Search Results (304)

The separation of rare earth elements (REEs) with similar chemical properties remains a relevant challenge today, most often addressed using liquid–liquid and solid-phase extraction with various chelating agents. Excellent complexing agents for REEs are 1,3-diketones and their analogs. We have for the first time proposed a method for preparing a material consisting of a covalently immobilized 3-acyl-4-hydroxycoumarin ligand on silica. For its synthesis, we employed a strategy based on the “click” reaction of 3-azidopropyl silica with a propargyl-containing coumarin–chalcone conjugate—this approach is the most tolerant and does not affect the coordinationally active fragment of the ligand. The material was characterized by thermal analysis, IR spectroscopy, and ¹³C NMR. The potential of the synthesized material for REE preconcentration was demonstrated at pH 5–5.5: high extraction efficiency for Gd(III), Dy(III), Er(III), Eu(III), Sm(III), and Yb(III) was observed, with fast adsorption kinetics (30 min) and extraction degrees of ~98%. Under unified conditions of static and dynamic extraction for Gd(III), Dy(III), Er(III), Eu(III), Sm(III), and Yb(III), affinity series toward the surface were obtained as a function of the distribution coefficient. It was shown that 10-fold molar excesses of Fe(III), Al(III), Cu(II), Ni(II), and Co(II) allow retention of more than 95% extraction for Dy(III) and Er(III). After adsorption of Dy(III) and Er(III), shifts in the carbonyl group absorption bands are visible in the IR spectra of the material, indicating a chelating mechanism of sorption. Additional studies are required for implementation in analytical and preparative REE separation schemes; however, preliminary data show that the material is a highly active adsorbent. Full article

Countries like Saudi Arabia receive abundant sunshine with exceptionally high solar irradiance. High temperatures in desert regions and the sunray angle dependence of solar modules are some of the key challenges of conventional solar cells. Dye-sensitized solar cells present a compelling alternative with the simple cell design and use of non-toxic materials without angle dependence, but their performance hinges on the solid redox mediators used for dye regeneration. These mediators must have an electrical conductivity (σ_25°C) of more than 10⁻⁴ S cm⁻¹ with an activation energy of less than 0.3 eV for device application. Our work focused on novel solid Co(II/III) redox mediators using cobalt complexes and LiClO₄ in different matrices: pure PEO (an abbreviation for poly(ethylene oxide) with its redox mediator as M1), a [PEO–SN] blend (M2A and M2B with ethylene oxide to lithium ions molar ratio of 112.9 and 225.8, respectively), and pure SN (an abbreviation for succinonitrile with its redox mediator as M3). Impedance spectroscopy was the key technique, showing M1 and M2 behave like a mediator explainable with an (R₁–C)-type circuit, while M3 is explainable with an (R₁ − [R₂‖C])-type circuit. M3 achieved the highest value of σ_25°C with 2 × 10⁻³ S cm⁻¹, while M1 had the lowest σ_25°C, 3 × 10⁻⁵ S cm⁻¹. M2 achieved an optimal balance with σ_25°C of 4 × 10⁻⁴ S cm⁻¹ (M2A) and 1.5 × 10⁻⁴ S cm⁻¹ (M2B). M2 exhibited a remarkably low pseudo-activation energy of 0.042 eV and a Vogel–Tammann–Fulcher behavior ideal for consistent performance across temperatures. In contrast, M1 and M3 showed higher Arrhenius-type activation energies (>0.74 eV) in their solid states. These results correlated with those of the XRD, FT-IR spectroscopy, XPS, SEM, DSC, and TGA analyses. Ultimately, the [PEO–SN] blend emerges as a robust matrix, enabling the combination of high conductivity and low activation energy needed for a durable device in harsh environments. Full article

This work presents the design of a novel electrochemical sensor for highly sensitive determination of LEV, utilizing a sensing platform based on a newly synthesized, high-purity manganese (III) porphyrin complex [5,10,15,20-tetrayltetrakis(2-methoxybenzene-4,1-diyl) tetraisonicotinateporphyrinato] manganese (III) porphyrin (MnTMIPP). The successful synthesis of the MnTMIPP complex was verified using ultraviolet–visible (UV–Vis) and infrared spectroscopy (IR). The sensing electrode was fabricated by depositing the synthesized material onto an indium tin oxide (ITO) electrode via a drop-coating method. Under optimized experimental conditions, the proposed sensor demonstrated a wide dynamic range, from 10⁻⁹ M to 10⁻³ M, with a low calculated detection limit of 4.82 × 10⁻¹⁰ M. Furthermore, the MnTMIPP/ITO electrode displayed interesting metrological performance: high selectivity, reproducibility, and stability. Successful application in spiked river water and saliva samples with satisfactory recovery rates confirms the sensor’s potential as a reliable and cost-effective platform for monitoring LEV in real-world environments. Full article

