Solid-State Properties of One-Dimensional Metals Based on bis(oxalato)platinate Anions with Divalent Cations

DEFF Research Database (Denmark)

Braude, A.; Carneiro, K.; Jacobsen, Claus Schelde

1987-01-01

The crystal structures, superstructures, dc conductivity, optical properties, and thermopower of six linear-chain conductors of the type M0.8[Pt(C2O4)2]⋅(M=Ni,Co,Zn,Fe,Mg,Mn), where M is a divalent metal (M=Ni,Co,Zn,Fe,Mg,Mn), have been studied. At high temperatures they form a common orthorhombi...

Macrocyclic receptor showing extremely high Sr(II)/Ca(II) and Pb(II)/Ca(II) selectivities with potential application in chelation treatment of metal intoxication.

Science.gov (United States)

Ferreirós-Martínez, Raquel; Esteban-Gómez, David; Tóth, Éva; de Blas, Andrés; Platas-Iglesias, Carlos; Rodríguez-Blas, Teresa

2011-04-18

Herein we report a detailed investigation of the complexation properties of the macrocyclic decadentate receptor N,N'-Bis[(6-carboxy-2-pyridil)methyl]-4,13-diaza-18-crown-6 (H(2)bp18c6) toward different divalent metal ions [Zn(II), Cd(II), Pb(II), Sr(II), and Ca(II)] in aqueous solution. We have found that this ligand is especially suited for the complexation of large metal ions such as Sr(II) and Pb(II), which results in very high Pb(II)/Ca(II) and Pb(II)/Zn(II) selectivities (in fact, higher than those found for ligands widely used for the treatment of lead poisoning such as ethylenediaminetetraacetic acid (edta)), as well as in the highest Sr(II)/Ca(II) selectivity reported so far. These results have been rationalized on the basis of the structure of the complexes. X-ray crystal diffraction, (1)H and (13)C NMR spectroscopy, as well as theoretical calculations at the density functional theory (B3LYP) level have been performed. Our results indicate that for large metal ions such as Pb(II) and Sr(II) the most stable conformation is Δ(δλδ)(δλδ), while for Ca(II) our calculations predict the Δ(λδλ)(λδλ) form being the most stable one. The selectivity that bp18c6(2-) shows for Sr(II) over Ca(II) can be attributed to a better fit between the large Sr(II) ions and the relatively large crown fragment of the ligand. The X-ray crystal structure of the Pb(II) complex shows that the Δ(δλδ)(δλδ) conformation observed in solution is also maintained in the solid state. The Pb(II) ion is endocyclically coordinated, being directly bound to the 10 donor atoms of the ligand. The bond distances to the donor atoms of the pendant arms (2.55-2.60 Å) are substantially shorter than those between the metal ion and the donor atoms of the crown moiety (2.92-3.04 Å). This is a typical situation observed for the so-called hemidirected compounds, in which the Pb(II) lone pair is stereochemically active. The X-ray structures of the Zn(II) and Cd(II) complexes show that

Spectroscopic and structural studies on some divalent metal salt of p-aminobenzoic acid (ABA(MG)) tetracyanonickelate complexes

International Nuclear Information System (INIS)

Atalay, Y.

2004-01-01

Infrared spectra of MLNi (CN) 4 [ M=Mn, Fe, Co, Ni, Zn or Cd and LDivalent metal salt of p- Aminobenzoic Acid or ABA (Mg) ] are reported. Their structure consists of polymeric layers of [M-Ni(CN) 4 ] α with the divalent metal salt of p-aminobenzoic acid [ABA(Mg)] molecules bound directly to the metal (M). These spectra were comparewith powder the Xray diffraction pattern of complexes. It is show that proposed structures for these complexes derived from Mattson 1000 FTIR spectra are consistent with the X-ray powder diffraction measurements and elemental analysis result

Adsorption preference for divalent metal ions by Lactobacillus casei JCM1134.

Science.gov (United States)

Endo, Rin; Aoyagi, Hideki

2018-05-09

The removal of harmful metals from the intestinal environment can be inhibited by various ions which can interfere with the adsorption of target metal ions. Therefore, it is important to understand the ion selectivity and adsorption mechanism of the adsorbent. In this study, we estimated the adsorption properties of Lactobacillus casei JCM1134 by analyzing the correlation between its maximum adsorption level (q max ) for seven metals and their ion characteristics. Some metal ions showed altered adsorption levels by L. casei JCM1134 as culture growth time increased. Although it was impossible to identify specific adsorption components, adsorption of Sr and Ba may depend on capsular polysaccharide levels. The maximum adsorption of L. casei JCM1134 (9 h of growth in culture) for divalent metal ions was in the following order: Cu 2+  > Ba 2+  > Sr 2+  > Cd 2+  > Co 2+  > Mg 2+  > Ni 2+ . The q max showed a high positive correlation with the ionic radius. Because this tendency is similar to adsorption occurring through an ion exchange mechanism, it was inferred that an ion exchange mechanism contributed greatly to adsorption by L. casei JCM1134. Because the decrease in the amount of adsorption due to prolonged culture time was remarkable for metals with a large ion radius, it is likely that the adsorption components involved in the ion exchange mechanism decomposed over time. These results and analytical concept may be helpful for designing means to remove harmful metals from the intestinal tract.

Drosophila divalent metal ion transporter Malvolio is required in dopaminergic neurons for feeding decisions.

Science.gov (United States)

Søvik, E; LaMora, A; Seehra, G; Barron, A B; Duncan, J G; Ben-Shahar, Y

2017-06-01

Members of the natural resistance-associated macrophage protein (NRAMP) family are evolutionarily conserved metal ion transporters that play an essential role in regulating intracellular divalent cation homeostasis in both prokaryotes and eukaryotes. Malvolio (Mvl), the sole NRAMP family member in insects, plays a role in food choice behaviors in Drosophila and other species. However, the specific physiological and cellular processes that require the action of Mvl for appropriate feeding decisions remain elusive. Here, we show that normal food choice requires Mvl function specifically in the dopaminergic system, and can be rescued by supplementing food with manganese. Collectively, our data indicate that the action of the Mvl transporter affects food choice behavior via the regulation of dopaminergic innervation of the mushroom bodies, a principle brain region associated with decision-making in insects. Our studies suggest that the homeostatic regulation of the intraneuronal levels of divalent cations plays an important role in the development and function of the dopaminergic system and associated behaviors. © 2017 John Wiley & Sons Ltd and International Behavioural and Neural Genetics Society.

Dispersion relations of the acoustic modes in divalent liquid metals

Directory of Open Access Journals (Sweden)

Inui Masanori

2017-01-01

Full Text Available Collective dynamics in liquid Ca and liquid Cd was studied by inelastic x-ray scattering (IXS. Using our experimental technique to prepare proper sample cells and high performance of an IXS beamline (BL35XU at SPring-8 in Japan, the dynamic structure factor with reasonable statistics was obtained for these divalent liquid metals. For both liquids, the dynamic structure factor at low Q exhibits a central peak with a shoulder or small hump clearly visible on each side, and the inelastic excitation energy determined using the model function composed of Lorentzian and the damped harmonic oscillator function disperses with increasing Q. The dispersion curves of these liquids were compared with that of the longitudinal acoustic phonon in each crystalline phase. From these results, clear difference in the interatomic interaction be- tween liquid Ca and liquid Cd was inferred.

Divalent Metal Ions Induced Osteogenic Differentiation of MC3T3E1

Science.gov (United States)

Wang, Guoshou; Su, Wenta; Chen, Pohung; Huang, Teyang

2017-12-01

Biomaterial scaffolds blended with biochemical signal molecules with adequate osteoinductive and osteoconductive properties have attracted significant interest in bone tissue engineering regeneration. The divalent metal ions can gradually release from the scaffold into the culture medium and then induced osteoblastic differentiation of MC3T3E1. These MC3T3E1 cells expressed high activity of alkaline phosphatase, bone-related gene expression of collagen type I, Runx2, osteopontin, osteocalcin, and significantly enhanced deposited minerals on scaffold after 21 days of culture. This experiment provided a useful inducer for osteogenic differentiation in bone repair.

Adsorption performances and mechanisms of the newly synthesized N,N'-di (carboxymethyl) dithiocarbamate chelating resin toward divalent heavy metal ions from aqueous media

International Nuclear Information System (INIS)

Jing Xiaosheng; Liu Fuqiang; Yang Xin; Ling Panpan; Li Lanjuan; Long Chao; Li Aimin

2009-01-01

N,N'-di (carboxymethyl) dithiocarbamate chelating resin (PSDC) was synthesized by anchoring the chelating agent of N,N'-di (carboxymethyl) dithiocarbamate to the chloromethylated PS-DVB (Cl-PS-DVB) matrix, as a new adsorbent for removing divalent heavy metal ions from waste-stream. The physicochemical structures of Cl-PS-DVB and PSDC were elaborately characterized using Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), and were further morphologically characterized using BET and BJH methods. The adsorption performances of PSDC towards heavy metals such as Cu(II), Pb(II) and Ni(II) were systematically investigated, based upon which the adsorption mechanisms were deeply exploited. For the above target, the classic batch adsorption experiments were conducted to explore the kinetics and isotherms of the removal processes with pH-value, initial concentration, temperature, and contact time as the controlling parameters. The kinetic and isotherm data could be well elucidated with Lagergren-second-order equation and Langmuir model respectively. The strong affinity of PSDC toward these target soft acids could be well demonstrated with the electrostatic attraction and chelating interaction caused by IDA moiety and sulphur which were namely soft bases on the concept of hard and soft acids and bases (HASB). Thermodynamic parameters, involving ΔH o , ΔS o and ΔG o were also calculated from graphical interpretation of the experimental data. The standard heats of adsorption (ΔH o ) were found to be endothermic and the entropy change values (ΔS o ) were calculated to be positive for the adsorption of Cu(II), Pb(II) and Ni(II) ions onto the tested adsorbents. Negative values of ΔG o indicated that adsorption processes for all tested metal ions onto PSDC were spontaneous.

