Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

Science.gov (United States)

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

[Biological significance of chromium III for the human organism].

Science.gov (United States)

Piotrowska, Anna; Pilch, Wanda; Tota, Łukasz; Nowak, Gabriel

2018-03-09

Currently, chromium is probably the most controversial transition metal. In recent publications it is clearly stated that it is not an essential micronutrient and should be considered to have a pharmacological effect. Conflicting scientific reports along with a huge amount of dietary supplements, as well as dietary and sports nutrients available on the market have prompted the authors to investigate the available information on the range of possible application, efficacy and safety of products containing salts or chelates of chromium III. The authors reviewed articles in electronic databases for the years 1959-2016, and selected works describing the biochemical, physiological and toxic properties of chromium salts and chelates and the range of possible applications in medicine, dietetics and sport. A critical analysis of reports dealing with the effect of chromium on the carbohydrate and lipid metabolism, body composition, lean body mass and sports performance was carried out. The authors indicated papers analyzing the mechanism of action of chromium in the cognitive and affective disorders. Much attention has been paid to the safety use of chromium III supplements. There are still some unsolved issues. In the field of toxicology, a limited number of reports about environmental exposure to trivalent chromium in the workplace draws our attention. In the field of biochemical research, there is still a need to clarify the mechanism of psychiatric and endocrinological activity, especially in conjunction with the immune system. Med Pr 2018;69(2):211-223. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

Study of the Thermodynamics of Chromium(III) and Chromium(VI) Binding to Fe3O4 and MnFe2O4 nanoparticles

Science.gov (United States)

Luther, Steven; Brogfeld, Nathan; Kim, Jisoo; Parsons, J.G.

2013-01-01

Removal of chromium(III) or (VI) from aqueous solution was achieved using Fe3O4, and MnFe2O4 nanomaterials. The nanomaterials were synthesized using a precipitation method and characterized using XRD. The size of the nanomaterials was determined to be 22.4 ± 0.9 nm (Fe3O4) and 15.5 ± 0.5 nm (MnFe2O4). The optimal binding pH for chromium(III) and chromium(VI) were pH 6 and pH 3. Isotherm studies were performed, under light and dark conditions, to determine the capacity of the nanomaterials. The capacities for the light studies with MnFe2O4 and Fe3O4 were determined to be 7.189 and 10.63 mg/g, respectively, for chromium(III). The capacities for the light studies with MnFe2O4 and Fe3O4 were 3.21 and 3.46 mg/g, respectively, for chromium(VI). Under dark reaction conditions the binding of chromium(III) to the MnFe2O4 and Fe3O4 nanomaterials were 5.74 and 15.9 mg/g, respectively. The binding capacity for the binding of chromium(VI) to MnFe2O4 and Fe3O4 under dark reaction conditions were 3.87 and 8.54 mg/g, respectively. The thermodynamics for the reactions showed negative ΔG values, and positive ΔH values. The ΔS values were positive for the binding of chromium(III) and for chromium(VI) binding under dark reaction conditions. The ΔS values for chromium(VI) binding under the light reaction conditions were determined to be negative. PMID:23558081

Oxidation of Cr(III)-Fe(III) Mixed-phase Hydroxides by Chlorine: Implications on the Control of Hexavalent Chromium in Drinking Water.

Science.gov (United States)

Chebeir, Michelle; Liu, Haizhou

2018-05-17

The occurrence of chromium (Cr) as an inorganic contaminant in drinking water is widely reported. One source of Cr is its accumulation in iron-containing corrosion scales of drinking water distribution systems as Cr(III)-Fe(III) hydroxide, i.e., FexCr(1-x)(OH)3(s), where x represents the Fe(III) molar content and typically varies between 0.25 and 0.75. This study investigated the kinetics of inadvertent hexavalent chromium Cr(VI) formation via the oxidation of FexCr(1-x)(OH)3(s) by chlorine as a residual disinfectant in drinking water, and examined the impacts of Fe(III) content and drinking water chemical parameters including pH, bromide and bicarbonate on the rate of Cr(VI) formation. Data showed that an increase in Fe(III) molar content resulted in a significant decrease in the stoichiometric Cr(VI) yield and the rate of Cr(VI) formation, mainly due to chlorine decay induced by Fe(III) surface sites. An increase in bicarbonate enhanced the rate of Cr(VI) formation, likely due to the formation of Fe(III)-carbonato surface complexes that slowed down the scavenging reaction with chlorine. The presence of bromide significantly accelerated the oxidation of FexCr(1-x)(OH)3(s) by chlorine, resulting from the catalytic effect of bromide acting as an electron shuttle. A higher solution pH between 6 and 8.5 slowed down the oxidation of Cr(III) by chlorine. These findings suggested that the oxidative conversion of chromium-containing iron corrosion products in drinking water distribution systems can lead to the occurrence of Cr(VI) at the tap, and the abundance of iron, and a careful control of pH, bicarbonate and bromide levels can assist the control of Cr(VI) formation.

Fractionation of chromium(III) compounds in biological matrices

Energy Technology Data Exchange (ETDEWEB)

Knoechel, A.; Weseloh, G. [Institute of Inorganic and Applied Chemistry, University of Hamburg (Germany)

1999-03-01

Many details of the metabolism and biological significance of trivalent inorganic cations have remained obscure up to now, not least because of the lack of appropriate tools for species analysis of these cations in biological matrices. In order to demonstrate the capabilities of reversed-phase ion-pair chromatography, the distribution of chromium species in brewer`s yeast, previously incubated with radiolabelled {sup 51}Cr chloride was investigated. Contradictory to the findings of most other researchers in this area, two low-molecular weight, anionic chromium species were detected in cytosolic yeast extracts. In conclusion, reversed-phase ion-pair chromatography may reveal new details of intracellular metabolism of chromium(III) and, possibly, other trivalent cations. (orig.) With 1 fig., 16 refs.

A novel solid phase extraction procedure on Amberlite XAD-1180 for speciation of Cr(III), Cr(VI) and total chromium in environmental and pharmaceutical samples

International Nuclear Information System (INIS)

Narin, Ibrahim; Kars, Ayse; Soylak, Mustafa

2008-01-01

Due to the toxicity of chromium, species depend on their chemical properties and bioavailabilities, speciation of chromium is very important in environmental samples. A speciation procedure for chromium(III), chromium(VI) and total chromium in environmental samples is presented in this work, prior to flame atomic absorption spectrometric determination of chromium. The procedure is based on the adsorption of Cr(III)-diphenylcarbazone complex on Amberlite XAD-1180 resin. After oxidation of Cr(III), the developed solid phase extraction system was applied to determinate the total chromium. Cr(III) was calculated as the difference between the total Cr content and the Cr(VI) content. The analytical conditions for the quantitative recoveries of Cr(VI) on Amberlite XAD-1180 resin were investigated. The effects of some alkaline, earth alkaline, metal ions and also some anions were also examined. Preconcentration factor was found to be 75. The detection limits (LOD) based on three times sigma of the blank (N: 21) for Cr(VI) and total chromium were 7.7 and 8.6 μg/L, respectively. Satisfactory results for the analysis of total chromium in the stream sediment (GBW7310) certified reference material for the validation of the presented method was obtained. The procedure was applied to food, water and pharmaceutical samples successfully

Removal of Chromium (III from Water by Using Modified and Nonmodified Carbon Nanotubes

Directory of Open Access Journals (Sweden)

Muataz Ali Atieh

2010-01-01

Full Text Available This study was carried out to evaluate the environmental application of modified and nonmodified carbon nanotubes through the experiment removal of chromium trivalent (III from water. The aim was to find the optimal condition of the chromium (III removal from water under different treatment conditions of pH, adsorbent dosage, contact time and agitation speed. Multi wall carbon nanotubes (MW-CNTs were characterized by field emission scanning electron microscopy (FE-SEM and transmission electron microscopy (TEM. The diameter of the carbon nanotubes produced varied from 20–40 nm with average diameter of 24 nm and 10 micrometer in length. Adsorption isotherms were used to model the adsorption behavior and to calculate the adsorption capacity of the absorbents. The results showed that, 18% of chromium (III removal was achieved using modified carbon nanotubes (M-CNTs at pH 7, 150 rpm, and 2 hours for a dosage of 150 mg of CNTs. The removal of Cr (III is mainly attributed to the affinity of chromium (III to the physical and chemical properties of the CNTs. The adsorption isotherms plots were well fitted with experimental data.

Determination of Chromium(III), Chromium(VI), and Chromium(III) acetylacetonate in water by ion-exchange disk extraction/metal furnace atomic absorption spectrometry

International Nuclear Information System (INIS)

Kamakura, Nao; Inui, Tetsuo; Kitano, Masaru; Nakamura, Toshihiro

2014-01-01

A new method for the separate determination of Chromium(III) (Cr(III)), Chromium(VI) (Cr(VI)), and Cr(III) acetylacetonate (Cr(acac) 3 ) in water was developed using a cation-exchange extraction disk (CED) and an anion-exchange extraction disk (AED) combined with metal furnace atomic absorption spectrometry (MFAAS). A 100-mL water sample was adjusted to pH 5.6 and passed through the CED placed on the AED. Cr(acac) 3 and Cr(III) were adsorbed on the CED, and Cr(VI) was adsorbed on the AED. The adsorbed Cr(acac) 3 was eluted with 50 mL of carbon tetrachloride, followed by the elution of Cr(III) with 50 mL of 3 mol L −1 nitric acid. Cr(VI) was eluted with 50 mL of 3 mol L −1 nitric acid. The chemical species of Cr eluted from the CED with carbon tetrachloride was identified as Cr(acac) 3 using infrared spectroscopy. The eluate of Cr(acac) 3 was diluted to 100 mL with carbon tetrachloride, and those of Cr(III) and Cr(VI) were diluted to 100 mL with deionized water. All of the solutions were subsequently analyzed by MFAAS. The calibration curve for the Cr(acac) 3 aqueous solutions exhibited good linearity in the range of 0.1 to 1 ng. The detection limit of Cr, which corresponded to three times the standard deviation (n = 10) of the blank values, was 20 pg. The recovery test for Cr(III), Cr(VI), and Cr(acac) 3 exhibited desirable results (96.0%–107%) when 5 μg of each species (50 μg L −1 ) was added to 100 mL water samples (i.e., tap water, rainwater, and bottled drinking water). In a humic acid solution, Cr(acac) 3 was quantitatively recovered (103%), but Cr(III) and Cr(VI) exhibited poor recoveries (i.e., 84.8% and 78.4%, respectively). - Highlights: • A determination method of Cr(III), Cr(VI), and Cr(III) acetylacetonate in water was developed. • The combination of ion-exchange resin disks with metal furnace AAS was used. • No effect of humic acid on the recovery of Cr(III) acetylacetonate was observed. • The proposed method enabled the determination

Molecular and electronic structure of chromium(V) nitrido complexes with azide and isothiocyanate ligands

DEFF Research Database (Denmark)

Bendix, Jesper; Birk, Torben; Weyhermüller, Thomas

2005-01-01

. This absorption provides the spectrochemical series for the equatorial ligands, which is found to be numerically almost identical to that determined for chromium(III). DFT calculations reproduce the observed structures and corroborate the ligand field picture of the electronic structure of these complexes....

Chromium allergy

DEFF Research Database (Denmark)

Hansen, M B; Johansen, J D; Menné, Torkil

2003-01-01

Most studies investigating chromium allergy have been performed with Cr(VI). However, real exposure to chromium from leather products includes both Cr(III) and Cr(VI). We have determined and compared the minimum elicitation threshold (MET) concentration for Cr(III) and Cr(VI) in Cr(VI)-sensitive ......Most studies investigating chromium allergy have been performed with Cr(VI). However, real exposure to chromium from leather products includes both Cr(III) and Cr(VI). We have determined and compared the minimum elicitation threshold (MET) concentration for Cr(III) and Cr(VI) in Cr......(III) was concluded to play an important role in chromium allergy, because Cr(III) and Cr(VI) were both capable of eliciting eczema at low concentrations. Rather than regarding chromium dermatitis as a result of Cr(VI) allergy alone, it may be more correct to consider it as a result of a combined Cr(III) and Cr......(VI) allergy....

Determination of stability constants of iron(III and chromium(III-nitrilotriacetate-methyl cysteine mixed complexes by electrophoretic technique

Directory of Open Access Journals (Sweden)

Brij Bhushan Tewari

2004-06-01

Full Text Available The stability constants of Fe(III and Cr(III with methyl cysteine and nitrilotriacetate (NTA were determined by paper electrophoretic technique. Beside binary ternary complexes have also been studied, in which nitrilotriacetate and methyl cysteine acts as primary and secondary ligand, respectively. The stability constants of mixed ligand complexes metal (M-nitrilotriacetate-methyl cysteine have been found to be 5.72 plus or minus 0.09 and 5.54 plus or minus 0.11 (log K values for Fe(III and Cr(III complexes, respectively, at 35 oC and ionic strength 0.1 M.

RECOVERY OF COPPER(II) AND CHROMIUM(III) FROM NITRATE ...

African Journals Online (AJOL)

Guerdouh A and Barkat D

2016-05-01

May 1, 2016 ... The ionic strength of the aqueous medium was ... phases were separated completely, concentrations of the copper(II) and chromium(III) ..... [18] Huff M M, Otu E O. Solvent Extraction and Ion Exchange, 2004, 22(4), 695-712.

Enhanced sludge processing of HLW: Hydrothermal oxidation of chromium, technetium, and complexants by nitrate. 1997 mid-year progress report

International Nuclear Information System (INIS)

Buelow, S.

1997-01-01

'Treatment of High Level Waste (HLW) is the second most costly problem identified by OEM. In order to minimize costs of disposal, the volume of HLW requiring vitrification and long term storage must be reduced. Methods for efficient separation of chromium from waste sludges, such as the Hanford Tank Wastes (HTW), are key to achieving this goal since the allowed level of chromium in high level glass controls waste loading. At concentrations above 0.5 to 1.0 wt.% chromium prevents proper vitrification of the waste. Chromium in sludges most likely exists as extremely insoluble oxides and minerals, with chromium in the plus III oxidation state [1]. In order to solubilize and separate it from other sludge components, Cr(III) must be oxidized to the more soluble Cr(VI) state. Efficient separation of chromium from HLW could produce an estimated savings of $3.4B[2]. Additionally, the efficient separation of technetium [3], TRU, and other metals may require the reformulation of solids to free trapped species as well as the destruction of organic complexants. New chemical processes are needed to separate chromium and other metals from tank wastes. Ideally they should not utilize additional reagents which would increase waste volume or require subsequent removal. The goal of this project is to apply hydrothermal processing for enhanced chromium separation from HLW sludges. Initially, the authors seek to develop a fundamental understanding of chromium speciation, oxidation/reduction and dissolution kinetics, reaction mechanisms, and transport properties under hydrothermal conditions in both simple and complex salt solutions. The authors also wish to evaluate the potential of hydrothermal processing for enhanced separations of technetium and TRU by examining technetium and TRU speciation at hydrothermal conditions optimal for chromium dissolution.'

Chromium III histidinate exposure modulates antioxidant gene expression in HaCaT human keratinocytes exposed to oxidative stress

Science.gov (United States)

While the toxicity of hexavalent chromium is well established, trivalent Cr (Cr(III)) is an essential nutrient involved in insulin and glucose homeostasis. Recently, antioxidant effects of chromium (III) histidinate (Cr(III)His) were reported in HaCaT human keratinocytes exposed to oxidative stress...

Chromium(III)-trisoxalate, a versatile building block for luminescent materials

Energy Technology Data Exchange (ETDEWEB)

Milos, Mia [Departement de chimie physique, Universite de Geneve, 30 quai Ernest-Ansermet, CH-1211 Geneve 4 (Switzerland); Hauser, Andreas, E-mail: andreas.hauser@unige.ch [Departement de chimie physique, Universite de Geneve, 30 quai Ernest-Ansermet, CH-1211 Geneve 4 (Switzerland)

2013-01-15

Chromium(III)-trisoxalate, [Cr(ox){sub 3}]{sup 3-} (ox=C{sub 2}O{sub 4}{sup 2-}), incorporated into polymeric networks of composition [NaCr(ox){sub 3}][M{sup II}(bpy){sub 3}] and [NaCr(ox){sub 3}][M{sup III}(bpy){sub 3}]ClO{sub 4} (ox=C{sub 2}O{sub 4}{sup 2-}, bpy=2,2 Prime -bipyridine, M{sup II}=Zn, Fe, Ru; M{sup III}=Rh, Cr), results in interesting features ranging from phonon-assisted and resonant energy migration within the R{sub 1} line the {sup 2}E state to persistent spectral side-hole burning via the latter, and manifestations of specific nearest-neighbour {pi}-{pi} interactions between bipyridine and oxalate. - Highlights: Black-Right-Pointing-Pointer We present the multifaceted photophysical behaviour of chromium(III)-tris-oxalate. Black-Right-Pointing-Pointer We differentiate between phonon-assisted and resonant energy migration. Black-Right-Pointing-Pointer Resonant energy migration results in spectral diffusion. Black-Right-Pointing-Pointer Resonant energy transfer can be tuned via pressure dependant spectral overlap. Black-Right-Pointing-Pointer {pi}-{pi} interactions with the second coordination sphere create specific spectroscopic sites.

Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

Energy Technology Data Exchange (ETDEWEB)

Feng, Xianghua; Ding, Shimin; Zhang, Lixian [Yangtze Normal Univ., Fuling (China)

2012-11-15

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly.

Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

International Nuclear Information System (INIS)

Feng, Xianghua; Ding, Shimin; Zhang, Lixian

2012-01-01

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly

40 CFR 721.2097 - Azo chromium complex dyestuff preparation (generic name).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Azo chromium complex dyestuff... New Uses for Specific Chemical Substances § 721.2097 Azo chromium complex dyestuff preparation... substance identified generically as an azo chromium complex dyestuff preparation (PMN P-95-240) is subject...

Bioavailability of a potato chromium complex to the laboratory rat

International Nuclear Information System (INIS)

Gilbert, H.K.

1985-01-01

Research objectives were to study the effect of food source, preparation method and chemical form on bioavailability of chromium. Chromium concentration in potatoes was determined and tubers labeled either intrinsically or extrinsically with radioactive chromate. A labeled chromium complexes was isolated from preparations of raw, baked or fried potatoes and chromatographed on gel permeation media. Availability of the potato chromium complex to the rat was examined in three feeding studies. Animals were dosed with radioactive extrinsically or intrinsically labeled potato extract or with chromate. A labeled chromium complex was isolated from gastrointestinal contents of rats and chromatographed. Potato pulp and peel contained 1.63 and 2.70 μg Cr/g tissue respectively. True and apparent absorption from extrinsically labeled feedings were 33.4 +/- 4.7 and 29.8 +/- 11.2% respectively, and no differences existed between absorption from raw and cooked potatoes. Absorption from the extrinsic labeled potatoes differed significantly from absorption of inorganic chromatium. Apparent absorption of raw (11.1 +/- 7.9%) and cooked (-0.7 +/- 2.8%) intrinsically labeled feedings differed significantly. Absorption of inorganic chromium was 17.8% (true) and 11.5% (apparent). Examination of the chromium complex isolated from gastrointestinal tract contents showed enlargement of the complex in the stomach after consumption

Removal of chromium(III) from tannery wastewater using activated carbon from sugar industrial waste.

Science.gov (United States)

Fahim, N F; Barsoum, B N; Eid, A E; Khalil, M S

2006-08-21

Chromium is commonly found in huge quantities in tannery wastewaters. For this reason, the removal and recovery of the chromium content of tannery wastewaters is crucial for environmental protection and economic reasons. Removal and recovery of chromium were carried out by using low-cost potential adsorbents. For this purpose three types of activated carbon; C1, the waste generated from sugar industry as waste products and the others (C2, C3) are commercial granular activated carbon, were used. The adsorption process and extent of adsorption are dependent on the physical and chemical characteristics of the adsorbent, adsorbate and experimental condition. The effect of pH, particle size and different adsorbent on the adsorption isotherm of Cr(III) was studied in batch system. The sorption data fitted well with Langmuir adsorption model. The efficiencies of activated carbon for the removal of Cr(III) were found to be 98.86, 98.6 and 93 % for C1, C2 and C3, respectively. The order of selectivity is C1>C2>C3 for removal of Cr(III) from tannery wastewater. Carbon "C1" of the highest surface area (520.66 m(2)/g) and calcium content (333.3 mg/l) has the highest adsorptive capacity for removal of Cr(III). The results revealed that the trivalent chromium is significantly adsorbed on activated carbon collected from sugar industry as waste products and the method could be used economically as an efficient technique for removal of Cr(III) and purification of tannery wastewaters.

40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

Science.gov (United States)

2010-07-01

... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject to...

Chromium (III) phosphate labelled with several radionuclides for use in radiosynoviothesis

International Nuclear Information System (INIS)

Cruz Arencibia, Jorge; Morin Zorrilla, Jose; Cruz Morales, Amed

2012-01-01

Radiosynoviorthesis is used in treating chronic synovitis, a frequent complication of some systemic diseases as rheumatoid arthritis and hemophilia. There are different colloids and radioactive suspensions recommended in the international clinical practice, but the number is reduced and the availability limited. A suspension of chromium (III) phosphate was obtained and characterized. It was found that the obtained product had a predominant particle size range of 0,8 to 5 μm and that when suspended in 2 % gelatin solution in 1mg/ml acetate buffer, it settled in no less than 3 hours. Technologies for the preparation of radiopharmaceuticals of Chromium (III) Phosphate labeled with 32P and 90Y were described. There was demonstrated the feasibility of labeling the obtained suspension with other trivalent radionuclides such as 177Lu and 68Ga.

Solvent Extraction and Separation of Chromium(III) and (V I) in Aqueous Solutions with Trioctylphosphine Oxide

International Nuclear Information System (INIS)

Sekine, T.; Yamada, M.

1999-01-01

The solvent extraction of chromium(III) and (V I) in aqueous solutions with a solvating type extractant, trioctylphosphine oxide(TOPO), in hexane is studied. Kinetically inert Cr 3+ is extracted from 1 mol dm -3 sodium perchlorate solution very quickly and quantitatively as Cr(H 2 O · TOPO) 6 3+ (CIO 4 -) 3 . Chromium(V I) in hydrochloric acid is extracted effectively as the H 2 CrO $ (H CI) n centre dot TOPO m species ( m = 2 or 3, n = 0 to 2) and the distribution ratio increased by an increase in the acid concentration. From these, a procedure is proposed for the extraction of both chromium(V I) and chromium(III) in aqueous solution separately with 0.1 mol dm -3 TOPO in hexane

THE DYNAMICS SORPTION FEATURES OF A COMPLEX 1,5- DIPHENILCARBAZONATE CHROMIUM(III BY USING ION-EXCHANGE RESINS CU-2-8 AND CB-4P-2 FROM DIFFERENT CATEGORIES OF WATER

Directory of Open Access Journals (Sweden)

Н. M. Guzenko

2014-12-01

Full Text Available The formation mechanism features of adsorption layers are established on a surface ionexchange resins CU-2-8 and CB-4p-2 in the presence of the inorganic ions amount, that are typical for natural and sewage water by using the dynamic and kinetic graphs considering change of complex 1,5-diphenylcarbazonate of chromium(III quantity, and also factor of sorption process speed.

Grafted chromium 13-membered dioxo-macrocyclic complex into aminopropyl-based nanoporous SBA-15

Energy Technology Data Exchange (ETDEWEB)

Tarlani, Aliakbar, E-mail: Tarlani@ccerci.ac.ir [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of); Joharian, Monika; Narimani, Khashayar [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of); Muzart, Jacques [Institut de Chimie Moléculaire de Reims, CNRS-Université de Reims Champagne-Ardenne, BP 1039, 51687 Reims Cedex 2 (France); Fallah, Mahtab [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of)

2013-07-15

In a new approach, chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 after four step reactions by using coordinating ability of anchored amino functionalized SBA-15. After the termination of each step, the obtained product was characterized by FT-IR, low-angle X-ray diffraction (LA-XRD), N{sub 2} adsorption–desorption isotherms (Brunauer–Emmett–Teller (BET)–Barret–Joyner–Halenda (BJH)) and thermogravimetric analysis (TGA), and used as catalyst for the efficient and regioselective alcoholysis of styrene oxide to 2-alkoxy-1-phenylethanol product at ambient temperature. - Graphical abstract: Chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 using coordinating ability of anchored amino functionalized SBA-15. Preparation of the catalyst is depicted in Scheme 1. - Highlights: • Dioxo tetraazachromium macrocyclic complex grafted into the SBA-15-NH{sub 2} channels. • The bond is created by coordinating ability of anchored amino functionalized SBA-15. • The prepared nanocatalyst has superior activity in the alcoholysis of styrene oxide. • The catalyst is reusable at ambient temperature for the mentioned reaction.

Role of paramagnetic chromium in chromium(VI)-induced damage in cultured mammalian cells.

OpenAIRE

Sugiyama, M

1994-01-01

Chromium(VI) compounds are known to be potent toxic and carcinogenic agents. Because chromium(VI) is easily taken up by cells and is subsequently reduced to chromium(III), the formation of paramagnetic chromium such as chromium(V) and chromium(III) is believed to play a role in the adverse biological effects of chromium(VI) compounds. The present report, uses electron spin resonance (ESR) spectroscopy; the importance of the role of paramagnetic chromium in chromium(VI)-induced damage in intac...

Anti-diabetic effects of Inonotus obliquus polysaccharides-chromium (III) complex in type 2 diabetic mice and its sub-acute toxicity evaluation in normal mice.

Science.gov (United States)

Wang, Cong; Chen, Zhongqin; Pan, Yuxiang; Gao, Xudong; Chen, Haixia

2017-10-01

Polysaccharides are important bioactive ingredients from Inonotus obliquus. This study aimed to synthesize and characterize a novel I. obliquus polysaccharides-chromium (III) complex (UIOPC) and investigate the anti-diabetic effects in streptozotocin (STZ) induced type 2 diabetes mellitus (T2DM) mice and sub-acute toxicity in normal mice. The molecular weight of UIOPC was about 11.5 × 10 4  Da with the chromium content was 13.01% and the chromium was linked with polysaccharides through coordination bond. After treatment of UIOPC for four weeks, the body weight, fasting blood glucose (FBG) levels, plasma insulin levels of the diabetic mice were significantly reduced when compared with those of the diabetic mice (p < 0.05). The results on serum profiles and antioxidant enzymes activities revealed that UIOPC had a positive effect on hypoglycemic and antioxidant ability. Histopathology results showed that UIOPC could effectively alleviate the STZ-lesioned tissues in diabetic mice. Furthermore, high dose administration of UIOPC had no obviously influence on serum profiles levels and antioxidant ability of the normal mice and the organ tissues maintained organized and integrity in the sub-acute toxicity study. These results suggested that UIOPC might be a good candidate for the functional food or pharmaceuticals in the treatment of T2DM. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carcinogenicity of chromium and chemoprevention: a brief update

Directory of Open Access Journals (Sweden)

Wang Y

2017-08-01

Full Text Available Yafei Wang,1,* Hong Su,1,* Yuanliang Gu,1 Xin Song,1 Jinshun Zhao1,2 1Department of Preventative Medicine, Zhejiang Key Laboratory of Pathophysiology, School of Medicine, Ningbo University, Ningbo, People’s Republic of China; 2Toxicology and Molecular Biology Branch, Health Effects Laboratory Division, National Institute for Occupational Safety and Health, Morgantown, WV, USA *These authors contributed equally to this work Abstract: Chromium has two main valence states: hexavalent chromium (Cr[VI] and trivalent chromium (Cr[III]. Cr(VI, a well-established human carcinogen, can enter cells by way of a sulfate/phosphate anion-transport system, and then be reduced to lower-valence intermediates consisting of pentavalent chromium (Cr[V], tetravalent chromium (Cr[IV] or Cr(III via cellular reductants. These intermediates may directly or indirectly result in DNA damage or DNA–protein cross-links. Although Cr(III complexes cannot pass easily through cell membranes, they have the ability to accumulate around cells to induce cell-surface morphological alteration and result in cell-membrane lipid injuries via disruption of cellular functions and integrity, and finally to cause DNA damage. In recent years, more research, including in vitro, in vivo, and epidemiological studies, has been conducted to evaluate the genotoxicity/carcinogenicity induced by Cr(VI and/or Cr(III compounds. At the same time, various therapeutic agents, especially antioxidants, have been explored through in vitro and in vivo studies for preventing chromium-induced genotoxicity/carcinogenesis. This review aims to provide a brief update on the carcinogenicity of Cr(VI and Cr(III and chemoprevention with different antioxidants. Keywords: hexavalent chromium, Cr(VI, trivalent chromium, Cr(III, genotoxicity, carcinogenicity, chemoprevention, antioxidant 

Glutamine-containing “turn-on” fluorescence sensor for the highly sensitive and selective detection of chromium (III) ion in water

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Zhao, Meili; Ma, Liguo; Zhang, Min; Cao, Weiguang; Yang, Liting; Ma, Li-Jun

2013-12-01

In this study, we reported a new fluorescence sensor for chromium (III) ion, dansyl-L-glutamine (1). The sensor displayed a unique selective fluorescence “turn-on” response to Cr3+ over other common metal ions in water. Notably, 1 still showed a ratiometric response to Cr3+ in UV-vis absorption spectra. The binding mechanism of 1 to Cr3+ was further clarified by using NMR and ESI-MS spectra. The experiment results indicated that the dual-responses of 1 to Cr3+ should attribute to the coordination of deprotonated sulfonamide group with Cr3+ and the protonation of the dimethylamino group due to the coordination of Cr3+ for 1. In addition, two chloride ions also coordinated to the complex of sensor-chromium (III) ion, which further strengthened the conformation of 1-Cr3+.

The study of Cr(III) complexation in the xylem sap using ion exchange and radiotracer

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Juneja, Shikha; Prakash, Satya

2003-01-01

Radiotracer was employed to carry out ion exchange experiments to study the chromium speciation in the in vitro samples of xylem sap of maize stem of 60 days old plants. Cr(III) radiolabelled with its radioactive isotope ( 51 Cr) was mixed with both the ion exchange fraction of the sap which represented the carboxylic acids, as well as the whole sap and was analysed for complexation after 10 and 30 days at 25 degC. Prior to this, the ion exchange elution chromatography of Cr(III), and the Cr(III) complexes with oxalic and citric acid were used to compare the complexes being formed in the in vitro studies. The in vitro Cr(III) complexation results indicated that Cr(III) was vitally present as anionic species. The elution curve trend was similar to that of citric acid complexation. Citric acid was also found to be the major complexing acid in the xylem sap as determined by HPLC. The results indicate the transportation of Cr(III) as a citrate complex in the xylem sap of maize plants. (author)

Interaction of Cr (III), Ni (II), Pb (II) with DTPA complexes of essential metal ions

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Gulzar, S.; Zahida; Maqsood, T.; Naqvi, R.R.

2002-01-01

With the increase of anthropogenic activities in the environment, heavy metal toxicity (Chromium, Nickel and Lead) is more common now. DTPA (diethylene triamine pentaacetic acid) a polyamino carboxylic acid is widely used to form hydrophilic and stable complexes with most of the metal ions. In this spectrophotometric study, concentration of Cr(III), Ni(II) and Pb(II) (toxic metal ions) exchanged with Fe(III), Zn(II) and Ca(II) from their DTPA complexes were estimated at pH 4,7 and 9. Concentration of added metal was varied from 1-4 times to that of complexed metal. (author)

Biosorption characteristics of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions by Chara sp. and Cladophora sp.

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Elmaci, Ayşe; Yonar, Taner; Ozengin, Nihan

2007-09-01

The aim of this research was to expose individual removals of copper, chromium, nickel, and lead from aqueous solutions via biosorption using nonliving algae species, Chara sp. and Cladophora sp. Optimum pH values for biosorption of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3 for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum adsorption capacities of Chara sp. [10.54 for chromium (III) and 61.72 for lead (II)] and Cladophora sp. [6.59 for chromium (III) and 16.75 and 23.25 for lead (II)] for chromium (III) and lead (II) are similar. On the other hand, copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for copper (II) and 11.76 for nickel (II)]. Significantly high correlation coefficients indicated for the Langmuir adsorption isotherm models can be used to describe the equilibrium behavior of copper, chromium, nickel, and lead adsorption onto Cladophora sp. and Chara sp.

Kinetic model building using advanced nuclear medicine techniques: the kinetics of chromium(III) in the human body

International Nuclear Information System (INIS)

Lim, T.H.

1978-06-01

The purpose of this study is to investigate whether a valid index of chromium (III) nutritional status can be determined with satisfaction through in vivo kinetic analysis. Three normal subjects and three patients suffering from hemochromatosis were periodically scanned with the Donner Laboratory computerized whole body scanners, starting seconds after radiochromium(III) was administered intravenously, up to a period of 84 days. The activity in the liver, adipose and muscle tissues, spleen and bone was quantitated and corrected, by subtraction of the blood circulation activity in that organ; the major concentration was found in the liver and spleen. From the series of scan images, a kinetic model for the radiochromium(III) metabolic pathway was constructed. Computer analysis showed a significant difference between the two classes of subjects in organs as well as whole body radiochromium(III) transfer. Interpretation of these results showed that in patients with excessive iron stores, a smaller amount of chromium bound to plasma protein was found and a corresponding decrease in transfer of chromium into stores in the liver and other tissues was also found

A pulse radiolysis study of the reaction of hydroxyl radicals with trans-dihydroxo(1,4,8,11-tetraazacyclotetradecane)chromium(3)

International Nuclear Information System (INIS)

Moensted, O.; Nord, G.; Pagsberg, P.

1987-01-01

Hydroxyl radicals react rapidly with the title chromium(III) complex. In weakly alkaline solution, around pH≅ the product rearranges by a first-order process followed by a second-order process. This sequence is interpreted as the formation of a chromium(IV) complex which then forms a μ-peroxochromium(III) dimer. The dimer decomposes by a two-electron oxidation of the macrocyclic ligan with the concomitant formation of a double bond. In more strongly basic solution and also in dilute acid, the decay kinetics are more complicated. Supplementary measurements using trans-difluoro(1,4,8,11-tetraazacyclotetradecane)Chromium(III), which does not contain coordinated hydroxide, and cis-dihydroxo(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)-chromium(III), for which dimerization is sterically hindered, support the above interpretation of the consecutive reactions for the title complex. (author)

Evidence of weak ferromagnetism in chromium(III) oxide particles

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Vazquez-Vazquez, Carlos; Banobre-Lopez, Manuel; Lopez-Quintela, M.A.; Hueso, L.E.; Rivas, J.

2004-01-01

The low temperature (4< T(K)<350) magnetic properties of chromium(III) oxide particles have been studied. A clear evidence of the presence of weak ferromagnetism is observed below 250 K. The magnetisation curves as a function of the applied field show coercive fields due to the canted antiferromagnetism of the particles. Around 55 K a maximum is observed in the zero-field-cooled curves; this maximum can be assumed as a blocking temperature, similarly to ultrafine ferromagnetic particles

Adsorption and desorption of hydrolyzed metal ions. 3. Scandium and chromium

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Gray, B.; Matijevic, E.; Clarkson Univ., Potsdam, NY

1987-01-01

Adsorption of scandium(III) and chromium(III) species on a PVC latex was measured using radioactive isotopes; the uptake increased with increasing pH. The data were interpreted by combining aspects of the models of James and Healy and also of Anderson and Bockris. The experimental and calculated results agree quite well for scandium, but not for chromium. The deviation in the latter case is believed to be due to polymerization of the hydrolyzed chromium cations and to the interaction of chromium with the anionic surface groups of the latex. Neither of these interactions occur with scandium. Hydrolyzed scandium species adsorbed on the latex were removed by acidifying the dispersion, while chromium complexes were not, substantiating the proposed difference in the chemical nature of chromium and scandium species at the solid/solution interface. 32 refs.; 8 figs.; 8 tabs

Effects of UV light and chromium ions on wood flavonoids

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Molnárné Hamvas, L.; Németh, K.; Stipta, J.

2003-01-01

The individual and simultaneous effect of UV light and chromium ions was investigated by spectrophotometric methods on inert surfaces impregnated with quercetin or robinetin. The UV-VIS spectra of the silica gel plates impregnated with these flavonoids were modified characteristically after irradiating ultraviolet light. Even a half an hour of irradiation has caused irreversible changes in the molecule structure. A certain chemical - presumably complexation - was concluded from the change of spectral bands assigned to flavonoids when impregnated with chromic ions. Hexavalent chromium caused more complex changes in the absorption spectra. The differences in the spectra could indicate either the oxidation and decomposition of flavonoids, or some kind of coordination process and the reduction of hexavalent chromium. The simultaneous application of UV light and chromium ions caused more pronounced effects. The complexation process between chromium(III) and flavonoid was completed

Utilization of modified corn silk as a biosorbent for solid-phase extraction of Cr(III) and chromium speciation.

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Yu, Hongmei; Pang, Jing; Wu, Mei; Wu, Qiaoli; Huo, Cuixiu

2014-01-01

The ues of corn silk modified with diluted nitric acid (HNO3-MCS) as a novel biosorbent has been established for solid-phase extraction of Cr(III) and chromium speciation in water samples. The functional groups of the HNO3-MCS surface are favorable for the adsorption of Cr(III). Effective extraction conditions were optimized in both batch and column methods. At pH 3.0 - 6.0, a discrimination of Cr(III) and Cr(VI) is achieved on the HNO3-MCS surface. Cr(III) ions are retained onto the HNO3-MCS surface, however, the adsorption of Cr(VI) is negligible under the same conditions. The adsorption isotherm of HNO3-MCS for Cr(III) has been demonstrated in accordance with a linear form of the Langmuir equation, and the maximum adsorption capacity is 35.21 mg g(-1). The well fitted linear regression of the pseudo-second order model showed the indication of a chemisorption mechanism for the entire concentration range. Thermodynamic studies have shown that the adsorption process is spontaneous and endothermic. The adsorbed Cr(III) was quantitatively eluted by a nitric acid solution with detection by flame atomic absorption spectrometry (FAAS). With a sample volume of 30 mL, a detection limit (3σ) of 0.85 μg L(-1) and a precision of 2.0% RSD at the 40 μg L(-1) level were achieved. The concentration of Cr(III) could be accurately quantified within a linear range of 3 - 200 μg L(-1). After Cr(VI) has been reduced to Cr(III) with hydroxylamine hydrochloride, the total amount of chromium was obtained, and the content of Cr(VI) was given by subtraction. The procedure was validated by analyzing chromium in a certified reference material (GBW (E) 080039). It was also successfully applied for the speciation of chromium in wastewater samples.

Progress in the chemistry of chromium(V) doping agents used in polarized target materials

International Nuclear Information System (INIS)

Krumpolc, M.; Hill, D.; Struhrmann, H.B.

1990-01-01

We wish to report progress in two areas of the chromium (V)-based doping agents: Two commonly used chromium (V) complexes, I and II, have been synthesized in perdeuterated form (i.e., all hydrogens replaced by deuterium). They are sodium bis(2-ethyl-2-deuteroxy-butyrato)oxochromate(V)monodeuterate, IV, (acronym EDBA-Cr(V)), and sodium bis(2-deuteroxy-2-methylpropionato)oxochromate(V), III, (acronym DMPA-Cr(V)). A synthetic route leading to the preparation of stable, chromium(III)-free solutions of chromium(V) in diols (1,2-ethanediol/ethylene glycol/and 1,2-propanediol/propylene glycol/) has been outlined

Influence of ligand-bridged substitution on the exchange coupling constant of chromium-wheels host complexes: a density functional theory study

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Sadeghi Googheri, Motahare; Abolhassani, Mohammad Reza; Mirzaei, Mahmoud

2018-05-01

Designing and introducing novel wheel-shaped supramolecular as host complexes with new magnetic properties is the theme of the day. So in this study, new eight binuclear chromium (III) complexes, as models of real chromium-wheel host complexes, were designed based on changing of bridged-ligands and exchange coupling constants (J) of them were calculated using the broken symmetry density functional theory approach. Substitution of fluorine ligand in fluoro-bridged model [Cr2F(tBuCO2)2(H2O)2(OH)4]-1 by halogen anions (Cl-, Br- and I- ) decreased the antiferromagnetic exchange coupling between Cr(III) centres such that by going from F- to I- the J values became more positive. In the case of hydroxo-bridged model [Cr2OH(tBuCO2)2(H2O)2(OH)4]-1, replacement of hydroxyl by methoxy anion (OMe-) strengthened the antiferromagnetic property of the complex but substitution by sulfanide (SH-) and amide (NH2-) anions weakened it and changed the nature of complexes to ferromagnetic. Because of their different magnetic properties, these new investigated complexes can be suggested as interesting synthetic targets. Also, the J value changes due to ligand substitution were evaluated and it was found that the Cr-X bond strength and partial charges of involved atoms were the most effective factors on it.

SYNTHESIS AND PHYSICO-CHEMICAL STUDIES OF HETEROMETALLIC NITRILOTRIACETATES OF CHROMIUM(III WITH SOME 3d METALS

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Victor Ciorne

2006-06-01

Full Text Available Heterometallic complexes of chromium (III with some 3d metals have been synthesized based on nitrilotriacetic acid (H3nta, like M(bpy2Cr2(OH2(nta2·nH2O, where M = Mn2+, Co2+, Ni2+ and Zn2+; bpy = α,α′- bipyridine; n = 8 or 9. Their chemical composition has been determined from the results of the elemental analysis and thermogravimetric study. The coordination modes of the nta3 ̄ ligand and the type of chemical bonds have been proposed basing on IR spectra.

Voltammetric study of chromium(VI)-ammonia/ammonium chloride solutions in the presence of dimethylglyoxime

International Nuclear Information System (INIS)

Ginzburg, V.G.; Salikhdzhanova, R.M.F.

1987-01-01

The authors believed complexation to be possible in the system Cr(VI)-dimethylglyoxime (DMG, H 2 D) by reduction of Cr(VI) to Cr(III) on a mercury electrode. The DMG can be used in chromium voltammetry and is promising for a number of reasons: The Cr(III) has an affinity for donor nitrogen atoms in the DMG molecule. Insertion of the H 2 D into the inner sphere of the complex is expected to weaken the bond between the Cr(III) and the hydroxyl group, slow down formation of the insoluble hydroxide Cr(OH) 3 , and lower the rate of the electrode reaction Cr(III) → Cr(II). Molecules of H 2 D adsorb on a mercury electrode. It is therefore possible to accelerate the electrode process by including adsorptive preconcentration of the chromium and thus lowering its detection limit. This paper reports the voltammetric behavior of the system Cr(VI)-DMG-NH 4 + (proton donor) for the purpose of lowering the chromium detection limit

Reactivity of Chromium(III) Nutritional Supplements in Biological Media: An X-Ray Absorption Spectroscopic Study

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Nguyen, A.; Mulyani, I.; Levina, A.; Lay, P.A.

2009-05-22

Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3]+ (A), [Cr(pic)3] (pic) = 2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4]+ (CrCl3 {center_dot} 6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of a library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].

Histopathological effects of Chromium (III Sulfate on Liver and Kidney of Swiss Albino Mice (Mus musculus

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Iffat Fatima

2016-08-01

Full Text Available Chromium (III sulfate has various industrial applications and is widely used in leather industry due to its high tanning properties. Cr (III is required for efficient metabolism of fats and carbohydrates in traces. Various studies have reported that its constant exposure may lead to severe health problems in both animals and humans. In this study, histopathological effect of dietary Cr (III was evaluated on liver and kidneys of rodents. For this purpose, adult Swiss albino mice (n=25 were divided into different treatment and control groups (n=5/group after sufficient acclimatization. After 3 weeks of treatment, animals were sacrificed and observations regarding histopathology of liver and kidneys were made in all treatment groups and compared to control. Microscopy and photography was performed after processing the tissues according to standard protocol of sectioning and staining. Liver cross sections of treated animals showed signs of fibrosis in portal area, and congestion of sinusoid and central vein. Whereas, more pronounced effects of Cr (III toxicity were observed in kidneys. These include mononuclear cell infiltration, necrosis and contraction of glomerulus within Bowman’s capsule. However, No pathological changes were observed in control group. These results support the hypothesis that enhanced level of Cr (III contamination of food can induce both hepatotoxicity and nephrotoxicity. These basic findings prove that currently increasing levels of trivalent chromium in environment are hazardous to living organisms. Therefore, to avoid health risks to both animals and humans, conversion of toxic chromium waste to less toxic compounds is required. Moreover, exposure level through any route should also be minimized.

Electronic spectroscopy and ligand-field analysis of cis-carbonato (rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) chromium(III) chloride

International Nuclear Information System (INIS)

Choi, Jong-Ha; Oh, In-Gyung; Linder, Rolf; Schoenherr, Thomas

2004-01-01

The absorption spectra of microcrystalline salts of cis-[Cr(cycb)(O 2 CO)] + (cycb=rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been measured between 13,000 and 50,000 cm -1 at temperatures down to 2 K. The vibrational intervals of the electronic ground state were extracted by recording emission and far-IR spectra. The zero-phonon line in the sharp-line absorption spectrum splits into two components by 144 cm -1 . The nine electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using the observed transitions, a ligand-field analysis has been performed to probe the ligand-field properties of carbonato group in the chromium(III) complex. It is found that the carbonato oxygen has moderately strong σ- and π-donor properties toward chromium(III) ion

INFLUENCES OF SOIL PROPERTIES ON CHROMIUM (III SORPTION

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R. Salmasi, F. Salmasi

2007-07-01

Full Text Available Soil adsorbing properties reduce sorption ability of the metal, which in turn may influence decision for remediation at contaminated sites. The objective of this study is presentation of a model based on soil properties to estimate the sorption of Cr(III in chromium contaminated soils. Twenty uncontaminated soil samples, with properties similar to the contaminated soils were selected from around of city of Tabriz and treated with Cr as CrCl3. A multiple regression analysis with statgraph software was used to drive an expression that related Cr sorption to common soil properties. The results showed that four soil properties were important in determining the amount of Cr adsorbed by the soils including pH, cation exchange capacity, total inorganic carbon and clay content with nearly 80% variability in Cr sorption and a reasonable level of confidence by this model. The obtained model suggested that Cr(III sorption was enhanced by higher soil pH, more total inorganic carbon, more clay, and higher cation exchange capacity.

The removal of toxic metals from liquid effluents by ion exchange resins. Part IV: Chromium(III)/H+ /Lewatit SP112

International Nuclear Information System (INIS)

Alguacil, F.J.

2017-01-01

This investigation presented results on the removal of chromium(III), from aqueous solution in the 0-5 pH range, using Lewatit SP112 cationic exchange resin. Several aspects affecting the ion exchange process were evaluated, including: the influence of the stirring speed, temperature, pH of the solution, resin dosage and aqueous ionic strength. The selectivity of the system was tested against the presence of other metals in the aqueous solution, whereas the removal of chromium(III) from solutions was compared with results obtained using multiwalled carbon nanotubes as adsorbents. From the batch experimental data, best fit of the results is obtained with the Langmuir model, whereas the ion exchange process is best explained by the pseudo-second order model, moreover, experimental data responded well to the film-diffusion controlled model. Elution of the chromium(III) loaded into the resin is well accomplished by the use of sodium hydroxide solutions. [es

Low-temperature heat capacity and the standard molar enthalpy of formation of compound chromium(III) tri(pyrazine-2-carboxylate)

International Nuclear Information System (INIS)

Gao, Shengli; Zhang, Sheng; Chen, Sanping; Yang, Desuo

2012-01-01

Highlights: ► Low-temperature heat capacities of chromium(III) tri(pyrazine-2-carboxylate) were measured from 78 to 400 K. ► Thermodynamic functions of the compound at 298.15 K were calculated based on low-temperature heat capacity. ► The standard molar enthalpy of formation of the target was determined to be −1207.86 ± 3.39 kJ mol −1 through a designed thermochemical cycle. - Abstract: Low-temperature heat capacities of the coordination compound, chromium(III) tri(pyrazine-2-carboxylate), formulated as Cr(pyza) 3 (pyza = pyrazine-2-carboxylate), were measured by a precision automated adiabatic calorimeter over the temperature range of 78–400 K. A polynomial equation of heat capacities as a function of the temperature was fitted by the least square method. Based on the fitted polynomial equation, the fitted heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated at the interval of 5 K. In accordance with a reasonable thermochemical cycle designed, the standard molar enthalpy of formation of the title complex was determined to be −1207.86 ± 3.39 kJ mol −1 by an isoperibol solution–reaction calorimeter.

Experimental patch testing with chromium-coated materials.

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Bregnbak, David; Thyssen, Jacob P; Jellesen, Morten S; Zachariae, Claus; Johansen, Jeanne D

2017-06-01

Chromium coatings on metal alloys can be decorative, and prevent corrosion and metal ion release. We recently showed that handling of a chromium-containing disc resulted in chromium deposition on the skin. To examine patch test reactivity to chromium-coated discs. We included 15 patients: 10 chromium-allergic patients, and 5 patients without chromium allergy. All were patch tested with potassium dichromate, cobalt chloride, nickel sulfate, and nine different metallic discs. The chromium-allergic patients were also patch tested with serial dilutions of potassium dichromate. Positive/weaker reactions were observed to disc B (1 of 10), disc C (1 of 10), and disc D, disc E, and disc I (4 of 10 each). As no controls reacted to any of the discs, the weak reactions indicate allergic reactions. Positive patch test reactions to 1770 ppm chromium(VI) in the serial dilutions of potassium dichromate were observed in 7 of 10 patients. When the case group was narrowed down to include only the patients with a current positive patch test reaction to potassium dichromate, elicitation of dermatitis by both chromium(III) and chromium(VI) discs was observed in 4 of 7 of patients. Many of the patients reacted to both chromium(III) and chromium(VI) surfaces. Our results indicate that both chromium(VI) and chromium(III) pose a risk to chromium-allergic patients. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

RECOVERY OF COPPER(II AND CHROMIUM(III FROM NITRATE MEDIUM WITH SALICYLIDENEANILINE DISSOLVED IN 1-OCTANOL

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A. Guerdouh

2016-05-01

Full Text Available The solvent extraction of copper(II and chromium(III from nitrate medium with salicylideneaniline (HL is studied as a function of various parameters: pH, concentration of salicylideneaniline, contact time and the nature of anoin (nitrate and sulfate in aqueous phase. Chromium(III is not extracted by salicylideneaniline  diluted in 1-octanol. Copper(II is only extracted by salicylideneaniline and it was found that the highest extractability achieved to 95% at pH 4.9, The stoichiometry of the extracted species was determined by using the method of slope analysis. Elemental analysis, UV–vis and IR-spectra were used to confirm the structure. It is found that the copper (II is extracted as CuL2.2H2O Their equilibrium constant, distribution coefficient, percentage extraction (%E and free energy are also calculated.

Biomonitoring chromium III or VI soluble pollution by moss chlorophyll fluorescence.

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Chen, Yang-Er; Mao, Hao-Tian; Ma, Jie; Wu, Nan; Zhang, Chao-Ming; Su, Yan-Qiu; Zhang, Zhong-Wei; Yuan, Ming; Zhang, Huai-Yu; Zeng, Xian-Yin; Yuan, Shu

2018-03-01

We systematically compared the impacts of four Cr salts (chromic chloride, chromic nitrate, potassium chromate and potassium bichromate) on physiological parameters and chlorophyll fluorescence in indigenous moss Taxiphyllum taxirameum. Among the four Cr salts, K 2 Cr 2 O 7 treatment resulted in the most significant decrease in photosynthetic efficiency and antioxidant enzymes, increase in reactive oxygen species (ROS), and obvious cell death. Different form the higher plants, although hexavalent Cr(VI) salt treatments resulted in higher accumulation levels of Cr and were more toxic than Cr(III) salts, Cr(III) also induced significant changes in moss physiological parameters and chlorophyll fluorescence. Our results showed that Cr(III) and Cr(VI) could be monitored distinguishably according to the non-photochemical quenching (NPQ) fluorescence of sporadic purple and sporadic lavender images respectively. Then, the valence states and concentrations of Cr contaminations could be evaluated according to the image of maximum efficiency of PSII photochemistry (Fv/Fm) and the quantum yield of PSII electron transport (ΦPSII). Therefore, this study provides new ideas of moss's sensibility to Cr(III) and a new method to monitor Chromium contaminations rapidly and non-invasively in water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solubility of chromium (III) oxide and metal chromates: development of MULTEQ models

International Nuclear Information System (INIS)

Dickinson, Shirley; Henshaw, Jim; Bachet Martin; Hussey, Dennis; Marks, Chuck; Tremaine, Peter; Eaker, Richard

2012-09-01

High-temperature solubility predictions for metal oxide systems are important for the understanding of corrosion processes, corrosion product behaviour and activity transport in PWR coolant systems. In the current work, literature data on chromium oxide and iron chromium solubility measurement have been used to derive equilibrium constant expressions for dissolution and hydrolysis reactions which have been incorporated in the latest revision of the EPRI MULTEQ database. Predicting the stable chromium phases in a PWR is important as these constitute the compact inner oxide layer that forms on most ex-core alloys used in this system. Likewise understanding the chromium chemistry is necessary for rationalising high chromium content crud that has been observed on several plant fuel pins. Chromium (III) oxide solubility measurements have shown that the equilibrium solid phase under hydrothermal conditions is CrOOH rather than Cr 2 O 3 . Expressions for the solubility product of this solid and the equilibrium constant for the 4. Cr (III) hydrolysis reaction Cr (OH) 3 (aq) + H 2 O = Cr (OH) 4 - + H + have been derived by fitting to the experimental solubility data in neutral to alkaline solution. The equilibrium constant for the 3rd hydrolysis reaction Cr (OH) 2 + +H 2 O = Cr (OH) 3 (aq) + H + has been revised for consistency with literature estimates of the hydrolysis constants at 298 K. There are insufficient high-quality solubility data at low pH to derive the lower hydrolysis constants so the existing MULTEQ entries, based on thermodynamic estimations, have been retained. This revised model gave reasonable agreement with the available data in acidic solution. A revised expression for the Cr 2 O 3 solubility product was derived from measurements of Fe concentrations produced from FeCr 2 O 4 dissolution, and this was used to obtain a consistent solubility product expression for FeCr 2 O 4 . The resulting model predicts that FeCr 2 O 4 would be unstable at temperatures

Biosorption and biotransformation of chromium by Serratia sp. isolated from tannery effluent.

