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The widespread existence of antibiotics in the environment has attracted growing concerns regarding the potential adverse effects on aquatic organisms, ecosystems, and human health even at low concentrations. Extensive efforts have been devoted to developing new methods for effective elimination of antibiotics from wastewater. Herein, a novel process of Fe 2+ catalytically enhanced vacuum ultraviolet (VUV) irradiation was proposed as a promising approach for the removal of antibiotic trimethoprim (TMP) in water. Compared with UVC photolysis, VUV photolysis, and UVC/Fe 2+ , VUV/Fe 2+ could increase the pseudo-first-order reaction rate constant of TMP removal by 6.6-38.4 times and the mineralization rate by 36.5%-59.9%. The excellent performance might originate from the synergistic effect of VUV and Fe 2+ , i.e., VUV irradiation could effectively split water and largely accelerate the Fe 3+ /Fe 2+ cycle to generate more reactive oxygen species (ROS). EPR results indicated that • OH and O 2 •- were identified as the main ROS in the UVC/Fe 2+ and VUV/Fe 2+ processes, while • OH, O 2 •- , and 1 O 2 were involved in the VUV process. The operating parameters, such as Fe 2+ dosage and initial TMP contents, were evaluated and optimized. Up to 8 aromatic intermediates derived from hydroxylation, demethylation, carbonylation, and methylene group cleavage were identified by UPLC-QTOF-MS/MS technique, the possible pathways of TMP degradation were proposed. Finally, the acute and chronic toxicity of intermediates formed during TMP degradation in the VUV/Fe 2+ process were also evaluated., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The transformation between hexavalent chromium (Cr6+) and trivalent chromium (Cr3+) has a significant impact on ecosystems, as Cr6+ has higher levels of toxicity than Cr3+. In this regard, a variety of Cr6+ reduction processes occurring in natural environments have been studied extensively. In this work, we investigate the reductive transformation of Cr6+ by ferrous ions (Fe2+) in ice at −20 °C, and compare the same process in water at 25 °C. The Fe2+-mediated reduction of Cr6+ occurred much faster in ice than it did in water. The accelerated reduction of Cr6+ in ice is primarily ascribed to the accumulation of Cr6+, Fe2+, and protons in the grain boundaries formed during freezing, which constitutes favorable conditions for redox reactions between Cr6+ and Fe2+. This freeze concentration phenomenon was verified using UV–visible spectroscopy with o-cresolsulfonephthalein (as a pH indicator) and confocal Raman spectroscopy. The reductive transformation of Cr6+ (20 µM) by Fe2+ in ice proceeded rapidly under various Fe2+ concentrations (20–140 µM), pH values (2.0–5.0), and freezing temperatures (–10 to −30 °C) with a constant molar ratio of oxidized Fe2+ to reduced Cr6+ (3:1). This result implies that the proposed mechanism (i.e., the redox reaction between Cr6+ and Fe2+ in ice) can significantly contribute to the natural conversion of Cr6+ in cold regions. The Fe2+-mediated Cr6+ reduction kinetics in frozen Cr6+-contaminated wastewater was similar to that in frozen Cr6+ solution. This indicates that the variety of substrates typically present in electroplating wastewater have a negligible effect on the redox reaction between Cr6+ and Fe2+ in ice; it also proposes that the Fe2+/freezing process can be used for the treatment of Cr6+-contaminated wastewater.

