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Recurrence and metastasis stand as the primary contributors to mortality among patients with triple-negative breast cancer post-surgery, presenting a formidable clinical obstacle. Chemodynamic therapy (CDT), leveraging metal-ion-mediated Fenton-like reactions within the tumor microenvironment (TME), emerges as a promising avenue for addressing cancer metastasis. Despite recent progress, challenges such as tumor cell antioxidant defenses and epithelial-mesenchymal transition (EMT) impede the efficacy of CDT. Here, we introduce a novel approach using DNA-templated nanosheets (Dz-MnO 2 ) that combine the functions of Mn 2+ -mediated CDT and DNAzyme-mediated gene therapy to suppress tumor growth and metastasis. The Dz-MnO 2 nanosheets respond effectively to the TME, releasing Mn 2+ and DNAzyme. The DNAzyme exhibits mRNA cleavage activity, specifically targeting oncogenic transcripts to reduce tumor progression. Mn 2+ not only facilitates a Fenton-like reaction, enhancing the chemodynamic treatment effect, but also serves as a cofactor for DNAzyme, improving its catalytic efficiency. Concurrently, the nanosheets robustly silence the Twist1 gene, mitigating the EMT process and reinforcing CDT efficacy by suppressing apoptosis resistance. Results indicate that Dz-MnO 2 nanosheets efficiently polarize M2-tumor-associated macrophages (TAMs) into M1-TAMs by locally mitigating tumor hypoxia via catalyzing the decomposition of H 2 O 2 into O 2 . This collaborative strategy presents a promising approach to enhance CDT, effectively inhibiting tumor recurrence and metastasis., 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.)

Techniques to improve the graphitization of lignin, the second most abundant natural polymer, are in great demand as a viable means to obtain cost-effective and less energy-intensive graphite for various applications. In this work, we report the effects of two-dimensional nanomaterials, graphene oxide (GO) and its derivative, reduced graphene oxide (RGO), used as templating agents for the graphitization of alkali-derived lignin. The hypothesis is that during heat temperature treatment, the GO additives act as a template that allows the lignin matrix to align on its basal planes through π-π interactions. In addition, possible chemical bonding between the GO additives and lignin may extend the two planar frameworks. Results from X-ray diffraction and Raman spectroscopy showed improved graphitic quality in the lignin-GO and lignin-RGO samples compared to pure lignin at 2500 °C. Transmission electron microscopy images and selected area electron diffraction patterns also revealed ordered nanostructures and defined polycrystalline patterns in the lignin-GO and lignin-RGO samples. This work presents a method to synthesize graphitic-like materials using carbon-based templates with the advantage that there is no need for further purification of the final material as in the case of transition metal catalysts.

Background: Simple, fast and low-cost paper-based analytical devices (PADs) have a good application prospect for point-of-care detection of GSH. However, effective immobilization of functional nanomaterials onto cellulose, as a critical factor in the construction of PADs, presents numerous difficulties and challenges., Results: In this study, we have developed an exceptionally straightforward and environmentally friendly synthetic approach by using ovalbumin (OVA) as a bio-mineralization template for the preparation of MnO 2 nanosheets. The MnO 2 nanosheets produced in the solution phase exhibited excellent intrinsic nano-enzyme activity and biodegradability. The OVA-MnO 2 nanosheets can effectively oxidize Amplex red in the absence of H 2 O 2 , enabling sensitive detection of GSH with a linear range of 5 nM-10 μM and a detection limit as low as 2.8 nM. Furthermore, we utilized this method to facilitate in situ synthesis of OVA-MnO 2 nanosheets directly on paper substrates. This approach eliminates the need for conventional stirring and centrifugation steps, greatly simplifying the fabrication process while reducing material usage and time expenditure. Characterization of the chemical composition and morphology confirmed the intimate growth of the 2D nano-enzymes on the cellulose fibers. Utilizing smartphone capabilities, the OVA-MnO 2 nanosheet-modified PAD enabled instrument-free detection of GSH, demonstrating high sensitivity (0.74 μM) and a wide linear response range (1-1000 μM)., Significance: The synthesis of MnO 2 nanosheets directly on cellulose substrates substantially streamlines the modification workflow of PADs and reduces detection costs, offering new avenues for clinical diagnostics of relevant 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 © 2024 Elsevier B.V. All rights reserved.)

Cobalt/iron bimetallic oxide coated with graphitized nitrogen-doped carbon (Fe 2 O 3 -CoO@NC) was synthesized by convenient solid phase coordination combined with calcination method to activate PMS for the degradation of BSM. A series of Co/Fe bimetallic oxides with different metal ratios were designed and prepared to select the most efficient catalyst and Fe 2 O 3 -CoO@NC(Co:Fe = 1:1) demonstrated the highest catalytic activity and the lowest ions leaching. The reasons for high catalytic activity of Fe 2 O 3 -CoO@NC(Co:Fe = 1:1) were evaluated by a range of characterization techniques and the results showed it stemmed from higher mental content and larger current density. Complete (100%) degradation of 10 g L -1 BSM was achieved within 10 min under the conditions of 0.05 g L -1 catalyst and 0.3 mmol/L PMS dosage at 25 °C. Moreover, Fe 2 O 3 -CoO@NC(Co:Fe = 1:1) showed more excellent catalytic activity and lower ions leaching than Fe 2 O 3 , CoO and Fe 2 O 3 -CoO, indicating superior bimetallic synergy and carbon encapsulation effect. Furtherly, radical experiments and XPS analysis revealed the main active species and catalytic mechanism of the Fe 2 O 3 -CoO@NC/PMS system, respectively. Finally, the degradation pathway of BSM by Fe 2 O 3 -CoO@NC/PMS system was deduced by LC-TOF-MS. This paper is aimed to provide a new insight into the convenient preparation method for the construction of catalysts which could reach efficient removal of complex organic pollutants., 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.)

In this study, a type-I heterojunction was synthesized based on eggshell waste doped mixed metal oxide (ES@ZnAl MMO) for the degradation of RhB dye under visible light irradiation. The ES@ZnAl MMO core-shell was synthesized using waste eggshell and layered double hydroxide (LDH) as primary precursors. After their mechanochemical assembly and thermal treatment, CaCO 3 was formed in both calcite and vaterite forms, alongside mixed metal oxides derived from the LDH (ZnO and Al 2 O 3 ). The formation of a heterojunction between the semiconductors results in an improved activation of sites, a decrease in bandgap energy from 5.72 to 3.44 eV, and an increase in degradation capacity. The elemental composition, morphology, structural, and optical properties of the ES@ZnAl MMO nanocomposite were analyzed using various techniques. The optimal ES@ZnAl MMO photocatalyst demonstrated superior performance, reaching over 98% of RhB dye degradation under optimal conditions, outperforming pure ZnAl LDH, ZnAl MMO, and ES. After five run cycles, the ES@ZnAl MMO heterojunction still maintained a high photocatalytic performance for RhB dye (99%). Furthermore, it displayed high performance in degrading various other pollutants, including OG, IC, MB, and 2.4-DP, with degradation efficiencies of 97%, 99%, 99%, and 87%, respectively. This economically advantageous heterojunction showed its importance in environmental remediation, presenting a promising solution for addressing diverse pollution challenges., 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.)

Lime pretreatment is commonly used for sludge hygienization. Appropriate lime dosage is crucial for achieving both sludge stabilization (lime dosage >0.2 g/g-TS) and promoting plant and soil health during subsequent landscaping (lime dosage <0.8 g/g-TS). While much research has been conducted on sludge lime treatment, few studies have examined the effects of lime dosing on integrating sludge stabilization and plant growth promotion during landscaping. In this study, we investigated microbial dynamics and dissolved organic matter (DOM) transformation during sludge landscaping with five lime dosage gradients (0, 0.2, 0.4, 0.6, 0.8 g lime/g-TS) over 90 days. Our results showed that a lime dosage of 0.4 g/g-TS is the lower threshold for achieving waste activated sludge (WAS) stabilization during landscaping, leading to maximum humic substance formation and minimal phytotoxicity. Specifically, at 0.4 g/g-TS lime dosage, protein degradation and decarboxylation-induced humification were significantly enhanced. The predominant microbial genera shifted from Aromatoleum to Exiguobacterium and Romboutsia (both affiliated with the phylum Firmicutes). Reactomics analysis further indicated that a 0.4 g/g-TS lime dosage promoted the hydrolysis of proteins (lyase reactions on C-C, C-O, and C-N bonds), amino acid metabolism, and decarboxylation-induced humification (e.g., C 1 H 2 O 2 , C 2 H 4 O 2 , C 5 H 4 O 2 , C 6 H 4 O 2 ). The co-occurrence network analysis suggested that the phyla Firmicutes, Proteobacteria, and Bacteroidetes were key players in DOM transformation. This study provides an in-depth understanding of microbe-mediated DOM transformation during sludge landscaping and identifies the optimal lime dosage for improving sludge landscaping efficiency., 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 Inc.)

