Search Results (242)

Catalytic and bioelectrocatalytic properties of four white rot fungal laccases (Trametes hirsuta, ThL; Coriolopsis caperata, CcL; Steccherinum murashkinskyi, SmL; and Antrodiella faginea, AfL) from different orthologous groups were comparatively studied in homogeneous reactions of electron donor substrate oxidation and in a heterogeneous reaction of dioxygen electroreduction. The ThL and CcL laccases belong to high-redox-potential enzymes (E⁰_T1 = 780 mV), while the AfL and SmL laccases are medium-redox-potential enzymes (E⁰_T1 = 620 and 650 mV). We evaluated the efficiency of laccases in mediatorless bioelectrocatalytic dioxygen reduction by the steady-state potential (E_ss), onset potential (E_onset), half-wave potential (E_1/2), and the slope of the linear segment of the polarization curve. A good correlation was observed between the T1 center potential of the laccases and their electrocatalytic characteristics; however, no correlation with the homogeneous reactions of electron donor substrates’ oxidation was detected. The results obtained are discussed in the light of the known data on the three-dimensional structures of the laccases studied. Full article

Dry Turkish oak (Quercus cerris) sawdust, untreated and treated with three activators, (H₃PO₄, NaOH and H₂O₂) was pyrolyzed under limited-oxygen conditions to obtain biochar samples. The electrochemical properties of these samples were tested and compared to the properties of several commercial carbon blacks. The electrochemical characterization was performed via cyclic voltammetry, analyzing the response toward two commonly used redox probes, [Fe(CN)₆]^3−/−4− and [Ru(NH₃)₆]^2+/3+. The influence of the scan rate on this response was investigated, and the resulting data were used to obtain the values of the heterogenous charge transfer constant, k₀. Higher k₀ values were observed for carbon blacks than for investigated biochar samples. The detection of 4-nitrophenol and heavy metal ions was used to assess the applicability of biochars for electroanalytical purposes. The response of untreated biochar was comparable with the response of Vulcan carbon black, which showed the best response of all analyzed carbon blacks. Full article

High-intensity interval training (HIIT) has emerged as a promising non-pharmacological intervention for improving cardiometabolic health. In populations with diabetes, cardiovascular disease, obesity, or metabolic dysfunction, redox imbalance—characterized by elevated oxidative stress and impaired antioxidant defense—is a key contributor to disease progression. This narrative review synthesizes current evidence on the effects of HIIT on oxidative stress and antioxidant capacity across diverse cardiometabolic disease cohorts. While findings are heterogeneous, the majority of studies demonstrate that HIIT intervention can reduce levels of oxidative stress markers and enhance antioxidant enzyme expression. These redox adaptations may underpin improvements in vascular endothelial function, inflammation, and metabolic regulation. Importantly, variations in intensity, duration, and health status influence these responses, highlighting the need for individualized exercise prescriptions. Safety considerations are emphasized, including the necessity for medical clearance, gradual progression, and individualized training prescriptions in higher-risk individuals. In conclusion, HIIT shows potential as a targeted strategy to restore redox homeostasis and improve cardiometabolic outcomes, although further research is needed to clarify optimal protocols and the underlying mechanisms. Full article

This study aimed to analyse the spatiotemporal evolution of phytoplankton community dynamics and its underlying mechanisms in the Liaoning section of the Liao River Basin in 2010, 2015, and 2020. Phytoplankton species diversity increased significantly, with an increase from three phyla and 31 species in 2010 to six phyla and 74 species in 2020. Concurrent increases in α-diversity indicated continuous improvements in habitat heterogeneity. The community structure shifted from a diatom-dominated assemblage to a green algae–diatom co-dominated configuration, contributing to an enhanced water purification capacity. The upstream agricultural zone (Tieling section) had elevated biomass and low diversity, indicating persistent non-point-source pollution stress. The midstream urban–industrial zone (Shenyang–Anshan section) emerged as a phytoplankton diversity hotspot, likely due to expanding niche availability in response to point-source pollution control. The downstream wetland zone (Panjin section) exhibited significant biomass decline and delayed diversity recovery, shaped by the dual pressures of resource competition and habitat filtering. The driving mechanism of community succession shifted from nutrient-dominated factors (NH₃-N, TN) to redox-sensitive factors (DO, pH). These findings support a ‘zoned–graded–staged’ ecological restoration strategy for the Liao River Basin and inform the use of phytoplankton as bioindicators in watershed monitoring networks. Full article

