Sample records for dimethylglyoxime
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Deutsch, E; Elder, R C; Lange, B A; Vaal, M J; Lay, D G
1976-01-01
Reduction of pertechnetate by tin(II) in the presence of dimethylglyoxime is shown, by single crystal x-ray analysis, to yield a technetium-tin-dimethylglyoxime complex in which tin and technetium are intimately connected by a triple bridging arrangement. One bridge consists of a single oxygen atom and it is hypothesized that this bridge arises from the inner sphere reduction of technetium by tin(II), the electrons being transferred through a technetium "yl" oxygen which eventually becomes the bridging atom. Two additional bridges arise from two dimethylglyoxime ligands that function as bidentate nitrogen donors towards Tc and monodentate oxygen donors towards Sn. The tin atom can thus be viewed as providing a three-pronged "cap" on one end of the Tc-dimethylglyoxime complex. The additional coordination sites around Tc are occupied by the two nitrogens of a third dimethylglyoxime ligand, making the Tc seven-coordinate. The additional coordination sites around Sn are occupied by three chloride anions, giving the Sn a fac octahedral coordination environment. From indirect evidence the oxidation states of tin and technetium are tentatively assigned to be IV and V, respectively. Since most 99mTc-radiopharmaceuticals are synthesized by the tin(II) reduction of pertechnetate, it is likely that the Sn-O-Tc linkage described in this work is an important feature of the chemistry of these species. This linkage also provides a ready rationale for the close association of tin and technetium observed in many 99mTc-radiopharmaceuticals. PMID:1069984
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NASA Astrophysics Data System (ADS)
Abidi, Syed Sibte Asghar; Azim, Yasser; Gupta, Abhishek Kumar; Pradeep, Chullikkattil P.
2017-12-01
With an aim to explore the interactions of (RR'Cdbnd Nsbnd OH) oxime moiety of dimethylglyoxime (DMG) with pyridyl ring of N-heterocyclic aromatic compounds and acetamide, three novel cocrystals of dimethylglyoxime with acridine (ACR), 1,10-phenanthroline monohydrate (PT) and acetamide (ACT) are reported. These three cocrystals were obtained with a mechanochemical synthesis approach and were characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), fourier transform-infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Additionally, Hirshfeld surface analysis is used to investigate the intermolecular interaction and the crystal packing of cocrystals.
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The sequential injection system with adsorptive stripping voltammetric detection.
Kubiak, W W; Latonen, R M; Ivaska, A
2001-03-16
Two sequential injection systems have been developed for adsorptive stripping voltammetric measurement. One is for substances adsorbing at mercury, e.g. riboflavin. In this case, a simple arrangement with only sample aspiration is needed. Reproducibility was 3% and detection limit 0.07 muM. The measuring system was applied to determination of riboflavin in vitamin pills and to study the photodegradation process of riboflavin in aqueous solutions. In the second case, metal ions were determined. They have to be complexed before deposition on the mercury surface. Thus, both the sample and the ligand have to be aspirated in the system. In this case, the reproducibility was approximately 6% and the detection limit <0.1 ppm for cadmium, lead and copper when complexation with oxine was used. Dimethylglyoxime was used in determination of nickel and cobalt and nioxime complexes were used in determination of nickel and copper. With these complexing agents, the reproducibility was the same as with oxine, but the metals could be determined at concentrations lower than 0.01 ppm. Application of two ligands in a SIA system with AdSV detection was also studied. Simultaneous determination of copper, lead, cadmium and cobalt was possible by using oxine and dimethylglyoxime. Copper and nickel were simultaneously determined by using dimethylglyoxime and nioxime.
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Chen, Xiangping; Chen, Yongbin; Zhou, Tao; Liu, Depei; Hu, Hang; Fan, Shaoyun
2015-04-01
Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt and lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe-Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC2O4 ⋅ 2H2O and Li2CO3 using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor. Copyright © 2015 Elsevier Ltd. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, Xiangping; Chen, Yongbin; Zhou, Tao, E-mail: zhoutao@csu.edu.cn
2015-04-15
Highlights: • Selective precipitation and solvent extraction were adopted. • Nickel, cobalt and lithium were selectively precipitated. • Co-D2EHPA was employed as high-efficiency extraction reagent for manganese. • High recovery percentages could be achieved for all metal values. - Abstract: Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt andmore » lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe–Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC{sub 2}O{sub 4}⋅2H{sub 2}O and Li{sub 2}CO{sub 3} using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor.« less
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ERIC Educational Resources Information Center
Gilbert, George L., Ed.; And Others
1980-01-01
Presents three different procedures in which reagents are added in a specified order to a large beaker containing an aqueous solution of nickel sulfate. Complex ions of nickel (II) are prepared by using aqueous solutions of ammonia, ethylenediamine, dimethylglyoxime, and cyanide ion. (CS)
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Ershova, N I; Ivanov, V M
2000-05-01
Cellulose and chromaton-N-super as solid supports for direct determination of the immobilized nickel complexes with dimethylglyoxime and benzyldioxime by diffuse reflection spectroscopy were compared. The advantage of chromaton-N-super with use of benzyldioxime is shown. Detection limit is 0.02 microg/mL. The proposed method was applied for the analysis of soil.
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Pokpas, Keagan; Jahed, Nazeem; Baker, Priscilla G.
