Search Results (365)

Organometallic chemistry deals with the synthesis, structure, reactivity, and applications of compounds containing metal–carbon covalent bonds. In recent years, there has been a growing interest in predicting the catalytic activity of organometallics using machine learning. However, the major drawback in developing algorithms that can be used in predicting organometallic reactions is the availability of organometallic reaction data and organometallic filtering tools. The main aim of the current study is to develop organometallic reaction-filtering tools that are crucial for building accurate and effective ML models in organometallic chemistry. Random Forest (RF), K-Nearest Neighbors (kNN), Support Vector Classifiers (SVC), and Multi-Layer Perceptrons (MLP) were employed, using feature subsets selected via Permutation Feature Importance from Morgan fingerprints and MACCS keys. The results demonstrate that the MACCS-based MLP architecture provides the most reliable filtering performance, achieving a superior F1 score of 0.85, a Recall of 0.85, and a high AUC-ROC of 0.837. Furthermore, the MACCS-MLP exhibited the highest predictive confidence, yielding the study’s lowest Log Loss of 0.312. In contrast, while Morgan fingerprints paired with kNN offered a specialized “strict” filter with absolute Precision (1.00), the sparse dimensionality of circular fingerprints generally resulted in lower calibration for probabilistic models. These findings underscore that dense, fragment-based descriptors refined by data-driven feature selection are most effective for identifying complex organometallic motifs. This study successfully provides a validated methodology for building precise filtering tools, establishing a critical foundation for automated catalyst discovery and the expansion of effective machine learning applications in organometallic chemistry. The study is limited to only identifying organometallic reactions and cannot filter based on organometallic reaction types. Future studies should also explore integrating multiple feature representations to classify or cluster the identified organometallic reactions based on the reaction types. Full article

Oxidative stress (OS) and inflammation are common causes of male infertility; antioxidants in spermatozoa and especially in seminal plasma play a protective role. The study aims to evaluate whether OS lipid mediators (F₂-isoprostanes: F₂-IsoPs; Resolvin D1: RvD1) measured in seminal plasma, and Trolox equivalent antioxidant capacity (TEAC), measured in both seminal plasma and spermatozoa, are associated with male infertility. Semen samples (18 fertile and 62 infertile subjects) were examined following WHO guidelines and with a mathematically elaborated transmission electron microscopy analysis (fertility index-FI-, % sperm pathologies). F₂-Isops were measured by GC/NICI-MS/MS, RvD1 by ELISA, and TEAC by a commercially available antioxidant assay. F₂-Isops, RvD1, and sperm TEAC (positively interrelated with each other) correlated negatively with seminal parameters and FI and positively with sperm pathologies. F₂-Isops, RvD1, and sperm TEAC levels were significantly higher in infertile vs fertile subjects (p < 0.001). ROC curve analysis demonstrated that sperm TEAC (J index: 0.13 mM) and seminal RvD1 (J index: 38.26 pg/mL) discriminated between fertile and infertile subjects. Spermatozoa stimulate antioxidant capacity in the presence of an OS environment; this data suggests an association in which antioxidant defences may vary in relation to the surrounding seminal plasma. Moreover, sperm TEAC, and to a lesser extent seminal RvD1, emerge as potential markers for identifying infertile patients. Full article

The ferrocidiphenol family brings together anticancer molecules featuring a [ferrocene-alkene-(p-phenol)₂] motif that can form upon oxidation a quinone methide metabolite targeting cellular proteins. Adding an imide group (imido-ferrocidiphenol) dramatically enhanced the anticancer activity of ferrocidiphenol. We aimed to explore whether molecules with two ferrociphenol motifs connected by bisimide moieties could provide even more effective compounds. Using amino-ferrocidiphenol and commercial bisanhydrides at reflux, for the first time, three symmetrical and bent bis(imido-ferrocidiphenols) were synthesized, with moderate yields, and characterized. However, these compounds were insoluble in most common organic solvents and unstable. This likely explains why their anticancer activity was nil. Full article

