Sensitive colorimetric detection of heparin using reverse modulation of peroxidase- and oxidase-mimetic activities in Fe3O4@PDA@MnO2 nanocomposites.

Heparin, a widely studied glycosaminoglycan, plays crucial roles in the regulation of various physiological and pathological processes. Therefore, it's important to develop highly selective and sensitive methods for convenient monitoring of heparin levels in biological systems. We report the design and synthesis of Fe3O4@PDA@MnO2 nanoparticles (FPM-NPs), which exhibit dual enzymatic activities, enabling quantitative detection of heparin. The FPM-NPs feature a unique tri-layer spherical shell structure, possessing both peroxidase-like and oxidase-like activities, and catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence or absence of H2O2. Remarkably, upon co-incubated with heparin, the oxidase activity of FPM-NPs decreases, while the peroxidase activity increases. By leveraging these dual enzymatic properties of FPM-NPs, a highly sensitive and specific colorimetric detection of heparin is achieved, with a detection limit reaching 6.51 nM and a good linear response to quantify heparin ranging 10-800 nM. Additionally, the developed FPM-NPs are successfully applied to measure heparin in fetal bovine serum samples. We also extend this detection method to a paper-based chip, enabling portable detection of heparin through grayscale analysis of mobile phone photographs. The multi-nanozyme-based heparin detection approach provides a new perspective for future research on expanding the application of nanocomposite materials in biomedical detection and analysis.

Rational design of Ag-doped MnFe2O4/HNTs for peroxidase-mimicking activity and colorimetric sensing of uric acid in human serum.

Mimicking enzyme have significantly advanced sensing assays by replicating native enzyme functions, yet achieving both high catalytic activity and easy recyclability remains a challenge. In this study, Ag-doped MnFe2O4/halloysite nanotubes (HNTs) were rationally designed as a novel nanozyme by depositing in-situ Ag and MnFe2O4 nanoparticles onto HNTs. The resulting nanocomposite exhibited excellent peroxidase-like activity along with magnetic properties. Leveraging these features, a highly efficient and sensitive colorimetric system for detecting uric acid (UA) was developed. The Ag-doped MnFe2O4/HNTs catalyzed the oxidation of 3,3',5,5'-tetramethylbenzidine in the presence of H2O2, causing a color change from colorless to blue. The system showed a linear absorbance response to UA concentrations ranging from 1 to 20 µM, with a detection limit of 59 nM. Mechanistic studies revealed that reactive oxygen species intermediates (1O2) were generated through the decomposition of H2O2, leading to peroxidase-like activity in the Ag-doped MnFe2O4/HNTs. The assay was successfully applied to detect UA in human serum with recoveries over 99.68 %. This study indicates the successful application of Ag-doped MnFe2O4/HNTs for colorimetric UA detection in human serum. This research introduces a novel approach for designing recyclable, high-performance mimicking enzyme and establishes an effective colorimetric sensing platform for UA detection in human serum.

Interfacial interaction mechanism between Mn doped highly conjugated biochar and berberine hydrochloride.

MnSO4-modified biochar (Mn-BC) was synthesized to remove berberine hydrochloride (BH) from wastewater by utilizing tea waste as raw material and MnSO4 as modifier. Brunel Emmett Taylor (BET) analysis reveals that the specific surface area (SSA) and average pore size (Dave) of Mn-BC are 1.4 and 7 times higher than those of pristine biochar apart, attributing to the dissociation effect can promote the dispersion of MnSO4 in the pores of the biochar. Meanwhile, the doping of Mn not only introduces additional oxygen-containing functional groups (OCFGs), but also modulates the π electron density. Furthermore, Response surface method (RSM) analysis reveals that Mn-BC dosage has the most significant effect on BH removal, followed by BH concentration and pH value. Kinetic and isothermal studies reveal that the BH adsorption process of Mn-BC was mainly dominated by chemical and monolayer adsorption. Meanwhile, density functional theory (DFT) calculations confirm the contribution of Mn doping to the conjugation effect in the adsorption system. Originally proposed Mn-BC is one potentially propitious material to eliminate BH from wastewater, meanwhile this also provides a newfangled conception over the sustainable utilization of tea waste resources.

Bamboo-like MnO2⋠Co3O4: High-performance catalysts for the oxidative removal of toluene.

