Search Results (387)

Aqueous organic redox flow batteries (AORFBs) represent an advancing class of electrochemical energy storage systems showing considerable promise for large-scale grid integration due to their unique aqueous organic chemistry. However, the use of small-molecule active materials in AORFBs is significantly limited by the issue of stability and crossover. To address these challenges, we designed a high-water-solubility polymer cathode material, P-T-S, which features a polyvinylimidazole backbone functionalized with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and sulfonate groups. P-T-S exhibits a solubility of 34 Ah L⁻¹ in water and 31 Ah L⁻¹ in 1.0 M NaCl aqueous solution (NaCl_aq). When paired with methyl viologen to assemble a pH-neutral AORFB with a theoretical capacity of 15 Ah L⁻¹, the system exhibits a material utilization rate of 92.0%, an average capacity retention rate of 99.74% per cycle (99.74% per hour), and an average Coulombic efficiency of 98.69% over 300 consecutive cycles at 30 mA cm⁻². This work provides a new design strategy for polymer materials for high-performance AORFBs. Full article

This study explores the magmatic and hydrothermal evolution of porphyry–skarn–transitional Cu-Mo-W-Au systems within the Nilüfer Mineralization Complex (NMC), located in the westernmost segment of the Eocene Tavşanlı Metallogenic Belt, NW Türkiye. Through integration of field data, whole-rock geochemistry, Re–Os molybdenite dating, and amphibole–biotite mineral chemistry, the petrogenetic controls on mineralization across four spatially associated mineralized regions (Kirazgedik, Güneybudaklar, Kozbudaklar, and Delice) were examined. The earliest and thermally most distinct phase is represented by the Kirazgedik porphyry system, characterized by high temperature (~930 °C), oxidized quartz monzodioritic intrusions emplaced at ~2.7 kbar. Rising fO₂ and volatile enrichment during magma ascent facilitated structurally focused Cu-Mo mineralization. At Güneybudaklar, Re–Os geochronology yields an age of ~49.9 Ma, linking Mo- and W-rich mineralization to a transitional porphyry–skarn environment developed under moderately oxidized (ΔFMQ + 1.8 to +0.5) and hydrous (up to 7 wt.% H₂O) magmatic conditions. Kozbudaklar represents a more reduced, volatile-poor skarn system, leading to Mo-enriched scheelite mineralization typical of late-stage W-skarns. The Delice system, developed at the contact of felsic cupolas and carbonates, records the broadest range of redox and fluid compositions. Mixed oxidized–reduced fluid signatures and intense fluid–rock interaction reflect complex, multistage fluid evolution involving both magmatic and external inputs. Geochemical and mineralogical trends—from increasing silica and Rb to decreasing Sr and V—trace a systematic evolution from mantle-derived to felsic, volatile-rich magmas. Structurally, mineralization is controlled by oblique fault zones that localize magma emplacement and hydrothermal flow. These findings support a unified genetic model in which porphyry and skarn mineralization styles evolved continuously from multiphase magmatic systems during syn-to-post-subduction processes, offering implications for exploration models in the Western Tethyan domain. Full article

The increasing threat of antimicrobial resistance (AMR), along with the limited availability of new lead compounds in the drug development pipeline, highlights the urgent need to discover antimicrobial agents with innovative mechanisms of action. In this regard, metal complexes offer a unique opportunity to access mechanisms distinct from those of conventional antibiotics. Although iron (Fe) is an essential element for all forms of life, including pathogenic bacteria, it also poses a serious risk of cytotoxicity due to its redox activity, which can trigger the production of reactive oxygen species (ROS) via the Fenton reaction. This review highlights recent advances in the development of iron-based antimicrobial agents that harness the toxicity resulting from dysregulated iron uptake, thereby inducing bacterial cell death through oxidative stress. These findings may guide the development of effective treatments for pathogenic infections and offer new perspectives on leveraging redox chemistry of iron to combat the growing threat of global bacterial resistance. Full article