Interaction of divalent metal ions with Zn(2+)-glycerophosphocholine cholinephosphodiesterase from ox brain.

Science.gov (United States)

Lee, K J; Kim, M R; Kim, Y B; Myung, P K; Sok, D E

1997-12-01

The effect of divalent metal ions on the activity of glycerophosphocholine cholinephosphodiesterse from ox brain was examined. Zn(2+)- and Co(2+)-glycerophosphocholine cholinephosphodiesterases were prepared from the exposure of apoenzyme to Zn2+ and Co2+, respectively, and the properties of two metallo-phosphodiesterases were compared to those of native phosphodiesterase. Although two metallo-enzymes were similar in expressing Km value, optimum pH or sensitivity to Cu2+, they differed in the susceptibility to the inhibition by thiocholine or tellurite; while Co(2+)-phosphodiesterase was more sensitive to tellurites, Zn(2+)-phosphodiesterase was more susceptible to inhibition by thiocholine. In addition, Zn(2+)-phosphodiesterase was more thermo-stable than Co2+ enzyme. Separately, when properties of native phosphodiesterase were compared to those of each metallo-phosphodiesterase, native phosphodiesterase was found to be quite similar to Zn(2+)-phosphodiesterase in many respects. Even in thermo-stability, native enzyme resembled Zn(2+)-phosphodiesterase rather than Co(2+)-enzyme. Consistent with this, the stability of native phosphodiesterase was maintained in the presence of Zn2+, but not Co2+, Mn2+ was also as effective as Zn2+ in the stabilization of the enzyme. Noteworthy, the native enzyme was found to be inhibited competitively by Cu2+ with a Ki value of 20 microM, and its inhibitory action was antagonized effectively by Zn2+ or Co2+. Also, choline, another competitive inhibitor of the enzyme, appeared to antagonize the inhibitory action of Cu2+. Taken together, it is suggested that there may be multiple binding sites for divalent metal ions in the molecule of glycerophosphocholine cholinephosphodiesterase.

Toxic and biochemical effects of divalent metal ions in Drosophila: correlation to effects in mice and to chemical softness parameters

Energy Technology Data Exchange (ETDEWEB)

Jacobson, K B; Turner, J E; Christie, N T; Owenby, R K

1983-01-01

The mechanism of toxicity of 11 divalent cations was evaluated by determining the effects of dietary administration to Drosophila melanogaster and measurement of the frequency of lethality at 4 days, alterations in the developmental patterns of proteins, and changes in specific transfer RNAs. The relative effectiveness of divalent cations to kill Drosophila is significantly correlated to the relative values of the coordinate bond energy of the metal ions. The resistance of Drosophila to cadmium toxicity appears to be genetically determined since different inbred strains vary markedly. Also, the resistance is maximal in the young adult. Two different genetic strains seem to respond to different cations (Cd/sup 2 +/, Hg/sup 2 +/, Cu/sup 2 +/, Co/sup 2 +/, Ba/sup 2 +/, and Sr/sup 2 +/) in a similar manner. Basic mechanisms of toxicity may be studied in Drosophila as well as mice since the chemical properties of the metals reflect their toxic effects on the former as closely as the latter. 25 references, 5 figures, 1 table.

Influence of divalent metal ions on degradation of dimethylsulphide ...

African Journals Online (AJOL)

SERVER

2007-06-04

Jun 4, 2007 ... Dimethylsulphide degradation by intact cells of Thiobacillus thioparus TK-m was stimulated by the addition of divalent .... plastic vials in ice-cooled water. .... tization of authotrophic sulphur bacteria oxidizing dimethyldisulphide.

Simultaneous spectrophotometric determination of heavy metal ions Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with Br-PADPA in primary reactor coolant system

Energy Technology Data Exchange (ETDEWEB)

Kim, Tae-Hyeong; Yun, Jong-Il [KAIST, Daejeon (Korea, Republic of)

2015-05-15

The performance with integrity of nuclear power plants is highly influenced by the presence of the corrosion products. The deposition of corrosion products in the steam generator is the one of the main concerns of power plants. The quantification of corrosion products is considered of importance. In this study, we applied the spectrophotometric method to detect metal ions such as iron, cobalt, nickel, copper, and zinc, which are major elements of structural material of the plant. In particular, the chemical complexation of those divalent metal ions with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP) provides high molar absorptivity. For the simultaneous determination of metal ions, a partial least square (PLS) regression method was applied. In the present work, the complexation of Br-PADAP with divalent metal ions (iron, cobalt, nickel, copper and zinc) was studied. The PLS regression method was successfully applied for simultaneous elemental detection in multi-element systems. These results suggests that the method is very ample to detect corrosion products in nuclear power plants.

Identification of a divalent metal cation binding site in herpes simplex virus 1 (HSV-1) ICP8 required for HSV replication.

Science.gov (United States)

Bryant, Kevin F; Yan, Zhipeng; Dreyfus, David H; Knipe, David M

2012-06-01

Herpes simplex virus 1 (HSV-1) ICP8 is a single-stranded DNA-binding protein that is necessary for viral DNA replication and exhibits recombinase activity in vitro. Alignment of the HSV-1 ICP8 amino acid sequence with ICP8 homologs from other herpesviruses revealed conserved aspartic acid (D) and glutamic acid (E) residues. Amino acid residue D1087 was conserved in every ICP8 homolog analyzed, indicating that it is likely critical for ICP8 function. We took a genetic approach to investigate the functions of the conserved ICP8 D and E residues in HSV-1 replication. The E1086A D1087A mutant form of ICP8 failed to support the replication of an ICP8 mutant virus in a complementation assay. E1086A D1087A mutant ICP8 bound DNA, albeit with reduced affinity, demonstrating that the protein is not globally misfolded. This mutant form of ICP8 was also recognized by a conformation-specific antibody, further indicating that its overall structure was intact. A recombinant virus expressing E1086A D1087A mutant ICP8 was defective in viral replication, viral DNA synthesis, and late gene expression in Vero cells. A class of enzymes called DDE recombinases utilize conserved D and E residues to coordinate divalent metal cations in their active sites. We investigated whether the conserved D and E residues in ICP8 were also required for binding metal cations and found that the E1086A D1087A mutant form of ICP8 exhibited altered divalent metal binding in an in vitro iron-induced cleavage assay. These results identify a novel divalent metal cation-binding site in ICP8 that is required for ICP8 functions during viral replication.

Evaluation of the effect of divalent metal transporter 1 gene polymorphism on blood iron, lead and cadmium levels

Energy Technology Data Exchange (ETDEWEB)

Kayaaltı, Zeliha, E-mail: kayaalti@ankara.edu.tr; Akyüzlü, Dilek Kaya; Söylemezoğlu, Tülin

2015-02-15

Divalent metal transporter 1 (DMT1), a member of the proton-coupled metal ion transporter family, mediates transport of ferrous iron from the lumen of the intestine into the enterocyte and export of iron from endocytic vesicles. It has an affinity not only for iron but also for other divalent cations including manganese, cobalt, nickel, cadmium, lead, copper, and zinc. DMT1 is encoded by the SLC11a2 gene that is located on chromosome 12q13 in humans and express four major mammalian isoforms (1A/+IRE, 1A/-IRE, 2/+IRE and 2/-IRE). Mutations or polymorphisms of DMT1 gene may have an impact on human health by disturbing metal trafficking. To study the possible association of DMT1 gene with the blood levels of some divalent cations such as iron, lead and cadmium, a single nucleotide polymorphism (SNP) (IVS4+44C/A) in DMT1 gene was investigated in 486 unrelated and healthy individuals in a Turkish population by method of polymerase chain reaction–restriction fragment length polymorphism (PCR–RFLP). The genotype frequencies were found as 49.8% homozygote typical (CC), 38.3% heterozygote (CA) and 11.9% homozygote atypical (AA). Metal levels were analyzed by dual atomic absorption spectrometer system and the average levels of iron, lead and cadmium in the blood samples were 446.01±81.87 ppm, 35.59±17.72 ppb and 1.25±0.87 ppb, respectively. Individuals with the CC genotype had higher blood iron, lead and cadmium levels than those with AA and CA genotypes. Highly statistically significant associations were detected between IVS4+44 C/A polymorphism in the DMT1 gene and iron and lead levels (p=0.001 and p=0.036, respectively), but no association was found with cadmium level (p=0.344). This study suggested that DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, lead and cadmium levels. - Highlights: • DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, cadmium and lead levels. �

Evaluation of the effect of divalent metal transporter 1 gene polymorphism on blood iron, lead and cadmium levels

International Nuclear Information System (INIS)

