Search

Chemodynamic therapy (CDT), deemed as a cutting-edge antineoplastic therapeutic tactics, efficaciously suppresses tumors via catalytically yielding hydroxyl radicals ( • OH) in tumor regions. Nevertheless, its biomedical applications are often restricted by the limited hydrogen peroxide (H 2 O 2 ) level and upregulated antioxidant defense. Herein, a versatile nanoreactor is elaborately designed via integrating Cu 2- x S and MnO 2 for T 1 -weighted magnetic resonance (MR) imaging-guided CDT, synergistically enhanced through hypothermal ablation and oxidation resistance reduction, thereby displaying splendid antitumor efficiency as well as suppression on pulmonary metastasis. The as-synthesized Cu 2- x S@MnO 2 nanoreactors afford acid-dependent Cu-based and glutathione (GSH)-activated Mn-based catalytic properties for bimodal CDT. Owing to excellent absorbance at the second near-infrared (NIR-II) window, the Cu 2- x S furnishes hypo-photo-thermal therapy (PTT) against tumor growth and ameliorates the catalytic performance for thermal-enhanced CDT. Additionally, MnO 2 significantly downregulates GSH and glutathione peroxidase 4, which synergistically boosts CDT via promoting oxidative stress, simultaneously generating Mn 2+ for MR contrast improvement and activatable tumor imaging. Therefore, this study proffers a new attempt centered on the collaborative strategy integrating NIR-II hypothermal PTT and synergistically enhanced CDT for tumor eradication.

Here, the synthesis of sub-micron MMnF 3 (M = Na or K) particles by a rapid microwave-assisted approach is reported. Adjustment of the Na + -to-Mn 2+ ratio in the reaction mixture yielded tuneable morphologies, i.e. , rods, ribbons, and plates. Relaxometric results indicated that poly(acrylic acid)-capped MMnF 3 particles exhibited characteristic magnetic properties, which endows them with potential T 1 -weighted contrast agent capabilities.

Rationale: Sensitive and accurate imaging of cancer is essential for early diagnosis and appropriate treatment. For generally employed magnetic resonance imaging (MRI) in clinic, comprehending how to enhance the contrast effect of T 1 imaging is crucial for improving the sensitivity of cancer diagnosis. However, there is no study ever to reveal the clear mechanism of how to enhance the effect of T 1 imaging and accurate relationships of influencing factors. Herein, this study aims to figure out key factors that affect the sensitivity of T 1 contrast-enhanced MRI (CE-MRI), thereby to realize sensitive detection of tumors with low dose of CAs. Methods: Manganese oxide (MnO) nanoparticles (NPs) with various sizes and shapes were prepared by thermal decomposition. Factors impacting T 1 CE-MRI were investigated from geometric volume, surface area, crystal face to r 2 / r 1 ratio. T 1 CE-MR imaging of liver, hepatic and subcutaneous tumors were conducted with MnO NPs of different shapes. Results: The surface area and occupancy rate of manganese ions have positive impacts on the sensitivity of T 1 CE-MRI, while volume and r 2 / r 1 ratio have negative effects. MnO octahedrons have a high r 1 value of 20.07 mM -1 s -1 and exhibit an excellent enhanced effect in liver T 1 imaging. ZDS coating facilitates tumor accumulation and cellular uptake, hepatic and subcutaneous tumors could be detected with MnO octahedrons at an ultralow dose of 0.4 mg [Mn]/kg, about 1/10 of clinical dose. Conclusions: This work is the first quantitative study of key factors affecting the sensitivity of T 1 CE-MRI of MnO nanoparticles, which can serve as a guidance for rational design of high-performance positive MRI contrast agents. Moreover, these MnO octahedrons can detect hepatic and subcutaneous tumors with an ultralow dose, hold great potential for sensitive and accurate diagnosis of cancer with lower cost, less dosages and side effects in clinic., Competing Interests: Competing Interests: The authors have declared that no competing interest exists., (© The author(s).)

Imaging the catalytic activity at the single-particle level can greatly promote the screening and rational design of highly efficient nanozymes, but conventional techniques are based on ensemble analysis. Here, we present a new absorption microscopy for in situ visualizing oxidase-mimicking activity of single MnOOH nanotubes. The particle with a size more than 700 nm roughly equally scatters all wavelengths of visible light via Mie scattering, and the scattering light is collected by dark-field optical microscopy. When the particles absorb a single color of the scattering light, each individual nanoparticle shows its complementary color, enabling a form of absorption microscopy that we name Mie scattering-based absorption microscopy. We find that MnOOH nanotubes can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to generate polyTMB nanowires at their tips. There are multiple active sites on the surface of the individual nanotube, and the nanozyme activity shows a large heterogeneity as well as pH-dependent characteristic.

In the present work, we report on the synthesis of crump-like nickel manganous oxide nanoparticles decorated partially reduced graphene oxide (NiMnO@pr-GO) nanocomposite through high-intensity ultrasonic bath sonication (ultrasonic frequency = 37 kHz and power = 150 W). The NiMnO@pr-GO nanocomposite modified glassy carbon electrode (GCE) was then employed for the electrochemical reduction of detrimental metronidazole (MNZ). The crystalline phase and formation of the NiMnO@pr-GO nanocomposites were confirmed by X-ray diffraction and other spectroscopic techniques. The cyclic voltammetry results demonstrate that this NiMnO@pr-GO nanocomposite modified GCE has a lower reduction potential and higher catalytic activity towards MNZ than do NiMnO and GO modified GCEs. Under optimized conditions, the fabricated NiMnO@pr-GO electrode can detect metronidazole over a wide linear range with a lower limit of detection of 90 nM. The sensitivity of the sensor was 1.22 µA µM -1 cm -2 and was found to have excellent selectivity and durability for the detection of MNZ., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Iron plays an important role in various physiological processes. However, the detailed biological functions of iron have not been sufficiently explored because of a lack of effective methods to monitoring iron, especially the labile ferrous ion (Fe 2+ ). In the current study, a novel turn-on phosphorescent probe for Fe 2+ quantification and visualization has been proposed based on the hybrid nanocomposite of manganese dioxide and gemini iridium complex (MnO 2 -GM-Ir). The surfactant-like GM-Ir with positive charges was beneficial to combine with the negatively charged manganese dioxide (MnO 2 ) nanosheets, and thus endowing the MnO 2 -GM-Ir nanocomposite excellent dispersion ability in the water as well as efficiently avoiding the interference to the detection caused by the agglomeration of nanocomposite. Phosphorescence of GM-Ir was effectively quenched by MnO 2 nanosheets through fluorescence resonance energy transfer (FRET) and the inner filter effect (IFE), while the phosphorescence could be significantly recovered in the presence of Fe 2+ via a selective Fe 2+ -mediated reduction of MnO 2 nanosheets, indicating a highly-specific selectivity towards Fe 2+ with a low detection limit (80 nM). The drug test assay and in vitro imaging studies further proved that the MnO 2 -GM-Ir nanocomposite could be employed as a promising probe for the quantitative detection of exogenous Fe 2+ in drug and in vitro imaging of living cells., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2020. Published by Elsevier B.V.)

