Symbiotic Supramolecular Chemistry - The Development of Smart Soaps

Supramolecular chemistry is continually being explored, applied and expanded in many countries all overthe world. The complexity of this area of science means that it is continually researched.This study has demonstrated the importance of the self-assembly between surfactants structuresand supramolecular aggregation. Within this thesis the design, synthesis, characterization and bindingproperties of five amphiphilic molecules are discussed. These molecules were investigated in the gaseousphase, solid and solution states by a variety of complementary analytical techniques with the resultsdemonstrating that the anionic monomers have a propensity to self-associate into a variety of aggregatedspecies.A selection of 1H and DOSY NMR experiments were conducted in DMSO-d6, providing evidencethat these molecules tend to form dimeric rather than larger aggregated species. The presence ofhydrogen bonding was further confirmed by 1H NMR self-association studies, showing a down fieldchange in chemical shift due to both the urea NH. The data when fitted to dimerization/Equal K (EK)binding model showed that the dimerization constant increases in line with the increase of aromaticsubstituents. By direct observation it was established that the sulfonate-anion molecules self-associatedthrough intermolecular hydrogen bonds to form aggregated species of either irregular or spherical shapein solution. The size and type of these species was both concentration, and solute dependent. CMC valuesand dimerization constants correlated well with the computationally derived Emax and Emin values, givingpreliminary evidence that self-association properties may be predicted by low level computationalmodelling methods. This innovative, cohesive branch of supramolecular chemistry will revolutionise thestudy and scope of non-covalent interactions beyond the molecule.