ED Sciences Chimiques
Synthesis of Single-Chain Nanoparticles for Catalysis and Sensing
by Jokin PINACHO OLACIREGUI (Laboratoire de Chimie des Polymères Organiques)
The defense will take place at 11h00 - Auditorium Paseo Manuel de Lardizabal, 5, 20018, Donostia – San Sebastián (Gipuzkoa) – SPAIN
in front of the jury composed of
- Maria PAULIS - Professeure - Polymat (UPV/EHU) - Examinateur
- Guillaume FLEURY - Professeur - LCPO - Organic Polymer Chemistry Laboratory - Examinateur
- Alexander BITTNER - Research Professor - CIC Biomagune - Rapporteur
- Jaime MARTIN - Docteur - Universidad de Coruña - Rapporteur
- Berta GOMEZ-LOR - Docteure - ICMM-CSIC - Examinateur
This thesis explores the design, synthesis, and applications of Single-Chain Nanoparticles (SCNPs), focusing on their integration with metallic elements for sensing and catalysis. SCNPs, formed by the folding and intramolecular cross-linking of single polymer chains, exhibit unique properties such as high surface area, tunable size, and encapsulation capabilities, making them promising for nanomedicine, catalysis, and material science. Chapter 1 provides an overview of SCNP formation, properties, and applications, setting the stage for the research. The study aims to enhance SCNP functionalities by incorporating metals like lanthanides (Eu, Tb, Dy), gold, platinum, and copper, leveraging their electronic, surface, and optical properties to improve catalytic and sensing performance. For instance, gold enhances electron transfer, platinum offers robust catalytic activity, and lanthanides enable sensitive environmental sensing. Chapter 2 focuses on synthesizing water-soluble lanthanide-containing SCNPs for visual sensing of Cu²⁺ ions in drinking water. These SCNPs, incorporating Eu, Tb, and Dy, exhibit distinct fluorescence color changes under UV light upon Cu²⁺ binding, enabling a simple visual test for copper levels. The synthesis involves an amphiphilic random copolymer with β-ketoester groups that complex lanthanides, forming water-soluble SCNPs. Characterization via SEC, DLS, ICP-MS, and fluorescence spectroscopy confirms successful SCNP formation and Cu²⁺ sensitivity. The results demonstrate the potential of lanthanide-based SCNPs as easy-to-use sensors for environmental monitoring, particularly for ensuring safe drinking water. Chapter 3 explores the synthesis of gold nanoclusters (Au-NCs) within SCNPs, mimicking metalloenzyme activity for aqueous catalysis. Using an amphiphilic copolymer, Au-NCs smaller than 5 nm are encapsulated within SCNPs, with β-ketoester groups acting as reductants and stabilizers. Characterization via TEM, DLS, and UV-Vis spectroscopy confirms stable Au-NC/SCNP formation. These nanostructures serve as catalytic nanoreactors for reducing nitro compounds in water, showcasing their potential in catalysis, biomedicine, and energy applications. This work highlights the promise of metal nanocluster-integrated SCNPs for advanced catalytic systems. Chapter 4 introduces heterobimetallic Pt(II)/Cu(II)-SCNPs for catalysis, utilizing photoactivated carbene generation and metal complexation to fold the polymer into nanoparticles. These SCNPs demonstrate high efficiency in one-pot alkyne semi-hydrogenation and alkene dioxygenation reactions, conducted in a green solvent, N-butylpyrrolidone. This approach aligns with green chemistry principles, minimizing toxic solvent use and enhancing sustainability. The study advances catalytic science by developing efficient, environmentally friendly nanocatalysts, with implications for organic synthesis and industrial processes. Overall, this thesis advances SCNP research by integrating metals to enhance their catalytic and sensing capabilities, contributing to nanotechnology, materials science, and green chemistry. The findings open new avenues for SCNP applications in environmental monitoring, catalysis, and sustainable industrial processes.