Kayaaltı, Zeliha; Akyüzlü, Dilek Kaya; Söylemezoğlu, Tülin

2015-01-01

Divalent metal transporter 1 (DMT1), a member of the proton-coupled metal ion transporter family, mediates transport of ferrous iron from the lumen of the intestine into the enterocyte and export of iron from endocytic vesicles. It has an affinity not only for iron but also for other divalent cations including manganese, cobalt, nickel, cadmium, lead, copper, and zinc. DMT1 is encoded by the SLC11a2 gene that is located on chromosome 12q13 in humans and express four major mammalian isoforms (1A/+IRE, 1A/-IRE, 2/+IRE and 2/-IRE). Mutations or polymorphisms of DMT1 gene may have an impact on human health by disturbing metal trafficking. To study the possible association of DMT1 gene with the blood levels of some divalent cations such as iron, lead and cadmium, a single nucleotide polymorphism (SNP) (IVS4+44C/A) in DMT1 gene was investigated in 486 unrelated and healthy individuals in a Turkish population by method of polymerase chain reaction–restriction fragment length polymorphism (PCR–RFLP). The genotype frequencies were found as 49.8% homozygote typical (CC), 38.3% heterozygote (CA) and 11.9% homozygote atypical (AA). Metal levels were analyzed by dual atomic absorption spectrometer system and the average levels of iron, lead and cadmium in the blood samples were 446.01±81.87 ppm, 35.59±17.72 ppb and 1.25±0.87 ppb, respectively. Individuals with the CC genotype had higher blood iron, lead and cadmium levels than those with AA and CA genotypes. Highly statistically significant associations were detected between IVS4+44 C/A polymorphism in the DMT1 gene and iron and lead levels (p=0.001 and p=0.036, respectively), but no association was found with cadmium level (p=0.344). This study suggested that DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, lead and cadmium levels. - Highlights: • DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, cadmium and lead levels. �

Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)

International Nuclear Information System (INIS)

Yang Bingping; Prosvirin, Andrey V.; Zhao, Han-Hua; Mao, Jiang-Gao

2006-01-01

Hydrothermal reactions of divalent transition metal salts with imino-bis(methylphosphonic acid), NH(CH 2 PO 3 H 2 ) 2 (H 4 L) afforded three new metal phosphonates, namely, Cu[NH(CH 2 PO 3 H) 2 ] 1, {Co[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 2 }.H 2 O 2 and Mn[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 3. When HO 2 C(CH 2 ) 3 N(CH 2 PO 3 H 2 ) 2 was used as the phosphonate ligand and 4,4'-bipy as the second metal linker, {Cu 4 [NH(CH 2 PO 3 ) 2 ] 2 (4,4'-bipy)(H 2 O) 4 }.9H 2 O 4 with a pillared layered architecture was obtained. The NH(CH 2 PO 3 ) 2 anion resulted from the cleavage of the HO 2 C(CH 2 ) 3 -group during the reaction. Although compounds 1-3 have a same M/L ratio (1:1), they exhibit totally different structures.Compound 1 has a linear chain structure, in which each pair of square-pyramidal coordinated copper(II) ions are bridged by two phosphonate oxygen atoms to form a Cu 2 O 2 dimeric unit, and such dimeric units are further interconnected via phosphonate groups to form a [010] chain. Compound 2 has a layered architecture built from CoO 6 octahedra bridged by phosphonate ligands. In compound 3, the interconnection of the manganese(II) ions by bridging imino-diphosphonate ligands leads to a 3D network. Compound 4 has a pillar-layered structure, the layers composed of Cu(II) ions bridged by aminodiphosphonate ligands are interconnected by 4,4'-bipy ligands to form channels along c-axis. Several factors that affect the structures of the metal phosphonates formed have also been discussed. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers. -- Graphical abstract: Four new metal phosphonates, namely, Cu[NH(CH 2 PO 3 H) 2 ] 1, {Co[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 2 }.H 2 O 2, Mn[NH 2 (CH 2 PO 3 H)(CH 2 PO 3 )](H 2 O) 3 and {Cu 4 [NH(CH 2 PO 3 ) 2 ] 2 (4,4'-bipy)(H 2 O) 4 }.9H 2 O 4 have been synthesized and structurally characterized. Compound 1 has a linear chain structure, and compound 2 is layered. Compound 3 is

Influence of commercial (Fluka) naphthenic acids on acid volatile sulfide (AVS) production and divalent metal precipitation.

Science.gov (United States)

McQueen, Andrew D; Kinley, Ciera M; Rodgers, John H; Friesen, Vanessa; Bergsveinson, Jordyn; Haakensen, Monique C

2016-12-01

Energy-derived waters containing naphthenic acids (NAs) are complex mixtures often comprising a suite of potentially problematic constituents (e.g. organics, metals, and metalloids) that need treatment prior to beneficial use, including release to receiving aquatic systems. It has previously been suggested that NAs can have biostatic or biocidal properties that could inhibit microbially driven processes (e.g. dissimilatory sulfate reduction) used to transfer or transform metals in passive treatment systems (i.e. constructed wetlands). The overall objective of this study was to measure the effects of a commercially available (Fluka) NA on sulfate-reducing bacteria (SRB), production of sulfides (as acid-volatile sulfides [AVS]), and precipitation of divalent metals (i.e. Cu, Ni, Zn). These endpoints were assessed following 21-d aqueous exposures of NAs using bench-scale reactors. After 21-days, AVS molar concentrations were not statistically different (pAVS production was sufficient in all NA treatments to achieve ∑SEM:AVS AVS) could be used to treat metals occurring in NAs affected waters. Copyright © 2016 Elsevier Inc. All rights reserved.

Determining the selectivity of divalent metal cations for the carboxyl group of alginate hydrogel beads during competitive sorption.

Science.gov (United States)

An, Byungryul; Lee, Healim; Lee, Soonjae; Lee, Sang-Hyup; Choi, Jae-Woo

2015-11-15

To investigate the competitive sorption of divalent metal ions such as Ca(2+), Cu(2+), Ni(2+), and Pb(2+) on alginate hydrogel beads, batch and column tests were conducted. The concentration of carboxyl group was found to be limited in the preparation of spherical hydrogel beads. From kinetic test results, 80% of sorption was observed within 4h, and equilibrium was attained in 48 h. According to the comparison of the total uptake and release, divalent metal ions were found to stoichiometrically interact with the carboxyl group in the alginate polymer chain. From the Langmuir equation, the maximum capacities of Pb(2+), Cu(2+), and Ni(2+) were calculated to be 1.1, 0.48, and 0.13 mmol/g, respectively. The separation factor (α) values for αPb/Cu, αPb/Ni, and αCu/Ni were 14.0, 98.9, and 7.1, respectively. The sorption capacity of Pb(2+) was not affected by the solution pH; however, the sorption capacities of Cu(2+) and Ni(2+) decreased with increasing solution pH, caused by competition with hydrogen. According to the result from the fixed column test, Pb(2+) exhibited the highest affinity, followed by Cu(2+) and Ni(2+), which is in exact agreement with those of kinetic and isotherm tests. The sorbent could be regenerated using 4% HCl, and the regenerated sorbent exhibited 90% capacity upto 9 cycles. Copyright © 2015 Elsevier B.V. All rights reserved.

Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd

OpenAIRE

Duguid, J.; Bloomfield, V.A.; Benevides, J.; Thomas Jr, G.J.

1993-01-01

Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) ind...

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

Science.gov (United States)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-05-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

Science.gov (United States)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-02-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Optical study of gamma irradiated sodium metaphosphate glasses containing divalent metal oxide MO (ZnO or CdO

Directory of Open Access Journals (Sweden)

E. Nabhan

Full Text Available Sodium metaphosphate glasses containing divalent metal oxide, ZnO or CdO with composition 50 P2O5 – (50 − x Na2O – x MO (ZnO, or CdO where x = 0, 10, 20 (mol% were prepared by conventional melt method. UV/visible spectroscopy and FTIR spectroscopy are measured before and after exposing to successive gamma irradiation doses (5–80 kGy. The optical absorption spectra results of the samples before irradiation reveal a strong UV absorption band at (∼230 nm which is related to unavoided iron impurities. The effects of gamma irradiation on the optical spectral properties of the various glasses have been compared. From the optical absorption spectral data, the optical band gap is evaluated. The main structural groups and the influence of both divalent metal oxide and gamma irradiation effect on the structural vibrational groups are realized through IR spectroscopy. The FTIR spectra of γ-irradiated samples are characterized by the stability of the number and position for the main characteristic band of phosphate groups. To better understood the structural changes during γ-irradiation, a deconvolution of FTIR spectra in the range 650–1450 cm−1 is made. The FTIR deconvolution results found evidence that, the changes occurring after gamma irradiation have been related to irradiation induced structural defects and compositional changes. Keywords: Sodium metaphosphate glass, UV–visible spectra, IR spectra, Deconvolution, Optical band gap, Gamma ray

Metal ion controlled self-assembly of a chemically reengineered protein drug studied by small-angle X-ray scattering

DEFF Research Database (Denmark)

Jesper, Nygaard; Munch, Henrik K.; Thulstrup, Peter W.

2012-01-01

. A small-angle X-ray scattering analysis of the bipyridine-modified insulin system confirmed an organization into a novel well-ordered structure based on insulin trimers, as induced by the addition of Fe(II). In contrast, unmodified monomeric insulin formed larger and more randomly structured assemblies......Precise control of the oligomeric state of proteins is of central importance for biological function and for the properties of biopharmaceutical drugs. Here, the self-assembly of 2,2′-bipyridine conjugated monomeric insulin analogues, induced through coordination to divalent metal ions, was studied....... This protein drug system was designed to form non-native homo-oligomers through selective coordination of two divalent metal ions, Fe(II) and Zn(II), respectively. The insulin type chosen for this study is a variant designed for a reduced tendency toward native dimer formation at physiological concentrations...

Divalent cations in tears, and their influence on tear film stability in humans and rabbits.

