Search Results (87)

The development of high-efficiency and stable oxygen evolution reaction (OER) electrocatalysts is crucial for sustainable hydrogen production via water splitting. Single-atom catalysts (SACs) represent a promising direction, yet their performance heavily relies on the support material. Herein, we report a highly active OER catalyst comprising ruthenium (Ru) species supported on Fe-doped nickel carbonate hydroxide (NFCH) grown on nickel foam (NF). The NFCH support, synthesized via a hydrothermal method, possesses a high specific surface area and excellent electrical conductivity. The incorporation of carbonate anions (CO₃²⁻) enhances structural stability and interfacial hydrophilicity. Ru was subsequently decorated onto NFCH via electrodeposition to form the NFCH-Ru_x series (where x denotes the mmol amount of Ru precursor). The optimized NFCH-Ru₃ catalyst exhibits outstanding OER performance in 1 M KOH, requiring a low overpotential of only 220 mV to achieve a current density of 10 mA cm⁻², with a small Tafel slope of 40.92 mV dec⁻¹. Furthermore, it demonstrates remarkable durability with negligible activity loss (2.9%) after 12 h of continuous operation, outperforming many recently reported non-precious metal-based catalysts. This work highlights the potential of metal carbonate hydroxides as superior supports for developing high-performance OER electrocatalysts. Full article

Bothrops species are responsible for the majority of envenomations in Argentina. In particular, Bothrops diporus is among the main species responsible for the majority of envenomations in Argentina and causes significant injury and coagulopathy. Given the significance of this venom, the authors sought to define the toxin responsible for coagulopathy with specialized spectrophotometric and thromboelastographic methods. Utilizing clotting time, spectrophotometry, and thromboelastography, it was determined that B. diporus venom has potent, procoagulant activity in human plasma and buffer milieu. Calcium-dependent and -independent activities consistent with serine protease activity were identified. The activity included both thrombin-generating and thrombin-like enzymatic activity. The venom cleaved the serine protease-specific chromogenic substrate β-Ala-Gly-Arg-p-nitroanilide diacetate, and its activity was inhibited in plasma by antithrombin after addition of heparin. Further, venom exposed in isolation to RuCl₃, a known inhibitor of serine protease-containing venoms, demonstrated decreased activity in human plasma. In conclusion, the present study contributes to a better understanding of B. diporus venom and may have implications for the rational design of inhibitors, antivenom formulations, or preclinical models to study venom-induced coagulopathies. Full article

Background: Mitis group non-pneumococcal streptococci (MGNPS), specifically Streptococcus mitis, Streptococcus infantis and Streptococcus oralis, have recently been shown to cause pneumonia and/or bacteremia. These organisms often have capsular (cps) operons resembling those in pneumococci, and some express cps-generated polysaccharides that antigenically cross-react with pneumococcal capsular serotypes. But, to date, a series of MGNPS isolates has not been studied by electron microscopy (EM) for the presence of a capsule. Methods: We studied 21 MGNPS; 11 were isolated from sputum and determined to have caused pneumonia, 3 were isolated from blood, and 7 were commensal isolates cultured from the oral cavity of healthy adults. Two reacted with a pneumococcal anticapsular antibody. Isolates were fixed with two different protocols and examined by transmission EM. Results: EM of MGNPS after standard fixation and staining with uranyl acetate did not show capsules. In contrast, the 21 MGNPS isolates that we studied after fixation with ruthenium red and lysine acetate were all shown to be encapsulated. The thickness and density of capsules was related to their species: Streptococcus pneumoniae had the most prominent encapsulation and Streptococcus oralis had the least. However, within a species, there was no apparent difference in capsules between disease-causing and colonizing strains. Conclusions: EM with ruthenium red staining demonstrated capsules on 21 MGNPS, but within a species, there was no apparent difference between disease-causing and commensal isolates. It seems reasonable to conclude that the capsule, together with inoculum size, host’s ability to clear aspirated organisms, and other as yet unidentified virulence factors, all contribute to the pathogenesis of MGNPS pneumonia. Full article

