Search Results (237)

Neurotoxicity caused by snake venom phospholipase A₂ (PLA₂) activity derived from coral snakes (e.g., Micrurus tener, Micrurus fulvius, group IA PLA₂) and some rattlesnakes (e.g., Crotalus scutulatus, group IIA PLA₂) is medically significant. Of interest, the catalytic site of PLA₂ also binds to activated clotting factor X, causing anticoagulation. Given that ruthenium (Ru)-containing compounds have been demonstrated to inactivate hemotoxic venoms in a solvent-dependent manner (e.g., 0.9% NaCl, phosphate-buffered saline), we wished to determine if RuCl₃ would cause solvent-dependent inhibition of snake venom group IA and group IIA PLA₂ in human plasma with thrombelastography. It was determined that RuCl₃ significantly decreased the anticoagulant effects of group IA PLA₂ derived from M. tener and M. fulvius venoms in the presence of 0.9% NaCl, but not phosphate-buffered saline. In contrast, group IIA PLA₂ anticoagulant activity derived from C. scutulatus venom was inhibited by RuCl₃ in both solvents. It is concluded that the different ions formed by RuCl₃ in different solvents may interact with novel disulfide bridges unique to group IA and IIA PLA₂ or through some other mechanism. In vivo validation of Ru-based enzyme inhibitor effects on neurotoxicity associated with either group IA or IIA remains a critical translational issue. Full article

The technological promise of nonlinear optical (NLO) compounds has stimulated intense interest in optoelectronic devices, data storage, photonics, and anticancer therapy. Thiosemicarbazone ruthenium materials are of growing interest because of their tunable ligand framework and coordination sphere, allowing fine control over geometry, electronics, and functional properties. Here, we report an N-substituted salicylaldehyde thiosemicarbazone ligand and a series of octahedral Ru(III) complexes bearing triphenylphosphine or triphenylarsine and halide (Cl, Br) co-ligands. The complexes were characterized by elemental analysis, FT-IR, UV–Vis, EPR, mass spectrometry, and magnetic susceptibility measurements, which together confirm NS-chelation to a low-spin Ru(III) center in a distorted octahedral environment. Their photophysical and NLO responses were assessed by UV–Vis spectroscopy and powder second-harmonic generation measurements (Kurtz–Perry method), revealing promising NLO behavior. In parallel, antioxidant activity and in vitro anticancer effects against HeLa cells were evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) cytotoxicity assays. These results provide insight into ligand-controlled structure–activity relationships, in which the halide (Cl/Br) and ancillary triarylphosphine co-ligands regulate electronic interactions and lipophilicity and ultimately increase biological performance, underscoring the dual materials and medicinal potential of these Ru(III) complexes. Full article

A modular synthetic route has been developed to prepare a new series of cationic ruthenium(II) complexes with electron-withdrawing 1,2-diacylcyclopentadienyl ligands. The 2-acyl-6-hydroxyfulvenes were synthesized from cyclopentadienide and acyl chlorides and converted to Tl(I) cyclopentadienyl salts using Tl₂SO₄/KOH. Transmetalation with [Ru(η⁶-p-cymene)(μ-Cl)Cl]₂ followed by PF₆⁻ metathesis gives the complexes [Ru{η⁵-1,2-C₅H₃(CO–R)₂}(η⁶-p-cymene)][PF₆] (R = t-Bu, p-Tol, p-ClC₆H₄, p-IC₆H₄) in moderate to high yields. The new compounds were characterized by NMR and IR spectroscopy; mass spectrometry and elemental analysis were performed where applicable. X-ray analysis of one of the complexes confirms that electron-deficient Cp ligands retain η⁵-coordination and structural planarity within Ru(II)–arene sandwich architectures, highlighting their potential utility in electronically tunable organometallic frameworks. Full article