Science.gov (United States)

Wei, Xiaojia Eric; Markoulli, Maria; Millar, Thomas J; Willcox, Mark D P; Zhao, Zhenjun

2012-06-05

Reduced tear film stability is reported to contribute to dry eye. Rabbits are known to have a more stable tear film than humans. Thus, we sought to examine the tears of rabbits and humans for metal cations, and to test how they influence tear film stability. Tears were collected from 10 healthy humans and 6 rabbits. Tear osmolality was measured by vapor pressure osmometer, and metals analyzed using inductively coupled plasma (ICP) mass spectrometry or ICP atomic emission spectroscopy. The influence of divalent cations on tears was analyzed by measuring surface tension using the Langmuir trough in vitro, using different concentrations of cations in the subphase, and grading the tear break-up in rabbits in vivo after instillation of chelating agents. Rabbit tears had a higher osmolality compared to humans. Major metals did not differ between species; however, rabbits had higher levels of Mg(2+) (1.13 vs. 0.39 mM) and Ca(2+) (0.75 vs. 0.36 mM). In rabbit tears in vitro, diminishing divalent cations resulted in a decrease in the maximum surface pressure from 37 to 30 mN/m. In vivo, an increase in the amount of tear film that was broken-up was found. In contrast, when changing divalent cation concentrations in human tears, the maximum surface pressure remained at 26 mN/m. The normal osmolality of rabbit tears is significantly higher than that in humans. While divalent cations had little influence on human tears, they appear to have an important role in maintaining tear film stability in rabbits.

Studies on the effect of divalent metal ions on exfoliative toxins from Staphylococcus hyicus: indications of ExhA and ExhB being metalloproteins.

Science.gov (United States)

Andresen, L O

1999-04-01

The exfoliative toxins ExhA and ExhB produced by Staphylococcus hyicus strains NCTC10350 and 1289D-88, respectively, were investigated with regard to the effect of divalent metal ions on toxin production as measured in indirect enzyme-linked immunosorbent assay (ELISA) using monoclonal antibodies. Data were obtained as endpoint titer values and used as semiquantitative measures for the amount of exfoliative toxin detected in culture supernatants. It was shown that the endpoint titers of ExhA in supernatants from cultures of strain NCTC10350 grown in the presence of 0.5 mM CaCl2, Cu(NO3)2 or ZnSO4 were higher compared to titers obtained by growth in medium supplemented with a number of other divalent metal salts. The titer of ExhB as determined in the indirect ELISA was increased by addition of 0.5 mM CoCl2, Cu(NO3)2 or CuSO4 to the growth medium. When ExhA or ExhB, prepared without addition of metal salt to the liquid growth medium, was subsequently incubated with 25 mM of Co2+, Cu2+ or Zn2+, the endpoint titers of the toxins were increased. Dialysis of ExhA and ExhB prepared with Zn2+ and Co2+, respectively, against certain metal chelators, resulted in a reduction of the titer determined in ELISA. Other metal chelators had varied effect in the detection of the toxins in ELISA. It was, however, not possible to restore the recognition of toxins by the monoclonal antibodies by incubation of EDDHA-dialyzed toxin preparations with Co2+, Cu2+ or Zn2+. The results of this study suggest that ExhA and ExhB are metalloproteins.

Noncooperative cadmium(II) binding to human metallothionein 1a

International Nuclear Information System (INIS)

Sutherland, Duncan E.K.; Stillman, Martin J.

2008-01-01

The two-domain (βα) mammalian metallothionein binds seven divalent metals, however, the binding mechanism is not well characterized and recent reports require the presence of the partially metallated protein. In this paper, step-wise metallation of the metal-free, two-domain βα-rhMT and the isolated β-rhMT using Cd(II) is shown to proceed in a noncooperative manner by analysis of electrospray ionization mass spectrometric data. Under limiting amounts of Cd(II), all intermediate metallation states up to the fully metallated Cd 3 -β-rhMT and Cd 7 -βα-rhMT were observed. Addition of excess Cd(II), resulted in formation of the supermetallated (metallation in excess of normal levels) Cd 4 -β- and Cd 8 -βα-metallothionein species. These data establish that noncooperative cadmium metallation is a property of each isolated domain and the complete two-domain protein. Our data now also establish that supermetallation is a property that may provide information about the mechanism of metal transfer to other proteins

Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd.

Science.gov (United States)

Duguid, J; Bloomfield, V A; Benevides, J; Thomas, G J

1993-11-01

Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) induce the greatest structural changes in B-DNA. The Raman (vibrational) band differences are extensive and indicate partial disordering of the B-form backbone, reduction in base stacking, reduction in base pairing, and specific metal interaction with acceptor sites on the purine (N7) and pyrimidine (N3) rings. Many of the observed spectral changes parallel those accompanying thermal denaturation of B-DNA and suggest that the metals link the bases of denatured DNA. While exocyclic carbonyls of dT, dG, and dC may stabilize metal ligation, correlation plots show that perturbations of the carbonyls are mainly a consequence of metal-induced denaturation of the double helix. Transition metal interactions with the DNA phosphates are weak in comparison to interactions with the bases, except in the case of Cu2+, which strongly perturbs both base and phosphate group vibrations. On the other hand, the Raman signature of B-DNA is largely unperturbed by Mg2+, Ca2+, Sr2+, and Ba2+, suggesting much weaker interactions of the alkaline earth metals with both base and phosphate sites. A notable exception is a moderate perturbation by alkaline earths of purine N7 sites in 160-base pair DNA, with Ca2+ causing the greatest effect. Correlation plots demonstrate a strong interrelationship between perturbations of Raman bands assigned to ring vibrations of the bases and those of bands assigned to exocyclic carbonyls and backbone phosphodiester groups. However, strong correlations do not occur between

Divalent Metal Ion Transport across Large Biological Ion Channels and Their Effect on Conductance and Selectivity

Directory of Open Access Journals (Sweden)

Elena García-Giménez

2012-01-01

Full Text Available Electrophysiological characterization of large protein channels, usually displaying multi-ionic transport and weak ion selectivity, is commonly performed at physiological conditions (moderate gradients of KCl solutions at decimolar concentrations buffered at neutral pH. We extend here the characterization of the OmpF porin, a wide channel of the outer membrane of E. coli, by studying the effect of salts of divalent cations on the transport properties of the channel. The regulation of divalent cations concentration is essential in cell metabolism and understanding their effects is of key importance, not only in the channels specifically designed to control their passage but also in other multiionic channels. In particular, in porin channels like OmpF, divalent cations modulate the efficiency of molecules having antimicrobial activity. Taking advantage of the fact that the OmpF channel atomic structure has been resolved both in water and in MgCl2 aqueous solutions, we analyze the single channel conductance and the channel selectivity inversion aiming to separate the role of the electrolyte itself, and the counterion accumulation induced by the protein channel charges and other factors (binding, steric effects, etc. that being of minor importance in salts of monovalent cations become crucial in the case of divalent cations.

Divalent thulium triflate. A structural and spectroscopic study

Energy Technology Data Exchange (ETDEWEB)

Xemard, Mathieu; Jaoul, Arnaud; Cordier, Marie; Nocton, Gregory [Univ. Paris-Saclay, Palaiseau (France). LCM, Ecole polytechnique, CNRS; Molton, Florian; Duboc, Carole [Grenoble Univ., Saint Martin d' Heres (France). Dept. de Chimie Moleculaire; Cador, Olivier; Le Guennic, Boris [Univ. de Rennes 1 (France). Inst. des Sciences Chimique de Rennes, UMR 6226 CNRS; Maury, Olivier [Univ. Claude Bernard Lyon 1 (France). Lab. de Chimie; Clavaguera, Carine [Univ. Paris-Saclay, Palaiseau (France). LCM, Ecole polytechnique, CNRS; Univ. Paris Sud, Univ. Paris-Saclay, Orsay (France). Lab. de Chimie Physique, CNRS

2017-04-03

The first molecular Tm{sup II} luminescence measurements are reported along with rare magnetic, X and Q bands EPR studies. Access to simple and soluble molecular divalent lanthanide complexes is highly sought for small-molecule activation studies and organic transformations using single-electron transfer processes. However, owing to their low stability and propensity to disproportionate, these complexes are hard to synthetize and their electronic properties are therefore almost unexplored. Herein we present the synthesis of [Tm(μ-OTf){sub 2}(dme){sub 2}]{sub n}, a rare and simple coordination compound of divalent thulium that can be seen as a promising starting material for the synthesis of more elaborated complexes. This reactive complex was structurally characterized by X-ray diffraction analysis and its electronic structure has been compared with that of its halide cousin TmI{sub 2}(dme){sub 3}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Polymerization of a divalent/tetravalent metal-storing atom-mimicking dendrimer

OpenAIRE

Albrecht, Ken; Hirabayashi, Yuki; Otake, Masaya; Mendori, Shin; Tobari, Yuta; Azuma, Yasuo; Majima, Yutaka; Yamamoto, Kimihisa

2016-01-01

The phenylazomethine dendrimer (DPA) has a layer-by-layer electron density gradient that is an analog of the Bohr atom (atom mimicry). In combination with electron pair mimicry, the polymerization of this atom-mimicking dendrimer was achieved. The valency of the mimicked atom was controlled by changing the chemical structure of the dendrimer. By mimicking a divalent atom, a one-dimensional (1D) polymer was obtained, and by using a planar tetravalent atom mimic, a 2D polymer was obtained. Thes...

Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table.

