Final Report Summary - ADAPTPOLY (Adaptive polymer assemblies) Within this project, the grantee has established his fully independent Supramolecular Chemistry Research group at Ghent University, which has grown from 5 researchers at the start of the project to ~ 20 today. Within this time period, the grantee has been fully integrated in the Department of Organic and Macromolecular Chemistry, Faculty of Sciences, where he has a permanent position. Furthermore, the grantee has been promoted to Full Professor per October 2014 and the initial 5-year research professorship has been elongated for another five years up to 2020 after which it will be converted into a regular professorship.Scientific progress of the project has been made in all three proposed research lines as outlined in the following:1. Hierarchical Supramolecular MaterialsWithin this research topic, we have been working on the synthesis of novel supramolecular binding units, based on cyclodextrins and porphyrins. Functional derivatives (both new structures and novel compounds) have been prepared to investigate the hierarchical self-assembly of these structures. Furthermore, we have been working on the combination of stimuli-responsive polymers and host-guest complexation to gain kinetic control over the supramolecular assembly process. Importantly, this has enabled the development of polymeric temperature sensors with memory function, whereby the memory function.2. Supramolecular Self-Healing MaterialsPolymers bearing supramolecularly interacting units have been designed and synthesized. Initial successful results on self-healing ability demonstrate that the chosen approach based on electrostatically interacting moieties in triblock copolymers can indeed lead to supramolecular self-healing thermoplastic elastomers. Detailed structure-morphology-property relationships have been identified in these novel class of supramolecular materials.3. Smart NanoparticlesPolymers that undergo a solution phase transition in water based on variation of pH, temperature and sugar concentration have been developed, whereby the polymer phase transition was translated into a visual output by incorporation of solvatochromic dyes.Secondly, the combination of thermoresponsivity and pH-degradability has attracted our attention as it would allow aqueous assembly of drug loaded nanoparticle and protein conjugation, whereby the polymers are soluble at low temperature and assembly at body temperature. Introducing pH degradability is important to trigger disassembly at slightly lower pH values as occurs in the presence of solid tumors as well as during endocytosis. This dual responsivity was obtained through copolymerization of an acetal monomer with a thermoresponsive monomer allowing accurate fine-tuning of the transition temperatures as well as the pH-degradability.Thirdly, the combination of gold nanoparticles (AuNPs) with thermoresponsive polymers was explored allowing the development of multiresponsive systems. An important discovery that was made is that ligand exchange from citrate to a thiol-functionalized thermoresponsive polymers leads to both polymer and citrate on the surface of the AuNPs leading to temperature and slat responsive systems, that could be exploited as logic AND gates.
