Fluoroethylene carbonate (FEC), as a key electrolyte component, has been extensively employed across diverse electrolyte systems owing to its excellent compatibility with different anode materials. However, its mechanistic role on the cathode side remains under debate due to the strong electron-withdrawing nature of the fluorine incorporation. Here, we demonstrate that lithium difluoro(oxalate)borate (LiDFOB) can effectively trigger the latent cathode-side functionality of FEC through a rationally designed dual-additive electrolyte. At the LiNi0.9Co0.05Mn0.05O2 cathode, oxidative cleavage of LiDFOB generates BOF2 intermediates that activate FEC and direct its decomposition toward LiF and B-O/B-F-rich inorganic species, constructing a compact and resilient cathode-electrolyte interphase (CEI). Simultaneously, the coupled reduction of FEC and DFOB- at the lithium metal anode yields a boron-rich, LiF-enriched solid electrolyte interphase (SEI) that enhances interfacial compatibility and suppresses dendrite growth. These LiDFOB-enabled, FEC-mediated interfacial pathways significantly improve ion transport and durability, delivering 73.4% capacity retention of Li||NCM9055 full cells after 1000 cycles at 4.7 V, versus 55.1% for the base electrolyte.

Enhanced methane yield from pistachio shells via a novel sodium perborate-based oxidative pretreatment and early prediction of methane yields using an ARIMA model.

Insight of synergy between biosurfactant-producing Klebsiella sp. HN02 and magnetic biochar mediators enables hydrophobic para-xylene-fed high-performance microbial fuel cells.

A water-soluble phenothiazine-based fluorescent probe for selective detection and bioimaging of hypochlorite.

Fungal AA9 lytic polysaccharide monooxygenases (LPMOs) play a central role in oxidative cellulose degradation and are key contributors to biomass conversion. While widely distributed in fungal genomes, many LPMOs remain uncharacterized, limiting our understanding of their functional diversity and biotechnological potential. Fusarium oxysporum, a genetically rich but underexplored species, contains several AA9 LPMOs. This study focuses on the characterization of one such enzyme named FoLPMO9A, demonstrating its role in lignocellulose degradation and its potential for cellulose-based material functionalization. The gene encoding FoLPMO9A was heterologously expressed in Pichia pastoris, and the produced recombinant protein was evaluated for its biochemical and functional properties, revealing C1/C4 regioselectivity on cellulosic substrates and higher H₂O₂ production compared to other AA9 fungal LPMOs. Its activity was assessed through the release of oxidized cello-oligosaccharides from various substrates and its synergistic action with cellulases. The stronger synergistic effect on lignocellulosic biomass likely reflects the enzyme's ability to target complex, less accessible structures, where oxidative cleavage complements cellulase activity. Attention was given to how FoLPMO9A responds to phenolic compounds and lignin-derived fractions, both in their native form and after enzymatic oxidation by redox enzymes such as laccases and polyphenol oxidases. In the case of lignin-derived fractions, the goal was to assess how these modifications influence their ability to drive FoLPMO9A activity as redox-active electron donors. Building on its characterized activity, FoLPMO9A was applied in two biotechnological contexts. First, it was integrated into a three-step enzymatic process for isolating micro-fibrillated cellulose from OxiOrganosolv-pretreated wheat straw. This treatment led to enhanced fibre disruption and finer fibrils, confirmed by determination of fibre diameter distribution, while fluorescence labelling with Rhodamine 110 verified C1-specific oxidation. Second, FoLPMO9A was applied to bacterial nanocellulose produced by Komagataeibacter medellinensis, where successful oxidation and introduction of carboxyl groups were confirmed, demonstrating its potential to modify material properties. This study underscores the versatile catalytic role of AA9 LPMOs in synergistic enzyme systems, emphasizing their impact on cellulose degradation and modification. The findings highlight the need for further exploration of LPMO mechanisms in biomaterial development and industrial applications.

