The strong interaction between polyamines and anionic surfactants results in pronounced adsorption at the air-water interface and can lead to the formation of layered surface structures. The transition from monolayer adsorption to more complex surface structures depends upon solution pH, and the structure and molecular weight of the polyamine. The effects of manipulating the polyamine molecular weight and structure on the adsorption of the anionic surfactant sodium dodecyl sulphate at the air-water interface are investigated using neutron reflectivity and surface tension, for the biogenic amines putrescine, spermidine and spermine. The results show how changing the number of amine groups and the spacing between the amine groups impacts upon the surface adsorption. At lower pH, 3-7, and for the higher molecular weight polyamines, spermidine and spermine, ordered multilayer structures are observed. For putrescine at all pH and for spermidine and spermine at high pH, monolayer adsorption with enhanced surfactant adsorption compared to the pure surfactant is observed. The data for the biogenic amines, when compared with similar data for the polyamines ethylenediamine, diethylenetriamine and triethylenetetramine, indicate that the spacing between amines groups is more optimal for the formation of ordered surface multilayer structures. (C) 2014 Elsevier Inc. All rights reserved.