The manganese-cobalt mixed oxide nanorods were fabricated using a hydrothermal method with different metal precursors (KMnO4 and MnSO4·H2O for MnOx and Co(NO3)2⋅6H2O and CoCl2⋅6H2O for Co3O4). Bamboo-like MnO2⋅Co3O4 (B-MnO2⋅Co3O4 (S)) was derived from repeated hydrothermal treatments with Co3O4@MnO2 and MnSO4⋅H2O, whereas Co3O4@MnO2 nanorods were derived from hydrothermal treatment with Co3O4 nanorods and KMnO4. The study shows that manganese oxide was tetragonal, while the cobalt oxide was found to be cubic in the crystalline arrangement. Mn surface ions were present in multiple oxidation states (e.g., Mn4+ and Mn3+) and surface oxygen deficiencies. The content of adsorbed oxygen species and reducibility at low temperature declined in the sequence of B-MnO2⋅Co3O4 (S) > Co3O4@MnO2 > MnO2 > Co3O4, matching the changing trend in activity. Among all the samples, B-MnO2⋅Co3O4 (S) showed the preeminent catalytic performance for the oxidation of toluene (T10% = 187°C, T50% = 276°C, and T90% = 339°C). In addition, the B-MnO2⋅Co3O4 (S) sample also exhibited good H2O-, CO2-, and SO2-resistant performance. The good catalytic performance of B-MnO2⋅Co3O4 (S) is due to the high concentration of adsorbed oxygen species and good reducibility at low temperature. Toluene oxidation over B-MnO2⋅Co3O4 (S) proceeds through the adsorption of O2 and toluene to form O*, OH*, and H2C(C6H5)* species, which then react to produce benzyl alcohol, benzoic acid, and benzaldehyde, ultimately converting to CO2 and H2O. The findings suggest that B-MnO2⋅Co3O4 (S) has promising potential for use as an effective catalyst in practical applications.

Synthesis of δ-MnO2 via ozonation routine for low temperature formaldehyde removal.

Nowadays, it is still a challenge to prepared high efficiency and low cost formaldehyde (HCHO) removal catalysts in order to tackle the long-living indoor air pollution. Herein, δ-MnO2 is successfully synthesized by a facile ozonation strategy, where Mn2+ is oxidized by ozone (O3) bubble in an alkaline solution. It presents one of the best catalytic properties with a low 100% conversion temperature of 85°C for 50 ppm of HCHO under a GHSV of 48,000 mL/(g·hr). As a comparison, more than 6 times far longer oxidation time is needed if O3 is replaced by O2. Characterizations show that ozonation process generates a different intermediate of tetragonal ß-HMnO2, which would favor the quick transformation into the final product δ-MnO2, as compared with the relatively more thermodynamically stable monoclinic γ-HMnO2 in the O2 process. Finally, HCHO is found to be decomposed into CO2 via formate, dioxymethylene and carbonate species as identified by room temperature in-situ diffuse reflectance infrared fourier transform spectroscopy. All these results show great potency of this facile ozonation routine for the highly active δ-MnO2 synthesis in order to remove the HCHO contamination.

Targeted nanoprobe for magnetic resonance imaging-guided enhanced antitumor via synergetic photothermal/immunotherapy.

Synergistic photothermal/immunotherapy has garnered significant attention for its potential to enhance tumor therapeutic outcomes. However, the fabrication of an intelligent system with a simple composition that simultaneously exerts photothermal/immunotherapy effect and imaging guidance function still remains a challenge. Herein, a glutathione (GSH)-responsive theranostic nanoprobe, named HA-MnO2/ICG, was elaborately constructed by loading photothermal agent (PTA) indocyanine green (ICG) onto the surface of hyaluronic acid (HA)-modified manganese dioxide nanosheets (HA-MnO2) for magnetic resonance (MR) imaging-guided synergetic photothermal/immuno-enhanced therapy. In this strategy, HA-MnO2 nanosheets were triggered by the endogenous GSH in tumor microenvironment to generate Mn2+ for MR imaging, where the longitudinal relaxation rate of HA-MnO2/ICG was up to 14.97 mM-1s-1 (∼24 times than that found in a natural environment), demonstrating excellent intratumoral MR imaging. Moreover, the HA-MnO2/ICG nanoprobe demonstrates remarkable photothermal therapy (PTT) efficacy, generating sufficient heat to induce immunogenic cell death (ICD) within tumor cells. Meanwhile the released Mn2+ ions from the nanosheets function as potent immune adjuvants, amplifying the immune response against cancer. In vivo experiments validated that HA-MnO2/ICG-mediated PTT was highly effective in eradicating primary tumors, while simultaneously enhancing immunogenicity to prevent the growth of distal metastasis. This hybrid HA-MnO2/ICG nanoprobe opened new avenues in the design of MR imaging-monitored PTT/immuno-enhanced synergistic therapy for advanced cancer.