In this study, an electrochemical valorization strategy on liquid byproducts from hazelnut shell gasification was developed to couple waste remediation with energy-efficient hydrogen production. The aqueous phase, rich in organic compounds, is processed in an anion exchange membrane (AEM) cell, where pure hydrogen evolved at the cathode while organic pollutants are oxidized at the anode. First, the feedstock is thoroughly characterized using gas chromatography–mass spectrometry (GC-MS), identifying a complex matrix of water-soluble aromatic compounds such as phenols, catechols, and other aromatics compounds, with concentrations reaching up to 2.9 g/kg for catechols. Then, the electro-reforming process is optimized using Nickel oxide–hydroxide (Ni(O)OH) electrodes with a loading of 0.75 mg/cm2. This methodology relies on the favorable thermodynamics of organic oxidation, which requires a lower onset potential (0.4 V) compared to the oxygen evolution reaction (OER) observed in the alkaline control (0.52 V), and the low overpotential of the Nickel oxide–hydroxide electrode towards the oxidized species. Consequently, the organic load undergoes progressive oxidation into hydrophilic and less bioaccumulating species and carbon dioxide, allowing for the simultaneous generation of pure hydrogen at the cathode at a reduced cell voltage. Elevated stability was observed, with a substantial abatement—78% of the initial organic load—of organic compounds achieved over 80 h at a fixed cell voltage of 0.5 V, and a specific energy consumption for hydrogen production of 38.5 MJ⋅kgH2−1. This represents a step forward in the development of technologies that reduce the energy intensity of hydrogen generation while valorizing biomass gasification residues.

Abstract Nitroarenes are versatile building blocks in organic synthesis, and their photochemical reactivity has recently enabled new transformations, including oxidative cleavage reactions. Here, we disclose a sustainable isomerization strategy in which nitroarenes function as energy-transfer (EnT) photocatalysts to convert cinnamyl chlorides into cyclopropanes. In contrast to conventional methods that rely on transition-metal photocatalysts, this approach capitalizes on the intrinsic triplet energy of nitroarenes, offering a metal-free and operationally simple solution. Preliminary studies indicate that the π,π* triplet state of nitroarenes is more efficient in EnT than the n,π* state, revealing a distinct divergence in their excited-state reactivity. Standard silica gel (SiO₂) serves as an effective additive to promote the reverse isomerization of the resulting 1-arylallyl chlorides to cinnamyl chlorides, further enhancing the overall process efficiency.

Ribosomally synthesized and post-translationally modified peptides (RiPPs) rely on a diverse array of enzymes to tailor peptide backbones and side chains. In this study, we characterized enzymes from two different biosynthetic gene clusters (BGCs) from Pseudomonas strains (pfl and pos) that catalyze new transformations in RiPP biosynthesis. Two α-ketoglutarate-dependent HEXXH enzymes, PflC and PosC, perform hydroxylation of multiple consecutive glutamine residues and selectively recognize a C-terminal ARMD tetrapeptide to trigger oxidative backbone cleavage that generates an amide terminus. Mutational analysis pinpoints the first position of this motif as a critical determinant. Notably, PflC displays proteolytic activity in the absence of the leader peptide, indicating that leader peptide-enzyme interactions modulate the observed reaction selectivity. The biosynthetic gene clusters also encode a unique MNIO-nitroreductase fusion enzyme that installs a rare Z-dehydrophenylalanine and hydroxylates an Asp residue. Collectively, this work expands both the catalytic repertoire and structural diversity accessible through bacterial RiPP biosynthesis.

Carotenoids and apocarotenoids constitute a structurally and functionally sundry class of isoprenoids whose significance extends from photosynthetic light capture and photoprotection to phytohormone signaling, flavor and aroma formation, and emerging biomedical applications. While recent appraisals have emphasized quantitative advances in microbial production, this mini-review adopts a pathway module-centric perspective. We examine each biosynthetic stage from precursor supply, condensation to geranylgeranyl diphosphate (GGPP), phytoene synthesis, desaturation/isomerization, cyclization, hydroxylation, ketolation, epoxidation, and oxidative cleavage, highlighting novel enzymatic variants, mutagenesis studies, fusion strategies, and compartmentalization approaches that impart metabolic control. Special emphasis is placed on recently discovered and engineered enzymes, as well as synthetic biology tools. This review integrates diverse enzyme sources, host ranges across plants, fungi, algae, yeasts, and bacteria, as well as pathway modularity, to provide an updated review of recent literature. We conclude by outlining future directions that highlight gaps and potential areas for future work. This focused synthesis aims to equip researchers with a hierarchical understanding of the pathways and strategies to advance carotenoid and apocarotenoid biosynthesis.

Moderate activation and mutual promotion of aluminum-iron covalent-bond coagulant with K2FeO4 for enhanced organic arsenic removal: Selective truncation-repolymerization of Fe(Ⅳ)/Fe(Ⅴ) and enhanced coagulation.

