Leaf Manganese Accumulation And Phosphorus-acquisition Efficiency.

Plants that deploy a phosphorus (P)-mobilising strategy based on the release of carboxylates tend to have high leaf manganese concentrations ([Mn]). This occurs because the carboxylates mobilise not only soil inorganic and organic P, but also a range of micronutrients, including Mn. Concentrations of most other micronutrients increase to a small extent, but Mn accumulates to significant levels, even when plants grow in soil with low concentrations of exchangeable Mn availability. Here, we propose that leaf [Mn] can be used to select for genotypes that are more efficient at acquiring P when soil P availability is low. Likewise, leaf [Mn] can be used to screen for belowground functional traits related to nutrient-acquisition strategies among species in low-P habitats.

Distribution and behavior of manganese in the Alto do Paranapanema Basin

This paper reports manganese (Mn) fractionation in samples collected from the water column and sediments in an environmental protection area in the Alto do Paranapanema Basin (Sao Paulo State, Brazil). The three locations studied showed equivalent Mn levels, with moderate seasonal differences (p < 0.05). The sediment samples contained five Mn species (p < 0.05): iron and manganese (hydr)oxides > Mn bound to carbonates approximate to exchangeable Mn approximate to Mn bound to silicates > Mn bound to organic matter (p < 0.05). The water samples contained three species (p < 0.05): particulate Mn > labile Mn approximate to non-labile Mn. The data suggest that Mn has a natural origin (Enrichment Factor EF < 2; Geoaccumulation Index I(geo) < 0) and moderate environmental risk (Risk Assessment Code RAC similar to 30%). At the same time, under certain conditions some manganese species could be present in a state of equilibrium between the water column and sediment. These results could provide a basis for Mn management in the Alto do Paranapanema Basin.

Evaluation of Several Carbon-Supported Nanostructured Ni-Doped Manganese Oxide Materials for the Electrochemical Reduction of Oxygen

Physical and electrochemical properties of nanostructured Ni-doped manganese oxides (MnO(x)) catalysts supported on different carbon powder substrates were investigated so as to characterize any carbon substrate effect toward the oxygen reduction reaction (ORR) kinetics in alkaline medium. These NiMnO(x)/C materials were characterized using physicochemical analyses. Small insertion of Ni atoms in the MnO(x) lattice was observed, which consists of a true doping of the manganese oxide phase. The corresponding NiMnO(x) phase is present in the form of needles or agglomerates, with crystallite sizes in the order of 1.5-6.7 nm (from x-ray diffraction analyses). Layered manganite (MnOOH) phase has been detected for the Monarch 1000-supported NiMnO(x) material, while different species of MnO(x) phases are present at the E350G and MM225 carbons. Electrochemical studies in thin porous coating active layers in the rotating ring-disk electrode setup revealed that the MnO(x) catalysts present better ORR kinetics and electrochemical stability upon Ni doping. The ORR follows the so-called peroxide mechanism on MnO(x)/C catalysts, with the occurrence of minority HO(2)(-) disproportionation reaction. The HO(2)(-) disproportionation reaction progressively increases with the Ni content in NiMnO(x) materials. The catalysts supported on the MM225 and E350G carbons promote faster disproportionation reaction, thus leading to an overall four-electron ORR pathway. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3528439] All rights reserved.

Exploiting Mn(III)/EDTA complex in a flow system with solenoid micro-pumps coupled to long pathlength spectrophotometry for fast manganese determination

The formation of the Mn(III)/EDTA complex in a flow system with solenoid micro-pumps was exploited for fast manganese determination in freshwater. Manganese(II) was oxidized in a solid-phase reactor containing lead dioxide immobilized on polyester. Long pathlength spectrophotometry was exploited to increase sensitivity, aiming to reach the threshold limit established by environmental legislation. A linear response was observed from 25 to 1500 mu g L(-1), with a detection limit of 6 mu g L(-1) (99.7% confidence level). Sample throughput and coefficient of variation were 36 samples/h and 2.6% (n = 10), respectively. EDTA consumption and waste generation were estimated as 500 mu g and 3 mL per determination, respectively. The amount of Pb in the residue corresponds to 250 mu g per determination and a solid-phase reactor could be used for up to 1600 determinations. Adsorption in active charcoal avoided interferences caused by organic matter and the developed procedure was successfully applied for determination of manganese in freshwater samples. Results were in agreement with those attained by GFAAS at the 95% confidence level. (C) 2010 Elsevier B.V. All rights reserved.

