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Abstract: We report a new 3D-ordered liquid-crystal (LC) phase where alkyl and fluoroalkyl side-chains are confined within separate stretched octahedral cages of a tetragonal framework with struts of aromatic rods held together by their hydrogen-bonded ends acting as flexible hinges. This is the first example of a multicolor micellar LC heralding the development of soft and dynamic dual-compartment frameworks, also capable of a martensitic-type phase transition.

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Abstract: Polymer electrolyte membranes composed of ionic liquids (IL), capable of conducting protons efficiently at elevated temperatures, without external humidification, could transform fuel cell technology. However, the molecular origins of such proton transport remain poorly understood, especially in the polymerized state. Here, we directly visualize a hierarchy of coupled elementary proton motion steps spanning picosecond to nanosecond timescales in polyIL membranes using pulse field gradient (PFG) NMR and multi-resolution quasi-elastic neutron scattering (QENS). Polymer dynamics comprise three-site jumps within methanesulfonate coordination shells, two-site hops along hydrogen-bond chains, and out-of-plane backbone flips which dynamically reconfigure the proton transfer pathway. The latter facilitates a correlated polymer-proton hopping mechanism above 60°C enabling rapid nano- and microscale proton transport at operational temperatures. Even trace water plasticizes the polymer and remarkably lowers this proton hopping barrier by nearly half. A critical transition occurs near 245 K, where water forms a continuous hydrogen-bonded network of acid-base pairs, enabling sub-10 ps Grotthuss proton hopping, approaching liquid water dynamics. This molecular-level understanding provides fundamental insight into polyIL conduction mechanisms and the long-standing question of how solid polymers achieve liquid-like proton mobility, providing a roadmap for polyILs in next-generation electrochemical energy technologies.

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Abstract: The transition to sustainable electronics requires electroactive materials that are processable in green solvents, operationally stable, and recyclable or recoverable at their end of life. This work explores recoverable electroactive cellulose coatings using a carboxylate-functionalized polar polythiophene (PCAT-K). PCAT-K is water-processable and can be reversibly fixated onto cellulose threads by modulation of the secondary interactions via acid–base chemistry, showing promise for circular material use. To obtain electrically conducting PCAT-K-cellulose threads, acid-mediated oxygen doping of the PCAT-K with p-toluenesulfonic acid was explored but led to undesired covalent cross-linking and loss of solubility and recoverability. Through spectroscopic and electrochemical analyses, it is shown that the covalent cross-linking originates from hydrogen peroxide generation during the doping process, which further reacts with PCAT to form hydroxyl radicals. To suppress radical formation, potassium iodide is introduced as a benign additive that catalytically decomposes hydrogen peroxide, preventing covalent cross-linking while maintaining electrical conductivity and recoverability. While the additive can negatively affect cellulose substrates at long doping times, this strategy allows for stable, conductive, and removable electroactive coatings on cellulose threads using water as the sole solvent. This study highlights a more reliable synthetic route to the water-processable conjugated polymer PCAT-K and suggests a mechanistic origin of acid-mediated oxygen doping-induced covalent cross-linking with a practical strategy to overcome it.

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Abstract: Supramolecular soft materials derived from low molecular weight gelators (LMWG) have been widely prepared using pH-switching strategies, in which the method of inducing the pH change plays a critical role in determining material properties and applications. In this thesis, three distinct pH-switching approaches were explored. Although each approach relies on a change in pH, it has been demonstrated that they produce materials with significantly different behaviours, structures, and functionalities. In chapter 2, plasma-induced gelation was investigated as a novel route for the in situ fabrication and 3D printing of supramolecular hydrogels. It was demonstrated that cold atmospheric plasma enables precise spatial and temporal control over gelation, allowing the formation of complex, patterned, and multilayered structures with defined geometries. Studies using Kineticolor showed that gelation is driven by plasma-induced pH changes. It was further demonstrated that this approach can be combined with the in situ formation of gold nanoparticles, enabling the fabrication of composite hydrogels with enhanced functionality. In Chapter 3, transient pH-switching systems were explored by combining a urea/urease reaction with formate hydrolysis in DMSO/H₂O hydrogel systems. The scope of the system was expanded by incorporating a range of LMWGs, and it was demonstrated that variation of the ester component, including methyl, ethyl, and n-propyl formate, allows control over hydrolysis rates and thus temporal behaviour. The effects of temperature and ageing were also investigated, revealing complex, non-linear, and sometimes unpredictable dynamics that are important for practical applications. In chapter 4, these pH triggers were further applied to a lipid-based system, where it was demonstrated that they can induce and control phase transitions in a monoolein-oleic acid mixture. Using flow-through small-angle X-ray scattering transitions, including Pn3m-to-HII, HII-to-Im3m, and HII-to-Im3m-to-HII, were successfully realised. It was shown that these nanoscale structural changes significantly influence the macroscopic properties of the materials, highlighting the versatility of transient pH control across different supramolecular systems. Finally, in chapter 5, electrochemically induced gelation and polymerisation of carbazole-functionalised amino acid-based hydrogels were investigated. In situ electrochemical small-angle X-ray scattering was used to examine the dynamic processes of self-assembly and polymerisation, showing how subtle molecular changes govern structural evolution and material properties. Overall, this thesis demonstrates that the choice of gelation method enables tailoring of material structure, dynamics, and functionality across multiple length scales.

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Abstract: Recent studies have highlighted the limitations of conventional high degrees of PEGylation in drug delivery systems, including immune recognition and reduced efficacy. Approaches such as poly(ethylene glycol) (PEG) isomerization and shortening of PEG chains have emerged as strategies to mitigate anti-PEG immune responses while preserving key physicochemical properties required for drug delivery. Inspired by these advancements, this study aims to enzymatically synthesize new hybrid polymers incorporating a limited fraction of PEG and biosourced polyols, such as glycerol and diglycerol, as the hydrophilic counterpart, minimizing the amount of PEG by 50% (compared to our previous work). These novel adipate-based tetrapolymers, generated using four different starting materials, outperformed previous systems, offering a tunable and sustainable design for nanomedicine. By strategically limiting the PEG fraction, we preserved the functional benefits of PEGylation, including stealth and amphiphilicity, while advancing toward greener chemistry. The resulting biodegradable PEGylated polyesters were formulated from film rehydration of solid dispersions and increased the water solubility of the model drug curcumin via direct encapsulation of the compound in polymeric nanoparticles. The best performing polymer variant consisted of diglycerol, 1,6-hexanediol, and PEG combined with divinyl adipate (PEGDGA-Hex 50%). Its drug interactions, colloidal stability, biodegradability, and biocompatibility, in both in vitro (Caco2, human intestinal epithelial cells MCF-7, human breast cancer cells, and MDA-MB-231 late-stage triple-negative breast cancer cells) and invertebrate in vivo models that align with 3R principles (Caenorhabditis elegans and Drosophila melanogaster), support its potential use in systemic drug delivery.