Search Results (353)

We report an investigation on the cobalt(II) chelation mechanism by a modified α-maltoside ligand 9 decorated with two iminodiacetate (IDA) residues on C6,C6′ positions. Herein we uncovered the capacity of this biodegradable ligand to chelate cobalt(II), an ionic metal contaminant in the environment that is used, in particular, in lithium-ion batteries. The interactions between cobalt(II) and synthesized ligand 9 were systematically studied using different analytical methods such as ¹H and ¹³C NMR, potentiometry, spectrophotometry, ITC, and ICP-AES. We observed a high affinity for the 1:1 complex, one cobalt(II) associated with two iminodiacetate groups, which is 10-fold higher than the 2:1 complex, where each of the two IDA groups interacts alone with a cobalt(II). Taking into account the log β_CoL value obtained (≈12.3) with the stoichiometry 1:1, the strength of this complexation with cobalt(II) can be ranked as follows for the most common ligands: IDA < MIDA < NTA < 9 < EDTA < TTHA < DTPA. We further completed a preliminary remediation test with water contaminated with cobalt(II) and recovered cobalt(II) metal using Chelex^® resin, which allowed a recycling of the synthetic ligand for future recovering experiments. The results shed light on the great potential of using this synthetic ligand as an effective and green remediation tool. Full article

The use of radiosensitizers is a beneficial approach in cancer radiotherapy treatment. However, the enhancement of radiation effects on cancer cells by radiosensitizers involves several different mechanisms, reflecting the chemical nature of the radiosensitizer. G-quadruplex (G4) DNA ligands have emerged in recent years as a potential new class of radiosensitizers binding to specific DNA sequences. Recently, we have shown that the Re(I) tricarbonyl complex PDF-Pz-Re and its pyrazolyl-diamine chelator PDF-Pz, carrying a N-methylated pyridostatin (PDF) derivative, act as G4 binders of various G4-forming DNA and RNA sequences. As described in this contribution, these features prompted us to evaluate PDF-Pz-Re and PDF-Pz as radiosensitizers of prostate cancer PC3 cells submitted to concomitant treatment with Co-60 radiation. The compound RHPS4 was also tested, as this G4 ligand was previously shown to exhibit strong radiosensitizing properties in other cancer cell lines. The assessment of the resulting radiobiological effects, namely through clonogenic cell survival, DNA damage, and ROS production assays, showed that PDF-Pz-Re and PDF-Pz were able to radiosensitize PC3 cells despite being less active than RHPS4. Our results corroborate that G4 DNA ligands are a class of compounds with potential interest as radiosensitizers, deserving further studies to optimize their radiosensitization activity and elucidate the mechanisms of action. Full article

The thioether-functionalized 2-azabutadienes (ArS)₂C=C(H)-N=CPh₂ (L1 Ar = Ph, L2 Ar = p-Tol) ligate to [Mn(CO)₅Br] to form the octahedral five-membered S, N-chelate complexes fac-[MnBr(CO)₃{(ArS)₂C=C(H)-N=CPh₂] (1 Ar = Ph; 2 Ar = p-Tol), whose crystal structures have been solved by X-ray diffraction. Complex 1 crystallizes in the non-centrosymmetric orthorhombic space group P2₁2₁2₁, whereas 2 crystallizes in the triclinic space group P$\overline{1}$. The secondary interactions occurring in the packing have also been assessed by an Atoms in Molecules (AIM) topological analysis. Full article

The synthesis and structural characterization of three new triple-stranded helical complexes ([Dy₂(L²)₃]2Cl∙15H₂O (C1), [Y₂(L²)₃]3(NO₃)Cl∙14H₂O∙DMSO (C2), and [Eu₂(L⁴)₃]∙12H₂O (C3), where L² and L⁴ are ligands derived from pyridoxal hydrochloride and succinic or adipic acid dihydrazides, respectively, were described. The X-ray data, combined with spectroscopic measurements, indicated that L² and L⁴ act as bis-tridentate ligands, presenting two tridentate chelating cavities O,N,O to obtain the dinuclear complexes C1–C3. Their antiviral profile was predicted via in silico calculations in terms of interaction with the structural severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) spike glycoprotein in the down- and up-states and complexed with the cellular receptor angiotensin-converting enzyme 2 (ACE2). The best affinity energy values (−9.506, −9.348, and −9.170 kJ/mol for C1, C2, and C3, respectively) were obtained for the inorganic complexes docked in the model spike-ACE2, with C1 being suggested as the most promising candidate for a future in vitro validation. The obtained in silico antiviral trend was supported by the prediction of the electronic and physical–chemical properties of the inorganic complexes via the density functional theory (DFT) approach, representing an original and relevant contribution to the bioinorganic and medicinal chemistry fields. Full article

