Search Results (605)

The highly fluorescent fluorene group is of interest for its unique optical and electronic properties. By incorporating it into a metal complex, these properties are extended to the complex and are useful in a number of different applications. Four β-diketone ligands were synthesized containing the fluorene-functional group, where the varying substituent on the β-diketone was CF₃ (1), PhCF₃ (2), Ph (3) and PhCH₃ (4). The corresponding cyclooctadiene rhodium(I) complexes of the type [Rh(cod)((fluorene)COCHCOR)], with R = CF₃ (5), PhCF₃ (6), Ph (7) and PhCH₃ (8) were also synthesized. A crystal structure determination of 2 and 6 was performed, highlighting important changes in the ligand structure as a result of metal complexation. The structure of 2 also showed a hydrogen interaction between the hydroxy and carboxyl groups, forming a pseudo six-membered ring that stabilizes the enol form of the compound. Cyclic voltammetry (CV) of the β-diketones 1–4 showed a reduction wave for the reduction of the β-diketonato backbone between −1500 mV and −2100 mV as measured against ferrocene (FcH). CVs of rhodium(I) complexes 5–8 showed a reduction of the β-diketonato backbone between −1800 and −2000 mV, as well as an oxidation wave for the oxidation of the rhodium(I) metal centre at approximately 300 mV. Full article

A novel ruthenium(II) complex, [RuCl₂(η⁶-p-cymene)(bph-κN)] (1), was synthesized and structurally characterized using FTIR and NMR spectroscopy. Density functional theory (DFT) calculations supported the proposed geometry and allowed for comparative analysis of experimental and theoretical spectroscopic data. The interaction of complex 1 with human serum albumin (HSA) and calf thymus DNA was investigated through fluorescence quenching experiments, revealing spontaneous binding driven primarily by hydrophobic interactions. The thermodynamic parameters indicated mixed quenching mechanisms in both protein and DNA systems. Ethidium bromide displacement assays and molecular docking simulations confirmed DNA intercalation as the dominant binding mode, with a Gibbs free binding energy of −34.1 kJ mol⁻¹. Antioxidant activity, assessed by EPR spectroscopy, demonstrated effective scavenging of hydroxyl and ascorbyl radicals. In vitro cytotoxicity assays against A375, MDA-MB-231, MIA PaCa-2, and SW480 cancer cell lines revealed selective activity, with pancreatic and colorectal cells showing the highest sensitivity. QTAIM analysis provided insight into metal–ligand bonding characteristics and intramolecular stabilization. These findings highlight the potential of 1 as a promising candidate for further development as an anticancer agent, particularly against multidrug-resistant tumors. Full article

In the present research, metal–organic framework-5 (MOF-5) was synthesized and loaded with zerumbone (ZER@MOF-5), followed by the evaluation of its anticancer, antibacterial, antifungal, DNA-binding, and free radical scavenging potentials. The synthesized nanoparticles were characterized using X-ray diffraction, ultraviolet–visible spectroscopy, Fourier-transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. The in vitro anticancer activity of ZER@MOF-5 was studied in a human breast cancer cell line (MCF-7) using the CCK-8 assay. The interaction of ZER@MOF-5 with pBR322 plasmid DNA was assessed by gel electrophoresis. The antimicrobial effect of ZER@MOF-5 was examined in gram-positive and gram-negative bacterial strains and yeast strains using the microdilution method. The free radical scavenging activity was assessed using the DPPH assay. Cytotoxicity assay revealed a notable enhancement in the anticancer activity of zerumbone upon its encapsulation into MOF-5. The IC₅₀ value for ZER@MOF-5 was found to be 57.33 µg/mL, which was lower than that of free zerumbone (IC₅₀: 89.58 µg/mL). The results of the DNA-binding experiment indicate that ZER@MOF-5 can bind to target DNA and cause a conformational change in DNA. The results of the antibacterial activity experiment showed that the antibacterial ability of ZER@MOF-5 was limited compared to free zerumbone. The results of the DPPH assay demonstrated that the antioxidant activity of free zerumbone was higher than that of ZER@MOF-5. MOFs encapsulate compounds within their porous crystalline structure, which leads to prolonged circulation time compared to single ligands. Although the unique structure of MOFs may limit their antibacterial and antioxidant activity in the short term, it may increase therapeutic efficacy in the long term. However, to fully understand the long-term antibacterial and antioxidant effects of the ZER@MOF-5, further comprehensive in vitro and in vivo experiments are necessary. This finding indicates that the MOF-5 could potentially be an impressive carrier for the oral administration of zerumbone. Full article

