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Complexation of Amphiphilic Polyelectrolytes with Surfactants of the Same Charge in Water Solutions

Bakeev, Kirill N. and Ponomarenko, Ekaterina A. and Shishkanova, Tat'yana V. and Tirrell, David A. and Zezin, Alexander B. and Kabanov, V. A. (1995) Complexation of Amphiphilic Polyelectrolytes with Surfactants of the Same Charge in Water Solutions. Macromolecules, 28 (8). pp. 2886-2892. ISSN 0024-9297. doi:10.1021/ma00112a039.

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Aqueous solutions containing amphiphilic polycations and micelle-forming surfactants of the same charge were examined by potentiometric, fluorescence, sedimentation, and viscometric techniques. Copolymers containing N-ethyl-4-vinylpyridinium bromide units and relatively small numbers of either N-dodecyl-4-vinylpyridinium bromide or N-cetyl-4-vinylpyridinium bromide units were used as amphiphilic polycations. The surfactants were dodecyl- and cetyltrimethylammonium bromides and their pyridinium analogs. The formation of copolymer-surfactant complexes in dilute solution was established, and the complexation behavior was shown to depend upon the copolymer to surfactant concentration ratio in the mixture. At surfactant concentrations lower than or equal to the critical micelle concentration (cmc) complexation leads to compact structures via formation of intrachain aggregates containing several hydrophobic chain units and surfactant molecules. At the cmc, the maximum number of surfactant ions bound per hydrophobic copolymer chain unit increases with increasing length of the polymer side group and decreases for copolymers that are initially in the compact conformation. At surfactant concentrations greater than the cmc the intrachain aggregates are disrupted and copolymer coil expansion occurs. The resultant copolymer-surfactant complexes consist of surfactant micelles, each bound to one hydrophobic chain unit of the copolymer.

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Tirrell, David A.0000-0003-3175-4596
Additional Information:© 1995 American Chemical Society. Received August 23, 1994; Revised Manuscript Received January 24, 1995. Abstract published in Advance ACS Abstracts, March 1, 1995. We thank N. V. Shvedene (Department of Analytical Chemistry, Chemistry Faculty, Moscow State University) for help with the potentiometry technique. We thank the Russian Fund for Fundamental Research (Project Code 93-03-5998) and NSF (additional grant to Grant DMR-8914359) for financial support of this work.
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Russian Fund for Fundamental Research93-03-5998
Issue or Number:8
Record Number:CaltechAUTHORS:BAKm1995
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Official Citation:Complexation of Amphiphilic Polyelectrolytes with Surfactants of the Same Charge in Water Solutions Kirill N. Bakeev, Ekaterina A. Ponomarenko, Tat'yana V. Shishkanova, David A. Tirrell, Alexander B. Zezin, and V. A. Kabanov Macromolecules 1995 28 (8), 2886-2892
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53479
Deposited By: Anne Hormann
Deposited On:29 Jan 2015 22:00
Last Modified:10 Nov 2021 20:02

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