Development of microalgal-bacterial granular sludge (MBGS) from saline-adapted microalgae is a promising approach for efficient mariculture wastewater treatment, whereas the elusive mechanisms governing granulation have impeded its widespread adoption. In this study, spherical and regular MBGS were successfully developed from mixed culture of pure Spirulina platensis and Chlorella sp. GY-H4 at 10 mg/L Fe 2+ concentration. The addition of Fe 2+ was proven to induce the formation of Fe-precipitates which served as nucleation sites for microbial attachment and granulation initiation. Additionally, Fe 2+ increased the prevalence of exopolysaccharide-producing cyanobacteria, i.e. Synechocystis and Leptolyngbya, facilitating microbial cell adhesion. Furthermore, it stimulated the secretion of extracellular proteins (particularly tryptophan and aromatic proteins), which acted as structural backbone for the development of spherical granule form microalgal flocs. Lastly, it fostered the accumulation of exogenous heterotrophic functional genera, resulting in the efficient removal of DOC (98 %), PO 4 3- -P (98 %) and NH 4 + -N (87 %). Nevertheless, inadequate Fe 2+ hindered microalgal floc transformation into granules, excessive Fe 2+ expanded the anaerobic zone within the granules, almost halved protein content in the TB-EPS, and inhibited the functional genes expression, ultimately leading to an irregular granular morphology and diminished nutrient removal. This research provides valuable insights into the mechanisms by which Fe 2+ promotes the granulation of salt-tolerant microalgae, offering guidance for the establishment and stable operation of MBGS systems in mariculture wastewater treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

In this study, hydrogel beads [SPI/HP-Fe (II)] were prepared by cross-linking soybean isolate protein (SPI) and hawthorn pectin (HP) with ferrous ions as a backbone, and the effects of ultrasound and Fe 2+ concentration on the mechanical properties and the degree of cross-linking of internal molecules were investigated. The results of textural properties and water-holding capacity showed that moderate ultrasonic power and Fe 2+ concentration significantly improved the stability and water-holding capacity of the hydrogel beads and enhanced the intermolecular interactions in the system. Scanning electron microscopy (SEM) confirmed that the hydrogel beads with 60% ultrasonic power and 8% Fe 2+ concentration had a denser network. X-ray photoelectron spectroscopy (XPS) and atomic absorption experiments demonstrated that ferrous ions were successfully loaded into the hydrogel beads with an encapsulation efficiency of 82.5%. In addition, in vitro, simulated digestion experiments were performed to understand how the encapsulated Fe 2+ is released from the hydrogel beads, absorbed, and utilized in the gastrointestinal environment. The success of the experiments demonstrated that the hydrogel beads were able to withstand harsh environments, ensuring the bioactivity of Fe 2+ and improving its bioavailability. In conclusion, a novel and efficient ferrous ion delivery system was developed using SPI and HP, demonstrating the potential application of SPI/HP-Fe (II) hydrogel beads as an iron supplement to overcome the inefficiency of intake of conventional iron supplements., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest related to the publication of this manuscript., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this study, the performance and mechanism of the integrated sulfidated nanosized zero-valent iron and ferrous ions (S-nZVI/Fe 2+ ) system for oxygen activation to remove emerging contaminants (ECs) were comprehensively explored. The S-nZVI/Fe 2+ system exhibited a 2.4-8.2 times of increase in the pseudo-first order kinetic rate constant for the oxidative degradation of various ECs compared to the S-nZVI system under aerobic conditions, whereas negligible removal was observed in both nZVI and nZVI/Fe 2+ systems. Moreover, remarkable EC mineralization efficiency and benign detoxification capacity were also demonstrated in the S-nZVI/Fe 2+ system. We revealed that dosing Fe 2+ promoted the corrosion of S-nZVI by maintaining an acidic solution pH, which was conducive to O 2 activation by dissolved Fe 2+ and surface-absorbed Fe(II) to produce •OH. Furthermore, the generation of H* was enhanced for the further reduction of Fe(III) and H 2 O 2 to Fe(II) and •O 2 - , resulting in the improvement of consecutive single-electron O 2 activation for •OH production. Additionally, bisphenol A (BPA) degradation by S-nZVI/Fe 2+ was positively correlated with the S-nZVI dosage, with an optimum S/Fe molar ratio of 0.15. The Fenton-like degradation process by S-nZVI/Fe 2+ was pH-insensitive, indicating its robust performance over a wide pH range. This study provides valuable insights for the practical implementation of nZVI-based technology in achieving high-efficiency removal of ECs from water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Ferrous ion (Fe 2+ ) is a crucial metal ion in the body and participates in the diseases related to oxidation and reduction. Golgi apparatus is the main subcellular organelle of Fe 2+ transport in cells, and the stability of its structure is related to the Fe 2+ at an appropriate concentration. In this work, a turn-on type Golgi-targeting fluorescent chemosensor Gol-Cou-Fe 2+ was rationally designed for sensitive and selective detection of Fe 2+ . Gol-Cou-Fe 2+ showed excellent capacity of detecting exogenous and endogenous Fe 2+ in HUVEC and HepG2 