Siderophores are low-molecular-weight chelating agents secreted by microorganisms under iron-limiting conditions, playing a crucial role in metal bioavailability and microbial survival. In this study, siderophores produced by Glutamicibacter sp. strain Al-Teq-24-F2, isolated from plant-associated samples, were characterized through a combination of spectroscopic and analytical methods. ESI-MS analysis of the crude extract revealed several abundant ions between 175 and 800 m/z, suggesting a mixture of secondary metabolites. After chromatographic purification, FT-IR and NMR analyses indicated the presence of amide, hydroxyl, and carboxylate functional groups. Integrating these data allowed for the proposal of a siderophore structure with a molecular weight of 438.25 Da. Thermogravimetric analysis showed thermal stability below 115 °C. During Fe (III) complexation, the zeta potential shifted from −21.15 mV to +42 mV, confirming strong interaction between the ligand and the metal. UV–Vis and fluorescence spectroscopy displayed characteristic bathochromic and hypochromic shifts, together with pronounced fluorescence quenching upon iron binding. These findings provide new insight into the structural and physicochemical properties of siderophores produced by Glutamicibacter sp. and highlight their potential applications in biosensing and metal chelation processes. Full article

This study describes a series of water-soluble half-sandwich ruthenium(II), rhodium(III), and iridium(III) complexes with α-diimine ligands containing substituted aromatic groups. These ligands were derived from glyoxal and 2-aminophenol (a), 4-methyl-2-aminophenol (b), 4-aminophenol (c), phenyl hydrazine (d), and 1-aminonaphthalene (e). The ruthenium(II) (1b–1e), rhodium(III) (2a–2c, 2e), and iridium(III) complexes (3a–3e) were obtained by reacting the ligands (a–e) with the corresponding dimeric precursor [(η⁶-p-cym)RuCl₂]₂ (p-cym = p-cymene) or [(η⁵-Cp*)MCl₂]₂ (Cp* = pentamethylcyclopentadienyl, M = Rh, Ir) in air and under nonanhydro conditions. The air-stable and water-soluble ruthenium(II), rhodium(III), and iridium(III) complexes were characterized via nuclear magnetic resonance spectroscopy and electrospray ionization–mass spectrometry. The structures of complexes [(η⁶-p-cym)Ru(d)Cl]Cl, 1d; [(η⁵-Cp*)Ir(a)Cl]Cl, 3a; and [(η⁵-Cp*)Ir(c)Cl]Cl, 3c were determined via single-crystal X-ray diffraction. Additionally, the complexes exhibited catalytic activity as precatalysts in formic acid decomposition. Complex [(η⁵-Cp*)Ir(d)Cl]Cl, 3d achieved turnover number (TON) and turnover frequency (TOF) values of up to 2150 and 3861 h⁻¹, respectively, at short reaction times. In the hydrogenation of carbon dioxide, [(η⁶-p-cym)Ru(e)Cl]Cl, 1e attained TON and TOF values of up to 1385 and 69.25 h⁻¹, respectively. 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

In this work, two novel nanoscale zero-valent iron (nZVI) composites (nanoscale zero-valent iron and copper-intercalated montmorillonite (MMT-nFe⁰/Cu⁰) and carbon microsphere-supported sulfurized nanoscale zero-valent iron (CMS@S-nFe⁰)) were used to treat soil contaminated with both Cr(VI) and p-nitrophenol (PNP), and added persulfate (PMS). Experiments found that the pollutant removal effect has a great relationship with the ratio of water to soil, the amount of catalyst, the amount of PMS, and the pH value. When the conditions are adjusted to the best (water–soil = 2:1, catalyst 30 g/kg, PMS 15 g/kg, pH 7–9), both materials fix Cr(VI) well and decompose PNP. The removal rates of Cr(VI) and PNP by the MMT-nFe⁰/Cu⁰ system are 90.4% and 72.6%, respectively, while the CMS@ S-nFe⁰ system is even more severe, reaching 94.8% and 81.3%. Soil column leaching experiments also proved that the fixation effect of Cr can last for a long time and PNP can be effectively decomposed. Through detection methods such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS), we found that Cr(VI) was effectively reduced to Cr(III) by Fe⁰ and Fe²⁺ ions and subsequently transformed into stable FeCr₂O₄ spinel oxides, and the groups produced after the decomposition of PNP could also help fix the metal. This work provides a way to simultaneously treat Cr(VI) and PNP pollution, and also allows the use of multifunctional nZVI composites in complex soil environments. Full article