Metal ions and ligand binding are crucial in various biological processes, and their rational design can be used to develop novel therapeutic drugs and diagnostic tools. Metal atoms are soluble in biological fluids due to their ability to easily lose electrons and form positively charged ions. Because of their electron deficiency, they can interact with electron-rich biomolecules like proteins and DNA, and potentially participate in catalytic mechanisms or stabilize their tertiary or quaternary structures. Antibacterial resistance has become a major global concern and requires novel strategies to combat resistance mechanisms in infectious microbes. Full article

The present work reports the synthesis and structural design of three novel Zn(II) complexes [Zn(L¹)(CH₃COO)(H₂O)] (1), [Zn(L²)₂] (2), and [Zn(L³)₂] (3) with carbazate ligands, 2-acetylpyridine-methylcarbazate (HL¹), 2-acetylpyridine-ethylcarbazate (HL²), and 2-acetylpyridine-benzylcarbazate (HL³). All compounds were characterized by spectroscopic methods, and the crystal structures of the complexes were elucidated by single-crystal X-ray. Based on the analysis, distorted square pyramid geometry is suggested for complex (1) and an octahedral geometry is suggested for complexes (2) and (3) with the ligands exhibiting an NNO-donor system. The 3D Hirshfeld surface and the 2D fingerprint plot were used to study the non-covalent interactions in the crystal structures. The in vitro antibacterial investigation of the free ligands and their complexes was performed against different strains of periodontopathogen bacteria. The Zn(II) complexes showed more potent antibacterial activity than the free ligand. Molecular docking studies showed the metal complexes as promising candidates for further therapeutic exploration, particularly in targeting the ATP-binding cassette transporter with peptidase domain of the cariogenic bacteria S. mutans (PDB code 5XE9) and the prolyl tripeptidyl aminopeptidase from P. gingivalis anaerobic bacteria (PDB code 2EEP) inhibition. Full article

Phenylene-based bis-oxamate polydentate ligands offer a unique opportunity for creating a large variety of coordination compounds, in which paramagnetic metal ions are strongly magnetically coupled. The employment of imino nitroxyl (IN) radicals as supplementary ligands confers numerous benefits, including the strong ferromagnetic interaction between Ni and IN. Furthermore, the chelating IN can act as a capping ligand, thereby impeding the formation of coordination polymers. In this study, we present the molecular and crystal structure and experimental and theoretical magnetic behavior of an exceptional neutral trinuclear complex [Ni(L³⁻)₂(IN)₃]∙5CH₃OH (1) (L is N,N′-1,3-phenylenebis-oxamic acid; IN is [4,4,5,5-tetramethyl-2-(6-methylpyridin-2-yl)-4,5-dihydro-1H-imidazol-1-yl]oxidanyl radical) with a cyclic triangular arrangement. Moreover, in this compound three Ni²⁺ ions are linked by the two bis-oxamate ligands playing a rare tritopic function due to an unprecedented triple deprotonation of the related meta-phenylene-bis(oxamic acid). The main evidence of such a deprotonation of the ligand is the neutrality of the cluster, since there are no anions or cations compensating for its charge in the crystals of the compound. Despite the presence of six possible magnetic couplings in the trinuclear cluster 1, its behavior was reproduced with a high degree of accuracy using a three-J model and ZFS, under the assumption that the three different Ni-IN interactions are equal to each other, whereas only two equivalent-in-value Ni-Ni interactions were taken into account, with the third one being equated to zero. Our study indicates the presence of two opposite-in-nature types of magnetic interactions within the triangular core. DFT and CASSCF/NEVPT2 calculations were completed to support the experimental magnetic data simulation. Full article

