Design, Synthesis And Properties Study On Functional Porphyrin Derivatives

Porphyrin compounds have distinctive structures and predominant physical, chemical, optical properties, and have been researched and applied in biological sciences, biochemistry, medical chemistry, material chemistry and supramolecular chemistry.In this thesis, new porphyrin derivatives were synthesized; the binding and photocleavage of multi-charged porphyrins or (metallo-) porphyrin-dextran to DNA have been investigated by using UV-visible absorption, fluorescence, and gel electrophoresis; the influence of porphyrin compounds on the bacteria metabolism with physical chemistry method as well as the thermodynamic theory was studied; the relaxivity mechanisms and applications of manganese porphyrin derivatives as magnetic resonance imaging (MRI) contrast agents were discussed; the interaction between the porphyrin and HSA were also researched by UV-visible absorption and fluorescence.The results in this thesis are concluded as below:In chapter 1, the evolution of the porphyrin chemistry is introduced briefly, including synthesis of porphyrin and their derivatives, pharmic chemistry, biochemistry and medicine.In chapter 2, a series of porphyrins containing functional group were synthesized, and all of these compounds were confirmed by IR, UV-Vis and1H NMR.In chapter 3, different metallo-porphyrin were binded with dextran, and investigated the property of UV-visible absorption, separately. The results showed the UV-visible absorption of manganese porphyrin derivative 29 was super-high type, while the UV-visible absorption of 30 was blue-shift type.Interaction of compounds 28,29 and 30 with CT DNA were determined by ultraviolet and fluorescence spectroscopy, and the competition method with ethidium bromide. The results showed porphyrin 29 had the most strongest affinity and the most biggest binding constant. Photocleavage of pBR322 plasmid DNA by the four porphyrins were analyzed by agarose gel electrophoresis experiments. The results showed photocleavage ability of the compound 29 was the strongest, and was consistent with the value of Kapp.In chapter 4, porphyrin compounds 33 and 35 were synthesized. And tested the influence of compounds 31,32 (un-bonded with dextran),33,35 on the bacteria metabolism with microcalorimetric technique. The manganese porphyrin derivatives inhibited the bacteria metabolism stronger, and when the dextran was binded with porphyrin (33), the inhibtion was strongest.In chapter 5, the longitudinal relaxivities of compound 31,33 and 34 were carefully discussed, and especially investigated the MR imagine,toxicity in vitro and the location of 33. The tumor-specific paramagnetic porphyrin-dextran complex 33 exhibited useful relaxivity and was nontoxic and high efficient.In chapter 6, a novel porphyrin-dextran coated Fe3O4 nanoparticle (37) was designed and synthesized. The structure of the 37 was confirmed by IR, UV-vis, inductively coupled plasma atomic emission spectrometry (ICP-AES) and dynamic laser scattering (DLS), and the magnetic property was also measured by a vibrating sample magnetometer (VSM). The interaction between the compound 37 and human serum albumin (HSA) was investigated through UV-vis absorbance spectra and fluorospectrophotometer, compared with the compound 25(un-bounded with dextan). The results showed the compound 37 containing porphyrin moiety and 25 could interact with HSA.