Ferrocene (Fc), a redox-active organometallic scaffold, has attracted significant attention in medicinal chemistry due to its favorable physicochemical and pharmacological properties. The present study explores the therapeutic potential of novel Fc-functionalized analogues of imatinib and nilotinib, aimed at targeting BCR-ABL1+ chronic myeloid leukemia (CML) cells. A series of Fc-based derivatives (compounds 6, 9, 14, and 18) were synthesized by systematically substituting key pharmacophoric regions of the parent tyrosine kinase inhibitors with Fc units. The antiproliferative activity of these compounds was evaluated against four BCR-ABL1-positive leukemia cell lines (K-562, BV-173, AR-230, and LAMA-84), with imatinib serving as a reference drug. Biological assays revealed distinct structure–activity relationships. Compounds 6 and 9 demonstrated superior activity against the K-562 cell line, while compounds 14 and 18 exhibited enhanced potency and higher ligand efficiencies (LEs) against BV-173 and AR-230 cells compared to imatinib. Selectivity assays further indicated favorable toxicity profiles of compounds 9 and 14 toward malignant versus non-malignant cells. Molecular docking studies supported these findings, showing that Fc substitution alters binding interactions within the c-Abl kinase ATP-binding site while retaining key stabilizing contacts. Computationally predicted LEs showed strong correlation with experimental data, especially for K-562 and LAMA-84 cells, confirming the kinase as a relevant target. Full article

The Tuztaşı low-sulfidation epithermal Au–Ag deposit (Biga Peninsula, Türkiye) records a multi-stage hydrothermal history that can be interpreted through the trace and rare-earth-element (REE) chemistry of quartz. High-precision LA-ICP-MS analyses of five representative quartz samples (23 ablation spots; 10 analytically robust) reveal two fluid stages. Early fluids were cold, dilute meteoric waters (δ¹⁸O₍H₂O₎ ≈ −6.8 to +0.7‰), whereas later fluids circulated deeper, interacted with felsic basement rocks, and evolved in composition. Mineralized quartz displays marked enrichment in As (raw mean = 2854 ± 6821 ppm; filtered mean = 70 ± 93 ppm; one spot 16,775 ppm), K (498 ± 179 ppm), and Sb (57.8 ± 113 ppm), coupled with low Ti/Al (<0.005) and elevated Ge/Si (0.14–0.65 µmol mol⁻¹). Chondrite-normalized REE patterns show pronounced but variable LREE enrichment ((La/Yb)_n ≤ 45.3; ΣLREE/ΣHREE up to 10.8) and strongly positive Eu anomalies (δEu ≤ 9.3) with slightly negative Ce anomalies (δCe ≈ 0.29); negligible Ce–Eu covariance (r² ≈ 0.05) indicates discrete redox pulses. These signatures indicate chemically evolved, reducing fluids conducive to Au–Ag deposition. By contrast, barren quartz is characterized by lower pathfinder-element contents, less fractionated REE profiles, higher Ti/Al, and weaker Eu anomalies. A composite exploration toolkit emerges: As > 700 ppm, As/Sb > 25, Ti/Al < 0.005, Ge/Si > 0.15 µmol mol⁻¹, and δEu ≫ 1 reliably identify ore-bearing zones when integrated with δ¹⁸O data and fluid-inclusion microthermometry from earlier studies on the same vein system. This study provides one of the first systematic applications of integrated trace-element and REE analysis of quartz to a Turkish low-sulfidation epithermal system, offering an applicable model for vectoring mineralization in analogous settings worldwide. Full article

The nitrogen cycle (N-cycle) is a cornerstone of global biogeochemistry, regulating nitrogen availability and affecting atmospheric chemistry, agricultural productivity, and ecological balance. Central to this cycle is the reversible interplay between nitrate (NO₃⁻) and nitrite (NO₂⁻), mediated by molybdenum-dependent enzymes—Nitrate reductases (NARs) and Nitrite oxidoreductases (NXRs). Despite catalyzing opposite reactions, these enzymes exhibit remarkable structural and mechanistic similarities. This review aims to elucidate the molecular underpinnings of nitrate reduction and nitrite oxidation by dissecting their enzymatic architectures, redox mechanisms, and evolutionary relationships. By focusing on recent structural, spectroscopic, and thermodynamic data, we explore how these two enzyme families represent “two sides of the same coin” in microbial nitrogen metabolism. Special emphasis is placed on the role of oxygen atom transfer (OAT) as a unifying mechanistic principle, the influence of environmental redox conditions, and the emerging evidence of bidirectional catalytic potential. Understanding this dynamic enzymatic interconversion provides insight into the flexibility and resilience of nitrogen-transforming pathways, with implications for environmental management, biotechnology, and synthetic biology. Full article

