Synthesis And Biological Activity Of Bridged Beta Porphyrin Derivatives

As a good light sensitivity,porphyrin can be used as photosensitizer in photodynamic therapy and treatment of cancer with a broad prospect of application.In this paper,5,10,15,20-tetraphenyl porphyrin was synthesized by pyrrole and benzaldehyde.Then,the β-nitro-tetraphenyl porphyrin was obtained by selective nitrification in porphyrin ring,and the β-amino-tetraphenyl porphyrin was generated by nitro reduction reaction.On this basis,beta bit-bridged double porphyrin compounds were synthesized by formaldehyde through condensation reaction.Further,a series of porphyrin complexes with metal ions were synthesized by metal complex reaction.Moreover,intermediates and target products were characterized through hydrogen nuclear magnetic resonance,mass spectro metry,middle infrared spectrum and raman spectroscopy.What’s more,Electrochemical properties were studied by cyclic voltammetry.When determined the ability of singlet oxygen generation,we tested it through ultraviolet-visible spectroscopy.In the end,the biological activity of target products with DNA were tested through ultraviolet-visible spectroscopy titration method and fluorescence spectroscopy titration method.The main works of this dissertation are composed as follows:(1)5,10,15,20-tetraphenyl porphyrin was synthesized as raw materials by distillation of pyrrole and benzaldehyde,acrylic acid as solvent.(2)Center core metal ligand 5,10,15,20-(copper)tetraphenyl porphyrin was prepared with 5,10,15,20-tetraphenyl porphyrin and Cupric Acetate Monohydrate in solvent of N,N’-dimenthyl formaide.(3)5,10,15,20-(copper)tetraphenyl porphyrin was taken as raw materials to react with acetic acid,acetic anhydride,copper nitrate in the solvent of chloroform,finally,theβ-nitro-5,10,15,20-(copper)tetraphenyl porphyrin was synthesized.(4)Using β-nitro-5,10,15,20-tetraphenyl copper porphyrin as raw material,then,put it react with sulfuric acid to obtain β-nitro-5,10,15,20-tetraphenyl porphyrin.(5)β-nitro porphyrin as raw material,was reacting with stannous chloride to getβ-amino-5,10,15,20-tetraphenyl porphyrin.(6)β-amino-5,10,15,20-(copper)tetraphenyl porphyrin was synthesized byβ-amino-5,10,15,20-tetraphenyl porphyrin which was regarded as raw material reacting with copper acetate.(7)The β-amino-5,10,15,20-tetraphenyl porphyrin was taken as raw meterial to react with formaldehyde,then β-aminoporphyrin derivatives were obtained by the condensation reaction.Based on that,the copper-porphyrin and nickel-porphyrin were generated by the reaction of copper acetate and nickel acetate respectively.(8)The structure of intermediates and target products were characterized by hydrogen nuclear magnetic resonance,mass spectrometry and infrared spectroscopy.(9)The properties of intermediates were studied by cyclic voltammetry and Raman spectroscopy.(10)The effects of substitutions and solvents on the optical properties of porphyrin compounds were analyzed by ultraviolet-visible spectroscopy and fluorescence emission spectroscopy.(11)1,3-Diphenylisobenzofuran as an active oxygen scvenger,the ability to produce singlet oxygen was detected by ultraviolet spectrophotometer to detect the porphyrin compounds under the irradiation of far-infrared light,it was found that theβ-aminoporphyrin derivatives had good single-line oxygen capacity.(12)After determining the combination of porphyrin compounds and calf thymus DNA by ultraviolet-visible spectrometric titration,we found their combination mode was the external bond which has been deposited on the surface.(13)Fluorescence spectrum titration was used to determined the fluorescence quenching degree and quenching patterns of porphyrin compounds with calf thymus DNA.In the end,the conclusion is that it can cause the dynamic surge of the fluorescence emission spectra of porphyrin compounds.