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Selected AbstractsCrystal growth of mixed-valence ammonium vanadatesCRYSTAL RESEARCH AND TECHNOLOGY, Issue 4 2007Tie-Zhen Ren Abstract A new method has been developed for the synthesis of mixed-valence ammonium vanadate crystals. Single crystals of (NH4)2V3O8 were synthesized on a large scale by hydrothermal reduction of NH4VO3 in ethanol-H2O solutions in the presence of triblock copolymer Pluronic P123. The crystals are shining thin plates with (001) cleavage planes. Calcination of the (NH4)2V3O8 crystals at 300°C or above resulted in pure phases of V2O5. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Evaluating the impact of pollution on plant,Lepidoptera relationshipsENVIRONMETRICS, Issue 4 2005Christian Mulder Abstract We monitored the biodiversity of plants, adult butterflies and leaf-miners in a Dutch nature reserve over a period of six years (1994,1999) within the International Co-operative Programme on Integrated Monitoring on Air Pollution Effects (ICP-IM). Butterfly abundance decreased steadily over the period, indicating a negative diversity trend, while the number of leaf-mining larvae of Microlepidoptera remained fairly constant. Also the concentration of pollutants (NH4, NO3, SO4, Cd, Cu and Zn) was determined in air, leaves, litter, throughfall and stemflow. We have no reason to expect a negative impact of acidification in rainwater or climate change, as temperature and ozone show no significant trends across the six years. It is shown that the nectar-plants of adult butterflies are much more sensitive to heavy metals than the nectar-plants of moths and other pollinating insects. It is hypothesized that the butterfly decline is a secondary effect of heavy metal stress on local plants, not resulting in a decrease in the number of host-plants, but in a selective pressure of pollutants on the plant vigour, subsequently affecting their pollinators (p,<,0.001). An alternative explanation, such as the possible coexistence of a direct effect of xenobiotics on the adult Lepidoptera occurring in the study area, is not supported by our data (p,>,0.05). Copyright © 2005 John Wiley & Sons, Ltd. [source] Niobium Oxide Mesophases Obtained by Self-Assembly of an Aqueous Soluble Niobium Complex Precursor and Organic TemplatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2007Marcos A. Bizeto Abstract In this paper the use of triammonium trioxalato(oxido)niobate {(NH4)3[NbO(C2O4)3]} as an inorganic precursor to assemble organized hybrid niobium oxide mesophases using n -octylamine (OCT) and cetyltrimethylammonium (CTA) bromide as structure-directing agents is described for the first time. The niobium complex is water-soluble and its hydrolysis at controlled pH and in the presence of organic templates leads to the formation of hybrid mesophases. A lamellar mesophase is produced by a neutral route based on the interaction of hydrolyzed units with the octylamine micelles. On the other hand, a hexagonal (p6m) mesophase is obtained when hydrolyzed species interact with CTA micelles through a charge-matching route (ionic route). This is the first time that such an ionic route has been described for the production of organized niobium oxide hybrids.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Phase Relations Between ,-Tricalcium Phosphate and Hydroxyapatite with Manganese(II): Structural and Spectroscopic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2006Isaac Mayer Abstract The preparation of Mn-containing ,-tricalcium phosphate (,-TCP) samples was achieved in two ways: a) transformation of precipitated Mn-containing calcium hydroxyapatite (HA) to ,-TCP by heating at 1100 °C, and b) preparation by solid-state reaction of a mixture of CaCO3, (NH4)2HPO4, and Mn(NO3)2 at 1100 °C. Powder X-ray diffraction (XRD) analyses of the samples, obtained by both methods, show well-defined patterns with structural data of the rhombohedral R3c, ,-TCP phase. The calculated lattice constants are smaller than those known for ,-Ca3(PO4)2 because of substitution of Ca2+ by Mn2+. EPR spectroscopy indeed reveals that manganese is divalent in the samples. Apparently, the Ca(5) site in the ,-TCP structure is occupied by Mn2+. The distribution of Mn2+ between the ,-TCP and the HA phase in the case of preparation (b) was studied by EPR spectroscopy, and a pronounced preference for the former lattice was found. Micron- and submicron-sized crystals with visible faces were observed by TEM in the case of ,-TCP prepared by solid-state reaction, and large micron-sized, droplike-shaped crystals, sensitive to beam radiation, were found in the case of samples prepared by heating HA at elevated temperatures. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] The Synthesis and Characterisation of Bis(phosphane)-Linked (6 - p -Cymene)ruthenium(II),Borane CompoundsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2005Adrian B. Chaplin Abstract The reaction of [(,6 - p -cymene)RuCl2]2 with some bis(phosphane) ligands (dppm, dppe, dppv, dppa, dpp14b, dppf) has been investigated. In general mixtures of products were obtained, although the pendant phosphane complexes [(,6 - p -cymene)RuCl2(,1 -dppv)] and [(,6 - p -cymene)RuCl2(,1 -dppa)] were isolated and characterized in the solid state by X-ray diffraction. The later complex was obtained in lower yield and undergoes an equilibration reaction resulting in the formation of a dimeric species, where the dppa bridges two ruthenium centres, and uncoordinated phosphane; the bridging species was also structurally characterised in the solid state. In contrast, the reaction of [(,6 - p -cymene)RuCl2(PPh3)] with dppa in the presence of [NH4]PF6 results in the formation of [(,6 - p -cymene)RuCl(PPh3)(,1 -dppa)]PF6, which is stable in solution. A series of linked ruthenium,borane complexes, viz. [(,6 - p -cymene)RuCl2(,1 -phosphane-BH3)] (phosphane = dppm, dppe, dppv, dppa, dpp14b, dppf) and [(,6 - p -cymene)RuCl(PPh3)(,1 -dppa-BH3)]PF6 have been prepared from isolated pendant phosphane complexes, those