Metals in Cancer Research: Beyond Platinum Metallodrugs

ACS Central Science, Journal Year: 2024, Volume and Issue: 10(2), P. 242 - 250

Published: Feb. 7, 2024

The discovery of the medicinal properties platinum complexes has fueled design and synthesis new anticancer metallodrugs endowed with unique modes action (MoA). Among various families experimental antiproliferative agents, organometallics have emerged as ideal platforms to control compounds' reactivity stability in a physiological environment. This is advantageous efficiently deliver novel prodrug activation strategies, well acting only via noncovalent interactions their pharmacological targets. Noteworthy, another justification for advance organometallic compounds therapy stems from ability catalyze bioorthogonal reactions cancer cells. When not yet drug leads, such can be used selective chemical tools that benefit advantages catalytic amplification either label target interest (e.g., proteins) or boost output biochemical signals. Examples so-called "catalysis cells" are considered this Outlook together other candidates. selected case studies discussed frame more general challenges field inorganic chemistry.

Language: Английский

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Synergy Between Metal and Molecular Catalysts for (Photo)electrocatalytic 1,4-NADH Regeneration

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(14), P. 5927 - 5933

Published: April 2, 2024

(Photo)electrocatalytic NAD+ reduction provides a promising approach for 1,4-NADH regeneration, but it remains challenging to achieve both high activity and selectivity. Here, we found prominent synergetic effects between various metals (Cu, Fe, Co, Ni) Rh-based complexes (M M') electrocatalytic reduction, promoting the selectivity simultaneously. Typically, normalized of Cu M coupled system is 15.6 times that M, while alone shows negligible at same potential. Meanwhile, enhanced from 63.3% as 95.3% system. We transfer hydrogen atoms metal electrode complex accelerates formation metal-hydride active species, which catalyzes regioselective production 1,4-NADH. This work universal strategy coupling proton-reduction electrocatalysts molecular catalysts efficient (photo)electrocatalytic 1,4-NAD(P)H regeneration.

Language: Английский

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Electrochemical NADH Regeneration Mediated by Pyridine Amidate Iridium Complexes Interconverting 1,4- and 1,6-NADH

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(13), P. 10334 - 10343

Published: June 25, 2024

Although there is a huge interest in redox mediators for the selective electrochemical regeneration of 1,4-NADH, only class rhodium compounds with bipyridine ligands, initially introduced by pioneering work Wienkamp and Steckhan (Wienkamp, R.; Steckhan, E. Angew. Chem. Int. Ed. Engl. 1982, 21, 782−783, 10.1002/anie.198207822), has been developed over last few decades. Here we report first two progenitors indirect NADH regeneration, namely [Cp*Ir(R′-pica)Cl] {pica = R′-picolinamidate κ2-R′-pyridine-2-carboxamide ion (−1), 1 R′ H 2 Me}, which exhibit high TOF values (0.51 1.34 s–1 2, respectively), production rate up to 3 μmol h–1 cm–2, faradaic efficiency 99% both complexes 0.1 M phosphate buffer (pH 7, 298 K). The reaction exclusively leads mixture desired product, 1,6-NADH always 91:9 molar ratio, independently mediator, degree conversion, applied potential. 1H EXSY NMR unequivocally shows that rapid equilibrium establishes between 1,4-NADH (Keq 10.1, ΔG0 −1.4 kcal mol–1, K), presence suggesting latter are capable rapidly interconverting regioisomers NADH, thus allowing utilization totality regenerated NADH.

Language: Английский

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Designing biomimetic catalytic systems for CO₂ reduction to formate using NAD(P)H

Inorganic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review article focuses on current achievements and identifies future research directions by designing biomimetic catalytic systems for CO 2 reduction to formate using NAD(P)H.

Language: Английский

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Light-enhancing ketone transfer hydrogenation catalyzed by diphosphine phenanthroline ruthenium complexes

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 564, P. 114337 - 114337

Published: June 27, 2024

Language: Английский

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Efficient, Facile, and Green Synthesis of Ruthenium Carboxylate Complexes by Manual Grinding

Processes, Journal Year: 2024, Volume and Issue: 12(7), P. 1413 - 1413

Published: July 6, 2024

Recently, scientists have been developing sustainable processes, and in this context, mechanochemistry is commonly associated with green chemistry for its ability to reduce waste generation from chemical reactions. The well-known acetate complex, diacetate bis(triphenylphosphine) ruthenium(II) [Ru(OAc)2(PPh3)2], a versatile precursor preparing active complexes several catalytic This report presents an efficient straightforward manual grinding protocol the synthesis of ruthenium carboxylate starting commercially available [RuCl2(PPh3)3] metal carboxylates. work represents novel preliminary investigation into precursors’ alternative solventless route based on grinding. To our knowledge, first time [Ru(OAc)2(PPh3)2] has prepared via mechanochemical procedure. method also investigated other alkali carboxylates yields ranging 30 80% were obtained. A comparison sustainability environmental impact between conventional solution carried out using E-factor Mass Productivity. While complex MP only slightly better compared solvent (3 vs. 4 ~6 5 MP), benzoate higher results found (1 ~4 10 MP).