Dye-sensitized solar cells (DSSCs) represent a promising low-cost photovoltaic technology with relatively high conversion efficiency and a simple fabrication process. Natural dyes have drawn growing interest compared to ruthenium-based dyes since they are greener. However, the power conversion efficiency (PCE) of natural dyes is generally low. In this study, we investigated novel approaches to improve the PCE of DSSCs using Delonix regia extracts by polarity-based separation using preparative thin-layer chromatography (PTLC). Our study indicated that polarity-based separation can significantly enhance the PCE, with one fraction achieving a PCE of 1.13%, which is high compared to most natural dye-based DSSCs, and is also 1.85 times that of the crude methanol extract. The major compounds in the highest-efficiency layer were flavanol-based dyes. Our study demonstrates the potential antagonistic effects within Delonix regia extracts in DSSC applications, which play a critical role in improving PCE. The study is expected to support future efforts to enhance the PCE of natural compound-based DSSCs, especially those using flavanol-based natural dyes. Full article

Cancer ranks as a major cause of morbidity and mortality across the globe, notably in economically developed regions, and its incidence is predicted to rise in the coming decades. Metal-based compounds represent a particularly promising class of pharmaceuticals for the treatment of cancer. Following the success of platinum in cancer therapy, attention soon turned to other transition metals, particularly the platinum group metals such as ruthenium and palladium. Despite the high anticancer efficacy of many of its compounds, osmium remained one of the least investigated of these metals for a long time, partly due to concerns about its toxicity. However, there has been a recent resurgence in the preparation and evaluation of osmium complexes, which exhibit high structural variability and demonstrate promising anticancer activity. The present review aims to survey recent developments in this exciting field, focusing on osmium complexes of the non-arene type reported during the last decade. Full article

Skin cancer (SC) is the most prevalent malignancy worldwide, with subtypes varying in aggressiveness: basal cell carcinoma tends to be locally invasive, squamous cell carcinoma has a higher metastatic risk, and melanoma remains the deadliest form. Current treatments such as surgery, radiotherapy, and systemic chemotherapy are associated with aesthetic and functional morbidity, recurrence, and/or systemic toxicity. Although targeted therapies and immunotherapies offer clinical benefits, their high cost and limited accessibility underscore the need for innovative, affordable alternatives. Metal-based compounds (metallopharmaceuticals) are promising anticancer agents due to their ability to induce oxidative stress, modulate redox pathways, and interact with DNA. However, clinical translation has been limited by poor aqueous solubility, rapid degradation, and low skin permeability. This review discusses the most recent preclinical findings on gold, silver, platinum, palladium, ruthenium, vanadium, and copper complexes, mainly in topical and systemic treatments of SC. Advances in chemical and physical enhancers, such as hydrogels and microneedles, and in drug delivery systems, including bacterial nanocellulose membranes and nanoparticles, as well as liposomes and micelles, for enhancing skin permeation and protecting the integrity of metal complexes are also discussed. Additionally, we examine the contribution of photodynamic therapy to SC treatment and the use of mathematical and computational modeling to simulate skin drug transport, predict biodistribution, and support rational nanocarrier design. Altogether, these strategies aim to bridge the gap between physicochemical innovation and clinical applicability, paving the way for more selective, stable, and cost-effective SC treatments. Full article

The ruthenium-catalysed silylative coupling (SC) reaction is a useful method for obtaining selectively functionalised organosilicon compounds, which have a wide range of applications in organometallic and organic chemistry. It is possible to prepare such compounds with norbornene matrices, which can be used for ring-opening metathesis polymerisation (ROMP) in the synthesis of linear-type polymers. Herein, we present a method for the synthesis of the aforementioned matrices by a condensation reaction between diol and vinylphenylboronic acids. Furthermore, these compounds were subsequently modified by SC reaction and polymerised by ROMP. To assess the possibility of using styryl-based silyl-derived monomers as building blocks in further organic transformations, the process of bromodesilylation was also investigated. We would also like to perform a comparative study on the selectivity of hydrosilylation and silylative coupling processes in the case of discovered materials. Full article