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Srivastava, Shaili; Thakur, Indu Shekhar

2012-01-01

A bacterium isolated from soil and sediment ofa leather tanning mill's effluent was identified as Serratia sp. by the analysis of 16S rDNA. Scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) and transmission electron microscopy (TEM) were used to assess morphological changes and confirm chromium biosorption in Serratia sp. both in a shake-flask culture containing chromium and in a tannery wastewater. The SEMEDX and the elemental analysis of the chromate-containing samples confirmed the binding of chromium with the bacterial biomass. The TEM exhibited chromium accumulation throughout the bacterial cell, with some granular deposits in the cell periphery and in the cytoplasm. X-ray diffraction analysis (XRD) was used to quantify the chromium and to determine the chemical nature of the metal-microbe interaction. The XRD data showed the crystalline character of the precipitates, which consisted of mainly calcium chromium oxide, chromium fluoride phosphate and related organo-Cr(III) complex crystals. The XRD data also revealed a strong involvement of cellular carboxyl and phosphate groups in chromium binding by the bacterial biomass. The results of the study indicated that a combined mechanism of ion-exchange, complexation, croprecipitation and immobilization was involved in the biosorption of chromium by bacterial cells in contaminated environments.

Electrochemistry of chromium subgroup transition metal ions in an ambient temperature chloroaluminate molten salt

International Nuclear Information System (INIS)

Scheffler, T.B.

1984-01-01

The electrochemistry of several chromium subgroup transition metal solutes was studied in the basic AlCl 3 -1-methyl-3-ethylimidazolium chloride (MEIC) ionic liquid at 40.0 0 C by using stationary and rotating disk electrode voltametry, chronoamperometry, coulometry, and UV-vis spectrophotometry. Chromium(III) was present in the melt as the chloro complex [CrCl 6 ] 3- . This complex underwent as essentially irreversible reduction, apparently as a result of slow charge-transfer, to a chromium(II) species at ca. -1.08 V versus an aluminum wire immersed in 66.7 mol % melt. Similar investigations of molybdenum and tungsten were also conducted. Mechanisms are proposed to account for the results

Improvement on simultaneous determination of chromium species in aqueous solution by ion chromatography and chemiluminescence detection

DEFF Research Database (Denmark)

Gammelgaard, Bente; Liao, Y.P.; Jons, O.

1997-01-01

A sensitive method for the simultaneous determination of chromium(III) and chromium(VI) was chromatography and chemiluminescence detection. Two Dionex ion-exchange guard columns in series, CG5 and AG7, were used to separate chromium(III) from chromium(VI). Chromium(VI) was reduced by potassium......, the stabilities of reductant and luminol solutions were studied. The linear range of the calibration curve for chromium(III) and chromium(VI) was 1-400 mu g l(-1). The detection limit was 0.12 mu g l(-1) for chromium(III) and 0.09 mu g l(-1) for chromium(VI), respectively. The precision at the 20 mu g l(-1) level...... was 1.4% for chromium(III) and 2.5% for chromium(VI), respectively. The accuracy of the chromium(III) determination was determined by analysis of the NIST standard reference material 1643c, Trace elements in water with the result 19.1 +/- 1.0 mu g Cr(III) l(-1) (certified value 19.0 +/- 0.6 mu g Cr...

Complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III)

International Nuclear Information System (INIS)

Ferenc, W.; Bernat, M; Gluchowska, H.W.; Sarzynski, J.

2010-01-01

The complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) have been synthesized as polycrystalline hydrated solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: violet for Nd(III), white for Gd(III) and cream for Ho(III) compounds. The carboxylate groups bind as bidentate chelating (Ho) or bridging ligands (Nd, Gd). On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to form anhydrous salts, that next decompose to the oxides of respective metals. The gaseous products of their thermal decomposition in nitrogen were also determined and the magnetic susceptibilities were measured over the temperature range of 76-303K and the magnetic moments were calculated. The results show that 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) are high-spin complexes with weak ligand fields. The solubility value in water at 293K for analysed 4-chlorophenoxyacetates is in the order of 10 -4 mol/dm 3 . (author)

Calculated electronic structure of chromium surfaces and chromium monolayers on iron

International Nuclear Information System (INIS)

Victora, R.H.; Falicov, L.M.

1985-01-01

A self-consistent calculation of the magnetic and electronic properties of the chromium (100) and (110) surfaces and of a chromium monolayer on the (100) and (110) iron surfaces is presented. It is found that (i) the (100) chromium surface is ferromagnetic with a greatly enhanced spin polarization (3.00 electrons); (ii) a substantial enhancement of the spin imbalance exists several (>5) layers into the bulk; (iii) the (110) chromium surface is antiferromagnetic with a large (2.31) spin imbalance; (iv) the (100) chromium monolayer on ferromagnetic iron is ferromagnetic, with a huge spin imbalance (3.63), and aligned antiferromagnetically with respect to the bulk iron; (v) the (110) chromium monolayer on ferromagnetic iron is also ferromagnetic, with a spin imbalance of 2.25 and antiferromagnetically aligned to the iron. The spin imbalance of chromium on iron (100) is possibly the largest of any transition-metal system

Selective and sensitive detection of chromium(VI) in waters using electrospray ionization mass spectrometry.

Science.gov (United States)

Weldy, Effie; Wolff, Chloe; Miao, Zhixin; Chen, Hao

2013-09-01

From 2000 through 2011, there were 14 criminal cases of violations of the Clean Water Act involving the discharge of chromium, a toxic heavy metal, into drinking and surface water sources. As chromium(VI), a potential carcinogen present in the environment, represents a significant safety concern, it is currently the subject of an EPA health risk assessment. Therefore, sensitive and selective detection of this species is highly desired. This study reports the analysis of chromium(VI) in water samples by electrospray ionization mass spectrometry (ESI-MS) following its reduction and complexation with ammonium pyrrolidinedithiocarbamate (APDC). The reduction and subsequent complexation produce a characteristic [Cr(III)O]-PDC complex which can be detected as a protonated ion of m/z 507 in the positive ion mode. The detection is selective to chromium(VI) under acidic pH, even in the presence of chromium(III) and other metal ions, providing high specificity. Different water samples were examined, including deionized, tap, and river waters, and sensitive detection was achieved. In the case of deionized water, quantification over the concentration range of 3.7 to 148ppb gave an excellent correlation coefficient of 0.9904 using the enhanced MS mode scan. Using the single-reaction monitoring (SRM) mode (monitoring the characteristic fragmentation of m/z 507 to m/z 360), the limit of detection (LOD) was found to be 0.25ppb. The LOD of chromium(VI) for both tap and river water samples was determined to be 2.0ppb. A preconcentration strategy using simple vacuum evaporation of the aqueous sample was shown to further improve the ESI signal by 15 fold. This method, with high sensitivity and selectivity, should provide a timely solution for the real-world analysis of toxic chromium(VI). Copyright © 2012 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

Responses of endogenous proline in rice seedlings under chromium exposure

Directory of Open Access Journals (Sweden)

X.Z. Yu

2016-12-01

Full Text Available Hydroponic experiments were performed to exam the dynamic change of endogenous proline in rice seedlings exposed to potassium chromate chromium (VI or chromium nitrate chromium (III. Although accumulation of both chromium species in rice seedlings was obvious, more chromium was detected in plant tissues of rice seedlings exposed to chromium (III than those in chromium (VI, majority being in roots rather than shoots. Results also showed that the accumulation capacity of chromium by rice seedlings was positively correlated to chromium concentrations supplied in both chromium variants and the accumulation curve depicted an exponential trend in both chromium treatments over the entire period of exposure. Proline assays showed that both chromium variants induced the change of endogenous proline in shoots and roots of rice seedlings. Chromium (VI of 12.8 mg/L increased proline content significantly (p

Peat and coconut fiber as biofilters for chromium adsorption from contaminated wastewaters.

Science.gov (United States)

Henryk, Kołoczek; Jarosław, Chwastowski; Witold, Żukowski

2016-01-01

Batch adsorption experiments were performed for the removal of chromium (III) and chromium (VI) ions from aqueous solutions using Canadian peat and coconut fiber. The Langmuir model was used to describe the adsorption isotherm. The maximum adsorption for peat reached 18.75 mg/g for Cr(III) and 8.02 mg/g for Cr(VI), whereas the value for fiber was slightly higher and reached 19.21 mg/g for Cr(III) and 9.54 mg/g for Cr(VI). Both chromium forms could be easily eluted from the materials. The adsorption of chromium forms to organic matter could be explained in terms of formation of donor-acceptor chemical covalent bound with hydroxyl groups as ligands and chromium as the central atom in the formed complex. The chromate-reducing activities were monitored with the use of electron paramagnetic resonance spectroscopy. The results showed that both adsorption and reduction occurred simultaneously and the maximum adsorption capacity of hexavalent chromium being equal to 95% for fiber and 92% for peat was obtained at pH 1.5. The reduction of Cr(VI) in wastewaters began immediately and disappeared after 20 h. Both materials contained yeast and fungi species which can be responsible for reduction of chromium compounds, due to their enzymatic activity (Chwastowski and Koloczek (Acta Biochim Pol 60: 829-834, 2013)). The reduction of Cr(VI) is a two-phase process, the first phase being rapid and based on chemical reaction and the second phase having biological features. After the recovery step, both types of organic materials can be used again for chromium adsorption without any loss in the metal uptake. Both of the materials could be used as biofilters in the wastewater treatment plants.

Biotransformation of hexavalent chromium into extracellular chromium(III) oxide nanoparticles using Schwanniomyces occidentalis.

Science.gov (United States)

Mohite, Pallavi T; Kumar, Ameeta Ravi; Zinjarde, Smita S

2016-03-01

To demonstrate biotransformation of toxic Cr(VI) ions into Cr2O3 nanoparticles by the yeast Schwanniomyces occidentalis. Reaction mixtures containing S. occidentalis NCIM 3459 and Cr(VI) ions that were initially yellow turned green after 48 h incubation. The coloration was due to the synthesis of chromium (III) oxide nanoparticles (Cr2O3NPs). UV-Visible spectra of the reaction mixtures showed peaks at 445 and 600 nm indicating (4)A2g → (4)T1g and (4)A2g → (4)T2g transitions in Cr2O3, respectively. FTIR profiles suggested the involvement of carboxyl and amide groups in nanoparticle synthesis and stabilization. The Cr2O3NPs ranged between 10 and 60 nm. Their crystalline nature was evident from the selective area electron diffraction and X-ray diffraction patterns. Energy dispersive spectra confirmed the chemical composition of the nanoparticles. These biogenic nanoparticles could find applications in different fields. S. occidentalis mediated biotransformation of toxic Cr(VI) ions into crystalline extracellular Cr2O3NPs under benign conditions.

Simultaneous biosynthesis of putrebactin, avaroferrin and bisucaberin by Shewanella putrefaciens and characterisation of complexes with iron(III), molybdenum(VI) or chromium(V).

Science.gov (United States)

Soe, Cho Zin; Telfer, Thomas J; Levina, Aviva; Lay, Peter A; Codd, Rachel

2016-09-01

Cultures of Shewanella putrefaciens grown in medium containing 10mM 1,4-diamino-2-butanone (DBO) as an inhibitor of ornithine decarboxylase and 10mM 1,5-diaminopentane (cadaverine) showed the simultaneous biosynthesis of the macrocyclic dihydroxamic acids: putrebactin (pbH 2 ), avaroferrin (avH 2 ) and bisucaberin (bsH 2 ). The level of DBO did not completely repress the production of endogenous 1,4-diaminobutane (putrescine) as the native diamine substrate of pbH 2 . The relative concentration of pbH 2 :avH 2 :bsH 2 was 1:2:1, which correlated with the substrate selection of putrescine:cadaverine in a ratio of 1:1. The macrocycles were characterised using LC-MS as free ligands and as 1:1 complexes with Fe(III) of the form [Fe(pb)] + , [Fe(av)] + or [Fe(bs)] + , with labile ancillary ligands in six-coordinate complexes displaced during ESI-MS acquisition; or with Mo(VI) of the form [Mo(O) 2 (pb)], [Mo(O) 2 (av)] or [Mo(O) 2 (bs)]. Chromium(V) complexes of the form [CrO(pb)] + were detected from solutions of Cr(VI) and pbH 2 in DMF using X-band EPR spectroscopy. Supplementation of S. putrefaciens medium with DBO and 1,3-diaminopropane, 1,6-diaminohexane or 1,4-diamino-2(Z)-butene (Z-DBE) resulted only in the biosynthesis of pbH 2 . The work has identified a native system for the simultaneous biosynthesis of a suite of three macrocyclic dihydroxamic acid siderophores and highlights both the utility of precursor-directed biosynthesis for expanding the structural diversity of siderophores, and the breadth of their coordination chemistry. Copyright © 2015 Elsevier Inc. All rights reserved.

Information profiles on potential occupational hazards: Inorganic chromium compounds. Draft report (Second)

Energy Technology Data Exchange (ETDEWEB)

1982-02-01

Information profiles are presented for the following inorganic chromium compounds: chromic(VI) acid, chromic(III) hydroxide, chromic(III) oxide, chromic(III) sulfate, chromic(III) sulfate (basic), chromium dioxide, potassium dichromate(VI), lead chromate, sodium-chromate(VI), sodium-dichromate(VI), and zinc-yellow-chromate(VI). Biological effects of hexavalent chromium in humans included skin ulceration, dermatitis, nasal membrane irritation and ulceration, nasal septal perforation, rhinitis, nosebleed, nephritis, liver damage, epigastric pain, pulmonary congestion and edema, and erosion and discoloration of teeth. Chromium(VI) compounds caused mutations in a variety of systems. Exposure to trivalent chromium in the work place has caused contact dermatitis and chrome ulcers. Epidemiological studies indicated respiratory carcinogenicity among workers occupationally exposed during chromate production.

Fosfato de cromo (III marcado con diferentes radionúclidos para uso en radiosinoviortesis Chromium (III phosphate labelled with several radionuclides for use in radiosynoviothersis

Directory of Open Access Journals (Sweden)

Jorge Cruz Arencibia

2012-06-01

suspensions recommended in the international clinical practice, but the number is reduced and the availability limited. Objective: obtaining and physical-chemical characterization of suspensions of chromium phosphate (III labeled with several radionuclides as potential radiopharmaceuticals for using in radiosynoviorthesis. Methods: the suspensions were obtained by chemical synthesis. Radionuclides were added at the beginning or after concluding the reaction. The particle size was estimated by means of optic microscopy and membrane filtration. Similarly, the stability of suspension when re-suspended in several media was evaluated by spectrophotometry. The radiochemical purity was determined by paper chromatography. Results: a suspension of chromium (III phosphate was obtained and characterized. It was found that the obtained product had a predominant particle size range of 0,8 to 5 µm and that when suspended in 2 % gelatin solution in 1mg/ml acetate buffer, it settled in no less than 3 hours. Technologies for the preparation of radiopharmaceuticals of Chromium (III Phosphate labeled with 32P and 90Y were described. There was demonstrated the feasibility of labeling the obtained suspension with other trivalent radionuclides such as 177Lu and 68Ga. Conclusions: the results allow considering the obtained Chromium (III Phosphate suspension as a matrix for the preparation of radiopharmaceuticals to be used in radiosinoviorthesis aimed at various joints, depending on the physical and nuclear characteristics of the radionuclides.

Study of color parameters of light exposed and light exposed wool fabrics dyed with 1:1 chromium (III) based complex dyes

International Nuclear Information System (INIS)

Kausar, N.; Ahmad, M.A.; Wahab, M.A.

2009-01-01

Derivatives of a-amino benzoic acid (anthranilic acid) were synthesized using 1-naphthol-3,6-disulfonic acid, 1-Naphthol-8 amino-3, 6-di-sulfonic acid; 1-naphthol-3-sulfonic acid, 6-methylamino-1-naphthol-3-sulfonic acid or 1-naphthol-3-sulfonic acid, 6-phenylamino-l-naphthol-3-sulfonic acid as a coupling component. These derivatives were used to synthesize chromium (Ill) complexes. After isolation, these complexes were applied on pure wool fabric by exhaust process to evaluate hue, wash fastness and light fastness properties. The complexes delivered a change in color equivalent to gray scale step 3/5 to 4/5 for wash fastness test. During the study of light fastness, it was monitored that the hue of dyed fabrics enhanced after exposing them to Light. (author)

Tecnology for the Management of Alum of Chromium (III) and Potasium as Ceramic Pigment

OpenAIRE

Idalberto Clemente Morales-Rodríguez; Katia Rivas-Fernández; Wilson Moro-Muñoz; Alfredo Calzadilla-Liens; Alyn Ferro-Nieto

2017-01-01

The lazy and expired reagents are among the dangerous waste generated in Cuba, some of which contain heavy metals. These substances accumulate without a final disposition, neither appropriate use, with the purpose of not contaminating the environment. In such a sense, the authors propose an alternative use for alum of chromium (III) and potassium, when transforming it into oxide by precipitation with alkalis to apply it as ceramic pigment. The present paper shows the use tests and the determi...

Ferrate treatment for removing chromium from high-level radioactive tank waste.

Science.gov (United States)

Sylvester, P; Rutherford, L A; Gonzalez-Martin, A; Kim, J; Rapko, B M; Lumetta, G J

2001-01-01

A method has been developed for removing chromium from alkaline high-level radioactive tank waste. Removing chromium from these wastes is critical in reducing the volume of waste requiring expensive immobilization and deep geologic disposition. The method developed is based on the oxidation of insoluble chromium(III) compounds to soluble chromate using ferrate. This method could be generally applicable to removing chromium from chromium-contaminated solids, when coupled with a subsequent reduction of the separated chromate back to chromium(III). The tests conducted with a simulated Hanford tank sludge indicate that the chromium removal with ferrate is more efficient at 5 M NaOH than at 3 M NaOH. Chromium removal increases with increasing Fe(VI)/Cr(II) molar ratio, but the chromium removal tends to level out for Fe(VI)/ Cr(III) greaterthan 10. Increasingtemperature leadsto better chromium removal, but higher temperatures also led to more rapid ferrate decomposition. Tests with radioactive Hanford tank waste generally confirmed the simulant results. In all cases examined, ferrate enhanced the chromium removal, with a typical removal of around 60-70% of the total chromium present in the washed sludge solids. The ferrate leachate solutions did not contain significant concentrations of transuranic elements, so these solutions could be disposed as low-activity waste.

Sparkle/PM3 for the modeling of europium(III), gadolinium(III), and terbium(III) complexes

International Nuclear Information System (INIS)

Freire, Ricardo O.; Rocha, Gerd B.; Simas, Alfredo M.

2009-01-01

The Sparkle/PM3 model is extended to europium(III), gadolinium(III), and terbium(III) complexes. The validation procedure was carried out using only high quality crystallographic structures, for a total of ninety-six Eu(III) complexes, seventy Gd(III) complexes, and forty-two Tb(III) complexes. The Sparkle/PM3 unsigned mean error, for all interatomic distances between the trivalent lanthanide ion and the ligand atoms of the first sphere of coordination, is: 0.080 A for Eu(III); 0.063 A for Gd(III); and 0.070 A for Tb(III). These figures are similar to the Sparkle/AM1 ones of 0.082 A, 0.061 A, and 0.068 A respectively, indicating they are all comparable parameterizations. Moreover, their accuracy is similar to what can be obtained by present-day ab initio effective core potential full geometry optimization calculations on such lanthanide complexes. Finally, we report a preliminary attempt to show that Sparkle/PM3 geometry predictions are reliable. For one of the Eu(III) complexes, BAFZEO, we created hundreds of different input geometries by randomly varying the distances and angles of the ligands to the central Eu(III) ion, which were all subsequently fully optimized. A significant trend was unveiled, indicating that more accurate local minima geometries cluster at lower total energies, thus reinforcing the validity of sparkle model calculations. (author)

Kinetics of chromium (VI) reduction by ferrous iron

International Nuclear Information System (INIS)

Batchelor, B.; Schlautman, M.; Hwang, I.; Wang, R.

1998-09-01

Chromium is a primary inorganic contaminant of concern at the Pantex Plant. Chromium concentrations have been found to be two orders of magnitude higher than the drinking water standards, particularly in certain wells in the perched aquifer below Zone 12. In situ reduction of a mobile form of chromium, Cr(VI) to an immobile form, Cr(III), was examined as a viable option to active soil restoration. Successfully immobilizing chromium in the vadose zone as Cr(III) will reduce the amount of chromium that reaches the groundwater table. The results from the solution experiments indicated that chromium was rapidly and stoichiometrically reduced by Fe(II) in solution. Also, the slurry experiments showed that the aquifer solids removed Fe(II) from solution, but a portion of the iron removed remained available for reaction with Cr(VI), but at a slower rate. A model to predict different amounts of iron pseudo-components was developed, which allowed prediction of iron amounts required to reduce chromium under in situ conditions

A comparative study of the removal of trivalent chromium from aqueous solutions by bentonite and expanded perlite

International Nuclear Information System (INIS)

Chakir, Achraf; Bessiere, Jacques; Kacemi, Kacem EL.; Marouf, Bouchaieb

2002-01-01

Local bentonite and expanded perlite (Morocco) have been characterised and used for the removal of trivalent chromium from aqueous solutions. The kinetic study had showed that the uptake of Cr(III) by bentonite is very rapid compared to expanded perlite. To calculate the sorption capacities of the two sorbents, at different pH, the experimental data points have been fitted to the Freundlich and Langmuir models, respectively, for bentonite and expanded perlite. For both sorbents the sorption capacity increases with increasing the pH of the suspensions. The removal efficiency has been calculated for both sorbents resulting that bentonite (96% of Cr(III) was removed) is more effective in removing trivalent chromium from aqueous solution than expanded perlite (40% of Cr(III) was removed). In the absence of Cr(III) ions, both bentonite and expanded perlite samples yield negative zeta potential in the pH range of 2-11. The changes of expanded perlite charge, from negative to positive, observed after contact with trivalent chromium(III) solutions was related to Cr(III) sorption on the surface of the solid. Thus, it was concluded that surface complexation plays an important role in the sorption of Cr(III) species on expanded perlite. In the case of bentonite, cation-exchange is the predominate mechanism for sorption of trivalent chromium ions, wherefore no net changes of zeta potential was observed after Cr(III) sorption. X-ray photoelectron spectroscopy measurements, at different pH values, were also made to corroborate the zeta potential results

Leaching of chromium from chromium contaminated soil: Speciation study and geochemical modeling

Directory of Open Access Journals (Sweden)

Anđelković Darko H.

2012-01-01

Full Text Available Distribution of chromium between soil and leachate was monitored. A natural process of percolating rainwater through the soil was simulated in the laboratory conditions and studied with column leaching extraction. Migration of chromium in the soil is conditioned by the level of chromium soil contamination, the soil organic matter content, and rainwater acidity. Chromium (III and chromium(VI were determined by spectrophotometric method with diphenilcarbazide in acidic media. Comparing the results of chromium speciation in leachate obtained by experimental model systems and geochemical modelling calculations using Visual MINTEQ model, a correlation was observed regarding the influence of the tested parameters. Leachate solutions showed that the concentration of Cr depended on the organic matter content. The influence of pH and soil organic matter content is in compliance after its definition through experimental and theoretical way. The computer model - Stockholm Humic Model used to evaluate the leaching results corresponded rather well with the measured values.

The influence of a selenium-chromium-lipid complex obtained from Chlorella vulgaris on the energy metabolism in rats with experimental diabetes

Directory of Open Access Journals (Sweden)

O. Y. Lukashiv

2017-07-01

Full Text Available One of the leading roles in treating diabetes mellitus belongs to chrome ions therapy (III, especially in the complex with selenium (IV. Currently selenium is obtained from unicellular algae, which contain biologically active substances and which are capable of accumulating exogenous microelements. By incubating unicellular algae Chlorella vulgaris Biej. in the conditions of aquaculture with sodium selenite (IV and chromium (III chloride, we obtained a biologically active lipid substance which contains selenium and chromium. The substance was tested for the impact on energy metabolism of animals exposed to experimentally induced diabetes mellitus. The diabetes was caused by modeling obesity of the animals with further injection of streptozotocin in the amount of 65 mg/kg and nicotinamide at the dose of 230 mg/kg. The rats were intragastrically injected with 1 ml of 1% starch solution which contained a selenium-chrome-lipid complex extracted from the Chlorella containing 0.6 µg of selenium, 1.05 µg of chrome and 0.5 mg of lipids for prophylactic, therapeutic and prophylactic-therapeutic purposes; the other group of rats for therapeutic purposes was injected with starch solution with the same composition of microelements in inorganic form – sodium selenite (IV and chromium chloride (III. This paper presents the results of our study of the impact of organic and inorganic compounds of chrome and selenium on the energetic metabolism of rats exposed to experimental diabetes mellitus. The analysis determined that in the rats’ organism, the selenium-chrome-lipid complex from the Chlorella improved the indicators of the energetic metabolism – in the group of rats which received it for therapeutic purposes, we observed an up to 7.5 fold increase in the activity of succinate dehydrogenase compared to the rats which did not receive therapeutic treatment. The increase in the activity of succinate dehydrogenase corresponded to the increase in the

FERRATE TREATMENT FOR REMOVING CHROMIUM FROM HIGH-LEVEL RADIOACTIVE TANK WASTE

International Nuclear Information System (INIS)

Sylvester, Paul; Rutherford, Andy; Gonzalez-Martin, Anuncia; Kim, J.; Rapko, Brian M.; Lumetta, Gregg J.

2000-01-01

A method has been developed for removing chromium from alkaline high-level radioactive tank waste. Removing chromium from these wastes is critical in reducing the volume of waste requiring expensive immobilization and deep geologic disposition. The method developed is based on the oxidation of insoluble chromium(III) compounds to soluble chromate using ferrate. The tests conducted with a simulated Hanford tank sludge indicate that the chromium removal with ferrate is more efficient at 5 M NaOH than at 3 M NaOH. Chromium removal increases with increasing Fe(VI)/Cr(III) molar ratio, but the chromium removal tends to level out for Fe(VI)/Cr(III) greater than 10. Increasing temperature leads to better chromium removal, but higher temperatures also led to more rapid ferrate decomposition. Tests with radioactive Hanford tank waste generally confirmed the simulant results. In all cases examined, ferrate enhanced the chromium removal, with a typical removal of around 60-70% of the total chromium present in the washed sludge solids. The ferrate leachate solutions did not contain significant concentrations of transuranic elements, so these solutions could be handled as low-activity waste

Chemical Properties And Toxicity of Chromium(III) Nutritional Supplements

Energy Technology Data Exchange (ETDEWEB)

Levina, A.; Lay, P.A.

2009-05-19

The status of Cr(III) as an essential micronutrient for humans is currently under question. No functional Cr(III)-containing biomolecules have been definitively described as yet, and accumulated experience in the use of Cr(III) nutritional supplements (such as [Cr(pic){sub 3}], where pic = 2-pyridinecarboxylato) has shown no measurable benefits for nondiabetic people. Although the use of large doses of Cr(III) supplements may lead to improvements in glucose metabolism for type 2 diabetics, there is a growing concern over the possible genotoxicity of these compounds, particularly of [Cr(pic){sub 3}]. The current perspective discusses chemical transformations of Cr(III) nutritional supplements in biological media, with implications for both beneficial and toxic actions of Cr(III) complexes, which are likely to arise from the same biochemical mechanisms, dependent on concentrations of the reactive species. These species include: (1) partial hydrolysis products of Cr(III) nutritional supplements, which are capable of binding to biological macromolecules and altering their functions; and (2) highly reactive Cr(VI/V/IV) species and organic radicals, formed in reactions of Cr(III) with biological oxidants. Low concentrations of these species are likely to cause alterations in cell signaling (including enhancement of insulin signaling) through interactions with the active centers of regulatory enzymes in the cell membrane or in the cytoplasm, while higher concentrations are likely to produce genotoxic DNA lesions in the cell nucleus. These data suggest that the potential for genotoxic side-effects of Cr(III) complexes may outweigh their possible benefits as insulin enhancers, and that recommendations for their use as either nutritional supplements or antidiabetic drugs need to be reconsidered in light of these recent findings.

Determination of dissociation constants for coordination compounds of Cr(III) and Co(III) using potentiometric and spectrophotometric methods

International Nuclear Information System (INIS)

Chylewska, A.; Jacewicz, D.; Zarzeczanska, D.; Chmurzynski, L.

2008-01-01

The acid-base properties of analogous complex ions of chromium(III) and cobalt(III) in aqueous solution have been studied. The equilibrium constants for all metal complexes were determined by using potentiometric and spectrophotometric titration methods. First, dissociation constants for the studied complexes of Cr(III) and Co(III) were determined by means of the potentiometric titration method and using the STOICHIO computer programme. Then, pH-spectrophotometric titrations were performed and the OriginPro 7.5 computer programme was used to calculate the same constants. The measurements using both methods were carried out under the same conditions of temperature, T = 298.15 K, and over the same pH range 2.00-10.00, respectively. It turned out that the two methods used enabled us to obtain acidity constants in very good agreement

Determination of dissociation constants for coordination compounds of Cr(III) and Co(III) using potentiometric and spectrophotometric methods

Energy Technology Data Exchange (ETDEWEB)

Chylewska, A.; Jacewicz, D.; Zarzeczanska, D. [Department of Chemistry, University of Gdansk, Sobieskiego 18/19, 80-952 Gdansk (Poland); Chmurzynski, L. [Department of Chemistry, University of Gdansk, Sobieskiego 18/19, 80-952 Gdansk (Poland)], E-mail: lech@chem.univ.gda.pl

2008-08-15

The acid-base properties of analogous complex ions of chromium(III) and cobalt(III) in aqueous solution have been studied. The equilibrium constants for all metal complexes were determined by using potentiometric and spectrophotometric titration methods. First, dissociation constants for the studied complexes of Cr(III) and Co(III) were determined by means of the potentiometric titration method and using the STOICHIO computer programme. Then, pH-spectrophotometric titrations were performed and the OriginPro 7.5 computer programme was used to calculate the same constants. The measurements using both methods were carried out under the same conditions of temperature, T = 298.15 K, and over the same pH range 2.00-10.00, respectively. It turned out that the two methods used enabled us to obtain acidity constants in very good agreement.

Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

Energy Technology Data Exchange (ETDEWEB)

Gomez-Gonzalez, Sergio Efrain [Departamento de Ingeniería Química, Universidad de Guadalajara, Blvd. Marcelino García Barragán # 1421, esq. Calzada Olímpica, C.P. 44430 Guadalajara, Jalisco (Mexico); Carbajal-Arizaga, Gregorio Guadalupe [Departamento de Química, CUCEI, Universidad de Guadalajara, Blvd. Marcelino García Barragán # 1421, esq. Calzada Olímpica, C.P. 44430 Guadalajara, Jalisco (Mexico); Manriquez-Gonzalez, Ricardo [Departamento de Madera, Celulosa y Papel, CUCEI, Universidad de Guadalajara, Km 15.5, carretera Guadalajara-Nogales, Las Agujas, C.P. 45020 Zapopan, Jalisco (Mexico); De la Cruz-Hernandez, Wencel [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Km 107 carretera Tijuana-Ensenada, C.P. 22830 Ensenada, Baja California (Mexico); Gomez-Salazar, Sergio, E-mail: sergio.gomez@cucei.udg.mx [Departamento de Ingeniería Química, Universidad de Guadalajara, Blvd. Marcelino García Barragán # 1421, esq. Calzada Olímpica, C.P. 44430 Guadalajara, Jalisco (Mexico)

2014-11-15

Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH{sub 3}COO){sub 2}Cr{sup +} ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. {sup 13}C, {sup 29}Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level.

Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

International Nuclear Information System (INIS)

Gomez-Gonzalez, Sergio Efrain; Carbajal-Arizaga, Gregorio Guadalupe; Manriquez-Gonzalez, Ricardo; De la Cruz-Hernandez, Wencel; Gomez-Salazar, Sergio

2014-01-01

Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH 3 COO) 2 Cr + ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. 13 C, 29 Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level

Synthesis and characterization of chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), cadmium(II) and dioxouranium(VI) complexes of 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone

International Nuclear Information System (INIS)

Abu El-Reash, G.M.; Ibrahim, M.M.; Kenawy; El-Ayaan, Usama; Khattab, M.A.

1994-01-01

A few complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and dioxouranium(VI) with 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone have been synthesised and characterized on the basis of elemental analysis, IR, electronic NMR, and magnetic moment data. An octahedral structure is proposed for the Cr(III), Fe(III), Co(II) and Ni(H 3 PBT) 2 Cl 2 .2H 2 O complexes; a tetrahedral structure for the Mn(II) and Ni 2 (PBT)OAc.H 2 0 complexes and a square planar structure for the Cu(II) complexes. The antimicrobial and antifungal activities of H 3 PBT and of its metal(II) complexes are investigated. The results reveal that H 3 PBT exhibits greater antimicrobial activities than its complexes. (author). 34 refs., 4 figs., 2 tabs

Cobalt(III) complex

Indian Academy of Sciences (India)

Administrator

e, 40 µM complex, 10 hrs after dissolution, f, 40 µM complex, after irradiation dose 15 Gy. and H-atoms result in reduction of Co(III) to Co. (II). 6. It is interesting to see in complex containing multiple ligands what is the fate of electron adduct species formed by electron addition. Reduction to. Co(II) and intramolecular transfer ...

Complexes of lanthanum(III), cerium(III), samarium(III) and dysprosium(III) with substituted piperidines

Energy Technology Data Exchange (ETDEWEB)

Manhas, B S; Trikha, A K; Singh, H; Chander, M

1983-11-01

Complexes of the general formulae M/sub 2/Cl/sub 6/(L)/sub 3/.C/sub 2/H/sub 5/OH and M/sub 2/(NO/sub 3/)/sub 6/(L)/sub 2/.CH/sub 3/OH have been synthesised by the reactions of chlorides and nitrates of La(III), Ce(III), Sm(III) and Dy(III) with 2-methylpiperidine, 3-methylpiperidine and 4-methylpiperidine. These complexes have been characterised on the basis of their elemental analysis, and IR and electronic reflectance spectra. IR spectral data indicate the presence of coordinated ethanol and methanol molecules and bidentate nitrate groups. Coordination numbers of the metal ions vary from 5 to 8. 19 refs.

Isothiocyanato complexes of Gd(III), Tb(III), Dy(III) and Ho(III) with 2-(2'-pyridyl)benzimidazole

Energy Technology Data Exchange (ETDEWEB)

Mishra, A; Singh, V K

1982-01-01

Six-coordinated complexes of the type (Ln(PyBzH)/sub 2/NCS.H/sub 2/O) (NCS)/sub 2/.nH/sub 2/O/mC/sub 2/H/sub 5/OH (Ln = Gd(III), Tb(III), Dy(III) and Ho(III), n=1-2; m=1) have been prepared from Ln(NCS)/sub 6//sup 3 -/. The room temperature magnetic moment values confirm the terpositive state of the lanthanide ions. Infrared spectra suggest the N-coordination of thiocyanate group. Electronic spectral studies of Tb(III), Dy(III) and Ho(III) complexes have been made in terms of LSJ term energies. 13 refs.

Biosynthesis of Cr(III) nanoparticles from electroplating wastewater using chromium-resistant Bacillus subtilis and its cytotoxicity and antibacterial activity.

Science.gov (United States)

Kanakalakshmi, A; Janaki, V; Shanthi, K; Kamala-Kannan, S

2017-11-01

The aim of this study was to synthesize and characterize Cr(III) nanoparticles using wastewater from electroplating industries and chromium-resistant Bacillus subtilis. Formation of Cr(III) nanoparticles was confirmed by UV-visible (UV-Vis) spectroscopy at 300 nm. The size of the nanoparticles varied from 4 to 50 nm and energy dispersive spectroscopy profile shows strong Cr peak approximately at 4.45 and 5.2 keV. The nanoparticles inhibited the growth of pathogenic bacteria Staphylococcus aureus and Escherichia coli. The cytotoxic effect of the synthesized Cr(III) nanoparticle was studied using HEK 293 cells, and the cell viability was found to decrease with increasing concentration of Cr(III) nanoparticles.

Optimization of a new polymeric chromium (III) membrane electrode based on methyl violet by using experimental design.

Science.gov (United States)

Kazemi, Sayed Yahya; Hamidi, Akram sadat; Asanjarani, Neda; Zolgharnein, Javad

2010-06-15

Plackett-Burman and Box-Behnken designs were applied as experimental design strategies to screen and optimize the influence of membrane ingredients on the electrode performance. A new poly(vinyl chloride) membrane sensor for Cr(III) based on methyl violet as an ionophore was planned. The major variables to find a model for achieving the best Nernstian slope as response were: PVC, plasticizers, methyl violet, KpClTPB, pH, conditioning time and internal solution concentration. Plackett-Burman design was used to screen the main factors and Box-Behnken response surface was led to find a model for optimizing the response. The optimized membrane electrode shows a Nernstian slope for chromium (III) ions over a wide linear range from 1.99x10(-6) to 3.16x10(-2)molL(-1) and a slope of 19.5+/-0.1mVdecade(-1) of activity. It would be successfully applied in the pH range from 3.5 to 6.5 with detection limit of 1.77x10(-6)molL(-1) (0.092mgL(-1)). The response time of the sensor is about 8s and the membrane can be used for more than 6 weeks without any deviation. The relative standard deviations (R.S.D.) for six replicate the measurements of 1.0x10(-4) and 1.0x10(-3)molL(-1) of Cr(III) were 3.2 and 3%, respectively. The electrode revealed comparatively good selectivity with respect to many cations including alkali earth, transition and heavy metal ions. The electrode was successfully used as an indicator in the potentiometric titration of Cr(III) with EDTA and was also applied to the direct determination chromium (III) content of spiked water and soil samples.

Crystal structure and conformational analysis of s-cis-(acetylacetonato)(ethylenediamine-N,N'-diacetato)-chromium(III): development of vibrationally optimized force field (VOFF).

Science.gov (United States)

Choi, Jong-Ha; Niketić, Svetozar R; Djordjević, Ivana; Clegg, William; Harrington, Ross W

2012-05-01

The crystal structure of [Cr(edda)(acac)] (edda = ethylediamine-N,N'-diacetate; acac = acetylacetonato) has been determined by a single crystal X-ray diffraction study at 150 K. The chromium ion is in a distorted octahedral environment coordinated by two N and two O atoms of chelating edda and two O atoms of acac, resulting in s-cis configuration. The complex crystallizes in the space group P2(1)/c of the monoclinic system in a cell of dimensions a = 10.2588(9), b = 15.801(3), c = 8.7015(11) Å, β =101.201(9)° and Z = 4. The mean Cr-N(edda), Cr-O(edda) and Cr-O(acac) bond distances are 2.0829(14), 1.9678(11) and 1.9477(11) Å while the angles O-Cr-O of edda and O-Cr-O of acac are 171.47(5) and 92.72(5)°, respectively. The crystal structure is stabilized by N-H···O hydrogen bonds linking [Cr(edda)(acac)] molecules in distinct linear strands. The visible electronic and IR spectroscopic properties are also discussed. An improved, physically more realistic force field, Vibrationally Optimized Force Field (VOFF), capable of reproducing structural and vibrational properties of [Cr(edda)(acac)] was developed and its transferability demonstrated on selected chromium(III) complexes with similar ligands.

Nitrato-complexes of Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III) and Ho(III) with 2-(2'-pyridyl) benzimidazole

Energy Technology Data Exchange (ETDEWEB)

Mishra, A; Singh, M P; Singh, V K

1982-05-01

The nitrato-complexes, (Y(PyBzH)/sub 2/(NO/sub 3/)/sub 2/)NO/sub 3/.H/sub 2/O and Nd, Sm, Gd, Tb, Dy, Ho ; n=1-3, m=0-0.5 ; PyBzh=2-(2 -pyridyl)benzimidazole) are formed on interaction of the ligand with metal nitrates in ethanol. The electrical conductance values (116-129 ohm/sup -1/cm/sup 2/mol/sup -1/) suggest 1:1 electrolyte-nature of the complexes. Magnetic moment values of Ce(2.53 B.M.), Pr(3.62 B.M.), Nd(3.52 B.M.), Sm(1.70 B.M.), Gd(8.06 B.M.), Tb(9.44 B.M.), Dy(10.56 B.M.) and Ho(10.51 B.M.) in the complexes confirm the positive state of the metals. Infrared evidences are obtained for the existance of both coordinated (C/sub 2/v) and uncoordinated (D/sub 3/h) nitrate groups. Electronic absorption spectra of Pr(III)-, Nd(III)-, Sm(III)-, Tb(III)-, Dy(III)- and Ho(III)-complexes have been analysed in the light of LSJ terms.

Nitrato-complexes of Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III) and Ho(III) with 2-(2'-pyridyl) benzimidazole

International Nuclear Information System (INIS)

Mishra, A.; Singh, M.P.; Singh, V.K.

1982-01-01

The nitrato-complexes, [Y(PyBzH) 2 (NO 3 ) 2 ]NO 3 .H 2 O and Nd, Sm, Gd, Tb, Dy, Ho ; n=1-3, m=0-0.5 ; PyBzh=2-(2 -pyridyl)benzimidazole] are formed on interaction of the ligand with metal nitrates in ethanol. The electrical conductance values (116-129 ohm -1 cm 2 mol -1 ) suggest 1:1 electrolyte-nature of the complexes. Magnetic moment values of Ce(2.53 B.M.), Pr(3.62 B.M.), Nd(3.52 B.M.), Sm(1.70 B.M.), Gd(8.06 B.M.), Tb(9.44 B.M.), Dy(10.56 B.M.) and Ho(10.51 B.M.) in the complexes confirm the terpositive state of the metals. Infrared evidences are obtained for the existance of both coordinated (C 2 v) and uncoordinated (D 3 h) nitrate groups. Electronic absorption spectra of Pr(III)-, Nd(III)-, Sm(III)-, Tb(III)-, Dy(III)- and Ho(III)-complexes have been analysed in the light of LSJ terms. (author)

Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

Science.gov (United States)

Audras, Matthieu; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Dumas, Thomas; Illy, Marie-Claire; Martin, Nicolas; Zilbermann, Israel; Moiseev, Yulia; Ben-Eliyahu, Yeshayahu; Bettelheim, Armand; Cammelli, Sebastiano; Hennig, Christoph; Moisy, Philippe

2017-10-16

The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am 3+ and Pu 3+ ) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H 2 O)] - , where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.

Magnetic interactions in oxide-bridged dichromium(III) complexes. Computational determination of the importance of non-bridging ligands

DEFF Research Database (Denmark)

Morsing, Thorbjørn Juul; Sauer, Stephan P. A.; Weihe, Høgni

2013-01-01

The magnetic susceptibility of the dinuclear chromium(III) complex [(CH3CN)5CrOCr(NCCH3)5](BF4)4 · 2 CH3CN has been measured and analyzed. With a fitted value of the triplet energy J = 650 cm-1, the antiferromagnetic coupling is the strongest hitherto determined for an unsupported linear oxide-br...... relative errors typically of less than 10 % ranging from the strongest coupled systems to systems with moderately strong couplings. A significant influence (>20%) of the chemical nature of the peripheral, non-bridging ligands on the exchange coupling was found and rationalized....

Tea-industry waste activated carbon, as a novel adsorbent, for separation, preconcentration and speciation of chromium

Energy Technology Data Exchange (ETDEWEB)

Duran, Celal, E-mail: cduran@ktu.edu.tr [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Ozdes, Duygu [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Gundogdu, Ali [Faculty of Engineering, Food Department of Food Engineering, 29100, Guemueshane (Turkey); Imamoglu, Mustafa [Department of Chemistry, Faculty of Arts and Sciences, Sakarya University, 54187 Sakarya (Turkey); Senturk, Hasan Basri [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey)

2011-02-28

Activated carbon was produced from tea-industry wastes (TIWAC) and employed as a low cost and effective solid phase material for the separation, preconcentration and speciation of chromium species without using a complexing agent, prior to determination by flame atomic absorption spectrometry (FAAS). The characterization of TIWAC was performed by utilizing several techniques such as Fourier Transform Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), and elemental analysis. The adsorption experiments were conducted in a batch adsorption technique. Under the experimental conditions, Cr(VI) adsorption amount was nearly equal to zero, however the adsorption percentage of Cr(III) was in the range of 95-100%. Therefore total chromium was determined after the reduction of Cr(VI) to Cr(III) and Cr(VI) was calculated by subtracting Cr(III) concentration from total chromium concentration. The suitable conditions for adsorption and speciation processes were evaluated in terms of pH, eluent type and volume, TIWAC concentration, adsorption and desorption contact time, etc. Adsorption capacity of TIWAC was found to be 61.0 mg g{sup -1}. The detection limit for Cr(III) was found to be 0.27 {mu}g L{sup -1} and the preconcentration factor was 50 for 200 mL of sample volume. The procedure was applied to the determination and speciation of chromium in stream, tap and sea water. Also, the proposed method was applied to total chromium preconcentration in microwave digested tobacco and dried eggplant samples with satisfactory results. The method was validated by analyzing certified reference materials (CRM-TMDW-500 Drinking Water and CRM-SA-C Sandy Soil C) and the results were in good agreement with the certified values.

Tea-industry waste activated carbon, as a novel adsorbent, for separation, preconcentration and speciation of chromium

International Nuclear Information System (INIS)

Duran, Celal; Ozdes, Duygu; Gundogdu, Ali; Imamoglu, Mustafa; Senturk, Hasan Basri

2011-01-01

Activated carbon was produced from tea-industry wastes (TIWAC) and employed as a low cost and effective solid phase material for the separation, preconcentration and speciation of chromium species without using a complexing agent, prior to determination by flame atomic absorption spectrometry (FAAS). The characterization of TIWAC was performed by utilizing several techniques such as Fourier Transform Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), and elemental analysis. The adsorption experiments were conducted in a batch adsorption technique. Under the experimental conditions, Cr(VI) adsorption amount was nearly equal to zero, however the adsorption percentage of Cr(III) was in the range of 95-100%. Therefore total chromium was determined after the reduction of Cr(VI) to Cr(III) and Cr(VI) was calculated by subtracting Cr(III) concentration from total chromium concentration. The suitable conditions for adsorption and speciation processes were evaluated in terms of pH, eluent type and volume, TIWAC concentration, adsorption and desorption contact time, etc. Adsorption capacity of TIWAC was found to be 61.0 mg g -1 . The detection limit for Cr(III) was found to be 0.27 μg L -1 and the preconcentration factor was 50 for 200 mL of sample volume. The procedure was applied to the determination and speciation of chromium in stream, tap and sea water. Also, the proposed method was applied to total chromium preconcentration in microwave digested tobacco and dried eggplant samples with satisfactory results. The method was validated by analyzing certified reference materials (CRM-TMDW-500 Drinking Water and CRM-SA-C Sandy Soil C) and the results were in good agreement with the certified values.

Investigation of the surface composition of electrodeposited black chromium by X-ray photoelectron spectroscopy

International Nuclear Information System (INIS)

Survilienė, S.; Češūnienė, A.; Jasulaitienė, V.; Jurevičiūtė, I.

2015-01-01

Highlights: • Black chromium electrodeposited from a Cr(III) bath is composed of oxide, hydroxide and metallic chromium. • Metallic phase is absent in black chromium electrodeposited from a Cr(III) + ZnO bath. • The near-surface layer is rich in hydroxides, whereas oxides of both metals predominate in the depth of the coatings. - Abstract: The paper reviews black chromium electrodeposited from a trivalent chromium bath containing ZnO as a second main component. The chemical compositions of the top layers of the black chromium coatings were studied by the X-ray photoelectron spectroscopy method. The surface of black chromium was found to be almost entirely covered with organic substances. To gain information on the state of each element in the deposit bulk, the layer-by-layer etching of the black chromium surface with argon gas was used. Analysis of XPS spectra has shown that the top layers of black chromium without zinc are composed of various Cr(III) components, organic substances and metallic Cr, whereas metallic Cr is almost absent in black chromium containing some amount of Zn(II) compounds. The ratios of metal/oxide phases were found to be 10/27 and 2/28 for black chromium without and with zinc, respectively. It has been determined that owing to the presence of ZnO in the Cr(III) bath, the percentage of metallic chromium is substantially reduced in black chromium which is quite important for good solar selective characteristics of the coating. The results confirm some of earlier observations and provide new information on the composition of the near-surface layers

Chromium(III) release from chromium‐tanned leather elicits allergic contact dermatitis: a use test study

Science.gov (United States)

Erfani, Behnaz; Matura, Mihály; Lidén, Carola

2018-01-01

Summary Background Chromium (Cr) is a common skin sensitizer. The use of Cr(VI) in leather is restricted in the EU, but that of Cr(III) is not. Objectives To assess whether prolonged exposure to Cr‐tanned leather with mainly Cr(III) release may elicit allergic contact dermatitis in Cr‐allergic individuals. Method Ten Cr‐allergic subjects and 22 controls were patch tested with serial dilutions of Cr(III) and Cr(VI), and with leather samples. They then conducted a use test with a Cr‐tanned and a Cr‐free leather bracelet over a period of 3 weeks, for 12 h per day. Cr deposited on the skin from the bracelets was measured in the controls, and the diphenylcarbazide test for Cr(VI) and extraction tests for Cr(III) and Cr(VI) were conducted for the different leathers. Results Four of 10 Cr‐allergic subjects developed positive reactions to the Cr‐tanned bracelet within 7–21 days, whereas only 1 of 10 had a positive patch test reaction to this leather. Cr released from the Cr‐tanned leather was most probably entirely Cr(III), with a quantifiable amount being deposited on the skin. Conclusions This study strongly suggests that prolonged and repeated exposure to Cr‐tanned leather with mainly Cr(III) release is capable of eliciting allergic contact dermatitis in Cr‐allergic individuals. PMID:29322530

Organometallic neptunium(III) complexes.

Science.gov (United States)

Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

2016-08-01

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

Chromium speciation in environmental samples using a solid phase spectrophotometric method

Science.gov (United States)

Amin, Alaa S.; Kassem, Mohammed A.

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H2SO4 and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11 × 107 and 3.90 × 107 L mol-1 cm-1 for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L-1 with RSD of <1.85% (n = 8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L-1 for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L-1, respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested.

Enhancement of the fluorescence of the samarium (III) complex by gadolinium (III)

International Nuclear Information System (INIS)

Yun-Xiang, C.; Zhang-Hua, L.

1988-01-01

The increase in sensitivity and selectivity of reactions in which colored species are formed by the addition of different metal ions is an area of research that has recently been developed. This phenomenon, which is sometimes called cocolaration effect, has been explained by the formation of mixed metal complex. The authors found an analogous phenomenon of reactions forming fluorescent complexes. The complexes of Sm(III)-thenoyltrifluoroacetone (TTA)-phenanthroline (Phen)-Triton-X-100 (TX-100) and Gd(III) (or La(III), Lu(III) and Y(III))-TTA-Phen-TX-100 had practically no fluorescence separately. Instead, a fluorescence-enhancement phenomenon caused by adding Gd or La, Lu and Y ions to the system was observed for the first time. The intensity of the enhanced fluorescence of Sm(III) complex was increased in the following order: La< Y< Lu< Gd. By analogy with cocoloration effect, the authors call this new fluorescence-enhancement phenomenon the co-fluorescence effect. The object of this work was to study the enhancement effect of Gd(III) on the fluorescence of the Sm(III)-TTA-Phen-TX-100 system. The recommended fluorimetric method has been applied to the determination of trace amounts of samarium in ytterbium oxide with satisfactory results. A general reaction mechanism for the system studied was proposed

Citric-acid preacidification enhanced electrokinetic remediation for removal of chromium from chromium-residue-contaminated soil.

Science.gov (United States)

Meng, Fansheng; Xue, Hao; Wang, Yeyao; Zheng, Binghui; Wang, Juling

2018-02-01

Electrokinetic experiments were conducted on chromium-residue-contaminated soils collected from a chemical plant in China. Acidification-electrokinetic remediation technology was proposed in order to solve the problem of removing inefficient with ordinary electrokinetic. The results showed that electrokinetic remediation removal efficiency of chromium from chromium-contaminated soil was significantly enhanced with acidizing pretreatment. The total chromium [Cr(T)] and hexavalent chromium [Cr(VI)] removal rate of the group acidized by citric acid (0.9 mol/L) for 5 days was increased from 6.23% and 19.01% in the acid-free experiments to 26.97% and 77.66% in the acidification-treated experiments, respectively. In addition, part of chromium with the state of carbonate-combined will be converted into water-soluble state through acidification to improve the removal efficiency. Within the appropriate concentration range, the higher concentration of acid was, the more chromium was released. So the removal efficiency of chromium depended on the acid concentration. The citric acid is also a kind of complexing agent, which produced complexation with Cr that was released by the electrokinetic treatment and then enhanced the removal efficiency. The major speciation of chromium that was removed from soils by acidification-electrokinetics remediation was acid-soluble speciation, revivification speciation and oxidation speciation, which reduced biological availability of chromium.

