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Diagenesis of archaeological bones proceeds via a complex combination of chemical, physical and/or microbial processes often over several millennia. These processes are influenced by the depositional environment, including fluctuations in pH, mineral availability and water table. This study investigates diagenetic alterations to the mineral and organic (collagen) phases of bones from a Neolithic site, Etton Causewayed Enclosure (Cambridgeshire, UK). Archaeological bones from some layers of the gravel site at Etton exhibit unusual staining patterns, including iron and manganese rich layers underneath the exterior bone surface and manganese speckling throughout the bone. A range of analytical techniques (micro-CT, FTIR, XRF and SEM-EDS) were employed to investigate the mineralisation within three bones from this site. Diagenesis appears to have occurred through a combination of bacterial degradation and mineral formation due to the changing redox conditions at the site caused by fluctuating groundwater. The reason for the positioning of the manganese layers beneath the iron layers at the surfaces of the bone remains unclear.

Bioaugmented sand filtration has attracted considerable attention because it can effectively remove contaminants in drinking water without additional chemical reagent addition. In this study, a synthesized chemical manganese dioxide (MnO

Nanostructured manganese oxides (nano-MnO

Motor synergies, i.e., neural mechanisms that organize multiple motor elements to ensure stability of actions, are affected by several neurological condition. Asymptomatic welders showed impaired synergy controlling the stability of multi-finger action compared to non-welders and this impairment was associated with microstructural damage in the globus pallidus. We further explored the effect of welding-related metal exposure on multi-finger synergy and extended our investigation to posture-stabilizing synergy during a standing task. Occupational, MRI, and performance-stabilizing synergies during multi-finger accurate force production and load releasing while standing were obtained from 29 welders and 19 age- and sex-matched controls. R2* and R1 relaxation rate values were used to estimate brain iron and manganese content, respectively, and diffusion tensor imaging was used to reflect brain microstructural integrity. Associations of brain MRI (caudate, putamen, globus pallidus, and red nucleus), and motor synergy were explored by group status. The results revealed that welders had higher R2* values in the caudate (p = 0.03), putamen (p = 0.01), and red nucleus (p = 0.08, trend) than controls. No group effect was revealed on multi-finger synergy index during steady-state phase of action (ΔV

Manganese-based catalysts attract extensive attentions in low-temperature selective catalytic reduction (SCR) of nitrogen oxide (NOIn this work, electron paramagnetic resonance spectrometer and density functional theory are combined to reveal surface characterizations of manganese oxide and Ce/La-doped manganese oxides.As a result, superoxide radical (O

Elevated exposure to multiple trace metals can be neurotoxic even at relatively low levels. These findings are primarily evident from adult occupational studies as well as in children exposed prenatally or in early childhood. Less research has focused on the neurodevelopmental impacts of exposure to metals among school-aged children. We examined associations between exposure to a mixture of four metals (arsenic, cadmium, manganese, lead) measured in hair and markers of cognition, attention, and behavior among 222 6-12 year old children who participated in a 2009-2010 neurodevelopmental follow-up to the C8 Health Project. Using quantile-based g-computation we estimated the adjusted overall metal mixture effect ψ (95 % CI) as the change in outcome per decile increase in all metals in the mixture. Hair metal levels varied by metal, with cadmium being lowest (median 0.007, interquartile range (IQR) 0.013 μg/g) and lead the highest concentration (median 0.152, IQR 0.252 μg/g). Children's cognitive skills and development, attention/impulsivity, and behavior were all close to standardized population means. Each decile increase in all metals was associated with a Full Scale IQ reduction of 1.01 points (95 % confidence interval (CI) -1.88, -0.15) and Verbal IQ reduction of 1.11 points (95 % CI -1.97, -0.25), adjusted for child age, sex, secondhand smoke exposure, HOME score, maternal education, maternal IQ, and examiner. Maternal report of ADHD-like behaviors and executive functioning also showed adverse associations with the metal mixture. Our findings suggest that similar to exposure during prenatal and early childhood periods, recent exposure to metals during middle childhood is associated with adverse neurodevelopmental consequences. Middle childhood may also be a developmental window of susceptibility to the negative consequences of exposure to environmental neurotoxicants.

Hydrogen technology is widely considered a novel clean energy source, and electrolysis is an effective method for hydrogen evolution. Therefore, efficient hydrogen evolution reaction (HER) catalysts are urgently needed to replace precious metal catalysts and meet ecological and environmental protection standards. Herein, Ni–Mn–P electrocatalysts are synthesized using facile electrodeposition technology. The influence of the Mn addition on the catalytic behavior is studied by the comprehensive analysis of catalytic performance and morphology of the catalysts. Among them, the Ni–Mn–P0.01 catalyst exhibits small coral-like structures, greatly improving the adsorption and desorption of hydrogen ions and reducing the overpotential hydrogen evolution. Consequently, overpotential at 10 mA cm−2 electric current density is 113 mV, and the value of the Tafel slope achieves 74 mV/dec. Furthermore, the Ni–Mn–P catalyst shows long-time (20 h) stability at current densities of 10 and 60 mA/cm2. The results confirm that the synergistic effect of Ni, Mn, and P accelerates the electrochemical reaction. Meanwhile, the addition of manganese element can change the micromorphology of the catalyst, thereby exposing more active sites to participate in the reaction, enhancing water ionization, improving the catalytic performance. This study opens a new way toward improving the activity of the catalyst by adjusting Mn concentration during the electrodeposition process.

Ferroptosis is a novel form of regulated cell death characterized by the iron-dependent accumulation of lipid peroxides to lethal levels, which is morphologically, biochemically, and genetically distinct from apoptosis, necroptosis, autophagy, and pyroptosis. Manganese play an important role in innate immunity and antitumor immunity. Many manganese-based nanomaterials induce tumor cell death by catalyzing the production of reactive oxygen species (ROS) within the tumor. However, the exact underlying mechanisms remain unclear. As research on ferroptosis advances and its regulatory mechanisms in tumors continue to be refined, more evidence has suggested that triggering ferroptosis in tumor cells is an effective strategy for tumor treatment. In this study, we found that administration of MnCl

