Half‐Sandwich Metal Complexes with β‐Diketone‐Like Ligands and Their Anticancer Activity

Pettinari, Riccardo; Marchetti, Fábio; Nicola, Corrado Di; Pettinari, Cláudio

doi:10.1002/ejic.201800400

Cited by 31 publications

(31 citation statements)

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“…These ligands are found in carbo-RAPTA and oxali-RAPTA as well [9]. -diketones are one of the oldest groups of (O,O) ligands used in analytical and synthetic approaches and a plenty of their half-sandwich complexes were synthesized [13]. The simplest -diketone molecule is acetylacetone (Hacac, Chart 1), however there are numerous natural compounds containing this motif such as dibenzoylmethane (Glycyrrhiza glabra) [14], gingerols (Zingiber officinale) or curcumin…”

Section: F][110-phenanthroline)]cl2mentioning

confidence: 99%

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Comparative solution and structural studies of half-sandwich rhodium and ruthenium complexes bearing curcumin and acetylacetone

Mészáros

Poljarević

Gál

et al. 2019

Journal of Inorganic Biochemistry

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Please cite this article as: J.P. Mészáros, J.M. Poljarevic, G.T. Gál, et al., Comparative solution and structural studies of half-sandwich rhodium and ruthenium complexes bearing curcumin and acetylacetone, Journal of Inorganic Biochemistry, https://doi.ABSTRACT Half-sandwich organometallic complexes of curcumin are extensively investigated as anticancer compounds. Speciation studies were performed to explore the solution stability of curcumin complexes formed with [Rh( 5 -C5Me5)(H2O)3] 2+ . Acetylacetone (Hacac), as the simplest -diketone ligand bearing (O,O) donor set, was involved for comparison and its Ru( 6 -p-cymene), Ru( 6 -toluene) complexes were also studied. 1 H NMR, UV-visible and pH-potentiometric titrations revealed a clear trend of stability constants of the acac complexes: Ru( 6 -p-cymene) > Ru( 6 -toluene) > Rh( 5 -C5Me5). Despite this order, the highest extent of complex formation is seen for the Rh( 5 -C5Me5) complexes at pH 7.4. Formation constant of [Rh( 5 -C5Me5)(H2curcumin)(H2O)] + reveals similar solution stability to that of the acac complex. Additionally, structures of two complexes were determined by Xray crystallography. The in vitro cytotoxicity of curcumin was not improved by the complexation with these organometallic cations. Highlights ► Solution stability of Ru(arene) and Rh(C5Me5) complexes of acac and curcumin ► Acac is used as curcumin binding model ► X-ray crystal structures of two complexes and comparison with analogous structures ► Antiproliferative activity against multidrug resistant human cancer cell lines ► Human serum albumin binding and interaction with cell culture medium components

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Section: F][110-phenanthroline)]cl2mentioning

confidence: 99%

“…[Rh( 5 -C5Me5)(H2curc)(H2O)] + complex is considered as a delivery system of curcumin since its cytotoxicity is similar to that of the ligand itself [23]. The combination of PTA and curcumin in half-sandwich organo-metallic complexes could enhance the bioactivity [13].…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Comparative solution and structural studies of half-sandwich rhodium and ruthenium complexes bearing curcumin and acetylacetone

Mészáros

Poljarević

Gál

et al. 2019

Journal of Inorganic Biochemistry

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“…Nevertheless, research on cyclometalated rhodium complexes has largely focused on non‐cyclopentadienyl cyclometalated rhodium complexes that target DNA, enzyme or protein–protein interfaces , , . Reported cyclopentadienyl rhodium anticancer complexes to date, have mainly contained N ^ N,, N ^ S, N ^ O, or O ^ O, , chelating ligands.…”

Section: Introductionmentioning

confidence: 99%

“…[15,16] Nevertheless, research on cyclometalated rhodium complexes has largely focused on non-cyclopentadienyl cyclometalated rhodium complexes that target DNA, enzyme or protein-protein interfaces. [5,9,[17][18][19][20] Reported cyclopentadienyl rhodium anticancer complexes to date, have mainly contained N^N, [21,22] N^S, [23] N^O, [24][25][26] or O^O [22,27,28] chelating ligands. ficient catalyst in coenzyme reduced nicotinamide adenine dinucleotide (NADH) oxidation to NAD + and induced an elevated level of reactive oxygen species (ROS) in A549 human lung cancer cells.…”