generated in situ, or from a preformed phosphane,borane adduct. The solid-state structures of [(,6 - p -cymene)RuCl2(,1 -dppm-BH3)], [(,6 - p -cymene)RuCl2(,1 -dppe-BH3)] and [(,6 - p -cymene)RuCl2(,1 -dppv-BH3)] have been determined by X-ray diffraction analysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Biomimetic Carbonate,Hydroxyapatite Nanocrystals Prepared by Vapor Diffusion,ADVANCED ENGINEERING MATERIALS, Issue 7 2010Michele Iafisco Abstract Biomimetic carbonate,hydroxyapatite (HA) nanocrystals have been synthesized by using the sitting drop vapor diffusion technique, for the first time. The method consists of diffusing vapors of an aqueous solution of NH4HCO3 through drops containing an aqueous mixture of (CH3COO)2Ca and (NH4)2HPO4 in order to increase slowly their pH. This synthesis has been performed in a crystallization mushroom, a glass device developed for protein and small molecules crystallization. The concentrations of the reagents, the final pH and the crystallization time have been optimized to produce pure carbonate,HA as a single phase. X-Ray diffraction, Fourier transformed infrared spectroscopy, and transmission electron microscopy have been utilized to characterize the synthesized carbonated substituted HA crystals which display nanometric dimensions, plate-like morphology, and low crystallinity degree, closely resembling the inorganic phase of bones, teeth, and many pathological calcifications. This novel method may prove to be suitable for the study of the interactions and/or the co-crystallization of hydroxyapatite with minute amounts of biomolecules, polymers, or drugs. [source] Inorganic sulphate extraction from SO2 -impacted AndosolsEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 1 2005T. Delfosse Summary Sulphate sorption on to the surface of short-range ordered minerals and precipitation of Al-hydroxy sulphate contribute to the acid neutralizing capacity of soils. The correct measurement of total inorganic sulphate is thus essential in soils that are accumulating SO42, anions. We extracted SO42, by various solutions, namely 0.005 m Ca(NO3)2, 0.016 m KH2PO4, 0.5 m NH4F and 0.2 m acidic NH4 -oxalate (pH 3), from Vitric and Eutric Andosols exposed to prolonged deposition of acid and SO2 from an active volcano (Masaya, Nicaragua). We attributed sulphate extractable by KH2PO4 (20,3030 mg kg,1) to anion-exchangeable SO42,, which was much smaller than NH4F- and oxalate-extractable SO42, (400,9680 and 410,10 480 mg kg,1, respectively). Our results suggest the occurrence of a sparingly soluble Al-hydroxy-mineral phase extractable by both NH4F and oxalate. The formation of Al-hydroxy minerals would result from the combination of enhanced weathering caused by strong acid loading and simultaneous occurrence of large SO42, concentrations in soil solution. Oxalate extracted slightly more inorganic SO42, than did NH4F, this additional amount of SO42, correlating strongly with oxalate-extractable Si and Fe contents. Preferential occlusion of SO42, by short-range ordered minerals, especially ferrihydrite, explains this behaviour. If we exclude the contribution of occluded sulphate then oxalate and NH4F mobilize similar amounts of SO42, and are believed to mobilize all of the inorganic SO42, pool. [source] BJ46a, a snake venom metalloproteinase inhibitorFEBS JOURNAL, Issue 10 2001Isolation, characterization, cloning, insights into its mechanism of action Fractionation of the serum of the venomous snake Bothrops jararaca with (NH4)2SO4, followed by phenyl-Sepharose and C4 -reversed phase chromatographies, resulted in the isolation of the anti-hemorrhagic factor BJ46a. BJ46a is a potent inhibitor of the SVMPs atrolysin C (class P-I) and jararhagin (P-III) proteolytic activities and B. jararaca venom hemorrhagic activity. The single-chain, acidic (pI 4.55) glycoprotein has a molecular mass of 46 101 atomic mass units determined by MALDI-TOF MS and 79 kDa by gel filtration and dynamic laser light scattering, suggesting a homodimeric structure. mRNA was isolated from the liver of one specimen and transcribed into cDNA. The cDNA pool was amplified by PCR, cloned into a specific vector and used to transform competent cells. Clones containing the complete coding sequence for BJ46a were isolated. The deduced protein sequence was in complete agreement with peptide sequences obtained by Edman degradation. BJ46a is a 322-amino-acid protein containing four putative N-glycosylation sites. It is homologous to the proteinase inhibitor HSF (member of the fetuin family, cystatin superfamily) isolated from the serum of the snake Trimeresurus flavoviridis, having 85% sequence identity. This is the first report of a complete cDNA sequence for an endogenous inhibitor of snake venom metalloproteinases (SVMPs). The sequence reveals that the only proteolytic processing required to obtain the mature protein is the cleavage of the signal peptide. Gel filtration analyses of the inhibitory complexes indicate that inhibition occurs by formation of a noncovalent complex between BJ46a and the proteinases at their metalloproteinase domains. Furthermore, the data shows that the stoichiometry involved in this interaction is of one inhibitor monomer to two enzyme molecules, suggesting an interesting mechanism of metalloproteinase inhibition. [source] Hev b 9, an enolase and a new cross-reactive allergen from Hevea latex and moldsFEBS JOURNAL, Issue 24 2000Purification, characterization, cloning, expression Natural rubber latex allergy is an IgE-mediated disease that is caused by proteins that elute from commercial latex products. A complementary DNA (cDNA) coding for Hev b 9, an enolase (2-phospho- d -glycerate hydrolyase) and allergen from latex of the rubber tree Hevea brasiliensis, was amplified by PCR. The PCR primers were designed according to conserved regions of enolases from plants. The obtained cDNA amplification product consisted of 1651 bp and encoded a protein of 445 amino-acid residues with a calculated molecular mass of 47.6 kDa. Sequence comparisons revealed high