MOFs have demonstrated outstanding properties for the protection and controlled release of different bio-entities, from proteins to living cells. Carbohydrates, as pure molecules or as a component of proteins and cells, perform essential biological functions. Thus, an understanding of the role of carbohydrates in the formation of MOF-based bio-composites will facilitate their application to biotechnology and medicine. Here, we investigate the role of carbohydrate molecular weight and chemical functionalization in the formation of carbohydrate@MOF composites. We find that chemical functionalization, such as carboxylation, that leads to an enhancement of metal cation concentration at the surface of the molecule triggers the rapid self-assembly of the MOF material, zeolitic-imidazolate framework 8 (ZIF-8). Furthermore, we determine the encapsulation efficiency and measure the release properties of the carbohydrate under controlled conditions. Our findings show that MOFs can be used to prepare a new class of biocomposites for the delivery of carbohydrate-based therapeutics. † Electronic supplementary information (ESI) available: Additional figures, movies and experimental details. Substrates used and their formulas, schematic overviews of the performed syntheses and workups, time-dependent MOFformation experiments induced by different carbohydrates and concentrations, yield calculations, SEM image of ZIF-8 on glass and paper, FTIR spectra of the starting materials and the obtained products, schematic of the ion-permeable spherical model, kinetics studies, UV-Vis analyses, photographs of solutions using different polysaccharides, and video showing the succesfull biomimetic mineralisation of CM-dextran. SeeCarbohydrate-based therapeutics are relevant drugs for the treatment of cancer, diabetes, viral and bacterial infections. Therefore the efficient encapsulation and controlled release of carbohydrates has great potential in biomedicine. Here, we present a successful strategy to trigger the spontaneous crystallization of metal-organic frameworks (MOFs) on carbohydrates. The encapsulation of carbohydrates within ZIF-8 and polymorphs (zinc-imidazolate-based MOFs) can be obtained in water. The identification of conditions suitable for the successful preparation of the composite were experimentally and computationally identified. By controlling the chemical functionalization of the carbohydrate, the formation of bio-composites can be obtained in seconds. A 100% encapsulation efficiency was obtained. The controlled release of carbohydrates from the MOF biocomposite was demonstrated. This proof-of-concept study shows that a new generation of MOF biocomposites can be exploited for biomedical applications.

A collection of new reversible glycosidase inhibitors of the iminoalditol type featuring Nsubstituents containing perfluorinated regions has been prepared for evaluation of physicochemical, biochemical and diagnostic properties. The vast variety of feasible oligofluoro moieties allows for modular approaches to customised structures according to the intended applications, which are influenced by the fluorine content as well as the distance of the fluorous moiety from the ring nitrogen. The first examples, in particular in the D-galacto series, exhibited excellent inhibitory activities. A preliminary screen with two human cell lines showed that, at subinhibitory concentrations, they are powerful pharmacological chaperones enhancing the activities of the catalytically handicapped lysosomal D-galactosidase mutants associated with GM1 gangliosidosis and Morquio B disease.

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