Our previous study demonstrated that thiophene-substituted synthetic curcumin analogs possessed better antibacterial activity and stability than natural curcumin, demethoxycurcumin, or bisdemethoxycurcumin in antibacterial photodynamic therapy (aPDT). In addition, the activity of the furan-substituted analogs was weaker than that of the thiophene-substituted compounds. As oxygen, sulfur, and selenium belong to the same group in the periodic table, the antibacterial and anticancer activities of these three different elemental analogs were compared and investigated. The thiophene-substituted analog (compound 3) exhibited the most potent antibacterial activity in aPDT experiments. However, the furan-substituted analog (compound 1) exhibited the most potent anticancer activity. These results indicate that the differences in atomic radii or energy levels in these compounds produce different cell-attack results on generated free radicals. Ruthenium(II) complexes have a good reputation for use in PDT for cancer treatment. Our results show that complexation of ruthenium(II) with thiophene-substituted curcumin analogs does not enhance their antibacterial or anticancer activity. Full article

The photochemistry of transition metal complexes has been crucial for the development of many fundamental topics, as well as to pave the way for several important applications. However, in most cases, photoactive transition metal complexes involved precious metals, with luminescent ruthenium polypyridine complexes playing the dominant role. Developing photoactive species based on earth-abundant metals is highly important for fundamental and applicative reasons. Iron is one of the most abundant metals on Earth’s crust, so luminescent iron complexes are highly desired. The recent search for iron complexes with long-lived and luminescent excited states is here presented, including Fe(II) species with metal-to-ligand charge transfer (MLCT) excited states and Fe(III) species with luminescent ligand-to-metal charge transfer (LMCT) states. The excited-state equilibration approach to prolong the luminescence lifetimes of Fe(III) compounds in multichromophoric species is also discussed. This latter approach can increase the possibility of luminescent iron complexes being involved in bimolecular processes as well as in photoinduced electron and energy transfer at interfaces, which is relevant for many applications. Full article

Chemotherapy for cutaneous leishmaniasis is hindered by high toxicity, adverse effects, and increasing drug resistance. Thus, safer and more selective therapies are urgently required. Here, we evaluated the antiparasitic efficacy of methylene blue (MB) and new MB, as well as novel ruthenium complex derivatives (NMB-B and NMB-P) against promastigote and amastigote forms of Leishmania amazonensis. Their cytotoxicity and selectivity on L929, HepG2, VERO, J774.G8 cells, and murine peritoneal macrophages were measured. Mechanisms of action were explored via flow cytometry, assessing morphological changes, mitochondrial depolarization, ROS production, and cell death. The compounds inhibited parasite proliferation in a dose and time-dependent manner, achieving submicromolar efficacy against amastigotes (NMB-P = 0.46 μM). No cytotoxicity was observed on L929, J774.G8, and VERO cells (except NMB), while HepG2 and murine peritoneal macrophages showed low to moderate toxicity. Selective indexes reached 84 for promastigotes and over 500 for amastigotes. The compounds induced mitochondrial depolarization by up to 61% and a five-fold increase in ROS levels, leading to structural damage and parasite death via late apoptosis/necrosis-like mechanisms. These findings indicate that the compounds act selectively and trigger the release of oxidative species, exerting leishmanicidal activity and warranting further investigation. Full article

