PROTON TRANSPORT AT THE MONOLAYER-WATER INTERFACE

It is shown that when monolayers of stearic acid, palmitic acid, DPPC, or DPPS are compressed above some critical area A(c) a lateral conduction mechanism is initiated at the monolayer/water interface. The interfacial conductance increases on further increasing the molecular packing density in the monolayer. All compounds also show major changes in surface potential at A(c) the potential becoming more positive in all cases. It is argued that this is a consequence of structural reorganisation at the headgroup/water interface causing a significant reduction in the local permittivity. The critical area, A(c), is approximately double the molecular areas estimated from the pressure-area isotherm, and experiments with stearic acid monolayers show that A(c) decreases significantly when the chaotropic ion SCN-, which is known to disrupt the molecular structure of water, is added to the subphase. It is likely, therefore, that the structural changes occurring at A(c) involve the formation of a hydrogen bonded network between monolayer headgroups and adjacent water molecules at the monolayer/water interface. It is suggested that the conduction mechanism initiated at A(c) arises from proton hopping along this hydrogen-bond network.