Background/Objectives: In the context of preclinical studies, we have hitherto showcased that a low-molecular-weight ruthenium(III) complex we named AziRu holds significant potential for further developments as an anticancer candidate drug. When appropriately converted into stable nanomaterials and delivered into tumor cells, AziRu exhibits superior antiproliferative activity, benefiting from a multimodal mechanism of action. The activation of regulated cell death (RCD) pathways (i.e., apoptosis and autophagy) has been proved in metastatic phenotypes, including triple-negative breast cancer (TNBC) cells. This study focuses on a bioengineered lipophilic derivative of AziRu, named PalmiPyRu, that we are currently developing as a potential anticancer drug in preclinical studies. When delivered in this way, AziRu confirms a multimodal mechanism of action in effectively blocking the growth and proliferation of TNBC phenotypes. Special focus is reserved for the activation of the ferroptotic pathway as a consequence of redox imbalance and interference with iron homeostasis, as well as the glutathione biosynthetic pathway. Methods: Human preclinical models of specific TNBC phenotypes and healthy cell cultures of different histological origin were selected. After in vitro treatments, cellular responses were carefully analyzed, and targeted biochemical and molecular biology experiments coupled to confocal microscopy allowed us to explore the antiproliferative effects of PalmiPyRu. Results: In this study, we unveil that PalmiPyRu can enter TNBC cells and interfere with both the iron homeostasis and the cystine-glutamate antiporter system Xc-, causing significant oxidative stress and the accumulation of lipid oxidation products. The increase in intracellular reactive free iron and depletion of glutathione engender a lethal condition, driving cancer cells toward the activation of ferroptosis. Conclusions: Overall, these outcomes allow us, for the first time, to couple the antiproliferative effect of a ruthenium-based candidate drug with the inhibition of the Xc- antiporter system and Fenton chemistry, thereby branding PalmiPyRu as an effective multimodal inducer of ferroptosis. Molecular mechanisms of action deserve further investigations, and new studies are underway to uncover how interference with Xc- controls cell fate, allowing us to explore the connection between iron metabolism regulation, oxidative stress and RCD pathways activation. Full article

Spinel-structured hausmannite (Mn(II)Mn(III)₂O₄) is a vital intermediate in Mn mineralogy and a key player in redox chemistry in the environment. Its transformation into other Mn oxides is a critical factor in controlling its environmental occurrence and reactivity. Yet structural impurities and solution pH, as well as the fate of impurities during transformation, which influence hausmannite transformation processes and products, remain largely unknown. In the present work, we address this knowledge gap by investigating pristine and metal-substituted hausmannite, specifically nickel (Ni) or cobalt (Co), equilibrated at two time periods (8 h and 30 days) and three different pH levels (4, 5, and 7). Solution chemistry data revealed that both the equilibration period and pH had a significant impact on hausmannite dissolution rates and the concomitant repartitioning of Ni or Co. Hausmannite with Ni or Co substitution exhibited lower dissolution rates than pristine mineral under acidic conditions. Mineralogy and crystal chemistry data indicated that hausmannite was the major host phase after 30-day equilibration, followed by minor transformed products, including birnessite and manganite. Although minor, birnessite became more abundant than manganite at low pHs. Analytical high-resolution transmission electron microscopy (HRTEM) analyses revealed a poorly crystalline, nano-scaled MnO₂ formed from hausmannite and the majority of metal impurities remaining in the host hausmannite. Yet Co was associated with both hausmannite and the newly formed birnessite, whereas Ni was only found with hausmannite, indicating the strong sequestration of Co by Mn(II/III) and Mn(IV) mineral phases. This study highlights the significant impacts of metal impurities and pH on the stability of hausmannite and its transformation into birnessite, as well as the control of Mn-oxide minerals on the solubility and sequestration of transition metals in the environment. Full article

