Water-mediated reduction of [Cu(dmp)2(CH3CN)]2+: implications of the structure of a classical complex on its activity as an anticancer drug

Levin, P.I.; Ruiz, Manuel; Romo, Adolfo I. B.; Nascimento, Otaciro Rangel; Virgilio, Ana Laura Di; Oliver, Allen G.; Ayala, A. P.; Diógenes, Izaura C.N.; León, Ignacio E.; Lemus, Luis

doi:10.1039/d1qi00233c

Cited by 24 publications

(24 citation statements)

References 76 publications

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“…The 1:2:2:1 integration ratio of the hyperfine signals, together with the values of α N = 14.9 G and α β H = 14.89 G, unequivocally prove that the species generated by the BDD substrate is [DMPO–OH] • (Figure b). This indicates the straightforward adduct-formation reaction between • OH and DMPO in eq . − Experiments at variable pH (Figure S2) showed that the formation of the [DMPO–OH] • is also observed at more acidic pH values. In contrast, the formation of the [DMPOO] • species was observed at pH 7.…”

Section: Resultsmentioning

confidence: 78%

Real-Time Detection of Hydroxyl Radical Generated at Operating Electrodes via Redox-Active Adduct Formation Using Scanning Electrochemical Microscopy

et al. 2022

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The hydroxyl radical (•OH) is one of the most attractive reactive oxygen species due to its high oxidation power and its clean (photo)(electro)generation from water, leaving no residues and creating new prospects for efficient wastewater treatment and electrosynthesis. Unfortunately, in situ detection of •OH is challenging due to its short lifetime (few ns). Using lifetime-extending spin traps, such as 5,5-dimethyl-1-pyrroline N-oxide (DMPO) to generate the [DMPO–OH]• adduct in combination with electron spin resonance (ESR), allows unambiguous determination of its presence in solution. However, this method is cumbersome and lacks the necessary sensitivity and versatility to explore and quantify •OH generation dynamics at electrode surfaces in real time. Here, we identify that [DMPO–OH]• is redox-active with E 0 = 0.85 V vs Ag|AgCl and can be conveniently detected on Au and C ultramicroelectrodes. Using scanning electrochemical microscopy (SECM), a four-electrode technique capable of collecting the freshly generated [DMPO–OH]• from near the electrode surface, we detected its generation in real time from operating electrodes. We also generated images of [DMPO–OH]• production and estimated and compared its generation efficiency at various electrodes (boron-doped diamond, tin oxide, titanium foil, glassy carbon, platinum, and lead oxide). Density functional calculations, ESR measurements, and bulk calibration using the Fenton reaction helped us unambiguously identify [DMPO–OH]• as the source of redox activity. We hope these findings will encourage the rapid, inexpensive, and quantitative detection of •OH for conducting informed explorations of its role in mediated oxidation processes at electrode surfaces for energy, environmental, and synthetic applications.

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Section: Resultsmentioning

confidence: 78%

Real-Time Detection of Hydroxyl Radical Generated at Operating Electrodes via Redox-Active Adduct Formation Using Scanning Electrochemical Microscopy

et al. 2022

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“…DHR‐123 is a mitochondria‐associated probe which specifically reacts with hydrogen peroxide. Complex 70 , incubated in different concentrations from 0.5 to 2.5 μ M in the cell lines of MG‐63, A549, MCF7 and MDA‐MB‐231 showed a huge increase on the ROS generation in a dose dependent manner from 0.5 to 2.5 μM, while complex 71 was silent in the same experimental condition [127] …”

Section: Copper Complexes Used In Chemotherapeutic Approachmentioning

confidence: 93%

Recent Development of Copper (II) Complexes of Polypyridyl Ligands in Chemotherapy and Photodynamic Therapy

Roy

2023

ChemMedChem

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Cancer is a deadly disease associated with abnormal cell growth and invasion to various parts of the body. Many drugs such as cisplatin and carboplatin have been used for the treatment of cancer over the years. However, a lack of selectivity toward cancer cells and associated side effects with current treatment options has fueled continued efforts throughout the world to find better anticancer drugs. Over the past decades, copper‐containing compounds have shown excellent anticancer activity. Cu(II) complexes are well studied and show broad‐spectrum pharmacological activity. The redox activity of copper ions contributes to cytotoxic activity in combination with ligands that possess bioactivity. Binding of copper with various types of bidentate, tridentate, and tetradentate ligands can activate the processes of necrosis, apoptosis, and angiogenesis. Copper induces the formation of reactive oxygen species to cleave DNA. Similarly, light‐assisted excitation of Cu(II) complexes in the red region of the electromagnetic spectrum helps produce different reactive species, thereby inducing anticancer activity through a photodynamic mechanism. In general, in vivo and in vitro studies have demonstrated that the administration of copper ions is effective against various cancer cell lines. Herein we discuss the past ten years of research into copper complexes of terpyridine‐, 2,2’‐bipyridine‐, and 1,10‐phenanthroline‐based ligands as potential anticancer agents. The aspects of chemotherapy by redox‐mediated pathways and photodynamic therapy using light‐assisted excitation are reviewed, with a focus on mechanisms of activity, details of important experimental procedures, as well as drawbacks in the design of copper‐containing drugs.