2017-01-01
The adsorptive stripping voltammetric detection of nickel and cobalt in water samples at metal film electrodes has been extensively studied. In this work, a novel, environmentally friendly, metal-free electrochemical probe was constructed for the ultra-trace determination of Ni2+ in water samples by Adsorptive Cathodic Stripping Voltammetry (AdCSV). The electrochemical platform is based on the adsorptive accumulation of Ni2+ ions directly onto a glassy carbon electrode (GCE) modified with dimethylglyoxime (DMG) as chelating agent and a Nafion-graphene (NGr) nanocomposite to enhance electrode sensitivity. The nafion-graphene dimethylglyoxime modified glassy carbon electrode (NGr-DMG-GCE) shows superior detection capabilities as a result of the improved surface-area-to-volume ratio and enhanced electron transfer kinetics following the incorporation of single layer graphene, while limiting the toxic effects of the sensor by removal of the more common mercury, bismuth and lead films. Furthermore, for the first time the NGr-DMG-GCE, in the presence of common interfering metal ions of Co2+ and Zn2+ demonstrates good selectivity and preferential binding towards the detection of Ni2+ in water samples. Structural and morphological characterisation of the synthesised single layer graphene sheets was conducted by Raman spectrometry, HRTEM and HRSEM analysis. The instrumental parameters associated with the electrochemical response, including accumulation potential and accumulation time were investigated and optimised in addition to the influence of DMG and graphene concentrations. The NGr-DMG-GCE demonstrated well resolved, reproducible peaks, with RSD (%) below 5% and a detection limit of 1.5 µg L−1 for Ni2+ reduction at an accumulation time of 120 s. The prepared electrochemical sensor exhibited good detection and quantitation towards Ni2+ detection in tap water samples, well below 0.1 mg L−1 set by the WHO and EPA standards. This is comparable to the South African drinking water guidelines of 0.15 mg L−1. PMID:28757588
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Serra, Antonio; Monteduro, Anna Grazia; Padmanabhan, Sanosh Kunjalukkal; Licciulli, Antonio; Bonfrate, Valentina; Salvatore, Luca; Calcagnile, Lucio
2017-01-01
Mixed iron-manganese oxide nanoparticles, synthesized by a simple procedure, were used to remove nickel ion from aqueous solutions. Nanostructures, prepared by using different weight percents of manganese, were characterized by transmission electron microscopy, selected area diffraction, X-ray diffraction, Raman spectroscopy, and vibrating sample magnetometry. Adsorption/desorption isotherm curves demonstrated that manganese inclusions enhance the specific surface area three times and the pores volume ten times. This feature was crucial to decontaminate both aqueous samples and food extracts from nickel ion. Efficient removal of Ni2+ was highlighted by the well-known dimethylglyoxime test and by ICP-MS analysis and the possibility of regenerating the nanostructure was obtained by a washing treatment in disodium ethylenediaminetetraacetate solution. PMID:28804670
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Nickel release from surgical instruments and operating room equipment.
Boyd, Anne H; Hylwa, Sara A
2018-04-15
Background There has been no systematic study assessing nickel release from surgical instruments and equipment used within the operating suite. This equipment represents important potential sources of exposure for nickel-sensitive patients and hospital staff. To investigate nickel release from commonly used surgical instruments and operating room equipment. Using the dimethylglyoxime nickel spot test, a variety of surgical instruments and operating room equipment were tested for nickel release at our institution. Of the 128 surgical instruments tested, only 1 was positive for nickel release. Of the 43 operating room items tested, 19 were positive for nickel release, 7 of which have the potential for direct contact with patients and/or hospital staff. Hospital systems should be aware of surgical instruments and operating room equipment as potential sources of nickel exposure.
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Artificial hydrogenases based on cobaloximes and heme oxygenase
Bacchi, Marine; Veinberg, Elias; Field, Martin J.; ...
2016-06-06
The insertion of cobaloxime catalysts in the heme-binding pocket of heme oxygenase (HO) yields artificial hydrogenases active for H 2 evolution in neutral aqueous solutions. These novel biohybrids have been purified and characterized by using UV/visible and EPR spectroscopy. These analyses revealed the presence of two distinct binding conformations, thereby providing the cobaloxime with hydrophobic and hydrophilic environments, respectively. Quantum chemical/molecular mechanical docking calculations found open and closed conformations of the binding pocket owing to mobile amino acid residues. HO-based biohybrids incorporating a {Co(dmgH) 2} (dmgH 2 = dimethylglyoxime) catalytic center displayed up to threefold increased turnover numbers with respectmore » to the cobaloxime alone or to analogous sperm whale myoglobin adducts. Here, this study thus provides a strong basis for further improvement of such biohybrids, using well-designed modifications of the second and outer coordination spheres, through site-directed mutagenesis of the host protein.« less
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Artificial hydrogenases based on cobaloximes and heme oxygenase
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bacchi, Marine; Veinberg, Elias; Field, Martin J.
The insertion of cobaloxime catalysts in the heme-binding pocket of heme oxygenase (HO) yields artificial hydrogenases active for H 2 evolution in neutral aqueous solutions. These novel biohybrids have been purified and characterized by using UV/visible and EPR spectroscopy. These analyses revealed the presence of two distinct binding conformations, thereby providing the cobaloxime with hydrophobic and hydrophilic environments, respectively. Quantum chemical/molecular mechanical docking calculations found open and closed conformations of the binding pocket owing to mobile amino acid residues. HO-based biohybrids incorporating a {Co(dmgH) 2} (dmgH 2 = dimethylglyoxime) catalytic center displayed up to threefold increased turnover numbers with respectmore » to the cobaloxime alone or to analogous sperm whale myoglobin adducts. Here, this study thus provides a strong basis for further improvement of such biohybrids, using well-designed modifications of the second and outer coordination spheres, through site-directed mutagenesis of the host protein.« less
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Ray, Chaiti; Dutta, Soumen; Sahoo, Ramkrishna; Roy, Anindita; Negishi, Yuichi; Pal, Tarasankar
2016-05-20
Inspired by the attractive catalytic properties of palladium and the inert nature of carbon supports in catalysis, a concise and simple methodology for in situ nitrogen-doped mesoporous-carbon-supported palladium nanoparticles (Pd/N-C) has been developed by carbonizing a palladium dimethylglyoximate complex. The as-synthesized Pd/N-C has been exfoliated as a fuel cell catalyst by studying the electro-oxidation of methanol and formic acid. The material synthesized at 400 °C,namely, Pd/N-C-400,exhibitssuperior mass activity and stability among catalysts synthesized under different carbonization temperaturesbetween300 and 500 °C. The unique 1D porous structure in Pd/N-C-400 helps better electron transport at the electrode surface, which eventually leads to about five times better catalytic activity and about two times higher stability than that of commercial Pd/C. Thus, our designed sacrificial metal-organic templatedirected pathway becomes a promising technique for Pd/N-C synthesis with superior catalytic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Nickel and cobalt release from children's toys purchased in Denmark and the United States.
