Carbohydrates@MOFs

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.Efwita Astria, Martin Thonhofer … Weibin Liang … David M. Huang, Christian J. Doonan, Paolo Falcaro ... et al

Ligand-Directed Chemistry on Glycoside Hydrolases – A Proof of Concept Study

Selective covalent labelling of enzymes using small molecule probes has advanced the scopes of protein profiling. The covalent bond formation to a specific target is the key step of activity-based protein profiling (ABPP), a method which has become an indispensable tool for measuring enzyme activity in complex matrices. With respect to carbohydrate processing enzymes, strategies for ABPP so far involve labelling the active site of the enzyme, which results in permanent loss of activity. Here, we report in a proof of concept study the use of ligand-directed chemistry (LDC) for labelling glycoside hydrolases near – but not in – the active site. During the labelling process, the competitive inhibitor is cleaved from the probe, departs the active site and the enzyme maintains its catalytic activity. To this end, we designed a building block synthetic concept for small molecule probes containing iminosugar-based reversible inhibitors for labelling of two model β-glucosidases. The results indicate that the LDC approach can be adaptable for covalent proximity labelling of glycoside hydrolases.T. M. W. thanks the FWF (Wien, Austria) for financial support (project number P30372-B21). Authors from TU Graz acknowledge support from NAWI Graz.Peer reviewe

Chemical vapor deposition of carbohydrate-based polymers: a proof of concept study

The aim of this work is to investigate if vinyl-modified carbohydrate compounds are suitable monomers for thin film polymerization via chemical vapor deposition in a proof-of-concept study. Synthetic carbohydrate-based polymers are explored as biodegradable, biocompatible, and biorenewable materials. A thin film of synthetic polymers bearing sugar residues can also offer a good surface for cell attachment, and thus might be applied in biomaterials and tissue engineering. The possibility of having such thin film deposited from the vapor phase would ease the implementation in complex device architectures. For a proof-of-concept study, sugar vinyl compound monomers are synthesized starting from methyl α-d-glucopyranoside and polymerized by initiated chemical vapor deposition (iCVD) leading to a thin polymer layer on a Si-substrate. Thus, a successful vapor polymerization of the sugar compounds could be demonstrated. Infrared spectroscopy shows that no unwanted crosslinking reactions take place during the vapor deposition. The solubility of the polymers in water was observed in situ by spectroscopic ellipsometry. Graphical abstract: [Figure not available: see fulltext.]