Groundwater sustains ecosystems, agriculture, and human consumption; therefore, its interaction with hydrocarbons is an important area of research under the umbrella of environmental science and resource exploration. Naturally occurring or anthropogenically introduced hydrocarbons can significantly impact groundwater through complex geochemical processes such as dissolution, adsorption, biodegradation, and redox reactions and can also affect groundwater chemistry in terms of pH, redox potential, dissolved organic carbon, and trace element concentrations. Accurate determination and identification of hydrocarbon contaminants requires advanced analytical methods like gas chromatography, GC–MS, and fluorescence spectroscopy, complemented with isotopic analysis and microbial tracers, which provide insights into sources of contamination and biodegradation pathways. The presence of hydrocarbons in groundwater is a matter of environmental concern but can also valuable data for petroleum exploration, tracing subsurface reservoirs and seepage pathways. This paper refers to the basic need for geochemical investigations combined with advanced detection techniques for successful regulation of thermal–mineral groundwater quality. This contributes towards successful sustainable hydrocarbon resource exploration and water resource conservation, with emphasis on the relationship between groundwater quality and hydrocarbon exploration. The study points out the significance of continuous observation of thermal mineral waters to identify their connection with the specific hydrocarbons of each study area. Full article

Acid rain alters soil chemistry significantly and is a key driver of heavy metal pollution. This study investigates the environmental impact of acid rain-induced heavy metal migration in the Siding Lead–Zinc mining area in south China. Tailings, surrounding soils, and riverbed sediments were examined through simulated acid rain soil column leaching experiments. Leachate parameters—including pH, redox potential (Eh), total dissolved solids (TDSs) and heavy metal concentrations—were used to develop machine learning models (Random Forest and Support Vector Machine) to quantify the influence of environmental factors on metal migration. The results showed that leachates were generally alkaline and reductive after leaching, with Cd, Pb, and Zn as the dominant migrating metals. Leachates from tailings and nearby soils exceeded safe drinking water standards, with significantly higher cumulative metal release than other samples. The RF model outperformed the SVM model in predicting heavy metal concentrations. Feature importance analysis revealed that, beyond sample characteristics, pH and Eh were critical factors driving metal migration. Zn and Cd showed strong sensitivity to these parameters, with pH and Eh contributing over 80% to their migration. The findings highlight that acid rain can enhance the solubility and migration of heavy metals, posing a serious threat to the quality of surrounding water and underscoring the requirement for effective mitigation strategies to protect the ecological environment in mining areas. Full article

This review offers an in-depth analysis of soil contamination, discussing the origins, impacts, and remediation strategies, as well as the complex connections with interfacial chemistry. Interfacial chemistry plays a critical role in addressing soil contamination by governing the interactions between pollutants, soil particles, water, and remediation agents at phase boundaries (solid–liquid, solid–gas). Some key aspects include adsorption/desorption that controls pollutants binding to soil surfaces; chemical transformation which facilitates redox, hydrolysis, or catalytic reactions at interfaces to degrade contaminants; colloidal transport that affects the movement of nanoparticle-bound contaminants through soil pores; and techniques like soil washing, phytoremediation and permeable reactive barriers that can neutralize soil pollutants. The combination of interfacial chemistry and soil remediation techniques offers rich opportunities for improving predictive models of contaminant fate. Such approaches represent a paradigm shift from equilibrium-based remediation to dynamic process management. The review demonstrates how heterogeneous interfaces and molecular-scale dynamics dictate contaminant behavior. Furthermore, in addition to consolidating existing knowledge, the review also pioneers new directions by revealing how interfacial processes can optimize soil decontamination, offering actionable insights for researchers and policy makers. By understanding and manipulating interfacial chemical processes, scientists can develop more precise and sustainable cleanup methods. Full article