In the current study, γ-AlOOH, γ-MnOOH, and α-Mn2O3 nanorods (NRs) were easily synthesized and applied as advanced antibacterial materials. γ-AlOOH NRs with 20 nm width, [100] crystal plane, and 200 nm length were fabricated through a surfactant-directed solvothermal method. γ-MnOOH NRs with 20 nm width, [101] crystal direction and 500 nm length were fabricated through a hydrothermal method. The prepared γ-MnOOH NRs were calcinated (for 5 h) at 700 °C to produce α-Mn2O3 NRs with 20 nm average width and increased surface area. The NRs' structures were confirmed through FT-IR, XRD, XPS, FESEM, and FETEM. The antibacterial activity of the NRs was studied against different Gram-negative and Gram-positive bacterial strains and yeast. The three NRs exhibited antibacterial activity against all of the used strains. Biological studies indicated that the NRs' antimicrobial activity increased in the order of γ-MnOOH < γ-AlOOH < α-Mn2O3 NRs. The α-Mn2O3 NRs exhibited the lowest MIC value (39 μg mL-1) against B. subtilis, B. pertussis, and P. aeruginosa. The prepared NRs exhibited a higher antimicrobial potential toward Gram-positive bacteria than Gram-negative bacteria. The higher antimicrobial activity of the α-Mn2O3 NRs is highlighted based on their larger surface area and smaller diameter. Consequently, uniform NR architectures, single crystallinity, small nanoscale diameters, and more highly exposed [110] Mn-polar surfaces outwards are promising structures for α-Mn2O3 antibacterial agents. These NRs adhered firmly to the bacterial cells causing cell wrapping and morphology disruption, and microbial death. The designed NRs provide a great platform for microbial growth inhibition.

Hypoxia within solid tumors severely limits the efficacy of photodynamic therapy (PDT). Biocompatible calcium peroxide nanoparticles (CaO2 NPs) have superior oxygen generating capacity for hypoxia relief but the relatively slow release of O2 from CaO2 NPs hampers the PDT efficacy enhancement. Herein, manganese dioxide (MnO2) is applied as a nanozyme to facilitate O2 release from CaO2 NPs. It is disclosed that the accelerated O2 release ensures a rapid and efficient amplification of the O2 level for an increased cytotoxic singlet oxygen production with chlorin e6 and leads to a down-regulated hypoxia-responsive protein expression, which eventually translates to a super-efficient PDT as evidenced by the complete eradication of mice bearing subcutaneous 4T1 tumors. Meanwhile, MnO2 imparts an MR T1 imaging modality for tumor detection and treatment planning. These findings signify the essential role of accelerated and efficient hypoxia relief in PDT efficacy enhancement and provide an effective paradigm to overcome hypoxia-associated resistance for an enhanced therapeutic efficacy.

In this work, a glutathione (GSH) sensing nano-platform using lucigenin as a fluorescent probe in the presence of MnO2 nanosheets was reported for the first time. Unlike the earlier fluorescent detection systems based on MnO2 nanosheets, which depend on Förster resonance energy transfer (FRET) or the dynamic quenching effect (DQE), the mechanism of the quenching process of MnO2 nanosheets on lucigenin fluorescence was attributed mainly to a static quenching effect (SQE) with a minor contribution of the inner filter effect (IFE). A double exponential fluorescence decay of lucigenin was obtained in various MnO2 nanosheet concentrations as a result of their SQE and IFE. Based on this phenomenon and taking advantage of the redox reaction between GSH and MnO2 nanosheets, we have developed a switch-on sensitive fluorescent method for GSH via the recovery of the MnO2 nanosheet-quenched fluorescence of lucigenin. A good linearity range of 1.0-150.0 μM with a low limit of detection (S/N = 3) of 180.0 nM was achieved, revealing the higher sensitivity for GSH determination in comparison with the previously reported MnO2 nanosheet-based turn-on fluorescent methods. The developed fluorescent nano-platform exhibits excellent selectivity with successful application for GSH detection in human serum plasma, indicating its good practicability for GSH sensing in biological and clinical applications.

Bacterial brown stripe (BBS) is one of the most economically important diseases of rice caused by Acidovorax oryzae (Ao). In order to ensure food security and safe consumption, the use of non-chemical approach is necessary. In this study, MgO and MnO 2 were synthesized using chamomile flower extract. The synthesized MgO and MnO 2 nanoparticles were characterized by UV-Visible spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, transmission/scanning electron microscopy. The sizes were 18.2 and 16.5 nm for MgO and MnO 2 nanoparticles, respectively. The MgO and MnO 2 nanoparticles reduced the growth of Ao strain RS-2 by 62.9 and 71.3%, respectively. Also, the biofilm formation and swimming motility were significantly reduced compared to the control. The antibacterial mechanisms of MgO and MnO 2 nanoparticles against RS-2 reveals that MgO and MnO 2 nanoparticles penetrated the cells and destroyed the cell membrane leading to leakage of cytoplasmic content. Also, the flow cytometry observation reveals that the apoptotic cell ratio of RS-2 increased from 0.97% to 99.52 and 99.94% when treated with MgO and MnO 2 nanoparticles, respectively. Altogether, the results suggest that the synthesized MgO and MnO 2 nanoparticles could serve as an alternative approach method for the management of BBS.

Herein, we report a turn-on strategy for selectively killing the tumor cell via combining the singlet-oxygen quenching MnO 2 and tumor cell-targeting aptamer. The photosensitizers were in the quenching state when loaded in the mesoporous MnO 2 (mMnO 2 ) nanoparticles and sealed by the aptamer on the particle surface. The aptamer can selectively recognize the specific membrane protein on the tumor cell and release the photosensitizers, activating the photosensitizer and killing the tumor cells. The specific binding-induced "off-on" switching of singlet oxygen generation reduced the damage to the nearby healthy cells to a large extent. The high loading ability for photosensitizer and the GSH consumption property of mMnO 2 endow the system with high local concentration of singlet-oxygen for killing the target tumor cell. The high selectivity and efficiency of the constructed singlet oxygen regulating system will pave a new way for utilizing PDT in cancer precise treatment., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Photodynamic therapy (PDT) was considered as an effective treatment. Whereas only PDT is not enough to achieve effective therapy on account of irradiation intensity decreases as depth increases as well as tumor hypoxia. Combination with gene therapy and photodynamic therapy have emerged as an effective strategy to improve therapeutic effectiveness. In the present study, a GSH responsive MnO 2 was employed to delivery TB and DNAzyme for cancer imaging and PDT-gene combination treatment. TB, a photosensiters with aggregation-induced emission characteristic, was employed for photodynamic therapy, while DNAzyme, acting as catalysts for the degradation of EGR-1 mRNA, was exploited for gene silencing. All of the results of tumor treatment in vitro have implied that MnO 2 -DNAzyme-TB nanocomposite (MDT) can internalize into cells. Subsequently, MDT could decrease the expression of EGR-1 by gene silencing that enabling inhibition of cell growth. In addition, the singlet oxygen which was generated by the aggregated TB were able to further suppress cell growth. Combination therapy of photodynamic as well as gene therapy greatly enhanced antitumor efficiencies. Furthermore, in vivo tumor treatment experiments demonstrated that MDT under illumination can effectively inhibit the tumor growth of MCF-7 tumor-bearing mice by photodynamic and gene silencing combination therapy., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Herein, novel manganese sulfide nanoparticles (MnS NPs) decorated reduced graphene oxide (rGOS) nanocomposite have been designed through a facile ultrasound-assisted method and followed by a sonication process. After then, as-synthesized α-MnS@rGOS was characterized by HRTEM, FESEM, XPS, XRD and EIS. Furthermore, the α-MnS@rGOS nanocomposite modified SPCE (screen-printed carbon electrode) shows excellent electrochemical sensing performance towards Parkinson's disease biomarker of dopamine (DA). Moreover, the fabricated sensor showed a wide linear range for dopamine between 0.02 and 438.6 µM and nanomolar detection limit (3.5 nM). In addition, the α-MnS@rGOS modified SPCE showed selectivity towards the detection of dopamine in presence of a 10-fold higher concentration of other important biomolecules. The nanocomposite film modified SPCE sensor was good stable and reproducible towards the detection of Parkinson's disease biomarker. Furthermore, the as-synthesized α-MnS@rGOS nanocomposite modified SPCE has been applied to the determination of dopamine in human serum, rat serum and pharmaceutical samples with acceptable recoveries., (Copyright © 2019 Elsevier B.V. All rights reserved.)

