Copper Binding Sites in the Manganese-Oxidizing Mnx Protein Complex Investigated by Electron Paramagnetic Resonance Spectroscopy.

Manganese-oxide minerals (MnOx) are widely distributed over the Earth's surface, and their geochemical cycling is globally important. A multicopper oxidase (MCO) MnxG protein from marine Bacillus bacteria plays an essential role in producing MnOx minerals by oxidizing Mn2+(aq) at rates that are 3 to 5 orders of magnitude faster than abiotic rates. The MnxG protein is isolated as part of a multiprotein complex denoted as "Mnx" that includes accessory protein subunits MnxE and MnxF, with an estimated stoichiometry of MnxE3F3G and corresponding molecular weight of ≈211 kDa. Herein, we report successful expression and isolation of the MCO MnxG protein without the E3F3 hexamer. This isolated MnxG shows activity for Mn2+(aq) oxidation to form manganese oxides. The complement of paramagnetic Cu(II) ions in the Mnx protein complex was examined by electron paramagnetic resonance (EPR) spectroscopy. Two distinct classes of type 2 Cu sites were detected. One class of Cu(II) site (denoted as T2Cu-A), located in the MnxG subunit, is identified by the magnetic parameters g∥ = 2.320 and A∥ = 510 MHz. The other class of Cu(II) sites (denoted as T2Cu-B) is characterized by g∥ = 2.210 and A∥ = 615 MHz and resides in the putative hexameric MnxE3F3 subunit. These different magnetic properties correlate with the differences in the reduction potentials of the respective Cu(II) centers. These studies provide new insights into the molecular mechanism of manganese biomineralization.

MnO2 Submicroparticles from Chinese Brush and Their Application in Treatment of Methylene Blue Contaminated Wastewater.

Eggshell membrane (ESM) is selected as biotemplate to prepare MnO2 submicroparticles (SMPs) using Chinese Brush with sodium hydroxide solution. The size with average 710 nm of the obtained materials is in good consistency with the microsructured biotemplate. An efficient and convenient absorbent for methylene blue (MB) is developed. The removal efficiency could reach up to 93% in 35 min under room temperature without pH adjusting owing to the excellent adsorption from ESM itself and hydroxyl group formed on the surface of MnO2 crystal in the aqueous solution. Materials on the membrane can be separated from the wastewater simply to avoid the secondary pollution caused by the leak of material. This interesting approach to MnO2 SMPs and facile operation for MB adsorption could open a new path to the submicro-materials based wastewater treatment.

A Water-Stable Cationic Metal-Organic Framework as a Dual Adsorbent of Oxoanion Pollutants.

A three-dimensional water-stable cationic metal-organic framework (MOF) pillared by a neutral ligand and with Ni(II)  metal nodes has been synthesized employing a rational design approach. Owing to the ordered arrangement of the uncoordinated tetrahedral sulfate (SO4 (2-) ) ions in the channels, the compound has been employed for aqueous-phase ion-exchange applications. The compound exhibits rapid and colorimetric aqueous-phase capture of environmentally toxic oxoanions (with similar geometries) in a selective manner. This system is the first example of a MOF-based system which absorbs both dichromate (Cr2 O7 (2-) ) and permanganate (MnO4 (-) ) ions, with the latter acting as a model for the radioactive contaminant pertechnetate (TcO4 (-) ).

Development of preparative and analytical methods of the hop bitter acid oxide fraction and chemical properties of its components.

The bitter acids in hops (Humulus lupulus L.) and beer, such as α-, ß-, and iso-α-acids, are known to affect beer quality and display various physiological effects. However, these compounds readily oxidize, and the effect of the oxides on the properties of beer or their potential health benefits are not well understood. In this study, we developed a simple preparative method for the bitter acid oxide fraction derived from hops and designated the constituents as matured hop bitter acids (MHBA). HPLC-PDA-ESI/HRMS and MS(2) revealed that MHBA are primarily composed of α-acid-derived oxides, which possess a common ß-tricarbonyl moiety in their structures similar to α-, ß-, and iso-α-acids. We also developed a quantitative analytical method of whole MHBA by HPLC, which showed high precision and reproducibility. Using our newly developed method, the concentration of whole MHBA in several commercial beers was evaluated. Our results will promote the study of bitter acid oxides.

Nanostructured metal oxide gas sensors, a survey of applications carried out at SENSOR lab, Brescia (Italy) in the security and food quality fields.