A Rare Terminal Dinitrogen Complex of Chromium

Energy Technology Data Exchange (ETDEWEB)

Mock, Michael T.; Chen, Shentan; Rousseau, Roger J.; O' Hagan, Molly J.; Dougherty, William G.; Kassel, W. S.; DuBois, Daniel L.; Bullock, R. Morris

2011-10-12

The reduction of dinitrogen to ammonia from N2 and H2 is currently carried out by the Haber-Bosch process, an energy intensive process that requires high pressures and high temperatures and accounts for the production of millions of tons of ammonia per year. The development of a catalytic, energy-efficient process for N2 reduction is of great interest and remains a formidable challenge. In this communication, we are reporting the preparation, characterization and computational electronic structure analysis of a rare 'Chatt-type' ((P-P)2M(N2)2, P-P = diphosphine ligand) complex of chromium, cis-[Cr(N2)2(PPh2NBn2)2] and its reactivity with CO. This complex is supported by the diphosphine ligand PPh2NBn2, containing non-coordinating pendant amine bases, to serve as proton relays. Future studies for this complex are aimed at answering fundamental questions regarding the role of proton relays in the second coordination sphere in their ability to facilitate proton movement from an external acid to metal-bound dinitrogen ligands in the challenging multi-proton/electron reduction of N2 to ammonia.

Reducing elution in anion exchange chromatography as a pretreatment of colorimetry of chromium(VI) and vanadium(V)

International Nuclear Information System (INIS)

Shigetomi, Yasumasa; Hatamoto, Takeji; Nagoshi, Kimie; Yamashige, Takashi.

1976-01-01

In order to increase the selectivity of the colorimetry of chromium and vanadium, the separation by means of anion exchange chromatography was tested. The column, phi 0.8x5.0 cm packing (50--100 mesh) Dowex 1x4 anion exchange resin was used for the separation of chromium. The solution containing chromium (VI), zinc(II), cadmium(II), iron(III) and reducing organic substances contained in industrial waste water was introduced into the column and then the substances other than chromium(VI) were removed by washing the column with distilled water. Finally chromium(VI) was reduced to chromium(III) by hydroxylamine in the eluent and eluted. The concentration of sulfuric acid and hydroxylamine in the eluent were 0.1 mol/l and 0.001 mol/l respectively. For analyzing chromium(III) in the mixture of chromium(VI) and chromium(III), after removal of chromium(VI) it should be oxidized to chromium(VI) anion with the oxidant, e.g., sodium peroxide or hydrogen peroxide, before introducing it into the column. In terms of the pretreatment by using the acetate form resin column, chromium (VI) and chromium(III) can be determined separately in the solution whose concentration ranges from 0.05 ppm to 0.5 ppm despite the presence of contaminants, which interfere with the colorimetric determination of chromium(VI) using diphenylcarbonohydrazide, in the original solution. The separation of vanadium(V) in the solution containing copper(II), cobalt(II) and etc. was made using the mixed solution of hydrochloric acid (2 mol/l) and hydroxylamine (0.2 mol/l) similarly to chromium(VI). In terms of the similar pretreatment vanadium could be determined precisely as far as 0.1 ppm by the colorimetry using 4-(2-pyridylazo) resorcinol despite the presence of copper(II), cobalt(II), nickel(II) and etc in the original solution. (auth.)

Inner-sphere and outer-sphere complexes of yttrium(III), lanthanum (III), neodymium(III), terbium(III) and thulium(III) with halide ions in N,N-dimethylformamide

International Nuclear Information System (INIS)

Takahashi, Ryouta; Ishiguro, Shin-ichi

1991-01-01

The formation of chloro, bromo and iodo complexes of yttrium(III), and bromo and iodo complexes of lanthanum(III), neodymium(III), terbium(III) and thulium(III) has been studied by precise titration calorimetry in N,N-dimethylformamide (DMF) at 25 o C. The formation of [YCl] 2+ , [YCl 2 ] + , [YCl 3 ] and [YCl 4 ] - , and [MBr] 2+ and [MBr 2 ] + (M = Y, La, Nd, Tb, Tm) was revealed, and their formation constants, enthalpies and entropies were determined. It is found that the formation enthalpies change in the sequence ΔH o (Cl) > ΔH o (l), which is unusual for hard metal (III) ions. This implies that, unlike the chloride ion, the bromide ion forms outer-sphere complexes with the lanthanide(III) and yttrium(III) ions in DMF. Evidence for either an inner- or outer-sphere complex was obtained from 89 Y NMR spectra for Y(ClO 4 ) 3 , YCl 3 and YBr 3 DMF solutions at room temperature. (author)

Adsorption of Chromium from Aqueous Solution Using Polyaniline

Directory of Open Access Journals (Sweden)

Majid Riahi Samani

2011-10-01

Full Text Available New group of polymers have been synthesized that are conductive of electricity so they are called conducting polymers. One of the most conducting polymers is "polyaniline". In the present study, polyaniline was synthesized by oxidizing aniline monomer under strongly acidic conditions using potassium iodate as an initiator of oxidative polymerization. Synthesized polyaniline as a powder used as an adsorbent to remove chromium from aqueous solution. Experiments were conducted in batch mode with variables such as amount of polyaniline, chromium solution pH and adsorbtion isotherms. Due to presence of Cr (III in solution after using polyaniline, removal mechanism is the combination of surface adsorption and reduction. It seems that polyaniline reduces the Cr(VI to Cr(III and adsorbs the Cr(III and a part of remaining  Cr(VI. It is well known that nitrogen atom in compounds of amine derivative makes co-ordinate bond with positive charge of metals due to the presence of electron in sp3 orbital of nitrogen. The majority of total chromium removal  occurred at 30minute for polyaniline  and the optimum  time for  hexavalent chromium  removal was about 5 min. Polyaniline has the maximum total cheomiume removal at pH, 3-9. The maximum hexavalent chromium removal occurred at acidic pH for polyanilines. The equilibrium adsorption data for polyaniline fitted both Freundlich’s and Langmuir’s isotherms. This research shows that polyaniline can be used as an adsorbent  for removal chromium from aqueous solution.

Preparation and characterisation of mixed ligand complexes of Co(III), Fe(III) and Cr(III) containing phthalimide and phenols

International Nuclear Information System (INIS)

Miah, M.A.J.; Islam, M.S.; Pal, S.C.; Barma, T.K.

1996-01-01

Some novel mixed ligand complexes of Co(III), Fe(III) and Cr(III) containing phthalimide as primary and 2-aminophenol and 3-aminophenol as secondary ligands have been synthesized and characterised on the basis of elemental analyses, conductivity and magnetic measurements and infrared and electronic spectral studies. Complexes containing 2-aminophenol are 1:1 electrolyte in N,N dimethylformamide. Spectral studies indicate that all the complexes exhibit octahedral geometry. The complexes have the general composition; K[M(pim)/sub 2/(L)/sub 2/]; where m=Co(III), Fe(III) and Cr(III), pim-anion of phthalimamide and L=anion of 2-aminophenol and 3-aminophenol. (author)

Enhanced sludge processing of HLW: Hydrothermal oxidation of chromium, technetium, and complexants by nitrate. 1998 annual progress report

International Nuclear Information System (INIS)

Buelow, S.J.; Robinson, J.M.

1998-01-01

'The objective of this project is to develop the scientific basis for hydrothermal separation of chromium from High Level Waste (HLW) sludges. The worked is aimed at attaining a fundamental understanding of chromium speciation, oxidation/reduction and dissolution kinetics, reaction mechanisms, and transport properties under hydrothermal conditions in both simple and complex salt solutions that will ultimately lead to an efficient chromium leaching process. This report summarizes the research over the first 1.5 years of a 3 year project. The authors have examined the dissolution of chromium hydroxide using different oxidants as a function of temperature and alkalinity. The results and possible applications to HLW sludges are discussed'

Kinetics and Products of Chromium(VI) Reduction by Iron(II/III)-Bearing Clay Minerals.

Science.gov (United States)

Joe-Wong, Claresta; Brown, Gordon E; Maher, Kate

2017-09-05

Hexavalent chromium is a water-soluble pollutant, the mobility of which can be controlled by reduction of Cr(VI) to less soluble, environmentally benign Cr(III). Iron(II/III)-bearing clay minerals are widespread potential reductants of Cr(VI), but the kinetics and pathways of Cr(VI) reduction by such clay minerals are poorly understood. We reacted aqueous Cr(VI) with two abiotically reduced clay minerals: an Fe-poor montmorillonite and an Fe-rich nontronite. The effects of ionic strength, pH, total Fe content, and the fraction of reduced structural Fe(II) [Fe(II)/Fe(total)] were examined. The last variable had the largest effect on Cr(VI) reduction kinetics: for both clay minerals, the rate constant of Cr(VI) reduction varies by more than 3 orders of magnitude with Fe(II)/Fe(total) and is described by a linear free energy relationship. Under all conditions examined, Cr and Fe K-edge X-ray absorption near-edge structure spectra show that the main Cr-bearing product is a Cr(III)-hydroxide and that Fe remains in the clay structure after reacting with Cr(VI). This study helps to quantify our understanding of the kinetics of Cr(VI) reduction by Fe(II/III)-bearing clay minerals and may improve predictions of Cr(VI) behavior in subsurface environments.

Effects of chromium on the immune system.

Science.gov (United States)

Shrivastava, Richa; Upreti, R K; Seth, P K; Chaturvedi, U C

2002-09-06

Chromium is a naturally occurring heavy metal found commonly in the environment in trivalent, Cr(III), and hexavalent, Cr(VI), forms. Cr(VI) compounds have been declared as a potent occupational carcinogen among workers in chrome plating, stainless steel, and pigment industries. The reduction of Cr(VI) to Cr(III) results in the formation of reactive intermediates that together with oxidative stress oxidative tissue damage and a cascade of cellular events including modulation of apoptosis regulatory gene p53, contribute to the cytotoxicity, genotoxicity and carcinogenicity of Cr(VI)-containing compounds. On the other hand, chromium is an essential nutrient required to promote the action of insulin in body tissues so that the body can use sugars, proteins and fats. Chromium is of significant importance in altering the immune response by immunostimulatory or immunosuppressive processes as shown by its effects on T and B lymphocytes, macrophages, cytokine production and the immune response that may induce hypersensitivity reactions. This review gives an overview of the effects of chromium on the immune system of the body. Copyright 2002 Federation of European Microbiological Societies

Chromium speciation in rainwater: temporal variability and atmospheric deposition

Energy Technology Data Exchange (ETDEWEB)

Kieber, R.J.; Willey, J.D.; Zvalaren, S.D. [University of North Carolina at Wilmington, Wilmington, NC (United States). Dept. of Chemistry

2002-12-15

Chromium is released into the atmosphere by a variety of anthropogenic activities which include steel manufacturing, leather tanning, wood presentation and fossil fuel combustion. The concentrations of the various chromium species were determined in 89 rainwater samples collected in Wilmington, NC from October 1, 1999 to December 31, 2001. Volume weighted annual average concentrations of Cr{sub total}, particulate Cr, Cr(III)(aq), and Cr(VI)(aq) were 4.6, 2.2, 0.8 and 1.2 nM, respectively. There was distinct seasonal and diurnal variability in the concentrations of the various chromium species. Chromium emissions to the global atmosphere by both natural and anthropogenic sources are estimated to be 2.2 x 10{sup 9} mol/yr. Using rainwater concentration data along with other published rainwater Cr concentrations and an estimate for total global annual rain, the total global flux of chromium removed from the atmosphere via wet deposition is 2.1 x 10{sup 9} mol/yr. This represents complete removal of Cr and indicates that essentially all chromium released into the global atmosphere is removed via rain. About half this chromium is dissolved with roughly equal concentrations of toxic Cr(VI) and relatively harmless Cr(III) species. 48 refs., 4 figs., 3 tabs.

Hexavalent Chromium reduction by Trichoderma inhamatum

Energy Technology Data Exchange (ETDEWEB)

Morales-Battera, L.; Cristiani-Urbina, E.

2009-07-01

Reduction of hexavalent chromium [Cr(VI)] to trivalent chromium [Cr(III)] is a useful and attractive process for remediation of ecosystems and industrial effluents contaminated with Cr(VI). Cr(VI) reduction to Cr(II) can be achieved by both chemical and biological methods; however, the biological reduction is more convenient than the chemical one since costs are lower, and sludge is generated in smaller amounts. (Author)

ChromiSense: A colourimetric lab-on-a-disc sensor for chromium speciation in water.

Science.gov (United States)

Duffy, G; Maguire, I; Heery, Brendan; Gers, Pauline; Ducrée, J; Regan, F

2018-02-01

The development of a centrifugal device for quantitative analysis of both chromium (III) and (VI) species in water is reported. ChromiSense is a colourimetric sensor system that has been applied to the measurement of chromium in spiked river water samples. For analysis, the sample is loaded into a reservoir on the disposable microfluidic disc, along with reagents. A centrifugal force is created by spinning the disc to pump liquids through microchannels, causing them to mix and react to form a coloured product. The coloured product is then presented to a low-cost optical detection system, where absorbance measurements can be recorded. The optical detection system consists of a light emitting diode (LED) and photodiode (PD) couple. Chromium (III) was measured using 2,6-pyridine dicarboxylic acid as a ligand, forming a complex that was measured at 535nm and at 335nm. While measuring at 535nm allowed for the use of a low cost LED, the sensitivity was improved 2.5 times by measuring at 335nm. However, 335nm also yielded a diminished linear range with little improvement in limit of deteciton (LOD), and required a lengthier manufacturing process due to the need for a UV-transparent material. Chromium (VI) was detected using 1,5-diphenyl carbazide (DPC). This standard analysis method was simplified for automation on-disc, and optimised to achieve a low LOD. The LOD for trivalent and hexavalent chromium using this device were 21mgL -1 and 4μgL -1 , respectively. The linear range for quantitative analysis was found to be 69-1000mgL -1 for Cr(III) and 14-1000μgL -1 for Cr (VI). While this range is high for Cr(III), incorporation of an off-disc pre-concentration method would make this technology suitable for environmental sample analysis. The device is simple to use, low in cost, and could provide rapid on-site measurements, with results comparable to those obtained using a benchtop spectrophotometer. Copyright © 2017 Elsevier B.V. All rights reserved.

Spectrophotometric and pH-Metric Studies of Ce(III, Dy(III, Gd(III,Yb(III and Pr(III Metal Complexes with Rifampicin

Directory of Open Access Journals (Sweden)

A. N. Sonar

2011-01-01

Full Text Available The metal-ligand and proton-ligand stability constant of Ce(III, Dy(III, Gd(III,Yb(III and Pr(III metals with substituted heterocyclic drug (Rifampicin were determined at various ionic strength by pH metric titration. NaClO4 was used to maintain ionic strength of solution. The results obtained were extrapolated to the zero ionic strength using an equation with one individual parameter. The thermodynamic stability constant of the complexes were also calculated. The formation of complexes has been studied by Job’s method. The results obtained were of stability constants by pH metric method is confirmed by Job’s method.

Permeation of chromium salts through human skin in vitro

DEFF Research Database (Denmark)

Gammelgaard, Bente; Fullerton, A; Avnstorp, C

1992-01-01

Chromium permeation studies were performed on full thickness human skin in diffusion cells. All samples were analysed for the total chromium content by graphite furnace Zeeman-corrected atomic absorption spectrometry. Some samples were analysed by an ion chromatographic method permitting...... the simultaneous determination of Cr(VI) and Cr(III) as well. The amounts of chromium found in all skin layers were significantly higher when potassium dichromate was applied to the skin compared with chromium chloride or chromium nitrate. Chromium could only be detected in the recipient phase after application...... of the dichromate solution. Chromium skin levels increased with increasing concentrations of applied chromium salts up to 0.034 M Cr. The amount of chromium in recipient phase and skin layers increased with increasing pH when the applied solution contained potassium dichromate. This was ascribed to a decreased skin...

Organometallic neptunium(III) complexes

Science.gov (United States)

Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

2016-08-01

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

[Cr(N)(acac)2]: A simple chromium nitride complex and its reactivity towards late transition metals

DEFF Research Database (Denmark)

Hedegaard, Erik Donovan; Schau-Magnussen, Magnus; Bendix, Jesper

2011-01-01

A new simple chromium(V) nitride complex, Cr(N)(acac)2 (1) has been prepared by nitrogen atom transfer. X-ray crystallography shows a short Cr-N bond at 1.5564(11) Å and equatorial Cr-O distances in the range 1.9387(9) – 1.9485(9) Å. 1 reacts as a p-backbonding ligand ......A new simple chromium(V) nitride complex, Cr(N)(acac)2 (1) has been prepared by nitrogen atom transfer. X-ray crystallography shows a short Cr-N bond at 1.5564(11) Å and equatorial Cr-O distances in the range 1.9387(9) – 1.9485(9) Å. 1 reacts as a p-backbonding ligand ...

Moessbauer study of Fe(III)-reducing sugar complexes

International Nuclear Information System (INIS)

Wolowiec, S.; Drabent, K.

1985-01-01

Iron(III) complexes with glucose, galactose, mannose and lactose were prepared. The Moessbauer and magnetic susceptibility data demonstrate the polymeric structure of the complexes. The thermal behaviour of the Fe(III)-glucose complex was monitored by Moessbauer spectroscopy. (author)

Stabilization and solidification of chromium-contaminated soil

Energy Technology Data Exchange (ETDEWEB)

Cherne, C.A.; Thomson, B.M. [Univ. of New Mexico, Albuquerque, NM (United States). Civil Engineering Dept.; Conway, R. [Sandia National Labs., Albuquerque, NM (United States)

1997-11-01

Chromium-contaminated soil is a common environmental problem in the United States as a result of numerous industrial processes involving chromium. Hexavalent chromium [Cr(VI)] is the species of most concern because of its toxicity and mobility in groundwater. One method of diminishing the environmental impact of chromium is to reduce it to a trivalent oxidation state [Cr(III)], in which it is relatively insoluble and nontoxic. This study investigated a stabilization and solidification process to minimize the chromium concentration in the Toxicity Characteristic Leaching Procedure (TCLP) extract and to produce a solidified waste form with a compressive strength in the range of 150 to 300 pounds per square inch (psi). To minimize the chromium in the TCLP extract, the chromium had to be reduced to the trivalent oxidation state. The average used in this study was an alluvium contaminated with chromic and sulfuric acid solutions. The chromium concentration in the in the in situ soil was 1212 milligrams per kilogram (mg/kg) total chromium and 275 mg/kg Cr(VI). The effectiveness of iron, ferrous sulfate to reduce Cr(VI) was tested in batch experiments.

Stabilization and solidification of chromium-contaminated soil

International Nuclear Information System (INIS)

Cherne, C.A.; Thomson, B.M.

1997-11-01

Chromium-contaminated soil is a common environmental problem in the United States as a result of numerous industrial processes involving chromium. Hexavalent chromium [Cr(VI)] is the species of most concern because of its toxicity and mobility in groundwater. One method of diminishing the environmental impact of chromium is to reduce it to a trivalent oxidation state [Cr(III)], in which it is relatively insoluble and nontoxic. This study investigated a stabilization and solidification process to minimize the chromium concentration in the Toxicity Characteristic Leaching Procedure (TCLP) extract and to produce a solidified waste form with a compressive strength in the range of 150 to 300 pounds per square inch (psi). To minimize the chromium in the TCLP extract, the chromium had to be reduced to the trivalent oxidation state. The average used in this study was an alluvium contaminated with chromic and sulfuric acid solutions. The chromium concentration in the in the in situ soil was 1212 milligrams per kilogram (mg/kg) total chromium and 275 mg/kg Cr(VI). The effectiveness of iron, ferrous sulfate to reduce Cr(VI) was tested in batch experiments

Complexation of trivalent actinides and lanthanides with hydrophilic N-donor ligands for Am(III)/Cm(III) and An(III)/Ln(III) separation; Komplexierung von trivalenten Actiniden und Lanthaniden mit hydrophilen N-Donorliganden zur Am(III)/Cm(III)- bzw. An(III)/Ln(III)-Trennung

Energy Technology Data Exchange (ETDEWEB)

Wagner, Christoph

2017-07-24

The implementation of actinide recycling processes is considered in several countries, aiming at the reduction of long-term radiotoxicity and heat load of used nuclear fuel. This requires the separation of the actinides from the fission and corrosion products. The separation of the trivalent actinides (An(III)) Am(III) and Cm(III), however, is complicated by the presence of the chemically similar fission lanthanides (Ln(III)). Hydrophilic N-donor ligands are employed as An(III) or Am(III) selective complexing agents in solvent extraction to strip An(III) or Am(III) from an organic phase loaded with An(III) and Ln(III). Though they exhibit excellent selectivity, the complexation chemistry of these ligands and the complexes formed during solvent extraction are not sufficiently characterized. In the present thesis the complexation of An(III) and Ln(III) with hydrophilic N-donor ligands is studied by time resolved laser fluorescence spectroscopy (TRLFS), UV/Vis, vibronic sideband spectroscopy and solvent extraction. TRLFS studies on the complexation of Cm(III) and Eu(III) with the Am(III) selective complexing agent SO{sub 3}-Ph-BTBP (tetrasodium 3,3{sup '},3'',3{sup '''}-([2,2{sup '}-bipyridine]-6,6{sup '}-diylbis(1,2,4-triazine-3,5,6-triyl)) tetrabenzenesulfonate) revealed the formation of [M(SO{sub 3}-Ph-BTBP){sub n}]{sup (4n-3)-} complexes (M = Cm(III), Eu(III); n = 1, 2). The conditional stability constants were determined in different media yielding two orders of magnitude larger β{sub 2}-values for the Cm(III) complexes, independently from the applied medium. A strong impact of ionic strength on the stability and stoichiometry of the formed complexes was identified, resulting from the stabilization of the pentaanionic [M(SO{sub 3}-Ph-BTBP){sub 2}]{sup 5-} complex with increasing ionic strength. Thermodynamic studies of Cm(III)-SO{sub 3}-Ph-BTBP complexation showed that the proton concentration of the applied medium impacts

Chromium in potatoes

International Nuclear Information System (INIS)

Stoddard-Gilbert, K.; Blincoe, C.

1989-01-01

Chromium concentration in potatoes was determined, and tubes were labeled either intrinsically or extrinsically with radioactive chromate ( 51 Cr). A labeled chromium complex was isolated from preparations of raw, baked, or fried potatoes and chromatographed on gel permeation media. Potato pulp and peel contained 1.63 and 2.70 μg of Cr/g tissue, respectively. There was no correlation between the two, nor did they respond similarly to changes of variety or locations. No significant differences were apparent in relative migration of the isolated complexes except between raw and cooked extrinsically labeled preparations

Synthesis of chromium containing pigments from chromium galvanic sludges

International Nuclear Information System (INIS)

Andreola, F.; Barbieri, L.; Bondioli, F.; Cannio, M.; Ferrari, A.M.; Lancellotti, I.

2008-01-01

In this work the screening results of the scientific activity conducted on laboratory scale to valorise chromium(III) contained in the galvanic sludge as chromium precursor for ceramic pigments are reported. The valorisation of this waste as a secondary raw material (SRM) is obtained by achievement of thermal and chemical stable crystal structures able to color ceramic material. Two different pigments pink CaCr 0.04 Sn 0.97 SiO 5 and green Ca 3 Cr 2 (SiO 4 ) 3 were synthesized by solid-state reactions using dried Cr sludge as chromium oxide precursor. The obtained pigments were characterized by X-ray diffraction and SEM analysis. Furthermore the color developed in a suitable ceramic glaze was investigated in comparison with the color developed by the pigments prepared from pure Cr 2 O 3 . The characterization carried out corroborates the thermal and chemical stability of the synthesized pigments and, especially for the Cr-Sn pink pigment, the powders develop an intense color that is very similar to the color developed by the pigments obtained starting from pure Cr 2 O 3

NMR and TRLFS studies of Ln(iii) and An(iii) C5-BPP complexes.

Science.gov (United States)

Adam, Christian; Beele, Björn B; Geist, Andreas; Müllich, Udo; Kaden, Peter; Panak, Petra J

2015-02-01

C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(iii), from trivalent lanthanides, Ln(iii). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(iii) and An(iii) complexes. C5-BPP is synthesized with 10% 15 N labeling and characterized by NMR and LIFDI-MS methods. 15 N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(iii) as a representative for trivalent actinide cations, revealing significant differences in 15 N chemical shift for coordinating nitrogen atoms compared to Ln(iii) complexes. The temperature dependence of NMR chemical shifts observed for the Am(iii) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal-ligand bonding in Am(C5-BPP) 3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP) 3 NMR sample is furthermore spiked with Cm(iii) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.

Magnesium analysis. Spectrophotometric determination of chromium

International Nuclear Information System (INIS)

Anon.

Chromium determination in magnesium used in uranium fabrication by magnesiothermics, applicable for chromium content between 2 to 10 ppm. Magnesium is dissolved in sulfuric acid, oxidized by potassium permanganate, the excess of permanganate is eliminated by sodium nitride. Spectrophotometry at 540 nm of the chromium (VI)-diphenylcarbazide complex [fr

Chromium(III) and chromium(VI) release from leather during 8 months of simulated use.

Science.gov (United States)

Hedberg, Yolanda S; Lidén, Carola

2016-08-01

Chromium (Cr) release from Cr-tanned leather articles is a major cause of Cr contact dermatitis. It has been suggested that Cr(VI) release from leather is not necessarily an intrinsic property of the leather, but is strongly dependent on environmental conditions. To test this hypothesis for long-term (8 months) simulated use. The release of total Cr and Cr(VI) from Cr-tanned, unfinished leather was analysed in subsequent phosphate buffer (pH 8.0) immersions for a period of 7.5 months. The effect of combined ultraviolet treatment and alkaline solution (pH 12.1) was tested. Dry storage [20% relative humidity (RH)] was maintained between immersions. Atomic absorption spectroscopy, X-ray fluorescence and diphenylcarbazide tests were used. Cr(VI) release was dependent on previous dry storage or alkaline treatment, but not on duration or number of previous immersions. Cr(III) release decreased with time. Fifty-two percent of the total Cr released during the last immersion period was Cr(VI). Cr(VI) release exceeded 9 mg/kg in all immersion periods except in the first 10-day immersion (2.6 mg/kg). Cr(VI) release is primarily determined by environmental factors (RH prior to immersion, solution pH, and antioxidant content). The RH should be kept low prior to testing Cr(VI) release from leather. © 2016 The Authors. Contact Dermatitis published by John Wiley & Sons Ltd.

Tecnology for the Management of Alum of Chromium (III and Potasium as Ceramic Pigment

Directory of Open Access Journals (Sweden)

Idalberto Clemente Morales-Rodríguez

2017-01-01

Full Text Available The lazy and expired reagents are among the dangerous waste generated in Cuba, some of which contain heavy metals. These substances accumulate without a final disposition, neither appropriate use, with the purpose of not contaminating the environment. In such a sense, the authors propose an alternative use for alum of chromium (III and potassium, when transforming it into oxide by precipitation with alkalis to apply it as ceramic pigment. The present paper shows the use tests and the determination of purity by oxidation-reduction titration; giving it a final disposition without any environmental risk and with the additional creation of economic values starting from immobilized resources, bringing about the substitution of import pigments, which are quite expensive.

Effect of pH on stability constants of Am(III)- and Cm(III)- humate complexes

International Nuclear Information System (INIS)

Samadfam, Mohammad; Jintoku, Takashi; Sato, Seichi; Ohashi, Hiroshi; Mitsugashira, Toshiaki; Hara, Mitsuo; Suzuki, Yoshimitsu

1999-01-01

The apparent stability constants of Am(III)- and Cm(III)-humate complexes were determined by dialysis method at ionic strength 0.1 in the pH range from 3.3 to 5.7 under N 2 bubbling. The Am(III) and Cm(III) loadings were about 10 -7 and 10 -10 mol/dm 3 . The concentrations of Am-241 and Cm-242 tracers were measured by α-spectrometry. It was found that the apparent stability constants were almost identical for both the Am(III)-humate and Cm(III)-humate complexes. The apparent stability constants showed a small pH-dependence, increasing from 10 4.6 at pH 3.3 to 10 5.1 at pH 5.7. The ionization of acidic functional groups of humic acid is possibly the primary factor. Above pH 6, the dialysis membrane was no langer permeable to Am(III) and Cm(III) ions and the apparent stability constant could not be experimentally obtained. The apparent stability constants between pH 6 and pH 8.5 were evaluated by considering that both binary metal-humate and ternary metal-hydroxo-humate complexes exist at pHs above 6. It was assumed that mono-hydroxo-humate complex Am(OH)HA and Cm(OH)HA are the major ternary complexes that exist below pH 9. The overall stability constants for Am(III)- and Cm(III)-humate complexes increased from 10 5.7 at pH 6 to 10 7.2 at pH 8. This implies that the formation of metal-hydroxo-humate species is preferred over the formation of hydroxide species. The apparent overall stability constants can be easily incorporated into geochemical modeling of trivalent actinide migration. The results of the present study show that the apparent stability constants determined experimentally at pH≤6 do not represent the complexation properties at higher pHs and the formation of ternary complexes should be considered in speciation calculations of radionuclides at terrestrial environment. (J.P.N.)

Use of flying ash in the chromium removal (III) of the liquid effluents of tanneries

International Nuclear Information System (INIS)

Gil Pavas, Edison; Saldarriaga Molina, Carlos

1998-01-01

This study describes a simple and economic method for the removal of chromium (III) from tannery waste waters using flying ash. The process is carried out batch-wise utilizing as variables the mass of flying ash, the time of contact and the temperature or pH. With these variables a Box-Wilson type of experimental design was done, which was then optimized with a statistical program. One as-received flying ash was utilized in the work as well as another one chemically treated. The results show the possibility of lowering the initial concentration in the waste liquor from 1850 ppm to 0,008, complying this way with environmental exigencies about this contaminant

Complexation of Cucurbit(7)uril with Eu(III)

International Nuclear Information System (INIS)

Kar, Aishwarya; Rawat, Neetika; Rao, Ankita; Tomar, B.S.; Nayak, S.K.; Ray, Alok

2014-01-01

Cucurbiturils (CBs) CB(n)s are macrocyclic molecules with carbonyl groups at the portals, which bind cations through ion dipole interactions and the cavity which stabilize hydrophobic moieties. The size of the portal and the volume of the interior cavities of CB(n)s are dependent on the number of glycoluril units present in CBs. CBs are widely used as supramolecular host systems in applications, such as formation of supramolecular hydrogels, drug delivery systems. Though the binding of CBs with organic guest molecules have been studied extensively where as metal complexation studies are very few. In the present work, complexation studies of Cucurbit(7)uril (with seven glycouril units, CB7) with Eu(III) were carried out using fluorescence, UV-vis spectrophotometry. The stability constant for 1:1 complex CB7-Eu(III) complex determined by monitoring the change in CB7 UV- vis absorption spectra on addition of Eu(III) was found to be 2.99 ± 0.08. The fluorescence spectra of increasing ligand to metal ratio exhibited the increase in the intensity ratio of peak at 616 and 592 which is the measure of complexation of Eu(III) with CB7 and was used to deduce the stability constant and the value (2.82 ± 0.07) obtained was in good agreement with that obtained from UV vis spectroscopy. Further, the life time of Eu(III) ion, which increased with CB7 to Eu(III) ratio, was used to deduce number of water molecules around Eu(III) metal ion which were found to decrease from 9 to 3 thereby suggesting inner sphere complexation. The stability constant of CB7 with Eu(III) is one order of magnitude less than CB5, derived in separate study by authors. The smaller cavity of CB5 (2.4 A 0 ) favors its interactions with Eu(III) ion of comparable diameter (2.16 A 0 ) leading to higher stability constant compared to CB7 (5.4 A 0 ) having larger cavity

Stabilization of chromium: an alternative to make safe leathers.

Science.gov (United States)

Gong, Ying; Liu, Xiaoling; Huang, Li; Chen, Wuyong

2010-07-15

In this study, the original causes for hexavalent chromium presence in the leather were first evaluated by ageing of chromium(III) solutions and chrome tanned hide powder (50 degrees C, UV lightening at 340 nm, 0-36 h). The results showed that the trivalent chromium at instable coordination state was easy to convert into hexavalent chromium in high pH environment, and the probability of the oxidation increased in this order: multi-coordinate chromium, mono-coordinate chromium, and free chromium. For this reason, the process for stabilizing chromium in the leather was designed with the specific material, which was mostly consisted of the reducers and the chelating agents. After treated with the developed process, these leathers were aged (50 degrees C, UV irradiance as 0.68 W/m(2) at 340 nm, 0-72 h) to estimate chromium(VI) presence. Hexavalent chromium was not found in these treated leathers even if the leathers were aged for 72 h. Moreover, the physical and mechanical properties for the leathers varied little after treating. In a word, an inherent safe and effective process was proved to avoid the formation of hexavalent chromium in the leather. 2010 Elsevier B.V. All rights reserved.

Light induced electron transfer reactions of metal complexes

International Nuclear Information System (INIS)

Sutin, N.; Creutz, C.

1980-01-01

Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

Synthesis and characterization of La(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III) and Dy(III) complexes of 2-acetylfuran-2-thenoylhydrazone

International Nuclear Information System (INIS)

Singh, B.; Singh, Praveen K.

1998-01-01

The reaction of 2-acetylfuran-2-thenoylhydrazone(afth) with Ln(III) trichlorides yields complexes of the type [Ln(afth)Cl 2 (H 2 O)(EtOH)]Cl, [Ln(III) = La, Pr, Nd, Sm, Eu, Gd, Tb and Dy]. The complexes have been characterized by molar conductance, magnetic susceptibility and TGA and DTA measurements, magnetic susceptibility and TGA and DTA measurements, FAB mass, infrared, proton NMR, electronic absorption and emission spectra. The terbium complex is found to be monomer from the FAB mass spectrum. The IR and NMR spectra suggest neutral tridentate behaviour of the Schiff base. A coordination number seven is proposed around the metal ions. Emission spectra suggest C 3v , symmetry around the metal ion with capped octahedron geometry for the europium complex. (author)

Study on chromium speciation in rats by the isotope tracer technique

International Nuclear Information System (INIS)

Feng Weiyue; Qian Qinfang; Ding Wenjun; Chai Zhifang

1999-01-01

The chromium speciation in the liver cytosol fraction, serum and urine of both normal and diabetic rats are studied by the enriched stable isotope tracer technique combined with the get chromatography and the neutron activating analysis (NAA). The results are as follows: (1) When Cr(III) enters the animal body, it is most likely to be combined with serum proteins. The chromium-protein compound acts as a carrier to transport Cr to the whole body. In the liver cytosol fraction, Cr (III) is also mainly combined with the high molecular weight protein and retains as chromium-protein substance in the liver. (2) A low molecular weight chromium-containing compound is found in all the liver cell cytosol fraction, serum and urine of the two group rats. (3) The diabetic rats lose more amount of low molecular weight of chromium compound in urine than the normal rats do. This might be a main reason to explain why the diabetic rats retain lower Cr in their bodies than the normal group

Characterization of the lanthanum(III) and europium(III) trichloroacetate complexes extracted with 18-crown-6

International Nuclear Information System (INIS)

Imura, H.; Saito, Y.; Ohashi, K.; Meguro, Y.; Yoshida, Z.; Choppin, G.R.

1996-01-01

Extraction of lanthanide(III) ions with 18-crown-6 (18C6) and trichloroacetate (tca) has been studied. The composition, hydration, and structure of the La(III) and Eu(III) complexes extracted into 1,2-dichloroethane were investigated by using several methods such as the liquid-liquid distribution technique, conductimetry, Karl Fisher titration, laser luminescence spectroscopy, and 1 H NMR. The La(III) complex was found to be a monohydrate, La(tca) 3 (18C6)(H 2 O), while that of Eu(III) was a mixture of a monohydrate and a dihydrate, i.e., Eu(tca) 3 (18C6)(H 2 O) and Eu(tca) 3 (18C6)(H 2 O) 2 . The origin of the selectivity by 18C6 which gives much higher extractability of La(III) than of Eu(III) is explained by considering the hydration and probable structure of their complexes. 12 refs., 5 figs., 4 tabs

Speciation of chromium compounds from humic acid-zeolite Y to an ionic liquid during extraction.

Science.gov (United States)

Huang, Hsin-Liang; Wei, Yu Jhe

2018-03-01

By synchrotron X-ray absorption spectroscopy, chemical structures of hexavalent chromium (Cr(VI))/trivalent chromium (Cr(III)) adsorbed on humic acid (HA)-zeolite Y and extracted in an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate ([C 4 mim][BF 4 ])) have been studied. By combining the competitive adsorption results and reduction of Cr(VI)-HA with the carboxyl groups of HA, Cr(III)-HA (58%) was shown to be the major compound in HA-zeolite Y using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy. In an ionic liquid phase, the reduction of Cr(VI)-HA to Cr(III)-HA and the desorption of Cr(III) from HA were caused by [C 4 mim][BF 4 ]. The 9 F nuclear magnetic resonance (NMR) spectra show that the perturbation of the [C 4 mim][BF 4 ] anion was affected by the extractable chromium species. The formation of a Cr(III) ion affected the increase in the bond distance for the 1st shell CrO of the chromium species in [C 4 mim][BF 4 ] using extended X-ray absorption fine structure (EXAFS) spectroscopy. The changes in the non-extractable chromium species remaining in HA-zeolite Y were also caused by [C 4 mim][BF 4 ] during extraction. The desorption of the absorbed Cr(III) on HA and zeolite Y was observed to form Cr(III) ions. As the percentage of Cr(III) ions remaining in HA-zeolite Y increased, a slightly greater bond distance for CrO was found at 2.01 Å. The enhanced reduction of Cr(VI)-HA and desorption of Cr(III) adsorbed on the HA and zeolite Y to form Cr(III) ions were affected by [C 4 mim][BF 4 ]. Increased mobility of Cr(III) in the simulated soil can promote the migration of Cr(III) ions into the H 2 O during soil washing for remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solvent extraction of anionic chelate complexes of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) with 2-thenoyltrifluoroacetone as ion-pairs with tetrabutylammonium ions

International Nuclear Information System (INIS)

Noro, Junji; Sekine, Tatsuya.

1992-01-01

The solvent extraction of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) in 0.1 mol dm -3 sodium nitrate solutions with 2-thenoyltrifluoroacetone (Htta) in the absence and presence of tetrabutylammonium ions (tba + ) into carbon tetrachloride was measured. The extraction of lanthanum(III), europium(III), and lutetium(III) was greatly enhanced by the addition of tba + ; this could be explained in terms of the extraction of a ternary complex, M(tta) 4 - tba + . However, the extractions of scandium(III) and indium(III) were nearly the same when tba + was added. The data were treated on the basis of the formation equilibrium of the ternary complex from the neutral chelate, M(tta) 3 , with the extracted ion-pairs of the reagents, tta - tba + , in the organic phase. It was concluded that the degree of association of M(tta) 3 with the ion-pair, tta - tba + , is greater in the order La(tta) 3 ≅ Eu(tta) 3 > Lu(tta) 3 , or that the stability of the ternary complex in the organic phase is higher in the order La(tta) 4 - tba + ≅ Eu(tta) 4 - tba + > Lu(tta) 4 - tba + . This is similar to those of adduct metal chelates of Htta with tributylphosphate (TBP) in synergistic extraction systems. (author)

Cr(III) reactivity and foot dermatitis in Cr(VI) positive patients

DEFF Research Database (Denmark)

Hansen, Malene Barré; Menné, Torkil; Johansen, Jeanne Duus

2006-01-01

Chromium allergy has become synonymous with Cr(VI) allergy. However, real exposure to chromium from leather products may include both Cr(III) and Cr(VI). In this study, we investigate the reactivity to both Cr(VI) and Cr(III) in consecutive patients to analyse the relation between foot eczema/leather...... to Cr(III). The increased risk was not due to a higher degree of sensitivity to Cr(VI). Leather was reported most frequently as the suspected cause of chromium dermatitis (54%). However, Cr(VI) allergics having foot eczema and positive or doubtful Cr(III) reactions often had positive reactions to other...

Heterobimetallic gadolinium(III)-iron(III) complex of DTPA-bis(3-hydroxytyramide)

International Nuclear Information System (INIS)

Parac-Vogt, Tatjana N.; Kimpe, Kristof; Binnemans, Koen

2004-01-01

A derivative of diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA), carrying two catechol functional groups has been synthesised by the reaction between DTPA-bis(anhydride) and 3-hydroxytyramine (dopamine). The ligand DTPA-bis(3-hydroxytyramide), [DTPA(HTA) 2 ], is able to form stable heterobimetallic complexes with gadolinium(III) and iron(III) ions. The gadolinium(III) occupies the internal coordination cage of DTPA formed by three nitrogens, two carboxylate and two amide oxygens, while the [Fe(NTA)(H 2 O) 2 ] (nitrilotriacetic acid, NTA) binds to catechol units by the substitution of two water ligands. The formation of polymeric species was avoided by using the tripodal NTA ligand. The heterobimetallic complex was characterised by means of visible absorption spectroscopy, electron spray ionisation-mass spectrometry (ESI-MS), and nuclear magnetic resonance (NMR) spectroscopy

Adsorption of basic chromium sulfate used in the tannery industries by calcined hydrotalcite

International Nuclear Information System (INIS)

Lopez M, B. E.; Rivera R, R.; Iturbe G, J. L.; Olguin G, M. T.

2011-01-01

The sorption behavior of the chemical species of Cr(III) from aqueous solutions by hydrotalcite calcined products was investigated considering the equilibrium ph (5.0 to 8.9) and the chromium concentration in aqueous solution (from 10.6 to 430.0 mmol/L) to obtain the corresponding isotherms. Each solution was prepared from basic Cr(III) sulphate which is a primary tanning agent used in the tannery industries. In this work no previous oxidation treatment was done to form Cr(vi) in order to remove the chromium from aqueous solutions by hydrotalcite. The amount of chromium in the remaining solutions after the sorption processes in a batch system by visible spectroscopy (Vis) was determined. The calcined hydrotalcite before and after the contact with the chromium(III) solutions by X-ray power diffraction, thermogravimetric analysis and Fourier transformed infrared spectroscopy, were characterized. The specific are by Brunauer, Emmett and Teller (Bet) method of each sample was also evaluated. It was found that under the experimental conditions of this work hydrolyzed species of Cr(III) are precipitated on the surface of the calcined hydrotalcite instead other adsorption mechanism, and the sulfate ions were the responsible to regenerated the crystalline structure of hydrotalcite, therefore the results are discussed in terms of both Cr(III) and sulfate chemical species. (Author)

Adsorption of basic chromium sulfate used in the tannery industries by calcined hydrotalcite

Energy Technology Data Exchange (ETDEWEB)

Lopez M, B. E.; Rivera R, R.; Iturbe G, J. L.; Olguin G, M. T., E-mail: beatriz.lopez@inin.gob.mx [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2011-07-01

The sorption behavior of the chemical species of Cr(III) from aqueous solutions by hydrotalcite calcined products was investigated considering the equilibrium ph (5.0 to 8.9) and the chromium concentration in aqueous solution (from 10.6 to 430.0 mmol/L) to obtain the corresponding isotherms. Each solution was prepared from basic Cr(III) sulphate which is a primary tanning agent used in the tannery industries. In this work no previous oxidation treatment was done to form Cr(vi) in order to remove the chromium from aqueous solutions by hydrotalcite. The amount of chromium in the remaining solutions after the sorption processes in a batch system by visible spectroscopy (Vis) was determined. The calcined hydrotalcite before and after the contact with the chromium(III) solutions by X-ray power diffraction, thermogravimetric analysis and Fourier transformed infrared spectroscopy, were characterized. The specific are by Brunauer, Emmett and Teller (Bet) method of each sample was also evaluated. It was found that under the experimental conditions of this work hydrolyzed species of Cr(III) are precipitated on the surface of the calcined hydrotalcite instead other adsorption mechanism, and the sulfate ions were the responsible to regenerated the crystalline structure of hydrotalcite, therefore the results are discussed in terms of both Cr(III) and sulfate chemical species. (Author)

Indium(III) complexes with some salicylidene aromatic Schiff bases

International Nuclear Information System (INIS)

Mahmoud, M.R.; Issa, I.M.; El-Gyar, S.A.

1980-01-01

In(III) complexes with salicylidene aromatic Schiff bases have been prepared. The nature of the complexes has been studied by microanalysis of the solid complexes, conductometric titration, uv and ir spectrophotometric measurements. The complexes are of the type 1 : 1 and 2 : 1 [Ligand : In(III)] depending upon the Schiff base. The tendency of the salicylidene Schiff base molecule towards complex formation with In(III) is found to depend largely on the strength of the intramolecular hydrogen bound established between the aldehydic OH group and C = N. Furthermore, it is concluded that these Schiff bases coordinate to In(III) as tri- or bidentate ligands depending upon the molecular structure of the Schiff base (not as monodentate ligand as previously described). The high molar absorbance of the 1 : 2 In(II) complex with salicylidene-o-hydroxyaniline I (17,800 mo1 -1 cm 2 ) can be applied for the micro determination of small amounts of Indium as low as 0.57 anti g/m1 solution. (author)

Thermodynamics of U(VI) and Eu(III) complexation by unsaturated carboxylates

Energy Technology Data Exchange (ETDEWEB)

Rawat, Neetika; Bhattacharyya, A. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Tomar, B.S., E-mail: bstomar@barc.gov.in [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Ghanty, T.K. [Theoretical Chemistry Section, Bhabha Atomic Research Centre, Mumbai 400085 (India); Manchanda, V.K. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2011-05-10

Highlights: {yields} {Delta}H and log K determined for U(VI) and Eu(III) complexes with maleate and fumarate. {yields} log K and coordination environment of Eu(III) complexes has been studied by TRFS. {yields} Higher log K of U(VI) complexes than Eu(III) complexes is due to higher entropy. {yields} Plot of log K vs log K{sub P} suggest charge polarization in fumarate complexes. {yields} Ab initio calculations support charge polarization in fumarate complexes. - Abstract: The thermodynamic parameters ({Delta}G, {Delta}H and {Delta}S) of complexation of U(VI) and Eu(III) by unsaturated dicarboxylic acids, namely, maleic and fumaric acid, has been determined by potentiometric and microcalorimetric titrations at fixed ionic strength (I = 1.0 M) and temperature (298 K). The results show formation of 1:1 complexes by both the ligands with Eu(III). In the case of U(VI), maleate forms both 1:1 and 1:2 complexes, while only 1:1 complex was formed with fumarate. The fluorescence emission spectra of Eu(III)-dicarboxylate solutions at varying ligand to metal ratio were also used to obtain their stability constants. In addition, the fluorescence lifetimes reveal higher dehydration of Eu(III)-maleate compared to Eu(III)-fumarate which corroborates the {Delta}S values. The thermodynamic quantities suggest charge polarization effects in the case of U(VI) and Eu(III) complexes of fumarate, which is further corroborated by theoretical calculations. For the same ligand, U(VI) complexes were found to be more stable which was mainly due to higher entropy term.

Studies of Some Lanthanide(III Nitrate Complexes of Schiff Base Ligands

Directory of Open Access Journals (Sweden)

Kishor Arora Mukesh Sharma

2009-01-01

Full Text Available The studies of 16 new lanthanide(III nitrate complexes of Schiff base ligands are discussed. Schiff bases were obtained by the condensation of 2–methyl–4–N,N–bis–2' –cyanoethyl aminobenzaldehyde with aniline and 3 different substituted anilines. Lanthanide(III nitrates, viz. gadolinium(III nitrate, lanthanum(III nitrate, samarium(III nitrate and cerium(III nitrate were chosen to synthesize new complexes. The complexes were characterized on the basis of physicochemical studies viz. elemental analysis, spectral, viz. IR and electronic spectral and magnetic studies. TGA studies of some of the representative complexes were also done. Some of the representative complexes were also screened for the anti microbial studies.

Genotoxicity of Tri- and Hexavalent Chromium Compounds In Vivo and Their Modes of Action on DNA Damage In Vitro

Science.gov (United States)

Fang, Zhijia; Zhao, Min; Zhen, Hong; Chen, Lifeng; Shi, Ping; Huang, Zhiwei

2014-01-01

Chromium occurs mostly in tri- and hexavalent states in the environment. Hexavalent chromium [Cr(VI)] compounds are extensively used in diverse industries, and trivalent chromium [Cr(III)] salts are used as micronutrients and dietary supplements. In the present work, we report that they both induce genetic mutations in yeast cells. They both also cause DNA damage in both yeast and Jurkat cells and the effect of Cr(III) is greater than that of Cr(VI). We further show that Cr(III) and Cr(VI) cause DNA damage through different mechanisms. Cr(VI) intercalates DNA and Cr(III) interferes base pair stacking. Based on our results, we conclude that Cr(III) can directly cause genotoxicity in vivo. PMID:25111056

Comparison of X-ray photoelectron spectroscopy multiplet splitting of Cr 2p peaks from chromium tris(β-diketonates) with chemical effects

Energy Technology Data Exchange (ETDEWEB)

Liu, R.; Conradie, J.; Erasmus, E., E-mail: erasmuse@ufs.ac.za

2016-01-15

Graphical abstract: Synopsis and pictogram for Table of contents The Cr 2p{sub 3/2} peaks obtained from X-ray photoelectron spectra (XPS) of a series of chromium(III) β-diketonato complexes were fitted with calculated multiplet peaks. The ratio of the fac and mer isomers obtained from XPS compared very well with the Boltzmann calculated ratio. The electronegativity of the R-groups on the β-diketonato ligand influences the XPS peak positions. - Highlights: • β-diketonato complexes Cr(RCOCHCOR’){sub 3} • Cr 2p{sub 3/2} XPS peaks fitted with calculated multiplet peaks. • Different calculated multiplet peaks fit the Cr 2p{sub 3/2} peak for fac and mer isomers. • XPS peak positions influenced by the electronegativity of the R- and R'-group. - Abstract: X-ray photoelectron spectra (XPS) measurements of a series of chromium(III) β-diketonato complexes of the Cr 2p spectra was fitted with calculated multiplet peaks. The XPS of these Cr(III) complexes did not exhibit fine structure, however, well-defined line shapes could be fitted to the Cr 2p{sub 3/2} envelope. The splitting patterns obtained for the Cr(III) β-diketonato complexes compared well with the multiplet splitting predicted by Gupta and Sen for the free Cr(III) ion. The Cr(III) β-diketonato complexes containing unsymmetrically substituted β-diketonato ligands, which display both the fac and mer isomers, could be fitted with two sets of multiplets and were useful in determining the ratio between the fac and mer isomers, which was compared with the Boltzman calculated ratio obtained from density functional theory energies. The obtained binding energy of the first multiplet splitting peak of the Cr 2p{sub 3/2} envelope was found to be dependent on the combined Gordy group electronegativity of the R-groups substituted on the β-diketonato ligand (RCOCHCOR′){sup −}.

The toxicity of arsenic(III), chromium(VI) and zinc to groundwater copepods.

Science.gov (United States)

Hose, G C; Symington, K; Lott, M J; Lategan, M J

2016-09-01

Groundwater ecosystems globally are threatened by anthropogenic contamination, yet there are few ecotoxicological data using obligate groundwater biota on which to base risk assessments. Copepods are found inhabiting aquifers of different geologies around the world and so are a useful taxon for use in ecotoxicological studies of groundwater. The aim of this study was to test the sensitivity of obligate groundwater copepods to metal contaminants (arsenic(III), chromium(VI) and zinc) in groundwater in static 96 h, 14 days and 28 days exposure tests. The copepods were variably sensitive to As, Cr and Zn, with Cr being the most toxic across all taxa. No taxon was consistently most sensitive and there was no apparent relationship between the hardness, pH and organic carbon concentration of the diluent water and the sensitivity of biota. As expected, toxicity increased with exposure period and we encourage the use of longer exposure periods in future toxicity tests with groundwater organisms to reflect the greater exposure periods likely to be associated with groundwater contamination.

Acetate-assisted Synthesis of Chromium(III) Terephthalate and Its Gas Adsorption Properties

International Nuclear Information System (INIS)

Zhou, Jingjing; Liu, Kaiyu; Kong, Chunlong; Chen, Liang

2013-01-01

We report a facile synthetic approach of high-quality chromium(III) terephthalate [MIL-101(Cr)] by acetate-assisted method in the absence of toxic HF. Results indicate that the morphology and surface area of the MIL-101(Cr) can be tuned by modifying the molar ratio of acetate/Cr(NO 3 ) 3 . The Brunauer-Emmett-Teller (BET) surface area of MIL-101(Cr) synthesized at the optimized condition can exceed 3300 m 2 /g. It is confirmed that acetate could promote the dissolution of di-carboxylic linker and accelerate the nucleation ratio. So the pure and small size of MIL-101(Cr) with clean pores can be obtained. CO 2 , CH 4 and N 2 adsorption isotherms of the samples are studied at 298 K and 313 K. Compared with the traditional method, MIL-101(Cr) synthesized by acetate-assisted method possess enhanced CO 2 selective adsorption capacity. At 1.0 bar 298 K, it exhibits 47% enhanced CO 2 adsorption capacity. This may be attributed to the high surface area together with clean pores of MIL-101(Cr)

Complexation and molecular modeling studies of europium(III)-gallic acid-amino acid complexes.

Science.gov (United States)

Taha, Mohamed; Khan, Imran; Coutinho, João A P

2016-04-01

With many metal-based drugs extensively used today in the treatment of cancer, attention has focused on the development of new coordination compounds with antitumor activity with europium(III) complexes recently introduced as novel anticancer drugs. The aim of this work is to design new Eu(III) complexes with gallic acid, an antioxida'nt phenolic compound. Gallic acid was chosen because it shows anticancer activity without harming health cells. As antioxidant, it helps to protect human cells against oxidative damage that implicated in DNA damage, cancer, and accelerated cell aging. In this work, the formation of binary and ternary complexes of Eu(III) with gallic acid, primary ligand, and amino acids alanine, leucine, isoleucine, and tryptophan was studied by glass electrode potentiometry in aqueous solution containing 0.1M NaNO3 at (298.2 ± 0.1) K. Their overall stability constants were evaluated and the concentration distributions of the complex species in solution were calculated. The protonation constants of gallic acid and amino acids were also determined at our experimental conditions and compared with those predicted by using conductor-like screening model for realistic solvation (COSMO-RS) model. The geometries of Eu(III)-gallic acid complexes were characterized by the density functional theory (DFT). The spectroscopic UV-visible and photoluminescence measurements are carried out to confirm the formation of Eu(III)-gallic acid complexes in aqueous solutions. Copyright © 2016 Elsevier Inc. All rights reserved.

