Garmendia, Sofiem (2020) Synthesis of new N-heterocyclic carbene (NHC)-based single chain nanoparticles (SCNPs) as catalytically active nanoreactors. PhD thesis, University of Warwick.
Preview |
PDF
WRAP_Theses_Garmendia_2020.pdf - Submitted Version - Requires a PDF viewer. Download (9MB) | Preview |
Abstract
Random copolymers based on poly(ionic liquids) have been developed under different architectures such as single chain nanoparticles (SCNPs) or as (macro)gels. Those different systems have been employed as N heterocyclic carbenes (NHCs) precurors to be used as organocatalysts. The incorporation of relatively basic counteranions in PIL units derived from imidazolium moieties allows the in situ generation of active NHC species for catalysis. Firstly, a reactive PIL based (macro)gel represents the preliminary study to better understand and analyse the catalytic performance in the macroscale. This study has permitted the identification of suitable model reactions as well as conditions and standards, becoming a reference system all along this thesis. Moreover, this (macro)gel has served as a base for the further development of more sophisticated nanogels known as single chain nanoparticles (aka SCNPs). These SCNPs have specially been designed based on their PIL tunability and synthesised by reversible additions fragmentation chain transfer (RAFT) polymerisation. In first place, the ionic nature of the NHC precatalyst was exploited by triggering the interaction between imidazolium derivatives and basic anions supported in the polymer leading to a ionically cross-linked SCNP. Secondly, the thermolatent properties of NHC precursors was harnessed by proving the compatibility of both substrates and precatalyst supported on the same polymer chain and triggering the folding by condensing the substrates by the simple application of heat. Finally, the intrinsic capacity of poly(NHC)s to act as poly-ligands was innovatively demonstrated by forming SCNPs after organometallic complexation using a silver salt. Overall, the different polymeric supports have served to highlight different aspects related to the catalytic performance of supported catalysts such as recycling, confinement effect, nanoreactor scaling up processes, NHC catalysts versatility as well as the adaptability of these systems for enabling and easy and efficient handling and storage.
| Item Type: | Thesis [via Doctoral College] (PhD) |
|---|---|
| Alternative Title: | Synthèse de nouvelles nanoparticules composées de chaines uniques basé sur de carbènes N-hétérocycliques comme de nanoréacteurs catalytiquement actifs |
| Subjects: | Q Science > QD Chemistry R Medicine > RS Pharmacy and materia medica T Technology > TP Chemical technology |
| Library of Congress Subject Headings (LCSH): | Nanoparticles -- Synthesis, Carbenes (Methylene compounds), Biocatalysis |
| Official Date: | 22 January 2020 |
| Dates: | Date Event 22 January 2020 UNSPECIFIED |
| Institution: | University of Warwick |
| Theses Department: | Department of Chemistry |
| Thesis Type: | PhD |
| Publication Status: | Unpublished |
| Supervisor(s)/Advisor: | Dove, Andrew P. ; Taton, Daniel ; O'Reilly, Rachel K. |
| Sponsors: | European Commission |
| Format of File: | |
| Extent: | 253 leaves : illustrations (some colour) |
| Language: | eng |
| URI: | https://wrap.warwick.ac.uk/149545/ |
Request changes or add full text files to a record
Repository staff actions (login required)
 |
View Item |