In this investigation, a hierarchical FeCo-layered double hydroxide (FeCo-LDH) electrochemical membrane material was prepared by a simple in situ hydrothermal method. The prepared material formed a 3D honeycomb-structured FeCo-LDH-modified carbon felt (FeCo-LDH/CF) catalytic layer with uniform open pores on a CF substrate with excellent catalytic activity and was served as the cathode in a flow-through electro-Fenton (FTEF) reactor. The electrocatalyst demonstrated excellent treatment performance (99%) in phenol simulated wastewater (30 mg L⁻¹) under the optimized operating conditions (applied voltage = 3.5 V, pH = 6, influent flow rate = 15 mL min⁻¹) of the FTEF system. The high removal rate could be attributed to (i) the excellent electrocatalytic oxidation performance and low interfacial charge transfer resistance of the FeCo-LDH/CF electrode as the cathode, (ii) the ability of the synthesized FeCo-LDH to effectively promote the conversion of H₂O₂ to •OH under certain conditions, and (iii) the flow-through system improving the mass transfer efficiency. In addition, the degradation process of pollutants within the FTEF system was additionally illustrated by the •OH dominant ROS pathway based on free radical burst experiments and electron paramagnetic resonance tests. This study may provide new insights to explore reaction mechanisms in FTEF systems. Full article

Triple-negative breast cancer (TNBC), characterized by the absence of estrogen receptor (ER), progesterone receptor (PR), and human epidermal growth factor receptor 2 (HER2), remains a therapeutic challenge due to its aggressive nature, limited treatment options, and high recurrence rates. Current therapies, including chemotherapy and immune checkpoint inhibitors, face resistance driven by tumor heterogeneity, immunosuppressive signaling, and dysregulated redox pathways. This review explores silibinin’s potential to modulate the tumor immune microenvironment (TIME) and overcome therapeutic resistance in TNBC. Silibinin exerts multifaceted anticancer effects by suppressing PD-L1 expression through the inhibition of JAK/STAT3 signaling and MUC1-C interaction, attenuating NF-κB-driven inflammation, and downregulating CCL2-mediated recruitment of tumor-associated macrophages (TAMs). Additionally, silibinin disrupts redox adaptation by targeting the Nrf2-EGFR-MYC-TXNIP axis, enhancing oxidative stress and chemosensitivity. Preclinical studies highlight its ability to inhibit epithelial–mesenchymal transition (EMT), reduce cancer stem cell (CSC) populations, and synergize with existing therapies like PD-1 inhibitors. Despite its low bioavailability, advanced formulations such as liposomes and nanoparticles show promise in improving delivery and efficacy. By reshaping TIME through dual antioxidant and immunomodulatory mechanisms, silibinin emerges as a viable adjunct therapy to reverse immunosuppression and chemoresistance in TNBC. Full article

Breast cancer (BC) is a highly heterogeneous disease with distinct molecular subtypes, each exhibiting unique metabolic adaptations that drive tumor progression and therapy resistance. Metabolomics has emerged as a powerful tool for understanding cancer metabolism and identifying clinically relevant biomarkers guiding personalized therapeutic strategies. Advances in analytical techniques such as mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy have enabled the identification of metabolic alterations associated with BC initiation, progression, and treatment response (dysregulated glycolysis, lipid metabolism, amino acid utilization, and redox homeostasis). This review aims to provide a comprehensive overview of the role of metabolomics in BC research, focusing on its applications in identifying metabolic biomarkers for early diagnosis, prognosis, and treatment response. It underscores how metabolomic profiling can unravel the metabolic adaptations of different BC subtypes, offering insights into tumor biology and mechanisms of therapy resistance. Ultimately, it highlights the promise of metabolomics in driving biomarker-guided diagnostics and the development of metabolically informed, personalized therapeutic strategies in the era of precision medicine. 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

Breast cancer remains a leading cause of cancer-related morbidity and mortality among women worldwide. Its treatment is complicated by molecular heterogeneity and the frequent development of multidrug resistance (MDR). Conventional drug delivery approaches are often limited by poor aqueous solubility, rapid systemic clearance, non-specific biodistribution, and off-target toxicity. This review will critically explore the possibility of surfactant-based drug delivery systems (DDSs) in addressing the constraints of standard breast cancer treatments. It focuses on the mechanisms by which surfactants promote solubility, facilitate cellular uptake, and overcome drug resistance, while also analyzing current therapeutic success and future directions. A thorough review of preclinical and clinical investigations was undertaken, focusing on important surfactant-based DDSs such as polymeric micelles, nanoemulsions, liposomes, and self-emulsifying systems (SEDDSs). Mechanistic insights into surfactant functions, such as membrane permeabilization and efflux pump inhibition, were studied alongside delivery systems incorporating ligands and co-loaded medicines. Pluronic^® micelles, TPGS-based systems, biosurfactant-stabilized nanoparticles, and lipid-based carrier surfactant platforms improve medication solubility, stability, and delivery. Genexol^® are examples of formulations demonstrating effective use and FDA translational potential. These systems now incorporate stimuli-responsive release mechanisms—such as pH, temperature, redox, immuno- and photodynamic treatment—artificial intelligence treatment design, and tailored treatment advancement, and responsive tailoring. Surfactant-enabled DDSs can improve breast cancer care. Innovative approaches for personalized oncology treatment are countered by the enduring challenges of toxicity, regulatory hurdles, and diminished scalability. Full article