Science.gov (United States)

Craciun, Smaranda; Donald, Kelling J

2009-07-06

We examine the bonding possibilities of the bis(phenalenyl) MP(2) sandwich complexes of the divalent metals M = Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, at the B3LYP level of theory. The outcome is an extraordinarily diverse class of low symmetry bis(phenalenyl)metal complexes in which bonding preferences and binding enthalpies differ dramatically. The lowest energy group 2 metal MP(2) complexes include an intriguing eta(1),eta(3) BeP(2) structure, and bent eta(6),eta(6) systems for M = Ca, Sr, and Ba. The group 12 bis(phenalenyl) complexes are thermodynamically unstable eta(1),eta(1) slip-sandwich structures. To better understand changes in the structural preferences going from the (eta(6),eta(6)) group 2 to the (eta(1),eta(1)) group 12 complexes, we explored the bonding in the bis(phenalenyl) complexes of transition metals with stable +2 oxidations states between Ca and Zn in period 4. The computed binding enthalpies are large and negative for nearly all of the minimum energy bis(phenalenyl) complexes of the group 2 and the transition metals; they are tiny for MgP(2), and are quite positive for the group 12 systems. The structural preferences and stability of the complexes is a subtle negotiation of several influences: the (un)availability of (n - 1)d and np, orbitals for bonding, the cost of the rehybridization at carbon sites in the phenalenyl rings in preparation for bonding to the metals, and the (P---P) interaction between the phenalenyl radicals.

Sequence of ligand binding and structure change in the diphtheria toxin repressor upon activation by divalent transition metals.

Science.gov (United States)

Rangachari, Vijayaraghavan; Marin, Vedrana; Bienkiewicz, Ewa A; Semavina, Maria; Guerrero, Luis; Love, John F; Murphy, John R; Logan, Timothy M

2005-04-19

The diphtheria toxin repressor (DtxR) is an Fe(II)-activated transcriptional regulator of iron homeostatic and virulence genes in Corynebacterium diphtheriae. DtxR is a two-domain protein that contains two structurally and functionally distinct metal binding sites. Here, we investigate the molecular steps associated with activation by Ni(II)Cl(2) and Cd(II)Cl(2). Equilibrium binding energetics for Ni(II) were obtained from isothermal titration calorimetry, indicating apparent metal dissociation constants of 0.2 and 1.7 microM for two independent sites. The binding isotherms for Ni(II) and Cd(II) exhibited a characteristic exothermic-endothermic pattern that was used to infer the metal binding sequence by comparing the wild-type isotherm with those of several binding site mutants. These data were complemented by measuring the distance between specific backbone amide nitrogens and the first equivalent of metal through heteronuclear NMR relaxation measurements. Previous studies indicated that metal binding affects a disordered to ordered transition in the metal binding domain. The coupling between metal binding and structure change was investigated using near-UV circular dichroism spectroscopy. Together, the data show that the first equivalent of metal is bound by the primary metal binding site. This binding orients the DNA binding helices and begins to fold the N-terminal domain. Subsequent binding at the ancillary site completes the folding of this domain and formation of the dimer interface. This model is used to explain the behavior of several mutants.

Foam separation of Cu (II) and Ni(II) from aqueous solutions and simulated wastewaters

International Nuclear Information System (INIS)

Shakir, K.; Beheir, Sh.G.; Aziz, M.

2003-01-01

Batch experiments on the removal of Cu(II) and Ni(II) from aqueous solutions were performed through two foam separation techniques: precipitate flotation (PTF) an adsorbing colloid flotation (ACF). In ACF, Fe(III), oxyhydroxide was used as co precipitant and/or adsorbing colloid and sodium lauryl sulfate was used as a collector. ACF required a lower collector concentration than PTF. foreign ions were found to decrease the percent removal, the extent of decrease being higher by divalent ions than that by monovalent ones. However, the percent removal could be improved, even in presence of foreign ions, by addition of Al(II) as an activator. High removals could be attained for Cu(II) and Ni(II) from simulated wastewaters containing different concentrations of both metal ions. The addition of concentrations below the limits recommended by the egyptian regulations for environmental discharge

Interactions of chlorphenesin and divalent metal ions with phosphodiesterase.

Science.gov (United States)

Edelson, J; McMullen, J P

1976-09-01

Chlorphenesin inhibition of the hydrolysis of cyclic AMP by guinea-pig lung phosphodiesterase was reversed by the addition of exogenous magnesium ions. Chlorphenesin and theophylline inhibition of this enzyme was shown to be noncompetitive when the substrate concentration was low. Kinetic studies of the inhibition of beef heart phosphodiesterase by chlorphenesin and theophylline indicated that the substrate concentration was a factor in determining whether inhibition was competitive or noncompetitive. Calcium, cobalt and copper ions were inhibitory to guinea-pig lung phosphodiesterase. The inhibition due to chlorphenesin was partially reversed by low (40 mM or less) concentrations of barium ions; high concentrations of barium ions, or manganese ions, were inhibitory. The concentration of the divalent cation did not affect the type of inhibition that was observed.

Solar photocatalytic removal of Cu(II), Ni(II), Zn(II) and Pb(II): Speciation modeling of metal-citric acid complexes

International Nuclear Information System (INIS)

Kabra, Kavita; Chaudhary, Rubina; Sawhney, R.L.

2008-01-01

The present study is targeted on solar photocatalytic removal of metal ions from wastewater. Photoreductive deposition and dark adsorption of metal ions Cu(II), Ni(II), Pb(II) and Zn(II), using solar energy irradiated TiO 2 , has been investigated. Citric acid has been used as a hole scavenger. Modeling of metal species has been performed and speciation is used as a tool for discussing the photodeposition trends. Ninety-seven percent reductive deposition was obtained for copper. The deposition values of other metals were significantly low [nickel (36.4%), zinc (22.2%) and lead (41.4%)], indicating that the photocatalytic treatment process, using solar energy, was more suitable for wastewater containing Cu(II) ions. In absence of citric acid, the decreasing order deposition was Cu(II) > Ni(II) > Pb(II) > Zn(II), which proves the theoretical thermodynamic predictions about the metals

Antimicrobial and Thermal Properties of Metal Complexes of Grafted Fabrics with Acrylic Acid by Gamma Irradiation

International Nuclear Information System (INIS)

Hassan, M.S.; Attia, R.M.; Zohdy, M.H.

2008-01-01

Cotton, cotton/PET blend and PET fabrics were treated against microbial effect by radiation - induced grafting of acrylic acid followed by metal complexation with some divalent transition metal ions Co (II), Ni (II) and Cu (II). The microbial resistance was evaluated by testing the mechanical properties of the treated fabrics after burring for one and two weeks in a moist soil reach with microorganisms. Also, the growth of microorganisms was examined by scanning electron microscope (SEM). Moreover, the effect of this treatment on the thermal decomposition behavior was investigated by thermogravimetric analysis (TGA). On the basis of microbial studies, it was found that the metal complexation of the grafted fabrics with acrylic acid enhanced the antimicrobial resistance of the fabrics and the antimicrobial resistance could be arranged according to the metal ions as follows: copper> nickel> cobalt. Also, the thermal stability of different fabrics could be arranged as follow: grafted fabrics complexed with Cu (II) > grafted fabrics complexed with Ni (II) > grafted fabrics complexed with Co (II)

Structure of the oxalate-ATP complex with pyruvate kinase: ATP as a bridging ligand for the two divalent cations

International Nuclear Information System (INIS)

Lodato, D.T.; Reed, G.H.

1987-01-01

The 2 equiv of divalent cation that are required cofactors for pyruvate kinase reside in sites of different affinities for different species of cation. The intrinsic selectivity of the protein-based site for Mn(II) and of the nucleotide-based site for Mg(II) has been exploited in electron paramagnetic resonance (EOR) investigations of ligands for Mn(II) at the protein-based site. Oxalate, a structural analogue of the enolate of pyruvate, has been used as a surrogate for the reactive form of pyruvate in complexes with enzyme, Mn(II), Mg(II), and ATP. Superhyperfine coupling between the unpaired electron spin of Mn(II) and the nuclear spin of 17 O, specifically incorporated into oxalate, shows that oxalate is bound at the active site as a bidentate chelate with Mn(II). Coordination of the γ-phosphate of ATP to this same Mn(II) center is revealed by observation of superhyperfine coupling from 17 O regiospecifically incorporated into the γ-phosphate group of ATP. By contrast, 17 O in the α-phosphate or in the β-phosphate groups of ATP does not influence the spectrum. Experiments in 17 O-enriched water show that there is also a single water ligand bound to the Mn(II). These data indicate that ATP bridges Mn(II) and Mg(II) at the active site. A close spacing of the two divalent cations is also evident from the occurrence of magnetic interactions for complexes in which 2 equiv of Mn(II) are present at the active site. The structure for the enzyme-Mn(II)-oxalate-Mg(II)-ATP complex suggests a scheme for the normal reverse reaction of pyruvate kinase in which the divalent cation at the protein-based site activates the keto acid substrate through chelation and promotes phospho transfer by simultaneous coordination to the enolate oxygen and to a pendant oxygen from the γ-phosphate of ATP

Affinity of Smectite and Divalent Metal Ions (Mg(2+), Ca(2+), Cu(2+)) with L-leucine: An Experimental and Theoretical Approach Relevant to Astrobiology.