Aiming at the effective remediation of antibiotic contaminants in groundwater, in-situ chemical oxidation (ISCO), using controlled release materials (CRMs) as an oxidant deliverer, has emerged as a promising technique due to their long-term effective pollutant removal performance. This study used different microstructures of mesoporous manganese oxide (MnO x ) and sodium persulfate as active components to fabricate CRMs. Following that, a comparative study of tetracycline (TC) degradation and the formation of reactive oxygen species (ROS) by mesoporous MnO x powder and CRMs were conducted. The ROS formed during peroxodisulfate (PDS) activation by powder catalysts and CRMs differed, but MnO x powder catalysts and CRMs both had good reaction stoichiometric efficiency (RSE) for PDS, thus completely mineralizing TC. In PDS activation by mesoporous MnO x powder, oxygen vacancies (OVs) caused by defects in the catalysts contributed to the generation of singlet oxygen ( 1 O 2 ). The 1 O 2 and free radicals (·SO 4 - and ·OH) both worked as major ROS participating in TC degradation. Concerning the release of CRMs in static groundwater, the immobilization of catalysts inside CRMs made it difficult to release 1 O 2 in the solution, thus slowing the degradation of TC by CRMs containing MnO x (1) in static groundwater. In the TC remediation in dynamic groundwater, the water flowing slowly passed through the CRM layer, and TC molecules were trapped. Therefore, 1 O 2 degraded the trapped TC in the CRM layer in dynamic groundwater. Compared to TC, the toxicity of most intermediates during the TC degradation by CRMs has decreased in static and dynamic groundwater., 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 Ltd. All rights reserved.)

High concentrations of manganese ion (Mn 2+ ) and ammonia nitrogen (NH 3 -N) in groundwater are indicative of a critical environmental issue that necessitates immediate attention. The gravity-driven ceramic membrane (GDCM) technology has shown great potential for groundwater treatment in rural communities, owing to its low energy demand and user-friendly operation. Active manganese oxide (MnO x ) is extensively used for the concurrent removal of Mn 2+ and NH 3 -N, leveraging its large specific surface area and abundant adsorption sites. Our research group has developed a GDCM-MnO x coupled system to address this challenge. However, membrane fouling, manifested as a reduction in flux or an increase in transmembrane pressure, has been a significant barrier to its widespread adoption. To address this challenge, we have implemented a continuous aeration system in conjunction with GDCM to fluidize birnessite to achieve the higher membrane flux, which has also proven effective in mitigating fouling while maintaining high water purification performance. Over a period of 100 days or more, the high membrane flux in the high-flux GDCM system (HF-GDCM) enhanced with aerated fluidized birnessite has been consistently maintained at approximately 34 L/(m 2 ·h) at a water head of 1 m. Moreover, the HF-GDCM system efficiently removed manganese and NH 3 -N from groundwater under a hydraulic retention time (HRT) of less than 2.5 h, while also improving membrane permeability. The involvement of manganese oxidizing bacteria (MnOB) and ammonium-oxidizing bacteria (AOB) of Hypomicrobium and Nocardioides in the removal processes within the HF-GDCM system was confirmed. Additionally, XPS analysis confirmed the predominant oxidation state of MnO x to be Mn(III). The MnO x , deposited on powdered activated carbon (PAC) particles in a flower-like configuration, progressively formed a birnessite-like functional layer as the manganese ion content increased over time. Consequently, the HF-GDCM coupled with aerated fluidized birnessite is deemed suitable for water purification in small-scale rural or reservoir settings., 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 Ltd. All rights reserved.)

This paper proposes a novel process of cobalt monoxide (CoO)-activated peracetic acid (PAA) for treating emerging micropollutant in water. PAA was activated under neutral conditions by combining a dominant heterogeneous phase on the catalyst surface and a homogeneous phase by dissolved Co 2+ . The system produced several reactive oxygen species, including hydroxyl radicals (HO ∙ HO • ), singlet oxygen ( 1 O 2 ), organic radicals (RO • (CH 3 C(O)O • , CH 3 C(O)OO • ) and high-valent cobalt (Co(IV)). Organic radicals and high-valent cobalt primarily drove the emerging micropollutants degradation, interacting via electron transfer. Further density functional theory calculations supported that the spontaneous adsorption of PAA onto the catalyst could break peroxy bonds that generate radicals. Furthermore, the CoO surface structure underwent minimal changes during the reaction, making it highly reusable. Thus, the novel CoO/PAA system could be an effective advanced oxidation process for water 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 Elsevier Inc. All rights reserved.)

In the context of the air quality co-benefits of carbon neutrality, conventional strategies for the end-of-pipe control aimed at reducing volatile organic compounds (VOCs) to carbon dioxide (CO 2 ) require a more realistic revision. This study explored the synergetic removal of carbonyls with low carbon emission by amine-functionalized manganese dioxide (MnO 2 ), obtained through a method involving freezing-thawing cycles. Molecular-level characterization revealed that an ordered array of interfacial water dimers (H 5 O 2 + , a class of water-proton clusters) on the MnO 2 surface enhanced the robust bonding of metal sites with amino groups. Amine-functionalized MnO 2 can be negatively charged under environmental acidity to further interfacial proton-coupled electron transfers. This cooperativity in interfacial chemical processes promoted the selective conversion of carbonyl carbons to bicarbonated amides (NH 3 + HCO 3 - ), serving as a reservoir of CO 2 . In comparison to a commercially used 2,4-dinitrophenylhydrazine (DNPH) control, this approach achieved nearly complete removal of a priority carbonyl mixture containing formaldehyde, acetaldehyde, and acetone synergically. The formation of secondary organic compounds in the gas phase and CO 2 off-gas were suppressed., 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.)

Developing a multi-functional green energy device that propels sustainable energy development and concurrently purifies environmental pollutants offers an irresistibly compelling vision for a cleaner future. Herein, we reported a bias-free glucose/O 2 bio-photoelectrochemical system (BPECS) for both energy conversion and phenolic pollutants degradation. Coupling a glucose dehydrogenase (GDH) modified self-assembled meso-tetrakis (4-carboxyphenyl)-porphyrin (SA-TCPP)-sensitized TiO 2 biophotoanode for glucose oxidation and nitrogen/oxygen doped cobalt single-atom catalyst (CoNOC) cathode for two-electron oxygen reduction, both solar and biochemical energies were converted into electric power in BPECS with a maximum power density of 296.98 μW cm -2 (0.49 V). Working in synergy with horseradish peroxidase (HRP) biocatalysis, the cathode-generated H 2 O 2 , a by-product, is effectively redeployed for degrading phenol, attaining an impressive degradation efficiency of approximately 100% within 60 min. Additionally, aiming to scale up this ingenious BPECS approach, peroxidase-mimicking Co 3 O 4 nanozyme were engineered as a substitute for natural HRP. Remarkably, these nanozyme demonstrated a comparable degradation efficiency, achieving the same result in 90 min. In this work, our results demonstrate that this bias-free glucose/O 2 BPECS model marks a significant step forward in integrating renewable energy harvesting with environmental remediation, but also opens new avenues for the versatile application of nanozymes., 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.)

At present, the combination of fingerprint recognition methods and environmentally friendly and economical analytical instruments is becoming increasingly important in the food industry. Herein, a dithiothreitol (DTT)-functionalized CsPbBr 3 -based colorimetric sensor array is developed for qualitatively differentiating multiple food oils. In this sensor array composition, two types of iodides (octadecylammonium iodide (ODAI) and ZnI 2 ) are used as recognition elements, and CsPbBr 3 is used as a signal probe for the sensor array. Different food oils oxidize iodides differently, resulting in different amounts of remaining iodides. Halogen ion exchange occurs between the remaining iodides and CsPbBr 3 , leading to different colors observed under ultraviolet light, enabling a unique fingerprint for each food oil. A total of five food oils exhibit their unique colorimetric array's response patterns and were successfully differentiated by linear discriminant analysis (LDA), realizing 100% classification accuracy., 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 Ltd.)