Jensen, Peter; Hamann, Dathan; Hamann, Carsten R; Jellesen, Morten S; Jacob, Sharon E; Thyssen, Jacob P
2014-01-01
Nickel is the most common allergen detected by patch testing in children. There is an increasing number of cases in children who have not had exposure to piercing. Although the clinical relevance of nickel patch test reactions in children is sometimes uncertain, continued vigilance to identify new sources of nickel exposure in this age group is important. Recent case reports have described allergic nickel contact dermatitis in children following exposure to toys, but the magnitude of this problem is unknown. The aim of this study was to evaluate nickel and cobalt release from children's toys. We purchased 212 toys in 18 different retail and online stores in the United States and Denmark. Nickel and cobalt release was tested using the dimethylglyoxime and cobalt screening spot tests. A total of 73 toys (34.4%) released nickel, and none released cobalt. Toys are a commonly overlooked source of nickel exposure and sensitization. Therefore, dermatologists, allergists, and pediatricians should consider the role of toys in their evaluation of children with dermatitis, and the parents of children with positive nickel patch test reactions should be told that toys may release nickel and be a potential chemical source in the manifestation of allergic contact dermatitis.
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Allafchian, Ali Reza; Farajmand, Bahman; Koupaei, Amin Javaheri
2018-04-01
In this research, the thin film microextraction method was applied for the extraction of Ni(II) ion from aqueous matrixes. Chemically modified cellulosic filter paper with phosphorus was used as a thin film extractor. After extraction, the thin film was treated with a solution of dimethylglyoxime. The colored film was captured by flatbed scanner and the absorbance of the images was extracted by some suitable software. Under the optimum conditions and at the pH 7.0, with the sample volume of 100 mL, the stirring rate of 800 rpm, and the extraction time of 50 min, the calibration curve was obtained in the range of 0.05-5 mg/L Ni(II) (R 2 = 0.989). Limit and relative standard deviation were achieved to be 18 µg/L and less than 6.7%, respectively. Relative recoveries were obtained in the range of 87%-105%. Finally, the proposed method was found to be simple and cost-effective, with adequate analytical performance for the rapid detection of Ni(II) in river and wastewater samples.
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NASA Technical Reports Server (NTRS)
Diaz, Neil C.; Gazda, Daniel B.; Fritz, James S.; Porter, Marc D.; Rutz, Jeff; Mudgett, Paul; Schultz, John
2004-01-01
Archived water samples collected on the International Space Station (ISS) and returned to Earth for analysis have, in a few instances, contained trace levels of heavy metals. Building on our previous advances using Colorimetric Solid Phase Extraction (C-SPE) as a biocide monitoring technique, we are devising methods for the low level monitoring of nickel(II), lead(II) and other heavy metals. C-SPE is a sorption-spectrophotometric platform based on the extraction of analytes onto a membrane impregnated with a colorimetric reagent that are then quantified on the surface of the membrane using a diffuse reflectance spectrophotometer. Along these lines, we have determined nickel(II) via complexation with dimethylglyoxime (DMG) and begun to examine the analysis of lead(II) by its reaction with 2,5- dimercapto-1,3,4-thiadiazole (DMTD) and 4-(2- pyridylazo)-resorcinol (PAR). These developments are also extending a new variant of C-SPE in which immobilized reagents are being incorporated into this methodology in order to optimize sample reaction conditions and to introduce the colorimetric reagent. This paper describes the status of our development of these two new methods.
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NASA Astrophysics Data System (ADS)
Zhang, Deyi; Lei, Longyan; Shang, Yonghua; Wang, Kunjie; Wang, Yi
2016-01-01
Heteroatoms doping provides a promising strategy for improving the energy density of supercapacitors based on the carbon electrodes. In this paper, we present a N and S dual doped ordered mesoporous carbon with ultrahigh doping level using dimethylglyoxime as pristine precursor. The N doping content of the reported materials varies from 6.6 to 15.6 at.% dependent on the carbonization temperature, and the S doping content varies from 0.46 to 1.01 at.%. Due to the ultrahigh heteroatoms doping content, the reported materials exhibit pronounced pseudo-capacitance. Meanwhile, the reported materials exhibit high surface areas (640⿿869 m2 g⿿1), large pore volume (0.71⿿1.08 cm2 g⿿1) and ordered pore structure. The outstanding textual properties endow the reported materials excellent electrical double-layer capacitance (EDLC). By effectively combining the pseudo-capacitance with EDLC, the reported materials exhibit a surprising energy storage/relax capacity with the highest specific capacitance of 565 F g⿿1, which value is 3.3 times higher than that of pristine CMK-3, and can compete against some conventional pseudo-capacitance materials.
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NASA Astrophysics Data System (ADS)
Bourosh, Paulina N.; Coropceanu, Eduard B.; Rija, Andrei P.; Bologa, Olga A.; Gdaniec, Maria; Bulhac, Ion I.
