Manganese dioxide (MnO2), renowned for its abundant natural crystal phases, emerges as a leading catalyst candidate for the degradation of pollutants. The relationship between its crystal phase and catalytic activity, particularly for periodate activation, has remained both ambiguous and contentious. This study delineates the influence of various synthetic MnO2 phase structures on their capabilities in catalyzing periodate-assisted pollutant oxidation. Five distinct MnO2 phase structures (α-, β-, γ-, δ-, and ε-MnO₂) were prepared and evaluated to activate periodate and degrade pollutants, following the sequence: α-MnO₂ > γ-MnO₂ > β-MnO₂ > ε-MnO₂ > δ-MnO₂. Through quenching experiments, electron paramagnetic resonance tests, and in situ electrochemical studies, we found an electron transfer-mediated process drive pollutant degradation, facilitated by a highly reactive metastable intermediate complex (MnO₂/PI*). Quantitative structure-activity relationship analysis further indicated that degradation efficiency is strongly associated with both the crystal phase and the Mn (IV) content, highlighting it as a key active site. Moreover, the α-MnO₂ phase demonstrated exceptional recycling stability, enabling an effective pollutant removal in a continuous flow packed-bed reactor for 168 h. Thus, α-MnO₂/PI proved highly effective in mineralizing organic pollutants and reducing their toxicities, highlighting its significant potential for environmental remediation.

The energy densities of conventional aqueous batteries are often unsatisfactory due to the limited capacities of electrode materials.Therefore, the design of creative aqueous batteries has to be considered. Herein, aqueous S-MnO2 batteries are constructed by matching S/Cu2S redox couples and MnO2 deposition/dissolution. In such batteries, S/Cu2S redox couples undergo the solid-solid conversion reaction with four-electron transfer, ensuring a high specific capacity of 2220 mAh g-1 in S anodes.Furthermore, the conversion reaction of S/Cu2S redox couples can take place stably in acidic electrolyte that is essential for the MnO2 deposition/dissolution. As a result, the S/Cu2S redox couples can match MnO2 deposition/dissolution well, which endow the batteries with a membrane-free configuration. As a proof of concept,  Ah-level prismatic and single-flow batteries were assembled and could operate stably for over 1000 h, demonstrating their great potential for large-scale energy storage. This work broadens the horizons of aqueous batteries beyond metal-manganese chemistry.

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 (MnO2 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, MnO2-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 MnO2 NPs in MnO2-DOX@mT/OMVs can generate potent CDT by accelerating the Fenton-like reaction with DOX-generated H2O2 and achieving glutathione (GSH)-depletion-induced glutathione peroxidase 4 (GPX4) inactivation. These results showed that MnO2-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.

Mildly-acidic MnO2-Zn batteries are considered as a promising alternative for large-scale energy storage systems for their low toxicity, high safety, and low cost. Though, the degradation of MnO2 with cycling still hinders the further development of the batteries. In this study, it is observed that the decrease in available capacity of MnO2 with charge and discharge is accompanied by a structural transformation with the emergence of Zn─Mn─O phases. An electrodeposition test indicates that the Zn─Mn─O phase is formed from a co-precipitation of Zn and Mn during the charge process. Further, the structural change of MnO2 is suppressed and its cycle stability is improved with the addition of TiOSO4 as a facile electrolyte additive. As a result, under a current of 1200 mA g-1, the MnO2 electrode still gives a capacity of 230 mAh g-1 for over 1500 cycles. Capacity retention is 75% after 10 000 cycles under a current rate of 4800 mA g-1. These findings provide fundamental insights on the degradation mechanism of MnO2 and a new strategy to improve the electrochemical performance of aqueous MnO2-Zn batteries.