Photothermal-catalytic activation periodate over MnO2/g-C3N4 S-scheme heterojunction for rapidly tetracycline removal: intermediates, toxicity evaluation and mechanism.

The MnO2/CN S-scheme heterojunctions were prepared using the hydrothermal method, which significantly promoted periodate (PI) activation for the TC removal. Notably, the MnO2/CN-0.1 achieved a TC removal rate of 79.7 % within 25 min in the PI/Vis system, which was 1.39 and 3.68 times that of MnO2 and g-C3N4, respectively. The improved TC degradation performance could be attributed to the synergetic effect of photothermal effect of MnO2 and the S-scheme heterojunction. On the basis of the infrared thermography images, the photothermal properties of MnO2 could increase temperatures of the reaction system, leading to the promotion of the PI activation. The formation of the MnO2/CN S-scheme not only effectively suppressed charge recombination, but also facilitated the Mn(IV)/Mn(III) redox cycle within the reaction. Under different pH and anion conditions, the MnO2/CN-0.1/PI system exhibited excellent capability in TC removal. Additionally, the toxicity of the degraded solution was evaluated based on the LC-MS test results and the growth experiment of Mung bean seeds. This work put forward an efficient approach on S-scheme photothermal catalysts to achieve efficient utilization of PI on TC degradation, which demonstrates a promising method for photothermal assistance PI activation to remediate the water environment efficiently.

Co-doped cryptomelane-type manganese oxide in situ grown on a nickel foam substrate for high humidity ozone decomposition.

Monolithic catalysts with excellent O3 catalytic decomposition performance were prepared by in situ loading of Co-doped KMn8O16 on the surface of nickel foam. The triple-layer structure with Co-doped KMn8O16/Ni6MnO8/Ni foam was grown spontaneously on the surface of nickel foam by tuning the molar ratio of KMnO4 to Co(NO3)2·6H2O precursors. Importantly, the formed Ni6MnO8 structure between KMn8O16 and nickel foam during in situ synthesis process effectively protected nickel foam from further etching, which significantly enhanced the reaction stability of catalyst. The optimum amount of Co doping in KMn8O16 was available when the molar ratio of Mn to Co species in the precursor solution was 2:1. And the Mn2Co1 catalyst had abundant oxygen vacancies and excellent hydrophobicity, thus creating outstanding O3 decomposition activity. The O3 conversion under dry conditions and relative humidity of 65%, 90% over a period of 5 hr was 100%, 94% and 80% with the space velocity of 28,000 hr-1, respectively. The in situ constructed Co-doped KMn8O16/Ni foam catalyst showed the advantages of low price and gradual applicability of the preparation process, which provided an opportunity for the design of monolithic catalyst for O3 catalytic decomposition.

Investigation into enhanced performance of toluene and Hg0 stimulative abatement over Cr-Mn oxides co-modified columnar activated coke.

In this study, a string of Cr-Mn co-modified activated coke catalysts (XCryMn1-y/AC) were prepared to investigate toluene and Hg0 removal performance. Multifarious characterizations including XRD, TEM, SEM, in situ DRIFTS, BET, XPS and H2-TPR showed that 4%Cr0.5Mn0.5/AC had excellent physicochemical properties and exhibited the best toluene and Hg0 removal efficiency at 200℃. By varying the experimental gas components and conditions, it was found that too large weight hourly space velocity would reduce the removal efficiency of toluene and Hg0. Although O2 promoted the abatement of toluene and Hg0, the inhibitory role of H2O and SO2 offset the promoting effect of O2 to some extent. Toluene significantly inhibited Hg0 removal, resulting from that toluene was present at concentrations orders of magnitude greater than mercury's or the catalyst was more prone to adsorb toluene, while Hg0 almost exerted non-existent influence on toluene elimination. The mechanistic analysis showed that the forms of toluene and Hg0 removal included both adsorption and oxidation, where the high-valent metal cations and oxygen vacancy clusters promoted the redox cycle of Cr3+ + Mn3+/Mn4+ ↔ Cr6+ + Mn2+, which facilitated the conversion and replenishment of reactive oxygen species in the oxidation process, and even the CrMn1.5O4 spinel structure could provide a larger catalytic interface, thus enhancing the adsorption/oxidation of toluene and Hg0. Therefore, its excellent physicochemical properties make it a cost-effective potential industrial catalyst with outstanding synergistic toluene and Hg0 removal performance and preeminent resistance to H2O and SO2.

