1610930-01-2Relevant academic research and scientific papers
Metal ion, light, and redox responsive interaction of vesicles by a supramolecular switch
Samanta, Avik,Ravoo, Bart Jan
, p. 4966 - 4973 (2014/05/06)
Chemical, photochemical and electrical stimuli are versatile possibilities to exert external control on self-assembled materials. Here, a trifunctional molecule that switches between an adhesive and a non-adhesive state in response to metal ions, or light, or oxidation is presented. To this end, an azobenzene-ferrocene conjugate with a flexible N,N-bis(3-aminopropyl)ethylenediamine spacer was designed as a multistimuli-responsive guest molecule that can form inclusion complexes with β-cyclodextrin. In the absence of any stimulus the guest molecule induces reversible aggregation of host vesicles composed of amphiphilic β-cyclodextrin due to the formation of intervesicular inclusion complexes. In this case, the guest molecule operates as a noncovalent cross-linker for the host vesicles. In response to any of three external stimuli (metal ions, UV irradiation, or oxidation), the conformation of the guest molecule changes and its affinity for the host vesicles is strongly reduced, which results in the dissociation of intervesicular complexes. Upon elimination or reversal of the stimuli (sequestration of metal ion, visible irradiation, or reduction) the affinity of the guest molecules for the host vesicles is restored. The reversible cross-linking and aggregation of the cyclodextrin vesicles in dilute aqueous solution was confirmed by isothermal titration calorimetry (ITC), optical density measurements at 600 nm (OD600), dynamic light scattering (DLS), ζ-potential measurements and cyclic voltammetry (CV). To the best of our knowledge, a dynamic supramolecular system based on a molecular switch that responds orthogonally to three different stimuli is unprecedented.
