NMR approaches to understand synthesis, assembly and properties of novel carbohydrate-based materials.

Gabrielli, Valeria (2021) NMR approaches to understand synthesis, assembly and properties of novel carbohydrate-based materials. Doctoral thesis, University of East Anglia.

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Abstract

The investigation conducted throughout this doctoral thesis covers the underpinning science of synthesis, assembly and characterisation of novel polysaccharide-based materials. Within the broad chemical family of "sugars", polysaccharides are excellent biopolymers for hydrogel preparation. Innovative glycobiology techniques such as enzymatic catalysis can be used for the functionalisation of these materials and the introduction of specific and tuneable properties.

Cellodextrin phosphorylase from Ruminiclostridium thermocellum (CDP) is a carbohydrate-active enzyme able to catalyse the synthesis of small fragments of cellulose. The enzyme’s loose specificity towards donor and acceptor substrates allows its exploitation for the introduction of functional groups in a regiocontrolled manner. Therefore, understanding the structural details of substrates molecular recognition is fundamental for a rational design of novel cellulose derivatives.

We applied several NMR approaches and computational tools to unveil the mechanistic details of substrates recognition. The investigation highlighted differences in the binding epitopes of cognate and non-cognate donor and acceptor substrates, and the enthalpic contribution in the energy of binding played by inorganic phosphate.

CDP has been used for the synthesis of a series of cellodextrin derivatives decorated with fluorine atoms. We combined state-of-the-art NMR spectroscopy (solution and solid-state) methodologies with PXRD technique to gain the molecular details of the novel materials self-assembly. In addition, we developed an NMR-based strategy to discern between surface/disordered and core/ordered domains.

Item Type: Thesis (Doctoral)
Faculty \ School: Faculty of Science > School of Pharmacy
Depositing User: Chris White
Date Deposited: 26 Aug 2021 08:13
Last Modified: 26 Aug 2021 08:13
URI: https://ueaeprints.uea.ac.uk/id/eprint/81240
DOI:

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