Aggregates Based On Supramolecular Interactions Of Cyclodextrin With Ferrocene Derivatives

Vesicle is formed by amphiphilic molecules in tail to tail orderly. For having cell-like structures, vesicles are the general model system for mimicking biological membranes. Vesicles have been widely applied to nano-materials and drug delivery.Supramolecular chemistry focuses on the chemical systems made up of assembled molecular subunits, components and interactions between molecules, which provide an effective way to construct functional aggregates. As one of the most important hosts, cyclodextrin (CDs) could form inclusion complexes with various kinds of guests. The supramolecular interaction is affected not only by the guest's polarity and size but also the environment of medium such as temperature, pH and radioactive stimulation. Therefore, the interaction between host and guest could be controlled by varying these conditions.Based on the above methodology, a series of ferrocene derivatives were designed and prepared here. The supramolecular interactions between them andβ-cyclodextrin derivative (Hydroxypropyl-β-cyclodextrin, HPβCD) were also studied. Vesicles based on the interactions were prepared, which were responsive to solvent composition, redox and external guests. The insight obtained from this study could be useful for the designation and preparation of novel supramolecular functional materials. This work composes the following two parts.1) Firstly, ferrocenecarboxaldehyde and acetylferrocene were obtained from ferrocene. A series of ferrocene derivatives were prepared based on the reactions of ferrocenecarboxaldehyde and acetylferrocene with a series of amine. The obtained compounds were characterized by 1H-NMR,13C-NMR and MS.2) Vesicles based on the supramolecular interaction of HPβCD with N,N'-bis (ferrocenylmethylene)-diaminohexane (BFD) were prepared, which were characterized by Dynamic Light Scattering (DLS) and Transmission Electron Microscopy (TEM). The interaction was studied by'H-NMR and 2D'H-'H NMR. The inclusion stoichiometry of HPβCD and BFD would tend to be a molar ratio of 1:1 from 2:1 based on the introduction of methanol to the solvent, especially when the volume ratio of methanol and water was more than 1:4. The inclusion constant decreased with methanol concentration increasing in the solvents. The inclusion was responsive to redox, when a chemical oxidizing agent was added to the system, the vesicles disappeared. When the inclusion ability between HPβCD and external guest was relatively stronger, the vesicles were easily destroyed. Based on the experimental data, the possible mechanism for the formation of the vesicles was proposed. This work provided a new idea to design and prepare new supramolecular materials.Major innovative points in this thesis are listed as follow:1) Various kinds of ferrocene derivatives with different chains were synthesized, which was useful to study the chain effect on these assembles.2) Vesicles based on the interactions of HPβCD with BFD were prepared. The effects of external guests on the aggregates were studied based on that the complexations of HPβCD with external guests were studied by UV using the double-reciprocal method, which was firstly reported in this area.