MnFe 2 O 4 NPs are successfully decorated on the surface of SiO 2 sheets to form the SiO 2 -MnFe 2 O 4 composite via one-pot hydrothermal synthesis method. The phase identification, morphology, crystal structure, distribution of elements, and microwave absorbing properties in S-band (1.55~3.4 GHz) of the as-prepared composite were investigated by XRD, SEM, TEM, and Vector Network Analyzer (VNA) respectively. Compared with the pure MnFe 2 O 4 NPs, the as-prepared SiO 2 -MnFe 2 O 4 composite exhibits enhanced microwave absorption performance in this frequency band due to the strong eddy current loss, better impedance matching, excellent attenuation characteristic, and multiple Debye relaxation processes. The maximum reflection loss of -14.87 dB at 2.25 GHz with a broader -10 dB bandwidth over the frequency range of 1.67~2.9 GHz (1.23 GHz) can be obtained at the thickness of 4 mm. Most importantly, the preparation method used here is relatively simple, hence such composite can be served as a potential candidate for effective microwave absorption in S-band., Competing Interests: The authors declare no conflict of interest.

In this study, amorphous Mn oxides (AMOs) and their composites with biochar (BC) were synthesized using different sugars (glucose, sucrose, and molasses), and their sorption efficiency toward Zn(II), Cd(II), and As(V) was tested. Additionally, detailed characterization of synthesized materials using various solid-state analysis methods (e.g. XRD, FTIR-ATR, and/or SEM-EDX) was also performed. Despite glucose-based AMOs presented higher sorption efficiency for As(V), i.e., 0.73 mmol g -1 (glucose) > 0.27 mmol g -1 (sucrose and molasses), similar sorption efficiency toward Zn(II), i.e., 0.80 mmol g -1 (glucose and molasses) > 0.66 (sucrose) and Cd(II) (0.71-0.74 mmol g -1 (sucrose and molasses) > 0.36 mmol g -1 (glucose), was observed for sucrose- and molasses-based AMOs under the given conditions. Next, the sorption efficiency of all AMO/BC composites was proportional to their AMO content. Finally, Mn(II) leaching from the structure of the new AMOs was negligible compared to that observed for the glucose-based AMOs, in this study as well as in other similar studies. Moreover, using molasses as reducing agent during AMO synthesis dramatically decreased the total cost of the final materials, which suggested that these new AMOs could represent interesting alternatives for standard remediation technologies. The AMOs synthesized using low-cost sugars could, therefore, be promising materials for real field applications, since the main disadvantages of using standard AMOs are mitigated. Nevertheless, the efficiency and stability of these composites under real-life conditions must be tested prior to their direct application for remediation technologies., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Poor O 2 supply to the infiltrated immune cells in the joint synovium of rheumatoid arthritis (RA) up-regulates hypoxia-inducible factor (HIF-1α) expression and induces reactive oxygen species (ROS) generation, both of which exacerbate synovial inflammation. Synovial inflammation in RA can be resolved by eliminating pro-inflammatory M1 macrophages and inducing anti-inflammatory M2 macrophages. Because hypoxia and ROS in the RA synovium play a crucial role in the induction of M1 macrophages and reduction of M2 macrophages, herein, we develop manganese ferrite and ceria nanoparticle-anchored mesoporous silica nanoparticles (MFC-MSNs) that can synergistically scavenge ROS and produce O 2 for reducing M1 macrophage levels and inducing M2 macrophages for RA treatment. MFC-MSNs exhibit a synergistic effect on O 2 generation and ROS scavenging that is attributed to the complementary reaction of ceria nanoparticles (NPs) that can scavenge intermediate hydroxyl radicals generated by manganese ferrite NPs in the process of O 2 generation during the Fenton reaction, leading to the efficient polarization of M1 to M2 macrophages both in vitro and in vivo. Intra-articular administration of MFC-MSNs to rat RA models alleviated hypoxia, inflammation, and pathological features in the joint. Furthermore, MSNs were used as a drug-delivery vehicle, releasing the anti-rheumatic drug methotrexate in a sustained manner to augment the therapeutic effect of MFC-MSNs. This study highlights the therapeutic potential of MFC-MSNs that simultaneously generate O 2 and scavenge ROS, subsequently driving inflammatory macrophages to the anti-inflammatory subtype for RA treatment.

As one kind of redox active layered transition-metal dioxide nanomaterials, single-layer manganese dioxide (MnO 2 ) nanosheets have gained significant research attention in the fields of biosensing and biomedicine because of their large surface area, intense and broad optical absorption, strong oxidation ability, catalytic activity, and robust mechanical properties. This review provides a brief overview of the recent advances in the development of MnO 2 nanosheet-based biosensors, bioimaging as well as drug delivery for cancer therapy. The methodologies for the preparation of MnO 2 nanosheets are summarized, followed by an introduction of the nanostructure and properties of MnO 2 nanosheets. Special attention is paid to their applications in biosensing, bioimaging and cancer therapy. Future perspectives and the challenges of high-performance MnO 2 nanosheets are also discussed.