2011-07-01
Multicomponent mixed metal ionic-type dioximates, [Со(DH) 2(Thio) 2][Rh(Thio) 6][BF 4] 4 ( 1), [Со(DH) 2(Thio) 2][Rh(Thio) 6][TiF 6] 2·H 2O ( 2) and [Со(NioxH) 2(Thio) 2] 2[Rh(Thio) 5Cl][TiF 6] 2·CH 3OH·3H 2O ( 3), where DH 2 is dimethylglyoxime, NioxH 2 is 1.2-cyclohexanedionedioxime, and Thio is thiourea, were synthesized and their structures were determined by an X-ray method. Compounds 1-3 consist of two different mononuclear coordination cations with cobalt(III) and rhodium(III) as octahedrally coordinated metal centers and fluorine-containing anions as counterions. In the studied systems, Rh(III) mostly binds Thio ligands instead of dioximes, while a typical bis-dioximate in trans geometry is formed by Co(III) with two Thio ligands placed in axial positions. A structural characterization of coordination cations [Rh(Thio) 6] 3+ and [Rh(Thio) 5Cl] 2+ is given for the first time. The interactions and arrangement of the components in crystals 1-3 are discussed.
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Novel Organic Membrane-based Thin-film Microsensors for the Determination of Heavy Metal Cations
Arida, Hassan A.; Kloock, Joachim P.; Schöning, Michael J.
2006-01-01
A first step towards the fabrication and electrochemical evaluation of thin-film microsensors based on organic PVC membranes for the determination of Hg(II), Cd(II), Pb(II) and Cu(II) ions in solutions has been realised. The membrane-coating mixture used in the preparation of this new type of microsensors is incorporating PVC as supporting matrix, o-nitrophenyloctylether (o-NPOE) as solvent mediator and a recently synthesized Hg[dimethylglyoxime(phene)]2+ and Bis-(4-hydroxyacetophenone)-ethylenediamine as electroactive materials for Hg(II) and Cd(II), respectively. A set of three commercialised ionophores for Cd(II), Pb(II) and Cu(II) has been also used for comparison. Thin-film microsensors based on these membranes showed a Nernstian response of slope (26-30 mV/dec.) for the respective tested cations. The potentiometric response characteristics (linear range, pH range, detection limit and response time) are comparable with those obtained by conventional membranes as well as coated wire electrodes prepared from the same membrane. The realisation of the new organic membrane-based thin-film microsensors overcomes the problem of an insufficient selectivity of solid-state-based thin-film sensors.
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Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.
Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang
2017-05-01
Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH) 2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.
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Ussher, Simon J; Milne, Angela; Landing, William M; Attiq-ur-Rehman, Kakar; Séguret, Marie J M; Holland, Toby; Achterberg, Eric P; Nabi, Abdul; Worsfold, Paul J
2009-10-12
A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II)+Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100microM concentrations of sulphite a reduction time of 4h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.
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Nickel on the Swedish market: follow-up 10 years after entry into force of the EU Nickel Directive.
Biesterbos, Jacqueline; Yazar, Kerem; Lidén, Carola
2010-12-01
The EU Nickel Directive, aimed at primary and secondary prevention of nickel allergy by limitation of nickel release from certain items, came fully into force in July 2001. To assess the prevalence on the market of items with nickel release and to compare the outcome with previous studies performed in Sweden in 1999 and 2002-2003. Nickel release from 659 items covered by the EU Nickel Directive was assessed with the dimethylglyoxime (DMG) test. Special attention, as compared with the previous surveys, was given to cheap jewellery in street markets and sewing materials in haberdashery shops. Nickel release was shown for 9% of the tested items, all of which were intended for direct and prolonged contact with the skin. A high proportion of items bought at haberdashery shops and street markets, 34% and 61%, respectively, showed nickel release. The Swedish market for products intended for direct and prolonged contact with the skin has largely adapted to the Nickel Directive. It is suggested that authorities should monitor the market regularly and give attention to areas where compliance with the requirements is poor, for protection of public health. © 2010 John Wiley & Sons A/S.
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Identification of metallic items that caused nickel dermatitis in Danish patients.
Thyssen, Jacob P; Menné, Torkil; Johansen, Jeanne D
2010-09-01
Nickel allergy is prevalent as assessed by epidemiological studies. In an attempt to further identify and characterize sources that may result in nickel allergy and dermatitis, we analysed items identified by nickel-allergic dermatitis patients as causative of nickel dermatitis by using the dimethylglyoxime (DMG) test. Dermatitis patients with nickel allergy of current relevance were identified over a 2-year period in a tertiary referral patch test centre. When possible, their work tools and personal items were examined with the DMG test. Among 95 nickel-allergic dermatitis patients, 70 (73.7%) had metallic items investigated for nickel release. A total of 151 items were investigated, and 66 (43.7%) gave positive DMG test reactions. Objects were nearly all purchased or acquired after the introduction of the EU Nickel Directive. Only one object had been inherited, and only two objects had been purchased outside of Denmark. DMG testing is valuable as a screening test for nickel release and should be used to identify relevant exposures in nickel-allergic patients. Mainly consumer items, but also work tools used in an occupational setting, released nickel in dermatitis patients. This study confirmed 'risk items' from previous studies, including mobile phones.
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Nickel on the Swedish market. Follow-up after implementation of the Nickel Directive.
Lidén, Carola; Norberg, Kristina
2005-01-01
The Nickel Directive aims at the prevention of sensitization and elicitation of nickel dermatitis. It limits nickel release from, and nickel content in, certain items. The Directive came into full force by July 2001. The aim of this study was to investigate the frequency on the market of items that release nickel and of nickel content in piercing posts, 2 years after coming into force of the Directive. Of special interest was to study changes compared to the situation in 1999, when a baseline study had been carried out. Nickel release from 786 items covered by the Nickel Directive was tested with the dimethylglyoxime (DMG) test, and nickel content in 18 piercing posts was analysed. Nickel release was shown from 8% of items intended for direct and prolonged contact with the skin, and 17% of the piercing posts contained too much nickel, a decrease compared to 1999. There has been significant adaptation to the requirements of the Nickel Directive. The DMG test is useful for screening for nickel release and for monitoring the market. Provided there is further adaptation to the requirements, the risk of sensitization and elicitation of nickel dermatitis will be significantly reduced.