The inhibitory properties and underlying mechanism of chlorine dioxide (ClO 2 ) fumigation on the pathogen Ceratocystis fimbriata (C. fimbriata) and resultant sweetpotato black rot were investigated in vitro and in vivo. Results revealed that the ClO 2 fumigation effectively inhibited fungal growth and induced obvious morphological variation of C. fimbriata mycelia. Furthermore, the mycelial membrane suffered damage, as evidenced by a significant increase in malondialdehyde content and the leakage of protein and nucleic acid from mycelia cells, accompanied by a marked decrease in ergosterol content. Additionally, ClO 2 fumigation caused spores cell membrane damage, a notable decrease in spore viability, and induced cell apoptosis as indicated by reductions in spore germination rate, two fluorescence staining observations, and flow cytometry analysis. Moreover, the decay diameter of sweetpotato black rot lesions decreased significantly after ClO 2 fumigation, and the growth of C. fimbriata was also inhibited. These findings present a novel and effective technology for inhibiting the progression of sweetpotato black rot., 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 Ltd.)

Species-specific enzymes provide a substantial boost to the precision and selectivity of identifying dairy products contaminated with foodborne pathogens, due to their specificity for target organisms. In this study, we developed cobalt oxyhydroxide nanosheets (CoOOH NSs) for a dual-mode biosensor capable of detecting β-galactosidase (β-Gal)-positive bacteria in milk and milk powder. The sensor exploits the oxidase-mimicking activity of CoOOH NSs, where β-Gal converts the substrate β-D-galactopyranoside to p-aminophenol, reducing CoOOH NSs to Co 2+ and inhibiting the formation of the blue product from 3,3',5,5'-tetramethylben-zidine. Sensitivity was enhanced through membrane filtration and β-Gal induction by isopropyl β-D-thiogalactoside. The assay achieved a detection limit of 5 cfu mL -1 and demonstrated recoveries (90.7 % to 103 %) and relative standard deviations <5.7 % in milk and milk powder samples. These findings underscore the potential of the sensor for detecting β-Gal-positive bacteria in dairy products., 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 Ltd. All rights reserved.)

Glioma is a prevalent brain malignancy associated with poor prognosis. Although chemotherapy serves as the primary treatment for brain tumors, its effectiveness is hindered by the limited ability of drugs to traverse the blood-brain barrier (BBB) and the development of drug resistance linked to tumor hypoxia. Herein, we report the creation of hybrid camouflaged multifunctional nanovesicles comprising membranes of tumor C6 cells (mT) and bacterial outer membrane vesicles (OMVs) and co-loaded with manganese dioxide nanoparticles (MnO 2 NPs) and doxorubicin (DOX) to synergistically enhance the chemotherapy/chemodynamic therapy (CDT) of glioma. Owing to OMV-mediated BBB penetration and mT-inherited tumor-homing properties, MnO 2 -DOX@mT/OMVs can penetrate the BBB and enhance the tumor cell-specific uptake of DOX via "proton sponge effect"-mediated lysosomal escape. This enhances the apoptotic effect induced by DOX and minimizing DOX-associated cardiotoxicity by facilitating the accumulation of DOX at the tumor site. Furthermore, the MnO 2 NPs in MnO 2 -DOX@mT/OMVs can generate potent CDT by accelerating the Fenton-like reaction with DOX-generated H 2 O 2 and achieving glutathione (GSH)-depletion-induced glutathione peroxidase 4 (GPX4) inactivation. These results showed that MnO 2 -DOX@mT/OMVs, designed for brain tumor targeting, significantly inhibited tumor growth and exhibited favorable biological safety. This innovative approach offers the augmentation of anticancer treatment efficacy via a potential combination of chemotherapy and CDT., 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. Fig. 1 was drawn by Figdraw., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Bimetallic nanozymes exhibited multi-enzyme activities, but glutathione (GSH) overexpression and weak catalytic capability restricted their catalytic therapeutic performance. Thus, this study developed a smart nanozyme (AuPt@MnO 2 ) with a core-shell structure by coating manganese dioxide (MnO 2 ) on the gold-platinum (AuPt) nanozyme (AuPt@MnO 2 ) surface to enhance catalytic therapy. In this nanozyme, AuPt possessed triple-enzyme activities, i.e., catalase, peroxidase, and glucose oxidase, which greatly improved oxygen, hydroxyl radicals (·OH), and hydrogen peroxide generation, due to cyclic reactions. Moreover, GSH consumption degraded the MnO 2 shell, which then enhanced ·OH generation of Mn 2+ . More importantly, the near-infrared-II (NIR-II) photothermal performance of AuPt@MnO 2 with a high conversion efficiency of 38.7 % further promoted multi-enzyme activities and enhanced catalytic therapy. Moreover, combining NIR-II photothermal therapy and enhancing catalytic therapy decreased the cell viability to 10.8 %, and thereby, the tumors were cleared. Thus, the AuPt@MnO 2 smart nanoplatform developed in this study exhibited NIR-II photothermal-promoted multi-enzyme activities and excellent antitumor efficacy, which will be promising for enhancing catalytic therapy., 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.)

In this study, zinc ions were employed as the central metal, while 4,4',4''-nitrilotribenzoic acid (H 3 NTB) served as the fluorescent organic ligand. Through a single-step solvothermal approach, a novel Zn-based metal-organic framework (Zn-MOF) fluorescent material was successfully synthesized. The Zn-MOFs exhibit a cubic morphology, outstanding fluorescence properties, excellent water dispersibility, and robust resistance to high temperature and strong alkaline conditions. Additionally, MnO 2 nanosheets (NSs) were effectively exfoliated from MnO 2 particles using ultrasonic treatment. These MnO 2 NSs possess a broad UV-Vis absorption band that overlaps with the fluorescence spectra of Zn-MOFs. Leveraging the inner filter effect (IFE) between MnO 2 and Zn-MOFs, a Zn-MOF-based fluorescence bioassay technique was developed for the detection of biothiols. The results demonstrate that this Zn-MOF-based fluorescence detection platform exhibits a remarkable sensitivity towards biothiols, achieving a detection limit of 0.067 μM, surpassing that of other reported MnO 2 -based detection methods. Furthermore, this detection platform has been successfully applied to the quantitation of glutathione (GSH) in human serum, highlighting its potential for highly sensitive and specific detection of biothiols.

Pyroptosis has gained attention for its potential to reinvigorate the immune system within the tumor microenvironment. However, current approaches employing pyroptosis inducers suffer from limitations. They primarily rely on single agents, lack precise targeting, and potentially disrupt the intricate bone formation microenvironment, hindering local repair of tumor-induced bone defects. Therefore, a therapeutic strategy is urgently needed that can effectively trigger pyroptosis while simultaneously promoting bone regeneration. This research introduces an all-in-one construct designed to address these limitations. It combines a cell-camouflaged shell with an autosynergistic reactive oxygen species (ROS) generating polymer. This construct incorporates a hollow core of manganese dioxide (HMnO 2 ) embedded with the photosensitizer IR780 and disguised by the cell membrane of an M1 macrophage. The M1 macrophage membrane grants the construct stealth-like properties, enabling it to accumulate selectively at the tumor site. Upon laser irradiation, IR780 acts as an exogenous trigger for ROS generation while simultaneously converting the light energy into heat. Additionally, the hollow structure of HMnO 2 serves as an efficient carrier for IR780. Furthermore, Mn 4+ ions released from HMnO 2 deplete glutathione (GSH) within the tumor, further amplifying ROS production. This synergistic cascade ultimately culminates in pyroptosis induction through caspase-3-mediated cleavage of gasdermin E (GSDME) upon laser activation. Meanwhile, the depletion of GSH by HMnO 2 within the tumor microenvironment (TME) leads to the generation of Mn 2+ ions. These Mn 2+ ions establish a supportive milieu, which promotes the transformation of bone marrow mesenchymal stem cells (BMSCs) into mature bone cells. This, in turn, promotes the repair of bone defects in rat femurs. Our findings strongly indicate that pyroptosis may be a strategy for osteosarcoma treatment, which presents a robust and versatile approach for targeted therapy and tissue regeneration in this patient population.

