Supercritical CO Synthesis of Porous Metalloporphyrin Frameworks : Application in Photodynamic Therapy
Kubovics, Márta (Institut de Ciència de Materials de Barcelona)
Careta, Oriol (Universitat Autònoma de Barcelona. Departament de Biologia Cel·lular, de Fisiologia i d'Immunologia)
Vallcorba Valls, Oriol (ALBA Laboratori de Llum de Sincrotró)
Romo-Islas, Guillermo (Universitat de Barcelona. Departament de Química Inorgànica i Orgànica)
Rodríguez Raurell, Laura (Universitat de Barcelona. Departament de Química Inorgànica i Orgànica)
Ayllon, Jose Antonio (Universitat Autònoma de Barcelona. Departament de Química)
Domingo, Concepción (Institut de Ciència de Materials de Barcelona)
Nogués, C. (Carme) (Universitat Autònoma de Barcelona. Departament de Biologia Cel·lular, de Fisiologia i d'Immunologia)
Lopez-Periago, Ana M (Institut de Ciència de Materials de Barcelona)

Date:	2023
Abstract:	A series of porous metalloporphyrin frameworks prepared from the 5,10,15,20-tetra(4-pyridyl)porphyrin (HTPyP) linker and four metal complexes, M(hfac) M = Cu(II), Zn(II), Co(II), and Ni(II) (hfac: 1,1,1,5,5,5-hexafluoroacetylacetonate), were obtained using supercritical CO (scCO) as a solvent. All the materials, named generically as [M-TPyP], 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, 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)}HTPyP]. 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.
Grants:	European Commission 754397 Agencia Estatal de Investigación PID2020-116844RB-C21 Agencia Estatal de Investigación PID2020-115631GB-I00 Agencia Estatal de Investigación PID2019-104121GB-I00 Ministerio de Ciencia e Innovación CEX2019-000917-S Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-503
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Published in:	Chemistry of materials, Vol. 35, Issue 3 (February 2023) , p. 1080-1093, ISSN 1520-5002

DOI: 10.1021/acs.chemmater.2c03018
PMID: 36818591

14 p, 10.5 MB

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