Structural characterization of the Actinides (III) and (IV) - DOTA complexes

International Nuclear Information System (INIS)

Audras, Matthieu

2014-01-01

The polyamino-carboxylate anions have been identified as compounds of interest in the operations of actinide separation, in actinide migration in the environment and in human radio-toxicology. The structural characterization of complexes formed between actinides and polyamino-carboxylates ligands is essential for a better understanding of actinide-ligands interactions. Among the polyamino-carboxylate anions, the DOTA ligand (1,4,7,10-tetraaza-cyclododecane tetraacetic acid) is described as a very strong complexing agent of the lanthanides(III), but has been little studied with actinides. The objective of this thesis is to describe the complexes formed between the actinides (III) and (IV) and the DOTA ligand, and compare them with the lanthanide complexes. For this, an approach has been introduced to characterize the complexes by complementary analytical techniques (spectrophotometry, electro-spray ionization mass spectrometry, NMR, EXAFS, electrochemistry), but also by calculations of theoretical chemistry to help the interpretation of the experimental data. The formation of a 1:1 complex is observed with the actinides(III) (plutonium and americium) as for lanthanides(III): rapid formation of intermediate species which evolves slowly towards the formation of a limit complex. Within this complex, the cation is located inside the cavity formed by the ligand. Four nitrogen atoms and four oxygen atoms from the carboxylate functions are involved in the coordination sphere of the cation. However, differences were observed in the bond lengths formed between the cation and the nitrogen atoms (the bonds are somewhat shorter in the case of actinide complexes) as well as the complexation kinetics, which is slightly faster for the actinides(III) than for lanthanide(III) ions of equivalent radius. The same behavior was observed in solution upon complexation of actinides(IV) (uranium, plutonium and neptunium): slow formation of a 1:1 complex (actinide(IV):ligand) in wherein the

Carrier element-free coprecipitation (CEFC) method for the separation, preconcentration and speciation of chromium using an isatin derivative

Energy Technology Data Exchange (ETDEWEB)

Bulut, Volkan Numan; Ozdes, Duygu; Bekircan, Olcay; Gundogdu, Ali; Duran, Celal [Department of Chemistry, Karadeniz Technical University, Faculty of Arts and Sciences, 61080 Trabzon (Turkey); Soylak, Mustafa [Department of Chemistry, Erciyes University, Faculty of Arts and Sciences, 38039 Kayseri (Turkey)], E-mail: soylak@erciyes.edu.tr

2009-01-19

A new, simple, rapid and sensitive separation, preconcentration and speciation procedure for chromium in environmental liquid and solid samples has been established. The present speciation procedure for Cr(III) and Cr(VI) is based on combination of carrier element-free coprecipitation (CEFC) and flame atomic absorption spectrometric (FAAS) determinations. In this method a newly synthesized organic coprecipitant, 5-chloro-3-[4-(trifluoromethoxy) phenylimino]indolin-2-one (CFMEPI), was used without adding any carrier element for coprecipitation of chromium(III). After reduction of chromium(VI) by concentrated H{sub 2}SO{sub 4} and ethanol, the procedure was applied for the determination of total chromium. Chromium(VI) was calculated as the difference between the amount of total chromium and chromium(III). The optimum conditions for coprecipitation and speciation processes were investigated on several commonly tested experimental parameters, such as pH of the solution, amount of coprecipitant, sample volume, etc. No considerable interference was observed from the other investigated anions and cations, which may be found in natural water samples. The preconcentration factor was found to be 40. The detection limit for chromium(III) corresponding to three times the standard deviation of the blank (N = 10) was found 0.7 {mu}g L{sup -1}. The present procedure was successfully applied for speciation of chromium in several liquid and solid environmental samples. In order to support the accuracy of the method, the certified reference materials (CRM-TMDW-500 Drinking Water and CRM-SA-C Sandy Soil C) were analyzed, and standard APDC-MIBK liquid-liquid extraction method was performed. The results obtained were in good agreement with the certified values.

Carrier element-free coprecipitation (CEFC) method for the separation, preconcentration and speciation of chromium using an isatin derivative

International Nuclear Information System (INIS)

Bulut, Volkan Numan; Ozdes, Duygu; Bekircan, Olcay; Gundogdu, Ali; Duran, Celal; Soylak, Mustafa

2009-01-01

A new, simple, rapid and sensitive separation, preconcentration and speciation procedure for chromium in environmental liquid and solid samples has been established. The present speciation procedure for Cr(III) and Cr(VI) is based on combination of carrier element-free coprecipitation (CEFC) and flame atomic absorption spectrometric (FAAS) determinations. In this method a newly synthesized organic coprecipitant, 5-chloro-3-[4-(trifluoromethoxy) phenylimino]indolin-2-one (CFMEPI), was used without adding any carrier element for coprecipitation of chromium(III). After reduction of chromium(VI) by concentrated H 2 SO 4 and ethanol, the procedure was applied for the determination of total chromium. Chromium(VI) was calculated as the difference between the amount of total chromium and chromium(III). The optimum conditions for coprecipitation and speciation processes were investigated on several commonly tested experimental parameters, such as pH of the solution, amount of coprecipitant, sample volume, etc. No considerable interference was observed from the other investigated anions and cations, which may be found in natural water samples. The preconcentration factor was found to be 40. The detection limit for chromium(III) corresponding to three times the standard deviation of the blank (N = 10) was found 0.7 μg L -1 . The present procedure was successfully applied for speciation of chromium in several liquid and solid environmental samples. In order to support the accuracy of the method, the certified reference materials (CRM-TMDW-500 Drinking Water and CRM-SA-C Sandy Soil C) were analyzed, and standard APDC-MIBK liquid-liquid extraction method was performed. The results obtained were in good agreement with the certified values

Antagonizing STAT3 dimerization with a rhodium(III) complex.

Science.gov (United States)

Ma, Dik-Lung; Liu, Li-Juan; Leung, Ka-Ho; Chen, Yen-Ting; Zhong, Hai-Jing; Chan, Daniel Shiu-Hin; Wang, Hui-Min David; Leung, Chung-Hang

2014-08-25

Kinetically inert metal complexes have arisen as promising alternatives to existing platinum and ruthenium chemotherapeutics. Reported herein, to our knowledge, is the first example of a substitutionally inert, Group 9 organometallic compound as a direct inhibitor of signal transducer and activator of transcription 3 (STAT3) dimerization. From a series of cyclometalated rhodium(III) and iridium(III) complexes, a rhodium(III) complex emerged as a potent inhibitor of STAT3 that targeted the SH2 domain and inhibited STAT3 phosphorylation and dimerization. Significantly, the complex exhibited potent anti-tumor activities in an in vivo mouse xenograft model of melanoma. This study demonstrates that rhodium complexes may be developed as effective STAT3 inhibitors with potent anti-tumor activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Species dependent radiotracer study of Cr(VI) and Cr(III) using an aqueous biphasic system

Energy Technology Data Exchange (ETDEWEB)

Roy, K.; Lahiri, S. [Chemical Sciences Div., Saha Inst. of Nuclear Physics, Kolkata (India)

2008-07-01

The speciation study of Cr(III) and Cr(VI) was carried out using a polyethylene glycol (PEG) based aqueous biphasic extraction system (ABS). Neutron activated Cr(III) and Cr(VI) salts were assayed in a HPGe detector before and after employing aqueous biphasic extraction. Different salts of various salting out abilities were taken as the salt rich phase. The best condition for extraction of Cr(VI) and the maximum differential attitude of ABS to Cr(VI) and Cr(III) was observed when 2 M Na{sub 2}SO{sub 4} and PEG 4000 (50% w/w) solutions were used. Cr(III) can also be extracted by the PEG with prior complexation with diphenylthiocarbazone (dithizone). The chromium dithizonate complex is quantitatively extracted by the PEG rich phase. (orig.)

Analysis of gold(I/III)-complexes by HPLC-ICP-MS demonstrates gold(III) stability in surface waters.

Science.gov (United States)

Ta, Christine; Reith, Frank; Brugger, Joël; Pring, Allan; Lenehan, Claire E

2014-05-20

Understanding the form in which gold is transported in surface- and groundwaters underpins our understanding of gold dispersion and (bio)geochemical cycling. Yet, to date, there are no direct techniques capable of identifying the oxidation state and complexation of gold in natural waters. We present a reversed phase ion-pairing HPLC-ICP-MS method for the separation and determination of aqueous gold(III)-chloro-hydroxyl, gold(III)-bromo-hydroxyl, gold(I)-thiosulfate, and gold(I)-cyanide complexes. Detection limits for the gold species range from 0.05 to 0.30 μg L(-1). The [Au(CN)2](-) gold cyanide complex was detected in five of six waters from tailings and adjacent monitoring bores of working gold mines. Contrary to thermodynamic predictions, evidence was obtained for the existence of Au(III)-complexes in circumneutral, hypersaline waters of a natural lake overlying a gold deposit in Western Australia. This first direct evidence for the existence and stability of Au(III)-complexes in natural surface waters suggests that Au(III)-complexes may be important for the transport and biogeochemical cycling of gold in surface environments. Overall, these results show that near-μg L(-1) enrichments of Au in environmental waters result from metastable ligands (e.g., CN(-)) as well as kinetically controlled redox processes leading to the stability of highly soluble Au(III)-complexes.

Chromium fractionation and speciation in natural waters.

Science.gov (United States)

Pereira, Catarinie Diniz; Techy, João Gabriel; Ganzarolli, Edgard Moreira; Quináia, Sueli Pércio

2012-05-01

It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 μg L(-1). Cr(vi) was always below of the DL (0.3 μg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.

Kinetic Study of Iron (III) Salicyl Hydroxamate Complexes

International Nuclear Information System (INIS)

Ali, K.; Ashiq, U.; Ara, R.; Kazmi, R.

2005-01-01

The formation of Salicylhydroxamic acid iron (III) complexes were studied at different pH. The reaction at pH 8 and 6 between iron nitrate and salicylhydroxamic acid is very fast and reddish brown colour with iron at 425 nm appears within seconds i.e. within mixing time. The concentration of salicylhydroxamic acid was 20-80 times higher than the concentration of iron (III) solution in order to fulfill pseudo first order conditions. The reddish brown colour appears within mixing time and further change in colour was very slow and observed at 425 nm wave length. The rate constant at pH 8 is 0.1886 sec and at pH 6 is 1.472 sec. The sharp appearance of colour is due to formation of 1:1 and 1:2 complexes while the observed slow change in colour may be due to rearrangement of salicylhydroxamic acid from bidentate to tridentate or it may be due to the formation of 1:3 complex. In the next set of reactions the 1:1 complex of salicylhydroxamic acid iron (III) was prepared by mixing iron (III) and salicylhydroxamic acid in 1:1 mole ratio and then the formation of 1:2 complex was observed at pH 5, 4.5 and 4. The concentration of salicylhydroxamic acid solution was 2-10 times higher than the 1:1 complex of salicylhydroxamic acid iron (III) complex. The observed reactions were very fast and were not truly a first order reaction. The rate constant is 24.85 sec at pH 4.5 and 16.98 sec at pH4. The reaction of 1:1 complex with salicylhydroxamic acid at pH3 was very fast. The lamda max of iron complex is 500 nm and of final mixture is 476 nm. The reaction was assumed to be reversible. The absorbance of both species at a particular wavelength is additive. Using this property the equilibrium constant was calculated which was not constant at different ratios of 1:1 complex and salicylhydroxamic acid, which further indicate the possibility of rearrangement reaction. (author)

Chromium reduces the in vitro activity and fidelity of DNA replication mediated by the human cell DNA synthesome

International Nuclear Information System (INIS)

Dai Heqiao; Liu Jianying; Malkas, Linda H.; Catalano, Jennifer; Alagharu, Srilakshmi; Hickey, Robert J.

2009-01-01

Hexavalent chromium Cr(VI) is known to be a carcinogenic metal ion, with a complicated mechanism of action. It can be found within our environment in soil and water contaminated by manufacturing processes. Cr(VI) ion is readily taken up by cells, and is recognized to be both genotoxic and cytotoxic; following its reduction to the stable trivalent form of the ion, chromium(Cr(III)), within cells. This form of the ion is known to impede the activity of cellular DNA polymerase and polymerase-mediated DNA replication. Here, we report the effects of chromium on the activity and fidelity of the DNA replication process mediated by the human cell DNA synthesome. The DNA synthesome is a functional multiprotein complex that is fully competent to carry-out each phase of the DNA replication process. The IC 50 of Cr(III) toward the activity of DNA synthesome-associated DNA polymerases α, δ and ε is 15, 45 and 125 μM, respectively. Cr(III) inhibits synthesome-mediated DNA synthesis (IC 50 = 88 μM), and significantly reduces the fidelity of synthesome-mediated DNA replication. The mutation frequency induced by the different concentrations of Cr(III) ion used in our assays ranges from 2-13 fold higher than that which occurs spontaneously, and the types of mutations include single nucleotide substitutions, insertions, and deletions. Single nucleotide substitutions are the predominant type of mutation, and they occur primarily at GC base-pairs. Cr(III) ion produces a lower number of transition and a higher number of transversion mutations than occur spontaneously. Unlike Cr(III), Cr(VI) ion has little effect on the in vitro DNA synthetic activity and fidelity of the DNA synthesome, but does significantly inhibit DNA synthesis in intact cells. Cell growth and proliferation is also arrested by increasing concentrations of Cr(VI) ion. Our studies provide evidence indicating that the chromium ion induced decrease in the fidelity and activity of synthesome mediated DNA replication

Surfactant-assisted emulsification dispersive liquid-liquid microextraction using 2-thenoyltrifluoroacetone as a chelating agent coupled with electrothermal atomic absorption spectrometry for the speciation of chromium in water and rice samples.

Science.gov (United States)

Dokpikul, Nattawut; Chaiyasith, Wipharat Chuachuad; Sananmuang, Ratana; Ampiah-Bonney, Richmond J

2018-04-25

A novel method was developed by SAE-DLLME for chromium speciation in water and rice samples using 2-thenoyltrifluoroacetone (TTA) as a chelating reagent by ETAAS. The speciation of Cr(III) and Cr(VI) was achieved by complexation of Cr(III)-TTA and the total Cr was measured after reduction of Cr(VI) to Cr. The calibration graph was linear in the range of 0.02-2.50 µg L -1 , with a detection limit of 0.0052 µg L -1 . The %RSD was in range of 2.90-3.30% at 0.5, 1.5 and 2.5 µg L -1 of Cr(III), n = 5 and the EF was 54.47. The method was applied to chromium speciation and total chromium determination in real samples and gave recoveries in the range of 96.2-103.5% and 97.1-102.7% for Cr(III) and Cr(VI) in water samples and 93.7-103.5% of total Cr in rice samples. The accuracy of the method was evaluated by analysis of SRM 1573a with good agreement compared to the certified value. Copyright © 2017 Elsevier Ltd. All rights reserved.

Aqueous phase complexation of Cm(III) and Cf(III) with ionizable macrocyclic ligands

International Nuclear Information System (INIS)

Manchanda, V.K.; Mohapatra, P.K.

1995-01-01

Complexation behaviour of Cm(III) and Cf(III) with 1,7-diaza-4,10,13-trioxacyclopentadecane-N,N'-diacetic acid (K21DA), 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid (K22DA) and ethylene diamine N,N'- diacetic acid (EDDA) has been investigated using dinonyl naphthalene sulphonic acid (DNNS), in tetramethyl ammonium form as liquid cation exchanger. The aqueous phase complex formation constants are computed from the distribution data. Though larger complex formation constants are observed with K21DA as well as K22DA compared to those with the acyclic analog EDDA, no size correlation is observed. (author). 5 refs., 1 tab

Chromium uptake by Saccharomyces cerevisiae and isolation of ...

Indian Academy of Sciences (India)

Unknown

In most models two nicotinate ligands are ... However, both biological extracts and synthetic GTF models have ..... chromium (III)-β-nicotinamide adenine dinucleotide phos- ... and free fatty acids levels in diabetic rats; J. Inorg. Biochem.

Alkali metal cation complexation and solvent interactions by robust chromium(III) fluoride complexes

DEFF Research Database (Denmark)

Birk, T.; Magnussen, M.J.; Piligkos, Stergios

2010-01-01

)] have been synthesized from mer-[CrF3(py)(3)] and shown to precipitate sodium salts from solution, of which 3[CrF3(Me(3-)tacn)]center dot 2Na(Bph(4)).solv and 6[CrF3(terpy)]center dot 4Na(Bph(4)).solv have been crystallographically characterized. In these clusters, the neutral fluoride complexes bring...

Dramatic improvement in photostability of luminescent Eu(III) complexes with tetraphenylimidodiphosphinate ligand

International Nuclear Information System (INIS)

Zheng, Wei; Li, Shu-Jing; Li, Cheng-Hui; Zheng, You-Xuan; You, Xiao-Zeng

2014-01-01

In this paper, we synthesized and characterized a new Eu(III) tetraphenylimidodiphosphinate complex with dimethyl sulfoxide (DMSO) as co-ligand. Moreover, we compared the photostability of a series of Eu(III) complexes containing tetraphenylimidodiphosphinate ligands, Eu(tpip) 3 , Eu(tpip) 3 Phen, Eu(tpip) 3 DMSO, with their analogs of 1,3-dibenzoylmethanate, Eu(dbm) 3 ∙2H 2 O, Eu(dbm) 3 Phen, Eu(dbm) 3 (DMSO) 2 . We found that the photostability of the luminescent Eu(III) complexes was significantly improved upon substitution of the 1,3-diketones with tetraphenylimidodiphosphinate ligands. -- Highlights: • We synthesized and characterized a new Eu(III) tetraphenylimidodiphosphinate complexes with dimethyl sulfoxide. • We compared the photostability of Eu(III) complex with tetraphenylimidodiphosphinate and 1,3-dibenzoylmethanate ligands. • The photostability is significantly improved in Eu(III) complexes with tetraphenylimidodiphosphinate ligands

Spectroscopic and thermodynamic study of the complexation of Cm(III) and Eu(III) with hydrophilic bis-triazinyl pyridines

International Nuclear Information System (INIS)

Ruff, Christian

2013-01-01

In the present work the complexation of Cm(III) and Eu(III) with a hydrophilic 2,6-bis-(1,2,4-triazinyl)-pyridine (aq-BTP) is studied. Aq-BTP complexes actinides(III) selectively over lanthanides(III) in nitric acid solution. The object of this work is the identification and the spectroscopic and thermodynamic characterization of the Cm(III) and Eu(III) complex species present in solution. The results should contribute to a better fundamental understanding of the driving force behind BTPs selectivity towards trivalent actinides on a molecular level. Time-resolved laser fluorescence spectroscopy (TRLFS), luminescence and UV/Vis spectroscopy are applied. Information on the structure of M(III)-aq-BTP complex species is obtained from density functional theory. Three different M(III) complex species containing one, two or three aq-BTP ligands are identified in H 2 O at pH 3.0. Relative fluorescence intensity factors are determined for each of the [M(aq-BTP) n ] complexes (M = Cm(III)/Eu(III), n = 1 - 3). These factors are required to quantify the complexes. The stability constant logβ 3 of the [Cm(aq-BTP) 3 ] complex (which is the one relevant to extraction processes) is two orders of magnitude higher than that of the corresponding Eu(III) complex. This difference is in agreement with the separation factor (SF Am(III)/Eu(III) = 150) determined experimentally by liquid-liquid extraction. The difference in the stability constants originates from the different reaction enthalpies for the formation of the [M(aq-BTP) 3 ] complexes. These results represent the thermodynamic driving force for the aq-BTPs selectivity towards trivalent actinides over lanthanides. Comparing the stability constants of the [M(aq-BTP) n ] species (M = Cm(III)/Eu(III), n = 1 - 3) shows an increasing selectivity with increasing number of coordinated aq-BTP ligands. Hence, high selectivity is achieved if the f-element ions are fully coordinated by nine N-donor atoms (three aq-BTP ligands). A less

On-line preconcentration and determination of chromium in parenteral solutions by inductively coupled plasma optical emission spectrometry

International Nuclear Information System (INIS)

Gil, R.A.; Cerutti, S.; Gasquez, J.A.; Olsina, R.A.; Martinez, L.D.

2005-01-01

A method for the preconcentration and speciation of chromium was developed. On-line preconcentration and determination were obtained using inductively coupled plasma optical emission spectrometry (ICP-OES) coupled with flow injection. To determinate the chromium (III) present in parenteral solutions, chromium was retained on activated carbon at pH 5.0. On the other hand, a step of reduction was necessary in order to determine total chromium content. The Cr(VI) concentration was then determined by difference between the total chromium concentration and that of Cr(III). A sensitivity enrichment factor of 70-fold was obtained with respect to the chromium determination by ICP-OES without preconcentration. The detection limit for the preconcentration of 25 ml of sample was 29 ng l -1 . The precision for the 10 replicate determinations at the 5 μg l -1 Cr level was 2.3% relative standard deviation, calculated with the peak heights. The calibration graph using the preconcentration method for chromium species was linear with a correlation coefficient of 0.9995 at levels near the detection limits up to at least 60 μg l -1 . The method can be applied to the determination and speciation of chromium in parenteral solutions

Adsorption of hexavalent chromium by graphite–chitosan binary ...

Indian Academy of Sciences (India)

Hexavalent chromium; graphite–chitosan composite; adsorption kinetics. 1. Introduction ... [2], while Cr(III) is less toxicity and relatively innocuous. Cr(VI) generates in ..... Human Environments (New York: Wiley Inter-Science) p 3. [4] U.S. EPA ...

A comparative study of sorption of chromium (III) onto chitin and chitosan

Science.gov (United States)

Singh, Pooja; Nagendran, R.

2016-06-01

Heavy metals have always been the most hazardous components in the wastewater of industries like electroplating, automobiles, mining facilities and fertilizer manufacturers. Treatment of heavy metal laden wastewater requires expensive operational and maintenance systems. Food processing industries create a huge amount of shell waste which is sold to poultry farms in powdered form but the quantity thus used is still not comparable to the left over waste. The shell contains chitin which acts as an adsorbent for the heavy metals and can be used to treat heavy metal wastewater. The paper presents a study on the use of chitin and its processed product, chitosan, to remove chromium. Shake flask experiment was conducted to compare the adsorptive capacity of chitin and chitosan for chromium removal from simulated solution and isotherm studies were carried out. The studies showed that the chitosan was a better adsorbent than chitin. Both chitin and chitosan gave best adsorption results at pH 3. Chitin exhibited maximum chromium removal of 49.98 % in 20 min, whereas chitosan showed 50 % removal efficiency at a contact time of 20 min showing higher adsorptive capacity for chromium than chitin. The Langmiur and Freundlich isotherm studies showed very good adsorption capacity and monolayer interaction according to the regression coefficient 0.973 for chitosan and 0.915 for chitin. The regression coefficient for Freundlich isotherm was 0.894 and 0.831 for chitosan and chitin, respectively.

Factors Affecting the Adsorption of Trivalent Chromium Ions by Activated Carbon Prepared from Waste Rubber Tyres

Directory of Open Access Journals (Sweden)

Sylvia E. Benjamin

2017-08-01

Full Text Available Economic gains are generally the outcome of industrialization and consequently urbanization. However, positive fiscal index generates a negative impact on natural environment sources heaving pollutant burden on soil, air and water. Industries throw tones of contaminated water into soil and water bodies without proper treatment and create a potential threat for both living and non-living species. Chromium in trivalent state (Cr3+ is added in water bodies and soil through waste water from tanneries, cooling water systems, chemical and pulp and paper industries. The present research work aims at the preparation of an inexpensive activated carbon prepared from non- degradable waste scrap rubber tyres. The carbon produced from scrap rubber tyres was activated by 5% solution of BaCl2 and 0.4 N solution of HCl and verified by ethylene blue solution. The adsorption capacity of the Tyre activated carbon (TAC was investigated for different parameters i.e., initial chromium (III ion concentration, activated carbon dosage, contact/ stirring time and pH. The adsorption capacity of TAC depends on the initial metal ion concentration and the TAC dose. pH of the chromium solution effects the adsorption capacity of TAC due to the formation of tetra hydroxochromate(III complexes,. The results show that TAC offers a cost effective reclamation process for the removal of Cr3+ from effluent waters.

Intracellular chromium localization and cell physiological response in the unicellular alga Micrasterias

Science.gov (United States)

Volland, Stefanie; Lütz, Cornelius; Michalke, Bernhard; Lütz-Meindl, Ursula

2012-01-01

Various contaminants like metals and heavy metals are constantly released into the environment by anthropogenic activities. The heavy metal chromium has a wide industrial use and exists in two stable oxidation states: trivalent and hexavalent. Chromium can cause harm to cell metabolism and development, when it is taken up by plants instead of necessary micronutrients such as for example iron. The uptake of Cr VI into plant cells has been reported to be an active process via carriers of essential anions, while the cation Cr III seems to be taken up inactively. Micrasterias denticulata, an unicellular green alga of the family Desmidiaceae is a well-studied cell biological model organism. Cr III and VI had inhibiting effects on its cell development, while cell division rates were only impaired by Cr VI. Transmission electron microscopy (TEM) revealed ultrastructural changes such as increased vacuolization, condensed cytoplasm and dark precipitations in the cell wall after 3 weeks of Cr VI treatment. Electron energy loss spectroscopy (EELS) and electron spectroscopic imaging (ESI) were applied to measure intracellular chromium distribution. Chromium was only detected after 3 weeks of 10 μM Cr VI treatment in electron dense precipitations found in bag-like structures along the inner side of the cell walls together with iron and elevated levels of oxygen, pointing toward an accumulation respectively extrusion of chromium in form of an iron–oxygen compound. Atomic emission spectroscopy (EMS) revealed that Micrasterias cells are able to accumulate considerable amounts of chromium and iron. During chromium treatment the Cr:Fe ratio shifted in favor of chromium, which implied that chromium may be taken up instead of iron. Significant and rapid increase of ROS production within the first 5 min of treatment confirms an active Cr VI uptake. SOD and CAT activity after Cr VI treatment did not show a response, while the glutathione pool determined by immuno-TEM decreased

Intracellular chromium localization and cell physiological response in the unicellular alga Micrasterias

Energy Technology Data Exchange (ETDEWEB)

Volland, Stefanie, E-mail: Stefanie.Volland@stud.sbg.ac.at [Plant Physiology Division, Cell Biology Department, University of Salzburg, Hellbrunnerstr 34, 5020 Salzburg (Austria); Luetz, Cornelius, E-mail: cornelius.luetz@uibk.ac.at [Institute of Botany, University of Innsbruck, Sternwartestrasse 15, 6020 Innsbruck (Austria); Michalke, Bernhard, E-mail: bernhard.michalke@helmholtz-muenchen.de [Helmholtz Zentrum Muenchen, German Research Centre for Environmental Health, Institute of Ecological Chemistry, Ingolstaedter Landstrasse 1, 85764 Neuherberg (Germany); Luetz-Meindl, Ursula, E-mail: ursula.luetz-meindl@sbg.ac.at [Plant Physiology Division, Cell Biology Department, University of Salzburg, Hellbrunnerstr 34, 5020 Salzburg (Austria)

2012-03-15

Various contaminants like metals and heavy metals are constantly released into the environment by anthropogenic activities. The heavy metal chromium has a wide industrial use and exists in two stable oxidation states: trivalent and hexavalent. Chromium can cause harm to cell metabolism and development, when it is taken up by plants instead of necessary micronutrients such as for example iron. The uptake of Cr VI into plant cells has been reported to be an active process via carriers of essential anions, while the cation Cr III seems to be taken up inactively. Micrasterias denticulata, an unicellular green alga of the family Desmidiaceae is a well-studied cell biological model organism. Cr III and VI had inhibiting effects on its cell development, while cell division rates were only impaired by Cr VI. Transmission electron microscopy (TEM) revealed ultrastructural changes such as increased vacuolization, condensed cytoplasm and dark precipitations in the cell wall after 3 weeks of Cr VI treatment. Electron energy loss spectroscopy (EELS) and electron spectroscopic imaging (ESI) were applied to measure intracellular chromium distribution. Chromium was only detected after 3 weeks of 10 {mu}M Cr VI treatment in electron dense precipitations found in bag-like structures along the inner side of the cell walls together with iron and elevated levels of oxygen, pointing toward an accumulation respectively extrusion of chromium in form of an iron-oxygen compound. Atomic emission spectroscopy (EMS) revealed that Micrasterias cells are able to accumulate considerable amounts of chromium and iron. During chromium treatment the Cr:Fe ratio shifted in favor of chromium, which implied that chromium may be taken up instead of iron. Significant and rapid increase of ROS production within the first 5 min of treatment confirms an active Cr VI uptake. SOD and CAT activity after Cr VI treatment did not show a response, while the glutathione pool determined by immuno-TEM decreased

Intracellular chromium localization and cell physiological response in the unicellular alga Micrasterias

International Nuclear Information System (INIS)

Volland, Stefanie; Lütz, Cornelius; Michalke, Bernhard; Lütz-Meindl, Ursula

2012-01-01

Various contaminants like metals and heavy metals are constantly released into the environment by anthropogenic activities. The heavy metal chromium has a wide industrial use and exists in two stable oxidation states: trivalent and hexavalent. Chromium can cause harm to cell metabolism and development, when it is taken up by plants instead of necessary micronutrients such as for example iron. The uptake of Cr VI into plant cells has been reported to be an active process via carriers of essential anions, while the cation Cr III seems to be taken up inactively. Micrasterias denticulata, an unicellular green alga of the family Desmidiaceae is a well-studied cell biological model organism. Cr III and VI had inhibiting effects on its cell development, while cell division rates were only impaired by Cr VI. Transmission electron microscopy (TEM) revealed ultrastructural changes such as increased vacuolization, condensed cytoplasm and dark precipitations in the cell wall after 3 weeks of Cr VI treatment. Electron energy loss spectroscopy (EELS) and electron spectroscopic imaging (ESI) were applied to measure intracellular chromium distribution. Chromium was only detected after 3 weeks of 10 μM Cr VI treatment in electron dense precipitations found in bag-like structures along the inner side of the cell walls together with iron and elevated levels of oxygen, pointing toward an accumulation respectively extrusion of chromium in form of an iron–oxygen compound. Atomic emission spectroscopy (EMS) revealed that Micrasterias cells are able to accumulate considerable amounts of chromium and iron. During chromium treatment the Cr:Fe ratio shifted in favor of chromium, which implied that chromium may be taken up instead of iron. Significant and rapid increase of ROS production within the first 5 min of treatment confirms an active Cr VI uptake. SOD and CAT activity after Cr VI treatment did not show a response, while the glutathione pool determined by immuno-TEM decreased

Development of a C3-symmetric benzohydroxamate tripod: Trimetallic complexation with Fe(III), Cr(III) and Al(III)

Science.gov (United States)

Baral, Minati; Gupta, Amit; Kanungo, B. K.

2016-06-01

The design, synthesis and physicochemical characterization of a C3-symmetry Benzene-1,3,5-tricarbonylhydroxamate tripod, noted here as BTHA, are described. The chelator was built from a benzene as an anchor, symmetrically extended by three hydroxamate as ligating moieties, each bearing O, O donor sites. A combination of absorption spectrophotometry, potentiometry and theoretical investigations are used to explore the complexation behavior of the ligand with some trivalent metal ions: Fe(III), Cr(III), and Al(III). Three protonation constants were calculated for the ligand in a pH range of 2-11 in a highly aqueous medium (9:1 H2O: DMSO). A high rigidity in the molecular structure restricts the formation of 1:1 (M/L) metal encapsulation but shows a high binding efficiency for a 3:1 metal ligand stoichiometry giving formation constant (in β unit) 28.73, 26.13 and 19.69 for [M3L]; Mdbnd Fe(III), Al(III) and Cr(III) respectively, and may be considered as an efficient Fe-carrier. The spectrophotometric study reveals of interesting electronic transitions occurred during the complexation. BTHA exhibits a peak at 238 nm in acidic pH and with the increase of pH, a new peak appeared at 270 nm. A substantial shifting in both of the peaks in presence of the metal ions implicates a s coordination between ligand and metal ions. Moreover, complexation of BTHA with iron shows three distinct colors, violet, reddish orange and yellow in different pH, enables the ligand to be considered for the use as colorimetric sensor.

Genetics Home Reference: mitochondrial complex III deficiency

Science.gov (United States)

... the energy from food into a form that cells can use. Complex III is one of several complexes that ... in mtDNA. Because egg cells, but not sperm cells, contribute mitochondria to the ... from their mother. These disorders can appear in every generation of ...

EPR investigation of the trivalent chromium complexes in SrTiO.sub.3./sub..

Czech Academy of Sciences Publication Activity Database

Azamat, Dmitry; Dejneka, Alexandr; Lančok, Ján; Jastrabík, Lubomír; Trepakov, Vladimír; Bryknar, Z.; Neverova, E.V.; Badalyan, A. G.

2014-01-01

Roč. 75, č. 2 (2014), s. 271-275 ISSN 0022-3697 R&D Projects: GA MŠk(CZ) LM2011029; GA TA ČR TA01010517; GA ČR GAP108/12/1941 Grant - others:SAFMAT(XE) CZ.2.16/3.1.00/22132 Institutional support: RVO:68378271 Keywords : electron paramagnetic resonance (EPR) * SrTiO 3 * chromium complexes Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.853, year: 2014

Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: A review.

Science.gov (United States)

Shahid, Muhammad; Shamshad, Saliha; Rafiq, Marina; Khalid, Sana; Bibi, Irshad; Niazi, Nabeel Khan; Dumat, Camille; Rashid, Muhammad Imtiaz

2017-07-01

Chromium (Cr) is a potentially toxic heavy metal which does not have any essential metabolic function in plants. Various past and recent studies highlight the biogeochemistry of Cr in the soil-plant system. This review traces a plausible link among Cr speciation, bioavailability, phytouptake, phytotoxicity and detoxification based on available data, especially published from 2010 to 2016. Chromium occurs in different chemical forms (primarily as chromite (Cr(III)) and chromate (Cr(VI)) in soil which vary markedly in term of their biogeochemical behavior. Chromium behavior in soil, its soil-plant transfer and accumulation in different plant parts vary with its chemical form, plant type and soil physico-chemical properties. Soil microbial community plays a key role in governing Cr speciation and behavior in soil. Chromium does not have any specific transporter for its uptake by plants and it primarily enters the plants through specific and non-specific channels of essential ions. Chromium accumulates predominantly in plant root tissues with very limited translocation to shoots. Inside plants, Cr provokes numerous deleterious effects to several physiological, morphological, and biochemical processes. Chromium induces phytotoxicity by interfering plant growth, nutrient uptake and photosynthesis, inducing enhanced generation of reactive oxygen species, causing lipid peroxidation and altering the antioxidant activities. Plants tolerate Cr toxicity via various defense mechanisms such as complexation by organic ligands, compartmentation into the vacuole, and scavenging ROS via antioxidative enzymes. Consumption of Cr-contaminated-food can cause human health risks by inducing severe clinical conditions. Therefore, there is a dire need to monitor biogeochemical behavior of Cr in soil-plant system. Copyright © 2017 Elsevier Ltd. All rights reserved.

Study of Stoichiometry and Stability of some Fe(III)-Amino Acid Complexes

International Nuclear Information System (INIS)

Latif, S.; Shirin, K.; Nisar, S.; Zahida, T. M.

2005-01-01

The complexation of ferric with three amino acids (Glycine, Glutamic acid and Aspartic acid) was studied spectrophotometrically and potentiometrically at pH 5.0 and in aqueous medium. The stoichiometry was calculated spectrophotometrically using mole ratio method and is found to be ML3 for Fe (III)-Glycine and ML2 for Fe (III)-Glutamate for Fe (III)-Glutamate and Aspartate complex. The stabilities of these complexes were calculated spectrophotometrically and potentiometrically. The experimental results of potentiometric titrations were treated by well known computer program B EST . The values were further refined till least sigma fit i.e. 0.03. The complexes were not formed under normal conditions. Each complex was studied at more than one wavelength and no kmax was obtained because Fe (III) solution and the complexes absorb in similar wavelength region. The formation constants of all these complexes are not very high shows weak complexation of Fe (III) with these amino acids. (author)

Voltammetric method to determine chromium (III) in potable water at level of ultra plans

International Nuclear Information System (INIS)

Jimenez B, Irene; Alvarado G, Ana L.

2004-01-01

It was established an analytical methodology to determine Cr (III) in drinking water using a voltammetric technique of Differential Pulse Cathodic Stripping Voltammetry with an Adsorptive Preconcentration of a complex Cr(III)-diethiltriaminpentaceticacid (Cr-DTPA) in a mercury drop. A dissolution of sodium nitrate was used as a supporting electrolyte. The optimized voltammetric parameters were: adsorption time, scan rate, absorption potential, p H, complex agent and sodium nitrate concentration. The linear range of the methodology is between 20 ng/L and 60 ng/L and the detection and quantification limits are 13 ng/L and 20 ng/L respectively. (Author) [es

Cobalt (III) complexes as novel matrix metalloproteinase-9 inhibitors

International Nuclear Information System (INIS)

Lee, Jiyoun

2012-01-01

We have synthesized a series of novel MMP-9 inhibitors containing cobalt(III) complexes. The synthesized cobalt(III) complexes are effective as enzyme inhibitors and the attachment of a biphenyl group enhanced the efficiency of enzyme inhibition up to 6-fold. When compared to the reported non-hydroxamate MMP inhibitors, the synthesized complexes showed comparable in vitro potency. The enzyme assay showed that the cobalt(III) complex can disrupt the zinc binding active site of MMP-9 and is proposed to work via a ligand exchange mechanism. Since histidine residues are essential for the catalytic activity of a large percentage of enzymes and zinc finger proteins, these cobalt(III) complexes can serve as a prototype inhibitor towards various zinc containing enzymes and proteins. Matrix metalloproteinases (MMPs) are a family of zinc binding endopeptidases that play crucial roles in various physiological processes and diseases such as embryogenic growth, angiogenesis, arthritis, skin ulceration, liver fibrosis and tumor metastasis. Because of their implications in a wide range of diseases, MMPs are considered as intriguing drug targets. The majority of MMP inhibitors are organic small molecules containing a hydroxamate functionality for the zinc binding group. This hydroxamate group binds to a zinc(II) center in a bidentate fashion and creates a distorted trigonal bipyramidal geometry

Cobalt (III) complexes as novel matrix metalloproteinase-9 inhibitors

Energy Technology Data Exchange (ETDEWEB)

Lee, Jiyoun [Sungshin Women' s Univ., Seoul (Korea, Republic of)

2012-04-15

We have synthesized a series of novel MMP-9 inhibitors containing cobalt(III) complexes. The synthesized cobalt(III) complexes are effective as enzyme inhibitors and the attachment of a biphenyl group enhanced the efficiency of enzyme inhibition up to 6-fold. When compared to the reported non-hydroxamate MMP inhibitors, the synthesized complexes showed comparable in vitro potency. The enzyme assay showed that the cobalt(III) complex can disrupt the zinc binding active site of MMP-9 and is proposed to work via a ligand exchange mechanism. Since histidine residues are essential for the catalytic activity of a large percentage of enzymes and zinc finger proteins, these cobalt(III) complexes can serve as a prototype inhibitor towards various zinc containing enzymes and proteins. Matrix metalloproteinases (MMPs) are a family of zinc binding endopeptidases that play crucial roles in various physiological processes and diseases such as embryogenic growth, angiogenesis, arthritis, skin ulceration, liver fibrosis and tumor metastasis. Because of their implications in a wide range of diseases, MMPs are considered as intriguing drug targets. The majority of MMP inhibitors are organic small molecules containing a hydroxamate functionality for the zinc binding group. This hydroxamate group binds to a zinc(II) center in a bidentate fashion and creates a distorted trigonal bipyramidal geometry.

Phosphate Suspension Chromium (III) radiolabelled with 32P and 90Y

International Nuclear Information System (INIS)

Cruz Arencibia, Jorge; Turiño Pérez, David; Cruz Morales, Amed; Morín Zorrilla, José; Taylor Delgado, Tamara; García Rodríguez, Enrique; Baganet Cobas, Aymara

2016-01-01

Chronic synovitis is a manifestation common joint of rheumatoid arthritis, hemophilia and other systemic diseases. The modalities of treatment of this complication radiosynoviorthesis stands out for its good response, ease of implementation and lower total cost. In the United States, Europe and some countries in Latin America they are used to this different radioactive colloids and suspensions. In Cuba it was developed and is approved suspension Chromic Phosphate 32 P-labeled. At work the consistency of the production process of this suspension is examined. As a result of the evaluation was found that the suspension is characterized by a radiochemical purity of 94 ± 1% and particle size predominantly of 91 ± 3 between 0.2-10 microns. The results achieved in regular production and application to patients with rheumatic diseases and hemophiliacs, with follow-up to one year prove their efficacy and safety, the latter associated with low leakage articular detected and the absence of adverse reactions. Also at work the results achieved in the development of a technology for the production of suspension Phosphate Chromium (III) labeled with 90 Y, similarly to existing 32 P composition is exposed, and properties even more favorable, in particular radiochemical purity of 97%, favoring the registration of a radiopharmaceutical with better technical and economic characteristics, which must ensures the use of this form of treatment in the country. (author)

Formation constants of Sm(III), Dy(III), Gd(III), Pr(III) and Nd(III) complexes of tridentate schiff base, 2-[(1H-benzimidazol-2-yl-methylene) amino] phenol

International Nuclear Information System (INIS)

Omprakash, K.L.; Chandra Pal, A.V.; Reddy, M.L.N.

1982-01-01

A new tridentate schiff base, 2- (1H-benzimidazol-2-yl-methylene)amino phenol derived from benzimididazole-2-carbo-xaldehyde and 2-aminophenol has been synthesised and characterised by spectral and analytical data. Proton-ligand formation constants of the schiff base and metal-ligand formation constants of its complexes with Sm(III), Dy(III), Gd(III), Nd(III) and Pr(III) have been determined potentiometrically in 50% (v/v) aqueous dioxane at an ionic strength of 0.1M (NaClO 4 ) and at 25deg C using the Irving-Rossotti titration technique. The order of stability constants (logβ 2 ) is found to be Sm(III)>Dy(III)>Gd(III)>Pr(III)>Nd(III). (author)

Formation constants of Sm(III), Dy(III), Gd(III), Pr(III) and Nd(III) complexes of tridentate schiff base, 2-((1H-benzimidazol-2-yl-methylene) amino) phenol

Energy Technology Data Exchange (ETDEWEB)

Omprakash, K L; Chandra Pal, A V; Reddy, M L.N. [Osmania Univ., Hyderabad (India). Dept. of Chemistry

1982-03-01

A new tridentate schiff base, 2- (1H-benzimidazol-2-yl-methylene)amino phenol derived from benzimididazole-2-carbo-xaldehyde and 2-aminophenol has been synthesised and characterised by spectral and analytical data. Proton-ligand formation constants of the schiff base and metal-ligand formation constants of its complexes with Sm(III), Dy(III), Gd(III), Nd(III) and Pr(III) have been determined potentiometrically in 50% (v/v) aqueous dioxane at an ionic strength of 0.1M (NaClO/sub 4/) and at 25deg C using the Irving-Rossotti titration technique. The order of stability constants (log..beta../sub 2/) is found to be Sm(III)>Dy(III)>Gd(III)>Pr(III)>Nd(III).

Synthesis of yellow fluorescent carbon dots and their application to the determination of chromium(III) with selectivity improved by pH tuning

International Nuclear Information System (INIS)

Chang, Melissa May Fung; Ginjom, Irine Runnie; Ng, Sing Muk; Ngu-Schwemlein, Maria

2016-01-01

Carbon dots with yellow fluorescence (y-CDs) were synthesized from sucrose by acid carbonization with phosphoric acid as the dehydrating agent. Optimal yield was obtained by heating sucrose in concentrated phosphoric acid to 85 °C for 30 min. The resulting y-CDs under the photo-excitation at 360 nm display an emission band peaking at 560 nm. The fluorescence is independent of pH values in the range from pH 4.0 to 11.4, and at ionic strengths of up to 4.7 M of potassium chloride. We also show that these y-CDs are viable fluorescent probes for the detection of chromium(III). At near neutral pH conditions, several metal ions quench the emission of the y-CDs, but under acidic conditions (pH 4), fluorescence is strongly affected by Cr(III) only. Quenching depends on the concentration of Cr(III) in the range up to 200 μM, and the limit of detection is 24.6 μM. (author)

Potentiometric studies on some ternary complexes of Nd(III), Sm(III), Gd(III) and Ho(III) with cyclohexanediaminetetraacetic acid as primary ligand

International Nuclear Information System (INIS)

Marathe, D.G.; Munshi, K.N.

1983-01-01

The formation constants of the ternary complexes of neodymium(III), samarium(III), gadlonium(III) and holmium(III) with cyclohexanediaminetetraacetic acid (CyDTA) as primary ligand and dihydroxynaphthalene (DHN), dihydroxynaphthalene-6-sulphonic acid (DHNSA) and cateechol-3,5-disulphonic acid (CDSA) as secondary ligands have been investigated by potentiometric titration technique. The secondary ligands have been investigated by potentiometric titration technique. The values of formation constants of 1:1:1 ternary chelates are reported at three different temperatures, and at a fixed ionic strength, μ = 0.1 M (NaClO 4 ). (author)

Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

International Nuclear Information System (INIS)

Fendorf, Scott; Francis, Chris; Jardine, Phil; Benner, Shawn

2009-01-01

In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - affecting both Cr and U

Lanthanoplatins: emissive Eu(iii) and Tb(iii) complexes staining nucleoli targeted through Pt-DNA crosslinking.

Science.gov (United States)

Singh, Khushbu; Singh, Swati; Srivastava, Payal; Sivakumar, Sri; Patra, Ashis K

2017-06-01

Two highly luminescent water-soluble heterometallic LnPt 2 complexes, [{cis-PtCl(NH 3 ) 2 } 2 Ln(L)(H 2 O)](NO 3 ) 2 (Ln = Eu (1), Tb (2)), have been designed for their selective nucleoli staining through formation of Pt-DNA crosslinks. The complexes showed significant cellular uptake and distinctive nucleoli localization through intrinsic emission from Eu III or Tb III observed through confocal fluorescence microscopy.

Speciation of chromium using chronoamperometric biosensors based on screen-printed electrodes

International Nuclear Information System (INIS)

Calvo-Pérez, Ana; Domínguez-Renedo, Olga; Alonso-Lomillo, MAsunción; Arcos-Martínez, MJulia

2014-01-01

Highlights: • Chronoamperometric determination of Cr(III) on tyrosinase based biosensors using SPCEs. • Chronoamperometric determination of Cr(VI) on GOx based biosensors using SPCEs. • High degree of sensitivity and selectivity in the analysis of both chromium species. • Bipotentiostatic chronoamperometric determination of both chromium species in the same sample. - Abstract: Chronoamperometric assays based on tyrosinase and glucose oxidase (GOx) inactivation have been developed for the monitoring of Cr(III) and Cr(VI). Tyrosinase was immobilized by crosslinking on screen-printed carbon electrodes (SPCEs) containing tetrathiafulvalene (TTF) as electron transfer mediator. The tyrosinase/SPC TTF E response to pyrocatechol is inhibited by Cr(III). This process, that is not affected by Cr(VI), allows the determination of Cr(III) with a capability of detection of 2.0 ± 0.2 μM and a reproducibility of 5.5%. GOx modified screen-printed carbon platinised electrodes (SPC Pt Es) were developed for the selective determination of Cr(VI) using ferricyanide as redox mediator. The biosensor was able to discriminate two different oxidation states of chromium being able to reject Cr(III) and to detect the toxic species Cr(VI). Chronoamperometric response of the biosensor towards glucose decreases with the presence of Cr(VI), with a capability of detection of 90.5 ± 7.6 nM and a reproducibility of 6.2%. A bipotentiostatic chronoamperometric biosensor was finally developed using a tyrosinase/SPC TTF E and a GOx/SPC Pt E connected in array mode for the simultaneous determination of Cr(III) and Cr(VI) in spiked tap water and in waste water from a tannery factory samples

Speciation of chromium using chronoamperometric biosensors based on screen-printed electrodes

Energy Technology Data Exchange (ETDEWEB)

Calvo-Pérez, Ana, E-mail: anacp@ubu.es; Domínguez-Renedo, Olga, E-mail: olgado@ubu.es; Alonso-Lomillo, MAsunción, E-mail: malomillo@ubu.es; Arcos-Martínez, MJulia, E-mail: jarcos@ubu.es

2014-06-23

Highlights: • Chronoamperometric determination of Cr(III) on tyrosinase based biosensors using SPCEs. • Chronoamperometric determination of Cr(VI) on GOx based biosensors using SPCEs. • High degree of sensitivity and selectivity in the analysis of both chromium species. • Bipotentiostatic chronoamperometric determination of both chromium species in the same sample. - Abstract: Chronoamperometric assays based on tyrosinase and glucose oxidase (GOx) inactivation have been developed for the monitoring of Cr(III) and Cr(VI). Tyrosinase was immobilized by crosslinking on screen-printed carbon electrodes (SPCEs) containing tetrathiafulvalene (TTF) as electron transfer mediator. The tyrosinase/SPC{sub TTF}E response to pyrocatechol is inhibited by Cr(III). This process, that is not affected by Cr(VI), allows the determination of Cr(III) with a capability of detection of 2.0 ± 0.2 μM and a reproducibility of 5.5%. GOx modified screen-printed carbon platinised electrodes (SPC{sub Pt}Es) were developed for the selective determination of Cr(VI) using ferricyanide as redox mediator. The biosensor was able to discriminate two different oxidation states of chromium being able to reject Cr(III) and to detect the toxic species Cr(VI). Chronoamperometric response of the biosensor towards glucose decreases with the presence of Cr(VI), with a capability of detection of 90.5 ± 7.6 nM and a reproducibility of 6.2%. A bipotentiostatic chronoamperometric biosensor was finally developed using a tyrosinase/SPC{sub TTF}E and a GOx/SPC{sub Pt}E connected in array mode for the simultaneous determination of Cr(III) and Cr(VI) in spiked tap water and in waste water from a tannery factory samples.

Preparation and chemical studies on Tc(III) complexes containing polyaminocarboxylic acids

International Nuclear Information System (INIS)

Gonzalez, R.; Kremer, C.; Chiozzone, R.; Torres, J.; Rivero, M.; Kremer, E.; Leon, A.

1998-01-01

Tc(III)-edta (edta = ethylenediaminetetraacetate), Tc(III)-dtpa (dtpa = diethylenetriaminepentaacetate) and Tc(III)-mebrofenin (mebrofenin = 3-bromo-2,4,6-trimethylacetanilideiminodiacetate) complexes were prepared by ligand substitution reactions on hexakis(thiourea)technetium(III) cation with the polycarboxylates. By a combination of different techniques (UV-Vis, IR and 1 H-NMR spectroscopy, Tc elemental analyses and cerimetric titrations) it was concluded that 1:1 complexes are formed with edta and dtpa while mebrofening adopts a 2:1 (ligand to metal) stoichiometry. Complementary, molecular mechanics calculations were performed to analyze the spatial arrangement of the molecules. The stability of the Tc(III) complexes was studied in aqueous solution by paper chromatography, paper electrophoresis and cyclic voltammetry. The chelates are rather stable, in particular when compared with the precursor. (orig.)

Binder-free carbon nanotube electrode for electrochemical removal of chromium.

Science.gov (United States)

Wang, Haitao; Na, Chongzheng

2014-11-26

Electrochemical treatment of chromium-containing wastewater has the advantage of simultaneously reducing hexavalent chromium (CrVI) and reversibly adsorbing the trivalent product (CrIII), thereby minimizing the generation of waste for disposal and providing an opportunity for resource reuse. The application of electrochemical treatment of chromium is often limited by the available electrochemical surface area (ESA) of conventional electrodes with flat surfaces. Here, we report the preparation and evaluation of carbon nanotube (CNT) electrodes consisting of vertically aligned CNT arrays directly grown on stainless steel mesh (SSM). We show that the 3-D organization of CNT arrays increases ESA up to 13 times compared to SSM. The increase of ESA is correlated with the length of CNTs, consistent with a mechanism of roughness-induced ESA enhancement. The increase of ESA directly benefits CrVI reduction by proportionally accelerating reduction without compromising the electrode's ability to adsorb CrIII. Our results suggest that the rational design of electrodes with hierarchical structures represents a feasible approach to improve the performance of electrochemical treatment of contaminated water.

Luminescence studies of Sm(III) and Cm(III) complexes in NaSCN/DHDECMP extraction systems

CERN Document Server

Chung, D Y; Kimura, T

1999-01-01

Laser-induced fluorescence (LIF) studies of Sm(III) and Cm(III) complexes in the NaSCN/DHDECMP solvent extraction system were carried out. Luminescence lifetimes were measured to determine the number of water molecules coordinated to Sm(III), Tb(III), Dy(III), and Cm(III) in the sodium thiocyanate solution and in the DHDECMP phase. The hydration number of Sm(III), Tb(III), Dy(III), and Cm(III) in the sodium thiocyanate solution decreased linearly with increasing sodium thiocyanate concentration. The hydration numbers of Sm(III), Dy(III), and Cm(III) in the DHDECMP phase decreased with increasing sodium thiocyanate concentration. The water molecules in the inner coordination sphere of Sm(III) and Dy(III) extracted into the DHDECMP were not completely removed at low sodium thiocyanate concentration but decreased with increasing sodium thiocyanate concentration. However, in the case of Cm(III) extracted into the DHDECMP phase from the sodium thiocyanate solution, there was no water in the inner coordination sphe...