In this work we report on metal oxide (MOX) based gas sensors, presenting the work done at the SENSOR laboratory of the CNR-IDASC and University of Brescia, Italy since the 80s up to the latest results achieved in recent times. In particular we report the strategies followed at SENSOR during these 30 years to increase the performance of MOX sensors through the development of different preparation techniques, from Rheotaxial Growth Thermal Oxidation (RGTO) to nanowire technology to address sensitivity and stability, and the development of electronic nose systems and pattern recognition techniques to address selectivity. We will show the obtained achievement in the context of selected applications such as safety and security and food quality control.

Uranyl ion extraction with conventional PUREX/TRUEX ligands assessed by electroanalytical chemistry at micro liquid/liquid interfaces.

The facilitated ion transfer (FIT) of uranyl or dioxouranium (UO(2)(2+)) was studied electrochemically using a micro interface between two immiscible electrolytic solutions (micro-ITIES) in order to evaluate the complexation stoichiometry and complexation constants (ß) of two widely used ligands in spent fuel reprocessing: tributylphosphate (TBP) and octyl(phenyl)-N,N-diisobutylcarbamoylmethyl-phosphine oxide (CMPO). For the first time, discrete interfacial complexation reaction steps of varying uranyl to the two ligands ratios were resolved using the micro-ITIES hosted at the tip of a 25 µm diameter glass capillary. Two stoichiometries for UO(2)NO(3)TBP(n)(+) were determined including n = 3 and 4 with ß values of 3.2 × 10(11) and 3.9 × 10(13), respectively. Subsequently, three distinct complexation reactions of CMPO with UO(2)(2+) were discovered corresponding to UO(2)NO(3)CMPO(2)(+), UO(2)NO(3)CMPO(3)(+), and UO(2)CMPO(5)(2+) whose respective complexation constants were determined to be 8.0 × 10(11), 8.8 × 10(14), and 6.5 × 10(32). The participation of nitrate anions in these complexation reactions is also discussed.

Izumiphenazine D, a new phenazoquinoline N-oxide from Streptomyces sp. IFM 11204.

A new phenazine derivative named izumiphenazine D (1), together with three known metabolites, 1-hydroxyphenazine (2), phenazine-1-carboxylic acid (3) and 6-hydroxyphenazine-1-carboxylic acid (4) has been isolated from the ethyl acetate extract of culture of Streptomyces sp. IFM 11204. The structure of 1 was established via spectroscopic methods, including 1D- and 2D-NMR measurements.

A novel approach for fast and simple determination pyrrolizidine alkaloids in herbs by ultrasound-assisted dispersive solid phase extraction method coupled to liquid chromatography-tandem mass spectrometry.

Pyrrolizidine alkaloids (PAs) are secondary plant metabolites witch can contaminate food, especially herbs. Due to the fact that alkaloids have a strong adverse effect on human health, it is necessary to use sensitive and selective detection methods. In present study a modified method based on LC-MS/MS was developed and validated for the simultaneous determination of thirty pyrrolizidine alkaloids and their corresponding N-oxides (PANOs) in herbs samples. Sample extraction was based on ultrasound-assisted dispersive solid phase extraction and clean-up using graphene. Method validation showed that the proposed method hold good recoveries (61-128 %) for PAs/PANOs with RSD <15 %. Limits of quantification has been set at 1 µg kg-1 level for all targeted alkaloids. The optimized method yielded a small matrix effect (-20-20 %) for most PAs/PANOs. The uncertainty associated with the analytical method was not higher than 38 %. The method is operationally simple, time-saving, and can be applied to the analysis of real herb samples.

Safranin O-functionalized cuboid mesoporous silica material for fluorescent sensing and adsorption of permanganate.

