Home > Publications database > Using Inclusion Complexes with Cyclodextrins To Explore the Aggregation Behavior of a Ruthenium Metallosurfactant |
Journal Article | FZJ-2015-02837 |
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2015
ACS Publ.
Washington, DC
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Please use a persistent id in citations: doi:10.1021/la504929x
Abstract: The aggregation behavior of a chiral metallosurfactant, bis(2,2′-bipyridine)(4,4′-ditridecyl-2,2′-bipyridine)ruthenium(II) dichloride (Ru24C13), synthesized as a racemic mixture was characterized by small-angle neutron scattering, light scattering, NMR, and electronic spectroscopies. The analysis of the SANS data indicates that micelles are prolate ellipsoids over the range of concentrations studied, with a relatively low aggregation number, and the micellization takes place gradually with increasing concentration. The presence of cyclodextrins (β-CD and γ-CD) induces the breakup of the micelles and helps to establish that micellization occurs at a very slow exchange rate compared to the NMR time scale. The open structure of this metallosurfactant enables the formation of very stable complexes of 3:1 stoichiometry, in which one CD threads one of the hydrocarbon tails and two CDs the other, in close contact with the polar head. The complex formed with β-CD, more stable than the one formed with the wider γ-CD, is capable of resolving the Δ and Λ enantiomers at high CD/surfactant molar ratios. The chiral recognition is possible due to the very specific interactions taking place when the β-CD covers—via its secondary rim—part of the diimine moiety connected to the hydrophobic tails. A SANS model comprising a binary mixture of hard spheres (complex + micelles) was successfully used to study quantitatively the effect of the CDs on the aggregation of the surfactant.
Keyword(s): Polymers, Soft Nano Particles and Proteins (1st) ; Key Technologies (1st) ; Soft Matter, Macromolecules, Complex fluids, Biophysics (1st) ; Soft Condensed Matter (2nd)
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