Science.gov (United States)

Pandey, Pramod; Pant, Chandra Kala; Gururani, Kavita; Arora, Priyanka; Pandey, Neetu; Bhatt, Preeti; Sharma, Yogesh; Negi, Jagmohan Singh; Mehata, Mohan Singh

2015-12-01

Earth is the only known planet bestowed with life. Several attempts have been made to explore the pathways of the origin of life on planet Earth. The search for the chemistry which gave rise to life has given answers related to the formation of biomonomers, and their adsorption on solid surfaces has gained much attention for the catalysis and stabilization processes related to the abiotic chemical evolution of the complex molecules of life. In this communication, surface interactions of L-leucine (Leu) on smectite (SMT) group of clay (viz. bentonite and montmorillonite) and their divalent metal ion (Mg(2+), Ca(2+) and Cu(2+)) incorporated on SMT has been studied to find the optimal conditions of time, pH, and concentration at ambient temperature (298 K). The progress of adsorption was followed spectrophotometrically and further characterized by FTIR, SEM/EDS and XRD. Leu, a neutral/non polar amino acid, was found to have more affinity in its zwitterionic form towards Cu(2+)- exchanged SMT and minimal affinity for Mg(2+)- exchanged SMT. The vibrational frequency shifts of -NH3 (+) and -COO(-) favor Van der Waal's forces during the course of surface interaction. Quantum calculations using density functional theory (DFT) have been applied to investigate the absolute value of metal ion affinities of Leu (Leu-M(2+) complex, M = Mg(2+), Ca(2+), Cu(2+)) with the help of their physico-chemical parameters. The hydration effect on the relative stability and geometry of the individual species of Leu-M(2+) × (H2O)n, (n =2 and 4) has also been evaluated within the supermolecule approach. Evidence gathered from investigations of surface interactions, divalent metal ions affinities and hydration effects with biomolecules may be important for better understanding of chemical evolution, the stabilization of biomolecules on solid surfaces and biomolecular-metal interactions. These results may have implications for understanding the origin of life and the preservation of

Multi-metals column adsorption of lead(II), cadmium(II) and manganese(II) onto natural bentonite clay.

Science.gov (United States)

Alexander, Jock Asanja; Surajudeen, Abdulsalam; Aliyu, El-Nafaty Usman; Omeiza, Aroke Umar; Zaini, Muhammad Abbas Ahmad

2017-10-01

The present work was aimed at evaluating the multi-metals column adsorption of lead(II), cadmium(II) and manganese(II) ions onto natural bentonite. The bentonite clay adsorbent was characterized for physical and chemical properties using X-ray diffraction, X-ray fluorescence, Brunauer-Emmett-Teller surface area and cation exchange capacity. The column performance was evaluated using adsorbent bed height of 5.0 cm, with varying influent concentrations (10 mg/L and 50 mg/L) and flow rates (1.4 mL/min and 2.4 mL/min). The result shows that the breakthrough time for all metal ions ranged from 50 to 480 minutes. The maximum adsorption capacity was obtained at initial concentration of 10 mg/L and flow rate of 1.4 mL/min, with 2.22 mg/g of lead(II), 1.71 mg/g of cadmium(II) and 0.37 mg/g of manganese(II). The order of metal ions removal by natural bentonite is lead(II) > cadmium(II) > manganese(II). The sorption performance and the dynamic behaviour of the column were predicted using Adams-Bohart, Thomas, and Yoon-Nelson models. The linear regression analysis demonstrated that the Thomas and Yoon-Nelson models fitted well with the column adsorption data for all metal ions. The natural bentonite was effective for the treatment of wastewater laden with multi-metals, and the process parameters obtained from this work can be used at the industrial scale.

Metal resistance sequences and transgenic plants

Science.gov (United States)

Meagher, Richard Brian; Summers, Anne O.; Rugh, Clayton L.

1999-10-12

The present invention provides nucleic acid sequences encoding a metal ion resistance protein, which are expressible in plant cells. The metal resistance protein provides for the enzymatic reduction of metal ions including but not limited to divalent Cu, divalent mercury, trivalent gold, divalent cadmium, lead ions and monovalent silver ions. Transgenic plants which express these coding sequences exhibit increased resistance to metal ions in the environment as compared with plants which have not been so genetically modified. Transgenic plants with improved resistance to organometals including alkylmercury compounds, among others, are provided by the further inclusion of plant-expressible organometal lyase coding sequences, as specifically exemplified by the plant-expressible merB coding sequence. Furthermore, these transgenic plants which have been genetically modified to express the metal resistance coding sequences of the present invention can participate in the bioremediation of metal contamination via the enzymatic reduction of metal ions. Transgenic plants resistant to organometals can further mediate remediation of organic metal compounds, for example, alkylmetal compounds including but not limited to methyl mercury, methyl lead compounds, methyl cadmium and methyl arsenic compounds, in the environment by causing the freeing of mercuric or other metal ions and the reduction of the ionic mercury or other metal ions to the less toxic elemental mercury or other metals.

Characterization and application of Mucuna urens seed husk as novel biosorbent for sequestration of some divalent metal ions from solution

Directory of Open Access Journals (Sweden)

Linda Obiageli ELUKE

2017-07-01

Full Text Available The utilization of Horse-Eye Bean (Mucuna urens Seed Husk (HEBSH as low cost biosorbent for the abstraction of Co (II, Pb (II and Zn (II ions from water was performed. The biosorbent was characterized by the Fourier Transform Infrared (FTIR spectroscopy, X-ray diffraction (XRD and Scanning Electron Microscopy (SEM. The influence of pH, initial metal ion concentration, biosorbent dosage and contact time on the biosorption was studied. Four isotherm and four kinetic models were used to determine the mechanism of biosorption. FTIR showed the presence of some functional groups such as OH, C=O, C=C, C-O, C-Cl on the surface of HEBSH, while XRD and SEM showed amorphous and non-porous surface structure respectively. Optimum biosorption of the metal ions was obtained at pH 6.0, biosorbent dosage 0.1 g, metal concentration 400 mg/L and contact time of 30, 40, and 60 min for Co (II, Zn (II and Pb (II respectively. The Freundlich gave the best fit for the three metal ions (R2 > 0.95 than the Langmuir, Tempkin and Dubinin-Radushkevich models indicating a multilayer biosorption on a heterogenous surface of HEBSH. Kinetic analysis showed the pseudo first order model presented good fits for Zn (II and Pb (II while the pseudo second order model for Co (II. The initial sorption rate h (mg/g min was 2.35 × 10-3, 2.1 × 10-4 and 6.3 × 10-7 for Co (II, Zn (II and Pb (II ions respectively. Liquid film diffusion was found to be the diffusion mechanism of biosorption rather than the intraparticle diffusion. The experimental investigation showed that HEBSH is effective as a low cost alternative biosorbent for the sequestration of heavy metal ions from aqueous stream.

New approach in modeling Cr(VI) sorption onto biomass from metal binary mixtures solutions

Energy Technology Data Exchange (ETDEWEB)

Liu, Chang [College of Environmental Science and Engineering, Anhui Normal University, South Jiuhua Road, 189, 241002 Wuhu (China); Chemical Engineering Department, Escola Politècnica Superior, Universitat de Girona, Ma Aurèlia Capmany, 61, 17071 Girona (Spain); Fiol, Núria [Chemical Engineering Department, Escola Politècnica Superior, Universitat de Girona, Ma Aurèlia Capmany, 61, 17071 Girona (Spain); Villaescusa, Isabel, E-mail: Isabel.Villaescusa@udg.edu [Chemical Engineering Department, Escola Politècnica Superior, Universitat de Girona, Ma Aurèlia Capmany, 61, 17071 Girona (Spain); Poch, Jordi [Applied Mathematics Department, Escola Politècnica Superior, Universitat de Girona, Ma Aurèlia Capmany, 61, 17071 Girona (Spain)

2016-01-15

In the last decades Cr(VI) sorption equilibrium and kinetic studies have been carried out using several types of biomasses. However there are few researchers that consider all the simultaneous processes that take place during Cr(VI) sorption (i.e., sorption/reduction of Cr(VI) and simultaneous formation and binding of reduced Cr(III)) when formulating a model that describes the overall sorption process. On the other hand Cr(VI) scarcely exists alone in wastewaters, it is usually found in mixtures with divalent metals. Therefore, the simultaneous removal of Cr(VI) and divalent metals in binary mixtures and the interactive mechanism governing Cr(VI) elimination have gained more and more attention. In the present work, kinetics of Cr(VI) sorption onto exhausted coffee from Cr(VI)–Cu(II) binary mixtures has been studied in a stirred batch reactor. A model including Cr(VI) sorption and reduction, Cr(III) sorption and the effect of the presence of Cu(II) in these processes has been developed and validated. This study constitutes an important advance in modeling Cr(VI) sorption kinetics especially when chromium sorption is in part based on the sorbent capacity of reducing hexavalent chromium and a metal cation is present in the binary mixture. - Highlights: • A kinetic model including Cr(VI) reduction, Cr(VI) and Cr(III) sorption/desorption • Synergistic effect of Cu(II) on Cr(VI) elimination included in the model • Model validation by checking it against independent sets of data.