Extraction of manganese peroxidase produced by Lentinula edodes

Lentinula edodes, commonly called shiitake, is considered a choice edible mushroom with exotic taste and medicinal quality. L. edodes grows very well and produces a range of enzymes when cultivated on eucalyptus residues. Development of appropriate experimental procedures for recovery and determination of enzymes became a widely important cash crop. In this work, enzymes produced by L. edodes were extracted using different pH buffer and determined regarding peroxidases and proteases. Lignin peroxidase (LiP) was not detected in the extracts based on veratryl alcohol or azure B oxidation. Proteases were very low while Mn-peroxidases (MnP) predominated. The optimal pH for MnP recovery was 5.0, under agitation at 25 degrees C. The oxidation of phenol red decreased after dark-colored small compounds or ions were eliminated by dialysis. The extract of L. edodes contained components of high molecular weight, such as proteases or high polyphenol, that could be involved in the LiP inactivation. L. edodes sample previously submitted to dialysis was also joined to UP of Phanerochaete chrysosporium and a total inhibition of UP was observed. (C) 2007 Elsevier Ltd. All rights reserved.

Optimal recovery process conditions for manganese-peroxidase obtained by solid-state fermentation of eucalyptus residue using Lentinula edodes

Enzyme production is a growing field in biotechnology and increasing attention has been devoted to the solid-state fermentation (SSF) of lignocellulosic biomass for production of industrially relevant lignocellulose deconstruction enzymes, especially manganese-peroxidase (MnP), which plays a crucial role in lignin degradation. However, there is a scarcity of studies regarding extraction of the secreted metabolities that are commonly bound to the fermented solids, preventing their accurate detection and limiting recovery efficiency. In the present work, we assessed the effectiveness of extraction process variables (pH, stirring rate, temperature, and extraction time) on recovery efficiency of manganese-peroxidase (MnP) obtained by SSF of eucalyptus residues using Lentinula edodes using statistical design of experiments. The results from this study indicated that of the variables studied, pH was the most significant (p < 0.05%) parameter affecting MnP recovery yield, while temperature, extraction time, and stirring rate presented no statistically significant effects in the studied range. The optimum pH for extraction of MnP was at 4.0-5.0, which yielded 1500-1700 IU kg (1) of enzyme activity at extraction time 4-5 h, under static condition at room temperature. (C) 2011 Elsevier Ltd. All rights reserved.

Spectroscopic identification of a dinuclear metal centre in manganese(II)-activated aminopeptidase P from Escherichia coli: implications for human prolidase

Electron paramagnetic resonance (EPR) spectra and X-ray absorption (EXAFS and XANES) data have been recorded for the manganese enzyme aminopeptidase P (AMPP, PepP protein) from Escherichia coli. The biological function of the protein, a tetramer of 50-kDa subunits, is the hydrolysis of N-terminal Xaa-Pro peptide bonds. Activity assays confirm that the enzyme is activated by treatment with Mn2+. The EPR spectrum of Mn2+-activated AMPP at liquid-He temperature is characteristic of an exchange-coupled dinuclear Mn(II) site, the Mn-Mn separation calculated from the zero-field splitting D of the quintet state being 3.5 (+/- 0.1) Angstrom. In the X-ray absorption spectrum of Mn2+-activated AMPP at the Mn K edge, the near-edge features are consistent with octahedrally coordinated Mn atoms in oxidation state +2. EXAFS data, limited to k less than or equal to 12 Angstrom(-1) by traces of Fe in the protein, are consistent with a single coordination shell occupied predominantly by O donor atoms at an average Mn-ligand distance of 2.15 Angstrom, but the possibility of a mixture of O and N donor atoms is not excluded. The Mn-Mn interaction at 3.5 Angstrom, is not detected in the EXAFS, probably due to destructive interference from light outer-shell atoms. The biological function, amino acid sequence and metal-ion dependence of E. coli AMPP are closely related to those of human prolidase, an enzyme that specifically cleaves Xaa-Pro dipeptides. Mutations that lead to human prolidase deficiency and clinical symptoms have been identified. Several known inhibitors of prolidase also inhibit AMPP. When these inhibitors are added to Mn2+-activated AMPP, the EPR spectrum and EXAFS remain unchanged. It can be inferred that the inhibitors either do not bind directly to the Mn centres, or substitute for existing Mn ligands without a significant change in donor atoms or coordination geometry. The conclusions from the spectroscopic measurements on AMPP have been verified by, and complement, a recent crystal structure analysis.