similarities of the Hevea latex enolase to mold enolases that have been identified as important allergens. In addition, the crucial amino-acid residues that participate in the formation of the catalytic site and the Mg2+ binding site of enolases were also conserved. Hevea latex enolase was produced as a recombinant protein in Escherichia coli with an N-terminal hexahistidyl tag, and purified by affinity chromatography. The yield amounted to 110 mg of purified Hev b 9 per litre of bacterial culture. The recombinant allergen bound IgE from latex, as well as mold-allergic patients, in immunoblot and ELISA experiments. The natural enolase was isolated from Hevea latex by (NH4)2SO4 precipitation and ion exchange chromatography. The natural and the recombinant (r)Hev b 9 showed equivalent enzymatic activity. Patients' IgE-antibodies preincubated with rHev b 9 lost their ability to bind to natural (n) Hev b 9, indicating the identity of the B-cell epitopes on both molecules. Cross-reactivity with two enolases from Cladosporium herbarum and Alternaria alternata was determined by inhibition of IgE-binding to these enolases by rHev b 9. Therefore, enolases may represent another class of highly conserved enzymes with allergenic potentials. [source] Stream macroinvertebrate occurrence along gradients in organic pollution and eutrophicationFRESHWATER BIOLOGY, Issue 7 2010NIKOLAI FRIBERG Summary 1.,We analysed a large number of concurrent samples of macroinvertebrate communities and chemical indicators of eutrophication and organic pollution [total-P, total-N, NH4,N, biological oxygen demand (BOD5)] from 594 Danish stream sites. Samples were taken over an 11-year time span as part of the Danish monitoring programme on the aquatic environment. Macroinvertebrate communities were sampled in spring using a standardised kick-sampling procedure whereas chemical variables were sampled six to 24 times per year per site. Habitat variables were assessed once when macroinvertebrates were sampled. 2.,The plecopteran Leuctra showed a significant negative exponential relationship (r2 = 0.90) with BOD5 and occurred at only 16% of the sites with BOD5 above 1.6 mg L,1. Sharp declines with increasing BOD5 levels were found for the trichopteran families Sericostomatidae and Glossosomatidae although they appeared to be slightly less sensitive than Leuctra. Other plecopterans such as Isoperla showed a similar type of response curve to Leuctra (negative exponential) but occurred at sites with relatively high concentrations of BOD5 up to 3,4 mg L,1. In contrast, the response curve of the isopod Asellus aquaticus followed a saturation function reaching a plateau above 3,4 mg L,1 BOD5 and the dipteran Chironomus showed an exponential increase in occurrence with increasing BOD5 concentration. 3.,Macroinvertebrate occurrence appeared to be related primarily to concentrations of BOD5, NH4,N and total-P whereas there were almost no relationships to total-N. Occurrence of a number of taxa showed a stronger relationship to habitat conditions (width and substrate) than chemical variables. 4.,Important macroinvertebrate taxa are reduced at concentrations of BOD5 that are normally perceived as indicating unimpacted stream site conditions. Our results confirmed sensitivity/tolerance patterns used by existing bioassessment systems only to some degree. [source] The effects of Daphnia on nutrient stoichiometry and filamentous cyanobacteria: a mesocosm experiment in a eutrophic lakeFRESHWATER BIOLOGY, Issue 7 2002M. J. PATERSON 1.,Stoichiometric theory predicts that the nitrogen : phosphorus (N : P) ratio of recycled nutrients should increase when P-rich zooplankton such as Daphnia become dominant. We used an enclosure study to test the hypothesis that an increased biomass of Daphnia will increase the relative availability of N versus P sufficiently to decrease the abundance of filamentous cyanobacteria. The experiment was conducted in artificially enriched Lake 227 (L227) in the Experimental Lakes Area (ELA), north-western Ontario, Canada. Previous studies in L227 have shown that the dominance of filamentous, N-fixing cyanobacteria is strongly affected by changes in the relative loading rates of N and P. 2.,We used a 2 × 2 factorial design with the addition or absence of D. pulicaria and high or low relative loading rates of N and P (+NH4, ,NH4) in small enclosures as treatment variables. If Daphnia can strongly affect filamentous cyanobacteria by altering N and P availability, these impacts should be greatest with low external N : P loading rates. The phytoplankton community of L227 was predominantly composed of filamentous Aphanizomenon spp. at the start of the experiment. 3.,Daphnia strongly reduced filamentous cyanobacterial density in all enclosures to which they were added. The addition of NH4 had only a small impact on algal community composition. Hence, we conclude that Daphnia did not cause reductions in cyanobacteria by altering the N : P ratio of available nutrients. 4.,Despite the lack of evidence that Daphnia affected filamentous cyanobacteria by altering the relative availability of N and P, we found changes in nutrient cycling consistent with other aspects of stoichiometric theory. In the presence of Daphnia, total P in the water column decreased because of an increase in P sedimentation. In contrast to P, a decrease in suspended particulate N was offset by an increase in dissolved N (especially NH4). Hence, dissolved and total N : P ratios in the water column increased with Daphnia as a result of differences in the fate of suspended particulate N versus P. There was minimal accumulation and storage of P in Daphnia biomass in the enclosures. 