Lead (Pb) and manganese (Mn) are common environmental pollutants, with high exposures potentially resulting in neurotoxicity. However, individuals are subject to co-exposures in real life, and it is therefore important to study these metals in combination. Weaning Sprague-Dawley rats (SD rats) were given ad libitum access to drinking water solutions containing Pb (100 ppm), Mn (2.5 mg/mL) or a mixture, and each treatment has its own minocycline (MC) (50 mg/Kg.d) supplement group. The results showed that in the Morris water maze (MWM) and Y maze a significant difference in the escape latency, percent time spent in target quadrant and correct response ratio were noted in all exposure groups when compared to controls. The combined exposure group exhibited the most pronounced effect when compared with each of the single metal exposure groups. The induction levels of hippocampal long-term potentiation (LTP) were significantly reduced in the single metal and combined exposure groups compared to the control group. Furthermore, the inhibitory effects of combined exposure group were significantly greter than in the single metal exposure groups. Microglia displayed activation at day 3 after exposure alone or in combination, while astrocytes showed activation at day 5 after exposure alone or in combination, accompanied by decreased expression levels of glutamate-glutamine cycle-related proteins GLAST, GLT-1, and GS. Furthermore, the levels of the excitatory neurotransmitter glutamate in the synaptic cleft increased significantly. When microglial activation and release of its activated factors were inhibited by minocycline, the activation of astrocytes, and the expression of glutamate-glutamine cycle-related proteins GLAST, GLT-1, and GS were both reversed. In addition, upon minocycline treatment the induction of hippocampal LTP and the cognitive injury were significantly alleviated in each of the exposure groups. Moreover, the effects mentioned above were more significant in the combined exposure group than in the single exposure group. These results suggest that combined exposure to lead and manganese can cause greater effects on cognition and synaptic plasticity when compared to single metal exposure groups. And the reason may involve in microglia abnormal activation leading to an excessive regulation of astrocytes, resulting in glutamate reuptake dysfunction in astrocytes and lead to perturbed cognition and synaptic plasticity.

Neurodegenerative diseases are associated with a multitude of dysfunctional cellular pathways. One major contributory factor is a redox stress challenge during the development of several protein misfolding conditions including Alzheimer's (AD), Parkinson's disease (PD), and less common conditions such as Creutzfeldt Jakob disease (CJD). CJD is caused by misfolding of the neuronal prion protein and is characterised by a neurotoxic unfolded protein response involving chronic endoplasmic reticulum stress, reduced protein translation and spongiosis leading subsequently to synaptic and neuronal loss. Here we have characterised prion disease in mice to assess redox stress components including nitrergic and oxidative markers associated with neuroinflammatory activation. Aberrant regulation of the homeostasis of several redox metals contributes to the overall cellular redox stress and we have identified altered levels of iron, copper, zinc, and manganese in the hippocampus of prion diseased mice. Our data show that early in disease, there is evidence for oxidative stress in conjunction with reduced antioxidant superoxide dismutase mRNA and protein expression. Moreover, expression of divalent metal transporter proteins was reduced for Atp7b, Atox1, Slc11a2, Slc39a14 at 6-7 weeks but increased for Slc39a14 and Mt1 at 10 weeks of disease. Our data present evidence for a strong pro-oxidant environment and altered redox metal homeostasis in early disease pathology which both may be contributory factors to aggravating this protein misfolding disease.

Carbon monoxide (CO) has been regarded as a "silent killer" for its toxicity toward biological systems. However, a low concentration of endogenously produced CO has shown a number of therapeutic benefits such as anti-inflammatory, anti-proliferative, anti-apoptosis, and cytoprotective activities. Carbon monoxide-releasing molecules (CORMs) have been developed as alternatives to direct CO inhalation, which requires a specialized setting for strict dose control. CORMs are efficient CO donors, with central transition metals (such as ruthenium, iron, cobalt, and manganese) surrounded by CO as a ligand. CORMs can stably store and subsequently release their CO payload in the presence of certain triggers including solvent, light, temperature, and ligand substitution. However, CORMs require appropriate delivery strategies to improve short CO release half-life and target specificity. Herein, we highlighted the therapeutic potential of inhalation and CORMs-delivered CO. The applications of conjugate and nanocarrier systems for controlling CO release and improving therapeutic efficacy of CORMs are also described in detail. The review concludes with some of the hurdles that limit clinical translation of CORMs. Keeping in mind the tremendous potential and growing interest in CORMs, this review would be helpful for designing controlled CO release systems for clinical applications.

As one of the most common cathode materials for aqueous zinc-ion batteries (AZIBs), manganese oxides have the advantages of abundant reserves, low cost, and low toxicity. However, the electrochemical mechanism at the cathode of aqueous zinc–manganese batteries (AZMBs) is complicated due to different electrode materials, electrolytes and working conditions. These complicated mechanisms severely limit the research progress of AZMBs system and the design of cells with better performance. Hence, the mechanism of AZMBs currently recognized by most researchers according to the classification of the main ions involved in faradaic reaction are introduced in the review. Then a series of reasons that affect the electrochemical behavior of the battery are summarized. Finally, the failure mechanisms of AZMBs over prolonged cycling are discussed, and the current insufficient research areas of the system are explained, along with the direction of further research being prospected.

The present work aimed to investigate the electrochemical properties of ITO substrates in propylene carbonate (PC) with 0.5 mol/L lithium perchlorate (LiClO4) medium in the presence of elaborated thin films of cerium dioxide pure and doped with manganese at varying percentages Ce1–xMnxO2 (x=0 wt%, 2 wt%, 4 wt% and 6 wt%) were successfully deposited by the spray pyrolysis (SP) technique on the glass substrate and ITO at 450 °C.The effects of manganese (Mn) doping thin films Ce1–xMnxO2 were studied and investigated by using different analyses namely X-ray diffraction (XRD) analysis, Raman spectroscopy method, UV-Vis spectrophotometer technique, atomic force microscopy (AFM) analysis and electrochemical properties. XRD data obtained present a polycrystalline with a face-centred cubic structure of fluorite type. Raman results of thin films undoped and Mn doped show two peaks at 465 and 600 cm–1, this letter due to the formation of extrinsic oxygen vacancies by the incorporation of Mn rate into Ce1–xMnxO2 matrix. Energy dispersive spectroscopy (EDS) data show the presence of Ce, O, and Mn elements in the elaborated films. The AFM results reveal that the surface roughness decreases with increasing Mn rate. Further, band gap energy of thin films decreases with increasing in Mn rate due to the formation of defect state between valence and conduction band. The storage capacity of the elaborated (Ce1–xMnxO2/ITO/PC+LiClO4) electrode reaches a maximum of 1.997 mF in the presence of 6% of Mn.

Accumulating evidence from observational studies, genetic research, and animal models suggests a relationship between toxic and nutritive elements and psychotic spectrum disorders (PSD). This review systematically evaluates the current research evidence for two hypotheses: 1) that exposures to abnormal levels of toxic and nutritive elements early in life contributes to the subsequent development of PSD, and 2) that an imbalance of element levels is linked to psychotic illness and clinical severity. We focused on the extant literature on five elements, lead (Pb), copper (Cu), magnesium (Mg), manganese (Mn), and zinc (Zn), because of their previously documented associations with psychiatric problems and the availability of pertinent literature. The review identified 38 studies of which 11 measured Pb, 27 measured Cu, 16 measured Mg, 15 measured Mn, and 25 measured Zn concentrations in PSD patients and controls. A majority of research has been conducted on nutritive element imbalance, and findings are largely mixed. While it is biologically plausible that element dysregulation is an important modifiable risk factor for PSD, more research into exposure in early life is needed to better characterize this relationship.