Arsenic (As) and cadmium (Cd) in rice grains are major global food safety concerns. Iron (Fe) can help reduce both, but current Fe treatments suffer from poor stability, low leaf absorption, and fast soil immobilization, with unclear underlying mechanisms. To address these issues, an Fe-based metal–organic framework (MIL-88) was modified with sodium alginate (SA) to form MIL-88@SA. Its stability as a foliar inhibitor and its leaf absorption were tested, and its effects on As and Cd accumulation in rice were compared with those of soluble Fe (FeCl₃) and chelating Fe (HA + FeCl₃) in a field study on As–Cd co-contaminated rice paddies. Compared with the control, MIL-88@SA outperformed or matched the other Fe treatments. A single foliar spray during the tillering stage increased the rice yield by 19% and reduced the inorganic As and Cd content in the grains by 22.8% and 67.8%, respectively, while the other Fe treatments required two sprays. Its superior performance was attributed to better leaf affinity and thermal stability. Laser ablation inductively coupled plasma–mass spectrometry (LA–ICP–MS) and confocal laser scanning microscopy (CLSM) analyses revealed that Fe improved photosynthesis and alleviated As–Cd stress in leaves, MIL-88@SA promoted As and Cd redistribution, and Fe–Cd co-accumulation in leaf veins enhanced Cd retention in leaves. Full article

The persistent contamination of aquatic environments by heavy metals, particularly Pb²⁺, Cd²⁺, and Cu^2+, poses a serious global threat due to their toxicity, persistence, and bioaccumulative behavior. In response, low-cost and eco-friendly adsorbents are being explored, among which CaCO₃-based biocomposites derived from mollusk shells have shown exceptional performance. In this study, a hybrid biocomposite composed of poly(vinyl alcohol) (PVA) and oyster shell-derived CaCO₃ was computationally investigated using Density Functional Theory (DFT) to elucidate the electronic and structural basis for its high metal-removal efficiency. Calculations were performed at the B3LYP/6-311++G(d,p), M05-2X/6-311+G(d,p), and M06-2X/6-311++G(d,p) levels using GAUSSIAN 16. Among them, B3LYP was identified as the most balanced in terms of accuracy and computational cost. The hybridization with CaCO₃ reduced the HOMO-LUMO gap by 20% and doubled the dipole moment (7.65 Debye), increasing the composite’s polarity and reactivity. Upon chelation with metal ions, the gap further dropped to as low as 0.029 eV (Cd²⁺), while the dipole moment rose to 17.06 Debye (Pb²⁺), signaling enhanced charge separation and stronger electrostatic interactions. Electrostatic potential maps revealed high nucleophilicity at carbonate oxygens and reinforced electrophilic fields around the hydrated metal centers, correlating with the affinity trend Cu²⁺ > Cd²⁺ > Pb²⁺. Fukui function analysis indicated a redistribution of reactive sites, with carbonate oxygens acting as ambiphilic centers suitable for multidentate coordination. Natural Bond Orbital (NBO) analysis confirmed the presence of highly nucleophilic lone pairs and weakened bonding orbitals, enabling flexible adsorption dynamics. Furthermore, NCI/RDG analysis highlighted attractive noncovalent interactions with Cu²⁺ and Pb²⁺, while FT-IR simulations demonstrated the formation of hydrogen bonding (O–H···O=C) and Ca²⁺···O coordination bridges between phases. Full article

