Intermolecular forces and scaling relations between heterogeneous macromolecular surfaces

Most theories regarding the behavior of intermolecular forces assume perfectly smooth surfaces with well-defined chemical and material properties. In this thesis, three separate systems are studied to explore the accuracy of this assumption in very different situations. In the first system, the effects of milli-molar amounts of dissolved gas (the amount typically present in normal atmospheric conditions) have been studied at a pristine oil/water interface. It was found that the removal of the dissolved gas significantly increased the lifetime of the oil droplets, effectively reducing the long-range hydrophobic attractive force present under standard conditions.; In the second system, the effect of varying normal and lateral roughness of solid surfaces in understanding the long-range steric forces and shorter-range adhesive (van der Waals) forces are studied. Various techniques to reproducibly control and vary the roughness were developed for a number of different types of polymeric surfaces. A strong correlation between the roughness and the repulsive steric force was observed for randomly rough surfaces. Similar scaling relations between the roughness and the magnitude of the adhesive force were measured. Friction measurements between these surfaces show that even a few nanometers of roughness significantly reduces the critical shear stress required to initiate sliding. However, the coefficient of friction was relatively unaffected by the range of roughness considered, in agreement with the macroscopic Amontons' law.; The third and final system dealt with the properties of adsorbed layers of polyampholytes (containing both positively and negatively charged groups), as opposed to the more common classes of neutral polymers or polyelectrolytes. These measurements took advantage of a naturally occurring family of proteins (a class of polyampholytes), known as tau, which exist in six different well-defined lengths and charge densities. Force measurements were made with a Surface Forces Apparatus (SFA) in various ionic solution conditions, combined with high resolution imaging by an Atomic Force Microscope (AFM). Scaling relations between the magnitude and range of the total interaction force are shown depending on the total length as well as the relative ratio of positive to negative groups along the backbone of the macromolecule.