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Excessive nickel release from mobile phones--a persistent cause of nickel allergy and dermatitis.
Jensen, Peter; Johansen, Jeanne D; Zachariae, Claus; Menné, Torkil; Thyssen, Jacob P
2011-12-01
Despite the political intention to limit nickel allergy and dermatitis in Europeans, nickel allergy remains frequent. There are several explanations for the persistence of nickel allergy and dermatitis, including the increasing use of mobile phones. Before regulation of nickel release from mobile phones, we showed that eight (19.5%) of 41 mobile phones marketed in Denmark between 2003 and 2007 released nickel in concentrations that may result in nickel allergy and dermatitis. In 2009, the EU Nickel Directive was revised to include nickel-releasing mobile phones. To investigate the proportion of mobile phones sold in Denmark that release nickel after regulation. Metallic parts from 50 randomly selected mobile phones currently for sale in Denmark were tested for nickel release by use of the dimethylglyoxime (DMG)-nickel spot test. Nine (18%) phones showed at least one positive DMG test reaction and two phones had more than one DMG test-positive spot. Apparently, the proportion of mobile phones with significant nickel release remains unchanged, despite the 2009 revision of the EU Nickel Directive. We encourage manufacturers to measure nickel release from metallic components used in the assembly of mobile phones to ensure safe products. © 2011 John Wiley & Sons A/S.
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Speciation studies of nickel and chromium in wastewater from an electroplating plant.
Kiptoo, Jackson K; Ngila, J Catherine; Sawula, Gerald M
2004-09-08
A speciation scheme involving the use of flame atomic absorption spectrometry (FAAS) and differential pulse adsorptive cathodic stripping voltammetry (DPAdCSV) techniques was applied to studies of nickel and chromium in wastewater from a nickel-chrome electroplating plant. Dimethylglyoxime (DMG) and diethylenetriaminepentaacetic acid (DTPA) were employed as complexing agents for adsorptive voltammetric determination of Ni and Cr, respectively. Cr(III) and Cr(VI) were determined by exploiting differences in their reactivity towards DTPA at HMDE. Total dissolved metal content was in the range 2906-3141 and 30.7-31.2mgl(-1) for Ni and Cr, respectively. A higher percentage of the metal was present as labile species (mean value of 67.9% for Ni and 79.8% for Cr) suggesting that strongly binding ligands are not ubiquitous in the sample. About 77.8% of Cr was found to exist in the higher oxidization state, Cr(IV). Results on effect of dilution on lability of the metal forms in the sample using DPAdCSV showed slight peak shifts to a more negative (cathodic) value by -0.036V for Ni and -0.180V for Cr with a dilution factor of 100, while peak intensity (cathodic current) remained fairly constant.
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Geochemical field method for determination of nickel in plants
Reichen, L.E.
1951-01-01
The use of biogeochemical data in prospecting for nickel emphasizes the need for a simple, moderately accurate field method for the determination of nickel in plants. In order to follow leads provided by plants of unusual nickel content without loss of time, the plants should be analyzed and the results given to the field geologist promptly. The method reported in this paper was developed to meet this need. Speed is acquired by elimination of the customary drying and controlled ashing; the fresh vegetation is ashed in an open dish over a gasoline stove. The ash is put into solution with hydrochloric acid and the solution buffered. A chromograph is used to make a confined spot with an aliquot of the ash solution on dimethylglyoxime reagent paper. As little as 0.025% nickel in plant ash can be determined. With a simple modification, 0.003% can be detected. Data are given comparing the results obtained by an accepted laboratory procedure. Results by the field method are within 30% of the laboratory values. The field method for nickel in plants meets the requirements of biogeochemical prospecting with respect to accuracy, simplicity, speed, and ease of performance in the field. With experience, an analyst can make 30 determinations in an 8-hour work day in the field.
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Nickel and cobalt release from jewellery and metal clothing items in Korea.
Cheong, Seung Hyun; Choi, You Won; Choi, Hae Young; Byun, Ji Yeon
2014-01-01
In Korea, the prevalence of nickel allergy has shown a sharply increasing trend. Cobalt contact allergy is often associated with concomitant reactions to nickel, and is more common in Korea than in western countries. The aim of the present study was to investigate the prevalence of items that release nickel and cobalt on the Korean market. A total of 471 items that included 193 branded jewellery, 202 non-branded jewellery and 76 metal clothing items were sampled and studied with a dimethylglyoxime (DMG) test and a cobalt spot test to detect nickel and cobalt release, respectively. Nickel release was detected in 47.8% of the tested items. The positive rates in the DMG test were 12.4% for the branded jewellery, 70.8% for the non-branded jewellery, and 76.3% for the metal clothing items. Cobalt release was found in 6.2% of items. Among the types of jewellery, belts and hair pins showed higher positive rates in both the DMG test and the cobalt spot test. Our study shows that the prevalence of items that release nickel or cobalt among jewellery and metal clothing items is high in Korea. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
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Nickel on the market: a baseline survey of articles in 'prolonged contact' with skin.
Ringborg, Evelina; Lidén, Carola; Julander, Anneli
2016-08-01
In April 2014, the European Chemicals Agency defined the concept of 'prolonged contact with skin' as used in the EU nickel restriction. To establish a baseline of nickel-releasing items on the Swedish market conforming with the EU nickel restriction according to the definition of 'prolonged contact' with the skin. We performed a limited market survey in Stockholm, Sweden. Items with metallic parts that come into contact with the skin, except those explicitly mentioned in the legal text, were chosen. The dimethylglyoxime (DMG) test was used to evaluate nickel release. One hundred and forty-one items belonging to one of three categories - accessories, utensils for needlework, painting and writing (called utensils), and electronic devices - were tested in the study. Forty-four percent of all items were DMG test-positive (releasing nickel), and 9% gave a doubtful DMG test result. The large proportion of nickel-releasing items in the present study shows clearly that broader parts of industry need to take action to prevent nickel allergy. The high proportion of DMG test-positive items indicates that there is still much work to be done to reduce the nickel exposure of the population. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Arguello, M.D.