The increasing demand for rapid identification of bacteria capable of degrading environmentally relevant organic compounds highlights the need for scalable and selective analytical tools. Cupriavidus necator catabolizes several hydroxybenzoic acids, including 2-hydroxybenzoate (salicylate, 2-HBA), 4-hydroxybenzoate (4-HBA), and 3-hydroxybenzoate (3-HBA), funneling them into central aromatic catabolism via monooxygenation to 2,5-dihydroxybenzoate (gentisate, 2,5-dHBA) and 3,4-dihydroxybenzoate (protocatechuate, 3,4-dHBA) followed by the oxidative cleavage reaction, enabling complete conversion to tricarboxylic acid (TCA) cycle intermediates. To quantify how readily C. necator is able to activate catabolic genes in response to hydroxybenzoic acid, an extracellular ligand, we applied an approach centered on a transcription-factor (TF)-based biosensor that combines ligand-bound regulator activity with a fluorescent reporter. This approach allowed to evaluate the ligand sensitivity by determining gene activation threshold ACmin and half-maximal effective concentration EC50. Amongst studied hydroxybenzoic acids, 2-HBA and 4-HBA sensors from C. necator showed very low thresholds 4.8 and 2.4 μM and EC50 values of 19.91 and 13.06 μM, indicating high sensitivity to these compounds and implicating a scavenging characteristic of associated catabolism. This study shows that the TF-based-biosensor approach applied for mapping functional sensing ranges of hydroxybenzoates combined with the research and informatics of catabolism can advance our understanding of how gene expression regulation systems have evolved to respond differentially to the availability and concentration of carbon sources. Furthermore, it can inform metabolic engineering strategies in the prevention of premature pathway activation or in predicting competitive substrate hierarchies in complex mixed environments.

Seven new polycyclic-fused cytochalasins (CYTs), harziachalasins A–G (1–7), together with three known analogues (8–10) were isolated from the solid culture of the endophytic fungus Trichoderma harzianum MLJ-4, which was originally isolated from the leaves of Asclepias curassavica. The planar and absolute structures of all new compounds were determined on the basis of extensive spectroscopic data (1D, 2D NMR and HR-ESI–MS), NMR calculations with DP4 + probability analysis, and theoretical simulations of ECD spectra. Compound 1 represents the first example of 5/6/6 tricyclic CYT featuring a 2-methyl-4-oxopentyl side chain at the C-14 position. This novel architecture originates from a 5/6/6/7 tetracyclic CYT precursor through sequential oxidative cleavage of the C-19–C-20 bond followed by decarboxylative elimination of C-19. Compound 2 features an unprecedented 5/6/6/6/7 pentacyclic scaffold incorporating a 1,3-dioxane moiety, may be constructed by the acetalization of the 7-OH and 13-OH on a 5/6/6/7 tetracyclic CYT with acetaldehyde. Compounds 1–10 were screened for HIV latency reversal activity using J-Lat A72 and J-Lat 10.6 cell models. Compound 4 showed strong activity, with half-maximal effective concentrations (EC50) values of 2.68 μM (J-Lat A72 cells) and 2.99 μM (J-Lat 10.6 cells), demonstrating consistent potency. Mechanistic studies revealed 4 activated the NF-κB pathway to reverse HIV latency, offering insights for new therapeutic strategies targeting this pathway.Graphic Supplementary InformationThe online version contains supplementary material available at 10.1007/s13659-025-00572-1.

This report exploits either electrochemical or photoredox triggers to promote the oxidative mesolytic cleavage of alkoxyamines to establish multicomponent Mumm rearrangement cascade reactions for the synthesis of imides and imidates. Readily accessible, bench-, air-, and moisture-stable alkoxyamines derived from 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) serve as masked carbocations in this approach.

Anion Effect in Electrocatalysts for Oxygen Evolution Reaction and Small Organic Molecule Oxidation