Seedling responses of four Australian tree species to toxic concentrations of manganese in solution culture

Little is known about the responses of Australian plants to excess metal, including Mn. It is important to remedy this lack of information so that knowledgeable decisions can be made about managing Mn contaminated sites where inhabited by Australian vegetation. Acacia holosericea, Melaleuca leucadendra, Eucalyptus crebra and Eucalyptus camaldulensis were grown in dilute solution culture for 10 weeks. The seedlings ( 42 days old) were exposed to six Mn treatments viz., 1, 8, 32, 128, 512 and 2048 muM. The order of tolerance to toxic concentrations of Mn was A. holosericea congruent to = E. crebra < M. leucadendra < E. camaldulensis, the critical external concentrations being approximately 5.1, 5.0, 21 and 330 muM, respectively. The critical tissue Mn concentrations for the youngest fully expanded leaf and total shoots were, respectively, 265 and 215 mug g(-1) DM for A. holosericea, 445 and 495 mug g(-1) DM for M. leucadendra, 495 and 710 mug g(-1) DM for E. crebra and 7230 and 6510 mug g(-1) DM for E. camaldulensis. The high tolerance of E. camaldulensis ( as opposed to the sensitivity of E. crebra) to excess Mn raises concern about fauna feeding on the plant and is consistent with hypotheses suggesting the Eucalyptus subgenus Symphomyrtus is particularly tolerant of stress, including excess Mn. The results from this paper provide the first comprehensive combination of growth responses, critical external concentrations, critical tissue concentrations and plant toxicity symptoms for three important Australian genera, viz., Eucalyptus, Acacia and Melaleuca, for use in the management of Mn toxic sites.

Carbamazepine oxidation catalyzed by iron and manganese porphyrins supported on aminofunctionalized matrices

This work describes the catalytic activity of manganese and iron porphyrins, Mn and Fe(TFPP)Cl, covalently immobilized on the aminofunctionalized supports montmorillonite K-10 (MontX) and silica (SilX), where X= 1 or 2 represents the length of the organic chain (""arms"") binding the metalloporphyrin to the support. These systems were characterized by UV-vis and Electronic Paramagnetic Resonance (EPR), and they were used as catalysts in the oxidation of carbamazepine (CBZ) by the oxidants iodosylbenzene (PhIO) and hydrogen peroxide. The manganese porphyrin (MnP) catalysts proved to be efficient and selective for the epoxide, the main CBZ metabolite in natural systems. MnMont1 was an excellent catalyst when PhIO was used as oxidant, even better than the same MnP in homogeneous system. Supports bearing short ""arms"" led to the best yields. Although H2O2 is an environmentally friendly oxidant, low product yields were obtained when it was employed in CBZ oxidation. Fe(TFPP)CI immobilized on aminofunctionalized supports was not an efficient catalyst, probably due to the presence of Fe(H) species in the matrix, which led to the less reactive intermediate PFe(IV)(O). (c) 2007 Elsevier B.V. All rights reserved.

Biomimetic Oxidation of Piperine and Piplartine Catalyzed by Iron(III) and Manganese(III) Porphyrins

Synthetic metalloporphyrins, in the presence of monooxygen donors, are known to mimetize various reactions of cytochrome P450 enzymes systems in the oxidation of drugs and natural products. The oxidation of piperine and piplartine by iodosylbenzene using iron(III) and manganese(III) porphyrins yielded mono- and dihydroxylated products, respectively. Piplartine showed to be a more reactive substrate towards the catalysts tested. The structures of the oxidation products were proposed based on electrospray ionization tandem mass spectrometry.