Enhancing ozone catalytic decomposition through acid treatment of α-MnO2 for improved activity and humidity resistance.

Post-etching method using dilute acid solutions is an effective technology to modulate the surface compositions of metal-oxide catalysts. Here the α-MnO2 catalyst treated with 0.1 mol/L nitric acid exhibits higher ozone decomposition activity at high relative humidity than the counterpart treated with acetic acid. Besides the increases in surface area and lattice dislocation, the improved activity can be due to relatively higher Mn valence on the surface and newly-formed Brønsted acid sites adjacent to oxygen vacancies. The remnant nitro species deposited on the catalyst by nitric acid treatment is ideal hydrophobic groups at ambient conditions. The decomposition route is also proposed based on the DRIFTS and DFT calculations: ozone is facile to adsorb on the oxygen vacancy, and the protonic H of Brønsted acid sites bonds to the terminal oxygen of ozone to accelerate its cleavage to O2, reducing the reaction energy barrier of O2 desorption.

Neuroprotective effects of punicalagin and/or micronized zeolite clinoptilolite on manganese-induced Parkinson's disease in a rat model: Involvement of multiple pathways.

BACKGROUND: Manganism, a central nervous system dysfunction correlated with neurological deficits such as Parkinsonism, is caused by the substantial collection of manganese chloride (MnCl2) in the brain. OBJECTIVES: To explore the neuroprotective effects of natural compounds, namely, micronized zeolite clinoptilolite (ZC) and punicalagin (PUN), either individually or in combination, against MnCl2-induced Parkinson's disease (PD). METHODS: Fifty male albino rats were divided into 5 groups (Gps). Gp I was used as the control group, and the remaining animals received MnCl2 (Gp II-Gp V). Rats in Gps III and IV were treated with ZC and PUN, respectively. Gp V received both ZC and PUN as previously reported for the solo-treated plants. RESULTS: ZC and/or PUN reversed the depletion of monoamines in the brain and decreased acetyl choline esterase activity, which primarily adjusted the animals' behavior and motor coordination. ZC and PUN restored the balance between glutamate/γ-amino butyric acid content and markedly improved the brain levels of brain-derived neurotrophic factor and nuclear factor erythroid 2-related factor 2/heme oxygenase-1 and decreased glycogen synthase kinase-3 beta activity. ZC and PUN also inhibited inflammatory and oxidative markers, including nuclear factor kappa-light-chain-enhancer of activated B cells, Toll-like receptor 4, nucleotide-binding domain, leucine-rich-containing family, pyrin domain-containing-3 and caspase-1. Bcl-2-associated X-protein and B-cell leukemia/lymphoma 2 protein (Bcl-2) can significantly modify caspase-3 expression. ZC and/or PUN ameliorated PD in rats by decreasing the levels of endoplasmic reticulum (ER) stress markers (p-protein kinase-like ER kinase (PERK), glucose-regulated protein 78, and C/EBP homologous protein (CHOP)) and enhancing the levels of an autophagy marker (Beclin-1). DISCUSSION AND CONCLUSION: ZC and/or PUN mitigated the progression of PD through their potential neurotrophic, neurogenic, anti-inflammatory, antioxidant, and anti-apoptotic activities and by controlling ER stress through modulation of the PERK/CHOP/Bcl-2 pathway.

Adsorption of Congo red on magnetic cobalt-manganese ferrite nanoparticles: Adsorption kinetic, isotherm, thermodynamics, and electrochemistry.