Porphyrins and their derivatives are excellent materials with specific physical and photochemical properties in medical, chemical, and technological applications. In chemistry, their properties are applied to create new functional materials with specific characteristics, such as porphyrin-based sorbents combined with porous organic polymers, silica, carbon nanostructures, or metal–organic frameworks. This review covers the applications of porphyrins and metalloporphyrins in preparing and using sorbents for metal ion enrichment and their separation. Uncommon applications that utilize specific properties of porphyrins, such as light-enhanced processes and redox properties for selective sorption and photocatalytic conversion of metal ions, are also discussed. These applications suggest new fields of use, such as the removal or recycling of metals from electronic waste or the selective elimination of heavy metals from the environment. Full article

Nitroxides are stable organic free radicals with a wide range of applications. They have found applications in chemistry, biochemistry, biophysics, molecular biology, and biomedicine as EPR/NMR imaging techniques. As spin labels and probes, they are used in electron paramagnetic resonance (EPR) spectroscopy in the study of proteins, lipids, nucleic acids, and enzymes, as well as for measuring oxygen concentration in cells and cellular organelles, as well as tissues and intracellular pH. Their unique redox properties have allowed them to be used as exogenous antioxidants. In this review, we have discussed the chemical properties of nitroxides and their antioxidant properties. Furthermore, we have considered their use as radioprotectors and protective agents in ischemia/reperfusion in vivo and in vitro. We also presented other applications of nitroxides in protecting cells and tissues from oxidative stress and in protein studies and discussed their use in EPR/MRI. Full article

The development of efficient electron transfer between enzymatic elements and the electrode is considered an important issue in the synthesis and design of bioelectrochemical devices. In this regard, the modification of the surface properties is an effective route to obtain a high-performance electrode using enzymatic elements. As we present here, understanding the role of surface functional groups generated by the electrochemical functionalization of graphene-based materials facilitates the design and optimization of effective electroactive bioelectrodes. In this sense, the surface chemistry directly influences the inherent electrocatalytic activity of cytochrome c (Cyt C) toward the electrochemical reduction of H₂O₂. Although the surface oxygen groups provide an immobilization matrix for the Cyt C in the pristine graphene oxide, the electrochemical functionalization with N and P species in one step significantly improves the electrocatalytic activity, since they may facilitate an optimal electrostatic interaction and orientation between the electrode material and the redox heme cofactor in the Cyt C, enhancing the electron transfer process. On the other hand, the lack of surface functional groups in the reduced graphene oxide does not favor the electron transfer with the Cyt C immobilized on the surface being completely inactive. Thus, the incorporation of surface groups using electrochemical functionalization with N and P species provokes a remarkable enhancement of the electrocatalytic activity of cytochrome c, up to four times more than the H₂O₂ reduction reaction. This demonstrated the effectiveness of the functionalization process and the impact in the electrochemical performance of Cyt C immobilized in graphene-based electrodes. Full article

Given the crucial roles of carbohydrates in energy supply, biochemical processes, signaling events and the pathogenesis of several diseases, the development of carbohydrate analogues, called glycomimetics, is a key research area in Glycobiology, Pharmacology, and Medicinal Chemistry. Among the many structural transformations explored, the replacement of endo- and exocyclic oxygen atoms by carbon (carbasugars) or heteroatoms, such as nitrogen (aza- and iminosugars), phosphorous (phosphasugars), sulfur (thiosugars), selenium (selenosugars) or tellurium (tellurosugars) have garnered significant attention. These isosteric substitutions can modulate the carbohydrate bioavailability, stability, and bioactivity, while introducing new properties, such as redox activity, interactions with pathological lectins and enzymes, or cytotoxic effects. In this manuscript we have focused on three major families of glycomimetics: thio-, seleno-, and tellurosugars. We provide a comprehensive review of the most relevant synthetic pathways leading to substitutions primarily at the endocyclic and glycosidic positions. The scope includes metal-catalyzed reactions, organocatalysis, electro- and photochemical transformations, free-radical processes, and automated syntheses. Additionally, mechanistic insights, stereoselectivity, and biological properties are also discussed. The structural diversity and promising bioactivities of these glycomimetics underscore their significance in this research area. Full article