Pathogenic biallelic variants in PCK1 coding for the cytosolic phosphoenolpyruvate carboxykinase (PEPCK-C) cause PEPCK-C deficiency, a rare disorder of gluconeogenesis presenting with hypoglycemia, lactic acidosis, and hepatopathy. To date, there has been no systematic analysis of its phenotypic, biochemical, and genetic spectrum.All currently published individuals and a novel patient with genetically confirmed PEPCK-C deficiency were included. Clinical, biochemical, and genetic findings were analyzed. Protein and in-silico prediction score modeling was applied to analyze potential variant effects.Thirty-two individuals from 25 families were found, including one previously unreported patient. The typical biochemical pattern was hypoglycemia triggered by catabolic situations, elevated urinary concentrations of tricarboxylic acid cycle metabolites, mildly elevated alanine and aspartate aminotransferase and elevated lactate concentrations in serum. Plasma glutamine concentrations were elevated in some patients and may be a suitable marker for newborn screening. With adequate treatment, biochemical abnormalities usually normalized following a hypoglycemic episode. Symptom onset usually occurred in infancy with a broad range from neonatal age to adulthood. Regardless of the genotype, different phenotypes with a broad clinical spectrum were found. To date, eight genotypes with nine different PCK1 variants were identified, of which alleles with the recurrent variant c.925GA; p.(Gly309Arg) are predominant and appear to be endemic in the Finnish population. Protein modeling suggests altered manganese- and substrate-binding as superordinate pathomechanisms.Environmental factors appear to be the main determinant for the phenotype in patients with biallelic variants in PCK1. Based on the biochemical pattern, PEPCK-C deficiency is a recognizable cause of childhood hypoglycemia. It is a treatable disease and early diagnosis is important to prevent metabolic derailment and morbidity. Newborn screening can identify at least a sub-cohort of affected individuals through elevated glutamine concentrations in dry blood.

Electrolytic manganese metal residue (EMMR) harmless treatment has always lacked a low-cost and quick processing technology. In this study, surfactants, namely tetradecyl trimethylammonium chloride (TTC), sodium dodecyl benzene sulfonate (SDBS), sodium lignin sulfonate (SLS), and octadecyl trimethylammonium chloride (OTC), were used in the solidification of Mn2+ and removal of NH4+-N from electrolytic manganese metal residue (EMMR). The Mn2+ and NH4+-N concentrations under different reaction conditions, Mn2+ solidification and NH4+-N removal mechanisms, and leaching behavior were studied. The results revealed that the surfactants could enhance the Mn2+ solidification and NH4+-N removal from EMMR, and the order of enhancement was as follows: TTC ＞ SDBS ＞ OTC ＞ SLS. The NH4+-N and Mn2+ concentrations were 12.3 and 0.05 mg/L with the use of 60.0 mg/kg TTC under optimum conditions (solid-liquid ratio of 1.5:1, EMMR to BRM mass ratio of 100:8, temperature of 20 ℃, and reaction duration of 12 h), which met the integrated wastewater discharge standard (GB8978-1996). Mn2+ was mainly solidified as Mn(OH)2, MnOOH and MnSiO3, and NH4+-N in EMMR was mostly removed in the form of ammonia. The results of this study could provide a new idea for cost-effective EMMR harmless treatment.

Manganese (Mn) ores contain substantial concentrations of mercury (Hg), and mining and smelting of Mn ores can bring Hg into the surrounding aquatic environment through atmospheric deposition, leaching of electrolytic Mn residue and Mn gangue dump. However, limited is known that how these processes influence the environmental behaviors of Hg in waterbody. Therefore, the seasonal distribution and existing form of Hg in water and sediment in one Mn ore area in Xiushan County, Chongqing were investigated. Our results showed that the mean Hg and methylmercury (MeHg) concentrations in water (n=35) were 5.8 ± 4.6 ng/L and 0.22 ± 0.14 ng/L, respectively. The mean Hg concentrations in retained riverbed and fluvial bank sediment (n=35) were 0.74 ± 0.26 mg/kg and 0.63 ± 0.27 mg/kg, respectively (the mean MeHg concentrations were 0.64 ± 0.40 µg/kg and 0.51 ± 0.30 µg/kg, respectively). It indicated that the mining and smelting of Mn ores were the main sources of anthropogenic Hg, and Mn may inhibit Hg methylation in rivers in Mn ore areas. Mercury in the bound to iron/ Mn (Fe/Mn) oxides of low crystallinity fraction (Hg-OX) accounted for 4.01% and 5.25% of the total Hg concentrations in the retained riverbed and fluvial bank sediment, respectively. The amount of Hg bound to Fe/Mn oxides in sediment increased significantly due to the manganese mining activities in the investigated area. Therefore, it could be hypothesized that high Hg concentrations in river sediment in Mn mining areas are closely related to high Mn concentration in sediment.

Zinc (Zn) transporter ZIP8, encoded by SLC39A8, is a unique transporter that can transport divalent manganese (Mn) and cadmium (Cd) in addition to Zn. Recently, associations between various human diseases and variant forms of ZIP8 have been reported. Four amino acid residues, V33, G38, S335, and I340, of human ZIP8 (hZIP8) are mutated in patients with congenital disorders of glycosylation (CDG), whose blood Mn levels are extremely low. Many genome-wide association studies have reported that the A391T mutation of hZIP8 caused by rs13107325 is associated with a wide range of diseases. However, the roles of individual mutations of hZIP8 on metal-transporting activity remain elusive. We established DT40 cells respectively expressing the four mutant hZIP8s and compared the Mn- and Cd-transporting activity between the mutants and wild-type hZIP8. Among the four mutations observed in the ZIP8-mutated CDG patients, the S335T and I340 N mutations in the predicted transmembrane domain 5 (TMD5) completely abolished Mn- and Cd-transporting activity, while V33 M or G35R mutations at the N-terminus did not. We also examined the A391T mutation, which slightly reduced metal transporting activity. Finally, we examined the effects of artificial mutations in the metal-binding motif EEXXH in the TMD5. Replacing EEXXH with HEXXH, which exists in most ZIP transporters, abolished the Mn- and Cd-transporting activity of hZIP8, indicating that glutamic acid in this motif plays a critical role in the unique affinity of ZIP8 for Mn and Cd. Thus, the utilization of DT40 cells enabled us to clarify the different functions of each residue of hZIP8 on metal transport.