A waste amidoxime chelate resin (WAR) was converted into a magnetic composite adsorbent (MCA) via carbonization and magnetization for the effective removal of Cr(VI). Under optimized conditions (pH = 1, 30 °C, 1 h), the adsorbent achieved a maximum Cr(VI) adsorption capacity of 197.63 mg/g. The adsorption process conformed to the pseudo-second-order kinetic model (R² > 0.98) and Langmuir isotherm model (R² > 0.99). The materials can be separated by magnetism. The primary mechanism for the adsorption of Cr(VI) involved monolayer chemisorption. FTIR spectroscopy confirmed the dominant role of -C=O, C-O, and Fe-O in the adsorption process. XPS spectroscopy confirmed the dominant role of -C=O and C-O in the adsorption process. The successful conversion of the WAR into an MCA not only mitigates waste accumulation but also provides a cost-effective strategy for heavy metal remediation. Full article

Cadmium (Cd) contamination in agricultural soils severely threatens rice production and food safety. To address this issue, this study developed transgenic rice lines co-expressing three Vitis vinifera genes: the ABCC transporter Vvmrp1 and metallothioneins Vvmt1 and Vvmt2. AlphaFold computational modeling confirmed the conserved ABCC-type transporter domain in VvMRP1. Under hydroponic conditions, transgenic rice showed remarkable Cd tolerance, surviving 30 mM Cd (lethal to wildtype, WT) without growth penalties, and exhibited 62.5% survival at 1 mM Cd vs. complete wild-type mortality. Field-relevant Cd exposure (1 mM) reduced Cd accumulation to 35.8% in roots, 83% in stems, and 76.8% in grains compared to WT. Mechanistic analyses revealed that Vvmrp1 mediates cellular Cd efflux while Vvmt1 and 2 chelate free Cd ions, synergistically inhibiting Cd translocation. Transgenic plants also maintained better Fe, P, and Mg homeostasis under Cd stress. This study pioneers the co-expression of a transporter with metallothioneins in rice, demonstrating their complementary roles in Cd detoxification without pleiotropic effects from endogenous gene modification. The findings provide an effective genetic strategy for cultivating low-Cd rice in contaminated soils, offering significant implications for food safety and sustainable agriculture. Full article

Lithium–air batteries (LABs) possess the highest energy density among all energy storage systems, and have drawn widespread interest in academia and industry. However, many arduous challenges are still to be conquered, one of them is Li₂CO₃, which is a ubiquitous product in LABs. It is inevitably produced but difficult to decompose; therefore, Li₂CO₃ is perceived as the “Achilles’ heel of LABs”. Among various approaches to addressing the Li₂CO₃ issue, developing Li₂CO₃-decomposing redox mediators (RMs) is one of the most convenient and versatile, because they can be electrochemically oxidized at the gas cathode surface, then they diffuse to the solid-state products and chemically oxidize them, recovering the RMs to a pristine state and avoiding solid-state catalysts’ contact instability with Li₂CO₃. Furthermore, because of their function mechanism, they can double as catalysts for Li₂O₂/LiOH decomposition, which are needed in LABs/LOBs anyway regardless of Li₂CO₃ incorporation due to the sluggish kinetics of oxygen reduction/evolution reactions. This review summarizes the progress in Li₂CO₃-decomposing RMs, including halides, metal–chelate complexes, and metal-free organic compounds. The insights into and discrepancies in the mechanisms of Li₂CO₃ decomposition and corresponding catalysis processes are also discussed. Full article

Recently, the emerging class of hydroxamate-based metal–organic frameworks (MOFs) has demonstrated significant structural diversity and chemical robustness, both essential for potential applications. Combining the favorable hard–hard Bi-O interactions and chelating chemistry of hydroxamate groups, a rigid and symmetrical three-dimensional bismuth-hydroxamate metal–organic framework was successfully prepared via solvothermal synthesis and structurally elucidated via X-ray crystallography. The MOF, namely SUM-91 (SUM = Sichuan University Materials), features one-dimensional Bi-oxo secondary building blocks (SBUs), which are bridged by chelating 1,4-benzenedihydroxamate linkers. With the demonstrated permanent porosity and molecular sieving effect (CO₂ vs. N₂), SUM-91 was also found to be stable under harsh chemical conditions (aqueous solutions with pH = 2–12 and various organic solvents). As the structural robustness of SUM-91 could be attributed to the finetuning of the coordinative sphere of Bi centers, this work shed light on the further development of (ultra-)microporous materials with high stability and selective adsorption properties. Full article