5.,Our experiment demonstrated that Daphnia can strongly limit filamentous cyanobacterial abundance and affect the biogeochemical cycling of nutrients. In our study, changes in nutrient cycling were apparently insufficient to cause the changes in phytoplankton community composition that we observed. Daphnia therefore limited filamentous cyanobacteria by other mechanisms. [source] Changes in abundance, composition and controls within the plankton of a fertilised arctic lakeFRESHWATER BIOLOGY, Issue 2 2002Neil D. Bettez 1. An oligotrophic arctic lake was fertilised with inorganic nitrogen and phosphorus as (NH4)2 NO3 and H3PO4 for five summers. The loading rate was 1.7,2.5 mmol N m,2 day,1 and 0.136,0.20 mmol P m,2 day,1 which is two to three times the annual loading of lakes in the area. The heterotrophic microzooplankton community was enumerated during the experiment as well as 1 year pre- and post-treatment. 2. The structure of the microplankton community changed from a nutrient limited system, dominated by oligotrich protozoans and small-particle feeding rotifers, to a system dominated by a succession of peritrich protozoans and predatory rotifers. These peritrich protozoans and predatory rotifers were not present prior to fertilisation and never constituted more than a small fraction of the biomass in other lakes at the research site. The average biomass of the rotifers and protozoans was more than seven and a half times larger by the end of fertilisation than it was initially. 3. Because of the increases in numbers of individuals in these new taxa, the structure of the microbial food web changed. When fertilisation stopped, most parameters returned to prefertilisation levels within 1 year. [source] Rational Color Tuning and Luminescent Properties of Functionalized Boron-Containing 2-Pyridyl Pyrrolide Complexes,ADVANCED FUNCTIONAL MATERIALS, Issue 4 2005H.-Y. Chen Abstract Three systematically functionalized pyrrolide ligands were prepared via the coupling of methyl vinyl ketone and the respective carbaldehyde reagents, followed by treatment of the pre-formed dicarbonyl compounds with (NH4)2CO3 in order to generate the required pyrrole fragment. These ligands readily reacted with the boron reagent BPh3 to afford the complexes [(pyro)BPh2] (2a), [(noro)BPh2] (2b), and [(xaro)BPh2] (2c), where (pyro)H, (noro)H, and (xaro)H represents the 2-pyridyl, 2-quinolinyl, and 2-quinoxalinyl pyrrole groups, respectively. Complexes 2a,2c give stable solutions in air, and show strong photoluminescence with emission peak maxima located at 490,nm, 510,nm, and 575,nm, respectively. Calculations based upon time-dependent density function theory (TDDFT) show that the S1 state in these complexes is attributed to an allowed (,-symmetry),,,,* (,-symmetry) transition located at the chelating pyrrolide moieties. Electroluminescence (EL) devices based on 2c were fabricated. The EL emission from 2c as the host-emitter, with the emission peak maximum shifted to 580,nm, was observed when BCP was used as the hole blocking material. This device produces saturated red-orange light-emission at an onset voltage of 8,V and a maximum brightness of 5000,cd,m,2 at a driving voltage of 15,V; the external quantum yield is estimated to be 0.5,%. [source] The solute budget of a forest catchment and solute fluxes within a Pinus radiata and a secondary native forest site, southern ChileHYDROLOGICAL PROCESSES, Issue 13 2002Geertrui Y. P. Uyttendaele Abstract Solute concentrations and fluxes in rainfall, throughfall and stemflow in two forest types, and stream flow in a 90 ha catchment in southern Chile (39°44,S, 73°10,W) were measured. Bulk precipitation pH was 6·1 and conductivity was low. Cation concentrations in rainfall were low (0·58 mg Ca2+ l,1, 0·13 mg K+ l,1, 0·11 mg Mg2+ l,1 and <0·08 mg NH4,N l,1), except for sodium (1·10 mg l,1). Unexpected high levels of nitrate deposition in rainfall (mean concentration 0·38 mg NO3,N l,1, total flux 6·3 kg NO3,N ha,1) were measured. Concentrations of soluble phosphorous in bulk precipitation and stream flow were below detection limits (<0·09 mg l,1) for all events. Stream-flow pH was 6·3 and conductivity was 28·3 ,s. Stream-water chemistry was also dominated by sodium (2·70 mg l,1) followed by Ca, Mg and K (1·31, 0·70 and 0·36 mg l,1). The solute budget indicated a net loss of 3·8 kg Na+ ha,1 year,1, 5·4 kg Mg2+ ha,1 year,1, 1·5 kg Ca2+ ha,1 year,1 and 0·9 kg K+ ha,1 year,1, while 4·9 kg NO3,N ha,1 year,1 was retained by the ecosystem. Stream water is not suitable for domestic use owing to high manganese and, especially, iron concentrations. Throughfall and stemflow chemistry at a pine stand (Pinus radiata D. Don) and a native forest site (Siempreverde type), both located within the catchment, were compared. Nitrate fluxes within both forest sites were similar (1·3 kg NO3,N ha,1 year,1 as throughfall). Cation fluxes in net rainfall (throughfall plus stemflow) at the pine stand generally were higher (34·8 kg Na+ ha,1 year,1, 21·5 kg K+ ha,1 year,1, 5·1 kg Mg2+ ha,1 year,1) compared with the secondary native forest site (24·7 kg Na+ ha,1 year,1, 18·9 kg K+ ha,1 year,1 and 4·4 kg Mg2+ ha,1 year,1). However, calcium deposition beneath the native forest stand was higher (15·9 kg Ca2+ ha,1 year,1) compared with the pine stand (12·6 kg Ca2+ ha,1 year,1). Copyright © 2002 John Wiley & Sons, Ltd. [source] One-Pot Three-Step Synthesis of Naphtho[2,3- a]carbazole- 5,13-diones using a Tandem Radical Alkylation,Cyclization, Aromatization Reaction SequenceADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 5 2010Chunyong Ding Abstract A three-step, one-pot tandem reaction including radical nucleophilic alkylation/cyclization/aromatization was developed using 0.3 equivalents of silver(I) acetate (AgOAc) as the catalyst and 2 equivalents of ammonium persulfate [(NH4)2S2O8] as the oxidant. This strategy is highly efficient for the assembly of pentacyclic complex carbazoles from aryl-fused bromobenzoquinones and indol-3-ylpropanoic acid acids in 52,72% overall yields (three steps). This new approach provides a significant improvement over the previously reported methods and would greatly facilitate analog library construction of pentacyclic complex carbazoles and benefit further biological evaluation of these compounds. [source] Highly Selective Oxidation of Alkylphenols to Benzoquinones with Hydrogen Peroxide over Silica-Supported Titanium Catalysts: