Porphyrin And Phthalocyanine Nanoscale Metal-organic Frameworks For Phototherapies Of Cancer

The research of Metal-Organic Frameworks（MOFs）is an active interdisciplinary area,these MOFs have tremendous applications in adsorption and separation,catalysis and biochemistry.In this thesis,a surface decorated porphyrinic nanoscale MOF for photodynamic therapy was discussed;A phthalocyaninic MOF and functionalization for photothermal and photodynamic therapy was synthesized.Their structures,morphologies and particle sizes fully characterized by X-ray powder diffraction,scanning electron microscopy and dynamic light scattering characterize.The applications in phototherapy by these compounds were also investigated.I.We report herein a new UiO-66 type of NMOF-based photosensitizer（UiO-66-TPP）which is generated from UiO-66 NMOF and S-ethylthiol ester monosubstituted metal free porphyrin（TPP）via a facile post-synthetic approach under mild conditions.The obtained NMOF（about 140 nm）with surface-decorated porphyrin photosensitizer retains its crystallinity,structural feature and size well,furthermore,exhibits highly efficient singlet oxygen generation.Compared to the porphyrin interior-located NMOF TCPP?UiO-66,UiO-66-TPP shows higher photodynamic activity and more efficient PDT tumor treatment.II.An organic ligand [p-terphenyl]-4,4’’-dicarboxylic acid fused with zinc phthalocyanine moiety H₂L-ZnPc has been synthesized and fabricated into UiO-68-type MOFs with zirconium chloride UiO-68-ZnPc.This nanoscale UiO-68-ZnPc reveals negligible toxicity and efficient photodytherapy based on the combination of photosensitizer and photothermal conversion agents using one system by a single laser irradiation.On the one hand,phthalocyanines located on the surface of MOF framework keeping the ability of generating 1O2.On the other hand,due to the strong π-stacking of phthalocyanines interior of this MOF framework obtaining an efficient light-to-heat energy conversion.In addition,the porous material with dicarboxylate linkages and Zr6O4（OH）4 cluster nodes makes it stabilities in aqueous solution.As expected,UiO-68-ZnPc displayed negligible toxicity and efficient photodynamic and photothermal effects toward phototherapy for treatment of liver cancer cells in vitro by a single laser irradiation.III.We have synthesised a nano-sized MOF（H₂L-ZnPc/UiO-68-NH-Met）decorated by the carboxy-functionalized zinc phthalocyanine（H₂L-ZnPc）into NMOFs（UiO-68-NH-Met）via solvent-assisted ligand exchange（SALE）.The molar ratio of H₂L-ZnPc and Zr6 cluster is that 12.9% by ICP analyze.We tested the 1O2 generating ability of H₂L-ZnPc,H₂L-ZnPc/UiO-68-NH₂ and UiO-68-ZnPc in DMF solution,the results of which exhibited 9.04-fold higher than UiO-68-ZnPc and a slight lower than H₂L-ZnPc（0.25-fold）at the equivalent ZnPc moiesty concentrations,indicating this H₂L-ZnPc/UiO-68-NH-Met could be used in PDT as an efficient photosensitizer.In order to increase the targeting ability of H₂L-ZnPc/UiO-68-NH-Met,the moisty of SH-PEG5000-FA was decorated into H₂L-ZnPc/UiO-68-NH-Met,namely H₂L-ZnPc/UiO-68-NH-Met-PEG5000-FA.This NMOF has potential application in photodyamic treatment.In conclusion,we have successfully synthesized and designed novel porphyrin and phthalocyanine compounds,and then fabricated NMOFs based on these componds to investigate their photothermal and photodynamic therapy.