Interfacial ordering of tristearin induced by glycerol monooleate and PGPR: A coarse-grained molecular dynamics study

We use coarse-grained molecular dynamics simulations to study the effect of surfactant structure on the ordering of bulk tristearin at an oil-water interface. In the absence of surfactant, tristearin acyl chains are marginally aligned normal to the interface. The surfactant glycerol monooleate (GMO), a common small-molecule monoacylglycerol (MW: 357 g/mol), preferentially adsorbs to the oil-water interface, displacing more of the tristearin as its concentration increases. The tristearin that remains at the interface is closely aligned normal to the interface. Adjacent to the interface, bulk tristearin increasingly aligns with its acyl chains entwined with the GMO acyl chain, which also preferentially aligns normal to the interface. In contrast, polyglycerol polyricinoleate (PGPR), a bulkier, polymeric surfactant (MW: 1398 g/mol for a molecule with five monomers), both displaces tristearin from the interface and reduces the alignment of the molecules that remain. We suggest that the similar fatty acid moieties of GMO (oleic acid) and tristearin (stearic acid) lead to liquid-state association and alignment, the latter of which can then serve as a template onto which tristearin crystals can nucleate. Conversely, by both displacing tristearin from the interface and reducing alignment below that of the surfactant-free system, PGPR eliminates the possibility of tristearin interfacial crystallisation.