Significant efforts have been devoted to discovering novel metal-based complexes with better cytotoxicity and specificity to tumor cells. Within the range of complexes studied for cytotoxic activity, Ru complexes have gained significant attention as one of the most promising classes of compounds offering advantages such as good scaffolds for the construction of new bioactive molecules with a variety of ligands. Ruthenium-based compounds demonstrate efficient penetration into cancer cells and show affinity for DNA binding with antitumor mechanisms, other than those of cisplatin. They were identified as perfect chemotherapeutics for cancer treatment due to their good tolerance by normal cells, negligible toxic effects and stronger activity towards Pt-drug-resistant tumor cell lines. Ru-based complexes may interact with multiple targets and show selective accumulation in cancer cells, which enhances their therapeutic potential. In recent years, the design of polynuclear complexes has aroused considerable interest in drug discovery research. The strategy to incorporate two or more metal centers into one precise molecular structure may result in better cytotoxic activity compared to the mononuclear precursors. That is why ruthenium-based multinuclear anticancer organometallic and complex compounds have attracted lots of attention. The objective of the current review is to highlight the key results obtained in research on ruthenium complexes, presenting the up-to-date advances of multinuclear homometallic ruthenium complexes as promising anticancer candidates. The reported outcomes shed new light on the fundamental biological interactions and antineoplastic modes of action of ruthenium-based complexes and organometallic compounds as well as significant information for the prediction of novel anticancer drugs. Full article

This review paper presents a comprehensive literature analysis that elucidates the global engagement of research teams in addressing the important problem of finding effective oncology drugs based on the following platinum group metal ions: ruthenium, rhodium and iridium. The necessity to search for new drugs can be attributed, in part, to the predominance of platinum-based chemotherapeutics in clinical practice. However, these drugs face limitations in their clinical application due to their inherent toxicity and the development of resistance by cancer cells. A distinctive attribute of these metal compounds is the formation of diamagnetic stable complexes on +II (Ru) and +III (Rh, Ir) oxidation degrees with a d⁶ electron configuration, a coordination number of six and an octahedral or pseudo-octahedral structure. In this paper we have systematised the findings presented in the literature by classifying the most significant categories of ruthenium, rhodium and iridium compounds, namely piano-stool-type arenes, polypyridine and cyclometalated complexes, dimers and multinuclear complexes. Additionally, the most crucial research challenges connected with metal complexes that have been addressed by scientists have been presented: (i) the application of prodrugs in cancer therapy; (ii) the deployment of complexes as sensitizers in PDT and PACT; (iii) the exploration of complexes as inhibitors of enzymes and biocatalysts; and (iv) the investigation of multiple-target complexes. Furthermore, the objective was to emphasise the accomplishments in this domain in recent years by identifying compounds that have entered the clinical trial phase. Full article

The aim of this work is to present a technologically feasible method for processing biomass into synthesis gas or hydrogen-rich gas. Three types of biomass with different lignin contents were pyrolyzed in a pyrolysis unit under well-defined conditions (ambient pressure, heating rate of 10 K min⁻¹, end temperature of 500 °C, operating particle size, variable catalyst mass) in the presence of a ruthenium catalyst (Ru/Al₂O₃, powder), and the effect of catalyst amount on the yield and gas composition was observed. Feedstock mass was always 50 g, and catalyst mass was 2.5, 5, and 10 g (mixing ratios 0.05, 0.1, and 0.2, resp.). During pyrolysis, the raw gas and vapors was passed through the catalyst bed and converted to the resulting gas and bio-oil. The gas obtained was cleaned by sequestration with CO₂ using commercial active carbon to obtain syngas with different H₂/CO ratios or hydrogen-rich gas. It was found that, depending on the catalyst amount, slow pyrolysis catalyzed by ruthenium yielded syngas with a H₂/CO ratio of approximately 0.5–5, which is further usable. The by-products obtained (bio-oil and biochar) are also described. Bio-oils from all three biomass types contained mainly carboxylic acids (33–46 wt.%) and phenols (18–33 wt.%), hydroquinone (up to 5 wt.%), and a high amount of stearate (up to 26 wt.%). All of these compounds have high utility value. The resulting biochar can probably be applied, after activation using CO₂, as a sorbent. In conclusion, under energy-efficient conditions (end temperature max. 500 °C), Ru/Al₂O₃-catalyzed pyrolysis of biomass provides syngas or hydrogen-rich gas and usable by-products. It should be emphasized that the maximum theoretical H₂ production from biomass is 60–70 g H₂/kg biomass. This limit value could negatively affect the technological development of the process. Full article

