Molecular segregation and aggregate shape in a lyotropic rectangular phase

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Abstract
The microstructure of the rectangular phase in the system sodium decylsulphate/decanol/water is investigated by means of deuterium NMR. By analysing the lineshape from selectively deuteriated decylsulphate and decanol, we separate the effects of (i) the shape anisotropy of the aggregate cross-section and (ii) the inhomogeneous distribution of the two surfactants within the aggregate. The aspect ratio of the cross-section is determined to 1.39±0.01, substantially smaller than previous estimates. We find no evidence for anisotropic growth of the aggregate cross-section in the hexagonal phase, as previously suggested. Rather, the aggregate shape appears to change abruptly at the hexagonal-rectangular phase transition with little change (with temperature) thereafter. The distribution of decylsulphate and decanol within the aggregates of the rectangular phase is highly non-uniform; the decanol concentration is 3 times higher in the central lamellar region than in the curved edges, while the decylsulphate accumulates in the curved regions. This molecular segregation can be rationalized in terms of electrostatic interactions within and between the aggregates.