmacy, University of Porto, Rua Jorge de Viterbo Ferreira 228, 4050-313 Porto, PortugalUCIBIO—Applied Molecular Biosciences Unit, MedTech-Laboratory of Pharmaceutical Technology, Faculty of Pharmacy, University of Porto, Rua Jorge de Viterbo Ferreira 228, 4050-313 Porto, PortugalIn this study, three new 3,7-dihydroxyflavone (<b>1</b>) derivatives with different sugars were designed and synthesised by click chemistry. Click chemistry requires the previously modification of building blocks with azide and alkyne groups and therefore, the 3,7-dihydroxyflavone (<b>1</b>) was first converted in 3,7-(prop-2-yn-yloxy)flavone (<b>2</b>) and acetobromo-<i>α</i>-D-glucose (<b>3</b>) was converted into 2,3,4,6-tetra-O-acetyl-<i>β</i>-glucopyranosyl azide (<b>4</b>). Subsequently, a click reaction was performed via copper-catalysed cycloaddition (CuAAC) between <b>2</b> and <b>4,</b> as well as between <b>2</b> and 2-acetamido-3,4,6-tetra-O-acetyl-2-deoxy-<i>β</i>-D-glucopyranosyl (<b>AG931</b>) and, <b>2</b> and commercial 2-azidoethyl 2,3,4,6-tetra-O-acetyl-<i>β</i>-D-glucopyranosyl (<b>AG358</b>), resulting in three distinct disubstituted flavone glycosides (<b>5a</b>–<b>5c</b>). Biological assays performed on L929 fibroblast cell lines and human glioblastoma astrocytoma U-251 cell lines indicated cytocompatibility with fibroblasts and reduced metabolic activity of GBM cells in the presence of compound <b>5b</b> and <b>5c</b>. To enhance therapeutic effect, improve local drug delivery, and overcome solubility issues of these high molecular weight compounds, the synthesised compounds were encapsulated in polymeric particles (polymersomes, PMs) composed of polylactic acid-polyethylene glycol (PEG-PLA) functionalized, once more by click chemistry, with 0.1 mol% transferrin mimetic (T7—HRPYIAH) peptide. The PMs were prepared by solvent displacement and exhibited stability over 100 days, encapsulation efficiency of 39–93%, and mean size diameters of 120–180 nm. The toxicity assays of the PMs on the U-251 cell line showed a significant decrease in metabolic activity, supporting the potential of this delivery system against GBM. Among the PMs tested, the flavone <b>5c</b>-based PM demonstrated the highest efficacy.https://www.mdpi.com/1999-4923/17/6/771click chemistryglioblastomaflavonespolymersomedrug delivery
spellingShingle Nuno M. Saraiva
Ana Alves
Ana Isabel Barbosa
Andreia Marinho
Salette Reis
Marta Correia-da-Silva
Paulo C. Costa
Click on Click: Click-Flavone Glycosides Encapsulated in Click-Functionalised Polymersomes for Glioblastoma Therapy
Pharmaceutics
click chemistry
glioblastoma
flavones
polymersome
drug delivery
title Click on Click: Click-Flavone Glycosides Encapsulated in Click-Functionalised Polymersomes for Glioblastoma Therapy
title_full Click on Click: Click-Flavone Glycosides Encapsulated in Click-Functionalised Polymersomes for Glioblastoma Therapy
title_fullStr Click on Click: Click-Flavone Glycosides Encapsulated in Click-Functionalised Polymersomes for Glioblastoma Therapy
title_full_unstemmed Click on Click: Click-Flavone Glycosides Encapsulated in Click-Functionalised Polymersomes for Glioblastoma Therapy
title_short Click on Click: Click-Flavone Glycosides Encapsulated in Click-Functionalised Polymersomes for Glioblastoma Therapy
title_sort click on click click flavone glycosides encapsulated in click functionalised polymersomes for glioblastoma therapy
topic click chemistry
glioblastoma
flavones
polymersome
drug delivery
url https://www.mdpi.com/1999-4923/17/6/771
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