Accumulation of manganese in Neisseria gonorrhoeae correlates with resistance to oxidative killing by superoxide anion and is independent of superoxide dismutase activity

As a facultative aerobe with a high iron requirement and a highly active aerobic respiratory chain, Neisseria gonorrhoeae requires defence systems to respond to toxic oxygen species such as superoxide. It has been shown that supplementation of media with 100 muM Mn(II) considerably enhanced the resistance of this bacterium to oxidative killing by superoxide. This protection was not associated with the superoxide dismutase enzymes of N. gonorrhoeae. In contrast to previous studies, which suggested that some strains of N. gonorrhoeae might not contain a superoxide dismutase, we identified a sodB gene by genome analysis and confirmed its presence in all strains examined by Southern blotting, but found no evidence for sodA or sodC. A sodB mutant showed very similar susceptibility to superoxide killing to that of wild-type cells, indicating that the Fe-dependent SOD B did not have a major role in resistance to oxidative killing under the conditions tested. The absence of a sodA gene indicated that the Mn-dependent protection against oxidative killing was independent of Mn-dependent SOD A. As a sodB mutant also showed Mn-dependent resistance to oxidative killing, then it is concluded that this resistance is independent of superoxide dismutase enzymes. Resistance to oxidative killing was correlated with accumulation of Mn(II) by the bacterium. We hypothesize that this bacterium uses Mn(II) as a chemical quenching agent in a similar way to the already established process in Lactobacillus plantarum. A search for putative Mn(II) uptake systems identified an ABC cassette-type system (MntABC) with a periplasmic-binding protein (MntC). An mntC mutant was shown to have lowered accumulation of Mn(II) and was also highly susceptible to oxidative killing, even in the presence of added Mn(II). Taken together, these data show that N. gonorrhoeae possesses a Mn(II) uptake system that is critical for resistance to oxidative stress.

Behavior of argon gas release from manganese oxide minerals as revealed by Ar-40/Ar-39 laser incremental heating analysis

Manganese oxides in association with paleo-weathering may provide significant insights into the multiple factors affecting the formation and evolution of weathering profiles, such as temperature, precipitation, and biodiversity. Laser probe step-heating analysis of supergene hollandite and cryptomelane samples collected from central Queensland, Australia, yield well-defined plateaus and consistent isochron ages, confirming the feasibility, dating very-fined supergene manganese oxides by Ar-40/(39) Ar technique. Two distinct structural sites hosting Ar isotopes can be identified in light of their degassing behaviors obtained by incremental heating analyses. The first site, releasing its gas fraction at the laser power 0.2-0.4 W, yields primarily Ar-40(atm), Ar-38(atm), and Ar-36(atm), (atmospheric Ar isotopes). The second sites yield predominantly Ar-40* (radiogenic Ar-40), Ar-39(K), and Ar-38(K) (nucleogenic components), at similar to0.5-1.0 W. There is no significant Ar gas released at the laser power higher than 1.0 W, indicating the breakdown of the tunnel sites hosting the radiogenic and nucleogenic components. The excellent match between the degassing behaviors of Ar-40*, Ar-39(K), and Ar-38(K) suggests that these isotopes occupy the same crystallographic sites and that Ar-39(K) loss from the tunnel site by recoil during neutron irradiation and/or bake-out procedure preceding isotopic analysis does not occur. Present investigation supports that neither the overwhelming atmospheric Ar-40 nor the very-fined nature of the supergene manganese oxides poses problems in extracting meaningful weathering geo-chronological information by analyzing supergene manganese oxides minerals.

Influence of foliar fertilization with manganese on germination, vigor and storage time of RR soybean seeds

ABSTRACTThis study aimed to evaluate the influence of foliar fertilizer doses containing Mn of phenological stages of suggested application in RR soybeans, to recover management damages with glyphosate at postemergence application on seed vigor in post-harvest and post six months storage. The seeds originated from a field experiment conducted , which included two applications of glyphosate, concomitant with foliar fertilizer in growth stages V4 and V6, with 0.00, 113.50 and 227.00 mg ha-1doses of Mn2+. Germination, GSI (Germination Speed Index), electrical conductivity tests and the first count of seeds were conducted. The application of Mn did not affect the physiological quality of RR soy in postharvest. However, in post-storage, higher doses of Mn had a negative effect on tests of abnormal seedlings, GSI and electrical conductivity. The applications of Mn, regardless of the developmental stage, did not interfere in the germination and first count tests, with and without storage. The electrical conductivity test showed a higher correlation with the seed germination test in the post-harvest treatment.