Journal
LANGMUIR
Volume 31, Issue 26, Pages 7242-7250Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.langmuir.5b01280
Keywords
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Funding
- Hungarian Scientific Research Fund [OTKA K 108646]
- COST Action project of the European Commission [CM1101]
- [NanoS3-290251 ITN]
- Novo Nordisk Fonden [NNF13OC0006627] Funding Source: researchfish
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The soluble complexes of oppositely charged macromolecules and amphiphiles, formed in the one-phase concentration range, are usually described on the basis of the beads on a string model assuming spherelike bound surfactant micelles. However, around and above the charge neutralization ionic surfactant to polyion ratio, a variety of ordered structures of the precipitates and large polyion/surfactant aggregates have been reported for the different systems which are difficult to connect to globular-like surfactant self-assembly units. In this article we have demonstrated through SAKS measurements that the structure of precipitates and those of the soluble polyion/mixed surfactant complexes of poly(diallyldimethylammonium chloride) (PDADMAC), sodium dodecyl sulfate (SDS), and dodecyl-maltoside (DDM) are strongly correlated. Specifically, SDS binds to the PDADMAC molecules in the form of small cylindrical surfactant micelles even at very low SDS-to-PDADMAC ratios. In this way, these anisometric surfactant self-assemblies formed in excess polyelectrolyte mimic the basic building units of the hexagonal structute of the PDADMAC/SDS precipitate and/or suspensions formed at charge equivalence or at higher SDS-to-PDADMAC ratios. The presence of DDM reduces the cmc and cac for the system but does not alter significantly the structure of the complexes in either the one-phase or two-phase region. The only exception is for samples at SDS-to-PDADMAC ratios close to charge neutralization and a high concentration of DDM where the precipitate forms a multiphasic or distorted hexagonal structure.
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