Application of high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for determination of chromium compounds in the air at the workplace.

Science.gov (United States)

Stanislawska, Magdalena; Janasik, Beata; Wasowicz, Wojciech

2013-12-15

The toxicity and bioavailability of chromium species are highly dependable on the form or species, therefore determination of total chromium is insufficient for a complete toxicological evaluation and risk assessment. An analytical method for determination of soluble and insoluble Cr (III) and Cr (VI) compounds in welding fume at workplace air has been developed. The total chromium (Cr) was determined by using quadruple inductively coupled plasma mass spectrometry (ICP-MS) equipped with a dynamic reaction cell (DRC(®)). Soluble trivalent and hexavalent chromium compounds were determined by high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A high-speed, reversed-phase CR C8 column (PerkinElmer, Inc., Shelton, CT, USA) was used for the speciation of soluble Cr (III) and soluble Cr (VI). The separation was accomplished by interaction of the chromium species with the different components of the mobile phase. Cr (III) formed a complex with EDTA, i.e. retained on the column, while Cr (VI) existed in the solutions as dichromate. Alkaline extraction (2% KOH and 3% Na2CO3) and anion exchange column (PRP-X100, PEEK, Hamilton) were used for the separation of the total Cr (VI). The results of the determination of Cr (VI) were confirmed by the analysis of the certified reference material BCR CRM 545 (Cr (VI) in welding dust). The results obtained for the certified material (40.2±0.6 g kg(-1)) and the values recorded in the examined samples (40.7±0.6 g kg(-1)) were highly consistent. This analytical method was applied for the determination of chromium in the samples in the workplace air collected onto glass (Whatman, Ø 37 mm) and membrane filters (Sartorius, 0.8 μm, Ø 37 mm). High performance liquid chromatography with inductively coupled plasma mass spectrometry is a remarkably powerful and versatile technique for determination of chromium species in welding fume at workplace air. Crown Copyright © 2013 Published by

Photocytotoxicity and DNA photocleavage activity of La(III) and Gd(III) complexes of phenanthroline bases

International Nuclear Information System (INIS)

Hussain, Akhtar; Saha, Sounik; Chakravarty, Akhil R.; Majumdar, Ritankar; Dighe, Rajan R.

2011-01-01

Lanthanide(III) complexes (La(B)(acac) 3 ) (1-3) and (Gd(B)(acac) 3 ) (4-6), where B is a N,N-donor phenanthroline base, viz., 1,10-phenanthroline (phen in 1, 4), dipyrido(3,2-d:2',3'-f)quinoxaline (dpq in 2, 5) and dipyrido(3,2-a:2',3'-c)phena-zine (dppz in 3, 6), have been prepared and characterized. The Gd(III) complexes 4 - 6 are structurally characterized by single crystal X-ray crystallography. The complexes display GdO 6 N 2 coordination with the ligands showing bidentate chelating mode of bonding. The complexes are non-electrolytic in aqueous DMF and exhibit ligand-centered absorption bands in the UV region. The dppz complexes show a band at 380 nm in DMF. The La(III) complexes are diamagnetic. The Gd(III) complexes are paramagnetic with magnetic moment that corresponds to seven unpaired electrons. The complexes are avid binders to calf thymus DNA giving K b values in the range of 4.7 x 10 4 - 6.1 x 10 5 M -1 with a relative binding order: 3, 6 (dppz) > 2, 5 (dpq) > 1, 4 (phen). The binding data suggest DNA surface and/or groove binding nature of the complexes. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form in UV-A light of 365 nm via formation of both singlet oxygen ( 1 O 2 ) and hydroxyl radical (HO · ) species. The dppz complexes 3 and 6 exhibit significant PDT effect in HeLa cervical cancer cells giving respective IC 50 value of 460(±50) and 530(±30) nM in UV-A light of 365 nm, and are essentially non-toxic in dark with an IC 50 value of >100 μM. The dppz ligand alone is cytotoxic in dark and UV-A light. A significant decrease in the dark toxicity of the dppz base is observed on binding to the Ln(Ill) ion while retaining its photocytotoxicity. (author)

Hexavalent chromium reduction by a hypocrea tawa fungal strain

International Nuclear Information System (INIS)

Morales-Battera, L.; Guillen-Jimenez, F. M.; Cristiani-Urbina, E.

2009-01-01

Microbial transformation of the highly toxic, water-soluble and mobile hexavalent chromium [Cr(VI)], to the less toxic, insoluble and immobile trivalent chromium [Cr(III)], is an economically feasible alternative for the treatment of wastewaters contaminated with Cr(VI). The main purpose of this work was to isolate, identify and characterize a microbial strain water by batch enrichment culture techniques, and further identified as Hypocrea tawa by its D1/D2 domain sequence of the 26S rRNA gene with 99,44% similarity. (Author)

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

Science.gov (United States)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

Improved Antileishmanial Activity of Dppz through Complexation with Antimony(III and Bismuth(III: Investigation of the Role of the Metal

Directory of Open Access Journals (Sweden)

Cynthia Demicheli

2012-10-01

Full Text Available Two novel trivalent antimony(III and bismuth(III complexes with the nitrogen-donor heterocyclic ligand dipyrido[3,2-a:2',3'-c]phenazine (dppz were synthesized and characterized as [Sb(dppzCl3]∙H2O∙CH3OH and [Bi(dppzCl3]. The crystal structure of Sb(III complex was determined by X-ray crystallography. These complexes were evaluated for their activity against the promastigote form of Sb(III-sensitive and –resistant Leishmania infantum chagasi and Leishmania amazonensis strains. Both complexes were more effective than dppz alone in inhibiting the growth of Leishmania promastigotes and were at least 77 and 2,400 times more active than potassium antimonyl tartrate in Sb(III-sensitive and -resistant Leishmania, respectively. The cytotoxicity of dppz and its complexes against mouse peritoneal macrophages occurred at dppz concentrations at least 6-fold greater than those found to be active against Leishmania promastigotes.To investigate the role of the metal in the improved antileishmanial activity of dppz, the activity of the Sb(III complex was compared between the Sb-resistant mutants and their respective parental sensitive strains. The lack of cross-resistance to the Sb(III-dppz complex together with the much lower activity of antimonyl tartrate, SbCl3 and BiCl3 strongly support the model that the metal is not active by itself but improves the activity of dppz through complexation.

The removal of toxic metals from liquid effluents by ion exchange resins. Part IV: Chromium(III)/H+ /Lewatit SP112; La eliminación de metales tóxicos presentes en efluentes líquidos mediante resinas de cambio iónico. Parte IV: cromo(III)/H+/Lewatit SP112

Energy Technology Data Exchange (ETDEWEB)

Alguacil, F.J.

2017-09-01

This investigation presented results on the removal of chromium(III), from aqueous solution in the 0-5 pH range, using Lewatit SP112 cationic exchange resin. Several aspects affecting the ion exchange process were evaluated, including: the influence of the stirring speed, temperature, pH of the solution, resin dosage and aqueous ionic strength. The selectivity of the system was tested against the presence of other metals in the aqueous solution, whereas the removal of chromium(III) from solutions was compared with results obtained using multiwalled carbon nanotubes as adsorbents. From the batch experimental data, best fit of the results is obtained with the Langmuir model, whereas the ion exchange process is best explained by the pseudo-second order model, moreover, experimental data responded well to the film-diffusion controlled model. Elution of the chromium(III) loaded into the resin is well accomplished by the use of sodium hydroxide solutions. [Spanish] En este trabajo se presentan los resultados obtenidos en la eliminación de cromo(III) de disoluciones acuosas (pH 0-5) mediante la resina de intercambio catiónico Lewatit SP112. Se han investigado algunas variables que pueden afectar al sistema: influencia de la agitación, temperatura, pH y fuerza iónica del medio acuoso y cantidad de resina; también se ha investigado acerca de la selectividad del sistema cuando otros metales están presentes en el medio acuoso, comparándose los resultados de la eliminación del cromo(III) usando la resina con los resultados obtenidos cuando se emplea otro adsorbente como son los nanotubos de carbono de pared múltiple. Los resultados experimentales indican que la carga del cromo(III) en la resina responde mejor al modelo de Langmuir, mientras que los modelos cinéticos indican que la carga del metal en la resina responde al modelo de pseudo-segundo orden y difusión en la capa límite. La elución del cromo(III) se realiza con disoluciones de hidróxid.

Single-molecule magnetism in three related {Co(III)2Dy(III)2}-acetylacetonate complexes with multiple relaxation mechanisms.

Science.gov (United States)

Langley, Stuart K; Chilton, Nicholas F; Moubaraki, Boujemaa; Murray, Keith S

2013-06-17

Three new heterometallic complexes with formulas of [Dy(III)2Co(III)2(OMe)2(teaH)2(acac)4(NO3)2] (1), [Dy(III)2Co(III)2(OH)2(teaH)2(acac)4(NO3)2]·4H2O (2), and [Dy(III)2Co(III)2(OMe)2(mdea)2(acac)4(NO3)2] (3) were characterized by single-crystal X-ray diffraction and by dc and ac magnetic susceptibility measurements. All three complexes have an identical "butterfly"-type metallic core that consists of two Dy(III) ions occupying the "body" position and two diamagnetic low-spin Co(III) ions occupying the outer "wing-tips". Each complex displays single-molecule magnet (SMM) behavior in zero applied magnetic field, with thermally activated anisotropy barriers of 27, 28, and 38 K above 7.5 K for 1-3, respectively, as well as observing a temperature-independent mechanism of relaxation below 5 K for 1 and 2 and at 3 K for 3, indicating fast quantum tunneling of magnetization (QTM). A second, faster thermally activated relaxation mechanism may also be active under a zero applied dc field as derived from the Cole-Cole data. Interestingly, these complexes demonstrate further relaxation modes that are strongly dependent upon the application of a static dc magnetic field. Dilution experiments that were performed on 1, in the {Y(III)2Co(III)2} diamagnetic analog, show that the slow magnetic relaxation is of a single-ion origin, but it was found that the neighboring ion also plays an important role in the overall relaxation dynamics.

Rare earth(III) complexes for the development of new magnetic and luminescent probes; Complexes de lanthanides(III) pour le developpement de nouvelles sondes magnetiques et luminescentes

Energy Technology Data Exchange (ETDEWEB)

Nonat, A

2007-10-15

The simultaneous optimisation of the molecular parameters determining the relaxivity (number of coordinated water molecules, water-exchange, rotation dynamics of the whole complex, electronic relaxation, Gd(III)-proton distance) is essential to prepare efficient contrast agents. The aim of this work is on the one hand to design and study complexes with a high number of bound water molecules and to understand the influence of the coordination sphere on the stability and on the electronic relaxation and on the other hand, to use the ligand as a chromophore for the development of luminescent probes for biomedical imaging. We present the structure, the stability and the relaxivity of Gd(III) complexes of two series of tripodal ligands containing picolinate units based either on the 1,4,7-tri-aza-cyclononane ring or on a tertiary amine. These complexes show high relaxivity in water and in serum and can establish a non covalent interaction with serum albumin. The interpretation of the water proton relaxivity with the help of new relaxometric methods based on an auxiliary probe solute has allowed us to show that both the presence of the picolinate groups and the 1,4,7-tri-aza-cyclononane framework can lead to Gd(III) complexes with favourable electronic relaxation properties. This ligands have also been used for Eu(III) and Tb(III) complexation leading to strong luminescence in visible light. Other complexes derived from 8-hydroxyquinoline unit which display a very high luminescence in infrared are also studied. (author)

Determination of Cr(VI) and Cr(III) in urine and dextrose by inductively coupled plasma emission spectroscopy

Science.gov (United States)

Mianzhi, Zhuang; Barnes, Ramon M.

The determination of Cr(VI) and Cr(III) in human urine and in commercial dextrose solution is performed by induclively coupled plasma-atomic emission spectroscopy after selective preconcentration of the chromium species at different pH values by poly(dithiocarbamate) and poly(acrylamidoxime) chelating resins. The chelating properties of these resins with chromium, including the kinetics of uptake and removal of Cr(III), and the influence of matrix concentrations were evaluated. Chromium in human urine was found to exist exclusively as Cr(III).

induced Oxidation of Chromium(iii) by Peroxodisulphate

African Journals Online (AJOL)

formation of Cr(VI) was observed as a first-order process at high [Cr(III)] and as a zero-order process at low [Cr(III)]. ..... thermodynamic equations, adapted to transition state theory. .... A theoretical rate law for the above-mentioned reaction.

On the structure and spin states of Fe(III)-EDDHA complexes.

Science.gov (United States)

Gómez-Gallego, Mar; Fernández, Israel; Pellico, Daniel; Gutiérrez, Angel; Sierra, Miguel A; Lucena, Juan J

2006-07-10

DFT methods are suitable for predicting both the geometries and spin states of EDDHA-Fe(III) complexes. Thus, extensive DFT computational studies have shown that the racemic-Fe(III) EDDHA complex is more stable than the meso isomer, regardless of the spin state of the central iron atom. A comparison of the energy values obtained for the complexes under study has also shown that high-spin (S = 5/2) complexes are more stable than low-spin (S = 1/2) ones. These computational results matched the experimental results of the magnetic susceptibility values of both isomers. In both cases, their behavior has been fitted as being due to isolated high-spin Fe(III) in a distorted octahedral environment. The study of the correlation diagram also confirms the high-spin iron in complex 2b. The geometry optimization of these complexes performed with the standard 3-21G* basis set for hydrogen, carbon, oxygen, and nitrogen and the Hay-Wadt small-core effective core potential (ECP) including a double-xi valence basis set for iron, followed by single-point energy refinement with the 6-31G* basis set, is suitable for predicting both the geometries and the spin-states of EDDHA-Fe(III) complexes. The presence of a high-spin iron in Fe(III)-EDDHA complexes could be the key to understanding their lack of reactivity in electron-transfer processes, either chemically or electrochemically induced, and their resistance to photodegradation.

Synthesis and Characterization of Hexahapto-Chromium Complexes of Single-Walled Carbon Nanotubes

KAUST Repository

Kalinina, Irina

2016-12-17

This chapter employs purified pristine single-walled carbon nanotubes (SWNTs) and octadecylaminefunctionalized-SWNTs. These SWNTs are employed for investigate the potential of the SWNT sidewall to function as a hexahapto ligand for chromium (Cr), with in-depth characterization of the products using some of the techniques, such as thermogravimetric analysis (TGA), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS). Purified electric arc (EA)-produced SWNTs (P2-SWNT) and octadecylaminefunctionalized SWNTs were obtained from Carbon Solutions, Inc. The TEM images show the removal of the Cr particles from the outer surface of the SWNT bundles in the SWNT-Cr complexes after decomplexation; Cr attachment to the surface of the as-prepared complexes (η6-SWNT)Cr(CO)3 and (η6-SWNT-CONH(CH2)17CH3)Cr(CO)3 is clearly evident. The positions of the bands in the Raman spectra of SWNTs are sensitive to doping and thus the chapter examines the effect of complexation of the Cr(CO)3 and Cr(η6-benzene) units on the position of the G and 2D bands in the (η6-SWNT)Cr(CO)3 and (η6-SWNT)Cr(η6-benzene) complexes.

Stability constants of mixed ligand complexes of lanthanide(III) and yttrium(III) with complexone and substituted salicylic acids

International Nuclear Information System (INIS)

Kolhe, Vishnu; Dwivedi, K.

1996-01-01

Salicylic acid and substituted salicylic acids are potential antimicrobial agents. Binary complexes of salicylic acid and its substituted derivatives with lanthanide(III) and yttrium(III) metal ions have been reported. There are reports on the ternary metal complexing equilibria with some lanthanide(III) and yttrium(III) metal ions involving aminopolycarboxylic acid as one ligand and salicylic acid (SA) and other related compounds as the second ligands. Ethylene glycol bis(2-aminoethylether)- N, N, N', N'-tetraacetic acid (EGTA) is an important member of aminopolycarboxylic acid and finds many applications in medicine and biology. Recently, few ternary complexes have been reported using EGTA as ligand. In view of biological importance of simple and mixed ligand complexes EGTA, SA and DNSA (3,5-dinitrosalicylic acid), a systematic study has been undertaken for the determination of stability constant and the results are reported. (author). 6 refs., 1 fig., 2 tabs

Bioaccessibility, bioavailability and toxicity of commercially relevant iron- and chromium-based particles: in vitro studies with an inhalation perspective

Directory of Open Access Journals (Sweden)

Hedberg Yolanda

2010-09-01

Full Text Available Abstract Background Production of ferrochromium alloys (FeCr, master alloys for stainless steel manufacture, involves casting and crushing processes where particles inevitably become airborne and potentially inhaled. The aim of this study was to assess potential health hazards induced by inhalation of different well-characterized iron- and chromium-based particles, i.e. ferrochromium (FeCr, ferrosiliconchromium (FeSiCr, stainless steel (316L, iron (Fe, chromium (Cr, and chromium(IIIoxide (Cr2O3, in different size fractions using in vitro methods. This was done by assessing the extent and speciation of released metals in synthetic biological medium and by analyzing particle reactivity and toxicity towards cultured human lung cells (A549. Results The amount of released metals normalized to the particle surface area increased with decreasing particle size for all alloy particles, whereas the opposite situation was valid for particles of the pure metals. These effects were evident in artificial lysosomal fluid (ALF of pH 4.5 containing complexing agents, but not in neutral or weakly alkaline biological media. Chromium, iron and nickel were released to very low extent from all alloy particles, and from particles of Cr due to the presence of a Cr(III-rich protective surface oxide. Released elements were neither proportional to the bulk nor to the surface composition after the investigated 168 hours of exposure. Due to a surface oxide with less protective properties, significantly more iron was released from pure iron particles compared with the alloys. Cr was predominantly released as Cr(III from all particles investigated and was strongly complexed by organic species of ALF. Cr2O3 particles showed hemolytic activity, but none of the alloy particles did. Fine-sized particles of stainless steel caused however DNA damage, measured with the comet assay after 4 h exposure. None of the particles revealed any significant cytotoxicity in terms of cell death

Ion exchange removal of chromium (iii) from tannery wastes by using a strong acid cation exchange resin amberlite ir-120 h+ and its hybrids

International Nuclear Information System (INIS)

Ahmad, T.

2014-01-01

A strong acid cation exchange resin Amberlite IR-120 H+ and its hybrids with Mn(OH)/sub 2/, Cu(OH)/sub 2/ and Fe(OH)/sub 3/ are used for the removal of chromium (III) from spent tannery bath. The experimental data give good fits with the Langmuir sorption model. The thermodynamic parameters entropy (delta S), enthalpy (delta H) and free energy (delta G) changes are computed, which reveal that the chromium removal from tannery wastes by ion exchangers is an endothermic, physical sorption and entropically driven process. The rate of sorption is found to increase with the increase of resin dosage, stirring speed and temperature. Different kinetic models such as film diffusion, particle diffusion and Lagergren pseudo first order are used to evaluate the mechanism of the process. It is found that the hybrid ion exchange resins have better removal capacity as compared to the parent ion exchanger. The increase in the removal capacity is found to be in the order of the corresponding PZC values of the hybrid ion exchangers. Further, it is suggested that the higher exchange capacity is the result of Donnan effect and specific adsorption of chromium by the oxides / hydroxides present inside the matrix of the organic cation exchanger. (author)

Chromium toxicity to nitrifying bacteria: implications to wastewater treatment

Science.gov (United States)

Chromium, a heavy metal that enters wastewater treatment plants (WWTPs) through industrial discharges, can be toxic to microorganisms carrying out important processes within biological wastewater treatment systems. The effect of Cr(III) and Cr(VI) on ammonia dependent specific ox...

Black and green pigments based on chromium-cobalt spinels

Energy Technology Data Exchange (ETDEWEB)

Eliziario, Sayonara A., E-mail: sayonaraea@iq.unesp.br [Departamento de Fisico-Quimica, Instituto de Quimica, UNESP - Univ Estadual Paulista, Araraquara, SP (Brazil); Departamento de Quimica, CCEN, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil); Andrade, Jeferson M. de [Departamento de Quimica, CCEN, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil); Lima, Severino J.G. [Departamento de Engenharia Mecanica, CT, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil); Paskocimas, Carlos A. [Universidade Federal do Rio Grande do Norte, CT, Natal, RN (Brazil); Soledade, Luiz E.B. [Departamento de Quimica, CCEN, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil); Hammer, P.; Longo, E. [Departamento de Fisico-Quimica, Instituto de Quimica, UNESP - Univ Estadual Paulista, Araraquara, SP (Brazil); Souza, Antonio G.; Santos, Ieda M.G. [Departamento de Quimica, CCEN, Universidade Federal da Paraiba, Campus I, Joao Pessoa, PB (Brazil)

2011-09-15

Highlights: {yields} Co(Co{sub 2-x}Cr{sub x})O{sub 4} powders with different chromium concentrations (x = 0, 0.25 and 1) were prepared by the polymeric precursor method. {yields} Co(CoCr)O{sub 4} and Co(Co{sub 1.75}Cr{sub 0.25})O{sub 4} displayed a dark color and CoCr{sub 2}O{sub 4} was green. {yields} The colors were related to the different oxidation states of Cr and Co. {yields} Cobalt enrichment result in an increasing presence of Co(III) and a decrease amount of Cr(VI). - Abstract: Chromium and cobalt oxides are widely used in the manufacture of industrial pigments. In this work, the Co(Co{sub 2-x}Cr{sub x})O{sub 4} powders with different chromium concentrations (x = 0, 0.25 and 1) were synthesized by the polymeric precursor method, heat treatment between 600 and 1000 deg. C. These powders were characterized by X-ray diffraction, infrared spectroscopy, colorimetry, UV-vis absorption and X-ray photoelectron spectroscopies. Even with the addition of chromium, the XRD patterns revealed that all powders crystallize in a single spinel cubic structure. The spinels with higher cobalt amount, Co(CoCr)O{sub 4} and Co(Co{sub 1.75}Cr{sub 0.25})O{sub 4}, displayed a dark color, without the Co{sup 3+} reduction observed in Co{sub 3}O{sub 4} between 900 and 950 deg. C. The spinel with higher chromium amount, CoCr{sub 2}O{sub 4}, was green. The colors were directly related to the occupation of tetrahedral and octahedral sites by the chromophores, as well as to the different oxidation states of chromium and cobalt. The different optical band gap values estimated from UV-vis spectra suggested the existence of intermediary energy levels within the band gap. X-ray photoelectron spectroscopy confirmed an increasing presence of Co(III) and a decreasing amount of Cr(VI) with cobalt enrichment.

2 : 2 Fe(III): ligand and "adamantane core" 4 : 2 Fe(III): ligand (hydr)oxo complexes of an acyclic ditopic ligand

DEFF Research Database (Denmark)

Ghiladi, Morten; Larsen, Frank B.; McKenzie, Christine J.

2005-01-01

A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X-ray struct......A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X...

Nanomagnetic domains of chromium deposited on vertically-aligned carbon nanotubes

International Nuclear Information System (INIS)

Wright, Andrew C.; Faulkner, Michael K.; Harris, Robert C.; Goddard, Alex; Abbott, Andrew P.

2012-01-01

The drive to create ever smaller magnetic memory devices has led to the development of new nanomagnetic domains on surfaces. This paper reports the development of nano-chromium magnetic domains obtained using electrodeposition on vertically aligned carbon nanofibers arrays. Attempts to achieve this using conventional aqueous solutions were unsuccessful even after thin nickel underlayers were applied. The use of a novel electrolyte, a deep eutectic solvent, made from choline chloride: chromium (III) chloride enabled highly conformal overcoatings of chromium on individual bare carbon nanotubes to be obtained. Very high aspect ratio metal microstructures could be obtained by this novel technology. Magnetic imaging of the coated nanoarrays showed there to be clear magnetic character to the coating when the thin coatings were applied but this disappeared when the deposits were thicker and more contiguous. - Highlights: ► Nanoscale chromium deposited from non-aqueous electrolyte shows magnetic behavior. ► Vertically aligned carbon nanotubes conformally coated with chromium metal. ► Ionic liquid electrolyte superior to chromic acid for plating high aspect ratio structures.

Nanomagnetic domains of chromium deposited on vertically-aligned carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Wright, Andrew C., E-mail: a.wright@glyndwr.ac.uk [Advanced Materials Research Laboratory, Materials Science Research Center, Glyndwr University, Wrexham LL11 2AW (United Kingdom); Faulkner, Michael K., E-mail: m.faulkner@manchester.ac.uk [Manchester Materials Science Centre, University of Manchester, Grosvenor Street, Manchester M13 9PL (United Kingdom); Harris, Robert C.; Goddard, Alex; Abbott, Andrew P., E-mail: apa1@le.ac.uk [Department of Chemistry, University of Leicester, Leicester LE1 7RH (United Kingdom)

2012-12-15

The drive to create ever smaller magnetic memory devices has led to the development of new nanomagnetic domains on surfaces. This paper reports the development of nano-chromium magnetic domains obtained using electrodeposition on vertically aligned carbon nanofibers arrays. Attempts to achieve this using conventional aqueous solutions were unsuccessful even after thin nickel underlayers were applied. The use of a novel electrolyte, a deep eutectic solvent, made from choline chloride: chromium (III) chloride enabled highly conformal overcoatings of chromium on individual bare carbon nanotubes to be obtained. Very high aspect ratio metal microstructures could be obtained by this novel technology. Magnetic imaging of the coated nanoarrays showed there to be clear magnetic character to the coating when the thin coatings were applied but this disappeared when the deposits were thicker and more contiguous. - Highlights: Black-Right-Pointing-Pointer Nanoscale chromium deposited from non-aqueous electrolyte shows magnetic behavior. Black-Right-Pointing-Pointer Vertically aligned carbon nanotubes conformally coated with chromium metal. Black-Right-Pointing-Pointer Ionic liquid electrolyte superior to chromic acid for plating high aspect ratio structures.

9,10-phenanthrenesemiquinone radical complexes of ruthenium(III), osmium(III) and rhodium(III) and redox series.

Science.gov (United States)

Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Weyhermüller, Thomas; Ghosh, Prasanta

2013-05-14

Reactions of 9,10-phenanthrenequinone (PQ) in toluene with [M(II)(PPh3)3X2] at 298 K afford green complexes, trans-[M(PQ)(PPh3)2X2] (M = Ru, X = Cl, 1; M = Os, X = Br, 2) in moderate yields. Reaction of anhydrous RhCl3 with PQ and PPh3 in boiling ethanol affords the dark brown paramagnetic complex, cis-[Rh(PQ)(PPh3)2Cl2] (3) in good yields. Diffusion of iodine solution in n-hexane to the trans-[Os(PQ) (PPh3)2(CO)(Br)] solution in CH2Cl2 generates the crystals of trans-[Os(PQ)(PPh3)2(CO)(Br)](+)I3(-), (4(+))I3(-)), in lower yields. Single crystal X-ray structure determinations of 1·2toluene, 2·CH2Cl2 and 4(+)I3(-), UV-vis/NIR absorption spectra, EPR spectra of 3, electrochemical activities and DFT calculations on 1, 2, trans-[Ru(PQ)(PMe3)2Cl2] (1Me), trans-[Os(PQ)(PMe3)2Br2] (2Me), cis-[Rh(PQ)(PMe3)2Cl2] (3Me) and their oxidized and reduced analogues including trans-[Os(PQ)(PMe3)2(CO)(Br)](+) (4Me(+)) substantiated that 1-3 are the 9,10-phenanthrenesemiquinone radical (PQ(˙-)) complexes of ruthenium(III), osmium(III) and rhodium(III) and are defined as trans/cis-[M(III)(PQ(˙-))(PPh3)2X2] with a minor contribution of the resonance form trans/cis-[M(II)(PQ)(PPh3)2X2]. Two comparatively longer C-O (1.286(4) Å) and the shorter C-C lengths (1.415(7) Å) of the OO-chelate of 1·2toluene and 2·CH2Cl2 and the isotropic fluid solution EPR signal at g = 1.999 of 3 are consistent with the existence of the reduced PQ(˙-) ligand in 1-3 complexes. Anisotropic EPR spectra of the frozen glasses (g11 = g22 = 2.0046 and g33 = 1.9874) and solids (g11 = g22 = 2.005 and g33 = 1.987) instigate the contribution of the resonance form, cis-[Rh(II)(PQ)(PPh3)2Cl2] in 3. DFT calculations established that the closed shell singlet (CSS) solutions of 1Me and 2Me are unstable due to open shell singlet (OSS) perturbation. However, the broken symmetry (BS) (1,1) Ms = 0 solutions of 1Me and 2Me are respectively 22.6 and 24.2 kJ mole(-1) lower in energy and reproduced the experimental bond

Synthesis of Cr(III-Morin Complex: Characterization and Antioxidant Study

Directory of Open Access Journals (Sweden)

Qadeer K. Panhwar

2014-01-01

Full Text Available The complex formation between Cr(III and morin was carried out in methanol and confirmed by analytical characterization using UV-Vis, IR, 1H NMR, and TG-DTA. UV-Vis shows significant bathochromic shift in benzoyl upon coordination as well as IR well illustrates the peak shift of C=O group and formation of a O–Cr(III bond. Likewise, 1H NMR studies clarify that Cr(III metal ion replaces the 5OH proton hence; 5-hydroxy-4-keto site is employed by morin in chelation to form six-membered stable ring system out of three available chelating sites. In addition, TG-DTA denotes the presence of coordinated and crystalline water molecules. The melting point of the complex was found to be 389°C by DSC. In addition, Cr(III-morin complex was found to be a more potent antioxidant than morin as evaluated by DPPH• and FRAP methods.

Lanthanide (III) complexes of 2-(N-salicylideneamino)-4-phenylthiazole

International Nuclear Information System (INIS)

Sasidharan, G.N.; Mohanan, K.; Lakshmi Prabha, A.N.

2002-01-01

Lanthanide(III) complexes of 2-(N-salicylideneamino)-4- phenylthiazole (HSAT) have been synthesised and characterised by elemental, analytical, thermogravimetric, molar conductance, UV- visible, IR and NMR spectral data. The ligand coordinates to the lanthanide(III) ion in a tridentate fashion without deprotonation, giving complexes of the type [Ln(HSAT) 2 (NO 3 ) 3 ] and [Ln(HSAT) 2 (H 2 0) 3 Cl 3 ]. The spectral data reveal that the ligand is bonded to the lanthanide ion through azomethine nitrogen, ring nitrogen and phenolic oxygen without deprotonation. The nitrate group acts in a bidentate fashion. The ligand and the metal complexes exhibit antibacterial and antifungal activities. (author)

Use of metallurgical dust for removal chromium ions from aqueous solutions

Science.gov (United States)

Pająk, Magdalena; Dzieniszewska, Agnieszka; Kyzioł-Komosińska, Joanna; Chrobok, Michał

2018-01-01

The aim of the study was to determine the potential for the application of dust from steel plant as an effective sorbent for removing Cr(III) and Cr(VI) in the form of simple and complex ions - Acid Blue 193 dye from aqueous solutions. Three isotherms models were used to interpret the experimental results namely: Langmuir, Freundlich, and Dubinin-Radushkevich. Estimated equations parameters allowed to determine the binding mechanism. Based on laboratory studies it was found that the dust was characterized by high sorption capacities for Cr ions and dye from the aqueous solution. The sorption capacity of the dust for Cr(III) and Cr(VI) ions depended on the degree of oxidation, pH of solution and kind of anion and changed in series: Cr(III)-Cl pH=5.0> Cr(III)-SO4 pH=5.0> Cr(III)-Cl pH=3.0> Cr(III)-SO4 pH=3.0> Cr(VI) pH=5.0> Cr(VI) pH=3.0. Dust was also characterized by a high maximum sorption capacity of dye at a range of 38.2 - 91.7 mg/g, depending on the dose of dust. Based on the study it was found that dust from a steel plant, containing iron oxides, can be used as low-cost and effective sorbent to remove pollutions containing chromium ions, especially from acidic wastewater.

Colloid formation as an approach to remediate toxic wastes containing chromium and lead

Energy Technology Data Exchange (ETDEWEB)

Barton, Larry L [Laboratory of Microbial Chemistry, Department of Biology, University of New Mexico, Albuquerque, NM (United States); Lindemann, William C [Department of Agronomy and Horticulture, New Mexico State University, Las Cruces, NM (United States); Bearden, Deborah L [Department of Chemical and Nuclear Engineering, University of New Mexico, Albuquerque, NM (United States)

1992-07-01

We have explored the use of bacteria to remediate soil and aquatic sites containing toxic levels of Pb II or Cr VI. Bacterial isolates from metal-containing sites are capable of detoxifying water containing up to 10 mM Pb II. This activity is a two step process with an initial binding of Pb II to the cells followed by production of a black Pb-containing colloid. Numerous bacteria will reduce Cr VI to Cr III and some isolates have been found to bind Cr III to the bacterial cell. Colloids consisting of Cr III would result from the formation of chromium hydroxide or from binding to bacteria. The bacterial metabolism of Pb II and Cr III converts the biologically toxic and chemically reactive metal to compounds of reduced toxicity and modified chemical activity. We propose a system which can employ bacteria for the bioremediation of toxic sites containing lead or chromium. (author)

THE COMBINED EFFECT OF SCUTELLARIA BAICALENSIS EXTRACT AND COENZYME Q10 IN OXIDATIVE STRESS INDUCED BY CHROMIUM COMPOUNDS

Directory of Open Access Journals (Sweden)

Ewa Sawicka

2010-03-01

Full Text Available Background: The common use of antioxidants and its joint application brings the question whether they are useful in oxidative stress induced by the chemicals or whether they cause harmful interaction. Both Scutellaria baicalensis and CoQ10 are known as antioxidants, however one exogenous, the second endogenous. Chromium belongs equal to essential microelements and toxic factors. Therefore the aim of work was the evaluation joint effect of two examined antioxidants in exposure to chromium compounds.Materials and methods: The material was fresh blood obtained from healthy volunteers. The concentration of malondialdehyde (MDA in erythrocytes was evaluated using Stock’s method. The activity of mixture of Antoxyd and coenzyme Q10 was tested after exposure to chromium III and VI at concentrations: 0,05; 0,5 and 1,0 µg/ml. Antioxidants were used in concentrations : 8,0; 20; 60 and 100 µg/ml. Results: The influence of coenzyme Q10 in exposure to chromium III and chromium VI was statistically insignificant, but CoQ10 given together with Antoxyd in all used concentration statistically significant decreased the level of MDA in erythrocytes exposed to chromium compounds (p*0,001. Conclusions: Application of both antioxidants has exerted synergistic action lowering MDA level, which was elevated after chromium. No harmful interactions in the examined sample between antioxidants and chromium ions were noted.

In situ remediation of hexavalent chromium with pyrite fines : bench scale demonstration

International Nuclear Information System (INIS)

Cathum, S.; Wong, W.P.; Brown, C.E.

2002-01-01

An in situ remediation technique for chromium contaminated soil with pyrite fines was presented. Past industrial activities and lack of disposal facilities have contributed to a serious problem dealing with chromium, which cannot be eliminated from the environment because it is an element. Both bench-scale and laboratory testing was conducted to confirm the efficiency of the proposed process which successfully converted Cr(VI) into Cr(III) in soil and water. Cr(III) is less toxic and immobile in the environment compared to Cr(VI) which moves freely in the soil matrix, posing a risk to the groundwater quality. pH in the range of 2.0 to 7.6 has no effect on the reactivity of pyrite towards Cr(VI). The optimization of the bench-scale treatment resulted in a large volume of chromium waste, mostly from the control experiments and column hydrology testing. These waste streams were treated according to municipal guidelines before disposal to the environment. Samples of chromium waste before and after treatment were analyzed. Cr (VI) was completely mineralized to below guideline levels. It was determined that several conditions, including contact time between pyrite and Cr(VI), are crucial for complete mineralization of Cr(VI). 13 refs., 8 tabs., 9 figs

Synthesis, characterization, antiplasmodial and antitrypanosomal activity of some metal(III complexes of sulfadiazine

Directory of Open Access Journals (Sweden)

P.A. Ajibade

2008-08-01

Full Text Available The Fe(III, Ru(III, Rh(III, and Cr(III complexes of 4-amino-N-(2-pyrimidinylbenzene sulfonamide (sulfadiazine have been synthesized and characterized by elemental analysis, electronic and IR spectroscopy, conductance and room temperature magnetic susceptibility measurements. Sulfadiazine acts as a bidentate ligand through the sulfonamido and the pyrimidinic N-atoms. The compounds are non-electrolytes and the electronic spectra are consistent with the proposed octahedral geometry around the metal ions. The complexes were tested for in vitro activity against cultures of the resistant strains of Plasmodium falciparum, tripamastigotes T. b. rhodesiense and amastigotes L. donovani to determine their antiprotozoal activities. The Fe(III complex is more active than the other complexes against the parasitic protozoa.

Mixed ligand complexes of some of the rare earths. La(III)-, Pr(III)- or Nd-(III)-CDTA-Hydroxy Acids

Energy Technology Data Exchange (ETDEWEB)

Rana, H S; Tandon, J P [Rajasthan Univ., Jaipur (India). Chemical Labs.

1975-11-01

Biligand complexes of the 1:1 Ln(III)-1,2-diaminocyclohexane-tetraacetic acid (CDTA) chelate with hydroxy acids (where hydroxy acids = salicylic acid (SA); Sulphosalicylic acid (SSA) and 8-hydroxyquinoline-5-sulphonic acid (HQSA)) have been investigated by potentiometric titration. Their formation constants have been calculated (..mu..=0.1M-KNO/sub 3/; and t=30+-1 deg C) as 4.60 +-0.03, 5.46+-0.03, 5.87+-0.05; 3.12+-0.04, 3.95+-0.05, 4.42+-0.07; 2.73+-0.06, 3.45+-0.05 and 3.90+-0.08 for Ln(III)-CDTA-SA,-SSA, and -HQSA respectively (where Ln=La, Pr or Nd). The value of log Ksub(MAB) follows the order: La(III)).

Organometallic rhodium(III) and iridium(III) cyclopentadienyl complexes with curcumin and bisdemethoxycurcumin co-ligands.

Science.gov (United States)

Pettinari, Riccardo; Marchetti, Fabio; Pettinari, Claudio; Condello, Francesca; Petrini, Agnese; Scopelliti, Rosario; Riedel, Tina; Dyson, Paul J

2015-12-21

A series of half-sandwich cyclopentadienyl rhodium(III) and iridium(III) complexes of the type [Cp*M(curc/bdcurc)Cl] and [Cp*M(curc/bdcurc)(PTA)][SO3CF3], in which Cp* = pentamethylcyclopentadienyl, curcH = curcumin and bdcurcH = bisdemethoxycurcumin as O^O-chelating ligands, and PTA = 1,3,5-triaza-7-phosphaadamantane, is described. The X-ray crystal structures of three of the complexes, i.e. [Cp*Rh(curc)(PTA)][SO3CF3] (5), [Cp*Rh(bdcurc)(PTA)][SO3CF3] (6) and [Cp*Ir(bdcurc)(PTA)][SO3CF3] (8), confirm the expected "piano-stool" geometry. With the exception of 5, the complexes are stable under pseudo-physiological conditions and are moderately cytotoxic to human ovarian carcinoma (A2780 and A2780cisR) cells and also to non-tumorigenic human embryonic kidney (HEK293) cells, but lack the cancer cell selectivity observed for related arene ruthenium(II) complexes.

Incremental binding free energies of aluminum (III) vs. magnesium (II) complexes

International Nuclear Information System (INIS)

Mercero, Jose M.; Mujika, Jon I.; Matxain, Jon M.; Lopez, Xabier; Ugalde, Jesus M.

2003-01-01

A sequential ligand addition to the aluminum (III) cation has been studied using the B3LYP functional and a combined all-electron/pseudopotentials basis set. The aluminum complexes are compared with analogous magnesium (II) complexes. Different thermodynamical data, such as incremental binding energies, enthalpies, entropies and free energies, are presented for these addition reactions. While the magnesium (II) cation can only accommodate three negatively charged ligands, aluminum (III) accommodates four even after including bulk solvent effects. The main differences between both cations complexing with the neutral ligands, is that aluminum (III) is not able to form complexes with methanol until the number of methanol ligands is equal to 3. Magnesium (II) prefers to bind methanol and formamide when the number of ligands is small, while aluminum prefers formamide. For the largest complexes both cations prefer to bind water

Chromium speciation in solid matrices and regulation: a review

Energy Technology Data Exchange (ETDEWEB)

Unceta, N. [University of the Basque Country, Department of Analytical Chemistry, Faculty of Pharmacy, Vitoria-Gasteiz (Spain); Seby, F. [Ultra Traces Analyses Aquitaine (UT2A), Helioparc Pau-Pyrenees, Pau (France); Malherbe, J.; Donard, O.F.X. [Universite de Pau et des Pays de l' Adour, Helioparc Pau-Pyrenees, Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, IPREM, UMR CNRS 5254, Pau (France)

2010-06-15

In recent years, the extensive use of chromium in industrial processes has led to the promotion of several directives and recommendations by the European Union, that try to limit and regulate the presence of Cr(VI) in the environment and to protect industrial workers using chromium and end-users of manufactured products. As a consequence, new standard methods and analytical procedures have been published at the EU level for Cr(VI) determination in soil, sludge, sediment, and similar waste materials, workplace atmospheres, cement, packaging materials, industrially produced samples, and corrosion-protection layers on some components of vehicles and electrical and electronic equipment. The objective of this article is to summarize the different directives and recommendations and to critically review the currently existing standard methods and the methods published in the literature for chromium speciation in the above mentioned solid matrices, putting the emphasis on the different extraction procedures which have been developed for each matrix. Particular attention has been paid to Cr(III) and Cr(VI) inter-conversions that can occur during extraction and efforts to minimize these unwanted reactions. Although the use of NaOH-Na{sub 2}CO{sub 3} solutions with hot plate extraction seems to be the more widespread procedure, species transformation can still occur and several studies suggest that speciated isotope-dilution mass spectrometry (SIDMS) could be a suitable tool for correction of these interconversions. Besides, recent studies have proved the role of Cr(III) in chromium toxicology. As a consequence, the authors suggest an update of standard methods in the near future. (orig.)

Chromium Salen Mediated Alkene Epoxidation

DEFF Research Database (Denmark)

Petersen, Kaare Brandt; Norrby, Per-Ola; Daly, Adrian M.

2002-01-01

The mechanism of alkene epoxidation by chromium(v) oxo salen complexes has been studied by DFT and experimental methods. The reaction is compared to the closely related Mn-catalyzed process in an attempt to understand the dramatic difference in selectivity between the two systems. Overall......-spin surface. The low-spin addition of metal oxo species to an alkene leads to an intermediate which forms epoxide either with a barrier on the low-spin surface or without a barrier after spin inversion. Supporting evidence for this intermediate was obtained by using vinylcyclopropane traps. The chromium...

Contribution of photoelectron spectrometry and infrared spectrometry to the study of various oxidised forms of chromium

International Nuclear Information System (INIS)

Feve, L.

1985-03-01

Securate knowledge of internal surface of primary coolant circuits of PWR is required for an estimation of dissolution of used materials and for estimation of decontamination efficiency. The binding energies of various electron levels of chromium were determined by photoelectron spectrometry (ESCA), both for the metal and for certain compounds. Because of the intensities of the signals obtained the 2 p 3/2 level alone can be used for analytical purposes. Owing to a possible interference between this level due to hexavalent chromium and a satellite peak caused by trivalent chromium the method is not able to show up small amounts of chromium VI in chromium III. Simultaneous detection of the hexavalent and trivalent forms was achieved by infrared spectrometry. The problem of revealing traces of chromium VI in surface layers of trivalent chromium oxide has thus been solved [fr

EFSA NDA Panel (EFSA Panel on Dietetic Products, Nutrition and Allergies), 2014. Scientific Opinion on Dietary Reference Values for chromium

DEFF Research Database (Denmark)

Tetens, Inge

2014-01-01

parenteral nutrition was considered to be the most convincing, but overall data do not provide sufficient information on the reversibility of the possible deficiencies and the nature of any dose–response curve in order to identify a dietary requirement for humans. The Panel concludes that no Average......Following a request from the European Commission, the Panel on Dietetic Products, Nutrition and Allergies (NDA) considered the evidence for setting Dietary Reference Values for chromium. Trivalent chromium (Cr(III)) has been postulated to be necessary for the efficacy of insulin in regulating...... models have not produced consistent results, and that there is no evidence of essentiality of Cr(III) in animal nutrition. Evaluating the possibility of Cr(III) as an essential element for humans, the evidence from reported improvements associated with chromium supplementation in patients on total...

Method for electrodeposition of nickel--chromium alloys and coating of uranium

International Nuclear Information System (INIS)

Stromatt, R.W.; Lundquist, J.R.

1975-01-01

High-quality electrodeposits of nickel-chromium binary alloys in which the percentage of chromium is controlled can be obtained by the addition of a complexing agent such as ethylenediaminetetraacetic disodium salt to the plating solution. The nickel-chromium alloys were found to provide an excellent hydrogen barrier for the protection of uranium fuel elements. (U.S.)

Sensing of phosphates by using luminescent Eu(III) and Tb(III) complexes: application to the microalgal cell Chlorella vulgaris.

Science.gov (United States)

Nadella, Sandeep; Sahoo, Jashobanta; Subramanian, Palani S; Sahu, Abhishek; Mishra, Sandhya; Albrecht, Markus

2014-05-12

Phenanthroline-based chiral ligands L(1) and L(2) as well as the corresponding Eu(III) and Tb(III) complexes were synthesized and characterized. The coordination compounds show red and green emission, which was explored for the sensing of a series of anions such as F(-), Cl(-), Br(-), I(-), NO3(-), NO2(-), HPO4(2-), HSO4(-), CH3COO(-), and HCO3(-). Among the anions, HPO4(2-) exhibited a strong response in the emission property of both europium(III) and terbium(III) complexes. The complexes showed interactions with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). Owing to this recognition, these complexes have been applied as staining agents in the microalgal cell Chlorella vulgaris. The stained microalgal cells were monitored through fluorescence microscopy and scanning electron microscopy. Initially, the complexes bind to the outer cell wall and then enter the cell wall through holes in which they probably bind to phospholipids. This leads to a quenching of the luminescence properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Final Report - Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

International Nuclear Information System (INIS)

Benner, Shawn G.; Fendorf, Scott

2009-01-01

In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - 'affecting both Cr and U

Synthesis, Characterization and Antibacterial Studies of N-(Benzothiazol-2-yl)-4-chlorobenzenesulphonamide and Its Neodymium(III) and Thallium(III) Complexes.

Science.gov (United States)

Obasi, Lawrence Nnamdi; Oruma, Uchechukwu Susan; Al-Swaidan, Ibrahim Abdulrazak; Ramasami, Ponnadurai; Ezeorah, Chigozie Julius; Ochonogor, Alfred Ezinna

2017-02-22

N -(Benzothiazol-2-yl)-4-chlorobenzenesulphonamide (NBTCS) was synthesized by condensation reaction of 4-chlorobenzenesulphonyl chloride and 2-aminobenzothiazole in acetone under reflux. Neodymium(III) and thallium(III) complexes of the ligand were also synthesized. Both ligand and metal complexes were characterized using UV-Vis, IR, ¹H- and 13 C-NMR spectroscopies, elemental analysis and molar conductance measurement. IR studies revealed that the ligand is tridentate and coordinates to the metal ions through nitrogen and oxygen atoms of the sulphonamide group and nitrogen atom attached to benzothiazole ring. The neodymium(III) complex displays a coordination number of eight while thallium(III) complex displays a coordination number of six. The ligand and its complexes were screened in vitro for their antibacterial activities against Escherichia coli strains ( E. coli 6 and E. coli 13 ), Proteus species, Staphylococcus aureus and Pseudomonas aeruginosa using the agar well diffusion technique. The synthesized compounds were found to be more active against the microorganisms screened relative to ciprofloxacin, gentamicin and co-trimoxazole.

Spectral intensities and bonding parameters for some praseodymium(III) and neodymium(III) complexes with benzimidazoles

Energy Technology Data Exchange (ETDEWEB)

Vyas, P C; Ojha, C K; Mittal, S; Joshi, G K

1988-09-01

The electronic spectral intensity parameters (Judd-Ofelt; Tsub(lambda)) calculated from absorption spectral data for the complexes of praseodymium(III) and neodymium(III) nitrates with benzimidazole and 2-methyl-, 2-ethyl- and 2-n-propyl-benzimidazoles are reported. The conductance of these derivatives in dimethylformamide suggests 1:1 electrolytic nature. The infrared spectral data indicate the presence of Csub(2v) as well Dsub(2h)-nitrate ions in the complexes. The correlation of the intensity of hypersensitive transitions with bonding (nephelauxetic ratio and degree of covalency) parameters are also reported. (author). 13 refs., 2 tables.

An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion.

Science.gov (United States)

Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D; Nam, Wonwoo

2014-02-18

Reaction of a nonheme iron(III)-peroxo complex, [Fe(III)(14-TMC)(O2)](+), with NO(+), a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2˙(-)) + NO], affords an iron(IV)-oxo complex, [Fe(IV)(14-TMC)(O)](2+), and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [Fe(III)(14-TMC)(NO3)(F)](+).

Studies of Binary Complexes of Tripodal Ligand cis,cis-1,3,5-tris(methylaminocyclohexane with Cr(III and Fe(III

Directory of Open Access Journals (Sweden)

S. Esakki Muthu

2005-01-01

Full Text Available The formation of binary complexes of Cr(III and Fe(III with a tripodal ligand cis,cis-1,3,5-tris(methylaminocyclohexane (tmach (L has been investigated in solution. The overall stability constants of tmach with Cr(III and Fe(III were determined by potentiometric method at an ionic strength of 0.1 M NaClO4 at 25±1°C in aqueous medium. The formation of species like MLH25+, MLH4+, ML3+, ML(OH2+ and ML(OH3 were observed. Fe(III was found to form more stable complexes than Cr(III. Molecular mechanics calculations were performed to explain the mode of coordination in solution.

Effects of reactive Mn(III)-oxalate complexes on structurally intact plant cell walls

Science.gov (United States)

Summering, J. A.; Keiluweit, M.; Goni, M. A.; Nico, P. S.; Kleber, M.

2011-12-01

Lignin components in the in plant litter are commonly assumed to have longer residence times in soil than many other compounds, which are supposedly, more easily degradable. The supposed resistance of lignin compounds to decomposition is generally attributed to the complex chain of biochemical steps required to create footholds in the non-porous structure of ligno-cellulose in cell walls. Interestingly, Mn(III) complexes have shown the ability to degrade ligno-cellulose. Mn(III) chelated by ligands such as oxalate are soluble oxidizers with a high affinity for lignin structures. Here we determined (i) the formation and decay kinetics of the Mn(III)-oxalate complexes in aqueous solution and (ii) the effects that these complexes have on intact ligno-cellulose. UV/vis spectroscopy and iodometric titrations confirmed the transient nature of Mn(III)-oxalate complexes with decay rates being in the order of hours. Zinnia elegans tracheary elements - a model ligno-cellulose substrate - were treated with Mn(III)-oxalate complexes in a newly developed flow-through reactor. Soluble decomposition products released during the treatment were analyzed by GC/MS and the degree of cell integrity was measured by cell counts, pre- and post-treatment counts indicate a decrease in intact Zinnia elegans as a result of Mn(III)-treatment. GC/MS results showed the release of a multitude of solubilized lignin breakdown products from plant cell walls. We conclude that Mn(III)-oxalate complexes have the ability to lyse intact plant cells and solubilize lignin. Lignin decomposition may thus be seen as resource dependent, with Mn(III) a powerful resource that should be abundant in terrestrial characterized by frequent redox fluctuations.

The Effect of Pressure and Temperature on Separation of Free Gadolinium(III) From Gd-DTPA Complex by Nanofiltration-Complexation Method

Science.gov (United States)

Rahayu, Iman; Anggraeni, Anni; Ukun, MSS; Bahti, Husein H.

2017-05-01

Nowdays, the utilization of rare earth elements has been carried out widely in industry and medicine, one of them is gadolinium in Gd-DTPA complex is used as a contrast agent in a magnetic resonance imaging (MRI) diagnostic to increase the visual contrast between normal tissue and diseased. Although the stability of a given complex may be high enough, the complexation step couldnot have been completed, so there is possible to gadolinium(III) in the complex compound. Therefore, the function of that compounds should be dangerous because of the toxicity of gadolinium(III) in human body. So, it is necessarry to separate free gadolinium(III) from Gd-DTPA complex by nanofiltration-complexation. The method of this study is complexing of Gd2O3 with DTPA ligand by reflux and separation of Gd-DTPA complex from gadolinium(III) with a nanofiltration membrane on the variation of pressures(2, 3, 4, 5, 6 bars) and temperature (25, 30, 35, 40 °C) and determined the flux and rejection. The results of this study are the higher of pressures and temperatures, permeation flux are increasing and ion rejections are decreasing and gave the free gadolinium(III) rejection until 86.26%.

