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Building with cucurbit[n]urils: a computational study of host-guest chemistry and inner-phase reactions

Lambert, Hugues; (2022) Building with cucurbit[n]urils: a computational study of host-guest chemistry and inner-phase reactions. Doctoral thesis (Ph.D), UCL (University College London). Green open access

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Abstract

Enzymes are nature's impressive supramolecular catalysts. Through the help of non-covalent forces, usually at least an order of magnitude weaker than chemical bonds, substrates can be transformed with high efficiency and exquisite selectivity to yield a wide array of products. Enzymes, however, routinely contain hundreds of amino acid residues and often reach thousands of atoms which make their study in silico costly for even the fastest methods and usually impractical for quantum chemical methods. Cucurbit[n]urils (CBn), are barrel-shaped macrocycles whose hydrophobic cavity reminds of certain metal-free enzymatic active sites in that they are able to bind guests with high specificity and assist their reactions through stabilisation of their transition states. With around a hundred heavy atoms, CBn, are small enough to lend themselves to thorough in silico characterisation using accurate methods and therefore constitute an interesting enzyme mimic. This work will dive into the driving force behind the host-guest binding process in CBn and leverage this knowledge to study a possible role for CB6 and CB7 in facilitating the isomerisation reaction of meta-xylene to para-xylene, an important petrochemical feedstock. Eventually, with the recognition that a catalytic effect through transition state stabilisation is linked to the macrocycle's cavity potential energy surface, capping ligands for CB7's portal are sought with the objective to form ternary complexes able to modulate the cavity's energy landscape and thereby expand the CBn platform. It is envisioned that this work will help further the understanding of catalysis in confined spaces and the design of metal-free nanoreactors.

Type: Thesis (Doctoral)
Qualification: Ph.D
Title: Building with cucurbit[n]urils: a computational study of host-guest chemistry and inner-phase reactions
Open access status: An open access version is available from UCL Discovery
Language: English
Additional information: Copyright © The Author 2021. Original content in this thesis is licensed under the terms of the Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0) Licence (https://creativecommons.org/licenses/by-nc/4.0/). Any third-party copyright material present remains the property of its respective owner(s) and is licensed under its existing terms. Access may initially be restricted at the author’s request.
UCL classification: UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > MAPS Faculty Office > Institute for Materials Discovery
URI: https://discovery.ucl.ac.uk/id/eprint/10162237
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