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“…Absorption in the UV region corresponds to the π–π* transitions of the phenanthroline ligands (and the pyrene group in the case of complex 3 ), and the absorption band at 450 nm accompanied with a shoulder band at 550 nm is characteristic of the metal-to-ligand charge transfer (MLCT) band of this 2,9-dialkylphenanthroline copper complex family. , This “autoreduction” phenomenon has been already investigated in the case of 6,6′-dialkyl-2,2′-bipyridine ligand . Partial and slow reduction have also been observed for the parent complex Cu II (dmp) 2 without being further investigated. , In this work, the fast reduction of all three complexes, especially in DMF, is undoubtedly triggered by the high redox potential and the higher constraint brought by the bulky substituent to the Cu(II) geometry. This is especially the case in non-coordinating solvents where the Cu(II) metal cannot coordinate a fifth ligand to adopt a more favorable geometry.…”

Section: Resultsmentioning

confidence: 97%

“…74 Partial and slow reduction have also been observed for the parent complex Cu II (dmp) 2 without being further investigated. 75,76 In this work, the fast reduction of all three complexes, especially in DMF, is undoubtedly triggered by the high redox potential and the higher constraint brought by the bulky substituent to the Cu(II) geometry. This is especially the case in non-coordinating solvents where the Cu(II) metal cannot coordinate a fifth ligand to adopt a more favorable geometry.…”

Section: ■ Introductionmentioning

confidence: 93%

Functionalizing Carbon Nanotubes with Bis(2,9-dialkyl-1,10-phenanthroline)copper(II) Complexes for the Oxygen Reduction Reaction

et al. 2022

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A new ligand, namely, 2-(5-(pyren-1-yl)pentyl)-9-methyl-1,10-phenanthroline, as well as new bis(2,9-dialkyl-1,10-phenanthroline)copper(II) complexes were designed, which were immobilized on multiwalled carbon nanotube (MWCNT) electrodes. These complexes show a high tendency of autoreduction into their copper(I) form according to electrochemical and EPR experiments. These complexes exhibit strong interactions with MWCNT sidewalls either with or without anchor functions such as the pyrene moiety. The pyrene-modified derivative can be electropolymerized on glassy carbon and MWCNT electrodes to form a poly-[bis(2-(5-(pyren-1-yl)pentyl)-9-methyl-1,10-phenanthroline)copper(II)] metallopolymer film. Furthermore, these MWCNT-supported bis(2,9-dialkyl-1,10-phenanthroline)copper complexes demonstrate a low overpotential for a 4H+/4e– oxygen reduction reaction at pH 5 with an onset potential of 0.86 V versus RHE. Integration of these functionalized MWCNTs at gas-diffusion electrodes of H2/air fuel cells led to a high open-circuit voltage of 0.84 V and a maximum current density of 1.77 mW cm–2 using a Pt/C anode.

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Water-mediated reduction of [Cu(dmp)₂(CH₃CN)]²⁺: implications of the structure of a classical complex on its activity as an anticancer drug

Abstract: The interplay between coordination geometry and reactivity in copper complexes has been widely studied for years. For CuII, it is known that the reduction is favored when the geometry is...

Cited by 24 publications

References 76 publications

Real-Time Detection of Hydroxyl Radical Generated at Operating Electrodes via Redox-Active Adduct Formation Using Scanning Electrochemical Microscopy

Real-Time Detection of Hydroxyl Radical Generated at Operating Electrodes via Redox-Active Adduct Formation Using Scanning Electrochemical Microscopy

Recent Development of Copper (II) Complexes of Polypyridyl Ligands in Chemotherapy and Photodynamic Therapy

Functionalizing Carbon Nanotubes with Bis(2,9-dialkyl-1,10-phenanthroline)copper(II) Complexes for the Oxygen Reduction Reaction

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