Mercury (Hg) and lead (Pb) pose significant risks to human health due to their high toxicity and bioaccumulative properties. This study aimed to develop a novel biochar composite (HMB-S), polyfunctionalized with manganese dioxide (α-MnO 2 ) and sulfur functional groups, for the effective immobilization of Hg(II) and Pb(II) from contaminated environments. HMB-S demonstrated superior adsorption capacities of 190.1 mg/g for Hg(II) and 259.9 mg/g for Pb(II), which significantly surpasses the capacities of unmodified biochar (HB) and biochar functionalized solely with Mn (HMB). Mechanistic studies revealed that the immobilization of these metals by HMB-S involved ion exchange, mineral precipitation, surface complexation, and electrostatic interactions. In soil incubation experiments, HMB-S significantly decreased the levels of extractable Hg(II) and Pb(II) compared to the control, reducing the mobility of these metals and converting 17 % of Hg(II) and 26 % of Pb(II) into less bioavailable residual forms. Pot experiments confirmed that all tested biochar materials (HB, HMB, and HMB-S) promoted spinach growth in contaminated soils, with HMB-S being the most effective at lowering Hg(II) and Pb(II) uptake by plants. Additionally, analysis of soil microbial communities indicated that HMB-S altered community composition and increased the relative abundance of metal-resistant bacteria. These findings highlight the potential of polyfunctionalized biochar HMB-S as an effective remediation strategy for Hg and Pb contamination in soil and aqueous environments., 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 B.V. All rights reserved.)

Breast cancer (BC) is the most frequently diagnosed cancer in women worldwide. Chemodynamic therapy (CDT), photothermal therapy (PTT), and ion interference therapy (IIT), used in combination, represent a common treatment. In this study, platelet membrane-camouflaged copper-doped CaO 2 biomimetic nanomedicines have been developed for breast cancer treatments. Copper-doped CaO 2 nanoparticles were first coated by polydopamine (PDA) and subsequently camouflaged by platelet membrane (PM) to form platelet membrane-camouflaged copper doped CaO 2 biomimetic nanomedicines (Cu-CaO 2 @PDA/PM). The as-fabricated Cu-CaO 2 @PDA/PM multifunctional nanomedicines could decompose within the tumor microenvironment to release Ca 2+ for ion interference therapy, and the generated H 2 O 2 could perform a Fenton-like reaction with the assistance of loaded copper ions to produce ·OH, thus realizing chemodynamic therapy. In addition, the copper ions could also consume glutathione and weaken its ability to scavenge reactive oxygen species, which was conducive to amplifying the effect of oxidative stress. The coating of the polydopamine layer could achieve local hyperthermia of the tumor site, and the surface modification of the platelet membrane could enhance the targeting and biocompatibility of nanomedicines. In vivo and in vitro tests demonstrated that the developed Cu-CaO 2 @PDA/PM biomimetic nanomedicines offer a promising biomimetic nanoplatform for efficient multimodal combination therapy for breast cancer.

A novel nanobiosensor was constructed by in situ locating nanometer MnO 2 particles with controllable size and morphology in a Zr-MOF substrate to serve as an electrochemical probe. The synergistic effect of the two components, Zr-MOFs with high specific surface area and compatibility as a carrier for MnO 2 , resulted in improved electrochemical activity and excellent electrochemical identification performance for the MnO 2 @Zr-MOF/GCE biosensor. Under optimized experimental conditions and using CV and DPV technology, the biosensor showed a wide linear detection range (2-200 μM), a low detection limit (2.577 × 10 -8  M), a recovery range (106.26-115.01%), and maximum relative standard deviation (5.155) for tetracycline (TC) identification. The recognition mechanism of the sensor was investigated adopting Laviron adsorption theory. The applicability of the sensor was verified through practical measurements. Overall, the MnO 2 @Zr-MOF/GCE sensor possesses the advantages of fast analysis speed, high sensitivity, high selectivity, and simple operation, making it suitable for detecting trace amounts of TC in food., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Due to continuous cultivation, high soil acidity, and low nutrient inputs, soil fertility depletion has been a major threat to northwest Ethiopia's crop productivity and food security. This study aimed to examine the effects of vermicompost and lime rates on soil properties and malt barley (Hordeum distichum L.) productivity under a furrow irrigation system on acidic soil in the Mecha district, northwest Ethiopia. The treatments were combinations of three levels of vermicompost (0, 2.66-, and 5.31-tons ha-1) and three levels of lime (0-, 2.16-, and 3.24-tons ha-1) arranged in a randomized complete block design with three replications. The results showed that the integrated application of 5.31 tons of vermicompost and 3.24 tons of lime ha-1 provided the highest soil pH (6.20), available phosphorus (8.55 mg kg-1), total nitrogen (0.25%), and organic carbon (3.40%). On the other hand, adding vermicompost and lime in combination or separately noticeably decreased the exchangeable acidity and aluminum toxicity. Besides, the integrated application of 5.31 tons vermicompost (VC) and 3.24 tons lime (L ha-1 provided the highest dry biomass (12.22 tons ha-1), grain yield (5.30 tons ha-1), and net benefit (197, 246 Ethiopian Birr (ETB). Overall, the integrated application of vermicompost and lime can substantially increase soil fertility and crop yields. However, this study needs further testing and validation at varied rates in other areas., Competing Interests: There are no any competing interest related to this research study., (Copyright: © 2024 Terefe et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

This manuscript reports for the first time a heterogenous catalytic route to monoglycerides (MAGs) from microalgal oil. Microalgae is an important biomass source with high-value applications, such as food ingredients with essential fatty acids. To date, the glycerolysis of microalgae has only been investigated for a microbial oil (Schizochytrium sp.) using enzyme catalysis. However, the use of enzymes on a large scale is currently economically impeditive and requires highly selective lipases. In this study, metal oxides were screened and the reaction conditions optimized for rapeseed oil. The optimized conditions were then used to investigate the production of MAGs from Scenedesmus sp. microalga. The most promising catalyst was found to be MgO/KOH, which gave a 44 % yield. Comparing two reaction systems (low temperature 70 °C/atmospheric pressure and high temperature at 200 °C/20 bar), it was found that the latter has a superior performance. Due to the stability of the product in air, the presence of an inert atmosphere is essential to achieve high yields., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

This study focuses on the in-situ catalytic pyrolysis of the Penicillin fermentation residue (PFR), a typical antibiotic fermentation residues (AFR), using a red mud-Ca(OH) 2 composite (RM-xCa) to enhance syngas production, tar conversion, and desulfurization. The invesitigation explored the effects of different preparation methods, amount of CaO addition, and final pyrolysis temperature on the performance of RM-xCa composites. The RM-xCa composite prepared by the hydrothermal method with pressure exhibited higher catalytic activity due to the formation of soluble Na through cation exchange. The amount of CaO added determined the sulfur adsorption capacity of RM-xCa, as well as the amount of H 2 O and CO 2 involved in tar reforming and char gasification reactions. Final pyrolysis temperature significantly influenced the reduction state of Fe 2 O 3 and decomposition of Ca(OH) 2 , affecting the catalytic activity and sulfur adsorption behavior of RM-xCa composites. The optimized RM-xCa composite, RM-4Ca-HT, decreased tar and H 2 S formationby 34 % and 38 %, respectively, at 700 °C. Additionally, RM-xCa composites can lower the oxygen and sulfur content of tar. Solid residues from PFR catalytic pyrolysis were found suitable for reused as catalysts in further tar removal process., 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 B.V. All rights reserved.)

The reliable detection of organophosphorus pesticides (OPs) in complex matrices remains an enormous challenge due to inevitable interference of sample matrices and testing factors. To address this issue, we designed a nanozyme-coated mesoporous COF with guest molecule loading, and successfully used it to construct a dual-ratio dual-mode sensor through target-regulated signal generation. The multifunctional COF-based composite (MB/COF@MnO 2 , MCM) featured high loading of methylene blue (MB), oxidase-like MnO 2 coatings as gatekeepers, and specific recognition of thiocholine (TCh). TCh, a regulator produced from acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylthiocholine, could decompose MnO 2 coatings, triggering the release of abundant MB and oxidation of few o-phenylenediamine (OPD). OPs, strong inhibitors of AChE, could restrain TCh production and MnO 2 decomposition, thereby controlling the release of less MB and oxidation of more OPD. This regulation boosted the dual-ratio dual-mode assay of OPs by using the released MB and oxidized OPD in the solution as testing signals, measured by both fluorescent and electrochemical methods. Experimental results demonstrated the sensitive detection of dichlorvos with LODs of 0.083 and 0.026 ng/mL via the fluorescent/electrochemical mode, respectively. This study represented a creative endeavor to develop dual-ratio dual-mode sensors for OPs detection in complex samples, offering high sensitivity, excellent selectivity, and good reliability., 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 B.V. All rights reserved.)