New approach in modeling Cr(VI) sorption onto biomass from metal binary mixtures solutions

International Nuclear Information System (INIS)

Liu, Chang; Fiol, Núria; Villaescusa, Isabel; Poch, Jordi

2016-01-01

In the last decades Cr(VI) sorption equilibrium and kinetic studies have been carried out using several types of biomasses. However there are few researchers that consider all the simultaneous processes that take place during Cr(VI) sorption (i.e., sorption/reduction of Cr(VI) and simultaneous formation and binding of reduced Cr(III)) when formulating a model that describes the overall sorption process. On the other hand Cr(VI) scarcely exists alone in wastewaters, it is usually found in mixtures with divalent metals. Therefore, the simultaneous removal of Cr(VI) and divalent metals in binary mixtures and the interactive mechanism governing Cr(VI) elimination have gained more and more attention. In the present work, kinetics of Cr(VI) sorption onto exhausted coffee from Cr(VI)–Cu(II) binary mixtures has been studied in a stirred batch reactor. A model including Cr(VI) sorption and reduction, Cr(III) sorption and the effect of the presence of Cu(II) in these processes has been developed and validated. This study constitutes an important advance in modeling Cr(VI) sorption kinetics especially when chromium sorption is in part based on the sorbent capacity of reducing hexavalent chromium and a metal cation is present in the binary mixture. - Highlights: • A kinetic model including Cr(VI) reduction, Cr(VI) and Cr(III) sorption/desorption • Synergistic effect of Cu(II) on Cr(VI) elimination included in the model • Model validation by checking it against independent sets of data

Metallothionein from Wild Populations of the African Catfish Clarias gariepinus: From Sequence, Protein Expression and Metal Binding Properties to Transcriptional Biomarker of Metal Pollution

Directory of Open Access Journals (Sweden)

Ethel M’kandawire

2017-07-01

Full Text Available Anthropogenic pollution with heavy metals is an on-going concern throughout the world, and methods to monitor release and impact of heavy metals are of high importance. With a view to probe its suitability as molecular biomarker of metal pollution, this study has determined a coding sequence for metallothionein of the African sharptooth catfish Clarias gariepinus. The gene product was recombinantly expressed in Escherichia coli in presence of Zn(II, Cd(II, or Cu, and characterised by Electrospray Ionisation Mass Spectrometry and elemental analysis. C. gariepinus MT displays typical features of fish MTs, including 20 conserved cysteines, and seven bound divalent cations (Zn(II or Cd(II when saturated. Livers from wild C. gariepinus fish collected in all three seasons from four different sites on the Kafue River of Zambia were analysed for their metal contents and for MT expression levels by quantitative PCR. Significant correlations were found between Zn and Cu levels and MT expression in livers, with MT expression clearly highest at the most polluted site, Chililabombwe, which is situated in the Copperbelt region. Based on our findings, hepatic expression of MT from C. gariepinus may be further developed as a major molecular biomarker of heavy metal pollution resulting from mining activities in this region.

Metallothionein from Wild Populations of the African Catfish Clarias gariepinus: From Sequence, Protein Expression and Metal Binding Properties to Transcriptional Biomarker of Metal Pollution.

Science.gov (United States)

M'kandawire, Ethel; Mierek-Adamska, Agnieszka; Stürzenbaum, Stephen R; Choongo, Kennedy; Yabe, John; Mwase, Maxwell; Saasa, Ngonda; Blindauer, Claudia A

2017-07-18

Anthropogenic pollution with heavy metals is an on-going concern throughout the world, and methods to monitor release and impact of heavy metals are of high importance. With a view to probe its suitability as molecular biomarker of metal pollution, this study has determined a coding sequence for metallothionein of the African sharptooth catfish Clarias gariepinus . The gene product was recombinantly expressed in Escherichia coli in presence of Zn(II), Cd(II), or Cu, and characterised by Electrospray Ionisation Mass Spectrometry and elemental analysis. C. gariepinus MT displays typical features of fish MTs, including 20 conserved cysteines, and seven bound divalent cations (Zn(II) or Cd(II)) when saturated. Livers from wild C. gariepinus fish collected in all three seasons from four different sites on the Kafue River of Zambia were analysed for their metal contents and for MT expression levels by quantitative PCR. Significant correlations were found between Zn and Cu levels and MT expression in livers, with MT expression clearly highest at the most polluted site, Chililabombwe, which is situated in the Copperbelt region. Based on our findings, hepatic expression of MT from C. gariepinus may be further developed as a major molecular biomarker of heavy metal pollution resulting from mining activities in this region.

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

International Nuclear Information System (INIS)

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)

Substrate specificity, metal binding properties, and spectroscopic characterization of the DapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase from Haemophilus influenzae.

Science.gov (United States)

Bienvenue, David L; Gilner, Danuta M; Davis, Ryan S; Bennett, Brian; Holz, Richard C

2003-09-16

The catalytic and structural properties of divalent metal ion cofactor binding sites in the dapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase (DapE) from Haemophilus influenzae were investigated. Co(II)-substituted DapE enzyme was 25% more active than the Zn(II)-loaded form of the enzyme. Interestingly, Mn(II) can activate DapE, but only to approximately 20% of the Zn(II)-loaded enzyme. The order of the observed k(cat) values are Co(II) > Zn(II) > Cd(II) > Mn(II) >Ni(II) approximately equal Cu(II) approximately equal Mg(II). DapE was shown to only hydrolyze L,L-N-succinyl-diaminopimelic acid (L,L-SDAP) and was inactive toward D,L-, L,D-, and D,D-SDAP. DapE was also inactive toward several acetylated amino acids as well as D,L-succinyl aminopimelate, which differs from the natural substrate, L,L-SDAP, by the absence of the amine group on the amino acid side chain. These data imply that the carboxylate of the succinyl moiety and the amine form important interactions with the active site of DapE. The affinity of DapE for one versus two Zn(II) ions differs by nearly 2.2 x 10(3) times (K(d1) = 0.14 microM vs K(d2) = 300 microM). In addition, an Arrhenius plot was constructed from k(cat) values measured between 16 and 35 degrees C and was linear over this temperature range. The activation energy for [ZnZn(DapE)] was found to be 31 kJ/mol with the remaining thermodynamic parameters calculated at 25 degrees C being DeltaG(++) = 64 kJ/mol, DeltaH(++) = 28.5 kJ/mol, and DeltaS(++) = -119 J mol(-1) K(-1). Electronic absorption and EPR spectra of [Co_(DapE)] and [CoCo(DapE)] indicate that the first Co(II) binding site is five-coordinate, while the second site is octahedral. In addition, any spin-spin interaction between the two Co(II) ions in [CoCo(DapE)] is very weak. The kinetic and spectroscopic data presented herein suggest that the DapE from H. influenzae has similar divalent metal binding properties to the aminopeptidase from Aeromonas proteolytica (AAP), and

Mercerized mesoporous date pit activated carbon-A novel adsorbent to sequester potentially toxic divalent heavy metals from water.

Science.gov (United States)

Aldawsari, Abdullah; Khan, Moonis Ali; Hameed, B H; Alqadami, Ayoub Abdullah; Siddiqui, Masoom Raza; Alothman, Zeid Abdullah; Ahmed, A Yacine Badjah Hadj

2017-01-01

A substantive approach converting waste date pits to mercerized mesoporous date pit activated carbon (DPAC) and utilizing it in the removal of Cd(II), Cu(II), Pb(II), and Zn(II) was reported. In general, rapid heavy metals adsorption kinetics for Co range: 25-100 mg/L was observed, accomplishing 77-97% adsorption within 15 min, finally, attaining equilibrium in 360 min. Linear and non-linear isotherm studies revealed Langmuir model applicability for Cd(II) and Pb(II) adsorption, while Freundlich model was fitted to Zn(II) and Cu(II) adsorption. Maximum monolayer adsorption capacities (qm) for Cd(II), Pb(II), Cu(II), and Zn(II) obtained by non-linear isotherm model at 298 K were 212.1, 133.5, 194.4, and 111 mg/g, respectively. Kinetics modeling parameters showed the applicability of pseudo-second-order model. The activation energy (Ea) magnitude revealed physical nature of adsorption. Maximum elution of Cu(II) (81.6%), Zn(II) (70.1%), Pb(II) (96%), and Cd(II) (78.2%) were observed with 0.1 M HCl. Thermogravimetric analysis of DPAC showed a total weight loss (in two-stages) of 28.3%. Infra-red spectral analysis showed the presence of carboxyl and hydroxyl groups over DPAC surface. The peaks at 820, 825, 845 and 885 cm-1 attributed to Zn-O, Pb-O, Cd-O, and Cu-O appeared on heavy metals saturated DPAC, confirmed their binding on DPAC during the adsorption.

Highly reversible open framework nanoscale electrodes for divalent ion batteries.

Science.gov (United States)

Wang, Richard Y; Wessells, Colin D; Huggins, Robert A; Cui, Yi

2013-01-01

The reversible insertion of monovalent ions such as lithium into electrode materials has enabled the development of rechargeable batteries with high energy density. Reversible insertion of divalent ions such as magnesium would allow the creation of new battery chemistries that are potentially safer and cheaper than lithium-based batteries. Here we report that nanomaterials in the Prussian Blue family of open framework materials, such as nickel hexacyanoferrate, allow for the reversible insertion of aqueous alkaline earth divalent ions, including Mg(2+), Ca(2+), Sr(2+), and Ba(2+). We show unprecedented long cycle life and high rate performance for divalent ion insertion. Our results represent a step forward and pave the way for future development in divalent batteries.

Method of microbially producing metal gallate spinel nano-objects, and compositions produced thereby

Science.gov (United States)

Duty, Chad E.; Jellison, Jr., Gerald E.; Love, Lonnie J.; Moon, Ji Won; Phelps, Tommy J.; Ivanov, Ilia N.; Kim, Jongsu; Park, Jehong; Lauf, Robert

2018-01-16

A method of forming a metal gallate spinel structure that includes mixing a divalent metal-containing salt and a gallium-containing salt in solution with fermentative or thermophilic bacteria. In the process, the bacteria nucleate metal gallate spinel nano-objects from the divalent metal-containing salt and the gallium-containing salt without requiring reduction of a metal in the solution. The metal gallate spinel structures, as well as light-emitting structures in which they are incorporated, are also described.