Magnetic Co0.5Mn0.5Fe2O4 nanoparticles were successfully prepared via the combustion and calcination process, with an average particle diameter of 31.5 nm and a saturation magnetization of 25.25 emu·g-1, they were employed to adsorbe Congo red (CR) from wastewater, the Pseudo-second-order kinetic and Freundlich isotherm were consistent with the adsorption data, indicating that their adsorption was a multilayer chemisorption process, the thermodynamic investigation showed that the adsorption was a favored exothermic process. The ionic strength of Cl- in CR solution had no obvious effect on the adsorption efficiency of Co0.5Mn0.5Fe2O4 nanoparticles, and the maximum adsorbance was 58.3 mg·g-1 at pH 2, decreasing as the pH of the CR solutions increased from 2 to 12. The ion leaching experiment and XRD demonstrated that Co0.5Mn0.5Fe2O4 nanoparticles had excellent stability, and the relative removal rate was 93.85% of the first time after 7 cycles. Cyclic voltammetry and electrochemical impedance spectroscopy demonstrated that CR was adsorbed onto Co0.5Mn0.5Fe2O4 nanoparticles, and the electrical conductivity of Co0.5Mn0.5Fe2O4 nanoparticles decreased after adsorption of CR. Magnetic Co0.5Mn0.5Fe2O4 nanoparticles displayed a promising application in wastewater treatment.

Biomineralization Synthesis of HoMn Nanoparticles for Ultrahigh-Field-Tailored and T1-T2 Dual-Mode MRI-Guided Cancer Theranostics.

Ultrahigh field magnetic resonance imaging (UHF-MRI) (≥7 T) can dramatically boost image resolution and signal-to-noise ratio, which have distinct advantages in multifunctional imaging. However, their research and application are currently limited by the absence of high-field contrast agents (CAs) and the low sensitivity and accuracy of T1/T2 single-modality CAs. Therefore, the development of T1-T2 dual-mode CAs that respond to UHF-MRI and nanoformulations with therapeutic sensitization can bring ideas for the integrated application of precise and synchronous tumor theranostics. Herein, we present a biomimetic mineralization strategy for synthesizing holmium/manganese oxide-bovine serum albumin-photosensitizer chlorin e6 nanohybrids. The hybrid nanoparticles exhibited better tumor accumulation, a suitable time imaging window, and excellent pH-response T1-T2 dual-mode UHF-MRI performance. The antitumor effect comes from the amelioration of the hypoxic tumor microenvironment to promote the synergistic effect of photodynamic therapy and radiotherapy, along with negligible acute toxicity. Undoubtedly, this work not only provides a different perspective for developing multifunctional nanotherapeutics but also promotes the potential clinical exploitation and translation of UHF CAs.

Highly integrated, self-powered and activatable bipedal DNA nanowalker for imaging of base excision repair in living cells.

DNA walkers have attracted considerable attention in biosensing and bioimaging. Compared with the conventional single leg-based DNA walker, the bipedal DNA walker has remarkable advantages, with improved sensitivity and fast kinetics, and can work efficiently in a crowded cellular environment. However, most reported bipedal DNA walkers are powered by exogenous supplementation, and elaborate DNA sequence designs, auxiliary additives or extra carriers are often needed. A highly integrated bipedal DNA walker that can address robustness, sensitivity and consistency issues in a single system is highly desirable but remains a great challenge. We herein report a novel bipedal DNA nanowalker system through simple assembly of a DNA substrate, hairpin functionalized-AuNPs (AuNPs-H2), and a blocked Mn2+-dependent DNAzyme hairpin (H1) on degradable MnO2 nanosheets, which holds great potential for living cell operation. Highly integrated features enable the simultaneous delivery of core components of the bipedal DNA walker, including a walking track (AuNPs-H2), a walking strand (H1 cleaved by APE1), and a driving force (Mn2+-dependent DNAzyme cleavage) as a whole, thereby enhancing the control of the spatiotemporal distribution of these components at the intracellular target sites. The redox reaction between the MnO2 nanosheets and GSH inside the cells not only consumed the intracellular GSH to improve the biostability of the walking track but also generated abundant Mn2+ as a cofactor of the DNAzyme. As a proof of concept, the developed nanowalker was demonstrated to work efficiently for monitoring base excision repair (BER)-related human apurinic/apyrimidinic endonuclease 1 (APE1) in living cells, highlighting the great potential of the bipedal DNA nanowalker in biological systems.

A molecularly imprinted electrochemiluminescence sensor based on mimic enzyme ZIF-90 and MnO2/g-C3N4 magnetic particles for detection of methidathion.

