Design And Synthesis Of Porphyrin Metal-Organic Frameworks With Photodynamic Anticancer Property In Vitro

Cancer is an important public safety issue that threatens human development in recent years.The number of cancer patients is rising all the time.It is urgent to find a better,more effective and more affordable cancer treatment method for patients.Photodynamic therapy(PDT)has become an important cancer treatment method in recent years and is widely used in skin cancers and melanoma treatments.PDT produces cytotoxic singlet oxygen and kills cells through the action of light,photosensitizer and oxygen.However,at present,PDT faces one of the most important obstacles,that is,the therapeutic field is limited due to insufficient penetration depth of light.Metal-organic frameworks(MOFs)have been used in PDT therapy due to their tunable pore sizes,the modulability of central metals and organic ligands and good stability.In this paper,the endogenous light source is inno vatively carried from MOFs to cancer lesions,effectively overcoming the defects of low light illumination depth in PDT.PCN-222(Pd)was synthesized using metalloporphyrin photosensitizer.The light-absorption property of metalloporphyrin was improved due to the chelation of palladium in it.Therefore,the ability to generate singlet oxygen of PCN-222(Pd)is comparable to the reported photosensitizer methylene blue.The toxicity test of PC12 in vitro showed that the material had certain phototoxicity to cells,which proved that the material could be used as a potential PDT drug.PCN-224 was synthesized using porphyrin and zirconium.Then bioluminescent molecule D-fluorescein(D-Lu)was loaded in the pores of PCN-224 as an inner light source for PDT.After physical soaking,D-fluorescein was successfully loaded into the pores of PCN-224 at a loading capacity of 7.32 wt%.The spectroscopic experiments showed that the luminescence of D-fluorescein can cover the absorption band of PCN-224.In the bioluminescence test,the luminescence of the(D-Lu)PCN-224 system was significantly weaker than D fluorescein,indicating that there was an energy transfer process.Confocal imaging assays and cytotoxicity assays have demonstrated that(D-Lu)PCN-224 is capable of producing singlet oxygen and decrease the cell viability of PC 12.This system is a PDT system that does not require an external light source,and provides a possibility for deep-level organization of PD T.A photodynamic system with inner light-Lu@CoTCPP(Pd)was designed and synthesized.A chemiluminescent molecule Luminol was loaded in the system as the light source.After physical soaking,luminol was successfully loaded into the pores of PCN-224 at a loading capacity of 20.45 wt%.The spectral test showed the emission spectrum of luminol can cover the Q-band absorption spectrum of the TCPP ligand.The chemiluminescence test showed that the chemiluminescence of Lu@CoTCPP(Pd)was weak,indicating that the chemiluminescence of luminol can be absorbed by CoTCPP(Pd).Confocal imaging tests and cytotoxicity tests have shown that Lu@CoTCPP(Pd)can produce singlet oxygen and is toxic to cells without external light.In the presence of H2O2,the cobalt metal clusters in CoTCPP(Pd)can catalyze Luminol luminescence,so the system is specific for cancer cells containing endogenous H2O2(ovarian tumors,breast cancer).The Lu@CoTCPP(Pd)system can be used as an endogenous PDT system to provide a potential solution for deep tissue PDT therapy.