MnO2/polypyrrole (PPy) composite films were deposited on fluorine-doped tin oxide (FTO) conductive glasses by a two-step wet-chemical method, including electrochemical deposition and chemical bath deposition (CBD). The porous MnO2 films were first grown on FTO glasses by an electrodeposition method. Second, polypyrrole nanoparticles were polymerized by the oxidation-reduction reaction between MnO2 and pyrrole, using the presynthesized MnO2 as the skeleton. Then, MnO2/PPy composite films with coral-like structures were obtained. The electrochemical and electrochromic (EC) properties of the prepared films were investigated. The results show that, compared to the single MnO2 or PPy film, the MnO2/PPy composite film has a larger optical modulation (67.3% at a wavelength of 900 nm), faster response times (4 s for coloration and 3 s for bleaching), and a higher coloration efficiency (218.16 cm2·C-1). The high coloration efficiency attests to the exceptional performance of the composite film in converting electrical signals into vivid color changes. The electrochemical stability test results show that the composite film maintains a stable EC performance after 200 coloration/bleaching cycles. The coral-like structures of the composite film are responsible for the better EC properties.

Ferroptosis-related tumor therapy based on nanomedicines has recently gained significant attention. However, the therapeutic performance is still hindered by the tumor\'s physical barriers such as the fibrotic tumor matrix and elevated interstitial fluid pressure, as well as chemical barriers like glutathione (GSH) overabundance. These physicochemical barriers impede the bioavailability of nanomedicines and compromise the therapeutic efficacy of lipid reactive oxygen species (ROS). Thus, this study pioneers a manganese-mediated overcoming of physicochemical barriers in the tumor microenvironment using organosilica-based nanomedicine (MMONs), which bolsters the synergy of photothermal-ferroptosis treatment. The MMONs display commendable proficiency in overcoming tumor physical barriers, due to their MnO2-mediated shape-morphing and softness-transformation ability, which facilitates augmented cellular internalization, enhanced tumor accumulation, and superior drug penetration. Also, the MMONs possess excellent capability in chemical barrier overcoming, including MnO2-mediated dual GSH clearance and enhanced ROS generation, which facilitates ferroptosis and heat shock protein inhibition. Notably, the resulting integration of physical and chemical barrier overcoming leads to amplified photothermal-ferroptosis synergistic tumor therapy both in vitro and in vivo. Accordingly, the comparative proteomic analysis has identified promoted ferroptosis with a transient inhibitory response observed in the mitochondria. This research aims to improve treatment strategies to better fight the complex defenses of tumors.

This study aimed to synthesize, characterize, and evaluate the effect of cocamidopropyl betaine-stabilized MnO2 nanoparticles (NPs) on the germination and development of pea seedlings. The synthesized NPs manifested as aggregates ranging from 50-600 nm, comprising spherical particles sized between 19 to 50 nm. These particles exhibited partial crystallization, indicated by peaks at 2θ = 25.37, 37.62, 41.18, 49.41, 61.45, and 65.79°, characteristic of MnO2 with a tetragonal crystal lattice with a I4/m spatial group. Quantum chemical modelling showed that the stabilization process of MnO2 NPs with cocamidopropyl betaine is energetically advantageous (∆E > 1299.000 kcal/mol) and chemically stable, as confirmed by the positive chemical hardness values (0.023 ≤ η ≤ 0.053 eV). It was revealed that the interaction between the MnO2 molecule and cocamidopropyl betaine, facilitated by a secondary amino group (NH), is the most probable scenario. This ascertain is supported by the values of the difference in total energy (∆E = 1299.519 kcal/mol) and chemical hardness (η = 0.053 eV). These findings were further confirmed using FTIR spectroscopy. The effect of MnO2 NPs at various concentrations on the germination of pea seeds was found to be nonlinear and ambiguous. The investigation revealed that MnO2 NPs at a concentration of 0.1 mg/L resulted in the highest germination energy (91.25%), germinability (95.60%), and lengths of roots and seedlings among all experimental samples. However, an increase in the concentration of preparation led to a slight growth suppression (1-10 mg/L) and the pronounced inhibition of seedling and root development (100 mg/L). The analysis of antioxidant indicators and phytochemicals in pea seedlings indicated that only 100 mg/L MnO2 NPs have a negative effect on the content of soluble sugars, chlorophyll a/b, carotenoids, and phenols. Conversely, lower concentrations showed a stimulating effect on photosynthesis indicators. Nevertheless, MnO2 NPs at all concentrations generally decreased the antioxidant potential of pea seedlings, except for the ABTS parameter. Pea seedlings showed a notable capacity to absorb Mn, reaching levels of 586.5 μg/L at 10 mg/L and 892.6 μg/L at 100 mg/L MnO2 NPs, surpassing the toxic level for peas according to scientific literature. However, the most important result was the observed growth-stimulating activity at 0.1 mg/L MnO2 NPs stabilized with cocamidopropyl betaine, suggesting a promising avenue for further research.

