Supramolecular assembly of a thermoresponsive steroidal surfactant with an oppositely charged thermoresponsive block copolymer.

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-pNIPAAM120 and 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.

EXAFS and molecular dynamics studies of ionic solutions.

This paper focuses on recent advances in the X-ray absorption spectroscopy (XAS) analysis of ionic solutions. The asymmetry of radial distribution functions g(r) associated with the solvent molecules surrounding the ions has to be taken into account to perform a reliable structural analysis. Molecular dynamics (MD) simulations provide reliable g(r)'s which can be used as starting models in the XAS data analysis. The combined MD-XAS investigation reduces meaningfully the indetermination of the structural parameters, especially for coordination numbers and Debye-Waller factors. Double-electron excitation channels can be present in the XAS spectra of ionic solutions and they have to be accounted for in the background extraction. The ability of the XAS technique to probe three-body correlation functions in ionic solutions with the aid of MD g(r1, r2, theta) has been shown. The analysis of the low-k region of the spectra allows the detection of a weak but significant hydrogen structural signal. The XAS technique is especially well suited to determine the detailed shape of the nearest-neighbor peak in the atom-atom pair correlation functions of disordered systems. The information that they contain about the short-range atom-atom pairwise interactions can be very helpful for specifying and properly modifying model potentials used in MD simulations.

K- and L-edge XAFS determination of the local structure of aqueous Nd(III) and Eu(III).

The short-range coordination of Nd(III) and Eu(III) ions in aqueous solutions has been investigated by means of K-edge x-ray absorption spectroscopy. Experimental data are presented which demonstrate that an accurate determination of the Nd(III) and Eu(III) hydration structural parameters can be obtained from the analysis of the K-edge spectra. It is shown that the large widths of the core hole states do not appreciably reduce the potential structural information of the K-edge EXAFS data. In addition the available k-range of the K-edge spectra is much wider compared to that of the L3-edge which is affected by the presence of double-electron excitations in a more severe fashion.