Emerging organic pollutants (EOPs) in aquatic environments have attracted increasing attention because many occur at trace levels, undergo transformation during environmental transport, and contribute to poorly resolved mixture risks. Traditional targeted analysis is inherently restricted to predefined compounds, whereas high-resolution mass spectrometry (HRMS)-based full-scan workflows provide broader opportunities for discovering known unknowns and previously unrecognized contaminants. This review critically synthesizes an omics-based analytical framework for aquatic environments, covering sample digitalization, instrumental analysis and acquisition modes, chemical fingerprint/non-target screening, suspect screening, effect-directed analysis, and confidence-based structural identification. Particular emphasis is placed on practical decision points and trade-offs, including dissolved versus particulate-associated analytes, LC-HRMS versus GC-HRMS coverage, hard versus soft ionization, DDA- versus DIA-type acquisition, database dependence, and the persistent difficulty of linking analytical features to toxicological relevance. The review also discusses emerging directions involving artificial intelligence, chemometrics, organometallic contaminants, and microplastic-associated chemicals. By clarifying conceptual boundaries and highlighting current limitations, this article aims to support the development of more critical, transparent, and risk-oriented workflows for the discovery and prioritization of emerging pollutants in aquatic environments. Full article

Baicalin is a natural compound sourced from Scutellaria baicalensis which possesses various biological activities. To date, a large amount of research has been conducted on the antibacterial activity and related mechanisms of baicalin, making it a promising candidate for new broad-spectrum antibacterial drugs. However, the solubility of baicalin is limited. To improve its solubility and overcome the clinical application bottleneck, researchers have developed various solubilization techniques. Therefore, this article introduces the biological characteristics of baicalin; explores its effects as an antibacterial agent on bacterial biofilms, quorum sensing, virulence factors, inflammatory responses, and the immune system; and discusses the applications of nano-carrier loading technology, cyclodextrin inclusion technology, metal ion coordination and organometallic complexation technology, and dynamic covalent hydrogel assembly technology in improving the solubility of baicalin, thereby enhancing its antibacterial activity. Full article

Background: Breast cancer (BC) remains the most prevalent malignancy among women worldwide, with one in eight at risk during their lifetime. Platinum-based chemotherapeutic drugs, despite of their binding to the DNA of cancer cells, are plagued by toxicity and resistance, necessitating the need for safer and more effective alternatives, such as organometallic complexes. Both synthetic organometallic complexes and natural compounds have attracted attention in this regard. Organotin(IV) complexes are promising chemotherapeutics due to their structural versatility and bioactivity, while vitamins such as Vitamin D (VD) and Vitamin E (VE) exhibit antiproliferative, anti-inflammatory, and antioxidant properties, making them valuable candidates for combination therapy. Methodology: In this study, six novel organotin(IV) dithiocarbamate complexes [LMe₃Sn (Complex 1), LBu₃Sn (Complex 2), LPh₃Sn (Complex 3), LMe₂SnCl (Complex 4), LBu₂SnCl (Complex 5), and L₂Me₂Sn (Complex 6), where L = (E)-4-styrylpiperazine-1-carbodithioate], were synthesized and characterized by FT-IR, ¹H-, ¹³C-NMR, and elemental analysis. Results: Structural studies confirmed penta- and hexacoordination geometries. In silico docking against six BC-related proteins identified Complexes 2 and 4 with both vitamins as promising candidates, exhibiting strong binding affinities, with stable interaction profiles. However, integration of pharmacokinetic, antioxidant, and anti-inflammatory analyses highlighted Complex 4 with both vitamins as the most potent candidate owing to its superior ADME characteristics and balanced biological properties. Subsequent in vitro assays confirmed these findings, as Complex 4 demonstrated strong cytotoxic activity against both MCF-7 (>1.16-fold) and MDA-MB-231 (>1.46-fold) cell lines, surpassing the efficacy of cisplatin. Remarkably, co-administration of VD or VE with Complex 4 further enhanced its anticancer potential, with Chou–Talalay combination index values < 1 (0.66–0.91) indicating a synergistic interaction. Conclusions: Collectively, these results identify Complex 4 as a promising lead compound, and its synergistic activity with natural vitamins may promote cell death, likely through apoptosis induction and modulation of oxidative stress, underscoring its potential as an effective and less toxic therapeutic strategy for breast cancer management. Full article