Background: This study pioneers the exploration of the role of cuproptosis (a novel form of regulated cell death) in the pathogenesis of atopic dermatitis (AD). Methods: We integrated two datasets (GSE157194 and GSE193309) from the GEO database and employed weighted gene co-expression network analysis (WGCNA) to identify disease-related modules. Through multi-dimensional approaches, including differential gene expression analysis, functional enrichment analysis, GeneMANIA network construction, GSEA/GSVA pathway enrichment analysis, and immune infiltration analysis, we systematically elucidated the regulatory mechanisms of cuproptosis-related genes (CRGs) in AD. Results: The findings reveal novel mechanisms underlying AD pathogenesis. We identified 14 co-expression modules and 1173 differentially expressed genes, among which SPTLC2, AMD1, and IGSF3 were identified as key hub genes (AUC > 0.75). In-depth mechanistic analysis uncovered critical pathophysiological features of AD, including significant enrichment in chemokine signaling pathways (p < 0.001) and copper-dependent metabolic reprogramming. Notably, immune infiltration analysis demonstrated abnormal activity in 20 out of 21 immune cell types, particularly Th2 cells and macrophages, which showed strong correlations with CRG expression patterns. These findings establish an innovative “metabolic checkpoint” model for AD progression, highlighting dysregulation of the sphingolipid-immune axis as a key pathogenic mechanism. Conclusions: This study provides novel evidence, suggesting a potential link between AD and copper metabolism dysregulation, and identifies several promising targets that may aid in diagnosis and treatment. Our findings contribute to the growing understanding of AD pathogenesis and hint at possible new therapeutic directions, including copper chelation or sphingolipid-modulating approaches for difficult-to-treat AD cases. The identified CRG signatures may serve as potential biomarkers and therapeutic targets for personalized management strategies of this complex skin disorder. Full article

To address the underutilization of Schizochytrium limacinum meal, polysaccharides from Schizochytrium limacinum meal (SLMPs) were prepared via ultrasonic-assisted eutectic-solvent-based extraction. Although polysaccharides exhibit promising application potential, the structural ambiguity of SLMPs necessitates systematic investigation to elucidate their structure–activity relationships, thereby providing a scientific foundation for their subsequent development and utilization. Using response-surface methodology (RSM), the optimized extraction conditions were determined as follows: ultrasonic temperature of 52 °C, ultrasonic duration of 31 min, ultrasonic power of 57 W, water content of 29%, and a material-to-liquid ratio of 1:36 g/mL. Under these conditions, the maximum polysaccharide yield reached 9.25%, demonstrating a significant advantage over the conventional water extraction method (4.18% yield). Following purification, the antioxidant activity and structural characteristics of SLMPs were analyzed. The molecular weight, monosaccharide composition, reducing groups, and higher-order conformation were systematically correlated with antioxidant activity. Fourier-transform infrared spectroscopy (FTIR), monosaccharide composition analysis, and ¹H nuclear magnetic resonance (NMR) spectroscopy revealed characteristic polysaccharide functional groups (C–O, O–H, and C=O). Monosaccharides such as glucose (Glc), galactose (Gal), and arabinose (Ara) were found to enhance antioxidant activity. High-performance gel permeation chromatography (HPGPC) indicated a molecular weight of 20.7 kDa for SLMPs, with low-molecular-weight fractions exhibiting superior antioxidant activity. Scanning electron microscopy (SEM) further demonstrated that ultrasonically extracted polysaccharides possess porous structures capable of chelating redox-active functional groups. These findings suggest that ultrasonic-assisted eutectic-solvent-based extraction is an efficient method for polysaccharide extraction while preserving antioxidant properties. Full article