Incorporation of dual functions, i.e., sensing and adsorption, into one single organic-inorganic hybrid material for the detection and removal of toxic permanganate (MnO4-) ions is of great importance, representing a challenging and new task in the design and application of new functional materials. However, most of the reported materials display only one function as either sensing probes or adsorbents. In this work, a fluorescent cuboid mesoporous silica-based hybrid material (SiO2@SFNO) is first prepared by the covalent coupling of a new safranin O-based fluorophore (2,8-dimethyl-5-phenyl-3,7-bis(3-(3-(triethoxysilyl)propyl)ureido)phenazin-5-ium chloride) (SFNO) and newly-made cuboid mesoporous silica, which showed selective dual-functional activities towards MnO4- and green emission at 575 nm with a long-range excitation wavelength that is suitable for bio-imaging application. The design of this SiO2@SFNO material is based on the position of -NHCONH- groups, which are mainly responsible for the strong and selective coordination with MnO4-. SiO2@SFNO is responsive to MnO4- at parts per billion (67 ppb) level; it also displays high adsorption ability (292 mg g-1) to MnO4- in aqueous solutions. The fluorescence responses of MnO4-in vivo (limnodrilus claparedianus and zebrafish) demonstrate the possibility of further application in biology. Interestingly, this SiO2@SFNO material is also capable of monitoring trace amounts of Hg2+ and Cu2+ in living organisms, holding great potential in bio-related applications.

Pseudolycorine N-oxide, a new N-oxide from Narcissus tazetta.

A new N-oxide, Pseudolycorine N-oxide (1) was characterised along with eleven known alkaloids homolycorine (2), O-methylmaritidine (3), 8-O-demethylhomolycorine (4), homolycorine N-oxide (5), lycorine (6), narciclasine (7), pseudolycorine (8), ungeremine (9), 8-O-demethylmaritidine (10), zefbetaine (11) and lycorine N-oxide (12), from Narcissus tazetta. Their structures were established on the basis of spectroscopic data analysis. The extract, fractions and isolated compounds were screened for in vitro cytotoxicity against two human cancer cell lines, human cervical cancer (SiHa) and human epidermoid carcinoma (KB) cells. The study demonstrated the cytotoxic potential of extract and its chloroform and n-butanol fractions. Further, the results revealed the bioactive potential of narciclasine, pseudolycorine and homolycorine alkaloids. However, new N-oxide (1) was not active against these cell lines.

Bioshell calcium oxide (BiSCaO) for cleansing and healing Pseudomonas aeruginosa-infected wounds in hairless rats.

BACKGROUND: Scallop shell powder is called bioshell calcium oxide (BiSCaO), which is known to possess deodorizing properties and broad antimicrobial activity against various pathogenic microbes, including viruses, bacteria, spores, and fungi. OBJECTIVE: This study aims to investigate the applications of BiSCaO suspension cleansing in clinical situations, for instance for the prevention and treatment of infections in chronic wounds in healing-impaired patients, without delaying wound healing. METHODS: The bactericidal activities of 1000 ppm BiSCaO suspension; 500 ppm hypochlorous acid; 1000 ppm povidone iodine; and saline were compared to evaluate in vivo disinfection and healing of Pseudomonas aeruginosa-infected wounds in hairless rats. RESULTS: Cleansing of the infected wounds with BiSCaO suspension daily for 3 days significantly enhanced wound healing and reduced the in vivo bacterial counts, in comparison to hypochlorous acid, povidone iodine, and saline. Furthermore, histological examinations showed significantly advanced granulation tissue and capillary formation in the wounds cleansed with BiSCaO suspension than in those cleansed with the other solutions. CONCLUSIONS: This study suggested that the possibility of using BiSCaO suspension as a disinfectant for infected wounds and limiting disinfection to 3 days may be sufficient to avoid the negative effects on wound repair.

Silica particles settling characteristics and removal performances of oxide chemical mechanical polishing wastewater treated by electrocoagulation technology.

The purpose of this study was to explore the feasibility of removing silica particles and reducing turbidity from oxide chemical mechanical polishing (oxide-CMP) wastewater. Based on the dynamic characteristics of batch electrocoagulation, three operating stages (lag, reactive, and stabilizing) are proposed to identify the relationships among the zeta potential of the silica particles, solution turbidity, and the corresponding mean particle size of the silica. Experimental results show that the silica particles were destabilized and settled at the critical mean particle size, which was estimated to be above 520nm after 10min, and the corresponding turbidity removal mostly occurred during the reactive stage. Furthermore, the corresponding mean particle size varied from 520 to 1900nm as the treatment time progressed from 10 to 20min, which also occurred during the reactive stage. Several parameters, including different electrode pairs, electrolyte concentration, applied voltage, and the optimum condition of power input were investigated. Experimental results indicate that a Fe/Al electrode pair is the most efficient choice of the four electrode pair combinations in terms of energy consumption. The optimum electrolyte concentration and applied voltage were found to be 200ppm NaCl and 30V, respectively.