89 Sr and 90 Sr are both fission products of high radiotoxicity, which can be released in significant amounts in the event of a nuclear accident. Radiostrontium isotopes will follow calcium all along the food chain and, after ingestion, accumulate in the bones. Therefore, it is imperative to be able to determine 89 Sr and 90 Sr in raw milk samples in case of an accidental situation to evaluate the dose given by both radionuclides to the population. Several methods exist for conducting 89 Sr and 90 Sr determination. However, most of them use at least one chromatographic step to purify strontium. This, unfortunately, increases the analytical time before the results can be released to the authorities. In addition, they often use liquid scintillation counting to determine the 89 Sr and 90 Sr activities, a method which can handle only one sample at a time. Here we propose using synthetic tunnel manganese oxides such as cryptomelane and todorokite and layered metal sulfides to selectively extract strontium from fresh milk and raw urine in a batch sorption method. We found that the method is very quick and yields very pure sources of (radio)-strontium, which can be counted in a proportional counter. Data (counts per minute) from the counter were fitted to a mathematical expression enabling the simultaneous determination of 89 Sr and 90 Sr. Because a proportional counter often has several drawers, it is typically possible to measure up to 16 samples at a time. Since cryptomelane is a binding phase easily synthesized in a large quantity, we anticipate that this technique could be an interesting alternative to conventional solid phase extraction chromatography methods., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The present study explored the one step extracellular green synthesis of Iron oxide (Fe x O y ) and manganese oxide nanoparticles (MnNPs) using aqueous extract of Acorus calamus rhizome. The organic chemicals including polyphenol compounds responsible for bio-reduction and stabilization from the polyphenol enriched microwave irradiated aqueous extract of Acorus calamus were studied using GC-MS analysis. Further, their synthesis conditions were optimized using response surface methodology (RSM) and central composite design (CCD) using three variables. The green synthesized Iron oxide and Manganese oxide NPs were characterized by UV, FTIR, XRD, TEM and SEM. Results indicated that the Iron oxide NPs and mixture of iron and manganese NPs showed photocatalytic excellent activities in reducing dyes like methylene blue (0.1%) and Congo red (0.25%) at 0.03% NPs. However, Mn NPs showed moderate activity. On a contrary, manganese showed better larvicidal activity compared to Iron oxide NPs against the phytopathogens commonly affecting the vegetable crops. The present finding showed that high mortality rate at 30 μg/ml concentration of manganese NPs was comparatively interesting. In addition, NPs overall had appreciable activity with P. aeruginosa being more sensitive to Iron oxide NPs (22 ± 2 mm zone of inhibition) and manganese NPs (13 ± 2 mm zone of inhibition) and Iron oxide NPs completely inhibited the growth of A. flavus at 40 μg/ml concentration., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Integration of biological macromolecules with inorganic materials via biomineralization has demonstrated great potential for development of nanotheranostic agents. To produce multifunctionality, integration of multiple components in the biomineralized theranostic agents is required; however, how to efficiently and reproducibly implement this is challenging. In this report, a universal biomineralization strategy is developed by incorporation of oxidization polymerization into albumin-templated biomineralization for facile synthesis of nanotheranostic agents. A series of biomineralized polymers and manganese dioxide hybrid nanoparticles (PMHNs) can be synthesized via the polymerization of various monomers, including dopamine (DA), epigallocatechin (EGC), pyrrole (PY), and diaminopyridine (DP), along with the reduction of KMnO 4 and formation of manganese dioxide nanoparticles in albumin templates. These biomineralized PMHNs demonstrate ultrahigh MRI (longitudinal relaxivity up to 38 mM -1 s -1 ) and ultrasonic (US) imaging contrasting capabilities and have excellent photothermal therapy efficacy with complete ablation of orthotopic tumors. Moreover, these biomineralized hybrid nanoparticles can be effectively excreted through the kidneys, avoiding potential systemic toxicity. Thus, integration of polymerization into biomineralization presents a strategy for the fabrication of hybrid nanomaterials, allowing the production of multifunctional and biocompatible nanotheranostic agents via a facile one-pot method.

This study concerns the optimisation of green synthesis of manganese oxide nanoparticles (MnO NPs) with Dittrichia graveolens (L.) extract via response surface methodology (RSM). Central composite design was used to evaluate the effect of pH, time, and the extract to the metal ratio on the synthesised nanoparticles (NPs). Nine runs were designed to investigate the effect of each parameter while NPs were synthesised under different conditions. Considering the p -values ( p -value < 0.05), it is indicated that the extract to the metal ratio was the most effective parameter. The synthesised NPs were characterised using UV-vis. Synthesis of the NPs by polyphenolic compounds of green reducing agent and their stabilisation by curcumin was confirmed by Fourier transform infrared spectra and the surface morphology of the spherical MnO NPs was studied by field-emission scanning electron microscopy and transmission electron microscope techniques. The present researchers claimed the optimal condition as follows: time = 56.7 min, pH = 7.2, and the extract to the metal ratio = 87.9 v/v. MnO NPs at optimum condition were then employed for degradation of industrial dyes and they showed high dye degradation activity against Rhodamine B and light green dye. The average size of the synthesised MnO NPs at optimal condition was claimed to be nearly 38 nm.

This work reports a facile approach to synthesize polyaniline nanotubes (PANI-NT) by using manganese oxide as sacrificial templates. This template assisted polyaniline nanotubes (t-PANI-NT) were utilized as electrode material after deposition onto the indium tin oxide (ITO) coated glass substrates by using the electrophoretic technique. The structural, morphological and electrochemical characterizations of the t-PANI-NT show relatively better results compared to chemically synthesized PANI-NT (c-PANI-NT). Moreover, the t-PANI-NT/ITO electrode exhibits improved electron transfer coefficient (α = 0.63) and charge transfer rate constant (k s = 0.05912 s -1 ) in comparison to c-PANI-NT/ITO electrode (α = 0.56 and k s = 0.06548 s -1 ). The obtained t-PANI-NT/ITO electrodes have been further immobilized with biotinylated DNA sequence, specific to chronic myelogenous leukemia (CML) by using avidin-biotin as a cross-linking agent. Electrochemical impedance spectroscopy studies revealed that the genosensor displays linearity in wide range of target DNA concentration (10 -6 to 10 -16 M) with an outstanding differentiation ability and low detection limit of 10 -16 M. The experimental results of this highly sensitive and specific genosensor with clinical samples of CML positive patients and control negative patients indicate its potential for clinical diagnostics., (Copyright © 2018 Elsevier B.V. All rights reserved.)

We have developed a supramoleuclar imaging probe based on thin-layer manganese dioxide functionalized with a fluorescent, multivalent glyco-poly-cycolodextrin for the targeted, stimulus-responsive bioimaging of cancer cells.

The authors describe MnO nanoparticles (NPs) with unique excitation-dependent fluorescence across the entire visible spectrum. These NPs are shown to be efficient optical nanoprobe for multicolor cellular imaging. Synthesis of the NPs is accomplished by a thermal decomposition method. The MnO NPs exhibit a high r 1 relaxivity of 4.68 mM -1  s -1 and therefore give an enhanced contrast effect in magnetic resonance (MR) studies of brain glioma. The cytotoxicity assay, hemolysis analysis, and hematoxylin and eosin (H&E) staining tests verify that the MnO NPs are biocompatible. In the authors' perception, the simultaneous attributes of multicolor fluorescence and excellent MR functionality make this material a promising dual-modal nanoprobe for use in bio-imaging. Graphical abstract A direct method to synthesize fluorescent MnO NPs is reported. The NPs are biocompatible and have been successfully applied for multicolor cellular imaging and MR detection of brain glioma.

Molecular nanodevices are computational assemblers that switch defined states upon external stimulation. However, interfacing artificial nanodevices with natural molecular machineries in living cells remains a great challenge. Here, we delineate a generic method for programming assembly of enzyme-initiated DNAzyme nanodevices (DzNanos). Two programs including split assembly of two partzymes and toehold exchange displacement assembly of one intact DNAzyme initiated by telomerase are computed. The intact one obtains higher assembly yield and catalytic performance ascribed to proper conformation folding and active misplaced assembly. By employing MnO 2 nanosheets as both DNA carriers and source of Mn 2+ as DNAzyme cofactor, we find that this DzNano is well assembled via a series of conformational states in living cells and operates autonomously with sustained cleavage activity. Other enzymes can also induce corresponding DzNano assembly with defined programming modules. These DzNanos not only can monitor enzyme catalysis in situ but also will enable the implementation of cellular stages, behaviors, and pathways for basic science, diagnostic, and therapeutic applications as genetic circuits.