The advent of lead-free perovskite materials with favorable toxicity profiles has made them candidates for in vivo and environmental applications. However, their tendency to leach A-site cations raises concerns about toxicity, catalytic efficiency, and slurry properties. The present study investigates the long-term leaching kinetics of BaTiO 3 powders over 31 days in aqueous solutions of varying pH levels. Using ICP-MS analysis and a numerical model based on the Unreacted Shrinking Core (USC) principle. The study extends the understanding of BaTiO 3 stability beyond previously reported timeframes. The findings highlight the material's long-term stability, with implications for biomedical and environmental applications.

Reactive oxygen species (ROS)-mediated immunogenic cell death (ICD) is crucial in radioimmunotherapy by boosting innate antitumor immunity. However, the hypoxic tumor microenvironment (TME) often impedes ROS production, limiting the efficacy of radiotherapy. To tackle this challenge, a combination therapy involving radiotherapy and immune checkpoint blockade (ICB) with anti-programmed death-ligand 1 (PD-L1) has been explored to enhance antitumor effects and reprogram the immunosuppressive TME. Here, we introduce a novel PD-L1 aptamer-functionalized nanoradiosensitizer designed to augment radiotherapy by increasing X-ray deposition specifically at the tumor site. This innovative X-ray-activated nanoradiosensitizer, comprising gold-MnO 2 nanoflowers, efficiently enhances ROS generation under single low-dose radiation and repolarizes M2-like macrophages, thereby boosting antitumor immunity. Additionally, the ICB inhibitor BMS-202 synergizes with the PD-L1 aptamer-assisted nanoradiosensitizer to block the PD-L1 receptor, promoting T cell activation. Furthermore, this nanoradiosensitizer exhibits exceptional photothermal conversion efficiency, amplifying the ICD effect. The PD-L1-targeted nanoradiosensitizer effectively inhibits primary tumor growth and eliminates distant tumors, underscoring the potential of this strategy in optimizing both radioimmunotherapy and photothermal therapy.

Natural manganese (Mn) oxide coatings, resulting from the heterogeneous nucleation on foreign substances, have garnered interest based on their importance in the reaction with organic substances and in environmental systems. However, the heterogeneous nucleation of the natural Mn oxide coatings still remains elusive. Here, via fast photochemical oxidation of Mn 2+ (aq), we show that Mn(IV) oxide nuclei form and aggregate on quartz in three distinct successive stages: (i) a nanocrystalline film of unaligned grain forms, (ii) nanoislands develop on the film, and (iii) nanorods form on the nanoislands. Each stage has different crystalline structures and forms by aligned attachment of nanoscale precursors on the preceding surface. Crystal lattice analyses confirm the crystalline development, from the short-range order of the Mn oxide film to the long-range order of the nanorods. Also, the heterogeneous nucleation observed in this work produced groutellite-like tunnel structures of Mn oxide on quartz. This revealed pathway of the heterogeneous nucleation can offer a new perspective on the variety of poorly crystalline structures of natural Mn oxides found in the environment, which can affect elemental redox cycles, contaminant sequestration and removal, and soil carbon storage.

Resource recovery from retired electric vehicle lithium-ion batteries (LIBs) is a key to sustainable supply of technology-critical metals. However, the mainstream pyrometallurgical recycling approach requires high temperature and high energy consumption. Our study proposes a novel mechanochemical processing combined with hydrogen (H 2 ) reduction strategy to accelerate the breakdown of ternary nickel cobalt manganese oxide (NCM) cathode materials at a significantly lower temperature (450 °C). Particle refinement, material amorphization, and internal energy storage are considered critical success factors for the accelerated decomposition of NCM cathode materials. In our proposed approach, NCM cathode materials can develop active sites with carbon defects (C v ) and oxygen vacancies (O v ), which improve the reduction and breakdown of H 2 . The adsorbed H 2 on the surface of NCM decomposes into H* and combines with oxygen to form OH species, which can be facilitated by O v via the enhanced charge transfer. The introduced C v can enhance H 2 cracking and generate *C-H species to promote the thermal decomposition of NCM. The presence of defects proves to foster the preferential reduction of Mn(IV) by H 2 , leading to a lower activation energy for the NCM decomposition (from 139 to 110 kJ/mol) with less H 2 consumption. Life cycle assessment suggests a reduction of 4.42 kg CO 2 eq for the recycling of every 1.0 kg of retired batteries. This study can promote material circularity and minimize the environmental burden of mining technology-critical metals for a low-carbon transition.

Engineered nanomaterials are widely used in water and wastewater treatment processes, and minimizing their adverse effects on biological treatment processes in wastewater treatment plants has become the primary focus. In this study, activated carbon fiber (ACF)-loaded manganese oxide nanomaterials (MnOx@ACF) were synthesized. A small-scale sequencing batch reactor (SBR) was constructed to simulate the synergistic degradation of pollutants by nanomaterials and microorganisms and the effects of nanomaterials on the structure of the microbial community in a wastewater treatment plant. The MnOx@ACF exhibited efficient removal of pollutants (98.7% in 30 cycles) and chemical oxygen demand (COD 96.4% in 30 cycles) through the formation of Mn-microbial complexes and enhanced cycling between Mn(III) and Mn(II) over 30 operating cycles. Metagenome analysis results showed that the microbial population composition and functional abundance increased when the SBR was exposed to different dosages of MnOx@ACF for a long time, among which 0.2 g/L MnOx@ACF exhibited the highest stimulation and influence on the functional abundance of microorganisms, which showed optimum ecological effects., Competing Interests: The authors declare there is no conflict., (© 2024 The Authors This is an Open Access article distributed under the terms of the Creative Commons Attribution Licence (CC BY-NC 4.0), which permits copying, adaptation and redistribution for non-commercial purposes, provided the original work is properly cited (http://creativecommons.org/licenses/by-nc/4.0/).)

A magnetic nanocomposite adsorbent, comprised of macroporous iron oxide/manganese oxide (α-Fe 2 O 3 /Mn 2 O 3 ), is prepared, characterized, and used for lead(II) removal from both industrial wastewater and leachate of electronic waste. The synergistic interaction between iron oxide and manganese oxide significantly enhances the adsorption performance. The surface characteristics and structural composition of the nanocomposite are examined using high-resolution transmission microscopy, X-ray spectroscopy, and Brunauer-Emmett-Teller methods. Under optimized conditions, the present method offers a significantly high adsorption capacity (377.5 ± 8.9 mg.g -1 ), short contact time (10 min), and an excellent removal efficiency (98.0 ± 0.9%) compared with most of the previously suggested methods. The adsorption kinetics of Pb(II) on the nanocomposite surface follows pseudo-second-order kinetics and exhibits a good fit with the Dubinin-Radushkevich (D-R) model. These findings highlight the applicability of the α-Fe 2 O 3 /Mn 2 O 3 magnetic nanocomposite as a promising efficient adsorbent for the rapid removal of lead(II) from hazardous wastewater. Moreover, the proposed nanocomposite adsorbent exhibits remarkable stability and can be easily isolated from the test sample solution for subsequent reuse. The efficacy of the developed adsorptive removal procedure is confirmed by achieving a complete lead(II) ion removal from some industrial wastewater discharged from lead battery factories and from the leachate of electronic waste., Competing Interests: Declarations. Ethical approval: All experiments adhered to the guidelines set forth in the Declaration of Helsinki (1964) and the Clinical Medical Research Regulation Act of 2020. Approval was granted by the Ethical Committee (EC) of the Faculty of Science, Ain Shams University, Cairo, Egypt. Consent to Participate: Not applicable. Consent for Publication: Not applicable. Competing of Interests: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

A series of green phosphors, Ca 1-y% MoO 4 :y%Tb 3+ (where y = 0.1, 0.5, 1, 2, 3, 4, and 5) were successfully prepared via hydrothermal synthesis. The pH levels were used to modulate the luminescent of CMO:Tb. To confirm the potential application of proposed phosphors, Blueberry anthocyanin (BBA) was loading onto CMO:Tb surface to form a luminescence probe. The synthesized phosphors and probes were characterized using X-ray diffraction (XRD), FT-IR spectra, transmission electron microscopy (TEM), and high-resolution TEM (HRTEM). As a proof-of-concept, the constructed probes were adopted to evaluate the acidity of solution. The results showed that luminescence emission intensity at 546 nm increased with pH value increasing in the range of 2-12. Meanwhile, the color of the sensor solution changed from bright red to pink, then to purple, and finally to yellow as the pH varies between 2 and 12. The above results indicated that the proposed probe could evaluate the acidity of solution via the dual-mode luminescence detecting and naked eye to obtain accurate results. This proposed strategy gives an insight to design the efficient probes to precisely and sensitively evaluate the acidity in complex samples., (© 2024 John Wiley & Sons Ltd.)