Manganese oxide nanoflakes/multi-walled carbon nanotubes/chitosan nanocomposite modified glassy carbon electrode as a novel electrochemical sensor for chromium (III) detection

International Nuclear Information System (INIS)

Salimi, Abdollah; Pourbahram, Bahareh; Mansouri-Majd, Samira; Hallaj, Rahman

2015-01-01

Highlights: • CNTs/chitosan/GC electrode used as platform for electrodeposition of MnO x -nanoflakes. • Modified electrode has excellent catalytic activity for oxidation of Cr 3+ at pH 3–7. • Detection limit and sensitivity of sensor for Cr 3+ detection were 0.3 μM and 18.7 nA/μM. • Sensor has good stability and high selectivity in the presence of common interferences. • Sensor applied for the detection of Cr 3+ in real samples with satisfactory results. - Abstract: In this research a nanocomposite containing chitosan (Chit) and maltiwalled carbon nanotubes (MWCNTs) was applied as platform for immobilization of electrodeposited manganese oxide (MnOx) nanostructures. First, glassy carbon (GC) electrode modified with thin film of Chitosan/MWCNTs nanocomposite. Then MnO x nanostructures was electrodeposited onto Chitosan/MWCNTs modified GC electrode using combination of constant potential step (0.6 V) and cyclic voltammetry(0.3–0.6 V) techniques. The XRD patterns and scanning electron microscope images indicated immobilization of uniformly MnOx nanoflakes with high crystallite onto MWCNTs/Chit film. The modified electrode shows a well-defined redox couple for Mn 2+ /MnO 2 system. Charge transfer coefficient (α), electron transfer rate constant (k s ) and surface concentration (Γ) were 0.394, 3.44 s −1 and 3.3 × 10 −11 mol cm −2 , respectively. The modified electrode showed excellent electrocatalytic activity toward oxidation of chromium (III) at natural pH solutions. Cyclic voltammetry and hydrodynamic amperometery were applied as measuring techniques for chromium detection. Detection limit, sensitivity and linear concentration range of the sensor were, 0.3 (μM), 18.7 nAμ M −1 and 3 μM to 200 μM, respectively. Moreover, the sensor retained about 90% of its original response toward Cr(III) after storage three months in ambient condition. Furthermore, the sensor response toward different common interferences was negligible. Finally, the

Impact of Fe(III)-OM complexes and Fe(III) polymerization on SOM pools reactivity under different land uses

Science.gov (United States)

Giannetta, B.; Plaza, C.; Zaccone, C.; Siebecker, M. G.; Rovira, P.; Vischetti, C.; Sparks, D. L.

2017-12-01

Soil organic matter (SOM) protection and long-term accumulation are controlled by adsorption to mineral surfaces in different ways, depending on its molecular structure and pedo-climatic conditions. Iron (Fe) oxides are known to be key regulators of the soil carbon (C) cycle, and Fe speciation in soils is highly dependent on environmental conditions and chemical interactions with SOM. However, the molecular structure and hydrolysis of Fe species formed in association with SOM is still poorly described. We hypothesize the existence of two pools of Fe which interact with SOM: mononuclear Fe(III)-SOM complexes and precipitated Fe(III) hydroxides. To verify our hypothesis, we investigated the interactions between Fe(III) and physically isolated soil fractions by means of batch experiments at pH 7. Specifically, we examined the fine silt plus clay (FSi+C) fraction, obtained by ultrasonic dispersion and wet sieving. The soil samples spanned several land uses, including coniferous forest (CFS), grassland (GS), technosols (TS) and agricultural (AS) soils. Solid phase products and supernatants were analyzed for C and Fe content. X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analysis were also performed. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was used to assess the main C functional groups involved in C complexation and desorption experiments. Preliminary linear combination fitting (LCF) of Fe K-edge extended X-ray absorption fine structure (EXAFS) spectra suggested the formation of ferrihydrite-like polymeric Fe(III) oxides in reacted CFS and GS samples, with higher C and Fe concentration. Conversely, mononuclear Fe(III) OM complexes dominated the speciation for TS and AS samples, characterized by lower C and Fe concentration, inhibiting the hydrolysis and polymerization of Fe (III). This approach will help revealing the mechanisms by which SOM pools can control Fe(III) speciation, and will elucidate how both Fe(III

An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion†

Science.gov (United States)

Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D.; Nam, Wonwoo

2014-01-01

Reaction of a nonheme iron(III)-peroxo complex, [FeIII(14-TMC)(O2)]+, with NO+, a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2•−) + NO], affords an iron(IV)-oxo complex, [FeIV(14-TMC)(O)]2+, and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [FeIII(14-TMC)(NO3)(F)]+. PMID:24394960

An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion†

OpenAIRE

Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D.; Nam, Wonwoo

2014-01-01

Reaction of a nonheme iron(III)-peroxo complex, [FeIII(14-TMC)(O2)]+, with NO+, a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2•−) + NO], affords an iron(IV)-oxo complex, [FeIV(14-TMC)(O)]2+, and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [FeIII(14-TMC)(NO3)(F)]+.

Interaction mode between methylene blue-Sm(III) complex and ...

African Journals Online (AJOL)

Spectroscopic and viscosity methods were applied to investigate the interaction between methylene blue (MB)-Sm(III) complex and herring sperm DNA by using acridine orange as a spectral probe in Tris-HCl buffer (pH 7.40). By means of molar ratio method, the binding ratios between MB-Sm(III)and DNA were determined ...

Effect Of Chromium- Picolinat On Biochemical And Histopathological ...

African Journals Online (AJOL)

Chromium III tris (picolinate) [Cr(pic)3]is a popular nutritional supplement; however its safety has been questioned, especially with regard to its ability to act as a clastogen. The aim of the present work was to evaluate the biochemical and morphological changes in the liver following oral administration of Cr-picolinate and ...

Syntheses, structures, and magnetic properties of a family of heterometallic heptanuclear [Cu5Ln2] (Ln = Y(III), Lu(III), Dy(III), Ho(III), Er(III), and Yb(III)) complexes: observation of SMM behavior for the Dy(III) and Ho(III) analogues.

Science.gov (United States)

Chandrasekhar, Vadapalli; Dey, Atanu; Das, Sourav; Rouzières, Mathieu; Clérac, Rodolphe

2013-03-04

Sequential reaction of the multisite coordination ligand (LH3) with Cu(OAc)2·H2O, followed by the addition of a rare-earth(III) nitrate salt in the presence of triethylamine, afforded a series of heterometallic heptanuclear complexes containing a [Cu5Ln2] core {Ln = Y(1), Lu(2), Dy(3), Ho(4), Er(5), and Yb(6)}. Single-crystal X-ray crystallography reveals that all the complexes are dicationic species that crystallize with two nitrate anions to compensate the charge. The heptanuclear aggregates in 1-6 are centrosymmetrical complexes, with a hexagonal-like arrangement of six peripheral metal ions (two rare-earth and four copper) around a central Cu(II) situated on a crystallographic inversion center. An all-oxygen environment is found to be present around the rare-earth metal ions, which adopt a distorted square-antiprismatic geometry. Three different Cu(II) sites are present in the heptanuclear complexes: two possess a distorted octahedral coordination sphere while the remaining one displays a distorted square-pyramidal geometry. Detailed static and dynamic magnetic properties of all the complexes have been studied and revealed the single-molecule magnet behavior of the Dy(III) and Ho(III) derivatives.

Soluble dendrimers europium(III) β-diketonate complex for organic memory devices

International Nuclear Information System (INIS)

Wang Binbin; Fang Junfeng; Li Bin; You Han; Ma Dongge; Hong Ziruo; Li Wenlian; Su Zhongmin

2008-01-01

We report the synthesis of a soluble dendrimers europium(III) complex, tris(dibenzoylmethanato)(1,3,5-tris[2-(2'-pyridyl) benzimidazoly]methylbenzene)-europium(III), and its application in organic electrical bistable memory device. Excellent stability that ensured more than 10 6 write-read-erase-reread cycles has been performed in ambient conditions without current-induced degradation. High-density, low-cost memory, good film-firming property, fascinating thermal and morphological stability allow the application of the dendrimers europium(III) complex as an active medium in non-volatile memory devices

Phosphorescent systems based on iridium(III) complexes

NARCIS (Netherlands)

Ulbricht, C.

2009-01-01

Phosphorescent iridium(III)-based complexes are experiencing a growing interest in a number of research fields. Aside from lighting and display technologies (i.e. OLEDs and LECs), they find use in various applications such as biolabeling, sensors, solar cells and water splitting. In particular, the

Lanthanum(III) and praseodymium(III) complexes with bidentate and tetradentate Schiff base ligands containing indole ring

International Nuclear Information System (INIS)

Rai, Anita; Sengupta, Soumitra Kumar; Pandey, Om Prakash

2000-01-01

Complexes of lanthanum(III) and praseodymium(III) with Schiff bases, prepared from isatin with aniline, 4-chloroaniline, 2- bromoaniline, 2-nitroaniline (Hl), ethylenediamine, o- phenylenediamine and 4-methyl-o-phenylenediamine (H 2 L') have been synthesised and their physico-chemical properties investigated using elemental analysis, molar conductivities, magnetic susceptibility measurements and spectral (visible, infrared and 1 H NMR) data. The Schiff bases HL bind in a bidentate manner while schiff bases H 2 L' bind in a tetradentate manner. The probable structures of the complexes are proposed. (author)

Reduction of chromium (VI by the indirect action of Thiobacillus thioparus

Directory of Open Access Journals (Sweden)

E. Donati

2003-03-01

Full Text Available The microbial reduction of chromium(VI to chromium(III has been one of the most widely studied forms of metal bioremediation. Recently, we have found that Thiobacillus ferrooxidans and Thiobacillus thiooxidans, growing on elemental sulphur, can indirectly promote chromium(VI reduction by producing reducing agents such as sulphite and thiosulphate, which abiotically reduce chromium(VI. Those species of Thiobacillus are acidophilic bacteria which grow optimally at pH values lower than 4. However, most of those reducing agents are stabilised at higher pH values. Thus, the present paper reports on the ability to reduce chromium(VI using another specie of Thiobacilli, Thiobacillus thioparus, which is able to grow at pH close to 7.0. T. thioparus cultures were carried out in a fermentation vessel containing medium and sulphur as the sole energy source and maintained at 30ºC and 400 rpm. The pH was adjusted to 6.0, 7.0 or 8.0 and maintained with the automatic addition of KOH. Our results show high chromium (VI reduction values (close to 100% at the end of bacterial growth at the three pH values. The results of these experiments are very promising for development of a microbiological process to be used in the detoxification of chromium(VI-polluted effluents.

Spectroscopic properties of chromium(III) in zirconium barium fluoride glass (ZBLA)

International Nuclear Information System (INIS)

Balda, R.; Fernandez, J.; Illarramendi, M.A.; Elejalde, M.J.

1988-01-01

The optical properties of trivalent chromium ions in ZBLA glass have been studied for different concentrations of Cr 3 + . Optical absorption, luminescence and lifetimes have been investigated in a wide range of temperatures. The relative quantum efficiencies of these systems have been determined from the integrated luminescence decay curves as a function of the excitation wavelength

Use of metallurgical dust for removal chromium ions from aqueous solutions

Directory of Open Access Journals (Sweden)

Pająk Magdalena

2018-01-01

Full Text Available The aim of the study was to determine the potential for the application of dust from steel plant as an effective sorbent for removing Cr(III and Cr(VI in the form of simple and complex ions – Acid Blue 193 dye from aqueous solutions. Three isotherms models were used to interpret the experimental results namely: Langmuir, Freundlich, and Dubinin–Radushkevich. Estimated equations parameters allowed to determine the binding mechanism. Based on laboratory studies it was found that the dust was characterized by high sorption capacities for Cr ions and dye from the aqueous solution. The sorption capacity of the dust for Cr(III and Cr(VI ions depended on the degree of oxidation, pH of solution and kind of anion and changed in series: Cr(III-Cl pH=5.0> Cr(III-SO4 pH=5.0> Cr(III-Cl pH=3.0> Cr(III-SO4 pH=3.0> Cr(VI pH=5.0> Cr(VI pH=3.0. Dust was also characterized by a high maximum sorption capacity of dye at a range of 38.2 – 91.7 mg/g, depending on the dose of dust. Based on the study it was found that dust from a steel plant, containing iron oxides, can be used as low-cost and effective sorbent to remove pollutions containing chromium ions, especially from acidic wastewater.

The electrochemistry of chromium, chromium-boron and chromium-phosphorus alloys

International Nuclear Information System (INIS)

Moffat, T.P.; Ruf, R.R.; Latanision, R.M.

1987-01-01

It is fairly well established that chromium-metalloid interactions represent the key to understanding the remarkable corrosion behavior of TM-Cr-M glasses; (Fe, Ni, Co,...)-Cr-(P, Si, C, S). The character and kinetics of passive film growth on the glasses are being studied ni order to assess the role of the film former, chromium, and the metalloids in the passivation process. A series of thin film microcrystalline chromium, Cr-B and Cr-P binary alloys have been fabricated by physical vapor deposition techniques. Vacuum melted conventionally processed chromium has also been studied. Examination of these materials in lM H/sub 2/SO/sub 4/ and lM HCl by voltammetry, potentiostatic and impedance techniques yields the following conclusion: 1. Pure chromium with a grain size varying from < 400 A to 0.5 mm exhibits no well defined differences in electrochemical behavior in lM H/sub 2/SO/sub 4/. 2. The tremendous corrosion resistance of Cr-B alloys has been confirmed. 3. The beneficial effects observed for boron alloyed with chromium may be considered surprising in view of the neutral/negative influence of alloying boron with iron, i.e. Fe/sub 80/B/sub 20/. 4. The interaction of the electrochemistry of the metalloid constituent with that of the transition base element determines the corrosion behavior. 5. Preliminary work with Cr-P alloys indicates that certain compositions exhibit promising properties - certain films were found to be intact after two days of immersion in concentrated HCl. Further work is in progress

Synthesis, Characterization and Antibacterial Studies of N-(Benzothiazol-2-yl-4-chlorobenzenesulphonamide and Its Neodymium(III and Thallium(III Complexes

Directory of Open Access Journals (Sweden)

Lawrence Nnamdi Obasi

2017-02-01

Full Text Available N-(Benzothiazol-2-yl-4-chlorobenzenesulphonamide (NBTCS was synthesized by condensation reaction of 4-chlorobenzenesulphonyl chloride and 2-aminobenzothiazole in acetone under reflux. Neodymium(III and thallium(III complexes of the ligand were also synthesized. Both ligand and metal complexes were characterized using UV-Vis, IR, 1H- and 13C-NMR spectroscopies, elemental analysis and molar conductance measurement. IR studies revealed that the ligand is tridentate and coordinates to the metal ions through nitrogen and oxygen atoms of the sulphonamide group and nitrogen atom attached to benzothiazole ring. The neodymium(III complex displays a coordination number of eight while thallium(III complex displays a coordination number of six. The ligand and its complexes were screened in vitro for their antibacterial activities against Escherichia coli strains (E. coli 6 and E. coli 13, Proteus species, Staphylococcus aureus and Pseudomonas aeruginosa using the agar well diffusion technique. The synthesized compounds were found to be more active against the microorganisms screened relative to ciprofloxacin, gentamicin and co-trimoxazole.

Wet skins tanning with chromium in dense CO2 under pressure

International Nuclear Information System (INIS)

Saldinari, L.; Dutel, Ch.; Perre, Ch.

2000-01-01

An ancestral gesture steadily improved through the centuries, the transformation of skins into leather includes several stages of which the principal one is tanning. Today, 90 % of the world's leather products are tanned with chromium. However, this stage is an environmental liability, and reducing the volume and chromium content of the waste has become a major issue. A first study on skin degreasing by dense CO 2 helped sharply reduce the volume of the fatty effluents. To replace water by dense CO 2 as the tanning medium was the logical next step. The present study was carried out in cooperation with three tanneries in the Rhone-Alpes-Auvergne area of France and a manufacturer of tanning materials. The difficulty of the study was the chemically opposed character of the two media involved. CO 2 is a non-polar and lipophilic solvent while inorganic chromium is insoluble. The water present in the treated skin is a polar and ionic reaction medium and one of the reagents in tanning chemistry. The mixture of these two partially miscible compounds gives a pH 3 by carbonic acid formation. Tanning is based on the reactivity of collagen, the main component of the skin, with hydroxylated complexes of chromium. Collagen is a protein containing some chemical functions, amines (R-NH 2 ) and carboxylic (R-COOH) for example. These functions impart an amphoteric character to the compound. The WERNER theory of complex salts explains the formation of hydroxylated complexes of chromium and their fixing on the carboxylic functions of collagen by oxolation. pH is the key parameter in tanning. The success of the process demands chromium impregnation without fixing it at a pH lower than 5, and then to fix it by increasing the pH. This opened two alternatives for transferring chromium in the skin: solubilize chromium in CO 2 via soluble organometallic complexes; or put the chromium salt into suspension without solubilizing it. The best results were obtained with the second option, which

Biosorption studies on shelled Moringa oleifera seeds for chromium removal using radiotracer

International Nuclear Information System (INIS)

Sharma, Parul; Srivastava, M.M.; Prakash, Satya; Srivastava, Shalini

2007-01-01

Shelled Moringa oleifera seeds (SMOS) have been explored as an indigenous, inexpensive and effective sorbent for chromium removal from water bodies. Sorption studies (batch) result into the standardization of optimum conditions for removal of 81.02% Cr (III) and 88.15% Cr (VI) pH 6.5 and 2.5 respectively. Percent sorption in each case was computed on the basis of chromium estimation using planar NaI (TI) detector, coupled to 4K MCA (Canberra Accuspec Card with PC AT 386). (author)

Complexation of the actinides (III, IV and V) with organic acids

International Nuclear Information System (INIS)

Leguay, S.

2012-01-01

A thorough knowledge of the chemical properties of actinides is now required in a wide variety of fields: extraction processes involved in spent fuel reprocessing, groundwater in the vicinity of radioactive waste packages, environmental and biological media in the case of accidental release of radionuclides. In this context, the present work has been focused on the complexation of Am(III), Cm(III), Cf(III), Pu(IV) and Pa(V) with organic ligands: DTPA, NTA and citric acid. The complexation of pentavalent protactinium with citric and nitrilotriacetic acids was studied using liquid-liquid extraction with the element at tracer scale (C Pa ≤ 10 -10 M). The order and the mean charge of each complex were determined from the analysis of the systematic variations of the distribution coefficient of Pa(V) as function of ligand and proton concentration. Then, the apparent formation constants related of the so-identified complexes were calculated. The complexation of trivalent actinides with DTPA was studied by fluorescence spectroscopy (TRLFS) and capillary electrophoresis (CE-ICP-MS). The coexistence of the mono-protonated and non-protonated complexes (AnHDTPA - and AnDTPA 2- ) in acidic media (1.5 ≤ pH ≤ 3.5) was shown unambiguously. Literature data have been reinterpreted by taking into account both complexes and a consistent set of formation constants of An(III)-DTPA has been obtained. The experimental study was completed by theoretical calculations (DFT) on Cm-DTPA system. The coordination geometry of Cm in CmDTPA 2- and CmHDTPA - including water molecules in the first coordination sphere has been determined as well as interatomic distances. Finally, a study on the complexation of Pu(IV) with DTPA was initiated in order to more closely mimic physiological conditions. A three-step approach was proposed to avoid plutonium hydrolysis: i/ complexation of Pu(IV) with (NTA) in order to protect Pu(IV) from hydrolysis (at low pH) ii/ increase of pH toward neutral conditions

Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine; Etude de la selectivite de molecules extractantes polyazotees dans la complexation des actinides (III) et des lanthanides (III) en solution dans la pyridine anhydre

Energy Technology Data Exchange (ETDEWEB)

Riviere, Ch

2000-10-05

The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

Characteristics of oxidation of low-alloyed chromium in nitrogen tetroxide

International Nuclear Information System (INIS)

Kamenev, A.Ya.; Goncharova, N.V.; Kopets, Z.V.; Tedushin, E.E.

1985-01-01

The effect of N 2 O 4 on corrosion properties of chromium-based alloys is studied. The method of structural materials analysis is described using as an example chromium-based alloys in the flow of chemically active N 2 O 4 at high temperatures. The method has been used to study corrosive behaviour of chromium at temperatures 923, 1073 and 1273 K. The time of exposure amounts up to 140 hours. The wave-like time dependence of mass velocity variation has been observed for all chromium samples under test. The time of the alloy exposure to N 2 O 4 medium and the nature of the alloying affect this dependence. The given metallograhic studies of chromium alloys show complex structure of the surface layer

Synthesis, characterization and stability of Cr(III) and Fe(III) hydroxides

Energy Technology Data Exchange (ETDEWEB)

Papassiopi, N.; Vaxevanidou, K.; Christou, C.; Karagianni, E.; Antipas, G.S.E., E-mail: gantipas@metal.ntua.gr

2014-01-15

Highlights: • Fe(III)–Cr(III) hydroxides enhance groundwater quality better than pure Cr(III) compounds. • Crystalline Cr(OH){sub 3}·3H{sub 2}O was unstable, with a solubility higher than 50 μg/l. • Amorphous Cr(OH){sub 3}(am) was stable with a solubility lower than 50 μg/l in the range 5.7 < pH < 11. • For mixed Fe{sub 0.75}Cr{sub 0.25}(OH){sub 3}, the stability region was extended to 4.8 < pH < 13.5. -- Abstract: Chromium is a common contaminant of soils and aquifers and constitutes a major environmental problem. In nature, chromium usually exists in the form of two oxidation states, trivalent, Cr(III), which is relatively innocuous for biota and for the aquatic environment, and hexavalent, Cr(VI) which is toxic, carcinogenic and very soluble. Accordingly, the majority of wastewater and groundwater treatment technologies, include a stage where Cr(VI) is reduced to Cr(III), in order to remove chromium from the aqueous phase and bind the element in the form of environmentally stable solid compounds. In the absence of iron the final product is typically of the form Cr(OH){sub 3}·xH{sub 2}O whereas in the presence of iron the precipitate is a mixed Fe{sub (1−x)}Cr{sub x}(OH){sub 3} phase. In this study, we report on the synthesis, characterisation and stability of mixed (Fe{sub x},Cr{sub 1−x})(OH){sub 3} hydroxides as compared to the stability of Cr(OH){sub 3}. We established that the plain Cr(III) hydroxide, abiding to the approximate molecular formula Cr(OH){sub 3}·3H{sub 2}O, was crystalline, highly soluble, i.e. unstable, with a tendency to transform into the stable amorphous hydroxide Cr(OH){sub 3}(am) phase. Mixed Fe{sub 0.75}Cr{sub 0.25}(OH){sub 3} hydroxides were found to be of the ferrihydrite structure, Fe(OH){sub 3}, and we correlated their solubility to that of a solid solution formed by plain ferrihydrite and the amorphous Cr(III) hydroxide. Both our experimental results and thermodynamic calculations indicated that mixed Fe(III)–Cr(III

Cr(III), Fe(III) and Co(III) complexes of tetradentate (ONNO) Schiff base ligands: Synthesis, characterization, properties and biological activity

Science.gov (United States)

Keskioğlu, Eren; Gündüzalp, Ayla Balaban; Çete, Servet; Hamurcu, Fatma; Erk, Birgül

2008-08-01

A series of metal complexes were synthesized from equimolar amounts of Schiff bases: 1,4-bis[3-(2-hydroxy-1-naphthaldimine)propyl]piperazine (bappnaf) and 1,8-bis[3-(2-hydroxy-1-naphthaldimine)- p-menthane (damnaf) with metal chlorides. All of synthesized compounds were characterized by elemental analyses, spectral (UV-vis, IR, 1H- 13C NMR, LC-MS) and thermal (TGA-DTA) methods, magnetic and conductance measurements. Schiff base complexes supposed in tetragonal geometry have the general formula [M(bappnaf or damnaf)]Cl· nH 2O, where M = Cr(III), Co(III) and n = 2, 3. But also Fe(III) complexes have octahedral geometry by the coordination of two water molecules and the formula is [Fe(bappnaf or damnaf)(H 2O) 2]Cl. The changes in the selected vibration bands in FT-IR indicate that Schiff bases behave as (ONNO) tetradentate ligands and coordinate to metal ions from two phenolic oxygen atoms and two azomethine nitrogen atoms. Conductance measurements suggest 1:1 electrolytic nature of the metal complexes. The synthesized compounds except bappnaf ligand have the antimicrobial activity against the bacteria: Escherichia coli (ATCC 11230), Yersinia enterocolitica (ATCC 1501), Bacillus magaterium (RSKK 5117), Bacillus subtilis (RSKK 244), Bacillus cereus (RSKK 863) and the fungi: Candida albicans (ATCC 10239). These results have been considerably interest in piperazine derivatives due to their significant applications in antimicrobial studies.

Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

Science.gov (United States)

André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

2018-03-01

The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

Complexes of molybdenum(III) with 2-(2'-pyridyl)benzimidazole

International Nuclear Information System (INIS)

Ghosh, S.P.; Prasad, K.M.

1979-01-01

Molybdenum(III) forms with 2-(2'-pyridyl) benzimidazole(LH) the trischelated complexes, [Mo(LH) 3 ]X 3 as well as the cationic-anionic complexes, [Mo(LH) 3 X 2 ] + [Mo(LH)X 4 ] - (X=Cl - ,Br - or NCS - ), depending on pH. These complexes have been synthesised and characterised from elemental analyses, i.r. and electronic spectra, magnetic moments and molar conductance. (auth.)

Fe (III) complex of mefloquine hydrochloride: Synthesis ...

African Journals Online (AJOL)

As part of the ongoing research for more effective antimalarial drug, Fe (III) complex of mefloquine hydrochloride (antimalarial drug) was synthesized using template method. Mefloquine was tentatively found to have coordinated through the hydroxyl and the two nitrogen atoms in the quinoline and piperidine in the structure, ...

Silver Nanoparticle-Enhanced Resonance Raman Sensor of Chromium(III) in Seawater Samples.

Science.gov (United States)

Ly, Nguyễn Hoàng; Joo, Sang-Woo

2015-04-29

Tris(hydroxymethyl)aminomethane ethylenediaminetetraacetic acid (Tris-EDTA), upon binding Cr(III) in aqueous solutions at pH 8.0 on silver nanoparticles (AgNPs), was found to provide a sensitive and selective Raman marker band at ~563 cm-1, which can be ascribed to the metal-N band. UV-Vis absorption spectra also supported the aggregation and structural change of EDTA upon binding Cr(III). Only for Cr(III) concentrations above 500 nM, the band at ~563 cm-1 become strongly intensified in the surface-enhanced Raman scattering spectra. This band, due to the metal-EDTA complex, was not observed in the case of 50 mM of K+, Cd2+, Mg2+, Ca2+, Mn2+, Co2+, Na+, Cu2+, NH4+, Hg2+, Ni2+, Fe3+, Pb2+, Fe2+, and Zn2+ ions. Seawater samples containing K, Mg, Ca, and Na ion concentrations higher than 8 mM also showed the characteristic Raman band at ~563 cm-1 above 500 nM, validating our method. Our approach may be useful in detecting real water samples by means of AgNPs and Raman spectroscopy.

Speciation and determination of ultra trace amounts of chromium by solidified floating organic drop microextraction (SFODME) and graphite furnace atomic absorption spectrometry

Energy Technology Data Exchange (ETDEWEB)

Moghadam, Masoud Rohani [Department of Chemistry, Faculty of Science, Yazd University, Yazd 89195-741 (Iran, Islamic Republic of); Dadfarnia, Shayessteh, E-mail: sdadfarnia@yazduni.ac.ir [Department of Chemistry, Faculty of Science, Yazd University, Yazd 89195-741 (Iran, Islamic Republic of); Haji Shabani, Ali Mohammad [Department of Chemistry, Faculty of Science, Yazd University, Yazd 89195-741 (Iran, Islamic Republic of)

2011-02-15

Solidified floating organic drop microextraction (SFODME) method in combination with graphite furnace atomic absorption spectrometry (GFAAS) has been used for the determination of chromium species in water and urine samples. 1-undecanol containing 2-thenoyltrifluoroacetone (TTA) was used as a selective chelating agent for the extraction of Cr(III). The total Cr was determined after the reduction of Cr(VI) to Cr(III) with hydroxylamine. The concentration of Cr(VI) was determined from the difference between the concentration of total chromium and the Cr(III). Several variables such as the sample pH, concentration of TTA, salt concentration, extraction time and the sample volume were investigated in detail. Under the optimum conditions, the limit of detection of the proposed method was 0.006 {mu}g l{sup -1} for Cr(III) and the relative standard deviation for six replicate determinations at 0.1 {mu}g l{sup -1} Cr(III) was 5.1%. The proposed method was successfully applied for the determination of chromium species in tap water, well water, mineral water, and urine samples.

Spectral, Electrochemical, Fluorescence, Kinetic and Anti-microbial Studies of Acyclic Schiff-base Gadolinium(III) Complexes

International Nuclear Information System (INIS)

Vijayaraj, A.; Prabu, R.; Suresh, R.; Narayanan, V.; Sangeetha Kumari, R.; Kaviyarasan, V.

2012-01-01

A new series of acyclic mononuclear gadolinium(III) complexes have been prepared by Schiff-base condensation derived from 5-methylsalicylaldehyde, diethylenetriamine, tris(2-aminoethyl) amine, triethylenetetramine, N,N-bis(3-aminopropyl)ethylene diamine, N,N-bis(aminopropyl) piperazine, and gadolinium nitrate. All the complexes were characterized by elemental and spectral analyses. Electronic spectra of the complexes show azomethine (CH=N) within the range of 410-420 nm. The fluorescence efficiency of Gd(III) ion in the cavity was completely quenched by the higher chain length ligands. Electrochemical studies of the complexes show irreversible one electron reduction process around -2.15 to -1.60 V. The reduction potential of gadolinium(III) complexes shifts towards anodic directions respectively upon increasing the chain length. The catalytic activity of the gadolinium(III) complexes on the hydrolysis of 4-nitrophenylphosphate was determined. All gadolinium(III) complexes were screened for antibacterial activity

Spectral, Electrochemical, Fluorescence, Kinetic and Anti-microbial Studies of Acyclic Schiff-base Gadolinium(III) Complexes

Energy Technology Data Exchange (ETDEWEB)

Vijayaraj, A.; Prabu, R.; Suresh, R.; Narayanan, V.; Sangeetha Kumari, R.; Kaviyarasan, V. [Univ. of Madras, Madras (India)

2012-11-15

A new series of acyclic mononuclear gadolinium(III) complexes have been prepared by Schiff-base condensation derived from 5-methylsalicylaldehyde, diethylenetriamine, tris(2-aminoethyl) amine, triethylenetetramine, N,N-bis(3-aminopropyl)ethylene diamine, N,N-bis(aminopropyl) piperazine, and gadolinium nitrate. All the complexes were characterized by elemental and spectral analyses. Electronic spectra of the complexes show azomethine (CH=N) within the range of 410-420 nm. The fluorescence efficiency of Gd(III) ion in the cavity was completely quenched by the higher chain length ligands. Electrochemical studies of the complexes show irreversible one electron reduction process around -2.15 to -1.60 V. The reduction potential of gadolinium(III) complexes shifts towards anodic directions respectively upon increasing the chain length. The catalytic activity of the gadolinium(III) complexes on the hydrolysis of 4-nitrophenylphosphate was determined. All gadolinium(III) complexes were screened for antibacterial activity.

Kinetic study of the isotopic exchange of Na+ and Zn2+ ions on iron and chromium titanates

International Nuclear Information System (INIS)

Zakaria, E.S.; Ali, I.M.; Aly, H.F.

2004-01-01

Iron(III) (FeTi) and chromium (III) titanates (CrTi) were prepared as cation exchange materials in a granular form. The rate of the isotopic exchange of Na + /*Na + and Zn 2+ /*Zn 2+ between aqueous solution and iron(III) and chromium(III) titanates in Na + or Zn 2+ form has been carried out radiometrically in the 25-60 deg C temperature range. The exchange rate is controlled by a particle diffusion mechanism and experimental and theoretical approaches have been used to obtain the rate of diffusion through the spherical particles of the exchangers. The values of self diffusion (D-bar) of Na + and Zn 2+ ions were measured at different operation conditions, particle size, reaction temperatures and drying temperatures of the matrix. The values of kinetic and thermodynamic parameters were calculated and their significance discussed. (author)

Novel Luminescent Probe Based on a Terbium(III) Complex for Hemoglobin Determination

Science.gov (United States)

Yegorova, A. V.; Leonenko, I. I.; Aleksandrova, D. I.; Scrypynets, Yu. V.; Antonovich, V. P.; Ukrainets, I. V.

2014-09-01

We have studied the spectral luminescent properties of Tb(III) and Eu(III) complexes with a number of novel derivatives of oxoquinoline-3-carboxylic acid amides (L1-L5 ). We have observed quenching of the luminescence of 1:1 Tb(III)-L1-5 complexes by hemoglobin (Hb), which is explained by resonance energy transfer of electronic excitation from the donor (Tb(III)-L1-5 ) to the acceptor (Hb). Using the novel luminescent probe Tb(III)-L1, we have developed a method for determining Hb in human blood. The calibration Stern-Volmer plot is linear in the Hb concentration range 0.6-36.0 μg/mL, detection limit 0.2 μg/mL (3·10-9 mol/L).

Effect of nickel and chromium exposure on buccal cells of electroplaters.

Science.gov (United States)

Qayyum, Saba; Ara, Anjum; Usmani, Jawed Ahmad

2012-02-01

The electroplating industry commonly involves the use of nickel and chromium. An assessment of the genotoxic effects of these metals can be carried out by micronucleus (MN) test in buccal cells. Other nuclear anomalies (NA) observed in buccal cells viz., karyorrhexis, pyknosis and karyolysis are also the indicators of genotoxicity. The current study aims at determining the extent of genotoxic damage in relation to the duration of exposure to nickel and hexavalent chromium via micronuclei induction and other nuclear anomalies. The present investigation included 150 subjects of which 50 individuals with no history of nickel/chromium exposure (Group I) were taken as control, 50 electroplaters exposed to nickel and hexavalent chromium for duration of less than 10 years (Group II) and 50 electroplaters exposed for ≥10 years (Group III) were included. Slides of buccal cells were prepared and the frequency of MN (‰) and NA (‰) were calculated. ANOVA was applied to test significance. Results were considered significant at p exposure increased. Plasma nickel and chromium levels were also determined which showed a positive correlation with frequency MN and other nuclear abnormalities (p < 0.01).

Reduction of Hexavalent Chromium Using Sorbaria sorbifolia Aqueous Leaf Extract

Directory of Open Access Journals (Sweden)

Shashi Prabha Dubey

2017-07-01

Full Text Available Aqueous plant leaves extract (PLE of an abundant shrub, Sorbaria sorbifolia, was explored for the reduction of hexavalent chromium, Cr(VI, to trivalent chromium, Cr(III. The effect of contact time, pH, PLE quantity, ionic strength, hardness, temperature and effective initial Cr(VI ion concentration were tested; Cr(VI reduction followed the pseudo-first order rate kinetics and maximum reduction was observed at pH 2. Significantly, Cr(VI reduction efficacies varied from 97 to 66% over the pH range of 2 to 10, which bodes well for PLE to be used for the reduction of Cr(VI also at a higher pH. PLE-mediated Cr(VI reduction displays considerable efficiency at various ionic strengths; however, hardness strongly affects the reduction ability. Higher temperature significantly enhances the Cr(VI reduction. This study reveals the potential use of PLE as a green reducing agent in aqueous extract for the efficient reduction of Cr(VI to Cr(III.

Thermodynamics of complex formation of natural iron(III)porphyrins with neutral ligands

International Nuclear Information System (INIS)

Lebedeva, Nataliya Sh.; Yakubov, Sergey P.; Vyugin, Anatoly I.; Parfenyuk, Elena V.

2003-01-01

Calorimetric titrations in benzene and chloroform at 298.15 K have been performed to give the complexes stability constants and the thermodynamic parameters for the complex formation of nature iron(III)porphyrins with pyridine. Stoichimetry of the complexes formed has been determined. It has been found that the thermodynamic parameters obtained depend on nature of peripheral substituents of the porphyrins. The estimation of the influence of Cl - and Ac - ions on the processes studied has been carried out. Using thermodynamic analysis method, the crystallsolvates of nature iron(III)porphyrins with benzene have been studied. Stoichiometry, thermal and energetic stability of the π-π-complexes formed have been determined. The data obtained have been used to the estimate solvent effect on the thermodynamic parameters of axial coordination of pyridine on the iron(III)porphyrins in benzene

Fate of trivalent chromium in presence of organic acids - a hydroponic study on soyabean plant using radiotracer

International Nuclear Information System (INIS)

Srivastava, Sonal; Prakash, Satya; Srivastava, M.M.

1999-01-01

Hydroponic experiments have been conducted to examine the uptake and translocation of root absorbed trivalent chromium in the presence of organic acid supplementation. Statistically significant increase in chromium accumulation in various plant tissues with increasing concentration of organic acids has been observed. Potentiality of organic acids to form labile organically bound Cr III is explored. (author)

Determination of total chromium in tanned leather samples used in car industry.

Science.gov (United States)

Zeiner, Michaela; Rezić, Iva; Ujević, Darko; Steffan, Ilse

2011-03-01

Despite the high competition of synthetic fibers leather is nowadays still widely used for many applications. In order to ensure a sufficient stability of the skin matrix against many factors, such as microbial degradation, heat and sweat, a tanning process is indispensable. Using chromium (III) for this purpose offers a multitude of advantages, thus this way of tanning is widely applied. During the use of chromium tanned leather as clothing material as well as for decoration/covering purposes, chromium is extracted from the leather and may then cause nocuous effects to human skin, e.g. allergic reactions. Thus the knowledge of the total chromium content of leather samples expected to come into prolonged touch with human skin is very important. In car industry leather is used as cover for seats, steering wheel and gearshift lever The chromium contents often chromium tanned leather samples used in car industry were determined. First all samples were dried at 65 degrees C overnight and then cut in small pieces using a ceramic knife, weighed and analyzed by inductively coupled plasma--optical emission spectrometry (ICP-OES) after acidic microwave assisted digestion. The total chromium amounts found were in the range from 19 mg/g up to 32 mg/g. The extraction yield of chromium from leather samples in sweat is approximately 2-7%. Thus especially during long journeys in summer chromium can be extracted in amounts which may cause nocuous effects for example on the palm of the hands or on the back.

Treatment of hexavalent chromium Cr (VI) in tanning effluent

International Nuclear Information System (INIS)

Ahmed, I.; Ali, S.

1999-01-01

Most common chemical used in chrome tanning is basic chromium sulphate (BCS). Manufacturing of BCS involves many steps producing liquid waste. Waste generated at every stage contains Cr (VI), which must be reduced to Cr (III) before being disposed to the environment. Different methods were studied for the reduction of toxic Cr (III). Pickle liquor (waste of electroplating industry) can also be used for the reduction of hexavalent chromium Cr (vi) along with other reducing materials / chemicals. In an electroplating process metal is treated with HCl or H/sub 2/SO/sub 4/ to remove scales and rust, the pickled items are then washed with water, washing contains FeCl/sub 2/ or fees/sub 4/ respectively called pickle liquor. During waste treatment pH adjustment to 6.0 - 9.0 and settling the sludge, is discharged to the lagoon. The sludge obtained is dried and disposed off in landfills. Other reducing agents like sodium bisulphite and sulfur dioxide were also studied, but pickle liquor was found to be more effective and economical. (author)

Synthesis and infrared spectra of Vanadium (III) prussian blue complexes

International Nuclear Information System (INIS)

Toma, H.E.; Lellis, F.T.P.

1987-01-01

The synthesis and characterization of a series of polymeric pigments containing vanadium (III) and hexacryano or substituted pentacyanoferrate (II) complexes are studied. The role of the intervalence transfer interactions in the complexes is discussed. (M.J.C.) [pt

Quantitative description and local structures of trivalent metal ions Eu(III) and Cm(III) complexed with poly-acrylic acid

International Nuclear Information System (INIS)

Montavon, G.; Huclier-Markai, S.; Grambow, B.; Bouby, M.; Geckeis, H.; Rabung, T.; Huclier-Markai, S.; Pashalidis, I.; Amekraz, B.; Moulin, C.

2008-01-01

The trivalent metal ion (M(III) = Cm, Eu)/poly-acrylic acid (PAA) system was studied in the pH range between 3 and 5.5 for a molar PAA-to-metal ratio above 1. The interaction was studied for a wide range of PAA (0.05 mg L -1 -50 g L -1 ) and metal ion concentrations (2*10 -9 - 10 -3 M). This work aimed at 3 goals (i) to determine the stoichiometry of M(III)-PAA complexes, (ii) to determine the number of complexed species and the local environment of the metal ion, and (iii) to quantify the reaction processes. Asymmetric flow-field-flow fractionation (AsFIFFF) coupled to ICP-MS evidenced that size distributions of Eu-PAA complexes and PAA were identical, suggesting that Eu bound to only one PAA chain. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements performed with Eu and Cm showed a continuous shift of the spectra with increasing pH. The environment of complexed metal ions obviously changes with pH. Most probably, spectral variations arose from conformational changes within the M(Ill)-PAA complex due to pH variation. Complexation data describing the distribution of complexed and free metal ion were measured with Cm by TRLFS. They could be quantitatively described in the whole pH-range studied by considering the existence of only a single complexed species. This indicates that the slight changes in M(III) speciation with pH observed at the molecular level do not significantly affect the intrinsic binding constant. The interaction constant obtained from the modelling must be considered as a mean interaction constant. (authors)

A general access to organogold(iii) complexes by oxidative addition of diazonium salts.

Science.gov (United States)

Huang, Long; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

2016-05-11

At room temperature under mild photochemical conditions, namely irradiation with a simple blue light LED, gold(i) chloro complexes of both phosphane and carbene ligands in combination with aryldiazonium salts afford arylgold(iii) complexes. With chelating P,N-ligands cationic six- or five-membered chelate complexes were isolated in the form of salts with weakly coordinating counter anions that were brought in from the diazonium salt. With monodentate P ligands or N-heterocyclic carbene ligands and diazonium chlorides neutral arylgold(iii) dichloro complexes were obtained. The coordination geometry was determined by X-ray crystal structure analyses of representative compounds, a cis arrangement of the aryl and the phosphane ligand at the square planar gold(iii) center is observed.

Synthesis, structure and photoluminescence of novel lanthanide (Tb(III), Gd(III)) complexes with 6-diphenylamine carbonyl 2-pyridine carboxylate

International Nuclear Information System (INIS)

An Baoli; Gong Menglian; Cheah, Kok-Wai; Wong, Wai-Kwok; Zhang Jiming

2004-01-01

A novel organic ligand, 6-diphenylamine carbonyl 2-pyridine carboxylic acid (HDPAP), and the corresponding lanthanide complexes, tris(6-diphenylamine carbonyl 2-pyridine carboxylato) terbium(III) (Tb-DPAP) and tris(6-diphenylamine carbonyl 2-pyridine carboxylato) gadolinium(III) (Gd-DPAP) have been designed and synthesized. The crystal structure and photoluminescence of Tb-DPAP and Gd-DPAP have been studied. The results showed that the lanthanide complexes have electroneutral structures, and the solid terbium complex emits characteristic green fluorescence of Tb(III) ions at room temperature while the gadolinium complex emits the DPAP ligand phosphorescence. The lowest triplet level of DPAP ligand was calculated from the phosphorescence spectrum of Gd-DPAP in N,N-dimethyl formamide (DMF) dilute solution determined at 77 K, and the energy transfer mechanisms in the lanthanide complexes were discussed. The lifetimes of the 5 D 4 levels of Tb 3+ ions in the terbium complex were examined using time-resolved spectroscopy, and the values are 0.0153±0.0001 ms for solid Tb(DPAP) 3 ·11.5H 2 O and 0.074±0.007 ms for 2.5x10 -5 mol/l Tb-DPAP ethanol solution

Rare earth(III) complexes for the development of new magnetic and luminescent probes

International Nuclear Information System (INIS)

Nonat, A.

2007-10-01

The simultaneous optimisation of the molecular parameters determining the relaxivity (number of coordinated water molecules, water-exchange, rotation dynamics of the whole complex, electronic relaxation, Gd(III)-proton distance) is essential to prepare efficient contrast agents. The aim of this work is on the one hand to design and study complexes with a high number of bound water molecules and to understand the influence of the coordination sphere on the stability and on the electronic relaxation and on the other hand, to use the ligand as a chromophore for the development of luminescent probes for biomedical imaging. We present the structure, the stability and the relaxivity of Gd(III) complexes of two series of tripodal ligands containing picolinate units based either on the 1,4,7-tri-aza-cyclononane ring or on a tertiary amine. These complexes show high relaxivity in water and in serum and can establish a non covalent interaction with serum albumin. The interpretation of the water proton relaxivity with the help of new relaxometric methods based on an auxiliary probe solute has allowed us to show that both the presence of the picolinate groups and the 1,4,7-tri-aza-cyclononane framework can lead to Gd(III) complexes with favourable electronic relaxation properties. This ligands have also been used for Eu(III) and Tb(III) complexation leading to strong luminescence in visible light. Other complexes derived from 8-hydroxyquinoline unit which display a very high luminescence in infrared are also studied. (author)

Structure and luminescent property of complexes of aryl carboxylic acid-functionalized polystyrene with Eu(III) and Tb(III) ions.

Science.gov (United States)

Gao, Baojiao; Shi, Nan; Qiao, Zongwen

2015-11-05

Via polymer reactions, naphthoic acid (NA) and benzoic acid (BA) were bonded onto the side chains of polystyrene (PS), respectively, and two aryl carboxylic acid-functionalized polystyrenes, PSNA and PSBA, were obtained. Using PSNA and PSBA as macromolecule ligands and Eu(3+) and Tb(3+) ions as central ions, various luminescent binary polymer-rare earth complexes were prepared. At the same time, with 1,10-phenanthroline (Phen) and 4,4'-bipyridine (Bipy) as small-molecule co-ligands, various ternary polymer-rare earth complexes were also prepared. On the basis of characterizing PSNA, PSBA and complexes, the relationship between structure and luminescent property for these prepared complexes were mainly investigated. The study results show that the macromolecule ligands PSNA and PSBA, or the bonded NA and BA ligands, can strongly sensitize the fluorescence emissions of Eu(3+) ion or Tb(3+) ion, but the sensitization effect is strongly dependent on the structure of the ligands and the property of the central ions, namely it is strongly dependent on the matching degree of energy levels. The fluorescence emission of the binary complex PS-(NA)3-Eu(III) is stronger than that PS-(BA)3-Eu(III), indicating ligand NA has stronger sensitization action for Eu(3+) ion than ligand BA; the binary complex PS-(BA)3-Tb(III) emit strong characteristic fluorescence of Tb(3+) ion, displaying that ligand BA can strongly sensitize Tb(3+) ion, whereas the binary complex PS-(NA)3-Tb(III) nearly does not emit the characteristic fluorescence of Tb(3+) ion, showing that ligand NA does not sensitize Tb(3+) ion. The fluorescence intensity of the ternary complexes is much stronger than that of the binary complexes in the same series. Copyright © 2015 Elsevier B.V. All rights reserved.

Chromium

Science.gov (United States)

... 2 Whole wheat bread, 2 slices 2 Red wine, 5 ounces 1–13 Apple, unpeeled, 1 medium ... chromium or a placebo) might simply show the benefits of supplementation in a chromium-deficient population. Overall, ...

Cyclic Voltammetric Study of Complexes of Fe (III) with Saponins Isolated from Cicer aritinum and Glycyrrhizin

International Nuclear Information System (INIS)

Khan, S.S.; Kazmi, S.A.; Anwar, H

2013-01-01

Cyclic voltammetric study was used to analyze three new saponins (isolated from the seeds of Cicer aritinum) along with a known saponin soyasaponin I and beta sitosterol glycoside isolated saponins as well as glycyrrhizin. These studies were carried out in aqueous medium at Glassy carbon (GCE) electrode vs. AgCl reference electrode. Results revealed that the voltammograms of Fe(III) with isolated saponins are irreversible while that of Fe(III)-glycyrrhizin complex is reversible. Even though precise Eo values of their Fe(III) complex could not be determined, it is clearly indicated that Fe(III) forms complexes with these saponins. The ability to form strong complexes with Fe(III) therefore reduces the availability of Fe(III) by saponins. (author)

Specification for corrosion-resisting chromium and chromium-nickel steel covered welding electrodes

International Nuclear Information System (INIS)

Anon.

1981-01-01

This specification prescribes requirements for covered corrosion-resisting chromium and chromium-nickel steel electrodes. These electrodes are normally used for shielded metal arc welding, and include those alloy steels designated as corrosion or heat-resisting chromium and chromium-nickel steels, in which chromium exceeds 4.0% and nickel does not exceed 50.0%

Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III-Fe(III-Cr(III-Cl-H2O system at 25°C

Directory of Open Access Journals (Sweden)

André Laurent

2018-03-01

Full Text Available The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(IIICl3(s (M= Al, Fe, Cr minerals solubility in Na-Al(III-Cr(III-Fe(III-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III remediation. Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production. Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

Syntheses and luminescence properties of two novel lanthanide (III) perchlorate complexes with phenacyl p-tolyl sulfoxide

Energy Technology Data Exchange (ETDEWEB)

Feng, Shu-Yan [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Li, Wen-Xian, E-mail: nmglwx@163.com [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Yu-Shan [Inner Mongolia Autonomous Region Product Quality Inspection Institute, Hohhot 010070 (China); Xin, Xiao-Dong; Guo, Feng; Cao, Xiao-Fang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China)

2015-06-15

Two novel solid binary complexes of rare earth perchlorate with phenacyl p-tolyl sulfoxide were synthesized and characterized by elemental analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, {sup 1}HNMR and UV spectra. The results indicated that the composition of these complexes was REL{sub 7} (ClO{sub 4}){sub 3}·6H{sub 2}O (RE=Eu (III), Tb (III), L=C{sub 6}H{sub 5}COCH{sub 2}SOC{sub 6}H{sub 4}CH{sub 3}). The study on IR spectra and {sup 1}HNMR spectra revealed that phenacyl p-tolyl sulfoxide bonded with RE{sup 3+} ions by the oxygen atom in sulfinyl group. The emission spectra illustrated that both the Eu (III) and Tb (III) complexes displayed excellent luminescence in solid state, and The most intensive characteristic emission of the Eu(III) and Tb(III) complexes were 245,400 a.u. and 298,000 a.u. respectively. The slit with was 1 nm. By analysis luminescence and phosphorescence spectrum, it was found that the ligand had the advantage to absorb energy and transfer it to the Eu (III) and Tb (III) ions. The fluorescence lifetimes of the complexes were measured as well as the quantum yield of the Eu (III) complex.

Synthesis and Luminescence Properties of Iridium(III Azide- and Triazole-Bisterpyridine Complexes

Directory of Open Access Journals (Sweden)

Timothy W. Schmidt

2013-07-01

Full Text Available We describe here the synthesis of azide-functionalised iridium(III bisterpyridines using the “chemistry on the complex” strategy. The resulting azide-complexes are then used in the copper(I-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition “click chemistry” reaction to from the corresponding triazole-functionalised iridium(III bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III bisterpyridines, but this effect can be reversed by the addition of copper(II sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III bisterpyridines can be functionalized for use in “click chemistry” facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

Specification for corrosion-resisting chromium and chromium-nickel steel covered welding electrodes

International Nuclear Information System (INIS)

Anon.

1981-01-01

This specification prescribes requirements for covered corrosion-resisting chromium and chromium-nickel steel electrodes. These electrodes are normally used for shielded metal arc welding, and include those alloy steels designated as corrosion or heat-resisting chromium and chromium-nickel steels, in which chromium exceeds 4.0 percent and nickel does not exceed 50.0 percent

Rhombus-shaped tetranuclear [Ln4] complexes [Ln = Dy(III) and Ho(III)]: synthesis, structure, and SMM behavior.

Science.gov (United States)

Chandrasekhar, Vadapalli; Hossain, Sakiat; Das, Sourav; Biswas, Sourav; Sutter, Jean-Pascal

2013-06-03

The reaction of a new hexadentate Schiff base hydrazide ligand (LH3) with rare earth(III) chloride salts in the presence of triethylamine as the base afforded two planar tetranuclear neutral complexes: [{(LH)2Dy4}(μ2-O)4](H2O)8·2CH3OH·8H2O (1) and [{(LH)2Ho4}(μ2-O)4](H2O)8·6CH3OH·4H2O (2). These neutral complexes possess a structure in which all of the lanthanide ions and the donor atoms of the ligand remain in a perfect plane. Each doubly deprotonated ligand holds two Ln(III) ions in its two distinct chelating coordination pockets to form [LH(Ln)2](4+) units. Two such units are connected by four [μ2-O](2-) ligands to form a planar tetranuclear assembly with an Ln(III)4 core that possesses a rhombus-shaped structure. Detailed static and dynamic magnetic analysis of 1 and 2 revealed single-molecule magnet (SMM) behavior for complex 1. A peculiar feature of the χM" versus temperature curve is that two peaks that are frequency-dependent are revealed, indicating the occurrence of two relaxation processes that lead to two energy barriers (16.8 and 54.2 K) and time constants (τ0 = 1.4 × 10(-6) s, τ0 = 7.2 × 10(-7) s). This was related to the presence of two distinct geometrical sites for Dy(III) in complex 1.

Determination of chromium (VI) in primary and secondary fertilizer and their respective precursors.