Pd modified electrodes possess problems such as easy agglomeration and low electrolytic ability, and the use of manganese dioxide (MnO2) to facilitate Pd reduction of organic pollutants is just started. However, there is still a limited understanding of how to match the Pd load and MnO2 to realize optimal dechlorination efficiency at minimum cost. Here, a Pd/MnO2/Ni foam cathode was successfully fabricated and applied for the efficient electrochemical dechlorination of 2,4,6-trichlorophenol (2,4,6-TCP). The optimal electrocatalytic hydrodechlorination (ECH) performance with 2,4,6-TCP dechlorination efficiency (92.58% in 180 min) was obtained when the concentration of PdCl2 precipitation was 1 mmol/L, the deposition time of MnO2 was 300 s and cathode potential was −0.8 V. Performance influenced by the exogenous factors (e.g., initial pH and coexisted ions) were further investigated. It was found that the neutral pH was the most favorable for ECH and a reduction in dechlorination efficiency (6% ∼ 47.6%) was observed in presence of 5 mmol/L of NO 2 − , NO 3 − , S2− or SO 3 2 − . Cyclic voltammetry (CV) and quenching experiments verified the existence of three hydrogen species on Pd surface, including adsorbed atomic hydrogen (H*ads), absorbed atomic hydrogen (H*abs), and molecular hydrogen (H2). And the introduction of MnO2 promoted the generation of atomic H*. Only adsorbed atomic hydrogen (H*ads) was confirmed that it truly facilitated the ECH process. Besides H*ads induced reduction, the direct reduction by cathode electrons also participated in the 2,4,6-TCP dechlorination process. Pd/MnO2/Ni foam cathode shows excellent dechlorination performance, fine stability and recyclable potential, which provides strategies for the effective degradation of persistent halogenated organic pollutants in groundwater.

Propylene molecule owns two active sites, the direct epoxidation of propylene by dioxygen is still a challenge due to the limitation of selectivity. In this work, the direct liquid-phase propylene aerobic epoxidation protocol by chloride manganese meso-tetraphenylporphyrin (MnTPPCl) was developed. The conversion of propylene was 12.7%, and the selectivity towards PO (propylene oxide) reached up to 80.5%. The formation of PO was attributed to the mechanism via high-valent Mn species, which was confirmed by means of in situ UV-vis spectrum.

Constructing cerium and manganese bimetallic catalysts with excellent catalytic performance for soot combustion is the research frontier at present. In order to find out the key factors for catalytic soot combustion of Ce-Mn-O catalysts, a series of Ce-Mn-O catalysts with different Ce/Mn proportions were prepared by co-precipitation method. The activity test results show that it increases first and then decreases with the increase of Mn content. The best catalytic activity is obtained for Ce0.64Mn0.36 catalyst, which shows a maximum rate temperature (Tm) at 306 °C for CO2 production in TPO curve. Compared with non-catalytic soot combustion, the Tm decreases by more than 270 °C. Systematical characterization results suggest that when the adsorbed surface oxygen, lattice oxygen, specific surface area and total reduction amount of the catalysts reach a certain value, the key factors leading to the difference of catalytic activity become the readily reducible and highly dispersed surface manganese oxide species and contact performance of the external surface. The surface manganese oxide species is beneficial to improving the low-temperature reducibility of catalysts and the porous surface is conducive to the contact between catalyst and soot. Furthermore, for the soot combustion reaction containing only O2, the promoting effect of Mn4+ is not obvious.

Metals are ubiquitous chemical entities involved in a myriad of biological processes. Despite their integral role in sustaining life, overexposure can lead to deleterious neurological outcomes posing a public health concern. Excess exposure to metals has been associated with aberrant neurodevelopmental and neurodegenerative diseases and prominently contributes to environmental risk for neurological disorders. Here, we use manganese (Mn) to exemplify the gap in our understanding of the mechanisms behind acute metal toxicity and their relationship to chronic toxicity and disease. This challenge frustrates understanding of how individual exposure histories translate into preventing and treating brain diseases from childhood through old age. We discuss ways to enhance the predictive value of preclinical models and define mechanisms of chronic, persistent, and latent neurotoxicity.

Higher manganese silicide (HMS) is a P-type medium temperature thermoelectric (TE) material, which has attracted widespread attention over the past few decades due to its remarkable mechanical properties, excellent chemical and thermal stability, as well as the non-toxicity, abundance and competitive price. The peak power factor (PF) of HMS is as high as ∼1.50 × 10−3 W m−1 K−2 because of its intrinsic high electrical conductivity and Seebeck coefficient. However, the thermal conductivity of HMS is also high, resulting in relatively low zT values. Introducing nano-dispersion in the matrix is one of the most effective methods to enhance the TE properties via reducing the lattice thermal conductivity significantly without drastic changes on the other parameters. In this study, CsPbBr3 QDs with uniform size were synthesized and introduced into HMS bulks. The PF (at 823 K) was enhanced to 1.71 × 10−3 W m−1 K−2, which is improved 14.0% approximately compared with that of pure HMS owing to the combined effect of element doping and energy filtering. The lattice thermal conductivity (at 823 K) decreased from 2.56 W m−1 K−1 to 1.99 W m−1 K−1 synchronously (∼22.0%) due to the intensive phonon scattering caused by Cs doping, and the embedding of Pb riched CsPbBr3 QDs and Pb QDs. A maximum zT value of 0.57 (823 K) is achieved in CsPbBr3 QDs/HMS composites, which is 36.0% higher than that of pure HMS. Predictably, for other TE materials, it is also feasible to improve the TE properties via introducing metastable quantum dots.

The cerium conversion coating (CeCC) containing copper and manganese cations was applied to the galvanized steel. The microstructure and the composition of specimen were analyzed by field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). Electrochemical impedance spectroscopy (EIS) and polarization tests were conducted in 3.5 wt% NaCl solution to investigate the coating corrosion resistance. The results show that there are improvements in corrosion resistance and microstructure of CeCC containing copper and manganese cations but copper ions increase corrosion resistance of CeCC from 5800 to 27000 Ω⋅cm2.

Manganese is a bioelement essential for the proper functioning of the body. MnTwenty kidneys from Polish Great White pigs were used in the study. Biolasol solution was modified with the addition of MnAfter 48 hours and 30 minutes of renal preservation, activities/concentrations of biochemical parameters in the Biolasol + MnManganese added to the Biolasol solution formulation at a dose of 1 µg/L showed low efficacy in protecting nephrons. We do not recommend adding manganese to the preservative solution formulation.

Manganese ion (Mn2+) generated from metallurgical, steel making and chemical industries enters sewage treatment plants and affects the sludge activity and flocculation. The effect of Mn2+ on the removal of chemical oxygen demand (COD) and total phosphorus (TP) and sludge activity were investigated in anoxic zone of an anaerobic/anoxic/oxic (A2O) process. The compositions and structures of extracellular polymeric substances (EPS) were characterized using three-dimensional excitation emission matrix fluorescence spectroscopy (3D-EEM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) to reveal the relationship among Mn2+, EPS and sludge flocculation. The results showed that low concentration of Mn2+ ( 10 mg/L) hindered microbial flocculation and reduced removal efficiencies of the pollutants. When Mn2+was 5 mg/L, removal efficiencies of COD and TP reached 65% and 90%, respectively. Sludge flocculation was the best and SVI was 70.56 mL/g. The changes of Mn2+ concentration caused deviation of groups’ compositions in LB-EPS and TB-EPS, where the main components were always protein (PN) and polysaccharide (PS). The addition of Mn2+ resulted in the degradation of humic acids. However, it did not give rise to significant morphology changes of EPS.