This work presents a novel and eco-friendly technique for the first time to create α-MoO 3 nanobelts (NBs) by employing a straightforward procedure with glycerol and ascorbic acid acting as green complexing and polymerizing agents, respectively. The produced α-MoO 3 NBs were characterized using a range of analytical techniques, including thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The NBs were used as a catalyst in the manufacturing of biodiesel. To assess the acidity strength of the catalyst, NH 3 was used in a temperature-programmed desorption (NH 3 -TPD) experiment. Biodiesel was effectively produced from oleic acid and ethyl alcohol by the α-MoO 3 NBs. Response surface methodology (RSM) was employed in the experimental design and optimization to get the ideal circumstances. Important variables, including temperature, reaction time, catalyst dosage, reaction time, temperature, and the molar ratio of alcohol to fatty acid, were examined. The outcomes demonstrated that the biodiesel production might approach 85% at ideal temperatures of 75 °C, 50 min of reaction time, a 30:1 molar ratio of alcohol to oleic acid, and 0.007 g of catalyst. The results also showed no appreciable activity loss throughout the catalyst's efficient recovery and reuse for four cycles., Competing Interests: Declarations. Ethics approval: Not applicable. Consent to participate: All named authors declare that they participated in this work and that the manuscript is original and has not been copied from another source. Consent for publication: All the authors consented to the publication of this manuscript. Competing interests: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Glucose oxidase (GOx)-mediated starvation therapy is an effective tumor treatment that blocks energy and activates the immune response. However, the insufficient tumor immunogenicity and immunosuppressive tumor microenvironment (TME) limited its therapeutic efficacy. To address this, we have designed a multifunctional cascade gas-nanoreactor with a MnO 2 coating, which serves as an out gatekeeper to encapsulate both GOx and a carbon monoxide (CO) donor (denoted as GCM). Due to the protective effect of MnO 2 coating, GCM maintains better stability in normal physiological environments, enhancing the catalytic activity of GOx and minimizing toxic side effects. Upon accumulation in the tumor, the degradation of MnO 2 coating exposes the GOx enzyme, thereby initiating a cascade catalysis reaction to generate hydrogen peroxide (H 2 O 2 ) and release CO in the hypoxic conditions. Additionally, the released Mn 2+ reacts with H 2 O 2 to generate toxic hydroxyl radical (•OH) as chemodynamic therapy (CDT). The synergistic treatments of starvation therapy, CO gas therapy and CDT effectively kill cancer cells and amplify immunogenic cell death (ICD), maturing DC cells and activating anti-tumor immune response. Furthermore, the released CO increases M1 macrophages infiltration and reduces myeloid-derived suppressor cells (MDSCs) infiltration, thus reversing the immunosuppressive TME. This multifunctional gas-nanoreactor provides a strategy for CO gas generation to trigger a robust anti-tumor immune response and has the potential for clinical application in cancer immunotherapy. STATEMENT OF SIGNIFICANCE: A multifunctional cascade gas-nanoreactor with a MnO 2 gatekeeper was developed to perform synergistic treatments involving starvation therapy, CO gas therapy and chemodynamic therapy (CDT) for tumor elimination. The MnO 2 gatekeeper enhanced the catalytic activity of GOx within the nanoreactor by generating oxygen, thereby minimizing toxic side effects after intravenous injection. The gas-nanoreactor amplified ICD through synergistic treatments to mature DC cells and activate anti-tumor immune response. Furthermore, the released CO could reverse the immunosuppression of the TME to enhance cancer immunotherapy. The combination strategy utilizing the gas-nanoreactor demonstrates clinical potential for facilitating cancer immunotherapy., 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 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Manganese dioxide (MnO 2 ) with high theoretical capacitance and natural abundance has attracted great attention but is still challenging for use in supercapacitors, due to the limited conductivity and lower electron and ion migration. Here, a facile in situ growth strategy is developed to prepare heterostructural graphitized cellulose nanocrystal (GCNC)/MnO 2 with unblocked conductive networks through a hydrothermal reaction. The GCNC with highly ordered graphitic carbon layers as conductive support framework solves the agglomeration problem of MnO 2 and increases effective specific surface areas in contact with electrolyte ions. Meanwhile, the stable connection of MnOC covalent bonds enhances the interface bonding, which effectively reduces the contact resistance at the interface of heterostructural GCNC/MnO 2 and enhances the interface firmness. The resulting GCNC/MnO 2 electrode shows a remarkable specific capacitance of 528.2 F g -1 at 0.5 A g -1 . Furthermore, the symmetric supercapacitor based on GCNC/MnO 2 -15 mM exhibits high rate capability and excellent cycle stability of 100 % capacitance retention after 3000 cycles. This work provides a new path to designing high performance electrode material for sustainable energy technologies., 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 B.V. All rights reserved.)

In this study, two nanomaterials with excellent adsorption capacities were developed to remove heavy metals efficiently from wastewater. Manganese dioxide MnO 2 nanoparticles and iron oxide Fe 2 O 3 nanoparticles were successfully synthesized using cassava peel carbon and characterized by different techniques. The experimental tests for the adsorption process were done in a batch system, and the influence of various parameters such as temperature (from 5 to 60 °C), initial concentration (from 10 to 60 mg/L), pH (2 to 8), and contact time (5 to 180 min) on the biosorption of cobalt (II) and chromium (VI) were fully investigated. Furthermore, the Q max were 546.32 mg/g and 349.59 mg/g for chromium (VI) and cobalt (II) respectively. The results fitted Langmuir with the pseudo-second-order model, revealing that chemisorption controls heavy metals removal, while the thermodynamic sorption was an endothermic and spontaneous reaction. Artificial Neural Network (ANN) model was developed to predict as well as to simulate the experimental results, for this purpose, the proposed model was based on five independent inputs or variables and one output or response which is the predicted adsorbed amount, the proposed ANN model showed an appreciable prediction accuracy with high optimization ability for chromium (VI) and cobalt (II) removal., Competing Interests: Declaration of competing interest Competing interests are not applicable for this research study., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Potassium (K), urea (N), phosphate (P), and selenite (Se) are widely used in modern agriculture for improvement of crop yield and quality. However, traditional fertilizer suffers from poor fertilizer utilization efficiency and noncontrollable slow-release behavior. To improve nutrient utilization, we developed a layered double oxides-silica (LDO@Si) based on calcined Mg/Al layered double hydroxide-silica nanocomposites (LDH@Si), for slow release of K, N, P, and Se to crops. In this study, SEM, XRD, FT-IR, XPS, BET, and TGA were employed to analyze the structure, morphology, and microstructures of the samples. Results show that LDH@Si successfully transforms into LDO@Si after calcination, where LDO is mainly connected to silica via M-O-Si bonds. Furthermore, after K, P, and Se loading, the LDH@Si structure was successfully restored, indicating that phosphate and selenite ions have been effectively embedded in the inner layer of LDH. K ions are firmly fixed to the material surface via M-O-K bonds. After urea introducing, the pore structure of the material was completely filled, and excess urea formed a urea layer on the surface of the material. LDO@Si can continuously release nutrients into water through diffusion and LDO@Si dissolution for up to 240 h. Compared with chemical fertilizers, LDO@Si based slow-release fertilizer (CRSF2) significantly improves plant fresh weight, dry weight and chlorophyll content, increasing them by 13.91 %-23.13 %, 18.20 %-34.40 % and 2.24 %-14.81 %, respectively. Furthermore, a modest increase in the levels of nutrients N, P, and K is observed, while the Se concentration in plants treated with CRSF2 demonstrates significant enhancements of 9.57 %, 72.49 %, and 50.97 % compared to control treatments. These results illustrate the potential agricultural application of LDO@Si as a slow-release fertilizer for improving crop yields while minimizing the required amount of fertilizer., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Radiotherapy (RT)-mediated immune activation is insufficient for effective therapy of triple-negative breast cancer (TNBC) due to the immunosuppressive tumor microenvironment. Herein, we developed an oxygen self-supplying nanoradiosensitizer to activate immunogenic cell death (ICD) and the cGAS-STING signaling pathway, elevating the anti-tumor immune response and improving radioimmunotherapy for TNBC. The nanoradiosensitizer was fabricated using astragaloside liposome-encapsulated FePt alloy and MnO nanocrystals (ALFM). The ALFM targeted the glucose transporter-1 (GLUT-1) receptor in TNBC and effectively entered tumor cells. Subsequently, the ALFM responded to the weakly acidic tumor microenvironment and degraded, releasing FePt and Mn 2+ ions. The released Mn 2+ ions not only elevated cellular ROS levels via a Fenton-like reaction but also activated the cGAS-STING signaling pathway, which stimulated the anti-tumor immune response. In addition, the FePt alloy catalyzed a cascade reaction, producing ROS and O 2 in tumor cells, alleviating tumor hypoxia, and enhancing the RT effect. Besides, ROS-mediated cell damage induced the ICD effect in TNBC, promoted dendritic cell maturation and the infiltration of cytotoxic T lymphocytes, ultimately eliciting cancer immunotherapy. In vivo experimental results demonstrated that ALFM effectively activated the antitumor immune response and improved the radioimmunotherapy effect for TNBC. Overall, this work presents an effective strategy for enhanced radioimmunotherapy of TNBC., 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.)