Science.gov (United States)

Krüger, Oliver; Fiedler, Francesca; Adam, Christian; Vogel, Christian; Senz, Rainer

2017-09-01

Hexavalent chromium species (Cr(VI)) are often carcinogenic, of high acute toxicity, highly mobile, and thus pose a severe risk to health and environment. Fertilizers usually contain significant amounts of chromium. Therefore, a reliable analysis of chromium and the fraction of Cr(VI) are crucial for safe use of fertilizers. This problem is expected to increase in the future, since more and more recycled fertilizers emerge due to increasing fertilizer demand and respective supply risks. However, existing analytical methods have been developed for conventional fertilizers and have to be tested whether they are suitable for the new materials. Thus, we performed a wet-chemical extraction for Cr(VI) on several matrices as well as respective quality control experiments including spiking with Cr(III) and Cr(VI) compounds. We found the Cr(VI) amounts to be below 2 mg/kg except for a thermally post-treated sewage sludge ash (SSA) that showed 12.3 mg/kg. The presence of organic matter e.g. in sludge or precipitated struvite caused a reduction of spiked Cr(VI) and thus no satisfying recovery for quality control. Cr(VI) reduction was also observed for SSA, presumably due to the presence of Fe(II) compounds. Even though the tested procedure can be hampered in some recycled fertilizer matrices, it might be adapted to be applicable also for these complex samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

Complexes of molybdenum(III) with 2-(2'-pyridyl)benzimidazole

Energy Technology Data Exchange (ETDEWEB)

Ghosh, S P [Patna Univ. (India). Dept. of Chemistry; Prasad, K M [H.D. Jain Coll., Arrah (India). Dept. of Chemistry

1979-07-01

Molybdenum(III) forms with 2-(2'-pyridyl) benzimidazole(LH) the trischelated complexes, (Mo(LH)/sub 3/)X/sub 3/ as well as the cationic-anionic complexes, (Mo(LH)/sub 3/X/sub 2/)/sup +/ (Mo(LH)X/sub 4/)/sup -/(X=Cl/sup -/,Br/sup -/ or NCS/sup -/), depending on pH. These complexes have been synthesised and characterised from elemental analyses, i.r. and electronic spectra, magnetic moments and molar conductance.

Enantiomeric separation of iridium (III) complexes using HPLC chiral stationary phases based on amylose derivatives

International Nuclear Information System (INIS)

Kim, Hee Eun; Seo, Na Hyeon; Hyun, Myung Ho

2016-01-01

Cyclometalated iridium (III) complexes formed with three identical cyclometalating (C-N) ligands (homoleptic) or formed with two cyclometalating (C-N) ligands and one ancillary (LX) ligand (heteroleptic) have been known as highly phosphorescent materials and, thus, they have been utilized as efficient phosphorescent dopants in organic light emitting diodes (OLEDs) 1–3 or as effective phosphorescent chemosensors. 4–7 Cylometalated iridium (III) complexes are chiral compounds consisting of lambda (Λ, left-handed) and delta (Δ, right-handed) isomers. Racemic cyclometa- lated iridium (III) complexes emit light with no net polarization, but optically active cyclometalated iridium (III) complexes emit circularly polarized light. 8,9 Circularly polarized light can be used in various fields including highly efficient three dimensional electronic devices, photo nic devices for optical data storage, biological assays, and others. 8,9 In order to obtain optically active cylometalated iridium (III) complexes and to determine the enantiomeric composition of optically active cylometalated iridium (III) complexes, liquid chromatogr aphic enantiomer separation method on chiral stationary phases (CSPs) has been used. For example, Okamoto and coworkers first reported the high performance liquid chromatographic (HPLC) direct enantiomeric separation of two homoleptic cylometalated iridium (III) complexes on immobilized amylose tris(3,5- dimethylphenylcarbamate) (Chiralpak IA), coated cellulose tris(3,5-dimethylphenylcarbamate) (Chiralc el OD), and coated cellulose tris(4-methylbenzoate) (Chiralce l OJ). 10 Supercritical fluid chromatography (SFC) was also used by Bernhard and coworkers for the enantiomeric separation of cylometalated iridium (III) complexes on coated amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H). 8 However, the general use of the HPLC method for the direct enantiomeric separation of homoleptic

Enantiomeric separation of iridium (III) complexes using HPLC chiral stationary phases based on amylose derivatives

Energy Technology Data Exchange (ETDEWEB)

Kim, Hee Eun; Seo, Na Hyeon; Hyun, Myung Ho [Dept. of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan (Korea, Republic of)

2016-12-15

Cyclometalated iridium (III) complexes formed with three identical cyclometalating (C-N) ligands (homoleptic) or formed with two cyclometalating (C-N) ligands and one ancillary (LX) ligand (heteroleptic) have been known as highly phosphorescent materials and, thus, they have been utilized as efficient phosphorescent dopants in organic light emitting diodes (OLEDs) 1–3 or as effective phosphorescent chemosensors. 4–7 Cylometalated iridium (III) complexes are chiral compounds consisting of lambda (Λ, left-handed) and delta (Δ, right-handed) isomers. Racemic cyclometa- lated iridium (III) complexes emit light with no net polarization, but optically active cyclometalated iridium (III) complexes emit circularly polarized light. 8,9 Circularly polarized light can be used in various fields including highly efficient three dimensional electronic devices, photo nic devices for optical data storage, biological assays, and others. 8,9 In order to obtain optically active cylometalated iridium (III) complexes and to determine the enantiomeric composition of optically active cylometalated iridium (III) complexes, liquid chromatogr aphic enantiomer separation method on chiral stationary phases (CSPs) has been used. For example, Okamoto and coworkers first reported the high performance liquid chromatographic (HPLC) direct enantiomeric separation of two homoleptic cylometalated iridium (III) complexes on immobilized amylose tris(3,5- dimethylphenylcarbamate) (Chiralpak IA), coated cellulose tris(3,5-dimethylphenylcarbamate) (Chiralc el OD), and coated cellulose tris(4-methylbenzoate) (Chiralce l OJ). 10 Supercritical fluid chromatography (SFC) was also used by Bernhard and coworkers for the enantiomeric separation of cylometalated iridium (III) complexes on coated amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H). 8 However, the general use of the HPLC method for the direct enantiomeric separation of homoleptic.

Dissociation kinetics of Fe(III)- and Al(III)-natural organic matter complexes at pH 6.0 and 8.0 and 25 °C

Science.gov (United States)

Jones, Adele M.; Pham, A. Ninh; Collins, Richard N.; Waite, T. David

2009-05-01

The rate at which iron- and aluminium-natural organic matter (NOM) complexes dissociate plays a critical role in the transport of these elements given the readiness with which they hydrolyse and precipitate. Despite this, there have only been a few reliable studies on the dissociation kinetics of these complexes suggesting half-times of some hours for the dissociation of Fe(III) and Al(III) from a strongly binding component of NOM. First-order dissociation rate constants are re-evaluated here at pH 6.0 and 8.0 and 25 °C using both cation exchange resin and competing ligand methods for Fe(III) and a cation exchange resin method only for Al(III) complexes. Both methods provide similar results at a particular pH with a two-ligand model accounting satisfactorily for the dissociation kinetics results obtained. For Fe(III), half-times on the order of 6-7 h were obtained for dissociation of the strong component and 4-5 min for dissociation of the weak component. For aluminium, the half-times were on the order of 1.5 h and 1-2 min for the strong and weak components, respectively. Overall, Fe(III) complexes with NOM are more stable than analogous complexes with Al(III), implying Fe(III) may be transported further from its source upon dilution and dispersion.

Extraction of bivalent vanadium as its pyridine thiocyanate complex and separation from uranium, titanium, chromium and aluminium

International Nuclear Information System (INIS)

Yatirajam, V.; Arya, S.P.

1975-01-01

A simple method is described for the extraction of V(II) as its pyridine thiocyanate complex. Vanadate is reduced to V(II) in 1 to 2 N sulphuric acid by zinc amalgam. Thiocyanate and pyridine are added, the solution is adjusted to pH 5.2 to 5.5 and the complex extracted with chloroform. The vanadium is back-extracted with peroxide solution. Zinc from the reductant accompanies the vanadium but alkali and alkaline earth metal ions, titanium, uranium, chromium and aluminium are separated, besides those ions reduced to the elements by zinc amalgam. The method takes about 20 min and is applicable to microgram as well as milligram amounts of vanadium. (author)

Aspartic acid complexation of Am(III) and U(VI)

International Nuclear Information System (INIS)

Saito, A.; Choppin, G.R.

1984-01-01

Stability constants of Am(III) and U(VI) with L-aspartic acid have been determined at pH 8.00 by means of the solvent extraction technique. It was found that Am(III) forms 1:1 and 1:2 complexes while U(VI) formed only the 1:1 complex under these conditions. The stability constants were: Am +3 : I = 0.10 M; log β 1 = 4.81 +- 0.03, log β 2 = 6.75 +- 0.03 I = 0.70 M; log β 1 = 4.53 +- 0.08 log β 2 = 6.65 +- 0.06 UO +2 2 : I = 0.70 M; log β 1 = 3.32 +- 0.04. Comparison of these stability constants with corresponding values of some dicarboxylate ligands suggests that at pH 8 the binding of Am +3 and UO +2 2 involves both carboxylates. In the Am-aspartate complex, the data indicate the possibility of weak interaction between the Am +3 and the amino group. (orig.)

A spectrophotometric investigation of the complex formation between lanthanum (III) and eriochrome cyanine R

International Nuclear Information System (INIS)

Boodts, J.F.C.; Saffioti, W.

1979-01-01

The complex formation between La(III) and Eriochrome Cyanine R has been investigated. Three complexes have been detected. A first one (Complex I) in the pH range of 5.3-5.5 with lambda sub(max) = 460nm. a second one (Complex II) in the pH range of 6.2-6.5 with lambda sub(max) = 490nm and a third one (complex III) in the pH range of 8.2 - 9.0 with lambda sub(max) = 545nm and a shoulder between 570-580nm. The composition and stability constants of the complexes, respectively: complex I: La(ECR) 2 and 4.9 x 10 7 , complex II: La(ECR) 2 and 7.0 x 10 7 , complex III: La.ECR and 1.0 x 10 4 . All measurements were taken at 25.0 +- 0.1 0 C and μ = 0.2 (NaClO 4 ). (Author) [pt

Cr(III) and Cr(VI) in leather and elicitation of eczema

DEFF Research Database (Denmark)

Hansen, Malene Barré; Menne, Torkil; Johansen, Jeanne Duus

2006-01-01

The aim of the present study was to investigate the relation between the content of Cr(VI) and soluble Cr(III) in leather and the ability of the leather to elicit eczema in chromium allergic patients. An array of chromium-tanned leather samples was analysed for the content of total Cr(VI) and sol...

Enhanced fluorescence of Tb(III), Dy(III) perchlorate by salicylic acid in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism

International Nuclear Information System (INIS)

Li Wenxian; Zheng Yushan; Sun Xiaojun; Chai Wenjuan; Ren Tie; Shi Xiaoyan

2010-01-01

Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C 6 H 5 COCH 2 SOCH 2 COC 6 H 5 ), salicylic acid as second ligand (L ' =C 6 H 4 OHCOO - ). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL 5 L'](ClO 4 ) 2 .nH 2 O (RE=Tb, Dy; n=6, 8 ). Based on IR, 1 HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L'), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.

Electrothermal Vaporization-QQQ-ICP-MS for Determination of Chromium in Mainstream Cigarette Smoke Particulate.

Science.gov (United States)

Fresquez, Mark R; Gonzalez-Jimenez, Nathalie; Gray, Naudia; Valentin-Blasini, Liza; Watson, Clifford H; Pappas, R Steven

2017-05-01

Chromium is transported in mainstream tobacco smoke at very low concentrations. However, when chromium is deposited too deeply in the lungs for mucociliary clearance, or is in a particle that is too large to pass directly through tissues, it bioaccumulates in the lungs of smokers. It is important to determine the concentrations of chromium that are transported in mainstream smoke. Several reliable studies have resulted in reports of chromium concentrations in smoke particulate that were below limits of detection (LODs) for the instruments and methods employed. In this study, electrothermal vaporization-triple quad-inductively coupled plasma-mass spectrometry (ETV-QQQ-ICP-MS) was chosen for determination of chromium concentrations in mainstream smoke because of the high sensitivity of ETV combined with QQQ-ICP-MS. The smoke from five reference, quality control, and commercial cigarettes was analyzed using ETV-QQQ-ICP-MS with isotope dilution for quantitative determination of chromium. The method LOD was sufficiently low that chromium concentrations in mainstream smoke could indeed be determined. The chromium concentrations in the smoke particulate were between 0.60 and 1.03 ng/cigarette. The range of chromium concentrations was at or below previously reported LODs. Determination of the oxidation state of the chromium transported in mainstream smoke would also be important, in consideration of the fact that both chromium(III) and chromium(VI) oxidation states cause inhalation toxicity, but chromium(VI) is also a carcinogen. It was possible to separate the oxidation states using ETV-QQQ-ICP-MS. However, determination of individual species at the levels found in mainstream smoke particulate matter was not possible with the present method. Published by Oxford University Press 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Spin-crossover behavior of polymeric iron(III) complexes

International Nuclear Information System (INIS)

Maeda, Yonezo; Miyamoto, Makoto; Takashima, Yoshimasa; Oshio, Hiroaki

1989-01-01

Polymeric spin-crossover iron(III) complexes possessing poly(4-vinylpyridine), poly(N-vinylimidazole) or poly(octylmethacrylate-co-4-vinylpyridine) as ligand are prepared. In this experience enriched 57 Fe was used to get strong Moessbauer absorption. The enriched behavior of the complexes were examined by magnetic susceptibilities measurement, and Moessbauer and esr spectroscopies. Some of them show spin-state behavior over a wide range of temperature. Some of them show rapid spin-state interexchange compared to the Moessbauer time scale and others not. Spin-crossover behavior of polymeric complexes is characterized of wide spin-state transition temperature range

Synthesis and reactivity of uranium (III) cyclopentadienyl complexes

International Nuclear Information System (INIS)

Foyentin, M.

1987-01-01

New uranium organometallic complexes are synthetized from the addition compound Cp U (THF). Reactions with lithium compounds, chlorides, alkynes and borohydrides. Oxidizing addition reactions are evidenced with alkyl halogenides. With a strong reducing agent, the complex Cp-UCH-Li allows the fixation and the reduction of nitrogen into ammonia. Lability of ligands bound to U (III) is evidenced, giving very reactive species and hence catalytic properties for these compounds. Catalytic hydrogenation of olefins is studied. Substitution reactions of alkyl groups of these complexes with olefins in presence or not of hydrogen or with alkyllithium are original [fr

Diminuição do teor de óxido de crômio (III usado como marcador externo Reduction in chromium (III oxide level as an external marker

Directory of Open Access Journals (Sweden)

Hermann Bremer Neto

2003-04-01

Full Text Available A sensibilidade do método espectrofotométrico da s-difenilcarbazida de determinação do crômio permite que esse metal possa ser determinado em teores e em massas de amostras tão pequenas que as concentrações atualmente usadas de óxido de crômio (III como marcador externo em ensaios biológicos poderiam ser drasticamente diminuídas. Utilizando-se do piauçu (Leporinus macrocephalus para um estudo sobre o coeficiente de digestibilidade aparente (CDA da fração protéica, seis níveis de óxido de crômio (III - 0,01% - 0,02% - 0,03% - 0,05% - 0,1% e 0,2% - foram incorporados em dietas isoprotéica e isoenergética, objetivando-se verificar se o cálculo do CDA seria afetado pela variação do teor do marcador. Os seis tratamentos foram dispostos em um delineamento em blocos inteiramente casualisados, sendo as fezes coletadas durante 16 dias. Verificou-se que os resultados do coeficiente de digestibilidade aparente da fração protéica não apresentaram diferenças estatísticas significativas devidas aos teores incorporados do marcador à ração e aos dias de coleta. Conseqüentemente, e em experimentos dessa natureza, nada impede que seja reduzido o teor de óxido de crômio (III ao menos até 0,01%: além da economia relativa ao consumo do mesmo e da facilidade na manipulação de menor quantidade de amostras de fezes, o método espectrofotométrico da s-difenilcarbazida permite dosar esse nível (e até menor do que 0,01% de modo simples e rápido, com precisão e exatidão.The objective of this study was to reduce the level of the biological marker Cr2O3 in animal diets, due to the sensibility of the sdiphenylcarbazide spectrophotometric method for chromium determination in feces, recently developed. Six levels of marker, chromium (III oxide (0.01% - 0.02% - 0.03% - 0.05% - 0.1% and 0.2%, were incorporated into isoproteic and isoenergetic diets, for the apparent digestibility assay of the "piauçu" (Leporinus macrocephalus, in a

Chromium isotope fractionation during oxidative weathering of a modern basaltic weathering profile

DEFF Research Database (Denmark)

D'Arcy, Joan Mary; Døssing, Lasse Nørbye; Frei, Robert

Chromium can be used as a tracer of redox sensitive environmental processes. In soils Cr (III) is inert, immobile and resides predominantly in minerals, clays and oxides. Cr (VI) is toxic, soluble and mobile and is usually lost from the soil to local run off. Chromium isotopes have been shown...... to fractionate under both reducing and oxidizing conditions [1, 2]. Recent studies on d53Cr isotopes in laterite soils show that oxidative weathering of Cr-bearing rocks is accompanied by an isotopic fractionation, where by the lighter isotopes are retained in the residual soil and the heavier isotope...... is enriched in local runoff [1]. This study aims to quantify the stable Cr isotope composition of two modern basaltic weathering profiles, to help better understand the processes that oxidize inert Cr (III) to toxic Cr (VI). We sampled basaltic weathering profiles and associated river waters from areas of two...

Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

DEFF Research Database (Denmark)

Dideriksen, Knud; Baker, Joel A.; Stipp, Susan Louise Svane

2008-01-01

be controlled by isotope fractionation between the free and complexed iron.We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fedesferrioxamine B (at pH 2). The two......-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of a56Fesolution-solid=1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically...... and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within...

Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

International Nuclear Information System (INIS)

P.M. Jardine; T.L. Bank; M. E. Baldwin; S.E. Fendorf; M.A. Ginder-Vogel; Kukkadapu, M.E.

2006-01-01

The greatest challenge to elucidating geochemical and biological chromium reduction in natural sediments is to create a sterile environment without destroying the chemical and physical properties of the system. In this study we determined the potential for geochemical and biological chromium reduction in a naturally reducing soil using carbon amendments and sterilization. To minimize alterations to the sediment samples, soils were sterilized via exposure to ?-irradiation which causes fewer changes in the physical and chemical properties of the soil compared to other methods of sterilization. The objective of our research was to determine if the absence of viable microorganisms significantly affected the extent of chromium reduction in a reducing soil. Our hypothesis was that if geochemical reduction pathways dominated the system then soil sterilization should have little to no effect on the amount and rate of chromium that was reduced. However, if the reduction of chromium in these soils was a synergistic process then significantly different amounts of chromium should be reduced in the sterilized versus non-sterilized samples

Hexavalent chromium reduction in a sulfur reducing packed-bed bioreactor

Energy Technology Data Exchange (ETDEWEB)

Sahinkaya, Erkan, E-mail: erkansahinkaya@yahoo.com [Department of Bioengineering, Istanbul Medeniyet University, Goeztepe, Istanbul (Turkey); Kilic, Adem [Department of Environmental Engineering, Harran University, Osmanbey Campus, 63000 Sanliurfa (Turkey); Altun, Muslum [Department of Chemistry, Hacettepe University, Beytepe, Ankara (Turkey); Komnitsas, Kostas [Department of Mineral Resources Engineering, Technical University of Crete, 73100 Chania (Greece); Lens, Piet N.L. [Unesco-IHE Institute for Water Education, Westvest 7, Delft 2611 AX (Netherlands)

2012-06-15

Highlights: Black-Right-Pointing-Pointer Elemental sulfur can be used as electron acceptor for sulfide production. Black-Right-Pointing-Pointer Biogenically produced sulfide reduces Cr(VI) to the much less toxic and immobile form of Cr(III). Black-Right-Pointing-Pointer Sulfur packed bioreactor is efficient for Cr(VI) containing wastewater treatment. Black-Right-Pointing-Pointer Reduced form of chromium precipitates in the bioreactor. - Abstract: The most commonly used approach for the detoxification of hazardous industrial effluents and wastewaters containing Cr(VI) is its reduction to the much less toxic and immobile form of Cr(III). This study investigates the cleanup of Cr(VI) containing wastewaters using elemental sulfur as electron acceptor, for the production of hydrogen sulfide that induces Cr(VI) reduction. An elemental sulfur reducing packed-bed bioreactor was operated at 28-30 Degree-Sign C for more than 250 days under varying influent Cr(VI) concentrations (5.0-50.0 mg/L) and hydraulic retention times (HRTs, 0.36-1.0 day). Ethanol or acetate (1000 mg/L COD) was used as carbon source and electron donor. The degree of COD oxidation varied between 30% and 85%, depending on the operating conditions and the type of organic carbon source. The oxidation of organic matter was coupled with the production of hydrogen sulfide, which reached a maximum concentration of 750 mg/L. The biologically produced hydrogen sulfide reduced Cr(VI) chemically to Cr(III) that precipitated in the reactor. Reduction of Cr(VI) and removal efficiency of total chromium always exceeded 97% and 85%, respectively, implying that the reduced chromium was retained in the bioreactor. This study showed that sulfur can be used as an electron acceptor to produce hydrogen sulfide that induces efficient reduction and immobilization of Cr(VI), thus enabling decontamination of Cr(VI) polluted wastewaters.

Fluorescent silver nanoclusters for ultrasensitive determination of chromium(VI) in aqueous solution

International Nuclear Information System (INIS)

Zhang, Jian Rong; Zeng, Ai Lian; Luo, Hong Qun; Li, Nian Bing

2016-01-01

Highlights: • Fluorescent Ag nanoclusters were first applied to Cr(VI) detection. • The proposed method is simple, rapid, and environmentally friendly. • The sensor shows a wide linear range, low detection limit, and good selectivity. • The system can also be used for the indirect assay of total chromium and Cr(III). • The analyses in real water samples are satisfactory. - Abstract: In this work, a simple and sensitive Cr(VI) sensor is proposed based on fluorescent polyethyleneimine-stabilized Ag nanoclusters, which allows the determination over a wide concentration range of 0.1 nM–3.0 μM and with a detection limit as low as 0.04 nΜ and a good selectivity. The quenching mechanism was discussed in terms of the absorption and fluorescence spectra, suggesting that Cr(VI) is connected to Ag nanoclusters by hydrogen bond between the oxygen atom at the vertex of tetrahedron structure of Cr(VI) and the amino nitrogen of polyethyleneimine that surrounded Ag nanoclusters and electron transfer from Ag nanoclusters to highly electron-deficient Cr(VI) results in fluorescence quenching. Despite the failure to quench the fluorescence efficiently, Cr(III) can also be measured using the proposed Ag nanoclusters by being oxidized to Cr(VI) in alkaline solution (pH ∼9) containing H 2 O 2 . Therefore, our approach could be used to detect Cr(VI), Cr(III) and the total chromium level in aqueous solution. In addition, Cr(VI) analysis in real water samples were satisfactory, indicating this method could be practically promising for chromium measurements.

Functionalization of Chitosan with 3,4,5-Trihydroxy Benzoic Acid Moiety for The Uptake of Chromium Species

Directory of Open Access Journals (Sweden)

Akhmad Sabarudin

2013-03-01

Full Text Available Chitosan-based chelating resin, the cross-linked chitosan functionalized with 3,4,5-trihydroxy benzoic acid moiety (CCTS-THBA resin, was newly synthesized and its adsorption behavior toward appropriate elements was investigated. At pH 5-9, the CCTS-THBA resin showed quantitative adsorption (87-91% for Cr (VI, while only < 15% for Cr (III. The addition of cyclohexanediamine tetraacetic acid (CyDTA to the samples resulted in a considerably increase of the adsorption of both chromium species. In this condition, Cr (III is chelated with CyDTA to form anionic complexes at pH 3-5, which was then completely adsorbed on the resin by ion exchange mechanism. Similarly, the adsorption of Cr (VI reached almost 100% in pH range of 3-6. The adsorption capacity of CCTS-THBA resin for Cr (VI was 109 mg g-1.

Optical absorption and photoluminescence properties of chromium in different host glasses

Energy Technology Data Exchange (ETDEWEB)

Lachheb, R., E-mail: raouialach66@gmail.com [LaboratoireGéoressources, Matériaux, Environnement et Changements Globaux, Faculty of Sciences of Sfax, Sfax University, 3018 Sfax (Tunisia); Herrmann, A. [Otto-Schott-Institut, Jena University, Fraunhoferstraße 6, 07743 Jena (Germany); Damak, K. [LaboratoireGéoressources, Matériaux, Environnement et Changements Globaux, Faculty of Sciences of Sfax, Sfax University, 3018 Sfax (Tunisia); Rüssel, C. [Otto-Schott-Institut, Jena University, Fraunhoferstraße 6, 07743 Jena (Germany); Maâlej, R. [LaboratoireGéoressources, Matériaux, Environnement et Changements Globaux, Faculty of Sciences of Sfax, Sfax University, 3018 Sfax (Tunisia)

2017-06-15

The optical absorption, excitation and fluorescence spectra, and emission lifetimes of chromium (III) were investigated in a wide variety of oxide glasses (aluminosilicate, aluminate and phosphate). For all glasses, weak crystal field strengths were deduced from the absorption spectra. The effect of the glass matrix and the Cr{sup 3+} concentration on the fluorescence properties of Cr{sup 3+} ions were investigated. An increased fluorescence intensity of Cr{sup 3+}was found for glasses of low optical basicity, the spectral position of the Cr{sup 3+} absorption and emission, however, was hardly influenced by the glass composition. The optical absorption spectra of the chromium doped aluminosilicate and aluminate glasses showed the presence of Cr{sup VI}, while in phosphate glasses most chromium occurred as Cr{sup 3+} ions. Furthermore, for the glass with the lowest basicity, the Cr{sup 3+}concentration was optimized in order to achieve maximum fluorescence emission intensity.

Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine

International Nuclear Information System (INIS)

Riviere, Ch.

2000-01-01

The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

Evaluación de la seguridad de una suspensión de fosfato de cromo(III para uso en radiosinoviortesis Evaluation of the safety a Chromium (III Phosphate suspension for radiosynoviorthesis

Directory of Open Access Journals (Sweden)

Jorge Cruz Arencibia

2013-03-01

Full Text Available Objetivo: evaluar la fuga de radiactividad de la cavidad articular después de la administración de suspensiones radiomarcadas de Fosfato de Cromo(III y la probabilidad de inducción de genotoxicidad. Métodos: las suspensiones se obtuvieron según método reportado. Para la evaluación de la fuga articular las suspensiones marcadas se administraron por vía intraarticular en ratas y conejos. El seguimiento se realizó por medición de la actividad retenida por cámara gamma. En los estudios de genotoxicidad se determinó la frecuencia de formación de micronúcleos en eritrocitos de médula ósea de ratas para 2 dosis y 2 tiempos para cada preparado. Resultados: para las suspensiones radiomarcadas en estudio la fuga fue no significativa durante 3 semanas (Objective: to evaluate the leakage of radioactivity after intraarticular administration of radioactive suspensions based on Chromium (III Phosphate as well as the probability of induction of genotoxic effect. Methods: the suspensions were obtained in line with the published procedure. For the articular leakage evaluation, the radioactive suspensions were intraarticulary administered in rats and rabbits. The radioactivity retention was measured by gamma chamber. A comparison with commercial radiopharmaceutical labeled with 32P was made. The genotoxicity studies determined the frequency of micronuclei formation in the rats´ bone marrow erythrocytes by using 2 doses and 2 time intervals for each preparation. Results: the radiolabeled suspensions under evaluation showed that the leakage was not significant during 3 weeks (<3% for the suspension labeled with 51Cr and ~5% in the one labeled with 32P and the advantages of having larger particle preparation were confirmed. For those suspension labeled with 32P and 90Y , no significant difference was seen in the frequency of micronuclei formation for the first time interval, regardless of the administered doses. The micronuclei formation increased

Intramolecular deactivation processes of electronically excited Lanthanide(III) complexes with organic acids of low molecular weight

Science.gov (United States)

Burek, Katja; Eidner, Sascha; Kuke, Stefanie; Kumke, Michael U.

2018-02-01

The luminescence of Lanthanide(III) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(III) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K ≤ T ≤ 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M ≤ I ≤ 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites.

Environmentally-relevant concentrations of Al(III) and Fe(III) cations induce aggregation of free DNA by complexation with phosphate group.

Science.gov (United States)

Qin, Chao; Kang, Fuxing; Zhang, Wei; Shou, Weijun; Hu, Xiaojie; Gao, Yanzheng

2017-10-15

Environmental persistence of free DNA is influenced by its complexation with other chemical species and its aggregation mechanisms. However, it is not well-known how naturally-abundant metal ions, e.g., Al(III) and Fe(III), influence DNA aggregation. This study investigated aggregation behaviors of model DNA from salmon testes as influenced by metal cations, and elucidated the predominant mechanism responsible for DNA aggregation. Compared to monovalent (K + and Na + ) and divalent (Ca 2+ and Mg 2+ ) cations, Al(III) and Fe(III) species in aqueous solution caused rapid DNA aggregations. The maximal DNA aggregation occurred at 0.05 mmol/L Al(III) or 0.075 mmol/L Fe(III), respectively. A combination of atomic force microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy revealed that Al(III) and Fe(III) complexed with negatively charged phosphate groups to neutralize DNA charges, resulting in decreased electrostatic repulsion and subsequent DNA aggregation. Zeta potential measurements and molecular computation further support this mechanism. Furthermore, DNA aggregation was enhanced at higher temperature and near neutral pH. Therefore, DNA aggregation is collectively determined by many environmental factors such as ion species, temperature, and solution pH. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis and physicochemical analysis of Sm (II, III) acetylacetone chelate complexes

International Nuclear Information System (INIS)

Kostyuk, N.N.; Dik, T.A.; Trebnikov, A.G.

2004-01-01

Sm (II, III) acetylacetone chelate complexes were synthesized by electrochemical method. It was shown that anode dissolution of the metal samarium over acetylacetone leads to formation of the Sm (II, III) chelate complexes: xSm(acac)2 · ySm(acac)3 · zH(acac). Factors x, y and z depend on quantity of the electricity, which flew through the electrolysis cell. The compositions of the obtained substances were confirmed by the physicochemical analysis (ultimate analysis, IR-, mass spectroscopy and thermal analysis (thermogravimetric, isothermal warming-up and differential scanning colorimetry). (Authors)

Roentgenoelectronic investigation into oxidation of iron-chromium and iron-chromium-nickel alloys

International Nuclear Information System (INIS)

Akimov, A.G.; Rozenfel'd, I.L.; Kazanskij, L.P.; Machavariani, G.V.

1978-01-01

Kinetics of iron-chromium and iron-chromium-nickel alloy oxidation (of the Kh13 and Kh18N10T steels) in oxygen was investigated using X-ray electron spectroscopy. It was found that according to X-ray electron spectra chromium oxidation kinetics in the iron-chromium alloy differs significantly from oxidation kinetics of chromium pattern. Layer by layer X-ray electron analysis showed that chromium is subjected to a deeper oxidation as compared to iron, and accordingly, Cr 2 O 3 layer with pure iron impregnations is placed between the layer of mixed oxide (Fe 3 O 4 +Cr 2 O 3 ) and metal. A model of the iron-chromium alloy surface is suggested. The mixed oxide composition on the steel surface is presented as spinel Fesub(2+x)Crsub(1-x)Osub(y)

An assessment of the environmental toxicity of hexavalent chromium in fish

NARCIS (Netherlands)

Putte, van der I.

1981-01-01

At present chromium is a common contaminant in surface waters in many countries. In water the metal may be present in the trivalent form (CrIII) or in the hexavalent form (CrVI), the latter of which is more toxic to aquatic organisms.
The investigations presented in this thesis

Moessbauer spectroscopic studies of alkylammonium iron(III) complexes

International Nuclear Information System (INIS)

Katada, M.; Kozawa, S.; Nakajima, Y.

2006-01-01

Alkylammonium iron(III) complexes, [(n-C n H 2n+1 )mNH 4-m ] 3 [Fe(CN) 6 ] were prepared and studied by Moessbauer spectroscopy, XRD, and DSC. In the complexes with m=2, the temperature dependences of the area intensity of Moessbauer are correlated to the motion of alkyl chains. The temperature dependence of the complex with n=4 was linear and smaller than that of other complexes. Especially in the complex with n=6, the deviation from the linear was the largest in the complexes observed. This result is attributed to the structural difference of the complex. The complexes with n≥8 consist of two-dimensional layer structure. The temperature dependence of the area intensity was similar to each other. This means that the motion of alkyl chain in these complexes are almost the same. The values of quadrupole splitting for the complexes were larger those that of the complexes (m=1). This indicates that the form of [Fe(CN) 6 ] 3- ion is affected by the differences of the number of alkyl groups. (author)

Enantioselective cellular localisation of europium(iii) coordination complexes.

Science.gov (United States)

Frawley, Andrew T; Linford, Holly V; Starck, Matthieu; Pal, Robert; Parker, David

2018-01-28

The selective mitochondrial localisation of the Λ enantiomer of three different emissive europium(iii) complexes in NIH 3T3 and MCF7 cells contrasts with the behaviour of the Δ enantiomer, for which a predominant lysosomal localisation was observed by confocal microscopy. In each case, cell uptake occurs via macropinocytosis.

Spectroscopic investigations on the complexation of Cm(III) and Eu(III) with organic model ligands and their binding mode in human urine (in vitro)

International Nuclear Information System (INIS)

Heller, Anne

2011-01-01

In case of incorporation, trivalent actinides (An(III)) and lanthanides (Ln(III)) pose a serious health risk to humans. An(III) are artificial, highly radioactive elements which are mainly produced during the nuclear fuel cycle in nuclear power plants. Via hazardous accidents or nonprofessional storage of radioactive waste, they can be released in the environment and enter the human food chain. In contrast, Ln(III) are nonradioactive, naturally occurring elements with multiple applications in technique and medicine. Consequently it is possible that humans get in contact and incorporate both, An(III) and Ln(III). Therefore, it is of particular importance to elucidate the behaviour of these elements in the human body. While macroscopic processes such as distribution, accumulation and excretion are studied quite well, knowledge about the chemical binding form (speciation) of An(III) and Ln(III) in various body fluids is still sparse. In the present work, for the first time, the speciation of Cm(III) and Eu(III) in natural human urine (in vitro) has been investigated spectroscopically and the formed complex identified. For this purpose, also basic investigations on the complex formation of Cm(III) and Eu(III) in synthetic model urine as well as with the urinary relevant, organic model ligands urea, alanine, phenylalanine, threonine and citrate have been performed and the previously unknown complex stability constants determined. Finally, all experimental results were compared to literature data and predictions calculated by thermodynamic modelling. Since both, Cm(III) and Eu(III), exhibit unique luminescence properties, particularly the suitability of time-resolved laser-induced fluorescence spectroscopy (TRLFS) could be demonstrated as a method to investigate these metal ions in untreated, complex biofluids. The results of this work provide new scientific findings on the biochemical reactions of An(III) and Ln(III) in human body fluids on a molecular scale and

Specification for corrosion-resisting chromium and chromium-nickel steel covered welding electrodes

International Nuclear Information System (INIS)

Anon.

1983-01-01

This specification prescribes requirements for covered corrosion-resisting chromium and chromium-nickel steel electrodes. These electrodes normally are used for shielded metal arc welding, and include those alloy steels designated as corrosion or heat-resisting chromium-nickel steels in which chromium exceeds 4.0 percent and nickel does not exceed 50.0 percent

Photocatalysis with chromium-doped TiO2: Bulk and surface doping

KAUST Repository

Ould-Chikh, Samy

2014-04-15

The photocatalytic properties of TiO2 modified by chromium are usually found to depend strongly on the preparation method. To clarify this problem, two series of chromium-doped titania with a chromium content of up to 1.56 wt % have been prepared under hydrothermal conditions: the first series (Cr:TiO2) is intended to dope the bulk of TiO2, whereas the second series (Cr/TiO2) is intended to load the surface of TiO2 with Cr. The catalytic properties have been compared in the photocatalytic oxidation of formic acid. Characterization data provides evidence that in the Cr/TiO2 catalysts chromium is located on the surface of TiO2 as amorphous CrOOH clusters. In contrast, in the Cr:TiO 2 series, chromium is mostly dissolved in the titania lattice, although a minor part is still present on the surface. Photocatalytic tests show that both series of chromium-doped titania demonstrate visible-light-driven photo-oxidation activity. Surface-doped Cr/TiO2 solids appear to be more efficient photocatalysts than the bulk-doped Cr:TiO2 counterparts. It\\'s classified! The photocatalytic properties of TiO2 modified by chromium depend strongly on the preparation method. To clarify this problem, two types of modified titania are discussed: one with CrIII doped in the bulk and one with CrOOH clusters on the TiO2 surface (see picture). Both series show visible-light-driven photo-oxidation activity. However, surface modification appears to be a more efficient strategy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ferromagnetic dinuclear mixed-valence Mn(II)/Mn(III) complexes: building blocks for the higher nuclearity complexes. structure, magnetic properties, and density functional theory calculations.

Science.gov (United States)

Hänninen, Mikko M; Välivaara, Juha; Mota, Antonio J; Colacio, Enrique; Lloret, Francesc; Sillanpää, Reijo

2013-02-18

A series of six mixed-valence Mn(II)/Mn(III) dinuclear complexes were synthesized and characterized by X-ray diffraction. The reactivity of the complexes was surveyed, and structures of three additional trinuclear mixed-valence Mn(III)/Mn(II)/Mn(III) species were resolved. The magnetic properties of the complexes were studied in detail both experimentally and theoretically. All dinuclear complexes show ferromagnetic intramolecular interactions, which were justified on the basis of the electronic structures of the Mn(II) and Mn(III) ions. The large Mn(II)-O-Mn(III) bond angle and small distortion of the Mn(II) cation from the ideal square pyramidal geometry were shown to enhance the ferromagnetic interactions since these geometrical conditions seem to favor the orthogonal arrangement of the magnetic orbitals.

Chromium in leather footwear-risk assessment of chromium allergy and dermatitis

DEFF Research Database (Denmark)

Thyssen, Jacob P; Strandesen, Maria; Poulsen, Pia B

2012-01-01

Background. Chromium-tanned leather footwear, which releases >3 ppm hexavalent Cr(VI), may pose a risk of sensitizing and eliciting allergic dermatitis. Objectives. To determine the content and potential release of chromium in leather footwear and to discuss the prevention of chromium contact...... allergy and dermatitis. Methods. Sixty pairs of leather shoes, sandals and boots (20 children's, 20 men's, and 20 women's) were purchased in Copenhagen and examined with X-ray fluorescence spectroscopy. Chromium was extracted according to the International Standard, ISO 17075. The detection level for Cr......(VI) was 3 ppm. Results. Chromium was identified in 95% of leather footwear products, the median content being 1.7% (range 0-3.3%). No association with store category or footwear category was found. A tendency for there to be a higher chromium content in footwear with high prices was shown (p(trend) = 0...

Emission properties of Sm(III) complex having ten-coordination structure

International Nuclear Information System (INIS)

Hasegawa, Yasuchika; Tsuruoka, Shin-ichi; Yoshida, Takahiko; Kawai, Hideki; Kawai, Tsuyoshi

2008-01-01

Sammarium(III) complex having ten-coordination structure, bis-(1,10-phenanthroline)tris-(hexafluoroacetylacetonato)samarium(III) (Sm(hfa) 3 (phen) 2 ) was prepared by chelation of tris-(hexafluoroacetylacetonato) samarium(III) (Sm(hfa) 3 (H 2 O) 2 ) with 1,10-phenantroline (phen). The characteristic ten-coordination structure of Sm(hfa) 3 (phen) 2 was determined by 1 H NMR and elemental analyses. Strong deep-red emission (λ max =643 nm) and narrow emission band (FWHM=5 nm) of Sm(hfa) 3 (phen) 2 originated from electronic allowed transition from characteristics ten coordinate structure. The emission quantum yields Sm(hfa) 3 (phen) 2 excited at absorption bands of ligands and Sm(III) ion were found to be 0.36 and 1.4%, respectively

A thermodynamic study of La(III)L-alanine complexes

International Nuclear Information System (INIS)

Elzawawy, F.M.

1991-01-01

The protonation constants of L-alanine and the complex formation constants of its La(III) complexes were determined by potentiometric studies at ionic strengths 0.06, 0.1, and 0.15 mol dm -3 (NaClO 4 ) and at different temperatures 20, 27, and 35 O C. The data together with the derived thermodynamic parameters ΔH O , ΔS O , and ΔG O are reported and discussed. (author)

Chromium stress in Brassica juncea L. cv. 'Pusa Jai Kissan' under ...

African Journals Online (AJOL)

Chromium (Cr) entering plant tissue inhibits most physiological processes at all levels of metabolism including inhibition of growth, photosynthesis and nitrate assimilation. Since Cr exists in many forms, its toxicity to plants depends on its valence state, with Cr (VI) found to be highly toxic and mobile than Cr (III). Different ...

Using microalgae scenedesmus obliquus in the removal of chromium present in plating wastewaters

International Nuclear Information System (INIS)

Pellon, A.; Benitez, F.; Frades, J.; Garcia, L.; Cerpa, A.; Alguacil, F.

2003-01-01

Dumping wastewaters from plating industry with a high content in chromium is a potential hazard for people and environment. It is known that some metals, including the heavy metals, at low concentrations participate in different metabolic routes, but at high concentration are toxic for many living organisms. Some microorganism taking the heavy metals from the environment are capable of concentrating and accumulating large quantities of them in different citiplasmatic structures with no-toxic effects. Microalgaehave affinity by the polyvalent metals making possible their use as depollutant agent in waters that contains dissolved metallic ions as alternative methods when others methods of recycle are unusable. In this report a chromium removal study from a plating wastewater, using scenedesmus obliquus culture was made. The removal efficiency of Cr (VI) was 12% and Cr (III) was 27% and for condition of algae's immobilization removal of Cr (III) was 95%. (Author) 19 refs

Heterogeneous chromium catalysts

NARCIS (Netherlands)

2005-01-01

The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based

Chromium 51 em K2CrO4: reactions of dopant atoms in solid state

International Nuclear Information System (INIS)

Valim, J.B.; Nascimento, R.L.G. do; Collins, C.H.; Collins, K.E.

1986-01-01

The study of the chemistry of 'dopant' 51 Cr(III) atoms in crystalline Cr(VI) compounds began as a sub-field of Hot Atom Chemistry. We shall review the attempts to use 'dopant' chromium-51 atoms as surrogate chromium recoil atoms with the special property of having a low-energy, recoil-dam-age-free history. These dopant atoms have shown behaviors very similar to those of high energy recoil 51 Gr atoms, thus offering little hope of learning about special damage site structures and reactions by behavioral differences. Recent work has shown that at least some of the 'dopant' 51 Cr(III) is present as a second, non-chromate solid phase in 'doped crystal' experiments. Monodisperse 51 Cr(OH) 3 particles mixed with pure K 2 CrO 4 are very reactive. (Author) [pt

Effects of an amylopectin and chromium complex on the anabolic response to a suboptimal dose of whey protein.

Science.gov (United States)

Ziegenfuss, T N; Lopez, H L; Kedia, A; Habowski, S M; Sandrock, J E; Raub, B; Kerksick, C M; Ferrando, A A

2017-01-01

Previous research has demonstrated the permissive effect of insulin on muscle protein kinetics, and the enhanced insulin sensitizing effect of chromium. In the presence of adequate whole protein and/or essential amino acids (EAA), insulin has a stimulatory effect on muscle protein synthesis, whereas in conditions of lower blood EAA concentrations, insulin has an inhibitory effect on protein breakdown. In this study, we determined the effect of an amylopectin/chromium (ACr) complex on changes in plasma concentrations of EAA, insulin, glucose, and the fractional rate of muscle protein synthesis (FSR). Using a double-blind, cross-over design, ten subjects (six men, four women) consumed 6 g whey protein + 2 g of the amylopectin-chromium complex (WPACr) or 6 g whey protein (WP) after an overnight fast. FSR was measured using a primed, continuous infusion of ring-d 5 -phenylalanine with serial muscle biopsies performed at 2, 4, and 8 h. Plasma EAA and insulin were assayed by ion-exchange chromatography and ELISA, respectively. After the biopsy at 4 h, subjects ingested their respective supplement, completed eight sets of bilateral isotonic leg extensions at 80% of their estimated 1-RM, and a final biopsy was obtained 4 h later. Both trials increased EAA similarly, with peak levels noted 30 min after ingestion. Insulin tended ( p  = 0.09) to be higher in the WPACr trial. Paired samples t-tests using baseline and 4-h post-ingestion FSR data separately for each group revealed significant increases in the WPACr group (+0.0197%/h, p  = 0.0004) and no difference in the WP group (+0.01215%/hr, p  = 0.23). Independent t-tests confirmed significant ( p  = 0.045) differences in post-treatment FSR between trials. These data indicate that the addition of ACr to a 6 g dose of whey protein (WPACr) increases the FSR response beyond what is seen with a suboptimal dose of whey protein alone.

Determination of chromium combined with DNA, RNA and protein in chromium-rich brewer's yeast

International Nuclear Information System (INIS)

Ding Wenjun; Qian Qinfang; Hou Xiaolin; Feng Weiyue; Chai Zhifang

2000-01-01

The contents of chromium in the DNA, RNA and protein fractions separated from chromium-rich and normal brewer's yeast were determined with the neutron activation analysis in order to study the combination of Cr with DNA, RNA and protein in chromium-rich brewer's yeast. The results showed that the extracting rats and concentrations of DNA, RNA and protein had no significant difference in two types of yeast, but the chromium contents of DNA, RNA and protein in the chromium-rich yeast were significantly higher than those in the normal. In addition, the content of chromium in DNA was much higher than that in RNA and protein, which indicated that the inorganic chromium compounds entered into the yeast cell, during the yeast cultivation in the culture medium containing chromium were converted into organic chromium compounds combined with DNA, RNA and protein

Synthesis, Characterization and Application of A Novel Carbon Bridged Half-metallocene Chromium Catalyst for Methyl Methacrylate Polymerization

Institute of Scientific and Technical Information of China (English)

CHENG Zhengzai; GONG Kai; WANG Yang; ZHOU Xue; ZHANG Weixing; LI Yin; SUN Junquan; LI Wenbing

2014-01-01

A new carbon bridged cyclopentadienyl chromium complex of the type [(C5H4)C(CH3)2 CH2(C5H4N)]CrCl2 was prepared by treatment of CrCl3•(THF)3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis(EA), and the crystal structure was determined by X-ray diffraction analysis. Activated by Al(i-Bu)3, the chromium complex displayed a very high activity for methyl methacrylate (MMA) polymerization. After 24 hours,more than 95.5%MMA was converted to polymethyl methacrylate (PMMA) with a viscosity average molecular weight (Wη) of 416000 g•mol-1 at 60℃for MMA/Al(i-Bu)3/chromium catalyst molar ratio of up to 2000:20:1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.

Arene activation by a nonheme iron(III)-hydroperoxo complex: pathways leading to phenol and ketone products.

Science.gov (United States)

Faponle, Abayomi S; Banse, Frédéric; de Visser, Sam P

2016-07-01

Iron(III)-hydroperoxo complexes are found in various nonheme iron enzymes as catalytic cycle intermediates; however, little is known on their catalytic properties. The recent work of Banse and co-workers on a biomimetic nonheme iron(III)-hydroperoxo complex provided evidence of its involvement in reactivity with arenes. This contrasts the behavior of heme iron(III)-hydroperoxo complexes that are known to be sluggish oxidants. To gain insight into the reaction mechanism of the biomimetic iron(III)-hydroperoxo complex with arenes, we performed a computational (density functional theory) study. The calculations show that iron(III)-hydroperoxo reacts with substrates via low free energies of activation that should be accessible at room temperature. Moreover, a dominant ketone reaction product is observed as primary products rather than the thermodynamically more stable phenols. These product distributions are analyzed and the calculations show that charge interaction between the iron(III)-hydroxo group and the substrate in the intermediate state pushes the transferring proton to the meta-carbon atom of the substrate and guides the selectivity of ketone formation. These studies show that the relative ratio of ketone versus phenol as primary products can be affected by external interactions of the oxidant with the substrate. Moreover, iron(III)-hydroperoxo complexes are shown to selectively give ketone products, whereas iron(IV)-oxo complexes will react with arenes to form phenols instead.

Complex formation of americium (III) with humic acid

International Nuclear Information System (INIS)

Zhang Yingjie; Zhao Xin; Wen Liansheng; Lin Zhangji

2004-01-01

The presence of humic substances in natural waters will modify the migration behavior of actinides in the geosphere due to the strong reaction properties of these ligands with actinides. Therefore, the possible reactions of humic acid with actinides have been studied widely in recent years. The complex formation of Am (III) with humic acid is studied with solvent extraction technique in this paper. The experiments are performed in the pH range from 4.0 to 8.0 in 0.1 M NaClO 4 solution at ambient temperature. Experimental results show that the complex formation constants of Am (III) with humic acid are varied with the variation of pH value in solution. 1:2 complex is obtained in the experiments and the complex formation constants determined at each pH are: lgβ 1 =6.56±0.05, lgβ 2 =10.77±0.31 at pH=4.0; lgβ 1 =7.94±0.11, lgβ 2 =11.80±0.21 at pH=5.0; lgβ 1 =10.74±0.28, lgβ 2 =12.88±0.49 at pH=6.0; lgβ 1 =12.85±0.30, lgβ 2 =14.80±0.62 at pH=7.0; lgβ 1 =14.88±0.48, lgβ 2 =15.65±0.69 at pH=8.0, respectively. The dependence of the complex of the complex formation constant on pH is: lgβ 1 =2.16(±0.98)pH-2.34(±1.03), lgβ 2 =1.28(±1.04)pH+5.52(±1.21), respectively. (author)

Solution-phase synthesis of chromium-functionalized single-walled carbon nanotubes

KAUST Repository

Kalinina, Irina V.; Al-Hadeethi, Yas Fadel; Bekyarova, Elena; Zhao, Chao; Wang, Qingxiao; Zhang, Xixiang; Al-Zahrani, Ali; Al-Agel, Faisal Abdulaziz M; Al-Marzouki, Fahad M.; Haddon, Robert C.

2015-01-01

The solution phase reactions of single-walled carbon nanotubes (SWNTs) with Cr(CO)6 and benzene-Cr(CO)3 can lead to the formation of small chromium clusters. The cluster size can be varied from less than 1 nm to about 4 nm by increasing the reaction time. TEM images suggest that the clusters are deposited predominantly on the exterior walls of the nanotubes. TGA analysis was used to obtain the Cr content and carbon to chromium ratio in the Cr-complexed SWNTs. It is suggested that the carbon nanotube benzenoid structure templates the condensation of chromium atoms and facilitates the loss of carbon monoxide leading to well defined metal clusters.

Solution-phase synthesis of chromium-functionalized single-walled carbon nanotubes

KAUST Repository

Kalinina, Irina V.

2015-03-01

The solution phase reactions of single-walled carbon nanotubes (SWNTs) with Cr(CO)6 and benzene-Cr(CO)3 can lead to the formation of small chromium clusters. The cluster size can be varied from less than 1 nm to about 4 nm by increasing the reaction time. TEM images suggest that the clusters are deposited predominantly on the exterior walls of the nanotubes. TGA analysis was used to obtain the Cr content and carbon to chromium ratio in the Cr-complexed SWNTs. It is suggested that the carbon nanotube benzenoid structure templates the condensation of chromium atoms and facilitates the loss of carbon monoxide leading to well defined metal clusters.

On the removal of hexavalent chromium from a Class F fly ash.

Science.gov (United States)

Huggins, F E; Rezaee, M; Honaker, R Q; Hower, J C

2016-05-01

Coarse and fine samples of a Class F fly ash obtained from commercial combustion of Illinois bituminous coal have been exposed to two long-term leaching tests designed to simulate conditions in waste impoundments. ICP-AES analysis indicated that the coarse and fine fly ash samples contained 135 and 171mg/kg Cr, respectively. Measurements by XAFS spectroscopy showed that the ash samples originally contained 5 and 8% of the chromium, respectively, in the hexavalent oxidation state, Cr(VI). After exposure to water for more than four months, the percentage of chromium as Cr(VI) in the fly-ash decreased significantly for the coarse and fine fly-ash in both tests. Combining the XAFS data with ICP-AES data on the concentration of chromium in the leachates indicated that, after the nineteen-week-long, more aggressive, kinetic test on the coarse fly ash, approximately 60% of the Cr(VI) had been leached, 20% had been reduced to Cr(III) and retained in the ash, and 20% remained as Cr(VI) in the ash. In contrast, during the six-month-long baseline test, very little Cr was actually leached from either the coarse or the fine fly-ash (ash was retained in the ash in that form, while the remainder, 34% and 80%, respectively, was reduced and retained in the ash as Cr(III). The results are interpreted as indicating that Cr(VI) present in Class F fly-ash can be reduced to Cr(III) when in contact with water and that such chemical reduction can compete with physical removal of Cr(VI) from the ash by aqueous leaching. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biochemical investigation of yttrium(III) complex containing 1,10-phenanthroline: DNA binding and antibacterial activity.