Their demonstrable bioactive characteristics, coupled with their wide structural diversity and coordination versatility, render Schiff bases and their coordination complexes biologically active compounds demonstrating outstanding properties. This research describes the synthesis and characterization of new Cu(II) and Ni(II) complexes with an NNO-donor hydrazone ligand (HL). The crystal structure of the HL ligand was determined through single-crystal X-ray diffraction studies. The in vitro antibacterial activities of the HL ligand and its metal(II) complexes against Gram-positive and Gram-negative bacteria demonstrated that the metal(II) complexes displayed greater antimicrobial activities compared to the free Schiff base ligand. Furthermore, the interaction of the ligand and the complexes with calf thymus DNA (CT-DNA) was explored through electronic absorption and viscosity measurements, suggesting intercalation as the most likely mode of binding. The compounds promoted oxidative DNA cleavage, as demonstrated by the strand breaks of the pmChery plasmid under oxidative stress conditions. Finally, fluorescence spectroscopy also revealed the strong binding affinity of these compounds for bovine serum albumin (BSA). Full article

The imidazo[4,5-b]pyridine scaffold, a versatile heterocyclic system, is renowned for its biological and chemical significance, yet its coordination chemistry with biologically relevant metal dications remains underexplored. This study investigates the proton and metal dication affinities of twelve tetracyclic organic molecules based on the imidazo[4,5-b]pyridine core, focusing on their interactions with Ca(II), Mg(II), Zn(II), and Cu(II). Employing a dual approach of electrospray ionization mass spectrometry (ESI-MS) and density functional theory (DFT) calculations, we characterized the formation, stability, and structural features of metal–ligand complexes. ESI-MS revealed distinct binding behaviors, with Cu(II) and Zn(II) forming stable mono- and dinuclear complexes, often accompanied by reduction processes (e.g., Cu(II) to Cu(I)), while Ca(II) and Mg(II) exhibited lower affinities. DFT analysis elucidated the electronic structures and thermodynamic stabilities, highlighting the imidazole nitrogen as the primary binding site and the influence of regioisomeric variations on affinity. Substituent effects were found to modulate binding strength, with electron-donating groups enhancing basicity and metal coordination. These findings provide a comprehensive understanding of the coordination chemistry of imidazo[4,5-b]pyridine derivatives, offering insights into their potential applications in metalloenzyme modulation, metal-ion sensing, and therapeutic chelation. Full article

Energetic metal–organic frameworks (E-MOFs) have recently emerged as a promising strategy to address the long-standing challenge of reconciling energy and sensitivity in energetic materials. Nitrogen-rich compounds, with their abundant nitrogen atoms and superior enthalpy of formation, are particularly beneficial for forming multiple coordination bonds while simultaneously elevating the energy content. This makes them ideal ligand molecules for constructing E-MOFs. In this work, we report the synthesis and structural design of a novel series of E-MOFs, constructed from the nitrogen-rich energetic ligand BNTA and a range of alkali metals (Na–Rb, compounds 2–5). The research indicates that the synthesized E-MOFs exhibit high thermal stability and low sensitivity. Specifically, Compound 3 displays a high decomposition temperature of 285 °C, with impact sensitivity and friction sensitivity values exceeding 40 J and 360 N, respectively. Moreover, Compound 3 also exhibits excellent computational detonation performance. Significantly, this study demonstrates how the aromatic character, coordination chemistry, and intermolecular interactions work synergistically to enhance the stability and safety of E-MOFs, thereby establishing fundamental criteria for engineering the next generation of energetic frameworks. Full article

