Molecular variations in aromatic cosolutes: critical role in the rheology of cationic wormlike micelles.

Autor: Ito TH; Department of Physical-Chemistry, Institute of Chemistry and ‡Department of Organic-Chemistry, Institute of Chemistry, University of Campinas-UNICAMP P.O. Box 6154, 13084-862, Campinas, SP Brazil., Miranda PC, Morgon NH, Heerdt G, Dreiss CA, Sabadini E
Jazyk: angličtina
Zdroj: Langmuir : the ACS journal of surfaces and colloids [Langmuir] 2014 Oct 07; Vol. 30 (39), pp. 11535-42. Date of Electronic Publication: 2014 Sep 25.
DOI: 10.1021/la502649j
Abstrakt: Wormlike micelles formed by the addition to cetyltrimethylammonium bromide (CTAB) of a range of aromatic cosolutes with small molecular variations in their structure were systematically studied. Phenol and derivatives of benzoate and cinnamate were used, and the resulting mixtures were studied by oscillatory, steady-shear rheology, and the microstructure was probed by small-angle neutron scattering. The lengthening of the micelles and their entanglement result in remarkable viscoelastic properties, making rheology a useful tool to assess the effect of structural variations of the cosolutes on wormlike micelle formation. For a fixed concentration of CTAB and cosolute (200 mmol L(-1)), the relaxation time decreases in the following order: phenol > cinnamate> o-hydroxycinnamate > salicylate > o-methoxycinnamate > benzoate > o-methoxybenzoate. The variations in viscoelastic response are rationalized by using Mulliken population analysis to map out the electronic density of the cosolutes and quantify the barrier to rotation of specific groups on the aromatics. We find that the ability of the group attached to the aromatic ring to rotate is crucial in determining the packing of the cosolute at the micellar interface and thus critically impacts the micellar growth and, in turn, the rheological response. These results enable us for the first time to propose design rules for the self-assembly of the surfactants and cosolutes resulting in the formation of wormlike micelles with the cationic surfactant CTAB.
Databáze: MEDLINE