title: Supramolecular assembly of a thermoresponsive steroidal surfactant with an oppositely charged thermoresponsive block copolymer.
abstract: Supramolecular rearrangements are crucial in determining the response of stimuli sensitive soft matter systems such as those formed by mixtures of oppositely charged amphiphiles. Here mixtures of this kind were prepared by mixing the cationic block copolymer pAMPTMA30-b-pNIPAAM120and an anionic surfactant obtained by the modification of the bile salt sodium cholate. As pure components, the two compounds presented a thermoresponsive self-assembly at around 30-35 °C; a micelle formation in the case of the copolymer and a transition from fibers to tubes in the case of the bile salt derivative. When both were present in the same solution they associated into mixed aggregates that showed complex thermoresponsive features. At room temperature, the core of the aggregate was comprised of a supramolecular twisted ribbon of the bile salt derivative. The block copolymers were anchored on the surface of this ribbon through electrostatic interactions between their charged blocks and the oppositely charged heads of the bile salt molecules. The whole structure was stabilized by a corona of the uncharged blocks that protruded into the surrounding solvent. By increasing the temperature to 30-34 °C the mixed aggregates transformed into rods with smooth edges that associated into bundles and clusters, which in turn induced clouding of the solution. Circular dichroism allowed us to follow progressive rearrangements of the supramolecular organization within the complex, occurring in the range of temperature of 20-70 °C.
authors.affiliation: Department of Chemistry, "Sapienza" University of Rome, P.le A. Moro 5, 00185 Rome, Italy. luciano.galantini@uniroma1.it.
authors.forename: M C
authors.initials: MC
authors.lastname: di Gregorio
authors.affiliation: Department of Chemistry, "Sapienza" University of Rome, P.le A. Moro 5, 00185 Rome, Italy. luciano.galantini@uniroma1.it.
authors.forename: M
authors.initials: M
authors.lastname: Gubitosi
authors.affiliation: Department of Chemistry, "Sapienza" University of Rome, P.le A. Moro 5, 00185 Rome, Italy. luciano.galantini@uniroma1.it.
authors.forename: L
authors.initials: L
authors.lastname: Travaglini
authors.affiliation: Department of Chemistry, "Sapienza" University of Rome, P.le A. Moro 5, 00185 Rome, Italy. luciano.galantini@uniroma1.it.
authors.forename: N V
authors.identifier: http://orcid.org/0000-0002-7637-4821
authors.initials: NV
authors.lastname: Pavel
authors.affiliation: Departamento de Química Física, Facultad de Ciencias, Universidad de Santiago de Compostela, Avda. Alfonso X El Sabio s/n, 27002 Lugo, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Jover
authors.affiliation: Departamento de Química Física, Facultad de Ciencias, Universidad de Santiago de Compostela, Avda. Alfonso X El Sabio s/n, 27002 Lugo, Spain.
authors.forename: F
authors.initials: F
authors.lastname: Meijide
authors.affiliation: Departamento de Química Física, Facultad de Ciencias, Universidad de Santiago de Compostela, Avda. Alfonso X El Sabio s/n, 27002 Lugo, Spain.
authors.forename: J
authors.initials: J
authors.lastname: Vázquez Tato
authors.affiliation: Department of Physics and CNR-IPCF UOS Roma, "Sapienza" University of Rome, P.le A. Moro 5, 00185 Rome, Italy.
authors.forename: S
authors.initials: S
authors.lastname: Sennato
authors.affiliation: Division of Physical Chemistry, Department of Chemistry, Lund University, SE-221 00 Lund, Sweden.
authors.forename: K
authors.initials: K
authors.lastname: Schillén
authors.affiliation: Department of Chemistry, "Sapienza" University of Rome, P.le A. Moro 5, 00185 Rome, Italy. luciano.galantini@uniroma1.it.
authors.forename: F
authors.initials: F
authors.lastname: Tranchini
authors.affiliation: Department of Chemistry, "Sapienza" University of Rome, P.le A. Moro 5, 00185 Rome, Italy. luciano.galantini@uniroma1.it.
authors.forename: S
authors.initials: S
authors.lastname: De Santis
authors.forename: G
authors.identifier: http://orcid.org/0000-0002-7213-8311
authors.initials: G
authors.lastname: Masci
authors.affiliation: Department of Chemistry, "Sapienza" University of Rome, P.le A. Moro 5, 00185 Rome, Italy. luciano.galantini@uniroma1.it.
authors.forename: L
authors.identifier: http://orcid.org/0000-0001-5484-2658
authors.initials: L
authors.lastname: Galantini