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Influence of Calcium Ions on Rhamnolipid and Rhamnolipid/Anionic Surfactant Adsorption and Self-Assembly
journal contribution
posted on 2013-03-26, 00:00 authored by Minglei Chen, Chuchuan Dong, Jeff Penfold, Robert K. Thomas, Thomas J. P. Smyth, Amedea Perfumo, Roger Marchant, Ibrahim M. Banat, Paul Stevenson, Alyn Parry, Ian Tucker, I. GrilloThe impact of Ca2+ counterions
on the adsorption at
the air–water interface and self-assembly in aqueous solution
of the rhamnolipid biosurfactant and its mixture with the anionic
surfactant sodium dodecylbenzenesulfonate, LAS, has been studied using
neutron reflectometry and small-angle neutron scattering. The results
illustrate how rhamnolipids are calcium tolerant and how their blending
with conventional anionic surfactants improves the calcium tolerance
of the anionic surfactant. Ca2+ has relatively little effect
upon the adsorption and self-assembly of the monorhamnose, R1, and
dirhamnose, R2, rhamnolipids, even at high pH, due to their predominantly
nonionic nature. For R1/R2 mixtures the addition of Ca2+ has little impact upon the adsorbed amount or the surface composition.
For R2/LAS mixtures the addition of Ca2+ results in an
increased adsorption and a surface slightly richer in R2. The weak
binding of Ca2+ to R1 and R2 does result in a change to
the degree of ionization of the micelles and especially for mixed
R1/R2 micelles at R1-rich solution compositions. The stronger binding
of Ca2+ to LAS results in the addition of Ca2+ having a much greater impact on the self-assembly of R1/LAS and
R2/LAS mixtures. For R1/LAS mixtures the addition of Ca2+ promotes the formation of more planar structures, even at low surfactant
concentrations where in the absence of Ca2+ mixed globular
micelle formation dominates. In R2/LAS mixtures, where there is a
greater contrast between the high and low preferred curvatures associated
with R2 and LAS, the addition of Ca2+ results in a more
complex evolution in micellar aggregation and the degree of ionization
of the micelles. This results in variations in Ca2+ binding
that promotes micellar structures in which a spatial segregation of
the two surfactant components within the micelle occurs.