Several efficient stabilizing amendments have been recently proposed for the remediation of metal(loid)-contaminated soils. However, information on their interactions with plants, which is a crucial factor in soil environments, are still scarce. An amorphous manganese oxide (AMO) synthesized from organic compounds and nano zerovalent iron (nZVI) have been previously tested as promising stabilizing agents usable both for the stabilization of metals and As. Experiments with rhizoboxes were performed in order to evaluate their influence on the mobility of metal(loid)s in the bulk soil and rhizosphere of sunflower (Helianthus annuus L.) together with their impact on metal uptake and biomass yield. Generally, AMO proved more efficient than nZVI in all stages of experiment. Furthermore, the AMO effectively reduced water- and 0.01 M CaCl 2 -extractable fractions of Cd, Pb and Zn. The decreased bioavailability of contaminating metal(loid)s resulted in significant increase of microbial activity in AMO-amended soil. Together with metal(loid) extractability, the AMO was also able to significantly reduce the uptake of metals and ameliorate plant growth, especially in the case of Zn, since this metal was taken up in excessive amounts from the control soil causing strong phytotoxicity and even death of young seedlings. On the other hand, AMO application lead to significant release of Mn that was readily taken up by plants. Resulting Mn concentrations in biomass exceeded toxicity thresholds while plants were showing emergent Mn phytotoxicity symptoms. We highlight the need of such complex studies involving plants and soil biota when evaluating the efficiency of stabilizing amendments in contaminated soils., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Small molecular weight proteins (5.21 kDa) were used as bio-templates to synthesize MnO 2 nanosheets (NSs). This work will open up a protein-directed avenue to synthesize 2D morphology. Further, the as-prepared MnO 2 NSs showed intrinsic peroxidase-like activity and were then applied for glucose detection and evaluation of antioxidant behaviours of typical antioxidants.

Large-scale synthesis of monodisperse ultrasmall metal ferrite nanoparticles as well as understanding the correlations between chemical composition and MR signal enhancement is critical for developing next-generation, ultrasensitive T 1 magnetic resonance imaging (MRI) nanoprobes. Herein, taking ultrasmall MnFe 2 O 4 nanoparticles (UMFNPs) as a model system, we report a general dynamic simultaneous thermal decomposition (DSTD) strategy for controllable synthesis of monodisperse ultrasmall metal ferrite nanoparticles with sizes smaller than 4 nm. The comparison study revealed that the DSTD using the iron-eruciate paired with a metal-oleate precursor enabled a nucleation-doping process, which is crucial for particle size and distribution control of ultrasmall metal ferrite nanoparticles. The principle of DSTD synthesis has been further confirmed by synthesizing NiFe 2 O 4 and CoFe 2 O 4 nanoparticles with well-controlled sizes of ∼3 nm. More significantly, the success in DSTD synthesis allows us to tune both MR and biochemical properties of magnetic iron oxide nanoprobes by adjusting their chemical composition. Beneficial from the Mn 2+ dopant, the synthesized UMFNPs exhibited the highest r 1 relaxivity (up to 8.43 mM -1 s -1 ) among the ferrite nanoparticles with similar sizes reported so far and demonstrated a multifunctional T 1 MR nanoprobe for in vivo high-resolution blood pool and liver-specific MRI simultaneously. Our study provides a general strategy to synthesize ultrasmall multicomponent magnetic nanoparticles, which offers possibilities for the chemical design of a highly sensitive ultrasmall magnetic nanoparticle based T 1 MRI probe for various clinical diagnosis applications.

Uniform wüstite Fe0.6 Mn0.4 O nanoflowers have been successfully developed as an innovative theranostic agent with T1 -T2 dual-mode magnetic resonance imaging (MRI), for diagnostic applications and therapeutic interventions via magnetic hyperthermia. Unlike their antiferromagnetic bulk counterpart, the obtained Fe0.6 Mn0.4 O nanoflowers show unique room-temperature ferromagnetic behavior, probably due to the presence of an exchange coupling effect. Combined with the flower-like morphology, ferromagnetic Fe0.6 Mn0.4 O nanoflowers are demonstrated to possess dual-modal MRI sensitivity, with longitudinal relaxivity r1 and transverse relaxivity r2 as high as 4.9 and 61.2 mm(-1) s(-1) [Fe]+[Mn], respectively. Further in vivo MRI carried out on the mouse orthotopic glioma model revealed gliomas are clearly delineated in both T1 - and T2 -weighted MR images, after administration of the Fe0.6 Mn0.4 O nanoflowers. In addition, the Fe0.6 Mn0.4 O nanoflowers also exhibit excellent magnetic induction heating effects. Both in vitro and in vivo magnetic hyperthermia experimentation has demonstrated that magnetic hyperthermia by using the innovative Fe0.6 Mn0.4 O nanoflowers can induce MCF-7 breast cancer cell apoptosis and a complete tumor regression without appreciable side effects. The results have demonstrated that the innovative Fe0.6 Mn0.4 O nanoflowers can be a new magnetic theranostic platform for in vivo T1 -T2 dual-mode MRI and magnetic thermotherapy, thereby achieving a one-stop diagnosis cum effective therapeutic modality in cancer management., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The aim of this study was to construct redox- and pH-responsive degradable manganese dioxide (MnO2) nanosheets for cancer theranostic application. The small MnO2 nanosheets were synthesized, and then functionalized by hyaluronic acid (HA), demonstrating excellent stability and tumor-targeting ability. Cisplatin (cis-diamminedichloroplatinum [CDDP]) was absorbed by the nanosheets through a physical action, which was designed as MnO2/HA/CDDP. The prepared MnO2/HA/CDDP formulation was able to efficiently deliver CDDP to tumor cells in vitro and in vivo, resulting in improved therapeutic efficiency. Subsequently, they were triggered by lower pH and higher level of reduced glutathione to generate Mn(2+), enabling magnetic resonance imaging. The smart multifunctional system combining efficient magnetic resonance imaging and chemotherapy has the potential to be used as a tumor-targeting theranostic nanomedicine.

Magnetic nanoparticles (MNPs) have been widely investigated as a hyperthermic agent for cancer treatment. In this study, thermally responsive Chitosan-coated MnFe2O4 (Chitosan-MnFe2O4) nanoparticles were developed to conduct localized magnetic hyperthermia for cancer treatment. Hydrophobic MnFe2O4 nanoparticles were synthesized via thermal decomposition and modified with 2,3-dimercaptosuccinic acid (DMSA) for further conjugation of chitosan. Chitosan-MnFe2O4 nanoparticles exhibited high magnetization and excellent biocompatibility along with low cell cytotoxicity. During magnetic hyperthermia treatment (MHT) with Chitosan-MnFe2O4 on MDA-MB 231 cancer cells, the targeted therapeutic temperature was achieved by directly controlling the strength of the external AC magnetic fields. In vitro Chitosan-MnFe2O4-assisted MHT at 42 °C led to drastic and irreversible changes in cell morphology and eventual cellular death in association with the induction of apoptosis through heat dissipation from the excited magnetic nanoparticles. Therefore, the Chitosan-MnFe2O4 nanoparticles with high biocompatibility and thermal capability can be an effective nano-mediated agent for MHT on cancer.