A new erythrinan N-oxide alkaloid from Erythrina stricta.

This phytochemical study of stems and leaves of Erythrina stricta led to the isolation of twenty-three alkaloids, one of them previously unreported, 11ß-hydroxyerythratidine N-oxide. Their structures were elucidated on the basis of extensive 1D and 2D NMR spectroscopic analyses including HSQC, HMBC, 1H-1H COSY, NOESY, as well as HRESIMS data in addition to comparison with reports in the literature.

Optimization and validation of analytical conditions for cholesterol and cholesterol oxides extraction in chicken meat using response surface methodology.

The analytical conditions for the extraction of cholesterol and cholesterol oxides in chicken meat were optimized by means of response surface methodology. The separation and identification were performed by normal phase HPLC using UV and refractive index (RI) detectors, and the confirmation of the 11 cholesterol oxides identities in the samples was verified by HPLC-APCI-MS. The developed methodology showed good analytical performance, presenting recovery levels from 84 to 103% and detection limits varying from 0.01 to 0.06 microg/g for UV detection and from 1.98 to 2.12 microg/g for RI detection. The present study demonstrated the presence of 22 R-hydroxycholesterol, 24 S-hydroxycholesterol, and 22 S-hydroxycholesterol for the first time in chicken meat.

Transmission electron microscopy (TEM) investigations of Mn-oxide rich cathodic material from spent disposable alkaline batteries.

Transmission electron microscopy (TEM) techniques were used to investigate the spent cathodic material of a single common brand of disposable alkaline batteries. Mn-oxide particles are anhedral and irregular in shape and compose an estimated 99-95% of the < 10 microm size fraction of sample material. Diameters of particles vary widely and typically are between 50 nm and 3 microm; however, most particles are approximately 200-400 nm in diameter. Chemical composition varies for Mn-oxide particles with concentrations being SiO2 (0.00-1.52 wt%), TiO2 (0.49-4.58 wt%), MnO (65.85-92.06 wt%), ZnO (1.00-7.53 wt%), K2O (4.97-20.48 wt%) and SO3 (0.43-2.21 wt%). Discrete prismatic zinc crystals occur and vary from a maximum of approximately 0.8 microm long x 0.15 microm wide, to 100 nm long x 20 nm wide. Titanium metal was also observed in samples and composes approximately 0.25-1.0% of the < 10 microm size fraction of sample material. Results of this study suggest that battery components may be recycled in some special applications. Examples are low energy-low material requirement products such as paint pigments and Zn nanoparticles. This investigation provides detailed constraints on the nature of spent cathodic materials to improve existing recycling methods and develop new technologies.

Soluble manganese removal by porous media filtration.

Filtration experiments were conducted to investigate soluble manganese removal in granular media filtration; sand, manganese oxide coated sand (MOCS), sand + MOCS (1:1) and granular activated carbon (GAC) were used as filter media. Manganese removal, manganese oxide accumulation, turbidity removal, and regeneration of MOCS under various conditions were examined. Soluble manganese removal by the MOCS column was rapid and efficient; most of the removal happened at the top (e.g. 5 cm) of the filter. When filter influent with an average manganese concentration of 0.204 mg l(-1) was fed through the filter columns, the sand + MOCS and MOCS columns removed 98.9% and 99.2% of manganese, respectively. However, manganese removal in sand and the GAC columns was not significant during the initial stage of filtration, but after eight months of filter run they could remove 99% and 35% of manganese, respectively. It was revealed that partial replacement of sand with MOCS showed comparable manganese removal to that of the MOCS filter media.

[Influence of Hydraulic Retention Time on the Treatment of Polluted River Water by an Activated Carbon Rotating Biological Contactor].

The study combined activated carbon with a rotating biological contactor. The activated carbon adsorption experiments were conducted and the biofilm was formed by using the river water directly. The effects of different hydraulic retention times on the removal of NH4+-N, TP, and permanganate index and on the biofilm properties were investigated at the optimum rotational speed of the disc. Experimental results are as follows. The Freundlich isotherm showed that activated carbon had better adsorption properties for NH4+-N, TP, and permanganate index in water.When the disk speed was 3 r·min-1, the removal efficiency was the best, and the removal rates of NH4+-N, TP and permanganate index were the best at 86.05%, 81.28%, and 77.09%, respectively. In addition, there was a significant linear correlation between the hydraulic retention time and the removal of NH4+-N and TP (R2>0.9), respectively. The removal rates of NH4+-N and TP at different hydraulic retention times were significantly different (P<0.05), but the permanganate index was not (P>0.05).Hydraulic retention time had effects on the biofilm activity, protein and polysaccharide contents,and the three-dimensional fluorescence peaks of S-EPS, LB-EPS, and TB-EPS of the biofilm.

