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Ru(II) Phenanthroline-Based Oligothienyl Complexes as Phototherapy Agents.
Cole, Houston D; Vali, Abbas; Roque, John A; Shi, Ge; Kaur, Gurleen; Hodges, Rachel O; Francés-Monerris, Antonio; Alberto, Marta E; Cameron, Colin G; McFarland, Sherri A.
Afiliação
  • Cole HD; Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019-0065, United States.
  • Vali A; Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019-0065, United States.
  • Roque JA; Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019-0065, United States.
  • Shi G; Department of Chemistry and Biochemistry, The University of North Carolina at Greensboro, Greensboro, North Carolina 27402, United States.
  • Kaur G; Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019-0065, United States.
  • Hodges RO; Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019-0065, United States.
  • Francés-Monerris A; Department of Chemistry and Biochemistry, The University of North Carolina at Greensboro, Greensboro, North Carolina 27402, United States.
  • Alberto ME; Institut de Ciència Molecular, Universitat de València, 46071 València, Spain.
  • Cameron CG; Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, Arcavacata di Rende 87036, Italy.
  • McFarland SA; Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019-0065, United States.
Inorg Chem ; 62(51): 21181-21200, 2023 Dec 25.
Article em En | MEDLINE | ID: mdl-38079387
Ru(II) polypyridyl complexes have gained widespread attention as photosensitizers for photodynamic therapy (PDT). Herein, we systematically investigate a series of the type [Ru(phen)2(IP-nT)]2+, featuring 1,10-phenanthroline (phen) coligands and imidazo[4,5-f][1,10]phenanthroline ligands tethered to n = 0-4 thiophene rings (IP-nT). The complexes were characterized and investigated for their electrochemical, spectroscopic, and (photo)biological properties. The electrochemical oxidation of the nT unit shifted by -350 mV as n = 1 → 4 (+920 mV for Ru-1T, +570 mV for Ru-4T); nT reductions were observed in complexes Ru-3T (-2530 mV) and Ru-4T (-2300 mV). Singlet oxygen quantum yields ranged from 0.53 to 0.88, with Ru-3T and Ru-4T being equally efficient (∼0.88). Time-resolved absorption spectra of Ru-0T-1T were dominated by metal-to-ligand charge-transfer (3MLCT) states (τTA = 0.40-0.85 µs), but long-lived intraligand charge-transfer (3ILCT) states were observed in Ru-2T-4T (τTA = 25-148 µs). The 3ILCT energies of Ru-3T and Ru-4T were computed to be 1.6 and 1.4 eV, respectively. The phototherapeutic efficacy against melanoma cells (SK-MEL-28) under broad-band visible light (400-700 nm) increases as n = 0 → 4: Ru-0T was inactive up to 300 µM, Ru-1T-2T were moderately active (EC50 ∼ 600 nM, PI = 200), and Ru-3T (EC50 = 57 nM, PI > 1100) and Ru-4T (EC50 = 740 pM, PI = 114,000) were the most phototoxic. The activity diminishes with longer wavelengths of light and is completely suppressed for all complexes except Ru-3T and Ru-4T in hypoxia. Ru-4T is the more potent and robust PS in 1% O2 over seven biological replicates (avg EC50 = 1.3 µM, avg PI = 985). Ru-3T exhibited hypoxic activity in five of seven replicates, underscoring the need for biological replicates in compound evaluation. Singlet oxygen sensitization is likely responsible for phototoxic effects of the compounds in normoxia, but the presence of redox-active excited states may facilitate additional photoactive pathways for complexes with three or more thienyl groups. The 3ILCT state with its extended lifetime (30-40× longer than the 3MLCT state for Ru-3T and Ru-4T) implicates its predominant role in photocytotoxicity.
Assuntos

Texto completo: 1 Base de dados: MEDLINE Assunto principal: Fotoquimioterapia / Rutênio Idioma: En Ano de publicação: 2023 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Assunto principal: Fotoquimioterapia / Rutênio Idioma: En Ano de publicação: 2023 Tipo de documento: Article