We synthesized manganese oxides supported on gold nanoparticles (diameter <100 nm) by the reaction of KMnO4 with gold nanoparticles under hydrothermal conditions. In this green method Mn oxide is deposited on the gold nanoparticles. The compounds were characterized by scanning electron microscopy, energy-dispersive spectrometry, high-resolution transmission electron microscopy, X-ray diffraction, UV-Vis spectroscopy, Fourier transform infrared spectroscopy, and atomic absorption spectroscopy. In the next step, the water-oxidizing activities of these compounds in the presence of cerium(IV) ammonium nitrate as a non-oxo transfer oxidant were studied. The results show that these compounds are good catalysts toward water oxidation with a turnover frequency of 1.0 ± 0.1 (mmol O2/(mol Mn·s)). A comparison with other previously reported Mn oxides and important factors influencing the water-oxidizing activities of Mn oxides is also discussed.

In this study, As(III) oxidation kinetics by a poorly-crystalline phyllomanganate (δ-MnO2) in the presence and absence of dissolved Fe(II) was investigated using stirred-flow and batch experiments. Chemically synthetic δ-MnO2 was reacted with four influent solutions, containing the same As(III) concentration but different Fe(II) concentrations, at pH 6. The results show an initial rapid As(III) oxidation by δ-MnO2, which is followed by an appreciably slow reaction after 8h. In the presence of Fe(II), As(III) oxidation is inhibited due to the competitive oxidation of Fe(II) as well as the formation of Fe(III)-(hydr)oxides on the δ-MnO2 surface. However, the sorption of As(III), As(V) and Mn(II) are increased, for the newly formed Fe(III)-(hydr)oxides provide additional sorption sites. This study suggests that the competitive oxidation of Fe(II) and consequently the precipitation of Fe(III) compounds on the δ-MnO2 surface play an important role in As(III) oxidation and As sequestration. Understanding these processes would be helpful in developing in situ strategies for remediation of As-contaminated waters and soils., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Nano-sized Mn oxides contain Mn3O4 and β-MnOOH have been prepared by a simple and high-yield method using β-cyclodextrin as a ligand for Mn ions, and decomposition of this Mn complex. Scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy and X-ray diffraction spectroscopy have been used to characterize morphologies and the phases of these prepared nano-sized Mn oxides., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Fe-doped cryptomelanes were synthesized by refluxing at ambient pressure, followed by characterization with multiple techniques and test in photocatalytic degradation of phenol. The introduction of Fe(III) into the structure of cryptomelane results in a decrease in particle size and the contents of Mn and K(+), and an increase in the Mn average oxidation state (AOS), specific surface area and UV-vis light absorption ability. Mn and Fe K-edge extended X-ray absorption fine structure spectroscopy analysis indicates that some Fe(III) is incorporated into the framework of cryptomelane by replacing Mn(III) while the remaining Fe(3+) is adsorbed in the tunnel cavity. These Fe-doped cryptomelanes have significantly improved the photocatalytic degradation rate of phenol, with the sample of ∼3.04 wt.% Fe doping being the most reactive and achieving a degradation rate of 36% higher than that of the un-doped one. The enhanced reactivity can be ascribed to the increase in the coherent scattering domain size of the crystals, Mn AOS and light absorption, as well as the presence of sufficient K(+) in the tunnel. The results imply that metal doping is an effective way to improve the performance of cryptomelane in pollutants removal and has the potential for modification of Mn oxide materials., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Todorokite, formed from Mn(II) in supergene environments, can affect the transformation and migration of dissolvable sulfides in soils and water. In this work, todorokite was synthesized with different degrees of crystallinity, and the redox mechanism of dissolvable sulfide and todorokite was studied in both closed and open aqueous systems. The influences of pH, temperature, crystallinity, the amount of manganese oxides, and oxygen gas on S(2-) oxidation process were investigated. It is found that S(2-) was oxidized to S(0), SO3(2-), S2O3(2-) and SO4(2-), and about 90% of S(2-) was converted into S(0) in closed systems. The participation of oxygen facilitated the further oxidation of S(0) to S2O3(2-). S(0) and S2O3(2-) were formed with the conversion rates of S(2-) about 45.3% and 38.4% after 1h of reaction, respectively, and the conversion rate for S2O3(2-) increased as reaction prolonged for a longer period. In addition, todorokite was reduced to Mn(OH)2 in the presence of nitrogen gas, and its chemical stability increased when oxygen gas was admitted into the reaction system during the process. The oxidation rate of dissolvable sulfide followed a pseudo-first-order kinetic law in the initial stage (within 10 min), and the initial oxidation rate constant of S(2-) increased with elevating temperature, increasing the quantity and decreasing crystallinity of todorokite. The initial oxidation rate of dissolvable sulfide decreased with continuous feeding of O2 into the test solution, possibly due to a decrease in active Mn(III) content in todorokite. The present work demonstrates the redox behaviors and kinetics of dissolvable sulfide and todorokite in aquatic environments., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Lithium-oxygen (Li-O2 ) batteries are receiving intense interest because of their high energy density. A new tubular δ-MnO2 material prepared by a simple hydrothermal synthesis is an efficient electrocatalyst for Li-O2 batteries. The synthesized δ-MnO2 exhibits a unique tubular structure, in which the porous walls are composed of highly dispersed ultrathin δ-MnO2 nanosheets. Such a unique structure and its intrinsic catalytic activity provide the right electrocatalyst characteristics for high-performance Li-O2 batteries. As a consequence, suppressed overpotentials-especially the oxygen evolution reaction overpotential-superior rate capability, and desirable cycle life are achieved with these submicron δ-MnO2 tubes as the electrocatalyst. Remarkably, the discharge product Li2 O2 of the Li-O2 battery exhibits a uniform nanosheet-like morphology, which indicates the critical role of the δ-MnO2 in the electrochemical process, and a mechanism is proposed to analyze the catalysis of δ-MnO2 ., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A mononuclear Mn(III) complex MnL·4H2O (H3L=1-[N-(2-pyridylmethyl),N-(2-hydroxybenzyl)amino]-3-[N'-(2-hydroxybenzyl),N'-(4-methylbenzyl)amino]propan-2-ol) has been prepared and characterized. This complex catalyzes the dismutation of superoxide efficiently, with catalytic rate constant kcat=1.7×10(6)M(-1)s(-1) and IC50 1.26μM, obtained through the nitro blue tetrazolium photoreduction inhibition superoxide dismutase assay, in aqueous solution of pH7.8. MnL is also able to disproportionate more than 300 equivalents of H2O2 in CH3CN, with initial rate of H2O2 decomposition given by ri=kcat [MnL](2) [H2O2] and kcat=1.32(2)mM(-2)min(-1). The accessibility of the Mn(IV) state (E(p)=0.53V vs. saturated calomel electrode), suggests MnL employs a high-valent catalytic cycle to decompose O2(-) and H2O2., (Copyright © 2015 Elsevier Inc. All rights reserved.)