Manganese dioxide (MnO2), as a catalyst in composting processes, can accumulate in soil over multiple fertilizations. However, its impact on crop growth remains to be explored. In this study, a pot experiment was conducted to investigate the impacts of MnO2 on the tomato plant performance across various growth stages. Results showed that MnO2 reduced the plant height, leaf number and length by 35.53 %, 27.61 %, and 37.00 %, respectively, and decreased the fruit weight (23.16 %) and sugar-acid ratio (29.7 %) of fruits compared to the MnO2-free control. The adverse impacts of MnO2 on plant growth might be attributed to the inhibition of microbial activity in soil reflected by the reduction of soil urease (9.30 %) and acid phosphatase (12.52 %) activities, which decreased the efficiency of nutrients conversion and uptake. The decrease of nutrient elements in roots resulted in oxidative stress in the plant, inhibiting the plasma membrane H+-ATPase activity thereby reducing the translocation of nutrients (e.g., calcium, magnesium, and phosphorus) translocation from roots to leaves. Furthermore, the phytohormones indolebutyric acid, gibberellin, and jasmonic acid of leaves were disturbed. This study reveals the risks associated with the application of MnO2-containing organic fertilizers.

Intervertebral disc degeneration (IVDD) is a worldwide disease that causes low back pain and reduces quality of life. Biotherapeutic strategies based on tissue engineering alternatives, such as intervertebral disc scaffolds, supplemented by drug-targeted therapy have brought new hope for IVDD. In this study, to explore the role and mechanism of MnO2/GelMA composite hydrogels in alleviating IVDD, we prepared composite hydrogels with MnO2 and methacrylate gelatin (GelMA) and characterized them using compression testing and transmission electron microscopy (TEM). Annulus fibrosus cells (AFCs) were cultured in the composite hydrogels to verify biocompatibility by live/dead and cytoskeleton staining. Cell viability assays and a reactive oxygen species (ROS) probe were used to analyze the protective effect of the composite hydrogels under oxidative damage. To explore the mechanism of improving the microenvironment, we detected the expression levels of antioxidant and autophagy-related genes and proteins by qPCR and Western blotting. We found that the MnO2/GelMA composite hydrogels exhibited excellent biocompatibility and a porous structure, which promoted cell proliferation. The addition of MnO2 nanoparticles to GelMA cleared ROS in AFCs and induced the expression of antioxidant and cellular autophagy through the common SIRT1/NRF2 pathway. Therefore, the MnO2/GelMA composite hydrogels, which can improve the disc microenvironment through scavenging intracellular ROS and resisting oxidative damage, have great application prospects in the treatment of IVDD.

The aim of this study was to assess effects of MnO2 addition (CK-0%, T1-2% and T2-5%) on humification and bacterial community during municipal sludge (MS) composting. The results suggested that MnO2 addition inhibited the growth of Nitrospira but stimulated Nonomuraea, Actinomadura, Streptomyces and Thermopolyspora, facilitating the lignocellulose degradation and humification with the increase in organic matter degradation by 13.8%-19.2% and humic acid content by 10.9%-20.6%. Compared to CK, the abundances of exoglucanase (EC:3.2.1.91), endo-1,4-beta-xylanase (EC:3.2.1.136) and endomannanase (EC:3.2.1.78) increased by 88-99, 52-66 and 4-15 folds, respectively. However, 5%-MnO2 induced the enrichment of Mizugakiibacter that harms the environment of agricultural production. The addition of 2%-MnO2 was recommended for MS composting. Furthermore, metabolic function analysis indicated that MnO2 addition altered amino acid and carbohydrate metabolism, especially enhancing propanoate metabolism and butanoate metabolism but inhibiting citrate cycle. Structural equation modeling revealed that Nonomuraea and Actinomadura were the main drivers for lignocellulose degradation. This study provided theoretical guidance in regulating humification via MnO2 for MS composting.