Among the large energy storage batteries, the sodium ion batteries (SIBs) are attracted huge interest due to the fact of its abundant raw materials and low cost, and has become the most promising secondary battery. Tunnel-type sodium manganese oxides (TMOs) are industrialized cathode materials because of their simple synthesis method and proficient electrochemical performance. Na0.44MnO2 (NMO) is considered the best candidate material for all tunnel-type structural materials. In this paper, the research progress in charge and discharge of cathode materials for tunnel-type structural SIBs is reviewed, the redox mechanism and all sorts of synthesis methods and different coating methods lead to different morphology and electrochemical properties of materials and the classification of electrolytes and non-aqueous electrolytes. The development and utility of aqueous solutions are discussed, and the mechanism is analyzed. Summarized the cationic potential of the transition metal oxide for tunnel structure, plays a vital role in predicting and designing the cathode material of this structure. In addition, the future opportunities and challenges for such tunnel-type SIBs in this field are described in detail.

The temperature of waste gas in refuse transfer station, airport smoking area, and RTO terminal is low, which needs deep oxidation. Catalytic ozonation is one of the most effective treatment techniques in these scenarios. In this study, we reported that catalysts were modified under the condition of magnetic field to simulate the low temperature dynamic conditions of low concentration toluene for catalytic ozonation. This paper aims to explore the relationship between oxygen vacancy and active oxygen species, and the specific pathways of toluene oxidation. The study found that citric acid can enhance the synergistic effect between Mn and Ce, and promote the generation of oxygen vacancies. The surface molecule adsorption oxygen is more conducive to catalytic oxidation than subsurface atom adsorption oxygen. Finally, we proposed the main pathways of toluene in this reaction system, which runs through the whole process of the reaction.

The ozone-initiated oxidation of 1,2-dichlorobenzene catalysed by manganese supported on metal oxide (γ-Al2O3 and SiO2) at ambient temperature and pressure conditions is reported in this study. Wet impregnation method was used to synthesise various percentages of Mn loading on γ-Al2O3 and SiO2 supports. The catalysts were characterised by FT-IR, SEM, EDX, TEM, ICP-OES, BET and XRD techniques. All the reactions were conducted in an impinger glass reactor using 25 mL pure 1,2-dichlorobenzene and 0.25 g of the catalysts. The reaction products were characterised by GC–MS and FT-IR for quantitative and qualitative identification of the products. The 2.5, 5, 7.5 and 10 % of Mn impregnated on γ-Al2O3 and SiO2 were found to be more active than γ-Al2O3 and SiO2 supports. The 5 % Mn/SiO2 catalyst was found to be the most active catalyst in the ozonation reaction of 1,2-dichlorobenzene with a percentage conversion of 44 % and percentage selectivity of 88 % towards the main product mucochloric acid. Whereas, 5 % Mn/γ-Al2O3 catalyst resulted in the percentage conversion of 40 % and percentage selectivity of 86 % towards the main product mucochloric acid. The activity of the catalysts is attributed to manganese loaded on γ-Al2O3 and SiO2 supports.

High-voltage and low-cost manganese-based P2-type oxides show real promise as promising cathode for sodium-ion batteries (SIBs). But the P2−O2 phase transformation and Na+/vacancy ordering results in the inferior structural stability and Na+ diffusion coefficient, which further leads to rapid decay of capacity and poor rate capability. Herein, in consideration of the synergetic effects of dual cationic doping, electrochemically inactive Li+ and active Co3+ co-doping are proposed to solve the above issues. The novel two-step doping strategy, Co doping during synthesis of precursors via co-precipitation reaction followed by Li doping during solid-state reaction, are rationally developed. As anticipated, the Li, Co co-doped P2-type oxide exhibits the absence of P2−O2 phase transformation and Na+/vacancy disordering, which gives rise to an outstanding cycling stability (86.7% capacity retention within 100 cycles at 0.1C) and high-rate capability (reversible capacity of 109 mAh g−1 even at 10C). In addition, the full-cells composed of the co-doped P2-type positive and hard carbon negative show high energy-density, good lifespan and high-rate property. This proposed cationic co-doping provides an effective and scalable tactics for modulating the structural properties of high-voltage P2-type cathodes for advanced SIBs.

Manganese has recently been exploited for cancer immunotherapy, fenton-like reaction-mediated chemo-dynamic therapy, and magnetic resonance imaging. The integration of multiple roles of manganese into one platform is of great significance for cancer theranostics and tumor inhibition. Here, we designed a multifunctional nanoplatform based on manganese, which consisted of a manganese-containing inner core and a phospholipid bilayer shell co-loaded with glucose oxidase (GOx), paclitaxel (PTX), and a NIR fluorescent dye (NanoMn-GOx-PTX). In a pH-dependent manner, the nanoplatform released manganese ions and payloads inside the tumor cells. In vitro characterization and cellular experiments indicated that NanoMn-GOx-PTX could catalyze the conversion of glucose into reactive oxygen species (ROS) through a cascade Fenton-like reaction as well as release free PTX. The consumption of glucose, ROS production, and the chemotherapeutic effect of PTX contributed to the superior cytotoxicity and apoptosis of 4T1 cancer cells. Moreover, NanoMn-GOx-PTX effectively induced the production of large amounts of type I interferon and pro-inflammatory cytokines in vivo, activating the innate immune response. Through the synergistic functions of the above components, NanoMn-GOx-PTX exerted the strongest anti-tumor effect in 4T1 tumor-bearing models. Therefore, the manganese-based nanoplatform could serve as a promising theranostic tool for breast cancer therapy. STATEMENT OF SIGNIFICANCE: 1) This nanoplatform can be used as a universal tool for delivering proteins and anticancer drugs into cells; 2) The PEG-modified phospholipid bilayer shell plays a significant role in retarding the release of overloaded manganese ions and drugs in a pH-sensitive manner; 3) The released Mn