Section: Introductionmentioning

confidence: 99%

Ligand‐Controlled Reactivity and Cytotoxicity of Cyclometalated Rhodium(III) Complexes

et al. 2019

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We report the synthesis, characterization and cytotoxicity of six cyclometalated rhodium(III) complexes [CpXRh(C^N)Z]0/+, in which CpX = Cp*, Cpph, or Cpbiph, C^N = benzo[h]quinoline, and Z = chloride or pyridine. Three X‐ray crystal structures showing the expected “piano‐stool” configurations have been determined. The chlorido complexes hydrolyzed faster in aqueous solution, and reacted preferentially with 9‐ethyl guanine or glutathione compared to their pyridine analogues. The 1‐biphenyl‐2,3,4,5‐tetramethylcyclopentadienyl complex [CpbiphRh(benzo‐[h]quinoline)Cl] (3a) was the most efficient catalyst in coenzyme reduced nicotinamide adenine dinucleotide (NADH) oxidation to NAD+ and induced an elevated level of reactive oxygen species (ROS) in A549 human lung cancer cells. The pyridine complex [CpbiphRh(benzo[h]quinoline)py]+ (3b) was the most potent against A549 lung and A2780 ovarian cancer cell lines, being 5‐fold more active than cisplatin towards A549 cells, and acted as a ROS scavenger. This work highlights a ligand‐controlled strategy to modulate the reactivity and cytotoxicity of cyclometalated rhodium anticancer complexes.

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“…In the monoanionic form, Cur ligand and derivatives can be conveniently engaged in binding to a metal ion, particularly iron, ruthenium, copper, and zinc, suggesting the option to employ metalation for enhancing chemical stability, bioavailability, and anticancer activity. 16,17 Notably, a water-soluble curcumin-modified Ru(II) arene complex has been recently reported with superior in vitro cytotoxicity and selectivity index in comparison with cisplatin. 18 Attention has also been focused on the development of Cur complexes of radioactive metals, including Technetium-99m 19 and Gallium-68 20 labeled radiopharmaceuticals, as new potential radiotracers for diagnosis of cancer and AD.…”

Section: Introductionmentioning

confidence: 99%

Vibrational signatures of curcumin’s chelation in copper(II) complexes: An appraisal by IRMPD spectroscopy

Corinti

Maccelli

Chiavarino

et al. 2019

The Journal of Chemical Physics

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Curcumin (Cur) is a natural polyphenol with a wide spectrum of biological activities and appealing therapeutic potential. Herein, it has been delivered by electrospray ionization as gaseous protonated species, [Cur + H] + , and as a Cu(II) complex, [Cu(Cur − H)] + , a promising antioxidant and radical scavenger. The gas phase structures were assayed by infrared multiple photon dissociation (IRMPD) spectroscopy in both the fingerprint (800-2000 cm −1) and hydrogen stretching (3100-3750 cm −1) ranges. Comparison between the experimental features and linear IR spectra of the lowest energy structures computed at the B3LYP/6-311+G(d,p) level reveals that bare [Cu(Cur − H)] + exists in a fully planar and symmetric arrangement, where the metal interacts with the two oxygens of the syn-enolate functionality of deprotonated Cur and both OCH 3 groups are engaged in H-bonding with the ortho OH. The effect of protonation on the energetic and geometric determinants of Cur has been explored as well, revealing that bare [Cur + H] + may exist as a mixture of two close-lying isomers associated with the most stable binding motifs. The additional proton is bound to either the diketo or the keto-enol configuration of Cur, in a bent or nearly planar arrangement, respectively.

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Half‐Sandwich Metal Complexes with β‐Diketone‐Like Ligands and Their Anticancer Activity

Abstract: Half-sandwich organometal complexes of Ru II , Os II , Rh III and Ir III with -diketone-like ligands have been extensively explored as potential prodrugs in anticancer therapy in recent

Cited by 31 publications

References 70 publications

Comparative solution and structural studies of half-sandwich rhodium and ruthenium complexes bearing curcumin and acetylacetone

Comparative solution and structural studies of half-sandwich rhodium and ruthenium complexes bearing curcumin and acetylacetone

Ligand‐Controlled Reactivity and Cytotoxicity of Cyclometalated Rhodium(III) Complexes

Vibrational signatures of curcumin’s chelation in copper(II) complexes: An appraisal by IRMPD spectroscopy

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