Three Ir(III) complexes 1–3 were synthesized using phenyl-modified 2-phenylpyridine derivatives as the cyclometalating ligands. All complexes exhibited aggregation-induced phosphorescence emission (AIPE) in CH₃CN/H₂O, which facilitated highly sensitive detection of 2,4,6-trinitrophenol (TNP). Among them, complex 3 containing a phenyl group at the para-position of the phenyl moiety in 2-phenylpyridine showed superior detection performance with the limit of detection (LOD) of 74 nM. 1–3 demonstrated excellent anti-interference and selectivity performances for the detection of TNP in different common water samples. In addition, ¹H NMR spectra, density functional theory calculations, and spectroscopic results indicate that the detection mechanism for TNP is attributed to the combined effects of photo-induced electron transfer and the inner-filter effect. Full article

4,7-di(N-morpholyl)-1,10-phenanthroline (morphen) was introduced for the first time as a ligand for the construction of metal–organic frameworks. The obtained MOF compound has the crystallographic formula {[Tb₂(morphen)₂Br₂(chdc)₂]}_n (1; chdc²⁻ = trans-1,4-cyclohexanedicarboxylate) and is based on binuclear {Tb₂(N^N)₂Br₂(OOCR)₄} carboxylate blocks, interlinked by ditopicchdc linkers into a layered coordination network with sql topology. Purity and integrity of the as-synthesized 1 were confirmed by common characterization techniques, such as PXRD, CHN, IR, and TGA. Compound 1 was found to be hydrolytically stable and possessing typical green emission for Tb(III) complexes. Exploiting its high stability, luminescent 1@PVA films were successfully prepared from 1 and polyvinyl alcohol (PVA) through the water solution drying approach. Full article

The rise in the number of cancer cases and the dissemination of strains with multiple drug resistance in the world pose a serious threat to public health care and human well-being. The design and study of new chemotherapeutic agents for cancer and infectious diseases are hot topics in science. Hydrazones, a versatile and diverse class of chemical compounds, gained a lot of attention as a promising base for future drugs. In this paper, we report on the synthesis of eight new gold(III) complexes with hydrazones derived from pyridoxal-5′-phosphate and pyridoxal. The complexes are thoroughly characterized using IR, ¹H, ³¹P NMR, and mass spectroscopy. The cytotoxic effect of twelve various hydrazones derived from pyridoxal 5′-phosphate on both immortalized (HEK293T) and tumor (HCT116) human cell lines was estimated using the MTT assay. In addition, this contribution describes the antibacterial action of complexes of gold(III) and pyridoxal and pyridoxal 5′-phosphate-derived hydrazones, as well as the mixtures of the solutions containing tetrachloroaurate(III) and hydrazones, using the zone of inhibition test. Gold(III) complexes exhibit moderate antibacterial activity against both Gram-positive and Gram-negative bacteria, while free hydrazones show low cytotoxicity and thus could be considered relatively safe for humans. Full article

Metabolic syndrome (MetS) is a complex condition characterized by a group of interconnected metabolic abnormalities. Due to its increasing prevalence, better predictive markers are needed. Therefore, this study aims to develop predictive models for MetS by integrating adipokines, metabolic and cardiovascular risk factors, and anthropometric indices. Data were collected from 381 subjects aged 20 to 59 years (242 women and 139 men) from Guadalajara, Jalisco, Mexico, who were classified as having MetS or non-MetS based on the ATP-III criteria. Four supervised machine learning models were developed—Logistic Regression (LR), Support Vector Machine (SVM), Random Forest (RF), and eXtreme Gradient Boosting (XGBoost)—and their performance was evaluated using the Area under the Curve (AUC), calibration curves, Decision Curve Analysis (DCA), and local interpretability analysis. The RF and XGBoost models achieved the highest AUCs (0.940 and 0.954). The RF and LR models were the best calibrated and showed the highest net benefit in DCA. Key variables included age, anthropometric indices (BRI and DAI), insulin resistance measures (HOMA-IR), lipid profiles (sdLDL-C and LDL-C), and high-molecular-weight adiponectin, used to classify the presence of MetS. The results highlight the usefulness of specific models and the importance of anthropometric variables, cardiovascular risk factors, metabolic profiles, and adiponectin as indicators of MetS. Full article