Due to the progressive shortage of primary resources and growing environmental concerns over industrial and household residues, proper management of electronic wastes is of great importance in addressing sustainability issues. Spent batteries are considered as important secondary sources of their constituting components. In this study, the co-recycling of used zinc-carbon and lithium-ion batteries was performed aiming at the recovery of their manganese and lithium contents as compounds which can be used as precursors for the synthesis of spinel LiMn2O4. Manganese was recovered in the form of amorphous, submicron, spherical nodules of MnO2 after acid leaching of zinc-carbon battery pastes. Lithium was obtained from nickel-manganese-cobalt (NMC) batteries as its monohydrate oxalate (C2HLiO4.H2O) through selective leaching in oxalic acid followed by crystallization. Lithium carbonate was also prepared by subsequent calcination of the oxalate. The synthesis of LiMn2O4 spinel cathode was carried out using the recycled Li- and Mn-containing compounds via solid-state synthesis method. The effect of such parameters as type of reactants (C2HLiO4.H2O, Li2CO3, Mn2O3, and MnO2), temperature (750, 800, and 850 °C), and time (8 and 10 h) on the synthesis of LiMn2O4 was investigated. The products were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The crystallographic parameters used to predict the electrochemical behavior of synthesized cathode materials were derived from XRD patterns. Based on these, the spinel powder synthesized at 850 °C for 10 h was determined as the sample with the best potential electrochemical properties among the synthesized samples. The galvanostatic charge/discharge characterization within the voltage range of 2.5–4.3 V showed the specific capacity of the 850°C-10 h sample to be 127.87 mAhg−1.

LnMnO3+σ (Ln = La, Pr, Nd, Sm, Eu, Gd or Dy) perovskites synthesized by sol-gel method were employed for gaseous elemental mercury (Hg0) removal from coal-fired flue gas. Characterization results revealed the structure of the perovskites presented a phase transition process from rhombohedral system to O- and O'-orthorhombic structure with the change of A-site rare earth elements. The perovskites showed satisfactory Hg0 removal capacity in a narrow temperature range of 100–150°C. NdMnO3+σ with an O-O’ orthorhombic structure presented the best Hg0 removal performance, which markedly depends on four factors: crystal structure, oxygen vacancy density, Mn4+/Mn3+ ratio and surface element segregation. The Hg0 removal mechanism was illustrated based on the mercury temperature programmed desorption experiment and X-ray photoelectron spectroscopy characterization. Both chemisorption and catalytic oxidation played a role in the Hg0 removal process. Chemisorption dominated the Hg0 removal, due to the slow catalytic oxidation rate at low temperature. This work preliminarily established the relation between the structure of rare earth manganese perovskite and Hg0 removal performance.

Due to high safety and excellent rate performance, the aqueous Zn-ion battery is a promising energy storage battery for practical application. However, most manganese-based compounds suffer from poor cycling and rate performance. Herein, a new concept of Zn-ions battery is assembled with the loofah-like LaMnO3 perovskite as a novel cathode, achieving fast ion kinetics through the co-intercalation of Zn2+ and H+ cations. In this work, the Ni-doping strategy is adopted to improve the electrochemical performance of LaMnO3 perovskite as a cathode material for Zn-ion batteries. The resultant LaNixMn1-xO3 (x = 0.2) exhibits a superior capacity of 226 mAh g-1 after 80 cycles at 100 mA g-1 and high working voltages at 1.4 V and 1.26 V vs. Zn2+/Zn in the electrolyte of 2 M ZnSO4 + 0.2 M MnSO4. Even at 500 mA g-1, the new Zn/LaNixMn1-xO3 battery still delivers a discharge capacity of 113 mAh g-1 after 1000 cycles. At medium current density, the electrochemical process of the LaNixMn1-xO3 (x = 0.2) electrode is co-controlled by the solid diffusive and surface-capacitive process with a fast ion diffusion rate. The lanthanum manganese perovskite is a potential cathode material for Zn-ion batteries with long cycle performance and high rate cyclability. This work significantly opens up the way of perovskite materials as new cathodes for high-rate ZIBs.

The enantioselective epoxidation of olefin by MnII(R,R-PMCP)(OTf)2, H2O2 and H2SO4 was explored by DFT calculations and experiments. Theoretical results suggest that [MnV(O)(R,R-PMCP)(SO4)]+ species with a triplet ground spin state serves as the active species for the olefin epoxidation. It can be generated by the H2SO4 assisted O-O heterolysis of MnIII(OOH) species. MnIII-persulfate is also involved in this system, but it cannot promote the olefin epoxidation directly, preferring instead to transform into MnV(O). Actually, the asymmetric epoxidation reactions with H2O2/H2SO4 or Oxone provide similar enantioselectivity in the presence of manganese catalyst. These observations further support the transformation of MnIII-persulfate to MnV(O) species.

To characterize the association between environmental (residential air) manganese (Mn) exposure and cognitive performance, focusing on cognitive control, in a Black African population.We administered the Go-No-Go, Digit Span, and Matrix Reasoning tests to population-based samples age ≥40 from a high Mn (smelter) exposed community, Meyerton (N = 629), and a demographically comparable low (background levels) non-exposed community, Ethembalethu, (N = 96) in Gauteng province, South Africa. We investigated the associations between community and performance on the cognitive tests, using linear regression. We adjusted a priori for age and sex, and examined the effect of adjustment for education, nonverbal IQ, smoking, and alcohol consumption. We measured airborne PMCompared to Ethembalethu residents, Meyerton residents' test scores were lower (poorer) for all tests: 0.55 (95 % confidence interval [CI] 0.08, 1.03) lower scores for Matrix Reasoning, 0.34 (95 % CI -0.07, 0.75) lower for Digit Span, and 0.15 (95 % CI 0.09, 0.21) lower for Go-No-Go (high frequency discriminability index [probability]). The latter represented the most marked difference in terms of z-scores (0.50, 95 % CI 0.30, 0.71 standard deviations lower). The mean of the z-score of each of the three tests was also lower (0.34, 95 % CI 0.18, 0.50 standard deviations lower). These associations were similar in men and women, but attenuated with adjustment for education. Differences for Matrix Reasoning and Digit Span between the two communities were observed only among those who had lived in Meyerton ≥10 years, whereas for Go-No-Go, differences were also apparent among those who had lived in Meyerton10 years. Mean PMResidence in a community near a high Mn emission source is associated with cognitive dysfunction, including aspects of cognitive control as assessed by the Go-No-Go test.

Commercial lithium-ion batteries (LIBs) have been widely used in various energy storage systems. However, many unfavorable factors of LIBs have prompted researchers to turn their attention to the development of emerging secondary batteries. Aqueous zinc ion batteries (AZIBs) present some prominent advantages with environmental friendliness, low cost and convenient operation feature. MnO2 electrode is the first to be discovered as promising cathode material. So far, manganese-based oxides have made significant progresses in improving the inherent capacity and energy density. Herein, we summarize comprehensively recent advances of Mn-based compounds as electrode materials for ZIBs. Especially, this review focuses on the design strategies of electrode structures, optimization of the electrochemical performance and the clarification of energy storage mechanisms. Finally, their future research directions and perspective are also proposed.