Searching for new and efficient transfer hydrogenation catalysts, a series of new organometallic ruthenium(II)-arene complexes of the formulae [Ru(η⁶-p-cymene)(L)Cl][PF₆] (1–8) and [Ru(η⁶-p-cymene)(L)Cl][Ru(η⁶-p-cymene)Cl₃] (9–11) were synthesized and fully characterized. These were prepared from the reaction of pyridine–quinoline and biquinoline-based ligands (L) with [Ru(η⁶-p-cymene)(μ-Cl)Cl]₂, in 1:2 and 1:1, metal (M) to ligand (L) molar ratios. Characterization includes a combination of spectroscopic methods (FT-IR, UV-Vis, multi nuclear NMR), elemental analysis and single-crystal X-ray crystallography. The pyridine–quinoline organic entities encountered, were prepared in high yield either via the thermal decarboxylation of the carboxylic acid congeners, namely 2,2′-pyridyl-quinoline-4-carboxylic acid (pqca), 8-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8-Mepqca), 6′-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (6′-Mepqca) and 8,6′-dimethyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8,6′-Me₂pqca), affording the desired ligands pq, 8-Mepq, 6′-Mepq and 8,6′-Me₂pq, or by the classical Friedländer condensation, to yield 4,6′-dimethyl-2,2′-pyridyl-quinoline (4,6′-Me₂pq) and 4-methyl-2,2′-pyridyl-quinoline (4-Mepq), respectively. The solid-state structures of complexes 1–4, 6, 8 and 9 were determined showing a distorted octahedral coordination geometry. The unit cell of 3 contains two independent molecules (Ru-3), (Ru′-3) in a 1:1 ratio, due to a slight rotation of the arene ring. All complexes catalyze the transfer hydrogenation of acetophenone, using 2-propanol as a hydrogen donor in the presence of KOiPr. Among them, complexes 1 and 5 bearing methyl groups at the 8 and 4 position of the quinoline moiety, convert acetophenone to 1-phenylethanol quantitatively, within approximately 10 min with final TOFs of 1600 h⁻¹. The catalytic performance of complexes 1–11, towards the transfer hydrogenation of p-substituted acetophenone derivatives and benzophenone, ranges from moderate to excellent. An inner-sphere mechanism has been suggested based on the detection of ruthenium(II) hydride species. Full article

Electrochemical disinfection systems are gaining attention as potential solutions for reducing microbial contamination in drinking water distribution networks. While numerous recent studies suggest that these systems are easy to implement, real-world application reveals significant challenges. Many published works suffer from fundamental flaws, including inappropriate material selection, unrealistic operating conditions, and non-compliance with regulatory standards. This review critically examines studies published over the past 24 months, highlighting key issues that limit practical applicability. It discusses common pitfalls, such as the use of unstable or toxic electrode materials and the failure to provide residual disinfectant effects. Additionally, the review outlines essential characteristics for effective electrochemical disinfection systems, emphasizing compliance with health regulations, scalability to real-world conditions, and long-term operational stability. By identifying these gaps, this review article aims to guide future research toward more viable, safe, and sustainable electrochemical disinfection solutions for drinking water treatment. Full article

Ruthenium-based catalysts were prepared through a deposition–precipitation approach, taking beta zeolites with Si/Al ratios of 12.5, 18.5, and 150, respectively, as supports, and 1–3 wt% loadings of metal. Their activation was performed in the presence of either H₂ or NaBH₄. The dispersion of the Ru species and the acid–base properties were influenced by both the preparation method and the activation protocol. The catalysts reduced under H₂ flow presented well-dispersed Ru(0) and RuO_x nanoparticles, while the reduction with NaBH₄ led to larger RuO_x crystallites and highly dispersed Ru(0). These characteristics exerted an important role in the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). The H₂ dissociation occurred via a heterolytic mechanism involving Lewis acid–base pairs associated with RuO_x and the framework oxygen (Si-O-Al) located near the zeolite pore edge. The Ru(0) nanoparticles activated the –C=O bond of the LA substrate, while the presence of the carrier zeolite Brønsted acid sites promoted the ring-closure esterification of the 4-hydroxyvaleric acid (4-HVA) intermediate to GVL. An optimal combination of these features was achieved for the catalyst with 3 wt% Ru and a Si/Al ratio of 150, which selectively converted LA (X_LA = 96.5%) to GVL (S_GVL = 97.8%) at 130 °C and 10 bars of H₂. Full article