To date, breast cancer remains one of the leading causes of death among women worldwide. Although various treatments are used in clinical settings, the efficacy and safety of such treatments are limited by tumor biology factors and patient preferences. Previous studies have shown that triple-negative BRCA1-deficient breast cancer is susceptible to DNA-damaging agents, including platinum-based drugs and poly(ADP-ribose) polymerase (PARP) inhibitors, alone or in combination. To address whether the combinative treatment of these DNA-damaging agents can be extended to the triple-negative BRCA1-proficient breast cancer population, we investigated the anticancer activity of the well-known FDA-approved PARP inhibitor olaparib in combination with the antimetastatic ruthenium(II)–arene PTA compound RAPTA-T for triple-negative BRCA1-competent breast cancer cells (MDA-MB-468 and MDA-MB-231), with consideration of sporadic breast cancer MCF-7 cells. RAPTA-T, olaparib, and the combined agents exhibited a dose-dependent inhibition of breast cancer cell growth in selected breast cancer cells. The combination compound inhibited colony formation most effectively in MDA-MB-468 cells. Additionally, the scratch-wound assay showed that MDA-MB-468 cells migrated more slowly than MCF-7 and MDA-MB-231 cells. The results indicated that the olaparib and RAPTA-T combination can reduce or inhibit the survival, invasion, and metastasis of breast cancer cells. Moreover, the combined agents promoted apoptotic cell death, with a higher percentage of apoptosis observed in MDA-MB-468 cells than in MDA-MB-231 and MCF-7 cells. Olaparib and RAPTA-T also interfered with cell cycle progression, with the greatest inhibition observed in the S and G2/M phases of MCF-7 cells (1.6- and 3.4-fold), followed by MDA-MB-468 cells (1.6- and 1.8-fold) and MDA-MB-231 cells (1.5- and 1.4-fold). Interestingly, MDA-MB-468 cells presented the highest degree of inhibition for BRCA1 replication and BRCA1 expression. The p53, PARP, and Chk1 proteins were more strongly upregulated in MDA-MB-231 cells than in Ru-untreated control cells. Moreover, the expression levels of protein biomarkers associated with the epithelial-to-mesenchymal transition (EMT), including E-cadherin and SLUG, were remarkably reduced in all tested breast cancer cells. Together, our results show the feasibility of extending the application of PARP inhibitors beyond breast cancer with BRCA1 mutations and optimizing the combinative treatment of PARP inhibitors with antimetastasis ruthenium-based chemotherapy as new therapeutic approaches for TNBC harboring wild-type BRCA1. Full article

The significant side effects associated with platinum-based anticancer agents have driven the continuous pursuit of novel, non-platinum-based metal compounds. Ruthenium-based organometallic compounds have emerged as promising alternatives, owing to their distinctive and adaptable biochemical properties. The research efforts are focused on the development of ruthenacarborane-based anticancer drugs. The combination of ruthenium(II) complexes, recognized for their inherent anticancer potential, with carboranes, boron-rich clusters possessing unique chemical and physical characteristics, and NSAIDs, known to inhibit COX, an enzyme overexpressed in tumors, offers a novel approach for cancer therapy. Consequently, combining these three moieties into a single molecule represents a compelling strategy to develop drugs with a dual mode of action. Herein, we report the synthesis of a series of ruthenacarborane-(η⁶-p-cymene)–NSAID conjugates (4a, 4b, 5b, and 6b) by linking NSAIDs (flurbiprofen, fenoprofen, and ibuprofen) to ruthenacarborane complexes using methylene and ethylene spacers, while maintaining the integrity of the sensitive ester groups present in the system. The synthesized conjugates were thoroughly characterized using multinuclear (¹H, ¹¹B, and ¹³C) NMR spectroscopy. Notably, the conjugates demonstrated low COX inhibition and no cytotoxic potential against different cancer cell lines, probably due to oxidative deactivation confirmed by cyclic voltammetry (CV). This indicates that the conjugation of this type of ruthenacarborane with NSAIDs does not result in novel anticancer drugs. Full article