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Thick poly(styrene-b-monomethoxydiethylenglycol-acrylate-b-styrene) [P(S-b-MDEGA-b-S)] films (thickness 5 mu m) are prepared from different solvents on flexible substrates by solution casting and investigated with small-angle X-ray scattering. As the solvents are either PS- or PMDEGA-selective, micelles with different core-shell micellar structures are formed. In PMDEGA-selective solvents, the PS block is the core and PMDEGA is the shell, whereas in PS-selective solvents, the order is reversed. After exposing the films to liquid D2O, the micellar structure inside the films prepared from PMDEGA-selective solvents remains unchanged and only the PMDEGA (shell part) swells. On the contrary, in the films prepared from PS-selective solvents, the micelles revert the core and the shell. This reversal causes more entanglements of the PMDEGA chains between the micelles. Moreover, the thermal collapse transition of the PMDEGA block in liquid D2O is significantly broadened. Irrespective of the solvent used for film preparation, the swollen PMDEGA shell does not show a prominent shrinkage when passing the phase transition, and the transition process occurs via compaction. The collapsed micelles have a tendency to densely pack above the transition temperature.
The influence of a polyampholyte, i.e., poly(N,N’-diallyl-N,N’-dimethyl-altmaleamic carboxylate) (PalH), on the lamellar liquid crystalline (LC) system sodium dodecyl sulfate (SDS)/decanol/water was investigated by means of microdifferential scanning calorimetry, small-angle X-ray diffraction (SAXS), and cryo-scanning electron microscopy. After incorporating PalH into the lamellar liquid crystalline system, SAXS measurements show that three different LC phases exist: i.e., a swelling, slightly swelling, and non-swelling one. At pH 4, the positively charged polymer with an extended conformation can directly adsorb at the anionic head groups of the surfactant and more compact vesicles are formed at room temperature. At pH 9, the electrostatic interactions between the polyampholyte (in a more coiled conformation) and the sulfate head groups of the SDS are leveled off and incompact vesicles are formed at room temperature. That means in presence of the polyampholyte the morphology of the LC phase, i.e., the supramolecular vesicle structure, can be tuned by varying the pH and/or the temperature.