Energetics: the fundamental thermodynamic parameters of molecular complexation via electrostatic interactions in water

The thermodynamic parameters that govern the molecular recognition phenomena continue to be a significant area of interest. As a molecular complex forms through non-bonded interactions, quantification of the fundamental enthalpy and entropy changes that occur, offer a more comprehensive understanding of the process. The research presented here specifically explores the energetics of host-guest complexes that form through electrostatic interactions in water at neutral pH. Chapter 1 provides an introduction to molecular recognition and the binding forces that promote binding. Chapter 2 details extensive studies involving phosphate binding to two metalloreceptors; entropy changes are the dominant driving force. In Chapter 3 we report studies focused on determining the thermodynamic origin of cooperative binding; we report the presence of negative cooperativity having entropy as its origin. Chapter 4 is comprised of extensive investigations into the formation of 1:1 host/guest complexes as well as higher ordered complexes. The predominance of either complex results in different thermodynamic profiles.