Astatine-211 (211At) is a highly promising α-emitter for targeted alpha therapy (TAT), combining near-100% α-emission with an optimal 7.21-h half-life. Yet clinical translation of 211At-based radiopharmaceuticals is hindered by oxidative cleavage of labile CAr-At bonds in conventional covalent constructs, leading to notable off-target and radiation hazards to normal tissues during therapy. Here, we propose a paradigm-shifting radiolabeling strategy within a preorganized zwitterionic covalent organic framework (ZVCOF, ZV = zwitterionic vinylene-linked) that stably immobilizes cationic 211At species (At(Ø)+) via synergistic multiple noncovalent interactions. The resulting dynamically reversible radiolabeling pathway in ZVCOFs achieves high labeling efficiency (RCY ≥ 90% and radiolabeling kinetics ≤ 2 min) and enhanced in vivo stability against deastatination, surpassing molecular organo-astatine complexes represented by N-succinimidyl 3-[211At]astatobenzoate, a gold standard in clinical trials. Theoretical studies provide fundamental insights into the coordination chemistry and dynamic behavior of At(Ø)+ in the ZVCOF, while cellular and in vivo experiments validate the practical potential of this strategy. This work establishes a robust, deastatination-resistant platform for next-generation α-therapeutics, providing pivotal hints for unlocking the full potential of 211At in precision oncology.

Hypochlorous acid (HClO), a reactive chlorine species produced by myeloperoxidase (MPO), contributes to neuroinflammation and oxidative stress implicated in neurodegenerative disorders. However, real-time quantification of HClO in the living brain remains challenging due to the lack of selective, miniaturized tools. Here, we report a ratiometric electrochemical microsensor based on a newly synthesized methylene blue-benzoyl (MB-Bz) probe for in vivo detection of HClO in the brain. The MB-Bz probe was immobilized on a three-dimensional (3D) electrochemically reduced graphene oxide-single-walled carbon nanotube (ERGO-SWCNT) nanocomposite-modified carbon fiber microelectrode. Upon reaction with HClO, the probe undergoes oxidative cleavage at the imine linkage adjacent to the benzoyl group, releasing benzoate and regenerating methylene blue, thereby producing two well-separated redox peaks for ratiometric quantification. The optimized microsensor exhibits a linear response toward HClO in the range of 2-40 μM (limit of detection 0.07 μM, S/N = 3) with excellent selectivity, stability, and reproducibility. When implanted into rat and mouse brains, the microsensor enables in vivo, region-specific electrochemical monitoring of HClO. Notably, elevated HClO levels are observed in the cortex, striatum, and hippocampus of PD model mice relative to normal mice, consistent with MPO-mediated oxidative stress. This work provides a molecularly engineered electrochemical platform for in vivo HClO analysis in living brain tissue, offering a valuable approach to investigate reactive chlorine species in neurodegeneration.

Lignin is a heteropolymer component of ligno-cellulosic biomass made up of monomers connected together by various linkages, the most common of which is the β-O-4 bond. As previously demonstrated, lytic polysaccharide monooxygenase (LPMO) can catalyse the oxidative cleavage of β-O-4 linkage of lignin model compound guaiacyl glycerol-β guaiacyl ether (GGE). But the enhancement of enzymatic activity and stability remains a critical challenge for biocatalytic lignin valorization. In this study, an LPMO-cobalt phosphate organic-inorganic hybrid nanoflower (Co@LPMO-HNF) was developed as a robust biocatalyst for the cleavage of β-O-4 bond. The Co@LPMO-HNF was biochemically and morphologically characterized. Co@LPMO-HNF displayed an optimum temperature of 100°C and pH 8, exhibiting 1.65-fold higher activity than free LPMO. The Michaelis-Menten kinetic parameters indicated that the Co@LPMO-HNF had 20 fold higher Vmax and 13 fold higher turnover number (kcat) as compared to free LPMO for GGE. The catalytic efficiency (kcat/Km) of Co@LPMO-HNF was found to be 700 M- 1s- 1which was significantly comparable to free LPMO (650 M- 1s- 1). Notably, Co@LPMO-HNF achieved 97% GGE conversion within 24h versus 40% for the free enzyme and retained 52% of its activity after four catalytic cycles. This is first study to report the synthesis of LPMO based cobalt phosphate nanoflowers (Co@LPMO-HNF) with enhanced activity and stability for the oxidative cleavage of lignin derived compounds. Thus, LPMO loaded hybrid nanoflowers could be of great potential for the sustainable oxidation of lignin and its model compounds.

Biodegradation of low-density polyethylene by actinomycete Nocardia asteroides isolated from agricultural soils.

Hematite-facilitated anaerobic oxidation of organics: Novel strategy to alleviate bioclogging in constructed wetlands.

As a highly reactive atmospheric oxidant, chlorine (Cl) atoms significantly contribute to the oxidation of volatile organic compounds (VOCs) and the formation of secondary organic aerosol (SOA) in coastal and industrial environments.