Titanium Cluster Site versus Titanium Single SiteADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2009Oxana Abstract Titanium-silica catalysts have been prepared by supporting titanium(IV) precursors with different nuclearity {mononuclear titanocene dichloride Ti(Cp)2Cl2, dinuclear titanium diethyl tartrate and the tetranuclear titanium peroxo complex (NH4)8[Ti4(C6H4O7)4(O2)4],8,H2O} onto the surface of silica materials with different textural characteristics. The supported catalysts have been explored as highly active and reusable catalysts for the oxidation of 2,3,6-trimethylphenol (TMP) and 2,6-dimethylphenol (DMP) to 2,3,5-trimethyl-1,4-benzoquinone (TMBQ, vitamin E key intermediate) and 2,6-dimethyl-1,4-benzoquinone (DMBQ), respectively, using aqueous hydrogen peroxide as green oxidant. Catalysts prepared by grafting mononuclear Ti(Cp)2Cl2 revealed a strong dependence of the product selectivity on the surface concentration of titanium active centers. Mesoporous materials with titanium surface concentration in the range of 0.6,1.0,Ti/nm2 were identified as optimal catalysts for the transformation of alkylphenols to benzoquinones. Catalysts having <0.6,Ti/nm2 produced a mixture of benzoquinones and dimeric by-products. Conversely, when di-/tetranuclear titanium precursors were employed for the catalyst preparation, a diminution of the titanium surface concentration had no impact on the benzoquinone selectivity, which was typically as high as 96,99%. DR-UV spectroscopic studies revealed that the catalysts capable of producing alkylbenzoquinones with nearly quantitative yields possess titanium dimers and/or subnanometer-size clusters homogeneously distributed on a silica surface. On the contrary, catalysts with isolated titanium sites give a considerable amount of dimeric by-products. This is the first example which clearly demonstrates the advantages of titanium cluster-site catalysts over titanium single-site catalysts in hydrogen peroxide-based selective oxidation reaction. [source] Aquatic Coleoptera Distribution and Environmental Relationships in a Large Patagonian RiverINTERNATIONAL REVIEW OF HYDROBIOLOGY, Issue 5 2006María Laura Miserendino Abstract The benthic coleopteran assemblages of the Chubut River basin were studied in order to assess the main factors affecting species composition and distribution along the upper, middle and lower catchments. A total of 13 sampling sites were selected and sampled seasonally. Eight taxa and 1,601 individuals were collected during the study. Richness was higher in the main channel of Chubut River at the upper basin than at the middle basin. Beetles were completely absent at the lower basin. Mean monthly density per sites varied from 0 to 85 ind m,2. Stethelmis kaszabi had a more restricted distribution whereas Hemiosus dejeanii, Austrelmis sp. and Austrolimnius spp. were more frequent and abundant. Austrelmis sp. appears as the most tolerant species, especially to higher TSS, ammonia, and conductivity values. Luchoelmis cekalovici was absent in stations associated with urban areas. A Canonical Correspondence Analysis shows that conductivity, total suspended solids, wet width, water temperature and pH were the most important variables structuring beetle assemblages. Land use related variables such as NH4, TP, and NO3 were less important but still significant. An increase in TSS affected negatively the coleopteran community; this could be related to both hydrogeological characteristics and agricultural activities (including overgrazing). This is the first approach to the knowledge of the ecological range of distribution of the coleopteran species in Patagonian rivers. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Seasonal Dynamics of Picocyanobacteria and Picoeukaryotes in a Large Shallow Lake (Lake Balaton, Hungary)INTERNATIONAL REVIEW OF HYDROBIOLOGY, Issue 1 2006Andrea Mózes Abstract The abundance and composition of autotrophic picoplankton (APP) were studied between February 2003 and March 2004 in Lake Balaton. Water samples were taken fortnightly in the eutrophic western basin and mesotrophic eastern basin. Our study, which took more than one year, revealed pronounced seasonal pattern of the picoplankton abundance and composition. According to our results there were three types of picoplankton in Lake Balaton: 1. Phycoerythrin-rich coccoid cyanobacteria (PE), dominant summer picoplankters in the mesotrophic lake area; 2. Phycocyanin-rich cyanobacteria (PC), the most abundant summer picoplankters in the eutrophic lake area; 3. Picoeukaryotes, dominant winter picoplankters in the whole lake. The observed abundance of picoeukaryotes (3 × 105 cells ml,1) was one of the highest ever found. Our study confirms that in Lake Balaton the colonial autotrophic picoplankton (colonial APP) become dominant in summer in the nutrient limited period. We have found strong negative relationship between the concentrations of available nitrogen forms (NH4,N, NO3,N, urea-N) and the colonial APP abundance. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Effect of Straw on Yield Components of Rice (Oryza sativa L.) Under Rice-Rice Cropping SystemJOURNAL OF AGRONOMY AND CROP SCIENCE, Issue 2 2006K. Surekha Abstract Field experiments were conducted at the Directorate of Rice Research experimental farm, ICRISAT campus, Patancheru, Hyderabad, during 1998,2000 for five consecutive seasons (three wet and two dry seasons) with five treatments [T1 , 100 % straw incorporation; T2 , 50 % straw incorporation; T3 , 100 % straw + green manure (GM) incorporation; T4 , 100 % straw burning and T5 , 100 % straw removal (control)] along with the recommended dose of fertilizers to evaluate the effect of different crop residue management (CRM) practices on yield components and yield of rice in rice,rice cropping sequence. The ammonium N measured at active tillering was higher in 100 % straw-added plots over 50 % straw addition and straw removal with maximum values in the straw + GM-incorporated plots. Among the yield components, tillers, panicles and spikelets