This work presents a multi-step strategy to fabricate chitosan-derived nitrogen-doped carbon (CCS) and CCS/NiCo 2 O 4 (CNCO) aerogels for supercapacitor application. The various mass fractions of NiCo precursors and chitosan as well as different carbonization temperatures, were investigated. The best rationally designed aerogel carbonized at 300 °C (CNCO-2) had the highest specific surface area and nitrogen content. It exhibited a high capacitance of 1200 F g -1 at 1.0 A g -1 as an active electrode material for supercapacitors. In addition, the fully solid-state CCS//CNCO-2 device had a high capacitance of 172 F g -1 at 1.0 A g -1 and excellent cyclic stability (over 87 % capacitance retention after 10,000 cycles). This device displayed a maximum energy density of 53 Wh kg -1 at 750 W kg -1 . Furthermore, two devices connected in series and parallel indicate typical voltage and capacitance expansion, highlighting practicable applications of chitosan-derived aerogel composites to meet different requirements in energy storage., 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 B.V. All rights reserved.)

The physicochemical properties of manganese oxides and their different applications mainly depend upon their crystallite size, morphology, phase structure, and surface properties, which are again dependent on the preparation methods. So, a simple, cost-effective, and versatile synthesis method for such materials is highly desirable. Intending to accomplish this, herein we report the synthesis of Mn 3 O 4 nanostructures by alkaline hydrolysis of the corresponding metal ions in an aqueous medium. The addition of a biodegradable polymer, sodium salt of carboxymethyl cellulose (Na-CMC) assisted the development of specific morphology, which is tunable by varying the concentration of the biopolymer. The spectroscopic, microscopic, and diffractometric analyses of the synthesized Mn 3 O 4 nanostructures confirm that this particular simple technique is very effective in controlling the morphology of the formed nanostructures. These Mn 3 O 4 nanostructures exhibit excellent adsorption capacity in the removal of malachite green (MG) from its aqueous solution under ambient conditions. The adsorption process is exothermic following pseudo-second-order kinetics with a maximum dye adsorption capacity of 489.68 mg g -1 according to the Sips isotherm model. The Mn 3 O 4 nanostructures can be reused for up to five cycles of dye adsorption without significant loss of their adsorption performance., 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 B.V. All rights reserved.)

To establish an acid-etching protocol for Biodentine and Cimmo DTA, evaluating compressive strength, bond strength, surface morphology in scanning electron microscope and failure modes after different etching times. Two test specimens were prepared for each cement and divided into four groups (n = 12) according to the acid-etching time (0, 5, 10 and 15 s). Compressive strength was tested using a universal testing machine, while bond strength was evaluated after bonding with Filtek Bulk Flow resin using Universal ESPE Single Bond adhesive. Failures were classified as surface-adhesive, cement-cohesive, resin-cohesive and mixed. Biodentine showed significantly higher compressive strength than Cimmo DTA (p < 0.001), regardless of acid etch time (p < 0.001). Different acid-etching strategies are required for Biodentine and Cimmo DTA, with Biodentine requiring selective etching and Cimmo DTA requiring a full 15-s etch to optimise bond strength properties., (© 2024 Australian Society of Endodontology Inc.)

The development of new structural materials with thermal insulation properties is urgently need in the construction of smart buildings. Besides, there is a need to develop environmentally friendly and sustainable concrete mix designs. Lignosulfonate (LS) macromolecule and graphene oxide (GO) were used to prepare non-autoclaved aerated concrete (NAC). The addition of a complex GO/LS additive of the composition (0.16/0.0002 wt%) increased the compressive strength by 54 %, and bending strength by 45 % at the age of 28 days' strength gain. The addition of an effective complex GO/LS additive to NAC made it possible to achieve a reduction in water absorption by up to 63 % and thermal conductivity by up to 29 % in comparison. The thermal conductivity coefficient of such NAC specimens was 0.092 W/m·K with water absorption of 9 %. The options for the interactions of the GO/LS modifier with calcium hydroaluminates using the type of ion exchange were proposed. Thus, the introduction of GO/LS nano modifier contributed to high-quality filling of free areas of the cement mixture with mineral formations, which helpd to increase the strength of the aerated concrete and its durability., 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 B.V. All rights reserved.)

Metal oxide nanoparticles (MONPs) is one of the most effective materials for medical applications with their substantial surface metallic ions and high surface area-volume ratio. Over decades, MONPs have been considered potential treatments due to their demonstrated ability and reactivity to target diverse cellular signaling pathways implicated in antimicrobial effects, as well as in the amelioration of oxidative stress, inflammation, cancer progression, and glucose together with lipid dysregulation. Based on their unique characteristics, MONPs have shown to be biodegradable and biocompatible vehicles for drugs, which have recently been applied in drug delivery as nanocarriers to enhance their delivery capacity for mechanistic membrane transport. However, little is known about the precise cellular responses, molecular mechanisms, and potential use of MONPs in the medical field. This review emphasizes on elaborating the biochemical reactivities of MONPs on molecular and cellular reactions, highlighting the physiological responses, mechanisms of action, certain drawbacks, and remediation of these functionalized materials. The significant goal of this literature is to shed light on the new perspectives of MONPs in pre-clinical application to pursue for clinical research as alternative-personalized medicines to prevent individuals from drastic 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 © 2024 Elsevier Inc. All rights reserved.)

This study explores the metal oxide-mediated NH 4 + -N reduction process: manganese ammonia oxidation efficiency, influencing factors and its resistance to low-temperature environments in water bodies. After 177d of stabilized startup of an up-flow reactor, NH 4 + -N removal efficiency was 63.51 %, total nitrogen (TN) removal rate was 0.021 kg/(m 3 .d), and effluent Mn 2+ concentration was 1.503 mg/L, which was in dynamic equilibrium. X-ray photoelectron spectroscopy exhibited manganese valence state 3.29, similar to biological manganese oxidation. High-throughput sequencing revealed that phyla's denitrification function increased relative abundance, and manganese-reducing bacterial genera appeared. The batch test showed that 5 mg MnO 2 had NH 4 + -N removal at 85.01 %. After 44 days, NH 4 + -N removal efficiency was 77.47 %, effluent Mn 2+ concentration was 3.280 mg/L, TN removal rate was 0.063 kg/(m 3 .d). The long-term effect of the influent load change on the denitrification and Mnammox efficiency at 25 ∼ 15 °C was examined. Effluent Mn 2+ concentration was 1.811 mg/L was relatively stable. Manganese valence decreased from 3.29 to 3.20, Mn 4+ decreased by 9.58 %, while Mn 3+ and Mn 2+ increased by 10.94 % and 1.37 %, respectively. A new phylum Thermotogota and genus SBR1031 appeared in the microbial community., 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 Ltd. All rights reserved.)