Methidathion (MTDT), a common organophosphorus pesticide with high insecticidal activity, is widely used for pest control. However, the misuse of MTDT leads to widespread residues and endangers human health. Therefore, it is crucial to develop a simple and highly sensitive method for the detection of MTDT residues. Herein, ZIF-90/MnO2/g-C3N4/Fe3O4 composite particles were synthesized: The  MnO2 nanosheets could absorb the energy of the excited g-C3N4 to quench the ECL of g-C3N4 while ZIF-90 acted as a mimetic enzyme to catalyze the formation of thiocholine from MTDT. The thiocholine caused the reduction of MnO2 to Mn2+, restoring the ECL signal of g-C3N4. Combined with molecular imprinting technique, an electrochemiluminescence sensor was constructed for the determination of MTDT. The determination range was 1.00 × 10-9 ~ 7.00 × 10-7 g/L, and the detection limit was 6.58 × 10-10 g/L. Structurally similar organophosphorus pesticides showed no cross-reactivity. The method has high sensitivity and specificity, and has been successfully applied to the determination of MTDT residue in fruits with recoveries in the range 93.75% ~ 102.37%.

Investigation of the Antibacterial Properties of Janus Micromotors Catalytic Propelled by Manganese Dioxide and Hydrogen Peroxide to Reduce Bacterial Density.

Between 2015 and 2017, 90% of Chinese adults were reported to have periodontitis of varying degrees, highlighting the importance of novel, inexpensive, and affordable treatments for the public. The fact that more and more pathogens are becoming resistant to antibiotics further highlights this prevalence. This article addresses a novel micromotor capable of generating reactive oxygen species, as proven by a Fenton-like reaction. Such reactions allow the targeting of Gram-negative bacteria such as Escherichia coli, which are eliminated order of magnitude more effectively than by pure hydrogen peroxide, thereby addressing pathogens relevant in oral infections. The basis of the micromotors, which generate reactive oxygen species on site, reduces the likelihood of resistance developing in these types of bacteria. Catalytically reducing hydrogen peroxide in this process, these micromotors propel themselves forward. This proof of principle study paves the way for the utilization of micromotors in the field of skin disinfection utilizing hydrogen peroxide concentrations which were in previous works proven noncytotoxic.

Impregnation of two-dimensional manganese dioxide nanosheets with 5-carboxyfluorescein as an immunoassay platform for sensitive detection of cardiac troponin T.

A novel immunoassay platform is presented utilizing a cardiac troponin T antibody (Ab-cTnT) labelled with 5-carboxyfluorescein (5-FAM) integrated into a two-dimensional (2D) manganese dioxide nanosheet (MnO2 NS) matrix. This strategy enables a turn-on response towards cTnT antigen within a mere 10-min incubation period, boasting an impressive lower detection limit of 0.038 ng/mL. Crucially, our probe demonstrates exceptional selectivity amidst the presence of coexisting biomolecules and ions, ensuring precise detection of cTnT. Moreover, the developed platform showcases promising utility in sensing cTnT from spiked human serum samples, yielding satisfactory recovery percentages ranging from 82 to 105%. Additionally, we introduce and easy-to-use and cost-effective test strip for point-of-care detection of cTnT, further enhancing accessibility to critical cardiovascular diagnostics.

Manganese Oxide-Doped Hierarchical Porous Carbon Derived from Tea Leaf Waste for High-Performance Supercapacitors.

Hierarchical porous carbon derived from discarded biomass for energy storage materials has attracted increasing research attention due to its cost-effectiveness, ease of fabrication, environmental protection, and sustainability. Brewed tea leaves are rich in heteroatoms that are beneficial to capacitive energy storage behavior. Therefore, we synthesized high electrochemical performance carbon-based composites from Tie guan yin tea leaf waste using a facile procedure comprising hydrothermal, chemical activation, and calcination processes. In particular, potassium permanganate (KMnO4) was incorporated into the potassium hydroxide (KOH) activation agent; therefore, during the activation process, KOH continued to erode the biomass precursor, producing abundant pores, and KMnO4 synchronously underwent a redox reaction to form MnO nanoparticles and anchor on the porous carbon through chemical bonding. MnO nanoparticles provided additional pseudocapacitive charge storage capabilities through redox reactions. The results show that the amount of MnO produced is proportional to the amount of KMnO4 incorporated. However, the specific surface area of the composite material decreases with the incorporated amount of KMnO4 due to the accumulation and aggregation of MnO nanoparticles, thereby even blocking some micropores. Optimization of MnO nanocrystal loading can promote the crystallinity and graphitization degree of carbonaceous materials. The specimen prepared with a weight ratio of KMnO4 to hydrochar of 0.02 exhibited a high capacitance of 337 F/g, an increase of 70%, owing to the synergistic effect between the Tie guan yin tea leaf-derived activated carbon and MnO nanoparticles. With this facile preparation method and the resulting high electrochemical performance, the development of manganese oxide/carbon composites derived from tea leaf biomass is expected to become a promising candidate as an energy storage material for supercapacitors.