Quercetin, one of the most abundant flavonoids in nature, has attracted the attention of many researchers due to its chemical and biological properties. A series of metal–quercetin complexes (Cu²⁺, Co²⁺, Zn²⁺, Sn²⁺, Al³⁺, Cd²⁺ and Mg²⁺) were synthesized and systematically characterized by Fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy (UV–Vis) and nuclear magnetic resonance (NMR). These analyses confirmed that the complexes predominantly form through coordination with the 4-carbonyl group and adjacent phenolic hydroxyls. This induces measurable shifts in the ν(C=O), ν(O–H), and π→π* transition bands relative to free quercetin. The antioxidant capacity of the complexes was evaluated using 2,2-Diphenyl-1-Picrylhydrazyl (DPPH^•) radical scavenging method, 2,2′-Azinobis(3-Ethylbenzothiazoline-6-Sulfonic Acid) (ABTS^•)⁺ radical activity, and Ferric Reducing Antioxidant Power (FRAP) assay. Several complexes exhibited higher radical scavenging efficiency than quercetin, with inhibition percentages exceeding 80% in the DPPH^• and ABTS^•+ assays. Others showed reduced activity due to the masking of redox-active hydroxyl groups during metal coordination. FRAP results corroborated these trends, indicating metal-dependent modulation of reducing power. Antimicrobial evaluation revealed that selected complexes were more active than free quercetin, particularly against Staphylococcus aureus and Candida spp., with minimum inhibitory concentrations (MICs) ranging from 75–250 μg mL⁻¹. Overall, metal complexation significantly alters the electronic structure and biological behavior of quercetin, highlighting the potential of metal–flavonoid complexes as multifunctional antioxidants and antimicrobials. 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

With no precedent in the literature, steel slag, an inexpensive and plentiful by-product of the steel industry, was discovered to be a highly selective and active catalyst for the hydrodeoxygenation (HDO) of triglycerides and fatty acids. This material, which is not always recyclable, proved to perform in the virgin state (without any chemical pretreatment), actually fostering the conversion, via a hydrothermal reaction, of palmitic and stearic acids into the corresponding (C16 and C18) alkanes with selectivity above 90%. In addition, by moving to a more complex system such as soybean oil, a complete conversion and the possibility of recycling the catalyst were maintained. Catalytic material, which came from an Italian steel industry (Acciaierie d’Italia), was characterized by XRF, XRD, N₂ physisorption analyses, TPR, and TPD techniques. Catalytic performance was successfully correlated with the characterization results, and mechanistic proofs were provided on the catalytic role played by the several iron species present in the slag. The results reported in this work represent a significant contribution to the large-scale production of green diesel and, thanks to the possibility of using a catalyst based on steel slag in HDO processes, open the way to decarbonization and climate neutrality processes. Full article

In this work, gellan gum microspheres (G–MPs) were developed as delivery systems for blueberry extract (Vaccinium myrtillus) (BEX), a source of natural antioxidants rich in anthocyanins (ATCs) and phenolic compounds (PHCs). Gellan gum, an anionic polysaccharide produced via fermentation by Sphingomonas elodea, was selected for its biocompatibility and gelling properties. BEX was obtained using a mild citric acid–based extraction method to preserve antioxidant capacity and was characterized for its total polyphenol, flavonoid, and anthocyanin content before loading. The extract was loaded into gellan gum microspheres via absorption (G–MPs–BEX). The resulting microspheres exhibited a spherical and porous morphology that favoured both encapsulation and controlled release. FT–IR analysis confirmed the absorption of the extract within the polymer network and revealed hydrogen bonding interactions between the matrix and active compounds. Despite these interactions, microspheres retained a high swelling capacity and enabled rapid release, with maximum release of polyphenols and anthocyanins within 30 min at pH 5.5. The antioxidant activity of BEX, assessed via DPPH assay, remained stable during storage (up to 60 days) and after incorporation into the microspheres. Overall, this study demonstrates that G–MPs can efficiently absorb, stabilize, and release natural antioxidant compounds, supporting their potential use in biomedical, nutraceutical, and cosmetic applications. Full article

