Construction Of Highly Efficient Near-infrared Composite Photosensitizers And Room Temperature Phosphorescent Probes Based On Porphyrins/Metalloporphyrins-DNA

Porphyrin and metalloporphyrin compounds play an important role in scientific research because of their unique molecular structure,electronic and optical properties.Research in the field of biochemistry is particularly prominent,including photosensitizers for photodynamic therapy,bioimaging probes,chemical sensors,metal ligands,photosynthesis,biocatalysis,and organic photovoltaic cells.In order to achieve these functions,the design and synthesis of porphyrin molecules of different structures and the assembly of porphyrin molecules are indispensable.Based on the above considerations,this paper studies the application of porphyrin compounds in life systems.The details are summarized as follows:1.A water-soluble composite photosensitizer was designed based on porphyrin TMPipEOPP and G-quadruplex AS1411.It were characterized by UV-vis absorption spectroscopy,fluorescence spectroscopy and Zeta potential.The biostability of this composite photosensitizer was evaluated and the ability of TMPipEOPP/AS1411 to produce singlet oxygen in cells and outside the cell was explored.The singlet oxygen production ability of the composite photosensitizer was 7.4 times that of the singlet oxygen generation of the porphyrin photosensitizer alone.In addition,the composite photosensitizer effectively shifts the characteristic wavelength from 650 nm to～700nm.2.On the basis of TMPipEOPP/AS1411 of composite photosensitizer,the nanosheet oxide graphene GO and manganese dioxide Mn O₂ were introduced,and the water-soluble nanocomposite photosensitizer was obtained by the assembly of the two.They were characterized by UV-vis absorption spectroscopy,fluorescence spectroscopy,Zeta potential and DLS.The biostability of Mn O₂@AS1411T₃₃/TMPipEOPP and its singlet oxygen production capacity both intracellularly and extracellularly were evaluated.The nanocomposite photosensitizer has a limited ability to generate singlet oxygen,but released the photosensitizer by simulating the physiological environment to enhance the photodynamic effect.We also evaluated the photodynamic therapy effects of composite photosensitizers and nanocomposite photosensitizers in vivo:after photodynamic therapy,TMPipEOPP/AS1411 and Mn O₂@AS1411T₃₃/TMPipEOPP effectively made tumors necrosis,and the effect of Mn O₂@AS1411T₃₃/TMPipEOPP on tumor treatment was more obvious.3.A new water-soluble cationic metalloporphyrin compound（palladium porphyrin,Pd-TMPipPrOPP）was synthesized and characterized by by FI-MS,¹H NMR,IR,etc.Pd-TMPipPrOPP with phosphorescence which was not found in general porphyrins/metalloporphyrins,indicating Pd-TMPipPrOPP was different from these porphyrins/metalloporphyrins.Its unique room temperature phosphorescence（RTP）properties made it promising as an RTP probe.