| Porphyrin compounds are a kind of macrocyclic conjugated organic molecules which have an extensive system of delocalizedπelectrons. Recently, they can be applied in many fields, such as macromolecule materials, chemical catalysis, electroluminescent materials and photodynamic therapy. Recent research has shown that some soluble porphyrin compounds are able to be used as sensitive material, anticancer and antibacterial drug. Syntheses and applications of porphyrins and metalloporphyrins have received continuous attentions. CDs with an interior hydrophobic cavity and exterior hydrophilic environment, as a building up element of second generation supramolecule, can accommodate many organic, inorganic and biological molecules in their toroidal cavity to form stable host-guest inclusion complexes. Therefore, they have been paid much attention by researchers of supramolecular chemistry. CDs have been used widely in pharmaceutical industry, food, environmental conservation, cosmetics, ect. Especially in pharmaceutical industry, CDs are able to be used to improve solubility, stability, stripping speed of drugs in the biological using. Recently, cyclodextrin-porphyrins are extremely attractive components of artificial enzymes minietic. The study on the interactions of porphyrin compounds and CDs have three meanings: First, improving some properties of porphyrin compounds, such as water-solubity; Second, preventing the molecules of porphyrin compounds from polymerizing; Third, protecting the porphyrin ring and its aromatic substituents.In this thesis, we report the design and syntheses of two series of porphyrin compounds with hydroxyphenyl or pyridyl substituentes. The NMR, element analysis were investigated here. The supramolecular systems of porphyrins withβ-CD were examined by UV absorption and fluorescence spectroscopy in neutral phosphate buffer solutions of PH 7.0. The stoichiometries and inclusion constants withβ-CD were determined by double reciprocal method.The results indicate that the porphyrin compounds can form inclusion complexes withβ-CD. For example, the TPyP can form the 1:1 inclusion complex. The TPyP display a sharp and intense Soret band accompanied by four weaker Q-bands at longer wavelengths in the absorption spectrum. Two red emission bands are observed. Whenβ-CD is added to the TPyP aqueous solution, the decrease of the Soret band is accompanied by minor change in the Q-band region. The TPyP molecule was included in the hydrophoblic cavity. Then the AdTPyP can form the 1:2 inclusion complex. Uponβ-CD addition, the fluorescence intensity of the AdTPyP increased. The cavity ofβ-CD can match the size of the adamantyl of the AdTPyP. The THPP is similar to the TPyP. Whereas the PdTHPP and the PdAdTHPP is phosphorescent dye. Oxygen molecule can quench the phosphorescence of the functional molecules. Maybe they can be used for optical oxygen sensing materials in organism.In recent years, many efforts have been made to investigate the aggregation process and aggregation structure of porphyrin because of their unique properties. So, our work also focuses on the self-assembly of organic nanocrystals based on porphyrins. The THPP has been employed as building block to fabricate organic nanocrystals based on reprecipitation and evaporation approaches, respectively. The THPP in DMF have formed the ribbon-like wires, with width of 10μm and length of hundred microns. A red fluorescence was observed. When in CH3OH, the THPP have formed the rod-like nanowires, with width of 10μm and length of 20~30μm. There is no fluorescence can be observed. These results elucidated the relationships between molecular structures/molecular packing structures and physical chemistry properties of materials. |
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