The Synthesis And Bioactivity Of Cyclodextrin Derivative Containing Zinc And Ruthenium

Since study on the functionalization of supramolecular system is very important for the electrochemistry, photochemistry, catalysis chemistry, mimetic enzyme, biology, and medical fields etc, it has become a hot issue for current scientific research. It is also one important subject for researchers to construct the supramolecular assembly with suitable function based on the design and synthesis of novel cyclodextrin derivative for further investigation to obtain its basic characteristics and disciplinarian. In this thesis, we constructed novel structure supramolecular system based on the cyclodextrin derivatives, and invested its possible function and application in biological, material, environmental fields. The major contents of this thesis are as follows:1. The history and recent development of supramolecular chemistry were introduced in briefly. Furthermore, the new progress and important achievements for molecular recognition, self-assembly, and nano-supramolecular assembly based on nature cyclodextrin and its derivatives were summarized and reviewed.2. A stoichiometric quinolinocyclodextrin/Zn2+ complex was prepared in situ in water and showed the specific fluorescence response to Hg2+ over other metal ions, which could be readily distinguished in either aqueous solution or the PVA-based thin film.3. A supramolecular hybrid is prepared by the supramoleuclar surface modification of single-walled carbon nanotube (SWCNT) with cationicβ-cyclodextrin-tethered ruthenium complexes through a spacer molecule that contains both an adamantane and a pyrene moiety. Employing the supramolecular hybrid, spatially controllable DNA condensation along the SWCNT skelecton is achieved through the anchoring cationic ruthenium complexes anchor on the surface. Furthermore, the cationic supramolecular hybrid, coupled with the unique physiological properties of SWCNT, can be used as a nonviral gene delivery system with the ruthenium complexes as a fluorescent probe to monitor DNA uptake by cell.4. Through the stoichiometric 2:1 coordination of Zn2+ with N-(2-methyl-8- amino-quinolyl)-p-amino-benzene-sulfonamide-modified per-methyl-β-cyclodextrin (MQAS-PMCD) and the strong inclusion complexation of permethyl-β-cyclodextrin cavity with meso-tetrakis-(4-sulfonatophenyl)-porphyrin tetrasodium salt (TSPP), an environmental sensitive Zn2+/cyclo-dextrin/porphyrin triad supramolecular assembly was constructed. Fluorescence spectrometric studies showed that this supramolecular assembly was very stable and barely emitted the green fluorescence in water due to the fluorescence resonance energy transfer (FRET) process, but gave the strong green fluorescence when.changing to a hydrophobic environment due to the disruption of the assembly. Further studies on the cell staining experiments by means of fluorescence microscopy showed that this supramolecular assembly was disrupted to release the MQAS-PMCD/Zn2+ and porphyrin components when interacting with the cell membrane. Subsequently, the released MQAS-PMCD/Zn2+ complex remained in the cell membrane, while the porphyrin component entered the cells.5. A fluorescence SWCNT assembly was constructed from cell-impermeable metal sensor (N-(2-methyl-8-amine-quinolinyl)-p-aminobenzenesulfonyl amide modifiedβ-cyclodextrin, MQAS-β-CD) and single-walled carbon nanotube (SWCNTs) through a spacer molecule that contains both a pyrene and an adamantane moiety (Py-Ad). The supramolecular hybrid, coupled with the unique physiological properties of SWCNTs, can monitor.metal ion in living cell.