The detection of zinc ions plays an essential role in protecting public health and maintaining ecological balance. However, traditional fluorescent probes for Zn²⁺ are limited in their specificity, especially under complex environments, due to their single-mode optical signal and inadequate recognization capacities. Herein we report a dual-mode supramolecular sensing system constructed from a unique three-component assembly involving a terpyridine platinum (II) complex, oxalate, and Zn²⁺, enabling highly specific detection performance for Zn²⁺. The supramolecular sensing system exhibits excellent selectivity among various interfering substances, accompanied by ultra-low detection limit (0.199 μM) and fast response (<3 s). The high recognization capacity comes from tri-component-based supramolecular assembly, while the dual-mode response arises from the generation of intermelcular Pt-Pt and π-π interactions, which yields absorption and emission originating from low-energy metal–metal-to-ligand charge transfer (MMLCT) transitions. This work marks a pioneering demonstration for highly specific detection of Zn²⁺ and inspires an alternative strategy for designing cation probes. Full article

Cu-based layered double hydroxides (LDH) have been extensively employed as catalyst precursors. However, due to the Jahn–Teller effect of copper ions, it is a challenge to synthesize well-crystallized LDH with a high Cu content, which usually contains considerable CuO impurity. By adding competitive ligands during the coprecipitation process, such as glycine, a well-crystallized Cu-rich LDH with less CuO impurity was successfully synthesized. The Cu-Mg-Al mixed oxides derived from the well-crystallized Cu-rich LDH have relatively high S_BET, large pore volume, and well dispersion of Cu nanoparticles. The derived catalyst exhibited unexpectedly high catalytic activity in the water–gas shift (WGS) reaction, and the mass-specific reaction rate was reached as high as 33.5 μmol_CO${·\mathrm{g}}_{\mathrm{cat}}^{-1}$·s⁻¹ at 200 °C. The high catalytic activity of this catalyst may originate from the high S_BET and well dispersion of Cu particles and metal oxides. Moreover, the derived catalyst also displayed outstanding long-term stability in the WGS reaction, which should benefit from the enhanced metal–support interaction. Full article

The coordination chemistry, structural characterization, and biomolecular interactions of europium(III) and iron(III) complexes with the pyridoxal-semicarbazone (PLSC) ligand were thoroughly examined using experimental and computational approaches. Single-crystal X-ray diffraction revealed that the europium complex exhibits a nine-coordinate geometry with one protonated and one deprotonated PLSC ligand and nitrato and aqua ligands. In contrast, the iron complex adopts a six-coordinate structure featuring a monoprotonated PLSC, two chlorido, and an aqua ligand. Hirshfeld surface analysis confirmed the significance of intermolecular contacts in stabilizing the crystal lattice. Theoretical geometry optimizations using DFT methods demonstrated excellent agreement with experimental bond lengths and angles, thereby validating the reliability of the chosen computational levels for subsequent quantum chemical analyses. Quantum Theory of Atoms in Molecules (QTAIM) analysis was employed to investigate the nature of metal–ligand interactions, with variations based on the identity of the donor atom and the ligand’s protonation state. The biological potential of the complexes was evaluated through spectrofluorimetric titration and molecular docking. Eu-PLSC displayed stronger binding to human serum albumin (HSA), while Fe-PLSC showed higher affinity for calf thymus DNA (CT-DNA), driven by intercalation. Thermodynamic data confirmed spontaneous and enthalpy-driven interactions. These findings support using PLSC-based metal complexes as promising candidates for future biomedical applications, particularly in drug delivery and DNA targeting. Full article