cells. It was used to capture the up-regulated Fe 2+ level during the hypoxia. Moreover, the fluorescence of sensor was enhanced over time under Golgi stress combining with the reduce of Golgi matrix protein GM130. However, elimination of Fe 2+ or addition of nitric oxide (NO) would restore the fluorescence intensity of Gol-Cou-Fe 2+ and the expression of GM130 in HUVEC. Thus, development of chemosensor Gol-Cou-Fe 2+ provides a new window for tracking Golgi Fe 2+ and elucidating Golgi stress-related diseases., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Tyrosine kinase inhibitors of epidermal growth factor receptor (EGFR-TKIs), such as osimertinib, show great success in non-small-cell lung cancer patients with EGFR mutated tumors. However, almost all patients develop resistance to EGFR-TKIs owing to secondary EGFR mutations. Although genetic and irreversible resistance mechanisms have been proposed, little is known about non-genetic and reversible resistance mechanisms. From this perspective, a recent study revealed that acute drug exposure generates drug-tolerant persister cells (DTPs) as a form of non-genetic resistance. However, the biological characteristics of DTPs remain unclear. As lipid peroxidation is related to cancer progression and drug resistance, we focused on ferroptosis, namely programmed cell death induced by the accumulation of lipid peroxides, in DTPs. We examined the biological characteristics of ferroptosis in osimertinib-mediated DTPs derived from PC9 lung adenocarcinoma cells. Unlike PC9 cells, established PC9 DTPs were highly sensitive to the ferroptosis inducer RSL3. Accordingly, PC9 DTPs had increased levels of lipid reactive oxygen species and ferrous ion accumulation. Moreover, RSL3-mediated cell death in PC9 DTPs was completely rescued by treatment with the iron chelator deferoxamine. These results suggest that PC9 DTPs showed increased intracellular ferrous ion accumulation and were susceptible to ferroptosis., Competing Interests: Declaration of competing interest All authors have no conflicts of interest., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Severe skin wound healing is mainly hindered by bacterial infection and uncontrolled inflammatory reaction. As a wound dressing, multifunctional hydrogel is expected to offer the potential possibility for overcoming current barriers in wound therapeutics. Herein, a natural drug molecule (glycyrrhizic acid, GA) and metal ion (Fe 2+ ) were used to achieve the metal coordination-induced gelation. This as-prepared Fe 2+ -induced GA hydrogel showed excellent injectability, self-healing property, and sustained release behavior at a relatively lower concentration of GA, thereby reducing the high dose-caused cytotoxicity. In addition to acting as an inducer of gelation, Fe 2+ promoted the antibacterial performance of hydrogel against Escherichia coli and Staphylococcus aureus through causing lipid peroxidation, membrane damage, and DNA degradation. Moreover, the released GA from hydrogel significantly accelerated cell migration and inhibited the inflammatory reaction by mediation of NF-κB signaling pathway to downregulate levels of important inflammatory cytokines in lipopolysaccharide-stimulated RAW264.7 cells. Using a mouse skin infected model, we revealed that the Fe 2+ /GA hydrogel applied to the wound resulted in the rapid wound healing. It is believed that the construction of natural drug molecule-derived hydrogel with antibacterial and anti-inflammatory capabilities may shed a new light to serve as a promising dressing for managing the severe skin wounds., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The availability of dissolved silicon (DSi) exerts an important control on phytoplankton communities in freshwater environments: DSi limitation can shift species dominance to non-siliceous algae and increase the likelihood of harmful algal blooms. The availability of DSi in the water column in turn depends on the dissolution kinetics of amorphous silica (ASi), including diatoms frustules and phytoliths. Here, batch dissolution experiments conducted with diatom frustules from three diatom species and synthetic Aerosil OX 50 confirmed the previously reported non-linear dependence of ASi dissolution rate on the degree of undersaturation of the aqueous solution. At least two first-order dissolution rate constants are therefore required to describe the dissolution kinetics at high (typically, ≥0.55) and low (typically, <0.55) degrees of undersaturation. Our results further showed aqueous ferrous ion (Fe 2+ ), which is ubiquitous in anoxic waters, strongly inhibited ASi dissolution. The inhibition is attributed to the preferential binding of Fe 2+ to Q 2 groups (i.e., surface silicate groups bonded to the silica lattice via two bridging oxygen) which stabilizes the silica surface. However, further increasing the aqueous Fe 2+ concentration likely catalyzes the detachment of Q 3 groups (i.e., silicate groups bonded to the silica lattice via three bridging oxygen) from the surface. Overall, our study illustrates the manyfold effects the aqueous solution composition, notably the inhibition effect of Fe 2+ under anoxic conditions, has on ASi dissolution. The results help to explain the controversial redox dependence of DSi internal loading from sediments, which is vital to quantitatively understanding silicon (Si) cycling in freshwater systems., Competing Interests: Declaration of competing interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Crown Copyright © 2022. Published by Elsevier B.V. All rights reserved.)