A rapid (1.5 h) one-step ball milling (BM) method was developed not only to modify commercial MnO2 via top-down approaches (BM0), but also to bottom-up synthesize MnO(x) by cogrinding of KMnO4 and MnC4H6O4 (BM1) or KMnO4 and MnSO4 (BM2). Catalysts activity on gaseous POPs removal was tested using hexachlorobenzene (HCBz) as surrogate. Catalytic performance decreases in the order of BM2 ≈ BM1 (T90% = 180-200 °C) > BM0 (260 °C) > CMO ≈ cryptomelane MnO2 (>300 °C). Both adsorption and destruction contribute to HCBz removal at 180 °C while destruction prevails at 200-300 °C. Mechanism studies show that destruction activity is lineally correlated with the amount of surface reactive oxygen species (Oads); stability is determined by the removal of surface chloride, which is associated with the mobility of bulk lattice oxygen (Olat); adsorption capacities are linearly correlated with surface area and pore structure. With the aid of extensive characterizations the excellent performance of BM prepared samples can be explained as (1) abundant surface vacancies enhance the generation of Oads; (2) massive bulk vacancies promote the mobility of bulk Olat; (3) large surface area and uniform pore size distribution facilitate the physisorption of HCBz.

Ordered mesoporous MnO, MnO4, Mn2O3 and MnO2 materials with 3-D pore structure were suc- cessfully synthesized via a nano-replication method by using ordered mesoporous silica, KIT-6 (Cubic Ia3d space group mesostructure) as the template under specific oxidation and reduction conditions. Notably, ordered mesoporous MnO with a crystalline wall (rock salt structure) was syn- thesized for the first time, to the best of our knowledge. The synthesis of the ordered mesoporous MnO was achieved by reducing the ordered mesoporous Mn3O4 under an H2 atmosphere, while preserving the ordered mesostructure and crystalline wall throughout the solid/solid transformation. All of the ordered mesoporous manganese oxides with different crystal structures and oxidation states demonstrated almost the same spherical-like morphology with several hundred nanometers of particles. The synthesized ordered mesoporous manganese oxides had uniform dual mesopores (2-3 nm, and ~20 nm) and crystalline frameworks with large surface areas (86-140 m2/g) and pore volumes (0.27-0.33 cm3/g).

Two new chiral mononuclear Mn((III)) complexes, [MnL((R)) Cl (C2 H5 OH)]•C2 H5 OH () and [MnL((S)) (CH3 OH)2 ]Cl•CH3 OH (), {H2 L = (R,R)-or (S,S)-N,N'-bis-(2-hydroxy-1-naphthalidehydene)-cyclohexanediamine} were synthesized and characterized by various physicochemical techniques. Bond valence sum (BVS) calculations and the Jahn-Teller effect indicate that the Mn centers are in a +3 oxidation state. The statuses of the two complexes in the solution were confirmed as a pair of enantiomers by electrospray ionization, mass spectrometry (ESI-MS) spectrum. The binding ability of the complexes with calf thymus CT-DNA was investigated by spectroscopic and viscosity measurements. Both of the complexes could interact with CT-DNA via an intercalative mode with the order of (R-enantiomer) > (S-enantiomer). Under the physiological conditions, the two compounds exhibit efficient DNA cleavage activities without any external agent, which also follows the order of R-enantiomer > S-enantiomer. Interestingly, the concentration-dependent DNA cleavage experiments indicate an optimal concentration of 17.5 μM. In addition, the interaction of the compounds with bovine serum albumin (BSA) was also investigated, which indicated that the complexes could quench the intrinsic fluorescence of BSA by a static quenching mechanism., (Copyright © 2014 Wiley Periodicals, Inc.)

Arsenic in groundwater is a major concern in many parts of the world and suitable sorbents are required for removal of arsenic from ground water. Removal of arsenic from groundwater has been studied using manganese dioxide, synthesized by solid state reaction of manganese acetate with potassium permanganate. Manganese dioxide was characterized by X-ray diffraction (XRD), zeta potential, surface area, particle size measurements and thermal analysis. XRD measurement showed that the manganese dioxide had α-MnO2 structure. Sorption of As(III) and As(V) on manganese dioxide was studied by radiotracer technique using (76)As radio isotope. Arsenic removal efficiency for both As(III) and As(V) at concentration of 2 mg L(-1) was ∼99% in the pH range of 3-9. The sorption capacities for As(III) and As(V) were ∼60 mg g(-1). Kinetic studies showed that the equilibrium was reached within 30 s. Arsenic sorbed on manganese dioxide was present as As(V) irrespective of initial oxidation state. The presence of Ca(2+), Mg(2+), Cl(-) and SO4(2-) up to a concentration of 1000 mg L(-1) had no significant effect on arsenic sorption. The sorption of arsenic decreased significantly in the presence of phosphate and bicarbonate anions above 10 mg L(-1). Arsenic sorbed on manganese dioxide was desorbed by 0.1M NaOH. Arsenic was effectively removed by manganese dioxide from groundwater samples collected from arsenic contaminated areas of West Bengal, India.

A new approach is developed for the aqueous phase formation of flake-like and wire-like β-MnO2 nanomaterials on a DNA scaffold at room temperature (RT) within a shorter time scale. The β-MnO2 nanomaterials having a band gap energy ∼3.54 eV are synthesized by the reaction of Mn(II) salt with NaOH in the presence of DNA under continuous stirring. The eventual diameter of the MnO2 particles in the wire-like and flake-like morphology and their nominal length can be tuned by changing the DNA to Mn(ii) salt molar ratio and by controlling other reaction parameters. The synthesized β-MnO2 nanomaterials exhibit pronounced catalytic activity in organic catalysis reaction for the spontaneous polymerization of aniline hydrochloride to emeraldine salt (polyaniline) at RT and act as a suitable electrode material in electrochemical supercapacitor applications. From the electrochemical experiment, it was observed that the β-MnO2 nanomaterials showed different specific capacitance (Cs) values for the flake-like and wire-like structures. The Cs value of 112 F g(-1) at 5 mV s(-1) was observed for the flake-like structure, which is higher compared to that of the wire-like structure. The flake-like MnO2 nanostructure exhibited an excellent long-term stability, retaining 81% of initial capacitance even after 4000 cycles, whereas for the wire-like MnO2 nanostructure, capacitance decreased and the retention value was only 70% over 4000 cycles. In the future, the present approach can be extended for the formation of other oxide-based materials using DNA as a promising scaffold for different applications such as homogeneous and heterogeneous organic catalysis reactions, Li-ion battery materials or for the fabrication of other high performance energy storage devices.

Three-dimensional (3D) flower-like hausmannite architectures of Mn3O4 with uniform morphology have been successfully synthesized by a novel chemical reaction route using cetyltrimethylammonium bromide as the template. Micro/nanostructures of the as-synthesized 3D flower-like Mn3O4 architectures were investigated in detail by a series of analytical techniques. The geometrical shape of 3D flower-like Mn3O4 architectures is structurally perfect, and they are produced with diameters in the range of several hundred nanometers to a few micrometers. Experimental results indicate that two-dimensional nanosheets associated with one-dimensional single-crystalline nanorods self-assembled into three-dimensional flower-like Mn3O4 architectures. The single-crystalline Mn3O4 nanorods are a few hundred nanometers long and several tens of nanometers wide. Different dimensional systems, such as two-dimensional nanosheets, one-dimensional nanorods, and three-dimensional nanoflowers, could provide different building blocks to constitute nanostructured materials. These specific building blocks, which constituted the complex hierarchical architectures with nanostructural features, may offer exciting opportunities for both fundamental research and technological applications.