Metal complexes of endogenous metals, such as iron, copper, and zinc, offer a biocompatible, cost-effective, and eco-friendly alternative to heavy metals for drug design. This study presents the synthesis, structural characterization, and evaluation of the biological activity of eight novel iron(III) complexes with substituted salicylaldehydes as ligands. The characterization of the complexes involved spectroscopic and physicochemical methods. The structures of two complexes were determined using single-crystal X-ray crystallography. The biological studies of the complexes focused on the interaction of calf-thymus DNA, the (photo)cleavage of pBR322 plasmid DNA (pDNA), the affinity for bovine and human serum albumins, and the antioxidant activity. The complexes interacted with calf-thymus DNA via intercalation with high DNA-binding constants. The complexes exhibited high pDNA-cleavage ability, which is significantly enhanced upon exposure to UVA or UVB irradiation. The complexes can bind tightly and reversibly to both serum albumins, and their binding locations were identified. Finally, the complexes showed moderate ability to scavenge 1,1-diphenyl-picrylhydrazyl and 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radicals with a high ability to reduce hydrogen peroxide. Full article

Mn(III)– and Co(III)–salen complexes (Mn-1 and Co-2) have been synthesized by a simple one-pot procedure through oxidation of Mn(II) and Co(II) precursors in air. X-ray structural analysis reveals that both complexes adopt similar coordination modes, including a typical square planar metal/salen coordination sphere, which is further occupied by two axial ligands, i.e., an acetate anion and a water molecule. Despite their structural similarity, they are not isomorphous given their distinct cell parameters. In the solid-state structures, both complexes exist as hydrogen-bonded dimers through hydrogen bonding interactions between the axially coordinating water molecules and outer O₄ cavity from another molecule of the complex. The reductive activity of both complexes has been explored. While the reaction of Mn-1 with potassium triethylborohydride was unsuccessful, leading to a complicated mixture, the use of Co-2 furnished the formation of a novel product (CoK-3) that was isolated as red crystals in reasonable yield. CoK-3 was characterized as a heterometallic dimer involving the coordination of a K⁺ ion within the O₄ cavity of a semi-hydrogenated salen/cobalt complex while the cobalt center has been reduced from Co(III) to Co(II). In addition, an attempt at reducing Co-2 with pinacolborane resulted in the isolation of crystals of Co-4, whose structure was determined as a simple square planar Co^II–salen complex. Finally, three complexes (Mn-1, Co-2 and CoK-3) have been investigated for their cytotoxic activities against two human breast cancer cell lines (MCF-7 and MDA-MB 468) and a normal breast epitheliel cell line (MCF-10A), with cisplatin used as a reference in order to discover potential drug candidates that may compete with cisplatin. The results reveal that Co-2 can be a promising drug candidate, specifically for the MCF-7 cancer cells, with minimal damage to healthy cells. Full article

Nuclear technology, while offering significant benefits across various sectors, poses potential health risks due to uranium (U) contamination, particularly through its internalization and subsequent interactions with biological systems. This study investigates the binding of uranyl (UO₂²⁺) and zinc (Zn²⁺) ions to Human Serum Albumin (HSA) that is already bound to fatty acids (FAs), using all-atom molecular dynamics (MD) simulations. The analysis focuses on the structural and dynamic alterations in the protein’s multi-metal binding site (MBS-A) caused by FA binding. Results reveal that FA binding induces a conformational change in HSA, disrupting the pre-formed MBS-A binding site, while still allowing uranyl and zinc ions to interact with residue D249 through strong Coulombic interactions. Secondary binding sites, associated with calcium and zinc binding, remain largely unaffected by FAs, providing alternative coordination for metal ions. This study also explores the binding and unbinding pathways of the metal ions using well-tempered meta-dynamics (WT-MtD), showing that while FA binding disrupts the primary metal binding site, it does not completely inhibit the binding of both uranyl and zinc ions. These findings offer new insights into the nature of uranium’s interactions with blood serum proteins and the role of fatty acids in modulating these interactions, which may help in designing future strategies for managing uranium contamination in biological systems. Full article