The inhibition of hydrogen peroxide (H 2 O 2 ) on the cysteine-mediated aggregation of gold nanoparticles (AuNPs) has great potential to rapidly visualize H 2 O 2 and disease-associated biomarkers. However, associated applications have been rigid due to the low cysteine-oxidation efficiency or the insufficient interference-resistance of previous catalysts. Here, we proposed a novel AuNPs colorimetric method termed Fe 2+ -catalyzed H 2 O 2 -preventing aggregation of AuNPs by oxidizing Cysteine (FeHOAuC) for the visible and rapid detection of H 2 O 2 with high specificity. Formed Fe 2+ -cysteine composites in the beginning, Fe 2+ accelerates the oxidation of cysteine by H 2 O 2 with an intramolecular electron-transferring model, and the generated cysteine oxides (including cysteic acid or cystine, dependent on the ratio of cysteine to H 2 O 2 molecules) lose the pro-aggregation effect on AuNPs. Notably, FeHOAuC can quantify 2-30 μM of H 2 O 2 within 5 min, and the monitoring process works well with tolerance to the impact of dissolved oxygen. The FeHOAuC paired with lactate oxidase was successfully used for measuring lactic acids in real sweat samples with a practicable detection window (2-60 μM) and a low variable coefficient (<10%). In summary, FeHOAuC is a feasible platform for rapid and convenient detection of H 2 O 2 and oxidase-specific substrates., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In this study, we determined the mechanisms and kinetics of the degradations of ibuprofen (IBP) and sulfamethoxazole (SMX), and identified the active species contributions in ferrous ion (Fe(II))/free chlorine (FC) system. Reactive chlorine species (RCS) were the major contributor to the degradations of IBP (73.0%) and SMX (59.3%), respectively, at pH 3. Due to the low reaction rates between Fe(IV) and target pollutants (k Fe(IV), IBP = (1.5 ± 0.03) × 10 3 M -1 s -1 and k Fe(IV), SMX = (4.8 ± 0.2) × 10 3 M -1 s -1 ) and the low [Fe(IV)] ss ((5.0 ± 0.6) × 10 -8 M), Fe(IV) was not the main contributor and only contributed 0.17% and 0.86% to the degradation of IBP and SMX, respectively, at pH 3. The degradations of pharmaceuticals were facilitated by acidic conditions. Chloride (Cl - ) accelerated the degradation of SMX and had a weak effect on the degradation of IBP. Natural organic matter limited the degradation of IBP and SMX. Overall, we demonstrated that multiple active oxidants (Fe(IV) and RCS) are produced by Fe(II)/FC and elucidated the mechanism of active oxidants degradation of pollutants., Competing Interests: Declaration of competing interest All of our authors declare no conflict of interest for this manuscript., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The inhibition of cadmium (Cd) absorption by selenium (Se) in rice may be associated with iron plaque (IP) formation, but the driving mechanisms are still unclear. This study investigated the effects of Se on the growth, oxidative toxicity, radial oxygen loss (ROL), IP formation, and Cd absorption of rice exposed to Cd. The results of this study showed that Cd stress elevated the levels of O 2 - and H 2 O 2 and depressed superoxide dismutase (SOD) and catalase (CAT) activities. The maximum ROL and IP were reduced by 43.3 % and 74.5 %, respectively. However, Se alleviated Cd toxicity by stimulating SOD and CAT activities by scavenging O 2 - and H 2 O 2 and enhancing the ROL profiles. Under culture conditions without Fe 2+ , Se had no impact on the total Cd levels in rice (T Cd ). However, with the addition of Fe 2+ , T Cd was significantly reduced by 23.3 % due to the enhancement of IP formation by Se. These results indicated that Se can reduce Cd accumulation in rice in the presence of Fe 2+ treatments. However, Se just alleviated Cd toxicity in the absence of Fe 2+ treatments. The enhancement of ROL was a potential reason for the elevated IP formation induced by Se., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Lipid peroxidation and alterations in cation loss have been induced in liposomes by ferrous ion, ascorbic acid, reduced and oxidized glutathione, and gamma radiation. Modifications of these effects by tocopherol and 2,6-di-tert-butyl-4-methylphenol (BHT) were studied when these antioxidants were either incorporated in the membrane or were added to already formed liposomes prior to the addition of the chemical agent or to irradiation.Lipid peroxidation, as indicated by the thiobarbituric acid test for malonic dialdehyde, did not correlate with alterations in cation loss. The largest amounts of lipid peroxidation induced by ascorbic acid and glutathione were associated with decreased cation loss. Inhibition of Fe2+- and radiation-induced lipid peroxidation by antioxidants did not inhibit the associated increase in cation loss. Tocopherol was a more effective antioxidant than BHT when it was incorporated in the membrane, whereas BHT was more effective when it was added to the liposomes after formation.