The ammonium (NH 4 + ) removal efficiency in constructed wetlands (CWs) is often limited by insufficient oxygen. In this study, an extract of Eucalyptus robusta Smith leaves was used to prepare multivalent manganese oxides (MVMOs) as substrates, which were used to drive manganese oxide (MnO x ) reduction coupled to anaerobic NH 4 + oxidation (Mnammox). To investigate the effects and mechanisms of MVMOs on ammonium nitrogen (NH 4 + -N) removal, four laboratory-scale CWs (0 %/5 %/15 %/25 % volume ratios of MVMOs) were set up and operated as continuous systems. The results showed that compared to controlled C-CW (0 % MVMOs), Mn25-CW (25 % MVMOs) improved the average NH 4 + -N removal efficiency from 24.31 % to 80.51 %. Furthermore, N 2 O emissions were reduced by 81.12 % for Mn25-CW. Isotopic tracer incubations provided direct evidence of Mnammox occurrence in Mn-CWs, contributing to 18.05-43.64 % of NH 4 + -N removal, primarily through the N 2 -producing pathway (73.54-90.37 %). Notably, batch experiments indicated that Mn(III) played a predominant role in Mnammox. Finally, microbial analysis revealed the highest abundance of the nitrifying bacteria Nitrospira and Mn-cycling bacteria Pseudomonas, Geobacter, Anaeromyxobacter, Geothrix and Novosphingobium in Mn25-CW, corresponding to its superior NH 4 + -N removal efficiency. The enhancement of NH 4 + oxidation, first to hydroxylamine and then to nitrite, in Mn25-CW was attributed to the upregulation of ammonia monooxygenase genes (amoABC and hao). This study enhanced our understanding of Mnammox and provided further support for the use of manganese oxide substrates in CWs for efficient NH 4 + -N removal., 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 Ltd. All rights reserved.)

The self-cementation characteristics of arsenic (As)-contaminated soil were comprehensively investigated in this study. Different non-thermal plasma-irradiated binary (hydro)oxides of polyvalent ferromanganese (poly-Fe-Mn) were synthesized and exploratorily dispersed to soil samples to activate solidification and stabilization during the self-cemented process. The maximum compressive strength of 56.35 MPa and the lowest leaching toxicity of 0.004 mg/L were obtained in the proof test under optimal conditions (i.e., the mass ratio of the poly-Fe-Mn to the soil sample of 0.05; the mass ratio of the composite alkali activator (NaOH + CaO) to the soil sample of 0.25; the mass ratio of CaO to NaOH of 1.5; the mass ratio of the DI water to the binder of 0.515). The composite alkaline activator primarily contributed to the strength formation of the self-cemented matrix while the poly-Fe-Mn significantly influenced the reduction of the As-leaching toxicities. The poly-Fe-Mn maintained diffusion-controlled polycondensation and strengthened the nucleation process during self-cementation. The amount of water and the dosage of poly-Fe-Mn caused an interactive influence on the self-cemented solidification of contaminated soils. The solidified samples with poly-Fe-Mn exhibited better thermal decomposition than their counterparts, reflecting the enhancement of poly-Fe-Mn to the matrix. Some minerals including C-S-H, kaolinite, gehlenite, diopside sodian, augite, and albite were matched in the samples, directly demonstrating the geopolymerization-steered self-cementation of the As soil. The employment of poly-Fe-Mn not only reinforced the immobilization of As pollutants in the matrix but also induced the self-cementation of soils by intensifying the composite alkaline-activated geopolymerization kinetics., 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 Ltd. All rights reserved.)

The use of bio-based composites to enhance the methane production in anaerobic digestion has attracted considerable attention. Nevertheless, the study of electron transfer mechanisms and the applications of biochar/MnO 2 (MBC) in complex systems remains largely unexplored. Biochar composited with MnO 2 at 10:1 mass ratio (MBC10) increased the content of volatile fatty acids by 9.09 % during acidogenic phase. During the methanogenic experiments using acetate, cumulative methane production (CMP) rose by 5.83 %, and in the methanogenic experiments using food waste, CMP increased by 24.32 %. Microbial community analysis indicated an enrichment of Syntrophomonas, Bacilli, and Methanosaetaceae in the MBC10 group. This enrichment occurred mainly due to the redox capability of MnO 2 enhancing MBC capacitance, thereby facilitating microbial electron transfer processes. Additionally, under 2 g/L ammonia nitrogen concentration and 30 g/L organic load, the CMP of MBC10 increased by 12.74 % and 9.44 %, respectively, compared to the BC600 group. This study illuminates MBC's electron transfer mechanisms and applications, facilitating its wider practical adoption and fostering future innovations., 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 B.V. All rights reserved.)

This work examines the predicted stable halide perovskites' elastic, acoustical, and thermal characteristics. The work uses the Full Potential-Linearized Augmented Plane Wave (FP-LAPW) technique through PBE-GGA to compute compounds in the WIEN2K algorithm. The ELATE program for the evaluation of elastic tensors to plot 2D and 3D graphs was also used. The bulk modulus, Young's modulus, shear modulus, anisotropy factors, Cauchy pressure, Pugh's ratio, Poisson's ratio, Kleinman's parameter, Lame's coefficient, Vicker's hardness, sound velocities, Gruneisen parameter and even melting and Debye temperature were computed. The mechanical and elastic properties are reported for the first time for most of the compounds, demonstrating that the investigated HPs-aside from TlBeF 3 , BaAgBr 3 , and CsTcl 3 -are mechanically stable and exhibit weaker resistance against shear distortion than they do to unidirectional compression. The results of Poisson's, Pugh's, and Frantsevich's ratios data prove that all materials are ductile except SrLiF 3 . The estimated Poisson's ratio data indicates the metallic bonding nature of HPs, whereas only SrLiF 3 exhibits covalent behavior with ν = 0.23. Debye temperature for SrLiF 3 , ZnLiF 3 , ZnScF 3 , CsRhCl 3 , CsRuCl 3 , and CsBeCl 3 is greater than 200 K which signifies their hardness, thermal conductivity, and high sound velocities. The large melting temperature values, make them suitable for high-temperature industrial applications. The anharmonicity effect is highest for CaCuBr 3 (3.265) and lowest for SrLiF 3 (1.402). The current approach calculates elastic and mechanical properties, providing a practical understanding of various physical processes and enabling technology developers to utilize compounds in diverse applications., 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 current research studied how Fe 3 O 4 nanomaterials (NMs) and CaO 2 affect humification and Cr(VI) immobilization and reduction during the composting of oil-tea Camellia meal and Cr-contaminated soil. The results showed that Fe 3 O 4 NMs and CaO 2 successfully construct a Fenton-like reaction in this system. The excitation-emission matrix-parallel factor (EEM-PARAFAC) demonstrated that this Fenton-like treatment increased the generation of humic acids and accelerated the humification. Meantime, RES-Cr increased by 5.91 % and Cr(VI) decreased by 16.36 % in the treatment group with CaO 2 and Fe 3 O 4 NMs after 60 days. Moreover, the microbial results showed that Fe 3 O 4 NMs and CaO 2 could promote the enrichment of Cr(VI) reducing bacteria, e.g., Bacillus, Pseudomonas, and Psychrobacter, and promote Cr(VI) reduction. This study gives a novel view and theoretical reference to remediate Cr(VI) pollution through composting., 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 Ltd. All rights reserved.)

Sulfate-radical-mediated photocatalysis technology peroxymonosulfate (PMS) activation via visible light irradiation shows great promise for water treatment applications. However, its effectiveness largely depends on the bifunctional performance of photocatalysis and PMS activation provided by the catalysts. In this study, we successfully synthesized a novel S-scheme MoS 2 /Co 3 O 4 (MC) heterojunction composite by a hydrothermal method and employed it for the first time to activate PMS for ofloxacin (OFX) degradation under visible light irradiation. The MC-5/PMS/Vis system achieved an impressive 85.11% OFX degradation efficiency within 1 min and complete OFX removal within 15 min under optimal conditions, with an apparent first-order kinetics rate constant of 0.429 min -1 . Reactive species trapping experiments and electron spin resonance analysis identified 1 O 2 , h + , and •O 2 - as the primary active species responsible for OFX degradation. Photoelectrochemical analyses and density functional theory calculations indicated the formation of a built-in electric field between MoS 2 and Co 3 O 4 , which enhanced the separation and migration of photoinduced carriers. Additionally, the Co-Mo interaction further increased the yield of dominant reactive species, thereby boosting photocatalytic activity. This work underscores the potential of visible-light-assisted PMS-mediated photocatalysis using Co 3 O 4 -based catalysts for effective pollutant control., 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.)