Rechargeable aqueous zinc ion batteries (ZIBs) have attracted more and more attention due to the advantages of high safety, low cost, and environmental friendly in recent years. However, the lack of high-performance cathode materials and uncertain reaction mechanisms hinder the large-scale application of ZIBs. Herein, a 1D structure interlaced by ZnxMnO2 nanowires and carbon nanotubes is synthesized as cathode material for ZIB. The ZnxMnO2/CNTs cathode exhibits excellent specific capacity of 400 mAh g-1 at 100 mA g-1 and outstanding long-cycle stability (with a capacity retention of 93% after 100 cycles at 1000 mA g-1), which indicates the Zn2+ pre-intercalation and composite carbon nanotubes can effectively change the storage space of the tunnel structure and increase the electron transmission rate. In addition, the energy storage mechanism of the highly reversible co-insertion of H+ and Zn2+ is further elaborated. This work has enlightenment and promotion for the future research of ZIBs cathode materials. Moreover, the simple preparation method, low cost and excellent performance of ZnxMnO2/CNTs cathode material provide a new way for the practical application of ZIBs.

Impairment of the astrocytic glutamate transporter excitatory amino acid transporter 2 (EAAT2) is associated with neurological disorders such as Parkinson’s disease (PD), Alzheimer’s disease (AD), and manganism, a neurological disorder caused by overexposure to manganese (Mn) which shares the features of sporadic PD. Mechanisms of Mn-induced neurotoxicity include dysregulation of EAAT2 following activation of the transcription factor Yin Yang 1 (YY1) by transcriptional upregulation, but the posttranslational mechanisms by which YY1 is activated to repress EAAT2 remain to be elucidated. In the present study, we tested if Mn activates YY1 through posttranslational phosphorylation in cultured H4 human astrocytes, leading to EAAT2 repression. The results demonstrate that Mn exposure induced phosphorylation of YY1 at serine residues via kinases Aurora B kinase (AurkB) and Casein kinase II (CK2), leading to YY1 nuclear translocation, YY1/HDAC interactions, binding to the EAAT2 promoter, and consequent decreases in EAAT2 promoter activity and mRNA/protein levels. Although further studies are warranted to fully elucidate the mechanisms of Mn-induced YY1 phosphorylation and resultant EAAT2 impairment, our findings indicate that serine phosphorylation of YY1 via AurkB and CK2 is critical, at least in part, to its activation and transcriptional repression of EAAT2.

Ozonation process alone is not sufficient to remove both the SO2 and NOX gases, when treated simultaneously. Therefore in this work, a suitable technique to remove SO2 and NOX simultaneously has been evaluated using combination of O3, H2O2 and a solid catalyst. OMS-2, a manganese based catalyst have been incorporated with O3 and H2O2 for enhanced radical generation. This preferably enhances the oxidation of SO2 and NOx species in aqueous medium simultaneously. The role of some important process parameters have been tested on the performance of SO2 and NOX absorption. To get the maximum removal of SO2 and NOX, the neutral pH, temperature close to 300–320 K, and H2O2 at 0.2 mol L−1 concentrations was found to be the optimum condition. The use of catalyst (approximately 2 g L−1) + O3 + H2O2 shows promising results on the removal of SO2 and NOX. In addition to that, the kinetics of the catalytic ozonation and peroxone removal of SO2 and NO2 has been evaluated. The cost estimation study for the ozone and peroxone based catalytic processes has been presented with comparison of the respective flue gas %removal.

A once overlooked source of electrolyte degradation incurred by dissolved manganese (II) species in lithium-ion batteries has been identified recently. In order to deactivate the catalytic activity of such manganese (II) ion, 1-aza-12-crown-4-ether (A12C4) with cavity size well matched manganese (II) ion is used in this work as electrolyte additive. Theoretical and experimental results show that stable complex forms between A12C4 and manganese (II) ions in the electrolyte, which does not affect the solvation of Li ions. The strong binding effect of A12C4 additive reduces the charge density of manganese (II) ion and inhibits its destruction of the PF6− structure in the electrolyte, leading to greatly improved thermal stability of manganese (II) ions-containing electrolyte. In addition to bulk electrolyte, A12C4 additive also shows capability in preventing Mn2+ from degrading SEI on graphite surface. Such bulk and interphasial stability introduced by A12C4 leads to significantly improved cycling performance of LIBs.

One of the most important priorities in the medicinal mushrooms cultivation is the selection and preparation of the substrate, which depends on factors such as price and easy access to different lignocellulosic compounds. In order to investigate the effect of mixed and non-mixed agro-waste substrates on some vegetative, reproductive, nutritional and medicinal properties of two Iranian and Chinese strains of Ganoderma lucidum, the factorial experiment was conducted as a completely randomized design with three replications. The experimental substrates of different poplar wood chip (PWC), wheat bran (WB), soybean meal (SM), date palm leaf (DPL) and olive oil extraction waste (OOEW) were used. They were enriched with chemical supplements (ammonium nitrate, manganese sulfate and Nano manganese oxide) using two cultivation techniques (open bag door and Polika-Cotton) for fruiting body production. The results showed that various substrates significantly affect dry weight, moisture content quantity, vegetative and fruit yield, total ganoderic acids content, total polysaccharide value and mineral elements amount (nitrogen, potassium and calcium) in fruiting body. The highest amount of N content in the fruiting body of both Iranian and Chinese strains (5.88 and 6.25 mg/100 g dry matter) was dedicated to the combined PWC + SM (70:30) substrate enriched with Nano manganese oxide supplement and Polika-Cotton method. The highest total fresh of Iranian and Chinese strains weight (109.60 and 127.66 g, respectively) obtained in the combined PWC + WB (70:30) substrate enriched with manganese sulfate. The highest amount of total ganoderic acids in fruiting organs in both strains (0.52 and 0.42 μg/mg dry matter) is achieved using a combined PWC + SM (70:30) enriched with manganese sulfate.

Dual-emitting manganese ions singly doped 5ZnO-(5–2.5x)Ga2O3-2.5 xAl2O3–90SiO2 glass-ceramic (GCs) samples, containing the alloyed Zn(Ga, Al)2O4 nanocrystals with a size of about 5 nm, were successfully prepared by a sol-gel method under different heat treatment temperatures, demonstrating an excellent white light emission. We found that the formation of the ZnGa2O4 nanocrystals began at 650 °C (absence of Al2O3, x = 0) while that of the ZnAl2O4 crystals required a higher temperature of about 900 °C (presence of Al2O3, x = 2) in SiO2 glasses. A nanostructured Zn(Ga, Al)2O4:Mn2+, Mn4+ in the glass-ceramic was synthesized by Al3+ replacing part of Ga3+. The doping of Al3+ has effectively contributed to the existence of Mn2+, thus realizing the regulation of the valence state of manganese ions. The glass ceramic samples showed red emission arrived from the 2Eg → 4A2g transitions of Mn4+, green emission originated from the 4T1→6A1 transition of Mn2+, and blue emission derived from the self-activation center of ZnGa2O4 nanocrystalline. In particular, the 0.1%Mn doped the 5ZnO-(5–2.5x)Ga2O3-2.5xAl2O3–90SiO2 glass-ceramic samples can provide white color emission depending on the Al doping concentration (x), x = 0.4–0.9 and the annealing temperature, 650–900 °C.