Flashes of superoxide anion (O₂⁻) in mitochondria are generated spontaneously or during the opening of the permeability transition pore (mPTP) and a sudden change in the metabolic state of a cell. Under certain conditions, O₂⁻ can leave the mitochondrial matrix and perform signaling functions beyond mitochondria. In this work, we studied the kinetics of the release of O₂⁻ and H₂O₂ from isolated mitochondria upon mPTP opening and the modulation of the metabolic state of mitochondria by the substrates of respiration and oxidative phosphorylation. It was found that mPTP opening leads to suppression of H₂O₂ emission and activation of the O₂⁻ burst. When the induction of mPTP was blocked by its antagonists (cyclosporine A, ruthenium red, EGTA), the level of substrates of respiration and oxidative phosphorylation and the selective inhibitors of complexes I and V determined the type of reactive oxygen species (ROS) emitted by mitochondria. It was concluded that upon complete and partial reduction and complete oxidation of redox centers of the respiratory chain, mitochondria emit H₂O₂, O₂⁻, and nothing, respectively. The results indicate that the mPTP- and substrate-dependent switching of the type of ROS leaving mitochondria may be the basis for O₂⁻- and H₂O₂-selective redox signaling in a cell. Full article

The hydrogenation of CO₂ to produce formic acid has garnered increasing interest as a means to address climate change and promote the hydrogen economy. This research investigates the nanocasting technique for the synthesis of ordered mesoporous nitrogen-doped carbon (MNC-An). KIT-6 functioned as the silica template, while aniline served as the nitrogen–carbon precursor. The resultant MNC-An exhibits cubic Ia3D geometry, possesses significant mesoporosity, and has a high nitrogen content, which is essential for stabilizing ruthenium single atoms. The catalyst exhibited a specific activity of 252 mmol_FAg_cat⁻¹ following a 2 h reaction at 120 °C. Moreover, the catalyst exhibited exceptional relative activity during five recycling experiments while preserving its catalytic efficacy. The atomically dispersed ruthenium and its Ru³⁺ oxidation state demonstrated perseverance both before and after the treatment. The results indicated that the synthesized catalyst possesses potential for the expedited commercialization of CO₂ hydrogenation to produce formic acid. The elevated carbon yield, along with excellent thermal stability, renders it a viable substrate for attaching and stabilizing atomically dispersed ruthenium catalysts. Full article

Colorectal cancer (CRC) is the third most common cancer in the world, with an ongoing rising incidence. Despite secure advancements in CRC treatments, challenges such as side effects and therapy resistance remain to be addressed. Photodynamic therapy (PDT) emerges as a promising modality, clinically used in treating different diseases, including cancer. Among the main challenges with current photosensitizers (PS), hydrophobicity and low selective uptake by the tumor remain prominent. Thus, developing an optimal design for PS to improve their solubility and enhance their selective accumulation in cancer cells is crucial for enhancing the efficacy of PDT. Targeted photoactivation triggers the production of reactive oxygen species (ROS), which promote oxidative stress within cancer cells and ultimately lead to their death. Ruthenium (Ru)-based compounds, known for their selective toxicity towards cancer cells, hold potential as anticancer agents. In this study, we investigated the effect of two distinct arene-Ru assemblies, which lodge porphin PS in their inner cavity, and tested them as PDT agents on the HCT116 and HT-29 human CRC cell lines. The cellular internalization of the porphin-loaded assemblies was confirmed by fluorescence microscopy. Additionally, significant photocytotoxicity was observed in both cell lines after photoactivation of the porphin in the cage systems, inducing apoptosis through caspase activation and cell cycle progression disruptions. These findings suggest that arene-Ru assemblies lodging porphin PS are potent candidates for PDT of CRC. Full article