The Escherichia coli gene initially named ygaT is located adjacent to lhgO, encoding L-2-hydroxyglutarate oxidase/dehydrogenase, and the gabDTP gene cluster, utilized for γ-aminobutyric acid (GABA) metabolism. Because this gene is transcribed specifically during periods of carbon starvation, it was renamed csiD for carbon starvation induced. The CsiD protein was structurally characterized and shown to possess a double-stranded ß-helix fold, characteristic of a large family of non-heme Fe(II)- and 2-oxoglutarate (2OG)-dependent oxygenases. Consistent with a role in producing the substrate for LhgO, CsiD was shown to be a glutarate L-2-hydroxylase. We review the kinetic and structural properties of glutarate L-2-hydroxylase from E. coli and other species, and we propose a catalytic mechanism for this archetype 2OG-dependent hydroxylase. Glutarate can be derived from l-lysine within the cell, with the gabDT genes exhibiting expanded reactivities beyond those known for GABA metabolism. The complete CsiD-containing pathway provides a means for the cell to obtain energy from the metabolism of l-lysine during periods of carbon starvation. To reflect the role of this protein in the cell, a renaming of csiD to glaH has been proposed., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The oxidation of s-triazines (using atrazine (ATZ) as a model compound) by a solar-enhanced Fenton-like process involving persulfate and ferrous ion was studied. A flow-through tubular photoreactor was employed for the experiments. The solar-enhanced oxidative system involving ferrous ion and persulfate (Solar/S 2 O 8 2- /Fe 2+ ) showed the highest ATZ degradation efficiency when compared with other treatments (unactivated S 2 O 8 2- , Solar - sunlight only, S 2 O 8 2- /Fe 2+ , Solar/S 2 radicals were shown to be involved in ATZ oxidation using the radical scavengers methanol and tert-butyl alcohol. Furthermore, iron compounds were shown to act not only as catalysts but also as photo-sensitizers, as the introduction of ferrous ion into the reaction mixture led to an increased absorbance of the solution and expansion of the absorption spectrum into the longer wavelength spectral region.8 2- ). Complete degradation of ATZ and 20% reduction in total organic carbon (TOC) content were observed after 30min of the treatment. The in situ generated • ОН and SO 4 -• radicals were shown to be involved in ATZ oxidation using the radical scavengers methanol and tert-butyl alcohol. Furthermore, iron compounds were shown to act not only as catalysts but also as photo-sensitizers, as the introduction of ferrous ion into the reaction mixture led to an increased absorbance of the solution and expansion of the absorption spectrum into the longer wavelength spectral region., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The application of calcium peroxide (CaO2) activated with ferrous ion to stimulate the degradation of trichloroethylene (TCE) was investigated. The experimental results showed that TCE could be completely degraded in 5 min at a CaO2/Fe(II)/TCE molar ratio of 4/8/1. Probe compound tests demonstrated the presence of reactive oxygen species HO· and O2(-·) in CaO2/Fe(II) system, while scavenging tests indicated that HO· was the dominant active species responsible for TCE removal, and O2(-·) could promote TCE degradation in CaO2/Fe(II) system. In addition, the influences of initial solution pH and solution matrix were evaluated. It suggested that the elevation of initial solution pH suppressed TCE degradation. Cl(-) had significant scavenging effect on TCE removal, whereas HCO3(-) of high concentration showed favorable function. The influences of NO3(-) and SO4(2-) could be negligible, while natural organic matter (NOM) had a negative effect on TCE removal at a relatively high concentration. The results demonstrated that the technique of CaO2 activated with ferrous ion is a highly promising technique in in situ chemical oxidation (ISCO) remediation in TCE contaminated sites., (Copyright © 2014. Published by Elsevier B.V.)

Iron binding to protein is common in biological processes of dioxygen transport, electron transfer as well as in stabilizing drug-protein complexes. α-Helix is the most prevalent secondary structure of proteins. In this study, Fe(2+) binding to α-helix has been studied by isothermal titration calorimetry (ITC) and explicitly solvated molecular dynamics (MD) simulation. Ferrous gluconate and α-helix-rich keratin are used for the ITC study and the results revealed followed one set of identical sites binding model. The MD simulations further revealed that only the acidic side-chain functional groups and η(2) (O,O) coordination modes are involved in the binding of Fe(2+) to α-helix. The ITC results also showed that the binding of ferrous gluconate to keratin was entropy driven and the higher the temperature, the stronger the binding free energy. The favorable entropy of Fe(2+) binding to keratin was attributed to the displacement of water molecules on the α-helix surface, and was confirmed via MD simulations. The most stable coordination states of Fe(2+) and α-helix were identified via simulation: Fe(2+) stacks between two glutamic acid side chain carboxylate groups, displacing water molecules. The binding free energies calculated using MD simulation and the theoretical values were in excellent agreement with the ITC results., (© 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.)