Macrophage membrane-functionalized manganese dioxide nanomedicine for synergistic treatment of atherosclerosis by mitigating inflammatory storms and promoting cholesterol efflux.

Atherosclerosis (AS) poses a significant threat to human life and health. However, conventional antiatherogenic medications exhibit insufficient targeting precision and restricted therapeutic effectiveness. Moreover, during the progression of AS, macrophages undergo polarization toward the proinflammatory M1 phenotype and generate reactive oxygen species (ROS) to accelerate the occurrence of inflammatory storms, and ingest excess lipids to form foam cells by inhibiting cholesterol efflux. In our study, we developed a macrophage membrane-functionalized hollow mesoporous manganese dioxide nanomedicine (Col@HMnO2-MM). This nanomedicine has the ability to evade immune cell phagocytosis, enables prolonged circulation within the body, targets the inflammatory site of AS for effective drug release, and alleviates the inflammatory storm at the AS site by eliminating ROS. Furthermore, Col@HMnO2-MM has the ability to generate oxygen autonomously by breaking down surplus hydrogen peroxide generated at the inflammatory AS site, thereby reducing the hypoxic microenvironment of the plaque by downregulating hypoxia-inducible factor (HIF-1α), which in turn enhances cholesterol efflux to inhibit foam cell formation. In an APOE-/- mouse model, Col@HMnO2-MM significantly reduced inflammatory factor levels, lipid storage, and plaque formation without significant long-term toxicity. In summary, this synergistic treatment significantly improved the effectiveness of nanomedicine and may offer a novel strategy for precise AS therapy.

Multifunctional EGCG@ZIF-8 Nanoplatform with Photodynamic Therapy/Chemodynamic Therapy Antibacterial Properties Promotes Infected Wound Healing.

Damaged skin is susceptible to invasion by harmful microorganisms, especially Staphylococcus aureus and Escherichia coli, which can delay healing. Epigallocatechin-3-gallate (EGCG) is a natural compound known for effectively promoting wound healing and its potent anti-inflammatory effects. However, its application is limited due to its susceptibility to oxidation and isomerization, which alter its structure. The use of zeolitic imidazolate framework-8 (ZIF-8) can effectively tackle these issues. This study introduces an oxygen (O2) and hydrogen peroxide (H2O2) self-supplying ZIF-8 nanoplatform designed to enhance the bioavailability of EGCG, combining photodynamic therapy (PDT) and chemodynamic therapy (CDT) to improve antibacterial properties and ultimately accelerate wound healing. For this purpose, EGCG and indocyanine green (ICG), a photosensitizer, were successively integrated into a ZIF-8, and coated with bovine serum albumin (BSA) to enhance biocompatibility. The outer layer of this construct was further modified with manganese dioxide (MnO2) to promote CDT and calcium peroxide (CaO2) to supply H2O2 and O2, resulting in the final nanoplatform EGCG-ICG@ZIF-8/BSA-MnO2/CaO2 (EIZBMC). In in vitro experiments under 808 nm laser, EIZBMC exhibited synergistic antibacterial effects through PDT and CDT. This combination effectively released reactive oxygen species (ROS), which mediated oxidative stress to inhibit the bacteria. Subsequently, in a murine model of wound infection, EIZBMC not only exerted antibacterial effects through PDT and CDT but also alleviated the inflammatory condition and promoted the regeneration of collagen fibers, which led to accelerated wound healing. Overall, this research presents a promising approach to enhancing the therapeutic efficacy of EGCG by leveraging the synergistic antibacterial effects of PDT and CDT. This multifunctional nanoplatform maximizes EGCG's anti-inflammatory properties, offering a potent solution for promoting infected wound healing.