Molecular level understanding of supramolecular gels

Supramolecular gels are complex materials which have an expanding scope of industrial and biomedical applications, due to their unique viscoelastic properties, high biocompatibility and possibility of functionalisation. The hierarchical structure of molecular materials combines domains with drastically different degrees of ordering and molecular mobility. This makes their full characterisation a significant methodological and experimental challenge. The focus of this work was therefore the understanding of a variety of supramolecular semicrystalline gels in which very rigid solid components coexist with a dynamic and highly mobile solution phase. Using the examples of amino acid and urea-derivatives gelators, control of the self-assembly processes was successfully gained and tuning of the mechanical properties of the resulting materials by incorporating molecular structure modifications or introducing a variety of structurally diverse additives was achieved. Modification of the structure of the gel fibres was observed, which modulated the dynamic properties of the gel/solution interfaces and dictated the overall behaviour of the system, an aspect which is not commonly investigated in molecular gels. The resulting single and multi-component gels were used as model materials for the development of an NMR-based general strategy capable of probing the several hierarchical levels present. The multiphasic character of molecular gels required the combined use of solid, solution-state and HR-MAS NMR methods. This project has expanded the understanding of saturation transfer difference NMR experiments, with special focus in their applicability and limitations for the study of supramolecular soft systems. This approach was validated using complementary techniques, more specifically, rheology, microscopy, X-ray diffraction and computational methods. By combining molecular level understanding and measurements of the bulk properties, a methodology which can be applied to other soft materials used in pharmaceutical, biomedical and food science applications was developed. Moreover, this approach might have a generic impact in different fields of science and technology, enabling one to direct the recognition and host-guest properties of soft solids, which is essential for their targeted applications