Functional cavitands as artificial enzymes: bridging computational and synthetic strategies for supramolecular catalysis and beyond
ENG- To address the limitations hindering the broader adoption of functional and expanded cavitands, this thesis combines computational studies, synthetic refinement, and novel application-driven design strategies. A central focus was placed on understanding cavitand flexibility and host-guest inter...
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| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | CBUC, CESCA |
| Repositorio: | TDR. Tesis Doctorales en Red |
| OAI Identifier: | oai:www.tdx.cat:10803/695484 |
| Acceso en línea: | http://hdl.handle.net/10803/695484 |
| Access Level: | acceso embargado |
| Palabra clave: | Química orgànica Química orgánica Organic chemistry Química supramolecular Supramolecular chemistry Receptors artificials Receptores artificiales Artificial receptors Cavitands funcionals Cavitandos funcionales Functional cavitands Disseny racional Diseño racional Rational design Catàlisi bioinspirada Catálisis bioinspirada Bioinspired catalysis Simulacions de dinàmica molecular Simulaciones de dinámica molecular Molecular dynamics (MD) simulations 547 |
| Sumario: | ENG- To address the limitations hindering the broader adoption of functional and expanded cavitands, this thesis combines computational studies, synthetic refinement, and novel application-driven design strategies. A central focus was placed on understanding cavitand flexibility and host-guest interactions through Molecular Dynamics simulations, which offered a deeper view of their behavior in solution and enabled the prediction of guest affinities—especially valuable for a new family of highly flexible calix[5]arene-based systems. Concurrently, synthetic strategies were revisited to enhance accessibility and functional diversity. Key intermediates in traditional routes were optimized to facilitate access and improve yields towards functional cavitands, while a more practical and safer pathway was developed for acridane[4]arene-derived expanded cavitands. Building on these advances, the catalytic potential of cavitands was explored through terpene cyclizations, demonstrating that even a simple functional receptor could promote selective transformations, favoring terpene formation despite its thermodynamic disadvantage. Finally, the lessons gathered throughout this work informed the development of a rational design strategy, integrating enzymatic inspiration with computational and synthetic tools. This new tool was exemplified with the design of de novo thiourea-bearing cavitands tailored for bioinspired catalysis. Together, these contributions help unlock the untapped potential of cavitands as versatile platforms in supramolecular chemistry and bioinspired catalysis, demonstrating that well-designed synthetic systems will soon begin to rival the precision and elegance of natural enzymes |
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