View in EDS

Mn(III) porphyrins as photosensitizers: structural, photophysical and anticancer studies.

Saved in:
Bibliographic Details
Title: Mn(III) porphyrins as photosensitizers: structural, photophysical and anticancer studies.
Authors: Bora, Bidisha1 (AUTHOR), Das, Namisha1 (AUTHOR), Sultana, Jakia Parbin1 (AUTHOR), Raza, Md Kausar2 (AUTHOR) kausarraza91@gmail.com, Goswami, Tridib K.1 (AUTHOR) tridibgoswami05@gmail.com
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 8/14/2025, Vol. 54 Issue 30, p11743-11756. 14p.
Subjects: Photosensitizers, Photochemotherapy, HeLa cells, Antineoplastic agents, Metalloporphyrins, Reactive oxygen species, Manganese porphyrins
Abstract: Herein, we synthesized, characterized and explored the photo-triggered anticancer activity of five Mn(III) porphyrins Mn1–Mn5 , viz. (diaqua)meso-(tetraphenylporphyrinato)manganese(III) propionate, [Mn(III)TPP(H2O)2]+(C3H5O2−) or Mn1 ; (diaqua)meso-tetrakis(4-methylphenylporphyrinato)manganese(III) propionate, [Mn(III)TMeP(H2O)2]+(C3H5O2−) or Mn2 ; (diaqua)meso-tetrakis(4-methoxyphenylporphyrinato)manganese(III) propionate, [Mn(III)TMP(H2O)2]+(C3H5O2−) or Mn3 ; (diaqua)meso-tetrakis(4-fluorophenylporphyrinato)manganese(III) propionate, [Mn(III)FTPP(H2O)2]+(C3H5O2−) or Mn4 and (diaqua)meso-tetrakis(4-chlorophenylporphyrinato)manganese(III) propionate, [Mn(III)ClTPP(H2O)2]+(C3H5O2−) or Mn5 , which remain virtually unexplored as photodynamic therapy (PDT) agents like other paramagnetic metalloporphyrins. These Mn(III) porphyrins, bearing different para-substituents on their meso-phenyl rings and two water molecules as axial ligands, were characterized using spectroscopic techniques and structurally through single-crystal X-ray diffraction, revealing an octahedral MnN4O2 geometry. Binding studies demonstrated a strong affinity of the metalloporphyrins for human serum albumin (HSA), indicating their potential for biological applications. The visible light-assisted generation of reactive oxygen species (ROS) by these Mn(III) porphyrins was confirmed via 1,3-diphenylisobenzofuran (DPBF) titration, identifying singlet oxygen (1O2) as one of the primary ROS. Photoredox activity under visible light, displayed by the Mn(III) porphyrins in the presence of ascorbic acid involving +3 and +2 oxidation states of manganese, further underscores the photochemotherapeutic potential of Mn1–Mn5. The ROS generation ability was further validated intracellularly in HeLa cells using Mn4 with the help of 2′,7′-dichlorofluorescein diacetate (DCFDA) assay under visible light irradiation (λ = 400–700 nm). Furthermore, among the five Mn(III) porphyrin complexes (Mn1–Mn5) evaluated for photo-triggered anticancer activity using MTT assays, Mn4 exhibited superior photocytotoxicity, with a half-maximal inhibitory concentration (IC50) of 4.93 ± 0.7 μM against HeLa cancer cells under visible light irradiation and negligible dark toxicity (IC50 > 50 μM). These results suggest that both type-I and type-II ROS generation pathways contribute to the observed photocytotoxicity. This study highlights the potential of paramagnetic metalloporphyrins, particularly Mn(III) porphyrins, in anticancer application by demonstrating their effectiveness as photosensitizers for photodynamic cancer therapy. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
Description
Abstract:Herein, we synthesized, characterized and explored the photo-triggered anticancer activity of five Mn(III) porphyrins Mn1–Mn5 , viz. (diaqua)meso-(tetraphenylporphyrinato)manganese(III) propionate, [Mn(III)TPP(H2O)2]+(C3H5O2−) or Mn1 ; (diaqua)meso-tetrakis(4-methylphenylporphyrinato)manganese(III) propionate, [Mn(III)TMeP(H2O)2]+(C3H5O2−) or Mn2 ; (diaqua)meso-tetrakis(4-methoxyphenylporphyrinato)manganese(III) propionate, [Mn(III)TMP(H2O)2]+(C3H5O2−) or Mn3 ; (diaqua)meso-tetrakis(4-fluorophenylporphyrinato)manganese(III) propionate, [Mn(III)FTPP(H2O)2]+(C3H5O2−) or Mn4 and (diaqua)meso-tetrakis(4-chlorophenylporphyrinato)manganese(III) propionate, [Mn(III)ClTPP(H2O)2]+(C3H5O2−) or Mn5 , which remain virtually unexplored as photodynamic therapy (PDT) agents like other paramagnetic metalloporphyrins. These Mn(III) porphyrins, bearing different para-substituents on their meso-phenyl rings and two water molecules as axial ligands, were characterized using spectroscopic techniques and structurally through single-crystal X-ray diffraction, revealing an octahedral MnN4O2 geometry. Binding studies demonstrated a strong affinity of the metalloporphyrins for human serum albumin (HSA), indicating their potential for biological applications. The visible light-assisted generation of reactive oxygen species (ROS) by these Mn(III) porphyrins was confirmed via 1,3-diphenylisobenzofuran (DPBF) titration, identifying singlet oxygen (1O2) as one of the primary ROS. Photoredox activity under visible light, displayed by the Mn(III) porphyrins in the presence of ascorbic acid involving +3 and +2 oxidation states of manganese, further underscores the photochemotherapeutic potential of Mn1–Mn5. The ROS generation ability was further validated intracellularly in HeLa cells using Mn4 with the help of 2′,7′-dichlorofluorescein diacetate (DCFDA) assay under visible light irradiation (λ = 400–700 nm). Furthermore, among the five Mn(III) porphyrin complexes (Mn1–Mn5) evaluated for photo-triggered anticancer activity using MTT assays, Mn4 exhibited superior photocytotoxicity, with a half-maximal inhibitory concentration (IC50) of 4.93 ± 0.7 μM against HeLa cancer cells under visible light irradiation and negligible dark toxicity (IC50 > 50 μM). These results suggest that both type-I and type-II ROS generation pathways contribute to the observed photocytotoxicity. This study highlights the potential of paramagnetic metalloporphyrins, particularly Mn(III) porphyrins, in anticancer application by demonstrating their effectiveness as photosensitizers for photodynamic cancer therapy. [ABSTRACT FROM AUTHOR]
ISSN:14779226
DOI:10.1039/d4dt03432e