Ruthenium(II) polypyridyl complexes are being tested as potential anticancer agents in different therapies, which include conventional chemotherapy and light-activated approaches. A mechanistic study on a recently synthesized dual-action Ru(II) complex [Ru(bpy)₂(sora)Cl]⁺ is described here. It is characterized by two mono-dentate leaving ligands, namely, chloride and sorafenib ligands, which make it possible to form a di-aquo complex able to bind DNA. At the same time, while the released sorafenib can induce ferroptosis, the complex is also able to act as a photosensitizer according to type II photodynamic therapy processes, thus generating one of the most harmful cytotoxic species, ¹O₂. In order to clarify the mechanism of action of the drug, computational strategies based on density functional theory are exploited. The photophysical properties of the complex, which include the absorption spectrum, the kinetics of ISC, and the character of all the excited states potentially involved in ¹O₂ generation, as well as the pathway providing the di-aquo complex, are fully explored. Interestingly, the outcomes show that light is needed to form the mono–aquo complex, after releasing both chloride and sorafenib ligands, while the second solvent molecule enters the coordination sphere of the metal once the system has come back to the ground-state potential energy surface. In order to simulate the interaction with canonical DNA, the di-aquo complex interaction with a guanine nucleobase as a model has also been studied. The whole study aims to elucidate the intricate details of the photodissociation process, which could help with designing tailored metal complexes as potential anticancer agents. Full article

Trinuclear and tetranuclear ruthenium carbonyls of the types Ru₃(CO)_n(NO)₂, Ru₃(N)(CO)_n(NO), Ru₃(N)₂(CO)_n, Ru₃(N)(CO)_n(NCO), Ru₃(CO)_n(NCO)(NO), Ru₄(N)(CO)_n(NO), Ru₄(N)(CO)_n(NCO), and Ru₄(N)₂(CO)_n related to species observed experimentally in the chemistry of Ru₃(CO)₁₀(µ-NO)₂ have been investigated using density functional theory. In all cases, the experimentally observed structures have been found to be low-energy structures. The low-energy trinuclear structures typically have a central strongly bent Ru–Ru–Ru chain with terminal CO groups and bridging nitrosyl, isocyanate, and/or nitride ligands across the end of the chain. The low-energy tetranuclear structures typically have a central Ru₄N unit with terminal CO groups and a non-bonded pair of ruthenium atoms bridged by a nitrosyl or isocyanate group. Full article

Organometallic ruthenium complexes with p-cymene = 1-methyl-4-(1-methylethyl)-benzene and N^N = bidentate polypyridyl ligands constitute interesting candidates with biological and catalytic properties. Towards this aim, we have synthesized four ruthenium(II)–arene complexes of the type [Ru(η⁶-p-cymene)(N^N)Cl][X] (N^N = Br-Qpy = 6-bromo-4-phenyl-2-pyridin-2-yl-quinoline, X = Cl⁻ (1a); PF₆⁻ (1b); N^N = OH-Ph-Qpy = 4-(4-phenyl-2-(pyridin-2-yl)quinolin-6-yl)phenol, X = Cl⁻ (2a); PF₆⁻ (2b)). This is the first report of ruthenium(II) p-cymene complexes incorporating substituted pyridine–quinoline ligands, with –Br and –C₆H₄OH groups in the 6-position of quinoline. We also refer to the cytotoxicity of the ligands and their possible effect of modulating the activity of the ruthenium(II) complexes. These were characterized by a combination of spectroscopic methods (ATR-IR, UV–Vis, multinuclear NMR), elemental analysis, and conductivity measurements. The solid-state structure of 2b, determined by single-crystal X-ray diffraction, reveals a three-legged piano-stool geometry. The in vitro cytotoxic activities of the new complexes were evaluated in HEK293T (human embryonic kidney cells) and in HeLa cells (cervical cancer cells), via the MTT assay. Poor in vitro anticancer activities were observed for the HeLa cancer cell line, with 2a being the most potent (IC₅₀ = 75 μΜ). The cytotoxicity of Br-Qpy in HEK293T is comparable to that of cisplatin. Both complexes 1a and 1b successfully catalyze the transfer hydrogenation of benzophenone to benzhydrol by 2-propanol at 82 °C. The catalytic performance of 1a in the ratio of S:Cat:B = 400:1:40 (S = substrate, Cat = catalyst, B = base = KOiPr) leads to a conversion of 94%, within 3 h of reaction. Presumably, catalytic transformation takes place via ruthenium(II) hydride species being the active catalyst. Full article

