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Langmuir. 2007 May 22;23(11):5906-13. Epub 2007 May 1.

Interactions of a hydrophobically modified polymer with oppositely charged surfactants.

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NSF IUCR Center for Advanced Studies in Novel Surfactants, Langmuir Center for Colloid and Interfaces, Columbia University, 3000 Broadway, New York, New York 10027, USA.


The interaction of a hydrophobically modified anionic polymer (PMAOVE) with a cationic surfactant (DTAB) was studied using a multi-technique approach: turbidity, surface tension, and viscosity measurements, as well as EPR (5-doxyl stearic acid) and fluorescence (pyrene) probe techniques were used. In the investigated pH range (4-10), the cationic surfactant headgroups interact with the anionic carboxylic groups of the polymer backbone. In addition, nonpolar interactions of the surfactant chains with the n-octyl chains of PMAOVE stabilize the PMAOVE-DTAB complexes. Charge neutralization of the anionic polymer by the cationic surfactant leads to precipitation of the PMAOVE-DTAB complex at a certain DTAB concentration range. Further addition of DTAB causes a charge reversal of the complex and, subsequently, resolubilization of the precipitate. At an acidic pH (pH = 4), a second precipitation was observed, which is probably caused by conformational changes in the PMAOVE-DTAB complex. This second precipitate can be resolubilized by further addition of surfactant. At a neutral and basic pH, this second precipitation is absent. EPR analysis indicates that the surfactants form an ordered structure at the extended polymer chain at a neutral and basic pH, whereas at an acidic pH, a less ordered surfactant layer is formed on the coiled polymer with more hydrophobic microdomains.

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