The nanoscaled metal-organic framework ICR-2 as a carrier of porphyrins for photodynamic therapy

Abstract

Nanosized porphyrin-containing metal-organic frameworks (MOFs) attract considerable attention as solid-state photosensitizers for biological applications. In this study, we have for the first time synthesised and characterised phosphinate-based MOF nanoparticles, nanoICR-2 (Inorganic Chemistry Rez). We demonstrate that nanoICR-2 can be decorated with anionic 5,10,15,20-tetrakis(4-R-phosphinatophenyl)porphyrins (R = methyl, isopropyl, phenyl) by utilizing unsaturated metal sites on the nanoparticle surface. The use of these porphyrins allows for superior loading of the nanoparticles when compared with commonly used 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin. The nanoICR-2/porphyrin composites retain part of the free porphyrins photophysical properties, while the photodynamic efficacy is strongly affected by the R substituent at the porphyrin phosphinate groups. Thus, phosphinatophenylporphyrin with phenyl substituents has the strongest photodynamic efficacy due to the most efficient cellular uptake.

Porphyrin‐Based Metal–Organic Frameworks for Biomedical Applications

“…Demel et al developed aphosphinate-based MOF (ICR-2, Inorganic Chemistry Rez No.2), which could be decorated with anionic 5,10,15,20-tetrakis(4-R-phosphinatophenyl)porphyrins (TPPPi(R), R = methyl, isopropyl, phenyl) by interaction with the unsaturated metal sites on the ICR-2 surface. [27] Thefraction of TPPPi(R) decorated on the MOFs was higher than that possible with the commercially available 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP). This might be explained by the fact that the bond between the metal ions and the phosphinic groups in TPPPi(R) is stronger than that between the metal ions and the carboxylic groups in TCPP.…”

“…developed a phosphinate‐based MOF (ICR‐2, Inorganic Chemistry Rez No. 2), which could be decorated with anionic 5,10,15,20‐tetrakis(4‐R‐phosphinatophenyl)porphyrins (TPPPi(R), R=methyl, isopropyl, phenyl) by interaction with the unsaturated metal sites on the ICR‐2 surface [27] . The fraction of TPPPi(R) decorated on the MOFs was higher than that possible with the commercially available 5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin (TCPP).…”

Metal-Organic Frameworks and Their Composites Towards Biomedical Applications

“…Both strategies could make MOFs conductive in PDT. Until now, various PSs such as porphyrin derivatives (Hynek et al, 2018;Kan et al, 2018), Ce6 (Fu et al, 2020), BODIPY (Wang et al, 2016;Guan et al, 2018), TMPyP4 (Meng et al, 2018), and ZnPc (Xu et al, 2018) have been successfully loaded in different MOFs for PDT. MOFs constructed with porphyrin derivatives as organic linkers were also widely used for PDT (Ma et al, 2017;Zhou et al, 2018b;Gao et al, 2019).…”

Porphyrin‐basierte Metall‐organische Gerüste für biomedizinische Anwendungen

“…B. Phosphinat‐basierte MOFs entwickelt (ICR‐2, Inorganic Chemistry Rez No. 2), die mit anionischen 5,10,15,20‐Tetrakis(4‐R‐phosphinatophenyl)porphyrinen (TPPPi(R), R=Methyl, Isopropyl, Phenyl) durch die Wechselwirkung zwischen koordinativ ungesättigten Metallzentren an der Oberfläche von ICR‐2 funktionalisiert werden konnten [27] . Ein höherer Anteil von TPPPi(R) konnte an der Oberfläche des MOF angebracht werden als bei Verwendung des kommerziell erhältlichen TCPP (5,10,15,20‐Tetrakis(4‐carboxyphenyl)porphyrin), was darauf zurückgeführt werden kann, dass die Bindung der Phosphinate in TPPPi(R) an die Metallzentren stärker ist als jene der Carboxylate in TCPP.…”