Croton cajucara Benth and Copaifera reticulata Ducke are prominent species in the traditional medicine of the Amazon region of Brazil. Copaifera species produce oil resin rich in bioactive diterpenes, and C. cajucara is a prolific producer of the diterpene 19-nor-clerodane trans-dehydrocrotonin (t-DCTN). This research aimed to develop a self-nanoemulsion drug delivery system (SNEDDS) by using copaiba oil resin (C. reticulata) as a carrier for t-DCTN. A stable SNEDDS single-phase nanoemulsion comprising Tween 80 (7%, w/w) and copaiba oil (0.5%, w/w) afforded a fine oil-in-water carrier system (SNEDDS-CO). The dropwise solubilization of t-DCTN (1 mg) into SNEDDS-CO resulted in the nanoformulation called SNEDDS-CO-DCTN. Transmission electron microscopy (TEM) analysis revealed spherical nanodevices, while particle size, polydispersity index (PDI), and zeta potential measurements indicated small nanodroplets (about 10 nm), uniformly distributed (between 0.1 and 0.2) and negatively charged for both systems. The in vitro kinetic of t-DCTN-loaded (SNEDDS-CO-DCTN) analyzed by using simulated conditions of the gastrointestinal microenvironment, as perspective for oral drug delivery, showed a controlled release profile, and corresponded to the Fickian diffusion model. The in vitro antioxidant activity of the samples (t-DCTN, SNEDDS-CO, and SNEDDS-CO-DCTN) was confirmed through total antioxidant capacity (TAC), reducing power, copper ion chelation, and hydroxyl radical scavenging assays. The antioxidant activity of SNEDDS-CO-DCTN which contained 1 mg of t-DCTN per mL⁻¹ of the carrier SNEDDS-CO was similar or even better when compared to the unload t-DCTN solubilized in DMSO (10 mg mL⁻¹). The SNEDDS formulations herein described were successfully obtained under moderated and controlled conditions, exhibiting effective physicochemical data and release characteristics with huge bioaccessibility for co-loading copaiba oil and t-DCTN. The novel colloidal system SNEDDS-CO-DCTN is a potential antioxidant nanoproduct and, from now on, is available for further pharmacological investigations. Full article

This study explores the use of a deep eutectic solvent (DES) composed of choline chloride and pyrogallol (1:1 molar ratio) for the recovery of lithium, cobalt, and nickel from spent lithium-ion battery cathodes based on LiNi_0.33Co_0.33Mn_0.33O₂ (NMC111). The DES exhibits moderate viscosity, intrinsic redox activity, and strong complexation ability, enabling efficient metal dissolution under mild conditions. The effects of both temperature (50–80 °C) and time (up to 12 h) on leaching efficiency were systematically investigated. Optimal leaching parameters—80 °C, 8 h, and a liquid-to-solid ratio of 50—yielded extraction efficiencies of 92% for Li, 85% for Co, and 88% for Ni. Kinetic modeling indicated pseudo-first-order behavior with activation energies of 26.6, 22.1, and 25.2 kJ/mol for Li, Co, and Ni, respectively. Mechanistic analysis confirmed the dual role of pyrogallol as both reducing agent (facilitating Co³⁺ to Co²⁺ conversion) and chelating ligand. Full article

A sustainable and efficient approach for converting carbohydrates into 5-hydroxymethylfurfural (HMF) via heterogeneous catalysis is crucial for effectively utilizing biomass. In this study, we synthesized a series of CrX-polyphenol-formaldehyde resin (PTF) catalysts, which are composites of Cr-doped phenolic-resin-based hydrothermal carbon, using a chelation-assisted multicomponent co-assembly strategy. The performance of the synthesized catalysts was assessed through various analytical techniques, including scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, pyrolysis–Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller analysis. Cr incorporation into the catalysts enhanced the total and Lewis acidities. Notably, the optimized catalyst, designated as Cr0.6-PTF, achieved an effective glucose conversion into HMF, yielding a maximum of 69.5% at 180 °C for 180 min in a saturated NaCl solution (NaClaq)/dimethyl sulfoxide (2: 18) solvent system. Furthermore, Cr0.6-PTF maintained excellent catalytic activity and a stable chemical structure after nine cyclic reactions, resulting in a 63.8% HMF yield from glucose. This study revealed an innovative approach for utilizing metal-doped phenolic resin hydrothermal carbon to transform glucose into platform chemicals. Full article