were influenced from the second season of residue incorporation with significant increase in 100 % straw-added treatments. The increase in tiller and panicle number could be attributed to the increased NH4 -N in these treatments, which is evident from the significant correlation between tiller number and NH4 -N (r = 0.82**) and panicle number and NH4 -N (r = 0.87**). The influence of residue treatments on rice grain yield was observed from the third season onwards where incorporation of straw alone or in combination with GM and burning of straw significantly increased grain and straw yields. Grain yield showed significant positive correlation with the number of tillers (r = 0.74*,0.81**) and panicles (r = 0.74*,0.84**) in three treatments (T1, T3 andT4) where grain yields were significantly higher. The regression analysis showed that 57,66 % and 64,75 % of the variation in yield could be explained by tillers and panicles together in these three treatments during wet and dry seasons respectively. Thus, CRM practices such as addition of 100 % straw either alone or with GM and straw burning influenced the yield components (tillers, panicles and spikelets) positively and thereby increased rice grain yields. [source] Effect of polymerization method on structure and properties of cationic polyacrylamideJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Yinghua Shen Abstract Acrylamide and 2-(methacryloyloxy)ethyltrimethylammonium chloride (AM/MADQUAT) copolymers were synthesized by solution and inverse microemulsion polymerization using (NH4)2S2O8/NaHSO3 as redox initiator at the same feed mole ratio, and their microstructure, such as sequence distribution and composition distribution, was calculated from monomer reactivity ratios of different polymerization methods. The results show that charge distribution is more uniform for copolymer prepared in inverse microemulsion than that in solution, and copolymer composition distribution is close to unity, and maintains approximately at the feed ratio. Furthermore, the influence of the two structures of cationic polyacrylamides on kaolinite floc size and effective floc density, reduction of Zeta potential and floc compressive yield stress had been investigated at pH 7. The results show that the kaolinite floc size and effective floc density are strongly dependent upon copolymer microstructure, with greater floc size and lower effective floc density being observed for copolymer prepared in inverse microemulsion than for that in solution. Copolymer microstructure has a marked effect on the Zeta potential, whose reduction in the magnitude was much greater in the presence of copolymer prepared in inverse microemulsion than that in solution. Greater compressive yield stress was achieved for the strong flocs produced by copolymer prepared in inverse microemulsion than for the weak flocs produced by that in solution. The difference in flocs compressive yield stress may be attributed to flocs structure. Therefore, in this article, a correlation between the cationic polyacrylamide structure and flocculation property for kaolinite suspension was established. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Transformation of 3DP gypsum model to HA by treating in ammonium phosphate solutionJOURNAL OF BIOMEDICAL MATERIALS RESEARCH, Issue 2 2007Rungnapa Lowmunkong Abstract Three-dimensional printing (3DP) is a CAD/CAM built-up using ink-jet printing technique. Commercially available 3DP system can form only gypsum model and not for bioceramics. On the other hand, transformation of hardened gypsum into hydroxyapatite (HA) by treatment in ammonium phosphate solution was found lately. In the present study, transformation of the 3DP gypsum block to HA was attempted. However, the fabricated 3DP block was soluble in water. To insolubilize, it was heated at 300°C for 10 min, and then, gypsum was transformed to calcium sulfate hemihydrate, CaSO4 · 0.5H2O. The 3D block was immersed in 1M (NH4)3PO4 · 3H2O solution at 80°C for 1,24 h, and the transformation into HA within 4 h was ascertained. A heat-treated plaster of Paris (POP) block was also investigated for comparison. The unheated POP block consisting of gypsum dihydrate took 24 h to complete the transformation, while the heat-treated POP consisting calcium sulfate hemihydrate promoted the transformation into HA; but the transformed thickness in the block was less than the 3DP block. This is probably due to higher solubility of the hemihydrate than gypsum dihydrate. Accelerated transformation of the 3DP block was also caused by its porous structure, which enabled an easy penetration of the phosphate solution. With the present method, it is possible to transform the fabricated gypsum by 3D printing that is adaptive to the osseous defect into HA prostheses or scaffold. © 2006 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2007 [source] Effects of butyric acid stress on anaerobic sludge for hydrogen production from kitchen wastesJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 6 2010Mingxing Zhao Abstract BACKGROUND: Anaerobic digestion is an alternative technology to achieve the dual benefits of hydrogen production and waste stabilization from kitchen wastes. In this work, the butyric acid stress on anaerobic sludge was investigated in order to improve the tolerance of sludge against organic acids, and to enhance hydrogen accumulation. RESULTS: The tolerance of butyric acid in anaerobic sludge increased with the stress concentration, however, it decreased at concentrations greater than of 4.0 g L,1. The maximum hydrogen yield reached 63.72 mL g,1 VS at 4.0 g L,1 stress, representing an increase of 114% compared with the control group. The concentration of volatile solids (VS) of the sludge and SCOD increased steadily with time up to 20 h. At 4.0 g L,1 butyric acid stress, the maximum activity of ,-glucosidase, BAA-hydrolysing protease and dehydrogenase enzyme were 14912.1 µmol PNP g,1 TS h,1, 134.14 µmol NH4 -N g,1 TS h,1 and 7316.42 µg TF g,1 TS h,1, which were 2.78, 1.90 and 2.01 