Molecular geometry, infrared (IR) vibrational frequencies, and ultraviolet–visible (UV-Vis) electronic absorption spectra of the trivalent iron tris(acetylacetonate) complex, Fe(III)(acac)₃, were computed using hybrid meta-generalized gradient approximation (meta-GGA) density functional theory (DFT). Calculations employed the Jorge double-$\zeta$ valence plus polarization basis sets (standard DZP and relativistic DZP + DKH). Solvent effects were modeled using the SMD continuum solvation framework with acetonitrile as the dielectric medium. This charge-neutral complex exhibits predominantly ionic metal–ligand bonding character, which simplifies the computational treatment. Despite extensive DFT applications to coordination compounds, systematic benchmarks for this bidentate ligand system remain limited. The computed harmonic frequencies ($\nu$) and electronic excitation energies (${\lambda }_{\max }$) demonstrate excellent agreement with available experimental measurements. These results enable comparative analysis of IR and UV-Vis spectral features, both with and without all-electron scalar relativistic effects with the second-order Douglas–Kroll–Hess approach. Full article

Three fluorophenyl-substituted cyclometalated Ir(III) complexes (Ir1–Ir3) have been synthesized by changing the position of the fluorine atom. All complexes exhibit distinct aggregation-induced phosphorescence emission (AIPE) characteristics in CH₃CN/H₂O and demonstrate satisfactory detection performance for 2,4,6-trinitrophenols (TNPs) with limits of detection of 124 nM, 101 nM, and 127 nM, respectively. In addition, Ir1–Ir3 possess excellent selectivity and anti-interference capability for TNP detection, showing outstanding performance even in different common water samples. The ultraviolet–visible absorption spectra and luminescence lifetimes of the complexes show that their quenching processes include both a static process and dynamic process, and the detection mechanism may be assigned to a combination of photo-induced electron transfer and an inner-filter effect. Full article

The experimental IR and Raman vibrational spectra of a hydrated La(III) complex with a 1,2,3-triazole ligand were characterized by using four different Density Functional Theory (DFT) levels and two accurate scaling procedures. In the theoretical calculations, the hydration water in the experimental sample was considered under the Discrete Model (DM) with different numbers of explicit water molecules and different positions around the La(III) ion and the carboxylate groups. The predicted IR spectra at the M06-2X/Lanl2dz level appear to be the closest to the experimental ones. Based on the optimized structures, molecular properties and global chemical descriptors were also calculated, and the findings obtained are discussed in detail herein. Additionally, several photophysical properties were determined in both the free ligand and in several lanthanide complexes, and with the sample in the solid state and in DMSO solution. A blue shift in the fluorescence of the complexes was observed compared to the free ligand, as well as in the solid-state sample compared to the solution. Full article

The present study reports the sono-chemical synthesis of novel nanosized Cr(III), Mn(II), and Pd(II) complexes incorporating the chloro-2-(quinolin-8-yliminomethyl)-phenol imine ligand. The synthesized complexes were characterized using various spectroscopic and analytical techniques, including Fourier-transform infrared (FT-IR) spectroscopy, ultraviolet–visible (UV–Vis) spectroscopy, scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA). The results confirmed the successful coordination of the ligand-to-metal centers, forming stable nanosized metal complexes with distinct physicochemical properties. Biological evaluations, including antimicrobial and antioxidant assays, revealed that the synthesized complexes exhibited enhanced biological activity compared to the free ligand, demonstrating potent antibacterial and antifungal properties against various pathogenic strains. The potential of the complexes to serve as efficient free-radical inhibitors was determined by employing DPPH radical scavenging assays, which underscored their significant antioxidant properties. Furthermore, molecular docking studies were conducted to elucidate the binding interactions of the metal complexes with biological targets, providing insights into their mechanism of action. The findings suggest that the synthesized nanosized Cr(III), Mn(II), and Pd(II) complexes possess promising biological properties, making them potential candidates for pharmaceutical and biomedical applications. The study also demonstrates the effectiveness of sono-chemical synthesis in producing nanosized metal complexes with enhanced physicochemical and biological characteristics. Full article