Science.gov (United States)

Khorasani-Motlagh, Mozhgan; Noroozifar, Meissam; Moodi, Asieh; Niroomand, Sona

2013-03-05

Characterization of the interaction between yttrium(III) complex containing 1,10-phenanthroline as ligand, [Y(phen)2Cl(OH2)3]Cl2⋅H2O, and DNA has been carried out by UV absorption, fluorescence spectra and viscosity measurements in order to investigate binding mode. The experimental results indicate that the yttrium(III) complex binds to DNA and absorption is decreasing in charge transfer band with the increase in amount of DNA. The binding constant (Kb) at different temperatures as well as thermodynamic parameters, enthalpy change (ΔH°) and entropy change (ΔS°), were calculated according to relevant fluorescent data and Vant' Hoff equation. The results of interaction mechanism studies, suggested that groove binding plays a major role in the binding of the complex and DNA. The activity of yttrium(III) complex against some bacteria was tested and antimicrobial screening tests shown growth inhibitory activity in the presence of yttrium(III) complex. Copyright © 2013 Elsevier B.V. All rights reserved.

complex formation of americium (III) with humic acid

International Nuclear Information System (INIS)

Zhang Yingjie; Zhao Xin; Wei Liansheng; Lin Zhangji

1998-01-01

The presence of humic substances in natural waters will modify the migration behavior of actinides in the geosphere due to the strong reaction properties of these ligands with actinides. Therefore, the possible reactions of humic acid with actinides have been studied widely in recent years. The complex formation of Am(III) with humic acid is studied with solvent extraction technique. The experiments are performed in the pH range from 4.0 to 8.0 in 0.1 mol/kg NaClO 4 solution at ambient temperature. Experimental results show that the complex formation constants of Am(III) with humic acid are varied with the variation of pH value in solution. 1:2 complex is obtained in the experiments and the complex formation constants determined at each pH are: lgβ 1 = 6.56 +- 0.05, lgβ 2 = 10.77 +- 0.31 at pH 4.0. lgβ 1 = 7.94 +- 0.11, lgβ 2 = 11.80 +- 0.21 at pH = 5.0. lgβ 1 = 10.74 +- 0.28, lgβ 2 = 12.88 +- 0.49 at pH = 6.0. lgβ 1 = 12.85 +- 0.30, lgβ 2 = 14.80 +- 0.62 at pH = 7.0. lgβ 1 = 14.88 +- 0.48, lgβ 2 = 15.65 +- 0.69 at pH = 8.0, respectively. The dependence of the complex formation constant on pH is: lgβ 1 = 2.16 (+-0.98)pH-2.34(+-0.93),lgβ 2 1.28(+-1.04)pH+5.52(+-1.21), respectively

Synthesis of novel fluorescent probe Tb(III)-7-carboxymethoxy-4-methylcoumarin complex for sensing of DNA

International Nuclear Information System (INIS)

Hussein, Belal H.M.; Azab, Hassan A.; Fathalla, Walid; Ali, Sherin A.M.

2013-01-01

New fluorescent probe Tb(III) (7-carboxymethoxy-4-methylcoumarin)2(SCN) (C2H5OH)(H2O) was synthesized and characterized by spectroscopy and thermal analysis. The absorption and fluorescence spectra of 7-carboxymethoxy-4-methylcoumarin (CMMC) and Tb(III)–CMMC complex have been measured in different solvents. The interactions of Tb(III)–CMMC complex with calf thymus nucleic acid (CT-DNA) have been investigated using steady state fluorescence measurements. The changes in the fluorescence intensity have been used for the quantitative determination of DNA with LOD of 3.45 ng in methanol–water (9:1, v/v). The association constants of DNA with Tb(III)–CMMC complex was found to be 2.62×1010 M −1 . - Highlights: ► New fluorescent probe Terbium (III)-7-carboxy methoxy-4-methylcoumarin complex has been synthesized and characterized. ► FTIR spectrum of Tb(III)-complex shows a characteristic band for thiocyanate group. ► DNA interaction with Terbium (III)-7-carboxy methoxy-4-methylcoumarin has been studied by fluorescence techniques. ► The change in the fluorescence intensity has been used for the quantitative determination of DNA. ► The result was better than most of the well-known methods including the ethidium bromide method.

Polarographic determination of stability constants of Eu(III) complexes with acrylic and crotonic acid

Energy Technology Data Exchange (ETDEWEB)

Rao, A L.J.; Singh, Makhan [Punjabi Univ., Patiala (India). Dept. of Chemistry

1979-07-01

Compositions and formation constants of Eu(III) complexes with acrylic acid and crotonic acid have been studied polarographically. The reductions are reversible and diffusion-controlled. The plot of Esub(1/2) versus--log Csub(x) is linear in the case of Eu(III)-acrylic acid system. The change in number of ligands bound to europium during reduction was found to be approximately 1 and ratio of dissociation constants of Eu(III) and Eu(II) was found to be 40.76X10sup(-2). In the case of Eu(III)-crotonic acid system, composition and formation constants have been calculated by the method of Deford and Hume. Crotonic acid forms two complex species with europium (..beta../sub 1/,60; ..beta../sub 2/, 4.2x10sup(+2)). The percentage distribution of various complex species as a function of ligand concentration has been calculated in the case of Eu(III)-crotonic acid system. A polarographic method for the determination of micro amounts of Eu(III) in the presence of diverse ions has been developed. Under optimum conditions Eu(III) in the concentration range 4x19sup(-4)-2x10sup(-2)M can be successfully determined in various mixtures.

Mechanistic studies on reactivities of organometallic macrocyclic complexes of chromium and cobalt

Energy Technology Data Exchange (ETDEWEB)

Shi, Shu.

1990-12-10

Reaction pathways leading to the formation and cleavage of a transition metal-carbon bond at various oxidation states of the metal occupy a central position in understanding many enzymatic reactions and designing catalysts. The report is divided into six parts that (1) focus on the homolysis vs heterolysis of a C-Cr(III) bond, (2) describes a unique chain reaction and a S{sub E}2 reaction I{sub 2} and RCrL{sup 2+}, (3) concerns the oxidation of organochromium(III) complexes by dihalide and pseudo-dihalide radical anions generated by pulse radiolysis, (4) concentrates on the oxidation mechanism of RCr(H{sub 2}O){sup 2+} and the fate of RCr(H{sub 2}O){sup 3+} as well as the corresponding reduction potentials, (5) extends study of organocobalt complexes with attention to reduction induced cleavages of a transition metal-carbon bond, and (6) describes the crystallization of ((CH{sub 3}){sub 4}N)(Co(dmgBF{sub 2}){sub 2}py) and reports its molecular structure as determined by x-ray diffraction. 182 refs., 25 figs., 16 tabs. (BM)

Mechanistic studies on reactivities of organometallic macrocyclic complexes of chromium and cobalt

International Nuclear Information System (INIS)

Shi, Shu.

1990-01-01

Reaction pathways leading to the formation and cleavage of a transition metal-carbon bond at various oxidation states of the metal occupy a central position in understanding many enzymatic reactions and designing catalysts. The report is divided into six parts that (1) focus on the homolysis vs heterolysis of a C-Cr(III) bond, (2) describes a unique chain reaction and a S E 2 reaction I 2 and RCrL 2+ , (3) concerns the oxidation of organochromium(III) complexes by dihalide and pseudo-dihalide radical anions generated by pulse radiolysis, (4) concentrates on the oxidation mechanism of RCr(H 2 O) 2+ and the fate of RCr(H 2 O) 3+ as well as the corresponding reduction potentials, (5) extends study of organocobalt complexes with attention to reduction induced cleavages of a transition metal-carbon bond, and (6) describes the crystallization of [(CH 3 ) 4 N][Co(dmgBF 2 ) 2 py] and reports its molecular structure as determined by x-ray diffraction. 182 refs., 25 figs., 16 tabs. (BM)

Biological activity of Fe(III) aquo-complexes towards ferric chelate reductase (FCR).

Science.gov (United States)

Escudero, Rosa; Gómez-Gallego, Mar; Romano, Santiago; Fernández, Israel; Gutiérrez-Alonso, Ángel; Sierra, Miguel A; López-Rayo, Sandra; Nadal, Paloma; Lucena, Juan J

2012-03-21

In this study we have obtained experimental evidence that confirms the high activity of aquo complexes III and IV towards the enzyme FCR, responsible for the reduction of Fe(III) to Fe(II) in the process of iron acquisition by plants. The in vivo FCR assays in roots of stressed cucumber plants have shown a higher efficiency of the family of complexes III and a striking structure-activity relationship with the nature of the substituent placed in a phenyl group far away from the metal center. The results obtained in this work demonstrate that all the aquo compounds tested interact efficiently with the enzyme FCR and hence constitute a new concept of iron chelates that could be of great use in agronomy.

Poly(neutral red) based hydrogen peroxide biosensor for chromium determination by inhibition measurements.

Science.gov (United States)

Attar, Aisha; Emilia Ghica, M; Amine, Aziz; Brett, Christopher M A

2014-08-30

Amperometric hydrogen peroxide enzyme inhibition biosensors based on horseradish peroxidase (HRP) immobilised on electropolymerised neutral red (NR) or directly on the surface of carbon film electrodes (CFE) have been successfully applied to the determination of toxic Cr(III) and Cr(VI). Parameters influencing the performance of the biosensor including the enzyme immobilisation method, the amount of hydrogen peroxide, applied potential and electrolyte pH were optimised. The inhibition of horseradish peroxidase by the chromium species was studied under the optimised conditions. Results from the quantitative analysis of chromium ions are discussed in terms of detection limit, linear range and sensitivity. The HRP kinetic interactions reveal mixed binding of Cr(III) with I50=3.8μM and inhibition binding constant Ki=11.3μM at HRP/PNR/CFE biosensors and uncompetitive binding of Cr(VI) with I50=3.9μM and Ki=0.78μM at HRP/CFE biosensors in the presence of H2O2 substrate. Interferences from other heavy metal ions were studied and the inhibition show very good selectivity towards Cr(III) and Cr(VI). Copyright © 2014 Elsevier B.V. All rights reserved.

Structure and luminescent investigation of new Ln(III)-TTA complexes containing N-methyl-ε-caprolactam as ligand

Energy Technology Data Exchange (ETDEWEB)

Borges, Alex Santos, E-mail: alexb@ifes.edu.br [Coordenadoria de Química e Biologia, IFES, Vitória, ES 29040-780 (Brazil); Caliman, Ewerton Valadares [Coordenadoria de Engenharia Metalúrgica, IFES, Vitória, ES 29040-780 (Brazil); Dutra, José Diogo L. [Departamento de Química Fundamental, UFPE, Recife, PE 50590-470 (Brazil); Da Silva, Jeferson G. [Departamento de Farmácia, UFJF, Governador Valadares, MG 35010-17 (Brazil); Araujo, Maria Helena, E-mail: maria.araujo@pq.cnpq.br [Departamento de Química, UFMG, Belo Horizonte, MG 31270-901 (Brazil)

2016-02-15

The synthesis and photoluminescent properties of Ln(III)-TTA complexes (Ln=Eu(III) and Sm(III) ions; TTA=3-thenoyltrifluoroacetonate) with N-methyl-ε-caprolactam (NMC) are reported. The Ln complexes were characterized by elemental analysis, complexometric titration with EDTA and infrared spectroscopy. The molecular structures of the [Eu(TTA){sub 3}(NMC)(H{sub 2}O)] and [Sm(TTA){sub 3}(NMC)(H{sub 2}O)]·H{sub 2}O compounds were determined by single crystal X-ray crystallography. In these structures, the three TTA molecules are coordinated to the metal in anionic form as bidentate ligands, while the H{sub 2}O and NMC molecules are coordinated to the metal in neutral form as monodentated ligands. The coordination polyhedron around the Ln(III) atom can be described as square antiprismatic molecular geometry. The geometry of the [Eu(TTA){sub 3}(NMC)(H{sub 2}O)] complex was optimized with the Sparkle/RM1 model for Ln(III) complexes, allowing analysis of intramolecular energy transfer processes of the Eu(III) compound. The spectroscopic properties of the 4f{sup 6} intraconfigurational transitions of the Eu(III) complex were then studied experimentally and theoretically. The low value of emission quantum efficiency of {sup 5}D{sub 0} emitting level (η) of Eu(III) ion (ca. 36%) is due to the vibrational modes of the water molecule that act as luminescence quenching. In addition, the luminescence decay curves, the experimental intensity parameters (Ω{sub λ}), lifetimes (τ), radiative (A{sub rad}) and non-radiative (A{sub nrad}) decay rates, theoretical quantum yield (q{sub cal}) were also determined and discussed. - Highlights: • New Ln-TTA complexes with lactam were obtained and their luminescence investigated. • Jablonsky diagram for the Eu(III) complex shows the main channel for the IET process. • Data confirm the potentiality of the Eu(III) complex to produce red luminescence. • LUMPAC has provided useful information on the luminescence of the Eu(III

Development of low-chromium, chromium-tungsten steels for fusion

International Nuclear Information System (INIS)

Klueh, R.L.; Alexander, D.J.; Kenik, E.A.

1995-01-01

High-chromium (9-12% Cr) Cr-Mo and Cr-W ferritic steels are favored as candidates for fusion applications. In early work to develop reduced-activation steels, an Fe-2.25Cr-2W-0.25V-0.1C steel (designated 2.25Cr-2WV) had better strength than an Fe-9Cr-2W-0.25V-0.07Ta-0.1C (9Cr-2WVTa) steel (compositions are in weight percent). However, the 2.25Cr-2WV had poor impact properties, as determined by the ductile-brittle transition temperature and upper-shelf energy of subsize Charpy impact specimens. Because low-chromium steels have some advantages over high-chromium steels, a program to develop low-chromium steels is in progress. Microstructural analysis indicated that the reason for the inferior impact toughness of the 2.25Cr-2WV was the granular bainite obtained when the steel was normalized. Properties can be improved by developing an acicular bainite microstructure by increasing the cooling rate after austenitization. Alternatively, acicular bainite can be promoted by increasing the hardenability. Hardenability was changed by adding small amounts of boron and additional chromium to the 2.25Cr-2WV composition. A combination of B, Cr, and Ta additions resulted in low-chromium reduced-activation steels with mechanical properties comparable to those of 9Cr-2WVTa. (orig.)

Disturbance response indicators of Impatiens walleriana exposed to benzene and chromium.

Science.gov (United States)

Campos, V; Lessa, S S; Ramos, R L; Shinzato, M C; Medeiros, T A M

2017-08-03

The purpose of this study was to evaluate the remediation potential and disturbance response indicators of Impatiens walleriana exposed to benzene and chromium. Numerous studies over the years have found abundant evidence of the carcinogenicity of benzene and chromium (VI) in humans. Benzene and chromium are two toxic industrial chemicals commonly found together at contaminated sites, and one of the most common management strategies employed in the recovery of sites contaminated by petroleum products and trace metals is in situ remediation. Given that increasing interest has focused on the use of plants as depollution agents, direct injection tests and benzene misting were performed on I. walleriana to evaluate the remediation potential of this species. I. walleriana accumulated hexavalent chromium, mainly in the root system (164.23 mg kg -1 ), to the detriment of the aerial part (39.72 mg kg -1 ), and presented visible damage only at the highest concentration (30 mg L -1 ). Unlike chromium (VI), chromium (III) was retained almost entirely by the soil, leaving it available for removal by phytotechnology. However, after the contamination stopped, I. walleriana responded positively to the detoxification process, recovering its stem stiffness and leaf color. I. walleriana showed visible changes such as leaf chlorosis during the ten days of benzene contamination. When benzene is absorbed by the roots, it is translocated to and accumulated in the plant's aerial part. This mechanism the plant uses ensures its tolerance to the organic compound, enabling the species to survive and reproduce after treatment with benzene. Although I. walleriana accumulates minor amounts of hexavalent chromium in the aerial part, this amount suffices to induce greater oxidative stress and to increase the amount of hydrogen peroxide when compared to that of benzene. It was therefore concluded that I. walleriana is a species that possesses desirable characteristics for phytotechnology.

Structural Properties of the Cr(III)-Fe(III) (Oxy)Hydroxide Compositional Series: Insights for a Nanomaterial 'Solid Solution'

International Nuclear Information System (INIS)

Tang, Y.; Zhang, L.; Michel, F.M.; Harrington, R.; Parise, J.B.; Reeder, R.J.

2010-01-01

Chromium(III) (oxy)hydroxide and mixed Cr(III)-Fe(III) (oxy)hydroxides are environmentally important compounds for controlling chromium speciation and bioaccessibility in soils and aquatic systems and are also industrially important as precursors for materials and catalyst synthesis. However, direct characterization of the atomic arrangements of these materials is complicated because of their amorphous X-ray properties. This study involves synthesis of the complete Cr(III)-Fe(III) (oxy)hydroxide compositional series, and the use of complementary thermal, microscopic, spectroscopic, and scattering techniques for the evaluation of their structural properties. Thermal analysis results show that the Cr end member has a higher hydration state than the Fe end member, likely associated with the difference in water exchange rates in the first hydration spheres of Cr(III) and Fe(III). Three stages of weight loss are observed and are likely related to the loss of surface/structural water and hydroxyl groups. As compared to the Cr end member, the intermediate composition sample shows lower dehydration temperatures and a higher exothermic transition temperature. XANES analysis shows Cr(III) and Fe(III) to be the dominant oxidation states. XANES spectra also show progressive changes in the local structure around Cr and Fe atoms over the series. Pair distribution function (PDF) analysis of synchrotron X-ray total scattering data shows that the Fe end member is nanocrystalline ferrihydrite with an intermediate-range order and average coherent domain size of ∼27 (angstrom). The Cr end member, with a coherent domain size of ∼10 (angstrom), has only short-range order. The PDFs show progressive structural changes across the compositional series. High-resolution transmission electron microscopy (HRTEM) results also show the loss of structural order with increasing Cr content. These observations provide strong structural evidence of chemical substitution and progressive structural

Quantum Calculations of Electron Tunneling in Respiratory Complex III.

Science.gov (United States)

Hagras, Muhammad A; Hayashi, Tomoyuki; Stuchebrukhov, Alexei A

2015-11-19

The most detailed and comprehensive to date study of electron transfer reactions in the respiratory complex III of aerobic cells, also known as bc1 complex, is reported. In the framework of the tunneling current theory, electron tunneling rates and atomistic tunneling pathways between different redox centers were investigated for all electron transfer reactions comprising different stages of the proton-motive Q-cycle. The calculations reveal that complex III is a smart nanomachine, which under certain conditions undergoes conformational changes gating electron transfer, or channeling electrons to specific pathways. One-electron tunneling approximation was adopted in the tunneling calculations, which were performed using hybrid Broken-Symmetry (BS) unrestricted DFT/ZINDO levels of theory. The tunneling orbitals were determined using an exact biorthogonalization scheme that uniquely separates pairs of tunneling orbitals with small overlaps out of the remaining Franck-Condon orbitals with significant overlap. Electron transfer rates in different redox pairs show exponential distance dependence, in agreement with the reported experimental data; some reactions involve coupled proton transfer. Proper treatment of a concerted two-electron bifurcated tunneling reaction at the Q(o) site is given.

Spectroscopic investigation of complexation of Cm(III) und Eu(III) with partitioning-relevant N-donor ligands

International Nuclear Information System (INIS)

Bremer, Antje

2014-01-01

The separation of trivalent actinides and lanthanides is an essential part of the development of improved nuclear fuel cycles. Liquid-liquid extraction is an applicable technique to achieve this separation. Due to the chemical similarity and the almost identical ionic radii of trivalent actinides and lanthanides this separation is, however, only feasible with highly selective extracting agents. It has been proven that molecules with soft sulphur or nitrogen donor atoms have a higher affinity for trivalent actinides. In the present work, the complexation of Cm(III) and Eu(III) with N-donor ligands relevant for partitioning has been studied by time-resolved laser fluorescence spectroscopy (TRLFS). This work aims at a better understanding of the molecular reason of the selectivity of these ligands. In this context, enormous effort has been and is still put into detailed investigations on BTP and BTBP ligands, which are the most successful N-donor ligands for the selective extraction of trivalent actinides, to date. Additionally, the complexation and extraction behavior of molecules which are structurally related to these ligands is studied. The ligand C5-BPP (2,6-bis(5-(2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine) where the triazine rings of the aromatic backbone of the BTP ligands have been replaced by pyrazole rings is one of these molecules. Laser fluorescence spectroscopic investigation of the complexation of Cm(III) with this ligand revealed stepwise formation of three (Cm(C5-BPP) n ) 3+ complexes (n = 1 - 3). The stability constant of the 1:3 complex was determined (log β 3 = 14.8 ± 0.4). Extraction experiments have shown that, in contrast to BTP and BTBP ligands, C5-BPP needs an additional lipophilic anion source such as a 2-bromocarboxylic acid to selectively extract trivalent actinides from nitric acid solutions. The comparison of the stability constant of the (Cm(C5-BPP) 3 ) 3+ complex with the stability constant of the (Cm(nPr-BTP) 3 ) 3+ complex

Luminescence and circularly polarized luminescence of macrocyclic Eu(III) and Tb(III) complexes embedded in xerogel and sol-gel SiO2 glasses

International Nuclear Information System (INIS)

Morita, M.; Rau, D.; Kai, T.

2002-01-01

Luminescence, time-resolved luminescence, circularly polarized luminescence (CPL) and decay profiles of Ln(III)(15-crownether-5) (Ln=Ce, Sm, Eu, Tb) and Tb(III)-(R),(S)-cyclen derivative complexes doped in xerogel and sol-gel silica glasses are measured at temperatures down to 10 K to characterize luminescence properties and the electronic structure in the excited states. Luminescence spectral profiles and calculation of crystal field parameters (B 0 (2) ,B 2 (2) ) in the 5 D 0 → 7 F J (J=1,2) transition give evidence of the fact that the pentagonal and planar structure of Eu(III) (15-crownether-5) does hold in xerogel and sol-gel glasses prepared at temperatures below 100 deg. C. As annealing temperatures are increased from 80 deg. C to 750 deg. C, Eu(III) complexes in sol-gel glasses are found to decompose gradually to SiO 2 :Eu 3+ . Tb(III)-(R) and (S)-cyclen derivative complexes in xerogel reveal at room temperature and 10 K sharp CPL spectra with luminescence dissymmetry factors g lum =-0.1 and 0.1, respectively. These complexes doped in sol-gel glasses represent luminescence characteristics of rare earth ions encapsulated in the nano-porous host

Technetium electrochemistry. 7. Electrochemical and spectroelectrochemical studies on technetium(III) and -(II) complexes containing polypyridyl ligands

International Nuclear Information System (INIS)

Wilcox, B.E.; Deutsch, E.

1991-01-01

The redox properties of a series of technetium(III/II) complexes of the general formula cis(X), trans(P)-[Tc III/II X 2 (PR w R') 2 L] 10+ , where X = Cl or Br, PR 2 R' = dimethylphenylphosphine or ethyldiphenylphosphine, and L = 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (Me 2 bpy), or 1,10-phenanthroline (phen), were investigated in 0.1 M TEAP/acetonitrile by cyclic voltammetry at a platinum-disk electrode. These complexes exhibit diffusion-controlled, 1-equiv Tc(IV)/Tc(III) redox couples and also Tc(III)/Tc(II) redox couples. Spectropotentiostatic experiments on three complexes of this class in 0.5 M TEAP/DMF confirm the 1-equiv character of the Tc(III)/Tc(II) couple. The electrochemical behavior of Tc(II) complexes of the general formula trans(P)-[TcX(PR 2 R') 2 terpy] + , terpy = 2,2':6',2 double-prime-terpyridine, was also investigated under the same conditions as above. These complexes exhibit diffusion-controlled, 1-equiv Tc(III)/Tc(II) redox couples and Tc(II)/Tc(I) redox couples. Spectropotentiostatic experiments on trans(P)-[TcCl(PMe 2 Ph) 2 terpy] + confirm the 1-equiv character of the Tc(III)/Tc(II) couple but show that the Tc(II)/Tc(I) couple is not reversible on the spectropotentiostatic time scale

Synthesis of novel fluorescent probe Tb(III)-7-carboxymethoxy-4-methylcoumarin complex for sensing of DNA

Energy Technology Data Exchange (ETDEWEB)

Hussein, Belal H.M., E-mail: belalhussein102@yahoo.com [Department of Chemistry, Faculty of Science, Suez Canal University, Ismailia (Egypt); Azab, Hassan A. [Department of Chemistry, Faculty of Science, Suez Canal University, Ismailia (Egypt); Fathalla, Walid [Department of Mathematical and Physical Sciences, Faculty of Engineering, Port-Said University, Port-Said (Egypt); Ali, Sherin A.M. [Department of Mathematical and Physical Sciences, Faculty of Engineering, Suez Canal University, Ismailia (Egypt)

2013-02-15

New fluorescent probe Tb(III) (7-carboxymethoxy-4-methylcoumarin)2(SCN) (C2H5OH)(H2O) was synthesized and characterized by spectroscopy and thermal analysis. The absorption and fluorescence spectra of 7-carboxymethoxy-4-methylcoumarin (CMMC) and Tb(III)-CMMC complex have been measured in different solvents. The interactions of Tb(III)-CMMC complex with calf thymus nucleic acid (CT-DNA) have been investigated using steady state fluorescence measurements. The changes in the fluorescence intensity have been used for the quantitative determination of DNA with LOD of 3.45 ng in methanol-water (9:1, v/v). The association constants of DNA with Tb(III)-CMMC complex was found to be 2.62 Multiplication-Sign 1010 M{sup -1}. - Highlights: Black-Right-Pointing-Pointer New fluorescent probe Terbium (III)-7-carboxy methoxy-4-methylcoumarin complex has been synthesized and characterized. Black-Right-Pointing-Pointer FTIR spectrum of Tb(III)-complex shows a characteristic band for thiocyanate group. Black-Right-Pointing-Pointer DNA interaction with Terbium (III)-7-carboxy methoxy-4-methylcoumarin has been studied by fluorescence techniques. Black-Right-Pointing-Pointer The change in the fluorescence intensity has been used for the quantitative determination of DNA. Black-Right-Pointing-Pointer The result was better than most of the well-known methods including the ethidium bromide method.

2,2',-bipyridine and 1,10-phenanthroline complexes of lanthanide(III) trifluoroacetates

International Nuclear Information System (INIS)

Misra, S.N.; Singh, M.

1983-01-01

The syntheses and characterization of lanthanide(III) triflloroacetate complexes with 2,2'-bipyridine and 1,10-phenanthroline are reported. Lanthanide(III) trifluoroacetates yield compounds of the type Ln(CF 3 COO) 3 .bipy or phen with 2,2'-bipyridine and 1,10-phenanthroline. Their properties and structures have been studied using chemical analyses. electronic and infrared spectra. Thermal analysis of a few complexes have also been done. The infrared data show that the trifluoroacetate group acts as a bidentate ligand making the coordination number of lanthanide eight. (author)

Chromium in aqueous nitrate plutonium process streams: Corrosion of 316 stainless steel and chromium speciation

International Nuclear Information System (INIS)

Smith, W.H.; Purdy, G.M.

1995-01-01

This study was undertaken to determine if chromium(+6) could exist in plutonium process solutions under normal operating conditions. Four individual reactions were studied: the rate of dissolution of stainless steel, which is the principal source of chromium in process solutions; the rate of oxidation of chromium(+3) to chromium(+6) by nitric acid; and the reduction of chromium(+6) back to chromium(+3) by reaction with stainless steel and with oxalic acid. The stainless steel corrosion rate was found to increase with increasing nitric acid concentration, increasing hydrofluoric acid concentration, and increasing temperature. Oxidation of chromium(+3) to chromium(+6) was negligible at room temperature and only became significant in hot concentrated nitric acid. The rate of reduction of chromium(+6) back to chromium(+3) by reaction with stainless steel or oxalic acid was found to be much greater than the rate of the reverse oxidation reaction. Based on these findings and taking into account normal operating conditions, it was determined that although there would be considerable chromium in plutonium process streams it would rarely be found in the (+6) oxidation state and would not exist in the (+6) state in the final process waste solutions

Chromium in aqueous nitrate plutonium process streams: Corrosion of 316 stainless steel and chromium speciation

International Nuclear Information System (INIS)

Smith, W.H.; Purdy, G.

1995-01-01

This study was undertaken to determine if chromium +6 could exist in plutonium process solutions under normal operating conditions. Four individual reactions were studied: the rate of dissolution of stainless steel, which is the principal source of chromium in process solutions; the rate of oxidation of chromium +3 to chromium +6 by nitric. acid; and the reduction of chromium +6 back to chromium +3 by reaction with stainless steel and with oxalic acid. The stainless steel corrosion rate was found to increase with increasing nitric acid concentration, increasing hydrofluoric acid concentration, and increasing temperature. Oxidation of chromium +3 to chromium +6 was negligible at room temperature and only became significant in hot concentrated nitric acid. The rate of reduction of chromium +6 back to chromium +3 by reaction with stainless steel or oxalic acid was found to be much greater than the rate of the reverse oxidation reaction. Based on these findings and taking into account normal operating conditions, it was determined that although there would be considerable chromium in plutonium process streams it would rarely be found in the +6 oxidation state and would not exist in the +6 state in the final process waste solutions

Spectroscopic investigation on the interaction of some surfactant-cobalt(III) complexes with serum albumins

Energy Technology Data Exchange (ETDEWEB)

Vignesh, Gopalaswamy; Nehru, Selvan; Manojkumar, Yesaiyan; Arunachalam, Sankaralingam, E-mail: arunasurf@yahoo.com

2014-01-15

The interaction of HSA/BSA with single and double chain surfactant-cobalt(III) complexes, cis-[Co(phen){sub 2}(UA)Cl](ClO{sub 4}){sub 2}·2H{sub 2}O (1), cis-[Co(phen){sub 2}(UA){sub 2}](ClO{sub 4}){sub 3}·2H{sub 2}O (2), cis-[Co(en){sub 2}(UA)Cl](ClO{sub 4}){sub 2}·2H{sub 2}O (3), cis-[Co(en){sub 2}(UA){sub 2}](ClO{sub 4}){sub 3}·2H{sub 2}O (4), were investigated by steady state fluorescence, UV–vis absorption, synchronous, three dimensional fluorescence and circular dichroism spectroscopy. The results reveal that the quenching of HSA/BSA by all the four complexes takes place through static mechanism. The binding constant, binding sites and thermodymamic parameter were calculated. The results illustrate that the double chain surfactant-cobalt(III) complexes bind more strongly than the corresponding single chain complexes. The distance between donor (HSA/BSA) and acceptor (surfactant-cobalt(III) complexes) was obtained according to FRET. The results of synchronous, three dimensional and circular dichroism spectroscopy studies show that all the complexes caused considerable amount of conformational and some amount of environment changes in HSA/BSA. -- Highlights: • Binding of single and double chain surfactant-cobalt(III) complexes with serum albumins. • Hydrophobic attraction plays a major role in the binding process. • Binding induces considerable amount of conformational changes in the protein.

Chromium containing silica: effect of ultrasonic and purification methods on color products

International Nuclear Information System (INIS)

Martines, M.A.U.; Jafelicci Junior, M.; Davolos, M.R.

1990-01-01

Chromium containing silica has numerous applications, such as: fiber-optics, luminescent materials, catalysts and pigments. In paint and ceramic pigments, chromate and dichromate ions, and silica are largely used. In this paper, it has been investigated the effect of pH, heating methods, and ultrasonic stirring on chromium oxidation states coprecipitated with silica. The material has been obtained from the coprecipitation of an aqueous diluted sodium silicate solution and acid chromium nitrate solution, purified by extractions and dialysis, and dried with microwave oven. Products have been characterized by X-ray powder diffraction, infrared vibrational spectroscopy and nitrogem adsorption isotherm (BET). Coprecipitates are non cristalline and the specific surface area value for sample obtained by conventional heating is smaller than the one for sample obtained by ultrasonic method. It is possible to obtain silica with different colors from blue due to the Cr(III), to yellow due to the Cr (VI), depending on the precipitation, purification and drying methods. (author) [pt

Mussel-Inspired Protein Nanoparticles Containing Iron(III)-DOPA Complexes for pH-Responsive Drug Delivery.

Science.gov (United States)

Kim, Bum Jin; Cheong, Hogyun; Hwang, Byeong Hee; Cha, Hyung Joon

2015-06-15

A novel bioinspired strategy for protein nanoparticle (NP) synthesis to achieve pH-responsive drug release exploits the pH-dependent changes in the coordination stoichiometry of iron(III)-3,4-dihydroxyphenylalanine (DOPA) complexes, which play a major cross-linking role in mussel byssal threads. Doxorubicin-loaded polymeric NPs that are based on Fe(III)-DOPA complexation were thus synthesized with a DOPA-modified recombinant mussel adhesive protein through a co-electrospraying process. The release of doxorubicin was found to be predominantly governed by a change in the structure of the Fe(III)-DOPA complexes induced by an acidic pH value. It was also demonstrated that the fabricated NPs exhibited effective cytotoxicity towards cancer cells through efficient cellular uptake and cytosolic release. Therefore, it is anticipated that Fe(III)-DOPA complexation can be successfully utilized as a new design principle for pH-responsive NPs for diverse controlled drug-delivery applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and DNA interaction of a Sm(III) complex of a Schiff base ...

African Journals Online (AJOL)

The interaction between the Sm(III) complex of an ionic Schiff base [HL]-, derived from vanillin and L-tryptophan, and herring sperm DNA at physiological pH (7.40) has been studied by UV-Vis absorption, fluorescence and viscosity methods. The binding ratios nSm(III) : nK[HL] = 1:1 and nSm(III)L: nDNA =5:1 were confirmed ...

Hexavalent Chromium Minimization Strategy

Science.gov (United States)

2011-05-01

Logistics 4 Initiative - DoD Hexavalent Chromium Minimization Non- Chrome Primer IIEXAVAJ ENT CHRO:M I~UMI CHROMIUM (VII Oil CrfVli.J CANCEfl HAnRD CD...Management Office of the Secretary of Defense Hexavalent Chromium Minimization Strategy Report Documentation Page Form ApprovedOMB No. 0704-0188...00-2011 4. TITLE AND SUBTITLE Hexavalent Chromium Minimization Strategy 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6

Characterization of some Pr(III) complexes in terms of electronic spectral parameters

International Nuclear Information System (INIS)

Bhati, P.R.; Soni, K.P.; Joshi, G.K.; Swami, S.N.

1992-01-01

Pr(III) complexes from the ligands derived from methyl acetoacetate, ethyl acetoacetate, veratraldehyde, ethyl vanillin and 2,5 dimethoxy benzaldehyde forming Schiff-bases with ortho, meta and para phenylene diamines have been synthesized. The complexes have been characterized in terms of various Slater-Condon Lande and Judd-Ofelt parameters. The various trends in the parametric values have also been described. The involvement of 4f-orbital in the Pr(III) complexes including deviation in the symmetry have been discussed on the basis of electronic spectral parameters. The validity of the theories used has been established while comparing observed and calculated energies and intensities of the various bands in the present complexes on the basis of r.m.s deviation. The trends of the curves observed in the solution spectra have also been discussed. (author). 21 refs., 5 tabs., 2 figs

Infinite Particle Systems: Complex Systems III

Directory of Open Access Journals (Sweden)

Editorial Board

2008-06-01

Full Text Available In the years 2002-2005, a group of German and Polish mathematicians worked under a DFG research project No 436 POL 113/98/0-1 entitled "Methods of stochastic analysis in the theory of collective phenomena: Gibbs states and statistical hydrodynamics". The results of their study were summarized at the German-Polish conference, which took place in Poland in October 2005. The venue of the conference was Kazimierz Dolny upon Vistula - a lovely town and a popular place for various cultural, scientific, and even political events of an international significance. The conference was also attended by scientists from France, Italy, Portugal, UK, Ukraine, and USA, which predetermined its international character. Since that time, the conference, entitled "Infinite Particle Systems: Complex Systems" has become an annual international event, attended by leading scientists from Germany, Poland and many other countries. The present volume of the "Condensed Matter Physics" contains proceedings of the conference "Infinite Particle Systems: Complex Systems III", which took place in June 2007.

Synthesis and characterization of Fe(III-piperazine-derived complexes encapsulated in zeolite Y

Directory of Open Access Journals (Sweden)

Márcio E. Berezuk

2012-01-01

Full Text Available Zeolite-encapsulated complexes have been widely applied in hydrocarbon oxidation catalysis. The "ship-in-a-bottle" encapsulation of iron(III complexes containing piperazine and piperazine-derivative ligands in zeolite-Y is described. The flexible ligand methodology was employed and the efficiency and reproducibility of the procedure was investigated. The catalysts were characterized employing several techniques and the results indicate the presence of coordinated and uncoordinated iron(III ions inside and outside the zeolitic cage.

Study of Physical modifications induced by chromium doping of uranium dioxide

International Nuclear Information System (INIS)

Fraczkiewicz, M.

2010-01-01

Improvement of nuclear fuel performances requires reducing fission gas release. Doping uranium dioxide with chromium is the improvement axis considered in this work. Indeed, chromium fastens crystal growth in UO 2 , and thus enables a significant increase of the grain size. This work aims at the identification of defects produced by chromium addition in UO 2 , and their impact on properties of interest of the material. First, defects existing in doped fuel directly after sintering have been studied. X-ray Absorption Spectroscopy allowed the identification of the environment of solubilised chromium in UO 2 . Chromium atoms are roughly substituting for uranium atoms, but generate a complete reorganisation of neighbouring oxygen atoms, and distortion of uranium sublattice. Characterisation of transport properties (electrical conductivity and oxygen self-diffusion) have shown that because of charge balance, chromium plays a leading role on such properties. A model of point defects in UO 2 has been proposed, showing how complex the involved phenomena are. Observations by Transmission Electron Microscopy of ion-irradiated thin foils have shown that chromium makes the coalescence of irradiation defects easier. This behaviour can be explained by a stabilisation of defect clusters due to precipitation of chromium. Finally, study of thermal diffusion of helium in doped UO 2 , performed by Nuclear Reaction Analysis, has confirmed this interaction between chromium atoms and irradiation defects. Indeed, μ-NRA measures have shown no fast gas diffusion close to grain boundaries, in contrast with standard UO 2 behaviour, which is associated with defects recovery in grain boundaries. (author) [fr

Mechanistic insight into chromium(VI) reduction by oxalic acid in the presence of manganese(II)

Energy Technology Data Exchange (ETDEWEB)

Wrobel, Katarzyna; Corrales Escobosa, Alma Rosa; Gonzalez Ibarra, Alan Alexander; Mendez Garcia, Manuel; Yanez Barrientos, Eunice; Wrobel, Kazimierz, E-mail: kazimier@ugto.mx

2015-12-30

Over the past few decades, reduction of hexavalent chromium (Cr(VI)) has been studied in many physicochemical contexts. In this research, we reveal the mechanism underlying the favorable effect of Mn(II) observed during Cr(VI) reduction by oxalic acid using liquid chromatography with spectrophotometric diode array detector (HPLC–DAD), nitrogen microwave plasma atomic emission spectrometry (HPLC–MP-AES), and high resolution mass spectrometry (ESI–QTOFMS). Both reaction mixtures contained potassium dichromate (0.67 mM Cr(VI)) and oxalic acid (13.3 mM), pH 3, one reaction mixture contained manganese sulfate (0.33 mM Mn(II)). In the absence of Mn(II) only trace amounts of reaction intermediates were generated, most likely in the following pathways: (1) Cr(VI) → Cr(IV) and (2) Cr(VI) + Cr(IV) → 2Cr(V). In the presence of Mn(II), the active reducing species appeared to be Mn(II) bis-oxalato complex (J); the proposed reaction mechanism involves a one-electron transfer from J to any chromium compound containing Cr=O bond, which is reduced to Cr−OH, and the generation of Mn(III) bis-oxalato complex (K). Conversion of K to J was observed, confirming the catalytic role of Mn(II). Since no additional acidification was required, the results obtained in this study may be helpful in designing a new, environmentally friendly strategy for the remediation of environments contaminated with Cr(VI).

Dietary Chromium Supplementation for Targeted Treatment of Diabetes Patients with Comorbid Depression and Binge Eating

Science.gov (United States)

Brownley, Kimberly A.; Boettiger, Charlotte A.; Young, Laura; Cefalu, William T.

2015-01-01

Dietary chromium supplementation for the treatment of diabetes remains controversial. The prevailing view that chromium supplementation for glucose regulation is unjustified has been based upon prior studies showing mixed, modest-sized effects in patients with type 2 diabetes (T2DM). Based on chromium's potential to improve insulin, dopamine, and serotonin function, we hypothesize that chromium has a greater glucoregulatory effect in individuals who have concurrent disturbances in dopamine and serotonin function – that is, complex patients with comorbid diabetes, depression, and binge eating. We propose, as suggested by the collective data to date, the need to go beyond the “one size fits all” approach to chromium supplementation and put forth a series of experiments designed to link physiological and neurobehavioral processes in the chromium response phenotype. PMID:25838140

Spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction of their cyclohexylthioglycolate complexes into chloroform

International Nuclear Information System (INIS)

Rao, A.L.J.; Gupta, Usha; Puri, B.K.

1986-01-01

Cyclohexylthioglycolate has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after the extraction of their complexes into chloroform. Various parameters involved in the extraction have been studied and the composition of the extracted complex has been established in each instance. Ruthenium and rhodium complexes are extracted into chloroform in the pH ranges 5.0-9.0 and 9.0-12.5, respectively. The ruthenium complex absorbs strongly at 365 nm, whereas the rhodium complex shows a maximum absorption at 345 nm. Beer's law is obeyed over the concentration range 6-96 μg for ruthenium and 2-41 μg for rhodium in 10 ml of the chloroform solution. The molar absorptivities are 5.02 x 10 3 l mol -1 cm -1 for ruthenium and 1.60 x 10 4 l mol -1 cm -1 for rhodium. Ten replicate determinations on a sample solution containing 60.3 μg of ruthenium or 20.6 μg of rhodium gave mean absorbances of 0.300 and 0.320 with standard deviations of 0.0021 and 0.0025 and relative standard deviations of 0.70% and 0.78%, respectively. The interference of various ions has been studied and the method has been applied to the determination of the metals in various synthetic samples. Conditions have also been developed for the simultaneous determination of ruthenium and rhodium. (author)

Effect of nitrate on corrosion of austenitic stainless steel in boiling nitric acid solution containing chromium ions

International Nuclear Information System (INIS)

Hasegawa, Satoshi; Kim, Seong-Yun; Ebina, Tetsunari; Ito, Tatsuya; Nagano, Nobumichi; Hitomi, Keitaro; Ishii, Keizo; Tokuda, Haruaki

2016-01-01

The oxidation behavior of chromium and the corrosion behavior of austenitic stainless steel in boiling nitric acid solution containing highly concentrated nitrates were investigated using UV-visible spectroscopic measurements, Raman spectral measurements, immersion tests, and potentiodynamic polarization measurements. The oxidation rate measurement of chromium from Cr(III) to Cr(VI) was performed by 1 M boiling nitric acid solution containing each highly concentrated nitrates: Al(NO_3)_3, Nd(NO_3)_3, Ca(NO_3)_2, Mg(NO_3)_2, and NaNO_3 as a simulant of uranium nitrate in uranium concentrator in reprocessing plants. As a result, the rate of chromium oxidation was different depending on the added nitrates even at the same nitric acid concentration. In addition, the oxidation rate of chromium was increased with increasing the calculated partial pressure of nitric acid in consideration of the hydration of cation of nitrates. Furthermore, the corrosion rate of type 310 stainless steel was accelerated by the solution having a high chromium oxidation rate containing nitrates. These results indicated that the acceleration of the corrosion rate in the solutions depending on the oxidation rate of chromium, and the rate is affected by the salt-effect of nitrates. (author)

A new organically templated gallium(III)-doped chromium(III) fluorophosphite, (C2H10N2)[Ga0.98Cr0.02(HPO3)F3] hydrothermal synthesis, crystal structure and spectroscopic properties

International Nuclear Information System (INIS)

Fernandez-Armas, Sergio; Mesa, J.L.; Pizarro, J.L.; Lezama, Luis; Arriortua, M.I.; Rojo, T.

2004-01-01

A new organically templated fluoro-phosphite gallium(III)-doped chromium(III) with formula (C 2 H 10 N 2 )[Ga 0.98 Cr 0.02 (HPO 3 )F 3 ] has been synthesized by using mild hydrothermal conditions under autogeneous pressure. The crystal structure has been solved from X-ray single-crystal data. The compound crystallizes in the P2 1 2 1 2 1 orthorhombic space group, with the unit-cell parameters a=12.9417(7) A, b=9.4027(6) A, c=6.3502(4) A and Z=4. The final R factors were R1=0.022 (all data) and wR2=0.050. The crystal structure consists of [Ga 0.98 Cr 0.02 (HPO 3 )F 3 ] 2- anionic chains extended along the c-axis, with the ethylenediammonium cations placed in the cavities of the structure delimited by three different chains. The IR and Raman spectra show the characteristic bands of the phosphite oxoanion. The diffuse reflectance spectroscopy allowed us to calculate the Dq and Racah parameters of the Cr(III) cations in octahedral environment. The values are Dq=1375 cm -1 , B=780 cm -1 and C=3420 cm -1 . The polycrystalline ESR spectra performed at X and Q-bands show the signals belonging to the diluted Cr(III) cation in this phase. From the fit of the X-band ESR spectrum at 4.2 K, the calculated values of the axial (D) and rhombic (E) distortion parameters are 0.075 and 0.042 cm -1 , respectively, the components of the g-tensor being g x =1.98, g y =1.99 and g z =1.90

Chromium in aqueous nitrate plutonium process streams: Corrosion of 316 stainless steel and chromium speciation

International Nuclear Information System (INIS)

Smith, W.H.; Purdy, G.

1994-01-01

According to the measurements made in this study, the only situation in which chromium (+6) could exist in a plutonium process solution is one in which a feed containing chromium is dissolved in a glass pot dissolver in high nitric acid concentration and at high temperature. But when the resulting feed is prepared for ion exchange, the chemical treatment reduces chromium to the +3 state. Any solution being processed through the evaporator will only contain chromium in the +3 state and any chromium salts remaining in the evaporator bottoms will be chromium +3 salts

Levels of chromium contamination in the estuary of the Iraja river (Guanabara Bay) and experimental incorporation of 51Cr in barnacles (Balanus sp)

International Nuclear Information System (INIS)

Weerelt, M.D.M.V.

1982-01-01

Levels were determined of chromium contamination in the estuary of Iraja River, produced by an electroplating industry located 3 km upstream the study area. Uptake-and release kinetics of Cr(VI) and Cr(III) in barnacles (Balanus sp.) were studied. Samples of barnacles and suspended particles from Guanabara Bay were analysed. Chromium concentrations (dry weight) ranged from not detectable (ND) to 154,66 μg/g for soft tissues and from ND to 423,76 μg/g for suspended particles. Mean of maximum concentrations of chromium in samples from Guanabara Bay are 3 and 4 times above those of identical samples from control area (Coroa Grande). Soft tissues presented a concentration factor (CF) of 10 3 related to chromium available in suspended particles. 51 Cr(VI) is preferentiably incorparated by soft tissues (biological half life being 100 days). Chromium uptake by Balanus sp from solution is as significant as it is from particulate matter available in sea water from experimental sets. CF for Cr(VI) in soft tissues in laboratory conditions was 10 2 related to 51 Cr present in sea water. Environmental chromium contamination was found to be of the same order of magnitude or above levels reported for other areas subjected to industrial impacts. Barnacles appear to be able to accumulate chromium in soft tissues from the available metal in the environment. Cr(VI) is the critical form, being greatly accumulated in soft tissues of barnacles, that act as a long-term integrator of this metal. For Cr(III), this organism can only be regarded as an instantaneous indicator of environmental contamination of chromium attached to suspended particles. (M.A.) [pt

Investigations on the nephrotoxicity and hepatotoxicity of trivalent and hexavalent chromium compounds.

Science.gov (United States)

Dartsch, P C; Hildenbrand, S; Kimmel, R; Schmahl, F W

1998-09-01

In contrast to trivalent chromium (Cr(III)) compounds, hexavalent chromium ((Cr(VI)) compounds are oxidizing agents capable of directly inducing tissue damage and possessing carcinogenic, mutagenic and teratogenic potency. After oral or dermal absorption of Cr(VI), the kidney is the main target organ for chromium accumulation, which might result in acute tubular necrosis in humans. In contrast, an acute toxic effect of Cr(VI) on the liver has not yet been described. Therefore, we used two established epithelial cell lines from the kidney (Opossum kidney cells) and the liver (Hep G2 cells) to design an in vitro-assay which is able to examine acute toxic effects of chromium compounds. Cells of both cell lines were treated with various concentrations of Cr(III) and Cr(VI) ranging from 0.01 micromol/l to 1 mmol/l for 24 h. Thereafter, cell morphology, organization of the intracellular cytoskeleton, number of viable cells and mean cell volume were examined. The results show that Cr(VI), but not Cr(III), has an acute cytotoxic effect and causes a dose-dependent loss in cell viability. The effective dose that caused 50% of cell death was 5 micromol/l for kidney epithelial cells and 50 micromol/l for liver epithelial cells. This means that kidney epithelial cells are 10 times more sensitive towards Cr(VI) treatment than liver epithelial cells and this might explain the known nephrotoxicity in vivo. The loss in cell viability was accompanied by a rounding and detachment of the cells and a marked reduction of intracellular F-actin-containing stress fibers. Microtubules and intermediate-sized filaments were observed to be unaffected. Only in the case of kidney epithelial cells, a dose-dependent cell volume increase was observed after Cr(VI) treatment at concentrations up to 50 micromol/l. At higher concentrations, the cell volume decreased due to the high number of cells undergoing lysis and the appearance of cellular fragments. Various chloride channel blockers with

Polarographic determination of stability constants of Eu(III) complexes with acrylic acid and crotonic acid

Energy Technology Data Exchange (ETDEWEB)

Rao, A L.J.; Makhan, S [Punjabi Univ., Patiala (India). Dept. of Chemistry

1979-07-01

Compositions and formation constants of Eu(III) complexes with acrylic acid and crotonic acid have been studied polarographically. The reductions are reversible and diffusion-controlled. The plot of Esub(1/2) versus -log Csub(x) is linear in the case of Eu(III)-acrylic acid system. The change in number of ligands bound to europium during reduction was found to be approximately equal to 1 and ratio of dissociation constants of Eu(III) and Eu(II) was found to be 40.76 x 10sup(-2). In the case of Eu(III)-crotonic acid system, composition and formation constants have been calculated by the method of Deford and Hume. Crotonic acid forms two complex species with europium (..beta../sub 1/, 60; ..beta../sub 2/, 4.2x10sup(+2)). The percentage distribution of various complex species as a function of ligand concentration has been calculated in the case of Eu(III)-crotonic acid system. A polarographic method for the determination of micro amounts of Eu(III) in the presence of diverse ions has been developed. Under optimum conditions Eu(III) in the concentration range 4x10sup(-4)-2x10sup(-3)M can be successfully determined in various mixtures.

Synthesis and structures of a pincer-type rhodium(iii) complex: reactivity toward biomolecules.

Science.gov (United States)

Milutinović, Milan M; Bogojeski, Jovana V; Klisurić, Olivera; Scheurer, Andreas; Elmroth, Sofi K C; Bugarčić, Živadin D

2016-10-04

A novel rhodium(iii) complex [Rh III (H 2 L tBu )Cl 3 ] (1) (H 2 L tBu = 2,6-bis(5-tert-butyl-1H-pyrazol-3-yl)pyridine) containing a pincer type, tridentate nitrogen-donor chelate system was synthesized. Single crystal X-ray structure analysis revealed that 1 crystallizes in the orthorhombic space group Pbcn with a = 20.7982(6), b = 10.8952(4), c = 10.9832(4) Å, V = 2488.80(15) Å 3 , and eight molecules in the unit cell. The rhodium center in the complex [Rh III (H 2 L tBu )Cl 3 ] (1) is coordinated in a slightly distorted octahedral geometry by the tridentate N,N,N-donor and three chloro ligands, adopting a mer arrangement with an essentially planar ligand skeleton. Due to the tridentate coordination of the N,N,N-donor, the central nitrogen atom N1 is located closer to the Rh III center. The reactivity of the synthesized complex toward small biomolecules (l-methionine (l-Met), guanosine-5'-monophosphate (5'-GMP), l-histidine (l-His) and glutathione (GSH)) and to a series of duplex DNAs and RNA was investigated. The order of reactivity of the studied small biomolecules is: 5'-GMP > GSH > l-Met > l-His. Duplex RNA reacts faster with the [Rh III (H 2 L tBu )Cl 3 ] complex than duplex DNA, while shorter duplex DNA (15mer GG) reacts faster compared with 22mer GG duplex DNA. In addition, a higher reactivity is achieved with a DNA duplex with a centrally located GG-sequence than with a 22GTG duplex DNA, in which the GG-sequence is separated by a T base. Furthermore, the interaction of this metal complex 1 with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) was examined by absorption (UV-Vis) and emission spectral studies (EthBr displacement studies). Overall, the studied complex exhibited good DNA and BSA interaction ability.

Zeolite-Y entrapped Ru(III and Fe(III complexes as heterogeneous catalysts for catalytic oxidation of cyclohexane reaction

Directory of Open Access Journals (Sweden)

Chetan K. Modi

2017-02-01

Full Text Available Catalysis is probably one of the greatest contributions of chemistry to both economic growth and environmental protection. Herein we report the catalytic behavior of zeolite-Y entrapped Ru(III and Fe(III complexes with general formulae [M(VTCH2·2H2O]+-Y and [M(VFCH2·2H2O]+-Y [where, VTCH = vanillin thiophene-2-carboxylic hydrazone and VFCH = vanillin furoic-2-carboxylic hydrazone] over the oxidation of cyclohexane forming cyclohexanone and cyclohexanol. The samples were corroborated by various physico-chemical techniques. These zeolite-Y based complexes are stable and recyclable under current reaction conditions. Amongst them, [Ru(VTCH2⋅2H2O]+-Y showed higher catalytic activity (41.1% with cyclohexanone (84.6% selectivity.

Complexation of Am(III) by oxalate in NaClO4 media

International Nuclear Information System (INIS)

Choppin, G.R.; Chen, J.F.

1995-01-01

The complexation of Am(III) by oxalate has been investigated in solutions of NaClO 4 up to 9.0 M ionic strength at 25 degrees C. The dissociation constants of oxalic acid were determined by potentiometric titration, while the stability constants of the Am(III)-oxalate complexation were measured by the solvent extraction technique. A thermodynamic model was constructed to predict the apparent equilibrium constants at different ionic strengths by applying the Pitzer equation using parameters for the Na + -HOx - , Na + -Ox - , AmOx + -ClO 4 - , and Na + -Am(Ox) 2 - interactions obtained by fitting the data