Increased environmental pressures and awareness is promoting a major drive towards an increased use of biosurfactants to produce more biosustainable and biodegradable consumer products, in home and personal care products, cosmetics and foodstuffs. There is also an accompanying strong drive towards new structures and functionalities. Recent NR studies on the highly surface active hydrophobin and the food grade polysorbate surfactant (Tween) mixtures show spectacular surface multilayer formation and a different control of wetting properties. We propose to explore how these structures can be controlled and manipulated by changing the Tween headgroup structure.