Heterogeneous electro-Fenton (HEF) technology utilizing iron-based cathode catalysts has emerged as an efficient advanced oxidation process for wastewater treatment, demonstrating outstanding performance in degrading emerging organic contaminants (EOCs) while maintaining environmental sustainability. The performance of this technology is governed by two critical processes: the accumulation of H₂O₂ and the electron transfer mechanisms governing the Fe(III)/Fe(II) redox cycle. This review comprehensively summarizes recent advances in understanding the electron transfer mechanisms in iron-based HEF systems and their applications for EOC degradation. Five representative catalyst categories are critically analyzed, including zero-valent iron/alloys, iron oxides, iron-carbon/nitrogen-doped carbon composites, iron sulfides/phosphides, and iron-based MOFs, with a particular focus on their structural design, catalytic performance, and electron transfer mechanisms. A particular focus is placed on strategies enhancing Fe(III)/Fe(II) cycling efficiency and the interplay between radical (^•OH) and non-radical (¹O₂) oxidation pathways, including their synergistic effects in complex wastewater systems. Major challenges, including catalyst stability, pH adaptability, and selective oxidation in complex matrices, are further discussed. Potential solutions to these limitations are also discussed. This review provides fundamental insights for designing high-efficiency iron-based HEF catalysts and outlines future research directions to advance practical applications. Full article

The monoculture planting in terraced tea plantations has led to severe soil degradation, which poses a significant threat to the growth of tea plants. However, the mechanisms by which intercropping systems improve soil health through the regulation of soil microbial communities at the micro-topographical scale of terraced tea plantations (i.e., terrace surface, inter-row, and terrace wall) remain unclear. This study investigates the effects of intercropping Ophiopogon japonicus in a five-year tea plantation on the soil physicochemical properties, enzyme activities, and microbial community structure and functions across different micro-topographical features of terraced tea plantations in Wuyi Mountain. The results indicate that intercropping significantly improved the soil organic matter, available nutrients, and redox enzyme activities in the inter-row, terrace surface, and terrace wall, with the effects gradually decreasing with increasing distance from the tea plant rhizosphere. In the intercropping group, tea leaf yield increased by 13.17% (fresh weight) and 19.29% (dry weight) compared to monoculture, and the disease indices of new and old leaves decreased by 40.63% and 38.7%, respectively. Intercropping strengthened the modularity of bacterial networks and the role of stochasticity in shaping bacterial communities in different micro-topographic environments, in contrast to the patterns observed in fungal communities. The importance of microbial phyla such as Proteobacteria and Ascomycota in different micro-topographical features was significantly regulated by intercropping. In different micro-topographical zones of the terraced tea plantation, beneficial bacterial genera such as Sinomonas, Arthrobacter, and Ferruginibacter were significantly enriched, whereas potential fungal pathogens like Nigrospora, Microdochium, and Periconia were markedly suppressed. Functional annotations revealed that nitrogen cycling functions were particularly enhanced in inter-row soils, while carbon cycling functions were more prominent on the terrace surface and wall. This study sheds light on the synergistic regulatory mechanisms between micro-topographical heterogeneity and intercropping systems, offering theoretical support for mitigating soil degradation and optimizing management strategies in terraced tea agroecosystems. Full article

A novel amorphous Fe-doped manganese carbonate (a-FeMn-1) was synthesized via a facile co-precipitation method and evaluated as an efficient heterogeneous catalyst for the activation of peroxymonosulfate (PMS) in the degradation of Orange II. Among various Fe/Mn molar ratios, the 1:1 composition (a-FeMn-1) showed optimal catalytic activity, achieving 98% removal efficiency within 60 min under near-neutral pH conditions. Characterization results indicated that Fe doping effectively induced an amorphous structure and increased surface area and oxygen defects, promoting PMS activation. The system displayed broad pH applicability and resistance to Cl⁻ and natural organic matter, while degradation was inhibited by HCO₃⁻ and PO₄³⁻. EPR and quenching experiments confirmed that surface-bound sulfate radicals (SO₄^•−), hydroxyl radicals (^•OH), and singlet oxygen (¹O₂) were the primary reactive species. XPS analysis further revealed the redox cycling of Fe and Mn and the involvement of defect oxygen in the PMS activation process. The catalyst also demonstrated excellent reusability over five cycles without significant loss in efficiency. This work provides insights into the rational design of amorphous bimetallic materials for sulfate radical-based advanced oxidation processes. Full article