1977-12-01
Modifications to the forced-flow chromatograph include a flow-through pH monitor to continuously monitor the pH of the final effluent and an active low-pass filter to eliminate noise in the spectrophotometric detector. All separations are performed using partially sulfonated XAD-2 as the ion exchanger. Elution of calcium and magnesium is accomplished using ammonium chloride and ethylenediammonium chloride solutions. Calcium and magnesium are detected by means of Arsenazo I and PAR-ZnEDTA color-forming reagents. Other metal ions are detected by means of PAR and Chromazurol S color-forming reagents. Calcium and magnesium distribution coefficients on partially sulfonated XAD-2 as functions of ammonium chloride andmore » ethylenediammonium chloride concentration are given together with distribution coefficients of other metal ions. Methods for the selective elution of interfering metal ions prior to the elution of calcium and magnesium are described. Beryllium and aluminum are selectively eluted with sulfosalicylic acid. Those elements forming anionic chloride complexes are selectively eluted with HCl-acetone. Nickel is selectively eluted with HCl-acetone-dimethylglyoxime. Synthetic samples containing calcium and magnesium, both alone and in combination with alkali metals, strontium, barium, beryllium, aluminum, transition metals, and rare earths, are analyzed. Hard water samples are analyzed for calcium and magnesium and the results compared to those obtained by EDTA titration, atomic absorption spectroscopy, and plasma emission spectroscopy. Several clinical serum samples are analyzed for calcium and magnesium and the results compared to those obtained by atomic absorption spectroscopy.« less
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NASA Astrophysics Data System (ADS)
Rajabi, Hamid Reza; Razmpour, Saham
2016-01-01
Here, the researchers report on the synthesis of ion imprinted polymeric (IIP) nanoparticles using a thermal polymerization strategy, and their usage for the separation of Ni2 + ion from water samples. The prepared Ni-IIP was characterized by colorimetry, FT-IR spectroscopy, and scanning electron microscopy. It was found that the particle size of the prepared particle to be 50-70 nm in diameter with the highly selective binding capability for Ni2 + ion, with reasonable adsorption and desorption process. After preconcentration, bound ions can be eluted with an aqueous solution of hydrochloric acid, after their complexation with dimethylglyoxime, these ions can be quantified by UV-Vis absorption spectrophotometry. The effect of various parameters on the extraction efficiency including pH of sample solution, adsorption and leaching times, initial sample volume, concentration and volume of eluent were investigated. In selectivity study, it was found that imprinting causes increased affinity of the prepared IIP toward Ni2 + ion over other ions such as Na+, K+, Ag+, Co2 +, Cu2 +, Cd2 +, Hg2 +, Pb2 +, Zn2 +, Mn2 +, Mg2 +, Cr3 +, and Fe3 +. The prepared IIP can be used and regenerated for at least eight times without any significant decrease in binding affinities. The prepared IIP is considered to be promising and selective sorbent for solid-phase extraction and preconcentration of Ni2 + ion from different water samples.
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Chemical stability of reactive skin decontamination lotion (RSDL®).
Bogan, R; Maas, H J; Zimmermann, T
2018-09-01
Reactive Skin Decontamination Lotion (RSDL ® ) is used for the decontamination of Chemical Warfare Agents and Toxic Industrial Compounds after dermal exposure. It has to be stockpiled over a long period and is handled in all climatic zones. Therefore stability is an essential matter of concern. In this work we describe a study to the chemical stability of RSDL ® as basis for an estimation of shelf life. We analysed RSDL ® for the active ingredient 2,3-butandione monoxime (diacetylmonooxime, DAM), the putative degradation product dimethylglyoxime (DMG) and unknown degradation products by means of a reversed phase high pressure liquid chromatography (HPLC). Calculations were done according to the Arrhenius equation. Based on the temperature dependent rate constants, the time span was calculated, until defined threshold values for DAM and DMG subject to specification and valid regulations were exceeded. The calculated data were compared to the ones gathered from stockpiled samples and samples exposed during foreign mission. The decline of DAM followed first order kinetics, while formation of DMG could be described by zero order kinetics. The rate constants were distinctively temperature dependent. Calculated data were in good accordance to the measured ones from stockpile and mission. Based on a specified acceptable DAM-content of 90% and a valid threshold value of 0.1% (w/w) for the degradation product DMG, RSDL ® proved to be stable for at least four years if stored at the recommended conditions of 15°C-30°C. If continuously stored at higher temperatures shelf life will decrease markedly. Therefore RSDL ® is an object for risk orientated quality monitoring during storage. Copyright © 2017 Elsevier B.V. All rights reserved.
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Long, Xiangbao; Miró, Manuel; Jensen, Rikard; Hansen, Elo Harald
2006-10-01
A highly selective procedure is proposed for the determination of ultra-trace level concentrations of nickel in saline aqueous matrices exploiting a micro-sequential injection Lab-On-Valve (muSI-LOV) sample pretreatment protocol comprising bead injection separation/pre-concentration and detection by electrothermal atomic absorption spectrometry (ETAAS). Based on the dimethylglyoxime (DMG) reaction used for nickel analysis, the sample, as contained in a pH 9.0 buffer, is, after on-line merging with the chelating reagent, transported to a reaction coil attached to one of the external ports of the LOV to assure sufficient reaction time for the formation of Ni(DMG)(2) chelate. The non-ionic coordination compound is then collected in a renewable micro-column packed with a reversed-phase copolymeric sorbent [namely, poly(divinylbenzene-co-N-vinylpyrrolidone)] containing a balanced ratio of hydrophilic and lipophilic monomers. Following elution by a 50-muL methanol plug in an air-segmented modality, the nickel is finally quantified by ETAAS. Under the optimized conditions and for a sample volume of 1.8 mL, a retention efficiency of 70 % and an enrichment factor of 25 were obtained. The proposed methodology showed a high tolerance to the commonly encountered alkaline earth matrix elements in environmental waters, that is, calcium and magnesium, and was successfully applied for the determination of nickel in an NIST standard reference material (NIST 1640-Trace elements in natural water), household tap water of high hardness and local seawater. Satisfying recoveries were achieved for all spiked environmental water samples with maximum deviations of 6 %. The experimental results for the standard reference material were not statistically different to the certified value at a significance level of 0.05.