The characterization results of influence of various concentration of Mn (II) ion on the properties and crystalline perfection of ammonium di hydrogen phosphate (ADP) crystal are presented. Using water as a solvent, pure and 1, 5, 10 and 20 mol % of Mn (II) ion in the form manganese (II) sulphate added ADP crystals are prepared by slow evaporation solution growth technique (SEST). Well faceted grown crystals are characterised by different experimental techniques. The presence of Mn (II) in the doped specimens is confirmed by energy dispersive X-ray spectroscopy (EDS) and inductively coupled plasma (ICP) technique. The surface morphology of the crystals is studied by scanning electron microscopy (SEM). The grown crystals are also characterized by FT-IR, UV–Vis and TG/DTA methods. The second harmonic generation (SHG) efficiency, which is an essential character required for the single crystals to identify the nonlinear optical (NLO) property, is performed by Kurtz powder technique. Moderate concentrations of dopant enhance the SHG efficiency of ADP crystal.

The present work deals with the synthesized Manganese (Mn) doped Nickel oxide nanoparticles. Using hydrothermal method, the Manganese (Mn) doped Nickel oxide nanoparticles were synthesized with the concentration ranges from 1 mol% to 2 mol%. The characterization done for the synthesized nanoparticles are X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), DSC spectroscopy and UV visible spectroscopy. The XRD reveals the amorphous nature with the size ranges from 60 nm to 20 nm. The chemical bonding nature and functional group analysis of the prepared material was confirmed by FTIR Spectroscopy. The optical behaviour of the Manganese (Mn) doped Nickel oxide nanoparticle was done using UV–Visible spectroscopy. The antibacterial activity of the prepared nanoparticles was done for both gram negative and gram-positive bacterial strains. The prepared nanoparticles have proven to be promising candidates to be utilized in drug delivery and food packaging applications.

MnO2-based aqueous Zn-ion batteries (ZIBs) hold great promising for large-scale energy storage applications owing to their safe and sustainable nature. However, rapid capacity decay under high depth of discharge limits the applications of MnO2 cathodes. In the meantime, the reaction chemistry and degradation process of MnO2 cathodes cannot be fully understood, leading to improvement of their cycling stability lacks of robust methods. Herein, ZIB performances of MnO2 polymorphs are investigated to disclose their detailed reaction chemistry and degradation mechanisms. Ex situ characterizations at different cycles exhibit evolution of active materials (original MnO2→Mn2+→birnessite→ZnMn2O4/Mn3O4) and coexisted reactions from co-insertion, dissolution/deposition and chemical conversion mechanisms. Variational contributions from these intermediate products and different reaction mechanisms cause fluctuated performance during cycling. Initial performance activation is from enhanced activity of birnessite, while the degradation is caused by its conversion to electrochemically inactive ZnMn2O4 and Mn3O4. By optimizing tunnel structures, it is found that R-MnO2 shows low manganese dissolution with its reaction mainly achieved by intercalation/extraction of Zn2+/H+, and theoretical calculations verify its low Jahn-Teller distortion at discharged state. This specific property circumvents conversion of R-MnO2 to metastable birnessite, giving rise to a stable capacity under high depth of discharge.

Photodynamic therapy (PDT) is an effective noninvasive therapeutic strategy that can convert oxygen to highly cytotoxic singlet oxygen (1O2) through the co-localization of excitation light and photosensitizers. However, compromised by the hypoxic tumor microenvironment, the therapeutic efficacy of PDT is reduced seriously. Herein, to overcome tumor-associated hypoxia, and further achieve tumor-targeted synergistic chemotherapy/PDT/photothermal therapy (PTT), we have constructed a biodegradable oxygen-producing nanoplatform (named Ini@PM-HP), which was composed of the porous metal-organic framework (PCN-224(Mn)), the poly (ADP-ribose) polymerase (PARP) inhibitor (Iniparib), and the polydopamine-modified hyaluronic acid (HA-PDA). Since HA can specifically bind to the overexpressed HA receptors (cluster determinant 44, CD44) on tumor cell, Ini@PM-HP prefers to accumulate at the tumor site once injected intravenously. Then iniparib can be released in tumor environment (TME), thereby dysfunctioning DNA damage repair and promoting cell apoptosis. At the same time, the chelating of Mn and tetrakis(4-carboxyphenyl) porphyrin (Mn-TCPP) can generate O2 in situ by reacting with endogenous H2O2, relieving the hypoxic TME and achieving enhanced PDT. Moreover, owing to the high photothermal conversion efficiency of PDA, PTT can be driven by the 808 nm laser irradiation. As systematically demonstrated in vitro and in vivo, this nanotherapeutic approach enables the combined therapy with great inhibition on tumor. Overall, the as-prepared nanoplatform provide a promising strategy to overcome tumor-associated hypoxia, and shows great potential for combination tumor therapy. Statement of significance A delicately designed biodegradable oxygen-producing nanoplatform Ini@PM-HP is constructed to achieve combination therapy of solid tumors. Taking advantage of the active-targeting, PTT, enhanced PDT and PARPi, this nanotherapeutic approach successfully enables the combined chemo/photothermal/photodynamic therapy with great inhibition of solid tumors.

This study was designed to evaluate the response of rainfed lentil to manganese (Mn) foliar application in high-calcareous soil located in the arid Mediterranean area. Field experiments on two clay calcareous soils containing different free carbonates and exchangeable Mn contents were carried out. The soil“1” has Mn content (DTPA extraction) of 7.5 mg kg−1 and it contains 8.9% of free carbonates. The soil“2” contains 3.3 mg kg−1 of Mn and it has a free carbonates level of 15.9%. Five foliar spray concentrations of Mn in lentil (0 as control; 0.5%; 1%; 3%; and 8%) were tested. Mn was applied in the sulfate form at flower bud and flowering. The soil“1” and soil”2” were evaluated during the 2016–17 and 2017–18 seasons, respectively. Results showed that foliar Mn feeding did not enhance grain yield and its components. Mn foliar spray over than 1% resulted in leaf damage during the rainfall season 2017–18 (429 mm) compared to 2016–17 (289 mm). At 8% of Mn, the phytotoxicity reduced grain yield by 34.5% compared to control. For both calcareous soils, shoot Mn content at the end of flowering was over 30 mg kg−1 for control and exceeded 1800 mg kg−1 at 8% of Mn. No antagonism or synergy between Mn and the other nutrients (N, P, K, Ca, Mg, Cu, and Zn) was recorded.