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Supercritical CO 2 Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy.

Márta KubovicsOriol CaretaOriol VallcorbaGuillermo Romo-IslasLaura RodríguezJosé A AyllónConcepción DomingoCarme NoguésAna M López-Periago
Published in: Chemistry of materials : a publication of the American Chemical Society (2023)
A series of porous metalloporphyrin frameworks prepared from the 5,10,15,20-tetra(4-pyridyl)porphyrin (H 2 TPyP) linker and four metal complexes, M(hfac) 2 M = Cu(II), Zn(II), Co(II), and Ni(II) (hfac: 1,1,1,5,5,5-hexafluoroacetylacetonate), were obtained using supercritical CO 2 (scCO 2 ) as a solvent. All the materials, named generically as [M-TPyP] n , formed porous metal-organic frameworks (MOFs), with surface areas of ∼450 m 2 g -1 . All MOFs were formed through the coordination of the metal to the exocyclic pyridine moieties in the porphyrin linker. For Cu(II), Zn(II), and Co(II), incomplete metal coordination of the inner pyrrole ring throughout the structure was observed, giving place to MOFs with substitutional defects and leading to a certain level of disorder and limited crystallinity. These samples, prepared using scCO 2 , were precipitated as nano- to micrometric powders. Separately, a layering technique from a mixture of organic solvents was used to crystallize high-quality crystals of the Co(II) based MOF, obtained with the formula [{Co(hfac) 2 } 2 H 2 TPyP] n . The crystal structure of this MOF was elucidated by single-crystal synchrotron X-ray diffraction. The Zn(II)-based MOF was selected as a potential photodynamic therapy drug in the SKBR-3 tumoral cell line showing outstanding performance. This MOF resulted to be nontoxic, but after 15 min of irradiation at 630 nm, using either 1 or 5 μM concentration of the product, almost 70% of tumor cells died after 72 h.
Keyphrases
  • metal organic framework
  • photodynamic therapy
  • magnetic resonance imaging
  • heavy metals
  • emergency department
  • magnetic resonance
  • radiation therapy
  • climate change
  • ionic liquid
  • quantum dots