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NASA Astrophysics Data System (ADS)
Doherty, W.; Lightfoot, P. C.; Ames, D. E.
2014-08-01
The effects of polynomial interpolation and internal standardization drift corrections on the inter-measurement dispersion (statistical) of isotope ratios measured with a multi-collector plasma mass spectrometer were investigated using the (analyte, internal standard) isotope systems of (Ni, Cu), (Cu, Ni), (Zn, Cu), (Zn, Ga), (Sm, Eu), (Hf, Re) and (Pb, Tl). The performance of five different correction factors was compared using a (statistical) range based merit function ωm which measures the accuracy and inter-measurement range of the instrument calibration. The frequency distribution of optimal correction factors over two hundred data sets uniformly favored three particular correction factors while the remaining two correction factors accounted for a small but still significant contribution to the reduction of the inter-measurement dispersion. Application of the merit function is demonstrated using the detection of Cu and Ni isotopic fractionation in laboratory and geologic-scale chemical reactor systems. Solvent extraction (diphenylthiocarbazone (Cu, Pb) and dimethylglyoxime (Ni) was used to either isotopically fractionate the metal during extraction using the method of competition or to isolate the Cu and Ni from the sample (sulfides and associated silicates). In the best case, differences in isotopic composition of ± 3 in the fifth significant figure could be routinely and reliably detected for Cu65/63 and Ni61/62. One of the internal standardization drift correction factors uses a least squares estimator to obtain a linear functional relationship between the measured analyte and internal standard isotope ratios. Graphical analysis demonstrates that the points on these graphs are defined by highly non-linear parametric curves and not two linearly correlated quantities which is the usual interpretation of these graphs. The success of this particular internal standardization correction factor was found in some cases to be due to a fortuitous, scale dependent, parametric curve effect.
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Lewis, Nerissa A; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G
2014-10-20
New mononuclear amidine complexes, fac-[Re(CO)3(Me2bipy)(HNC(CH3)(pyppz))]BF4 [(4,4'-Me2bipy (1), 5,5'-Me2bipy (2), and 6,6'-Me2bipy (3)] (bipy = 2,2'-bipyridine), were synthesized by treating the parent fac-[Re(I)(CO)3(Me2bipy)(CH3CN)]BF4 complex with the C2-symmetrical amine 1-(4-pyridyl)piperazine (pyppzH). The axial amidine ligand has an exposed, highly basic pyridyl nitrogen. The reaction of complexes 1-3 with a B12 model, (py)Co(DH)2Cl (DH = monoanion of dimethylglyoxime), in CH2Cl2 yielded the respective dinuclear complexes, namely, fac-[Re(CO)3(Me2bipy)(μ-(HNC(CH3)(pyppz)))Co(DH)2Cl]BF4 [(4,4'-Me2bipy (4), 5,5'-Me2bipy (5), and 6,6'-Me2bipy (6)]. (1)H NMR spectroscopic analysis of all compounds and single-crystal X-ray crystallographic data for 2, 3, 5, and 6 established that the amidine had only the E configuration in both the solid and solution states and that the pyridyl group is bound to Co in 4-6. Comparison of the NMR spectra of 1-3 with spectra of 4-6 reveals an unusually large "wrong-way" upfield shift for the pyridyl H2/6 signal for 4-6. The wrong-way H2/6 shift of (4-Xpy)Co(DH)2Cl (4-Xpy = 4-substituted pyridine) complexes increased with increasing basicity of the 4-Xpy derivative, a finding attributed to the influence of the magnetic anisotropy of the cobalt center on the shifts of the (1)H NMR signals of the pyridyl protons closest to Co. Our method of employing a coordinate bond for conjugating the fac-[Re(I)(CO)3] core to a vitamin B12 model could be extended to natural B12 derivatives. Because B12 compounds are known to accumulate in cancer cells, such an approach is a very attractive method for the development of (99m)Tc and (186/188)Re radiopharmaceuticals for targeted tumor imaging and therapy.
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Torjussen, W; Haug, F M; Olsen, A; Andersen, I
1978-01-01
Histochemical methods and energy dispersive X-ray micro-analysis (EDX-analysis) were evaluated in model experiments and on tissue sections for their usefulness in detecting traces of metals in biological tissue. The goal for this study was to establish a method for localization of nickel deposits in the nasal mucosa, where it has been found in concentrations between 1 and 40 microgram/g in nickel exposed individuals. The histochemical methods tested were staining with dimethylglyoxime, rubeanic acid and dithizone, the Turnbull and Prussian blue methods and TIMM'S sulphide silver procedure. In model experiments nickel-, cobalt-, copper-, zinc- and ironsalts were applied to thin-layer chromatography sheets (TLC-sheets) and stained by the histochemical methods. Spots containing 500 and 50 ng of these metals represented the smallest amounts that could consistently be detected in these experiments, except for the sulphide silver method which seemed a little more sensitive. With the latter method, moreover, zinc was detected in 40 micrometer thick cryostat sections of gelatine made up with 1 microgram/g of the metal. For nickel the corresponding figure was 10 to 50 microgram/g. On specimens of nasal mucosa from nickel-exposed workers, a faint colour was obtained in 40 micron thick cryostat sections from specimens that had been immersed in dithizone, but the colour was too weak for histological analysis. None of the other coloured chelating agents caused noticeable staining when applied to blocks or to cryostat sections. TIMM'S sulphide silver method caused strong staining of the basal layers of the surface epithelium and of fibroblast-like cells in the underlying connective tissue. This staining pattern is described in more detail in a separate report. Rat liver tissue was analyzed by atomic absorption before and after araldite embedding. Blocks of gelatine made up with nickel, copper, zinc and iron were embedded in epoxy resin and analyzed by atomic absorption. Large changes in the metal concentrations, usually an increase, were found after embedding. Ultrathin sections from this material were used to test the sensitivity of the EDX-equipment. Referring to the concentrations determined by atomic absorption in the embedded material, iron was detected at 1215 microgram/g and 362 microgram/g (gelatine standards) but not at 167 microgram/g (rat liver). Similar values could not be determined for nickel, copper or zinc, because of background radiation resulting from the presence of these metals in the instrument. We did not succeed in establishing a procedure for detecting nickel deposits in nasal mucosa with any of the methods which were tested. The most sensitive but least specific of the tested methods for visualizing heavy metals in the nasal mucosa, was TIMM'S sulphide silver procedure. The preparation of tissue for this method is discussed.