times that of the control, respectively. CONCLUSIONS: The feasibility of butyric acid stress on anaerobic sludge to increase hydrogen production from kitchen wastes was demonstrated. Remarkably, 4.0 g L,1 butyric acid stress was found to be favorable for improving the tolerance of butyric acid in sludge as well as hydrogen yield in the experiment. Copyright © 2010 Society of Chemical Industry [source] Performance assessment of a UASB,anoxic,oxic system for the treatment of tomato-processing wastesJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 6 2006Alpesh Gohil Abstract An upflow anaerobic sludge blanket (UASB),anoxic,oxic system was used to achieve biochemical oxygen demand, NH4 and total suspended solids (TSS) criteria of 15, 1 and 15 mg dm,3 at 1.17 days of system hydraulic retention time during treatment of tomato-processing waste. The incorporation of an anoxic tank was found to affect the improvement in sludge-settling characteristics, as reflected by about 25,33% reduction in the sludge volume index, along with final effluent TSS and soluble biochemical oxygen demand concentrations of 13 and 9 mg dm,3, respectively, which met the discharge criteria. Despite incomplete denitrification, sludge settleability was very good (sludge volume index < 60 cm3 g,1) owing to reduction in volatile suspended solids/TSS ratio from 0.75 to 0.6 as a result of higher alkalinity in the UASB effluent. Also in this study, phosphorus release was observed in the anoxic tank, predominantly due to abundance of acetic acid in the UASB effluent. A phosphate release of 5.4 mg P dm,3 was observed in the anoxic tank with subsequent P uptake in the following aerobic stage. Copyright © 2006 Society of Chemical Industry [source] Recovery of cadmium from a zinc hydrometallurgical leachate using reactive emulsion liquid membrane technologyJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2004Jianzhang Fang Abstract A new emulsion liquid membrane process using 3,5-diisopropylsalicylic acid (DIPSA) and triisobutylphosphine sulfide (TIBPS) as carriers, and ammonium sulfide (NH4)2S as precipitant is described. The reactive nature of sulfide ions with extracted cadmium ions in the internal aqueous phase significantly increases cadmium recovery and minimizes zinc impurities. The new process is applied to the enrichment of a low concentration of cadmium ions from a solution containing a high concentration of zinc ions. Under optimum operating conditions, a single stage process produced a cadmium recovery of 98% at a cadmium sulfide content of 99.6%. The results are encouraging for potential applications in zinc hydrometallurgy for recovery of cadmium from sulfuric acid leaching solution of zinc ores. Copyright © 2004 Society of Chemical Industry [source] Electrolytic removal of ammonia from brine wastewater: scale-up, operation and pilot-scale evaluationJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 3 2004Catalino G Alfafara Abstract Brine wastewater with a high ammonia content from an iodine processing plant (commonly called kansui in Japan) was treated by electrolysis. The system, which can be considered as an indirect electrolytic treatment process, generates chlorine at the anodes and initiates the formation of mixed oxidants like hypochlorous acid. The oxidants then act as agents for ammonia destruction. Laboratory-scale experiments showed that high ammonia concentrations (as much as 200 mg dm,3) could be completely removed within a few minutes, and could be considered a good alternative for efficient ammonia removal from saline wastewaters. From laboratory-scale experiments in the batch and continuous modes, the charge dose was analyzed and used as the operating and scale-up factor. The value of the charge dose was not severely affected by changes in operating conditions such as electrode spacing and temperature. The charge dose from batch and continuous runs was found to be in the range of 23 C (mg NH4 -N removed),1 to 29 C (mg NH4 -N removed),1. Using the charge dose obtained from laboratory-scale continuous electrolysis experiments as the scale-up factor, a pilot-scale reactor was designed, and the operating conditions were calculated. In the pilot-scale reactor tests at different flow rates, the effluent ammonia concentrations were reasonably close to the calculated values predicted from the charge dose equation. Copyright © 2004 Society of Chemical Industry [source] Nitrite accumulation characteristics of high strength ammonia wastewater in an autotrophic nitrifying biofilm reactorJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2003Ho-Joon Yun Abstract Selective nitrification was carried out to accumulate nitrite from high strength ammonia wastewater in an autotrophic nitrifying biofilm reactor. Nitrification efficiencies and nitrite accumulation characteristics were investigated at various operating conditions such as ammonium load, oxygen supply and free ammonia concentration. The biofilm reactor showed very stable nitrification efficiencies of more than 90% at up to 2,kg,NH4 -N,m,3,d,1 and the nitrite content was maintained at around 95%. Inhibition by free ammonia on nitrite oxidizers seems to be the major factor for nitrite accumulation. Batch kinetic analyses of ammonium and nitrite oxidation showed that nitrite oxidation activity was selectively inhibited in the presence of free ammonia. However, the activity recovered quickly as the free ammonia concentration decreased below the threshold inhibition concentration. Examination of specific ammonia and nitrite oxidation activities and the most probable number indicated that the number of nitrite-oxidizing microorganisms in the nitrite-accumulating system was less than that in the normal nitrification system due to long-term free ammonia inhibition of the nitrite oxidizers. The reduced population of nitrite oxidizers in the biofilm system was also responsible for the accumulation of nitrite in the biofilm reactor. © 2003 Society of Chemical Industry [source] Impact of dissolved wastewater constituents on peroxidase-catalyzed