Production of biogenic manganese oxides by repeated-batch cultures of laboratory microcosms.

We investigated the production of manganese (Mn) oxides using repeated-batch bioreactors maintained over long periods under laboratory conditions. Freshwater epilithic biofilms were used as the initial inocula. The bioreactors yielded suspended solids that could remove 0.1 mM dissolved Mn(II) within a few days. Chemical titration, X-ray absorption near-edge structure spectroscopy, and X-ray diffraction analysis revealed that the Mn(II) had been converted to poorly crystallized layer-type Mn(IV) oxides, which were similar to known biogenic Mn oxides from pure bacterial cultures. Spherical or rod-shaped Mn microconcretions occurred in the suspended solids; transmission electron microscopy showed that these structures likely resulted from the microbial activity but not represent living cells. Instead, the presence of encapsulated, sheathed, and hyphal budding cells in the suspended solids indicated that a range of Mn-depositing bacteria contributed to the Mn oxide formation. To our knowledge, our data represent the first observation of production of such Mn oxides in a laboratory microcosm wherein a range of Mn-depositing bacteria coexist. The fact that sorption of trace Zn(II) and Ni(II) ions onto the suspended solids co-occurred with the removal of dissolved Mn(II) emphasizes the important role of Mn-oxidizing microorganisms in the fates of trace or contaminant metals in the aquatic environment.

Simultaneous removal of NO and SO2 from dry gas stream using non-thermal plasma.

In order to investigate the feasibility of sequential removal NO and SO2 using non-thermal plasma and adsorbent simultaneously, the removal of NO and SO2 from dry gas stream (NO/SO2/N2/O2) with very little O2 using non-thermal plasma was investigated using a coaxial dielectric barrier discharge. Comparative experiments were carried out in the dry gas stream with and without Ar respectively at O2 concentration of 0.1%. The results showed that NO could be removed remarkably and it would be enhanced in the presence of Ar in the dry gas stream. It seems that SO2 could not be removed unless there is Ar in the dry gas stream. The mechanism of removal of NO and SO2 in the dry gas stream was discussed.

[Purification of Slightly Salt-alkaline Water Bodies by Microorganism Enhanced Combined Floating Bed].

In order to study the purifying effect of combined floating bed constucted by salinity plant Suaeda salsa and microorganisms on the slightly salt-alkaline water, blank floating bed A, S.salsa floating bed B, microbes floating bed C and S.salsa + microorganisms combined floating bed D were established, and slightly salt-alkaline eutrophic water body (pH 8.5-9.0, salinity 5‰-7‰) was purified under continuous flow conditions in the laboratory. Results showed that the removal rates of total nitrogen, total phosphorus, permanganate index by S.salsa floating bed were 32.5%, 14.3% and 28.2%, respectively. And the removal rates of total nitrogen, total phosphorus and permanganate index by S.salsa + microorganisms combined floating bed D which installed artificial medium with microorganisms reached 70.5%, 34.7% and 70.8%, respectively, of which the removal rates of total nitrogen, total phosphorus and permanganate index by microbial units were 37.7%, 21.6% and 44.5%, respectively. Synergies removal rates of nitrate nitrogen and total nitrogen by S.salsa + microorganisms combined floating bed were 12.2% and 0.3%, but there was no synergy in the process of removing ammonia nitrogen, total phosphorus and permanganate index, which indicated that the synergies of S.salsa and microorganisms in the combined floating bed were suppressed in slightly salt-alkaline environment. The high-throughput sequencing technique was adopted to analyze the microbial community in the floating bed C and D, which indicated that the abundance and diversity of microbial community in the combined floating bed were higher, and this was consistent with the result of the higher removal rate of the flotation bed D. Principal component analysis showed that the microbial degradation was a major factor in reducing the concentration of pollutants. This study provided a guide for the using of floating bed in purifying slightly salt-alkaline eutrophic water bodies in coastal area.