Polymer–vesicle association Filipe E. Antunes a, ⁎, Eduardo F. Marques b , Maria G. Miguel a , Björn Lindman a,c a Chemistry Department, University of Coimbra, 3004-535 Coimbra, Portugal b Centro de Investigação em Química, Department of Chemistry, University of Porto, Rua do Campo Alegre, n° 687, P-4169-007 Porto, Portugal c Physical Chemistry 1, Center for Chemistry and Chemical Engineering, Lund University, P.O. Box 124, SE-22100 Lund, Sweden abstract article info Available online 21 October 2008 Keywords: Vesicles Polymer–vesicle association Lipid vesicles Liposomes DNA Mixed polymer–surfactant systems have been intensively investigated in the last two decades, with the main focus on surfactant micelles as the surfactant aggregate in interaction. The main types of phase behavior, driving forces and structural/rheological effects at stake are now fairly well understood. Polymer–vesicle systems, on the other hand, have received comparatively less attention from a physico-chemical perspective. In this review, our main goal has been to bridge this gap, taking a broad approach to cover a field that is in clear expansion, in view of its multiple implications for colloid and biological sciences and in applied areas. We start by a general background on amphiphile self-assembly and phase separation phenomena in mixed polymer–surfactant solutions. We then address vesicle formation, properties and stability not only in classic lipids, but also in various other surfactant systems, among which catanionic vesicles are highlighted. Traditionally, lipid and surfactant vesicles have been studied separately, with little cross-information and comparison, giving duplication of physico-chemical interpretations. This situation has changed in more recent times. We then proceed to cover more in-depth the work done on different aspects of the associative behavior between vesicles (of different composition and type of stability) and different types of polymers, including polysaccharides, proteins and DNA. Thus, phase behavior features, effects of vesicle structure and stability, and the forces/mechanisms of vesicle–macromolecule interaction are addressed. Such association may generate gels with interesting rheological properties and high potential for applications. Finally, special focus is also given to DNA, a high charge polymer, and its interactions with surfactants, and vesicles, in particular, in the context of gene transfection studies. © 2008 Elsevier B.V. All rights reserved. Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2. Polymer–surfactant systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.1. Polymer-induced surfactant self-assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.2. Phase separation phenomena in mixed polymer–surfactant solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.3. Polymer–surfactant gelation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.4. Polymers in lamellar phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 3. Vesicles as a self-assembled structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 3.1. Structure, dynamics and composition of vesicles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 3.2. Vesicle formation and stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 3.3. Lipid and block co-polymer vesicles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 3.4. Catanionic vesicles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 Advances in Colloid and Interface Science 147–148 (2009) 18–35 Abbreviations: C 12 E 5 , Pentaethylene glycol monododecyl ether; C 12 E 4 , Tetraethylene glycol dodecylether; CdS, Cadmium Sulfide; Cryo-TEM, Cryogenic transmission electron microscopy; CTAB, Cetyltrimethylammonium bromide; CTAT, Cetyltrimethylammonium tosylate; DDAB, Didodecyldimethylammonium bromide; DNA, Deoxyribonucleic acid; DOPC, Dioleoylphosphatydilcholine; DOTAP, Dioleoyltrimethylammonium propane; DSC, Differential scanning calorimetry; DTAB, Dodecyltrimethylammonium bromide; HEC, Hydroxyethylcellulose; JR400, Hydroxyethylcellulose derivative with a charge concentration of 10 mM (1 wt.% polymer); LM200, Hydroxyethylcellulose derivative with a charge concentration of 2 mM (1 wt.% polymer) and 0.76% of hydrophobic modification; NaBr, Sodium Bromide; NaCl, Sodium Chloride; PEG, Poly(ethylene glycol); PPO, Poly(propylene oxide); PS-PEO, Polystyrene-poly(ethylene oxide); SDBS, Sodium dodecylbenzenesulfonate; SDS, Sodium dodecylsulphate; SOS, Sodium octylsulfate; TTAB, Tetradecyltrimethy- lammonium bromide. ⁎ Corresponding author. Tel.: +351239852080; fax: +351239827703. E-mail address: fcea@ci.uc.pt (F.E. Antunes). 0001-8686/$ – see front matter © 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.cis.2008.10.001 Contents lists available at ScienceDirect Advances in Colloid and Interface Science journal homepage: www.elsevier.com/locate/cis