To address the issues of poor Co²⁺ regeneration and limited interfacial electron transfer in heterogeneous catalytic systems, this study proposes the synthesis of highly efficient and stable Co₃O₄/ZnO composites through the pyrolysis–oxidation reaction of Co/Zn MOFs for the degradation of rhodamine B (RhB) using activated peroxymonosulfate (PMS). The results confirmed that the catalyst exhibited a high electron transfer capacity, and the synergistic effect between the bimetals enhanced the reversible redox cycle of Co³⁺/Co²⁺. Under optimal conditions, complete removal of RhB was achieved in just 6 min using the Co₃O₄/ZnO composite, which demonstrated excellent stability after five cycles. Furthermore, the catalyst exhibited a high degradation efficiency in real water samples with a total organic carbon (TOC) removal rate of approximately 65% after 60 min. The electrochemical measurements, identification of active species, and X-ray photoelectron spectroscopy (XPS) analysis revealed that non-radicals (¹O₂ and direct charge transfer) played a major role in the degradation of RhB. Finally, the potential mechanisms and degradation pathways for RhB degradation using this catalyst were systematically investigated. This study opens new avenues for the development of efficient and stable PMS catalysts, and provides insights into the preparation of other emerging metal oxides. Full article

The tumor microenvironment (TME) has a major role in malignancy and its complex nature can mediate tumor survival, metastasis, immune evasion, and drug resistance. Thus, reprogramming or regulating the immunosuppressive TME has a significant contribution to make in cancer therapy. Targeting TME with nanocarriers (NCs) has been widely used to directly deliver anticancer drugs to control TME, which has revealed auspicious outcomes. TME can be reprogrammed by using a range of NCs to regulate immunosuppressive factors and activate immunostimulatory cells. Moreover, TME can be ameliorated via regulating the redox environment, oxygen content, and pH value of the tumor site. NCs have the capacity to provide site-specific delivery of therapeutic agents, controlled release, enhanced solubility and stability, decreased toxicities, and enhanced pharmacokinetics as well as biodistribution. Numerous NCs have demonstrated their potential by inducing distinct anticancer mechanisms by delivering a range of anticancer drugs in various preclinical studies, including metal NCs, liposomal NCs, solid lipid NCs, micelles, nanoemulsions, polymer-based NCs, dendrimers, nanoclays, nanocrystals, and many more. Some of them have already received US Food and Drug Administration approval, and some have entered different clinical phases. However, there are several challenges in NC-mediated TME targeting, including scale-up of NC-based cancer therapy, rapid clearance of NCs by the mononuclear phagocyte system, and TME heterogeneity. In order to harness the full potential of NCs in tumor treatment, there are several factors that need to be carefully studied, including optimization of drug loading into NCs, NC-associated immunogenicity, and biocompatibility for the successful translation of NC-based anticancer therapies into clinical practice. In this review, a range of NCs and their applications in drug delivery to remodel TME for cancer therapy are extensively discussed. Moreover, findings from numerous preclinical and clinical studies with these NCs are also highlighted. Full article

Heap leaching of copper is faced with a complex set of challenges, including mineral heterogeneity, the formation of passivating species, and the need to regulate critical variables such as pH, redox potential (Eh), oxidant concentration, and irrigation rate. If these factors are not properly managed, copper recovery is reduced, and significant environmental impacts may be generated, highlighting the urgency for systematic and sustainable approaches. To address this challenge, a systematic literature review (SLR) was conducted, screening 2344 documents and selecting 106 primary sources to analyze operational drivers and environmental considerations. Statistical methodologies (factorial designs, response surface methodology), multiscale modeling, and laboratory column tests were used to validate key variables, including pH (1.5–2.0), Eh (600–$750 \mathrm{mV}$), temperature (25–55 °C), irrigation rate (5–$15 \mathrm{L}/\left(\mathrm{h}·{\mathrm{m}}^2\right)$), acid concentration (0.5–$2.0 \mathrm{M}$), and emerging “green” reagents (e.g., glycine, organic surfactants). Precise control of these factors was found to reduce passivation, minimize fine-particle migration, and improve copper extraction up to 90%. The incorporation of oxidizing agents (e.g., Fe³⁺, H₂O₂) further accelerated mineral dissolution while preventing unwanted precipitates. In parallel, bioleaching strategies maintained high recoveries with lower chemical demand. Reviews of pilot studies confirmed the scalability of these optimized conditions, emphasizing both sustainability and cost-effectiveness. Full article