Synthesis And Property Studies Of Two Groups New Phototherapeutic Photosensitizers

Phototherapy is a new therapy for tumor cell and pathogen inhibition.It mainly includes photodynamic therapy?PDT?and photothermal therapy?PTT?,which has a special killing mechanism andwill not produce the drug resistance of tumor cells or super bacteria due to the use of drugs;and it can actively control the light area,selectively irradiate in the cancerous part and effectively avoid the damage to the healthy part of the human body.As a result,phototherapy that shows less side effect possesses a huge advantage in the treatment of cancer and super bacteria.At present,the general research methods of phototherapeutic photosensitizers are to modify the structure of some anti-tumor/antibacterial molecules with biological activity,introduce photosensitive groups to make them have phototherapeutic effect and enhance their anti-tumor/antibacterial activity;or to modify the structure of phototherapeutic photosensitizers to improve their water solubility and biocompatibility and enhance their anti-tumor/antibacterial activity.In this paper,coumarin was introduced into half-sandwich complexes of Ru,Rh and Ir to enhance their antitumor activity through phototherapy.In addition,the phthalocyanine nanoparticles with better phototherapeutic effect were obtained by structural modification,in order to improve the water solubility and biocompatibility of?-tetraaminophthalocyanine zinc.The following is the main work of this paper:1.Synthesis,structure and antitumor activity of coumarin-metal complexes:7-diethylamino-4-hydroxycoumarin was obtained by the reaction of 3-hydroxy-N,N-diethylanilineanddiphenylmalonate,andthen7-diethylamino-4-hydroxy-3-acetylcoumarin?L1?was obtained by the reaction of the7-diethylamino-4-hydroxycoumarin derivative with acetic anhydride.Then,L1 was used as the ligand to react with[Ru??⁶-p-cymene?Cl₂]₂?[Rh??⁵-C₅Me₅?Cl₂]₂?[Ir??⁵-C₅Me₅?Cl₂]₂,respectively.As a result,the novel half sandwich ruthenium?II?,rhodium?III?and iridium?III?complexes?1?3?were obtained by O,O-bidentate coordination.These complexes are characterized by 1H-NMR,Mass spectum,and the single-crystal X-ray structures,and investigated for their UV-Vis absorption spectrum and Fluorescence emission spectrum.The fluorescence quantum efficiency and singlet oxygen yield were studied.The PDT activities toward T47D cells were investigated.Under the dark condition,L1 showed little toxicity to T47D cells,while IC₅₀value of 1?3 to T47D cells was 54.9-63.0?M,showing only mild inhibitory activity.Under the illumination of?>400 nm,the IC₅₀value of 1?3 to T47D cells decreased to 3.4?31.9?M.The IC₅₀value of complex 1 was 3.4±0.3?M,which showed good phototoxicity PI value of 18.3.2.Synthesis,characterization and phototherapy antibacterial research of phthalocyanine implanted carbon nanoparticle TAPZn@CA:?-tetranitrophthalocyanine zinc was synthesized by the reaction of4-nitrophthalonitrile and zinc acetate,then reduced to?-tetraaminophthalocyanine zinc by sodium sulfide,then?-tetraaminophthalocyanine zinc and citric acid were dissolved in dilute hydrochloric acid solution,and the phthalocyanine was implanted into carbon nanoparticle TAPZn@CA through microwave heating reaction,filtration,dialysis and freeze-drying.The particle was characterized by UV-Vis absorption spectrum and fluorescence emission spectrum.The thermogravimetry and zeta potential of the particle were studied.The structure and morphology of the particle were studied by transmission electron microscopy and particle size analyzer.The singlet oxygen yield and photoinduced thermal reaction of the particle confirmed its PDT and PTT functions.The phototherapeutic inhibitory activity of TAPZn@CA on E.coli and S.aureus was studied.Under the combined action of 660 nm and 808 nm light,when the concentration of Zn Pc in TAPZn@CA is 0.27?mol/m L,the inhibition rate of nanoparticles against E.coli and S.aureus is 94%and 99%,respectively,which shows that TAPZn@CA is a good PDT/PTT antibacterial agent.