Article pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Surface Decorated Porphyrinic Nanoscale Metal−Organic Framework for Photodynamic Therapy Jing-Lan Kan,*,†,‡ Yuan Jiang,†,‡ Anqi Xue,§ Ying-Hao Yu,† Quanbo Wang,§ Yang Zhou,† and Yu-Bin Dong*,† †
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, People’s Republic of China § Shandong Analysis and Test Center, Qilu University of Technology (Shandong Academy of Sciences), Jinan, Shandong 250014, People’s Republic of China S Supporting Information *
ABSTRACT: Nanocrystallization of organic molecular photosensitizers (PSs) by means of NMOF platforms has been demonstrated to be a promising approach to build up highly efficient PDT therapeutics. We report herein a new UiO-66 type of NMOF-based PS (UiO-66-TPP-SH), which is generated from UiO-66 NMOF and S-ethylthiol ester monosubstituted metal free porphyrin (TPP-SH) via a facile postsynthetic approach under mild conditions. The obtained NMOF (size less than 150 nm) with surface-decorated porphyrinic PS can not only retain MOF crystallinity, structural feature, and size, but also exhibit highly efficient singlet oxygen generation. Compared to the interior-located porphyrinic NMOF, UiO-66TPP-SH shows significantly higher photodynamic activity and more efficient PDT tumor treatment.
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overcome these drawbacks. For example, Lin14,15 and Zhou16,17 groups reported a series of interesting porphyrinic linker-based Zr- and Hf-MOFs via one-pot synthetic approach for PDT treatment. Indeed, the introduction of porphyrinic moiety into periodic and porous NMOF frameworks in this way effectively avoided their aggregation and largely improved their cellular uptake at the tumor sites during the PDT treatment.6 In principle, PSs can also be nanocrystallized via NMOF platform by postsynthetic approach.18 It is different from one-pot synthesis of porphyrin-based NMOFs, the grafting of large sized porphyrinic PSs via postmodification would result in an external surface decoration of the MOF nanoparticles. Reasonably, the surface modification on nanoparticles by predesigned porphyrinic moieties could preserve not only the NMOF structural integrity but also the porphyrinic photosensitive property. The postsynthetic porphyrinic NMOF with 1O2 generation, to our knowledge, still remains undeveloped. On the other hand, the reactive oxygen species (ROS) feature high reactivity and short half-life. For example, the 1O2 half-life in biological system is