Organometallic and metal–organic compounds are widely used in different fields of chemistry and allied disciplines, including bioinorganic and medicinal chemistry. Of particular interest is the development of novel potential anticancer agents based on palladium(II) complexes of the so-called pincer-type ligands, featuring a specific monoanionic tridentate framework. In this work, hybrid imine–thiocarbamate ligands are shown to readily undergo direct cyclopalladation in solution and under solvent-free conditions, in particular upon mechanochemical activation, yielding a series of Pd(II) pincer complexes. The latter exhibit promising cytotoxic activity against several solid and hematopoietic cancer cell lines. Full article

Proteoglycans are macromolecules consisting of a core protein and one or more glycosaminoglycan side chains. Proteoglycans synthesized by vascular endothelial cells modulate various functions such as anticoagulant activity and vascular permeability. We previously reported that some heavy metals interfere with proteoglycan expression, and that organic–inorganic hybrid molecules, such as metal complexes and organometallic compounds, serve as useful tools to analyze proteoglycan synthesis mechanisms. However, the effects of metal compounds lacking electrophilicity on proteoglycan synthesis remain unclear. Au₂₅(SG)₁₈, a nanoscale gold cluster consisting of a metal core protected by gold–glutathione complexes, exhibits extremely low intramolecular polarity. In this study, we investigated the effect of Au₂₅(SG)₁₈ on proteoglycan synthesis in vascular endothelial cells. Au₂₅(SG)₁₈ accumulated significantly in vascular endothelial cells at low cell density and suppressed the expression of perlecan, a major heparan sulfate proteoglycan in cells, by inactivating ADP-ribosylation factor 6 (Arf6). Additionally, Au₂₅(SG)₁₈ reduced the expression of biglycan, a small dermatan sulfate proteoglycan, in vascular endothelial cells at low cell density; however, the underlying mechanisms remain unclear. Overall, our findings suggest that organic–inorganic hybrid molecules regulate the activity of Arf6-mediated protein transport to the extracellular space and that perlecan is regulated through this mechanism, highlighting the importance of Arf6-mediated extracellular transport for maintaining vascular homeostasis. Full article

In this explorative work, molybdenum trioxide (MoO₃) and representative doped MoO₃ materials, i.e., Cu-doped MoO₃ (2% Cu, “Cu-MoO₃”) and H-doped MoO₃ (H_0.31MoO₃, “H-MoO₃”), have been tested for the first time as photocatalysts in the UV-vis light-driven depolymerization of lignin. The catalysts have been characterized by XRD, TEM, ATR-FTIR, and UV-vis DRS. Under the adopted conditions (UV-vis irradiation, solvent 0.01 M aqueous NaOH, lignin 200 ppm, catalyst 1 g/L, rt, 5 h), photocatalytic depolymerization of wheat-straw lignin (WSL) produced increasing amounts of bio-oil on changing the catalyst from pristine MoO₃ to Cu-MoO₃ and H-MoO₃ (23%, 28% and 30%, respectively). Also, quantification of vanillin and vanillic acid shows a similar increasing trend. These results appear in line with the estimated band gap energies, which decrease in the order: MoO₃ (2.91 eV) > Cu-MoO₃ (2.86 eV) > H-MoO₃ (2.77 eV). H-MoO₃ shows the best catalytic performance, which was then fruitfully explored in the photocatalytic depolymerization of benchmark commercial Kraft lignin (bio-oil yield 32%, vanillin and vanillic acid yields 1.28% and 0.78%, respectively). In view of the results obtained, this work is expected to provide new ideas for the design of heterogeneous photocatalytic system for lignin cleavage. 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