Cholinesterase (ChE) inhibitors are crucial therapeutic agents for the symptomatic treatment of certain chronic neurodegenerative diseases linked to functional disorders of the cholinergic system. Significant research efforts have been made to develop novel derivatives of classical ChE inhibitors and ChE inhibitors with novel scaffolds. Over the past decade, ruthenium complexes have emerged as promising novel therapeutic alternatives for the treatment of neurodegenerative diseases. Our research group has investigated a number of newly synthesized organoruthenium(II) complexes for their inhibitory activity against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). Three complexes (C1a, C1-C, and C1) inhibit ChE in a pharmacologically relevant range. C1a reversibly inhibits AChE and BChE without undesirable peripheral effects, making it a promising candidate for the treatment of Alzheimer’s disease. C1-Cl complex reversibly and competitively inhibits ChEs, particularly AChE. It inhibits nerve-evoked skeletal muscle twitch and tetanic contraction in a concentration-dependent manner with no effect on directly elicited twitch and tetanic contraction and is promising for further preclinical studies as a competitive neuromuscular blocking agent. C1 is a selective, competitive, and reversible inhibitor of BChE that inhibits horse serum BChE (hsBChE) without significant effect on the peripheral neuromuscular system and is a highly species-specific inhibitor of hsBChE that could serve as a species-specific drug target. This research contributes to the expanding knowledge of ChE inhibitors based on ruthenium complexes and highlights their potential as promising therapeutic candidates for chronic neurodegenerative diseases. Full article

Prostate cancer remains a significant global health concern, posing a substantial threat to men’s well-being. Despite advancements in treatment modalities, the progression of prostate cancer still presents challenges, warranting further exploration of novel therapeutic strategies. In this study, osthole, a natural coumarin derivative, inhibited cell viability in cancer cells but not in the normal prostate cell line. Moreover, osthole disrupted cell cycle progression. Furthermore, osthole reduces mitochondrial respiration with mitochondrial membrane potential (ΔΨm) depolarization and reactive oxygen species (ROS) generation, indicating mitochondrial dysfunction. In particular, osthole-induced ROS generation was reduced by N-acetyl-L-cysteine (NAC) in prostate cancer. In addition, using calcium inhibitors (2-APB and ruthenium red) and endoplasmic reticulum (ER) stress inhibitor (4-PBA), we confirmed that ER stress-induced calcium overload by osthole causes mitochondrial dysfunction. Moreover, we verified that the osthole-induced upregulation of tiRNA^HisGTG expression is related to mechanisms that induce permeabilization of the mitochondrial membrane and calcium accumulation. Regarding intracellular signaling, osthole inactivated the PI3K and ERK pathways while activating the expression of the P38, JNK, ER stress, and autophagy-related proteins. In conclusion, the results suggest that osthole can be used as a therapeutic or adjuvant treatment for the management of prostate cancer. Full article

In this study, dinuclear and tetranuclear arene ruthenium porphyrins were synthesized and assessed for their potential as photosensitizers (PSs) in photodynamic therapy (PDT) using the Colo205 colon cancer cell line as a model system. Reactive oxygen species (ROS) production, cellular uptake, impact on cell viability, and mechanisms of cell death induced by the synthesized compounds were comprehensively investigated. Our results revealed that the number of arene ruthenium units, as well as zinc (Zn) metalation of the porphyrin core, significantly influenced ROS production and increased it two-folds compared to the Zn-free analogs. The uptake of tetra-substituted Zn-porphyrins by the cancer cells increased to 2.8 nmol/10⁶ cells compared to 0.6 nmol/10⁶ cells of the disubstituted Zn-free and Zn-chelating porphyrins. The anticancer photo-activity of the complexes, where the percentage of metabolic activity of disubstituted Zn-porphyrins decreased to 26% when Zn was inserted, was compared to disubstituted Zn-free analogs. A further decrease in metabolic activity was observed, when the number of arene ruthenium units increased in the tetra-substituted Zn-porphyrins and tetra-substituted Zn-free compounds, reaching 4% and 14% respectively. Moreover, the percentage of apoptotic cell deaths increased to 40% when Zn was inserted into disubstituted porphyrins, compared to disubstituted Zn-free analog, and 50% when the number of arene ruthenium units increased. Overall, the tetra-substituted Zn chelating porphyrins exhibited the highest PDT efficiency, followed by the di-substituted Zn-porphyrins. These findings underscore the importance of structural design in optimizing the efficacy of arene ruthenium porphyrins as PSs for PDT, offering valuable insights for the development of targeted cancer therapeutics. Full article