treatment of phenolJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2002Monika Wagner Abstract The impact of dissolved wastewater constituents on the treatment of synthetic phenol solutions using horseradish peroxidase (HRP) and hydrogen peroxide was investigated under a variety of reaction conditions. The constituents studied included various inorganic salts, organic compounds and heavy metals. Higher H2O2 doses were required to treat phenol in the presence of sodium sulfite, thiosulfate and sulfide; however, enhanced levels of phenol conversion were achieved once sufficient H2O2 was supplied. Sulfide and cyanide inhibited phenol transformation. The inhibition of sulfide was overcome by supplying sufficient H2O2 to oxidize the sulfide to sulfur. However, increasing the H2O2 dose was ineffective in attempting to overcome the strong inhibiting effect of cyanide. Among the heavy metal ions tested, only Mn(II) substantially inhibited phenol removal when it was present at a concentration of 1,mmol,dm,3. The presence of inorganic salts including NaCl, CaCl2, MgCl2, NH4Cl and (NH4)2SO4 reduced phenol conversion as compared with the treatment in distilled-deionized water. This can be attributed to the increased ionic strength of the solution. © 2002 Society of Chemical Industry [source] CHARACTERIZATION OF POLYPHENOL OXIDASE FROM ROOSTER POTATO (SOLANUM TUBEROSUM CV ROOSTER)JOURNAL OF FOOD BIOCHEMISTRY, Issue 1 2010D. NI EIDHIN ABSTRACT The isolation and purification of polyphenol oxidase from potatoes (Solanum tuberosum cv. Rooster) is described. A 64-fold purified preparation has been obtained with 10% yield by a procedure involving (NH4)2SO4 precipitation, phenyl sepharose chromatography, ion exchange chromatography and hydroxyapatite chromatography. The partially purified enzyme has both cresolase and catecholase activity. Activity was lower toward monophenols than diphenols. Enzyme activity was optimal at pH 6.0,6.5 and at 30C. Greater than 50% activity was retained during storage for 72 h at pH 6.0,7.5. Residual activity was greater than 50% after incubation at 20C for 72 h, 30C for 48 h, 40C for 24 h, 50C for 2 h and 60C for 15 min. The most effective inhibitors tested were sodium metabisulfite and ascorbic acid. Sodium dodecyl sulphate appeared to activate the enzyme. The enzyme was capable of cross-linking casein but did not increase gel-strengths in acidified milk gels. PRACTICAL APPLICATIONS Rooster is the most important potato cultivar grown in Ireland and data on its isolation and characterization has not been reported previously. This work describes a method to isolate polyphenol oxidase and characterization of the enzyme. Information on characterization of the enzyme could be valuable in relation to control of enzymatic browning during current processing and in minimum processing. There is potential for use of the enzyme in the emerging cross-linking area, as the results show some success and there may be potential of more cross-linking as the field develops and as interest in natural methods of cross-linking for food texture grows. This could lead to an important use for potato waste. Food product applications are given. [source] Studies on Temporal and Spatial Variations of Phytoplankton in Lake ChaohuJOURNAL OF INTEGRATIVE PLANT BIOLOGY, Issue 4 2007Dao-Gui Deng Abstract Temporal and spatial variations of the phytoplankton assemblage in Lake Chaohu, a large shallow eutrophic lake in China, were studied from September 2002 to August 2003. A total of 191 phytoplankton species was identified, among which Chlorophytes (101) ranked the first, followed by Cyanophytes (46) and Bacillariophytes (28). On average over the entire lake, the maximum total algal biomass appeared in June (19.70 mg/L) with a minimum (5.05 mg/ L) in November. In terms of annual mean biomass, cyanobacteria contributed 45.43% to total algal biomass, followed by Chlorophytes (27.14%), and Bacillariophytes (20.6%). When nitrate (NO3 -N) and ammonium (NH4 -N) concentrations dropped in spring, fixing-nitrogen cyanobacterium (Anabaena) developed quickly and ranked the first in terms of biomass in summer. It is likely that dominance of zooplanktivorous fish and small crustacean zooplankton favored the development of the inedible filamentous or colony forming cyanobacteria. The persistent dominance of cyanobacteria throughout all seasons may indicate a new tendency of the response of phytoplankton to eutrophication in Lake Chaohu. [source] Improved protonation, collision-induced decomposition efficiency and structural assessment for ,red tide' brevetoxins employing nanoelectrospray mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 8 2006Weiqun Wang Abstract Brevetoxins are a group of natural neurotoxins found in blooms of red tide algae. Previous electrospray mass spectrometry (ES-MS) studies show that all brevetoxins have high affinities for sodium ions, and they form abundant sodium adduct ions, [M + Na]+, in ES-MS, even when trace contamination is the only source of sodium ions. Attempts to obtain informative product ions from the collision-induced decomposition (CID) of [M + Na]+ brevetoxin precursor ions resulted only in uninformative sodium ion signals, even under elevated collision energies. In this study, a nano-ES-MS approach was developed wherein ammonium fluoride was used to form cationic [M + NH4]+ adducts of brevetoxin-2 and brevetoxin-3; a significant increase in the abundance of protonated brevetoxin molecules [M + H]+ also resulted, whereas the abundance of sodium adducts of brevetoxins [M + Na]+ was observed to decrease. Under CID, both [M + NH4]+ and [M + H]+ gave similar, abundant product ions and thus underwent the same types of fragmentation. This indicated that ammonium ions initially attached to brevetoxins forming [M + NH4]+ easily lose neutral ammonia in a first step in the gas phase, leaving protonated brevetoxin [M + H]+ to readily undergo further fragmentation under CID. Copyright © 2006 John Wiley & Sons, Ltd. 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