Rodríguez Marín, RocíoRodríguez Gómez, SalvadorHamad, SaidSánchez Fernández, Elena MatildeCarrillo Carrión, Carolina2025-02-032025-02-032025-03Rodríguez Marín, R., Rodríguez Gómez, S., Hamad, S., Sánchez Fernández, E.M. y Carrillo Carrión, C. (2025). Engineering nanoscale glyco-zeolitic-imidazolate frameworks: Insights into the mechanism of formation. Materials Today Chemistry, 44, 102546. https://doi.org/10.1016/j.mtchem.2025.102546.2468-5194https://hdl.handle.net/11441/168137The efficient encapsulation of large carbohydrates into porous metal-organic frameworks (MOFs), and not simply attached to the MOF's surface, is still challenging and underexplored. In this work we have investigated the scope of an optimized synthetic procedure following a biomimetic mineralization strategy for the encapsulation of a variety of therapeutic glycolipids within a Zeolitic-Imidazolate Framework-8 nanostructure (GlycoZIFs). In all cases, regardless of the glycosidic linkage nature of the glycolipid, we obtained uniform, crystalline and reproducible GlycoZIFs nanoparticles by using the same optimized experimental conditions, which demonstrate the versatility of our approach. Our experimental data revealed that the formation of glyco-micelles, by taking advantage of the surfactant-like character of these glycolipids, is key to promote the nucleation of ZIF-8 around, allowing thus a precise control of the spatial location and amount of glycodrug encapsulated in each ZIF-particle. In turn, the electronic structure calculations showed that there is a strong interaction between the hydroxyl groups in positions C3 and C4 of the glycone core of the glycolipid and the Zn atoms on the ZIF-8 surface, suggesting that those favourable glyco-ZIF interactions also played an important role to induce the ZIF-8 nucleation. Experimental control data and computational studies obtained with a protected glycolipid featuring O-acetyl groups supported that conclusion.application/pdf13 p.engAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/Zeolitic-imidazolate frameworksGlycomimeticsGlycolipidsDe novo encapsulationElectronic structure calculationsinfo:eu-repo/semantics/articleinfo:eu-repo/semantics/openAccesshttps://doi.org/10.1016/j.mtchem.2025.102546