Language: Английский

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Electrochemistry of ruthenium solid-state surface: fabrication and application

Electrochemistry, Journal Year: 2024, Volume and Issue: unknown, P. 136 - 173

Published: Nov. 27, 2024

The requirement for energy, stokehole chemicals, quality controls, monitoring public health, and environmental pollution encouraged the investigation rate to develop compounds with distinctive properties special applications. Researchers have proven that ruthenium (Ru) solid-state substances possess potential characteristics such as conductivity, stability, catalytic activity, ability integrate many other compounds. Intensive research has led progression of novel technologies, these nanomaterials demonstrated their enormous in various industries, especially field chemical industrial catalysts. Ru surfaces demonstrate high effectiveness efficiency catalyzing large numbers reactions. recent trend involves nanoparticles, graphene, gold, bimetallic alloys. critical enhancements were stability improving active site numbers. based electronic devices capacitors show excellent performance terms current density charge/discharge recycling ability. Also, most progress Ru-complexes base electromigrated chemiluminescent sensor unlimited its analytical gradually, researchers enabled creation surface sensors an number analytes. In this chapter, electrochemistry applications attractive fields are explored, is synthesis properties.

Language: Английский

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Cyclometalated and NNN Terpyridine Ruthenium Photocatalysts and Their Cytotoxic Activity

Molecules, Journal Year: 2024, Volume and Issue: 29(9), P. 2146 - 2146

Published: May 5, 2024

The cyclometalated terpyridine complexes [Ru(η2-OAc)(NC-tpy)(PP)] (PP = dppb 1, (R,R)-Skewphos 4, (S,S)-Skewphos 5) are easily obtained from the acetate derivatives [Ru(η2-OAc)2(PP)] dppb, 2, 3) and tpy in methanol by elimination of AcOH. precursors 3 prepared [Ru(η2-OAc)2(PPh3)2] Skewphos cyclohexane. Conversely, NNN [Ru(η1-OAc)(NNN-tpy)(PP)]OAc 6, 7) synthesized a one pot reaction [Ru(η2-OAc)2(PPh3)2], PP methanol. neutral NC-tpy 5 cationic NNN-tpy 7 catalyze transfer hydrogenation acetophenone (S/C 1000) 2-propanol with NaOiPr under light irradiation at 30 °C. Formation (S)-1-phenylethanol has been observed 6 MeOH/iPrOH mixture, whereas R-enantiomer is 5, (50–52% ee). show cytotoxic activity against anaplastic thyroid cancer 8505C SW1736 cell lines (ED50 0.31–8.53 µM), displaying an ED50 0.31 µM, four times lower compared to enantiomer 6.

Language: Английский

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Ir(III) Diamine Transfer Hydrogenation Catalysts in Cancer Cells

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

Abstract The development of catalytic metallodrugs is an emerging field that may offer new approaches to cancer chemotherapeutic design. By exploiting the unique properties transition metal complexes, in‐cell catalysis can be applied modulate cellular redox balance as part a multi‐targeting mechanism action. We describe synthesis and characterization six coordinatively unsaturated iridium(III) diamine catalysts are stable at physiological pH in aqueous solution. Reduction colorimetric substrate 2,6‐dichlorophenolindophenol by transfer hydrogenation under biologically compatible conditions achieved turnover frequencies up 63 ± 2 h −1 demonstrated source hydride (sodium formate) limiting reagent, despite being 1000‐fold excess catalyst. catalyst showed low vivo acute toxicity zebrafish embryos modest vitro potency towards cells. When administered alone, generated oxidative stress cells (an effect was conserved vivo), but co‐treatment with nontoxic dose sodium formate negated this effect. Co‐treatment significantly enhanced (A2780 ovarian MCF7 breast cells) drug‐resistant (A2780cis MCF7‐TAMR1) not non‐tumorigenic (MRC5), demonstrating redox‐targeting generate selectivity for

Language: Английский

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Micellar Transfer Hydrogenation Catalysis in Water with Monocarbonyl Ruthenium(II)-poly(vinylphosphonate)-Containing Polymers: Achieving Reduction of Biomass-Derived Aldehydes

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(22), P. 13855 - 13864

Published: Nov. 7, 2024

With the aim to build a supramolecular organometallic catalyst for transfer hydrogenation (TH) reactions of hydrophobic substrates, micellar architectures different sizes were obtained using amphiphilic diblock copolymers (BCPs) tethered Ru(II) monocarbonyl complex. An end-group functionalization strategy was employed incorporate bipyridyl end-group, used further coordinate cationic ruthenium fragment, poly(2-vinylpyridine)-b-poly(diethyl vinylphosphonate). Owing their character, polymers form spherical micelles in water, which characterized by spectroscopic and analytical methods at pH values temperatures. The most suitable core–shell system could level catalytic activity complex toward biomass-derived aldehydes, be successfully reduced corresponding alcohols water potassium formate as hydride source. Depending on substrate's hydrophobicity concentration, varied significantly. In addition, polymer's properties hardly changed during catalysis, facilitating effective recycling until third cycle.

Language: Английский

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