Transition metal oxides belong to a class of versatile materials that are vitally important for developing new materials with functionality and smartness. Research on manganese oxides has been a key topic among studies on transition metal oxides. This is due to their potential applications in diverse areas, including rechargeable lithium ion batteries, catalysis, molecular adsorption, gas sensors, energy storage, and magnetics. In this review, we will elucidate in detail various characterization strategies, including temperature-dependent growth, micro/nanostructures, Raman, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and electron spin resonance, for Mn2O3 nanocrystals, highlighting contributions from our laboratory. This review article mainly focuses on the wide-ranging research effort on the development of preparation methodologies and the assessment of various characterization strategies in Mn2O3 nanomaterials. The main purpose is to provide the readers a comprehensive understanding of the research progress of manganese oxides. This is an interdisciplinary work that integrates the areas of physics, chemistry, materials science, and nanotechnology.

Products containing silver ion (Ag(+)) are widely used, leading to a large amount of Ag(+)-containing waste. The deep-sea manganese-oxidizing bacterium Marinobacter sp. MnI7-9 efficiently oxidizes Mn(2+) to generate biogenic Mn oxide (BMO). The potential of BMO for recovering metal ions by adsorption has been investigated for some ions but not for Ag(+). The main aim of this study was to develop effective methods for adsorbing and recovering Ag using BMO produced by Marinobacter sp. MnI7-9. In addition, the adsorption mechanism was determined using X-ray photoelectron spectroscopy analysis, specific surface area analysis, adsorption kinetics and thermodynamics. The results showed that BMO had a higher adsorption capacity for Ag(+) compared to the chemical synthesized MnO2 (CMO). The isothermal absorption curves of BMO and CMO both fit the Langmuir model well and the maximum adsorption capacities at 28°C were 8.097 mmol/g and 0.787 mmol/g, for BMO and CMO, respectively. The change in enthalpy (ΔH(θ)) for BMO was 59.69 kJ/mol indicating that it acts primarily by chemical adsorption. The change in free energy (ΔG(θ)) for BMO was negative, which suggests that the adsorption occurs spontaneously. Ag(+) adsorption by BMO was driven by entropy based on the positive ΔS(θ) values. The Ag(+) adsorption kinetics by BMO fit the pseudo-second order model and the apparent activation energy of Ea is 21.72 kJ/mol. X-ray photoelectron spectroscopy analysis showed that 15.29% Ag(+) adsorbed by BMO was transferred to Ag(0) and meant that redox reaction had happened during the adsorption. Desorption using nitric acid and Na2S completely recovered the Ag. The results show that BMO produced by strain MnI7-9 has potential for bioremediation and reutilization of Ag(+)-containing waste.

In this study we investigated two manganese chelates in order to improve the image enhancement of manganese-enhanced MRI and decrease the toxicity of free manganese ions. Since both MnCl₂ and a low-affinity chelate were associated with a slow continuous decrease of cardiac functions, we investigated intermediate-affinity chelates: manganese N-(2-hydroxyethyl)iminodiacetic acid (Mn-HIDA) and Mn-citrate. The T₁ relaxivity values for Mn-citrate (4.4 m m⁻¹ s⁻¹) and Mn-HIDA (3.3 m m⁻¹ s⁻¹) in artificial cerebrospinal fluid (CSF) were almost constant in a concentration range from 0.5 to 5 m m at 37 °C and 4.7 T. In human plasma, the relaxivity values increased when the concentrations of these Mn chelates were decreased, suggesting the presence of free Mn²⁺ bound with serum albumin. Mn-HIDA and Mn-citrate demonstrated a tendency for better contractility when employed with an isolated perfused frog heart, compared with MnCl₂. Only minimal changes were demonstrated after a venous infusion of 100 m m Mn-citrate or Mn-HIDA (8.3 µmol kg⁻¹ min⁻¹) in rats and a constant heart rate, arterial pressure and sympathetic nerve activity were maintained, even after breaking the blood-brain barrier (BBB). Mn-citrate and Mn-HIDA could not cross the intact BBB and appeared in the CSF, and then diffused into the brain parenchyma through the ependymal layer. The responses in the supraoptic nucleus induced by the hypertonic stimulation were detectable. Therefore, Mn-citrate and Mn-HIDA appear to be better choices for maintaining the vital conditions of experimental animals, and they may improve the reproducibility of manganese-enhanced MRI of the small nuclei in the hypothalamus and thalamus., (Copyright © 2012 John Wiley & Sons, Ltd.)

Sorption of As(III) and As(V) on manganese dioxide was studied by batch equilibration method using (76)As radioactive tracer. Manganese dioxide was prepared by two different methods viz. reacting (a) KMnO(4) solution with MnSO(4) solution, and (b) KMnO(4) solution with concentrated hydrochloric acid. Manganese dioxide was characterized by zeta potential measurement, surface area measurement, thermogravimetry (TG), differential thermal analysis (DTA) and X-ray diffraction (XRD) techniques. Point of zero charge (PZC) for manganese dioxide was between pH 3 and 4. Radioactive tracer ((76)As) was prepared by neutron irradiation of arsenious oxide in self serve facility of CIRUS reactor followed by conversion to As(III) and As(V), by appropriate chemical methods. Sorption of As(III) and As(V) were studied separately, between pH 1 to 11, using (i) freshly prepared, (ii) air-dried and (iii) aged manganese dioxide. Sorption of As(III) and As(V) on freshly prepared as well as aged manganese dioxide, from both the methods was greater than 98% between pH 1 to 9 and decreased above pH 9. Percentage sorption was comparable for manganese dioxide prepared by both the methods in different batches. Sorption capacity was ∼2 mg g(-1) for both As(III) and As(V). Arsenic was desorbed from the manganese dioxide by 0.1 M sodium hydroxide and oxidation state of desorbed arsenic was determined by solvent extraction method. It was found that the desorbed arsenic was present in As(V) oxidation state, independent of the initial oxidation states. This simple and direct chemical evidence, establishing that As(III) is converted to As(V) by manganese dioxide, is reported for the first time. Sorption of As(III) and As(V) on manganese dioxide did not cause an increase in manganese concentration above solubility limit confirming that Mn(2+), formed during oxidation of As(III) to As(V), was re-adsorbed.

A new process for the production of electrolytic amorphous nanomanganese oxides (EAMD) with uniform size and morphology is described. EAMD are produced for the first time by cathodic deposition from a basic aqueous solution of potassium permanganate at a constant temperature of 16°C. The synthesized materials are characterized by XRD, SEM, TEM, and HRTEM. The materials produced at 5.0 V at constant temperature are amorphous with homogeneous size and morphology with an average particle size around 20 nm, which appears to be much lesser than the previously reported anodic EAMD. A potentiostatic electrodeposition with much lesser deposition rate (with respect to previously reported anodic depositions) is considered to be the reason behind the very low and homogenous particle size distribution due to the lesser agglomeration of our as-synthesized nanoparticles., (Copyright © 2012 Elsevier Inc. All rights reserved.)