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NASA Astrophysics Data System (ADS)
Carraher, Jack McCaslin
Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding 'greener' sources of commodity chemicals and fuels. High-valent Chromium from Hydroperoxido-Chromium(III). The decomposition of pentaaquahydroperoxido chromium(III) ion (hereafter Cr aqOOH2+) in acidic aqueous solutions is kinetically complex and generates mixtures of products (Craq3+, HCrO 4-, H2O2, and O2). The yield of high-valent chromium products (known carcinogens) increased from a few percent at pH 1 to 70 % at pH 5.5 (near biological pH). Yields of H 2O2 increased with acid concentration. The reproducibility of the kinetic data was poor, but became simplified in the presence of H2O2 or 2,2‧-azinobis(3-ethylbenzothiazoline-6-sulfonate) dianion (ABTS2-). Both are capable of scavenging strongly oxidizing intermediates). The observed rate constants (pH 1, [O2] ≤ 0.03 mM) in the presence of these scavengers are independent of [scavenger] and within the error are the same (k,ABTS2- = (4.9 +/- 0.2) x 10-4 s-1 and kH2O2 = (5.3 +/- 0.7) x 10-4 s-1); indicating involvement of the scavengers in post-rate determining steps. In the presence of either scavenger, decomposition of CrOOH2+ obeyed a two-term rate law, k obs / s-1 = (6.7 +/- 0.7) x 10-4 + (7.6 +/- 1.1) x 10-4 [H+]. Effect of [H+] on the kinetics and the product distribution, cleaner kinetics in the presence of scavengers, and independence of kobs on [scavenger] suggest a dual-pathway mechanism for the decay of Craq OOH2+. The H+-catalyzed path leads to the dissociation of H2O2 from Cr(III), while in the H+-independent reaction, CraqOOH2+ is transformed to Cr(V). Both scavengers rapidly remove Cr(V) and simplify both the kinetics and products by impeding formation of Cr(IV, V, VI). Syntheses, Reactivity, and Thermodynamic Considerations LRhR2+. Macrocyclic rhodium(II) complexes LRh(H 2O)2+ (L = L1= cyclam and L2 = meso-Me6-cyclam) react with alkyl hydroperoxides R(CH3)2COOH to generate the corresponding rhodium(III) alkyls LRh(H2O)R2+ (R = CH3, C2 H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgX) 2(H2O)CoR (where R = CH3, CH2Ph and dmgX is either dimethylglyoxime or a BF2-capped derivative of dmg) to LRh(H2O)2+. When R = C2H5, C3H7 or C4H9, the mechanism changes from group transfer to hydrogen atom abstraction from the coordinated alkyl and produces LRh(H2O)H2+ and an a-olefin. The new LRh(H2O)R2+ complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis. 'Green' Model for Decarboxylation of Biomass Derived Acids via Photolysis of in situ formed Metal-Carboxylate Complexes. Photolysis of aqueous solutions containing propionic acid and Fe 3+ aq in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. Photolysis in the presence of O2 yields catalytic amounts of hydrocarbon products. When halide ions are present during photolysis; nearly quantitative yields of ethyl halides are produced via extraction of a halide atom from FeX2+ by ethyl radical. The rate constants for ethyl radical reactions with FeCl2+ (k = 4.0 (+/- 0.5) x 106 M-1s-1) and with FeBr 2+ (k = 3.0 (+/- 0.5) x 107 M-1s -1) were determined via competition reactions. Irradiation of solutions containing aqueous Cu2+ salts and linear carboxylic acids yield alpha-olefins selectively. This process is made catalytic by the introduction of O2. Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu +. Longer-chain acids also yield alpha olefins as exclusive products. In the absence of continued purging with O2 to aid removal of olefin, Cu+(olefin) complexes accumulate and catalytic activity slows dramatically due to depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids. Free Oxygen Atom in Solution from 4-Benzoylpyridine N-Oxide Excited Singlet. Photolysis of 4-benzoylpyridine N-oxide (BPyO) in the presence of quenchers of the triplet excited state produces up to 41% O(3P) (as determined by generation of ethylene upon scavenging with cyclopentene). In the absence of 3BPyO* quenchers a maximum of 13% O(3P) relative to consumed BPyO is obtained. The remaining products are hydroxylated-4-benzoylpyridine and 4-benzoylpyridine. Additionally, the rate of BPyO consumption (as determined by UV-vis) decreases in the presence of 3BPyO* quenching agents. Second order rate constants for 3BPyO* quenching were determined. A mechanism for photochemical deoxygenation of BPyO is proposed on the basis of kinetic data and product distribution under various conditions. Additionally, comparisons are made between the observed intermediates and similar triplet excited states and radical anions.