Latest ArticlesBenzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
No. 86 Xueyuan South Road, Haidian District, Beijing
010-62662699(Operation and Technical Support)
qkjq@cast.org.cn
Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House
