Blue-to-red light triggered nitric oxide release in cytotoxic/cytostatic ruthenium nitrosyl complexes bearing biomimetic ligands

Stolyarova, Elena D.; Михайлов, А. М.; Ulantikov, Anton A.; Eremina, Julia A.; Klyushova, Lyubov S.; Kuratieva, Natalia V.; Nadolinny, V. A.; Костин, Г. А.

doi:10.1016/j.jphotochem.2021.113520

Cited by 13 publications

(3 citation statements)

References 46 publications

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“…Both new crystal structures (2)-(3), as well as the previously reported structure (1), are built from the anionic [RuNOCl 4 L] − fragments, which are combined into 1D or 2D structures due to the additional interactions of the chloride ligands or oxygen atoms of nitroxide radicals with sodium cations. The structural parameters of the [RuNOCl 4 L] − moiety in all three structures (Table 1) are close to typical for nitrosyl complexes [23,25,26]. The Ru-Cl distances vary in the range of 2.34-2.40 Å.…”

Section: Structure and Synthesissupporting

confidence: 60%

“…The potentials of the reduction process (nitroxide-hydroxylamine) varies from −1.4 to −0.8 V and the electron acceptors also shift the potentials to higher values [36]. Thus, we can suppose that the cathodic peaks are related to the nitroxide transformations, as well as the anodic peaks, with potentials of 0.6 and 1-1.2 V. The irreversible oxidation process at potentials of 1.2-1.4 V can be assigned to the oxidation of the (RuNO) 3+ group according to the literature data for ruthenium nitrosyls [25,41].…”

Section: Electrochemistrymentioning

confidence: 93%

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New Ruthenium Nitrosyl Complexes Combining Potentially Photoactive Nitrosyl Group with the Magnetic Nitroxide Radicals as Ligands

Kostin,

Kozlov,

Bogomyakov

et al. 2023

IJMS

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Two ruthenium nitrosyl complexes of Na[RuNOCl4L] with nitronyl nitroxide radicals coordinated to ruthenium with N-donor pyridine rings were prepared and described. The crystal structure of both complexes is 1D or 2D polymeric, due to the additional coordination of sodium cation by bridging the chloride ligands or oxygen atoms of nitroxides. Partially, the oligomeric forms remain in the solutions of the complexes in acetonitrile. The magnetic measurements in the solid state demonstrate the presence of antiferromagnetic interactions through the exchange channels, with the distance between paramagnetic centers equal to 3.1–3.9 Å. The electrochemical behavior of the prepared complexes was investigated in acetonitrile solutions.

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Section: Structure and Synthesissupporting

confidence: 60%

Section: Electrochemistrymentioning

confidence: 93%

New Ruthenium Nitrosyl Complexes Combining Potentially Photoactive Nitrosyl Group with the Magnetic Nitroxide Radicals as Ligands

Kostin,

Kozlov,

Bogomyakov

et al. 2023

IJMS

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“…Our previous studies focused on the photolysis processes of the complexes solely in pure solvents (DMSO, acetonitrile, water), while biological studies were conducted in buffer solutions containing about 0.5 % of DMSO by volume. [36][37][38] In this report, to mimic cytotoxicity measurement conditions, phosphatebuffered saline solutions (PBS) containing 0.5 % DMSO were employed to evaluate the behavior of new complex with L = methyl isonicotinate (1), along with previously reported compounds bearing L = ethyl isonicotinate (2), [39] methyl nicotinate (3) and ethyl nicotinate (4). [36] Given that IC 50 values of the complexes range from 1 to 50 μM, a concentration of 50 μM was chosen as adequate for studying photolysis in PBS.…”

Section: Introductionmentioning

confidence: 99%

Ligand Environment and Light: Two Triggers for Controlling Cytotoxicity of Ruthenium Nitrosyl Complexes

Yakovlev,

Golubeva,

Klyushova

et al. 2024

ChemPhotoChem

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Photoinduced nitric oxide (NO) release for complexes [RuNO(L)2(NO2)2OH], where L = methyl isonicotinate (1), ethyl isonicotinate (2), methyl nicotinate (3) and ethyl nicotinate (4) was studied in DMSO, MeCN and water solutions (PBS, CTAB) using spectroscopic methods (UV‐vis, IR, EPR) and spectrometric techniques (ESI‐МS). Additionally, we present methodological evidence for improving the calculation of the quantum yield (QY) of NO release through the utilization of a combined IR‐UV‐vis‐spectroscopy flow‐through setup. According to DFT calculations, the production of nitric oxide occurs through the photoinduced cleavage of the Ru‐NO bond, triggered by irradiation at 445 or 532 nm. This cleavage is a consequence of charge transfer from the orbitals of the Ru‐OH group and the equatorial ligands (HOMO, HOMO‐1) to the Ru‐NO antibonding orbital (LUMO). The cytotoxicity and photoinduced cytotoxicity of the investigated compounds were assessed against the breast adenocarcinoma cell line MCF‐7. Moreover, the investigation of the lipophilic properties of compounds 1‐4 unveiled a significant influence of their lipophilicity on cytotoxic behavior, allowing for the modification of cytotoxicity through changes in the ligand L or by light irradiation.

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Bimetallic Ruthenium Nitrosyl Complexes with Enhanced Two‐Photon Absorption Properties for Nitric Oxide Delivery

Juarez-Martinez

Labra‐Vázquez

Enríquez-Cabrera

et al. 2022

Chemistry A European J

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One monometallic and three bimetallic ruthenium nitrosyl (RuNO) complexes are presented and fully characterized in reference to a parent monometallic complex of formula [FTRu(bpy)(NO)] 3 + , where FT is a fluorenyl-substituted terpyridine ligand, and bpy the 2,2'-bipyridine. These new complexes are built with the new ligands FFT, TFT, TFFT, and TF-CC-TF (where an alkyne C�C group is inserted between two fluorenes). The crystal structures of the bis-RuNO 2 and bis-RuNO complexes built from the TFT ligand are presented. The evolution of the spectroscopic features (intensities and energies) along the series, at one-photon absorption (OPA) correlates well with the TD-DFT computations. A spectacular effect is observed at two-photon absorption (TPA) with a large enhancement of the molecular cross-section (σ TPA ), in the bimetallic species. In the best case, σ TPA is equal to 1523 � 98 GM at 700 nm, in the therapeutic window of transparency of biological tissues. All compounds are capable of releasing NO * under irradiation, which leads to promising applications in TPA-based drug delivery.

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Blue-to-red light triggered nitric oxide release in cytotoxic/cytostatic ruthenium nitrosyl complexes bearing biomimetic ligands

Cited by 13 publications

References 46 publications

New Ruthenium Nitrosyl Complexes Combining Potentially Photoactive Nitrosyl Group with the Magnetic Nitroxide Radicals as Ligands

New Ruthenium Nitrosyl Complexes Combining Potentially Photoactive Nitrosyl Group with the Magnetic Nitroxide Radicals as Ligands

Ligand Environment and Light: Two Triggers for Controlling Cytotoxicity of Ruthenium Nitrosyl Complexes

Bimetallic Ruthenium Nitrosyl Complexes with Enhanced Two‐Photon Absorption Properties for Nitric Oxide Delivery

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