Thermal study of monovalent-divalent phase transition in npBifc-F1TCNQ System

International Nuclear Information System (INIS)

Sato, Michiko; Nishio, Yutaka; Kajita, Koji; Mochida, Tomoyuki

2009-01-01

In a new molecular solid composed of di-neopentyl-biferrocene (npBifc) and fluorotetracyanoquinodimethane (F 1 TCNQ) 3 , Mochida reported the discovery of a reversible valence transfer that can be regarded as an 'ionic(I)-ionic(II)' phase transfer between the monovalent state (D + A - ) and the divalent state (D 2+ A 2- ). We have studied thermo-dynamical properties of this transformation for this complex using the differential thermal analyses (DTA). We observed a broad excess specific heat with multi-peaks attributed to micro-domain structure over the corresponding temperature range (100-150K) accompanied by temperature hysteresis of 7K. The transition entropy (ΔS) was determined to be 22 ± 2 J/mol-K and almost satisfied a Clausius-Clapeyron relation. These experimental results provide an experimental confirmation of the first order phase transition for the monovalent-divalent transfer. At the transition, we observe that the electronic degrees of freedom remained constant values, while large entropy absorbed crossing from low temperature phase to high temperature one is contributed by the lattice one. We finally estimated the internal energy and concluded that delicate energy valance between Madelung, ionization and affinity energies enable this system to exhibit a temperature induce monovalent-divalent phase transition.

Divalent metal (Ca, Cd, Mn, Zn) uptake and interactions in the aquatic insect Hydropsyche sparna.

Science.gov (United States)

Poteat, Monica D; Díaz-Jaramillo, Mauricio; Buchwalter, David B

2012-05-01

Despite their ecological importance and prevalent use as ecological indicators, the trace element physiology of aquatic insects remains poorly studied. Understanding divalent metal transport processes at the water-insect interface is important because these metals may be essential (e.g. Ca), essential and potentially toxic (e.g. Zn) or non-essential and toxic (e.g. Cd). We measured accumulation kinetics of Zn and Cd across dissolved concentrations ranging 4 orders of magnitude and examined interactions with Ca and Mn in the caddisfly Hydropsyche sparna. Here, we provide evidence for at least two transport systems for both Zn and Cd, the first of which operates at concentrations below 0.8 μmol l(-1) (and is fully saturable for Zn). We observed no signs of saturation of a second lower affinity transport system at concentrations up to 8.9 μmol l(-1) Cd and 15.3 μmol l(-1) Zn. In competition studies at 0.6 μmol l(-1) Zn and Cd, the presence of Cd slowed Zn accumulation by 35% while Cd was unaffected by Zn. At extreme concentrations (listed above), Cd accumulation was unaffected by the presence of Zn whereas Zn accumulation rates were reduced by 58%. Increasing Ca from 31.1 μmol l(-1) to 1.35 mmol l(-1) resulted in only modest decreases in Cd and Zn uptake. Mn decreased adsorption of Cd and Zn to the integument but not internalization. The L-type Ca(2+) channel blockers verapamil and nifedipine and the plasma membrane Ca(2+)-ATPase inhibitor carboxyeosin had no influence on Ca, Cd or Zn accumulation rates, while Ruthenium Red, a Ca(2+)-ATPase inhibitor, significantly decreased the accumulation of all three in a concentration-dependent manner.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters

Energy Technology Data Exchange (ETDEWEB)

Jones, Adele M.; Xue, Youjia [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Kinsela, Andrew S. [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Institute for Environmental Research (IER), Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234 (Australia); Wilcken, Klaus M. [Institute for Environmental Research (IER), Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234 (Australia); Collins, Richard N., E-mail: richard.collins@unsw.edu.au [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia)

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values < 3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with {sup 55}Fe and {sup 26}Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (> 70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO{sub 4}){sub 2}{sup −} and/or Me–NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. - Highlights: • CLASS discharge large amounts of metals and their speciation is poorly

Equilibrium modeling of mono and binary sorption of Cu(II and Zn(II onto chitosan gel beads

Directory of Open Access Journals (Sweden)

Nastaj Józef

2016-12-01

Full Text Available The objective of the work are in-depth experimental studies of Cu(II and Zn(II ion removal on chitosan gel beads from both one- and two-component water solutions at the temperature of 303 K. The optimal process conditions such as: pH value, dose of sorbent and contact time were determined. Based on the optimal process conditions, equilibrium and kinetic studies were carried out. The maximum sorption capacities equaled: 191.25 mg/g and 142.88 mg/g for Cu(II and Zn(II ions respectively, when the sorbent dose was 10 g/L and the pH of a solution was 5.0 for both heavy metal ions. One-component sorption equilibrium data were successfully presented for six of the most useful three-parameter equilibrium models: Langmuir-Freundlich, Redlich-Peterson, Sips, Koble-Corrigan, Hill and Toth. Extended forms of Langmuir-Freundlich, Koble-Corrigan and Sips models were also well fitted to the two-component equilibrium data obtained for different ratios of concentrations of Cu(II and Zn(II ions (1:1, 1:2, 2:1. Experimental sorption data were described by two kinetic models of the pseudo-first and pseudo-second order. Furthermore, an attempt to explain the mechanisms of the divalent metal ion sorption process on chitosan gel beads was undertaken.

Removal of Pb(II), Cu(II) and Cd(II) from aqueous solution by some fungi and natural adsorbents in single and multiple metal systems

International Nuclear Information System (INIS)

Shoaib, A.; Badar, T.; Aslam, N.

2011-01-01

Six fungal and 10 natural biosorbents were analyzed for their Cu(II), Cd(II) and Pb(II) uptake capacity from single, binary and ternary metal ion system. Preliminary screening biosorption of assays revealed 2 fungi (Aspergillus niger and Cunninghamella echinulata) and three natural [Cicer arietinum husk, Moringa oleifera flower and soil (clay)] adsorbents hold considerable high adsorption efficiency and capacity for 3 meta l ions amongst the adsorbents. Further biosorption trials with five elected adsorbents showed a considerable reduction in metal uptake capability of adsorbents in binary- and ternary systems as compared to singly metal system. Cd(II) manifested the highest inhibitory effect on the biosorption of other metal ions, followed by Pb(II) and Cu(II). On account of metal preference, the selectivity order for metal ion towards the studied biomass matrices was Pb(II) (40-90%) > Cd(II) (2-53%) > Cu(II) (2-30%). (author)

Effects of inorganic acids and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process.

Science.gov (United States)

Zhang, Jian; Xia, Yuguo; Zhang, Li; Chen, Dairong; Jiao, Xiuling

2015-11-07

In-depth understanding of the sol-gel process plays an essential role in guiding the preparation of new materials. Herein, the effects of different inorganic acids (HCl, HNO3 and H2SO4) and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process were studied based on experiments and density functional theory (DFT) calculations. In these experiments, the sol originating from the γ-AlOOH suspension was formed only with the addition of HCl and HNO3, but not with H2SO4. Furthermore, the DFT calculations showed that the strong adsorption of HSO4(-) on the surface of the γ-AlOOH particles, and the hydrogen in HSO4(-) pointing towards the solvent lead to an unstable configuration of electric double layer (EDL). In the experiment, the gelation time sequence of γ-AlOOH sol obtained by adding metal ions changed when the ionic strength was equal to or greater than 0.198 mol kg(-1). The DFT calculations demonstrated that the adsorption energy of hydrated metal ions on the γ-AlOOH surface can actually make a difference in the sol-gel process.

Thermal study of monovalent-divalent phase transition in npBifc-F{sub 1}TCNQ System

Energy Technology Data Exchange (ETDEWEB)

Sato, Michiko; Nishio, Yutaka; Kajita, Koji [Department of Physics, Faculty of Science, Toho University, Miyama 2-2-1, Funabashi, Chiba, 274-8510 (Japan); Mochida, Tomoyuki, E-mail: nishio@ph.sci.toho-u.ac.j [Department of Chemistry, Faculty of Science, Kobe University, Rokkodai, Nada, Kobe 657-8501 (Japan)

2009-03-01

In a new molecular solid composed of di-neopentyl-biferrocene (npBifc) and fluorotetracyanoquinodimethane (F{sub 1}TCNQ){sub 3}, Mochida reported the discovery of a reversible valence transfer that can be regarded as an 'ionic(I)-ionic(II)' phase transfer between the monovalent state (D{sup +}A{sup -}) and the divalent state (D{sup 2+}A{sup 2-}). We have studied thermo-dynamical properties of this transformation for this complex using the differential thermal analyses (DTA). We observed a broad excess specific heat with multi-peaks attributed to micro-domain structure over the corresponding temperature range (100-150K) accompanied by temperature hysteresis of 7K. The transition entropy (DELTAS) was determined to be 22 +- 2 J/mol-K and almost satisfied a Clausius-Clapeyron relation. These experimental results provide an experimental confirmation of the first order phase transition for the monovalent-divalent transfer. At the transition, we observe that the electronic degrees of freedom remained constant values, while large entropy absorbed crossing from low temperature phase to high temperature one is contributed by the lattice one. We finally estimated the internal energy and concluded that delicate energy valance between Madelung, ionization and affinity energies enable this system to exhibit a temperature induce monovalent-divalent phase transition.

The role of electrolyte anions (ClO4-, NO3-, and Cl-) in divalent metal (M2+) adsorption on oxide and hydroxide surfaces in salt solutions

International Nuclear Information System (INIS)

Criscenti, L.J.; Sverjensky, D.A.

1999-01-01

Adsorption of divalent metal ions (M 2+ ) onto oxide and hydroxide surfaces from solutions of strong electrolytes has typically been inferred to take place without the involvement of the electrolyte anion. Only in situations where M 2+ forms a strong enough aqueous complex with the electrolyte anion (for example, CdCl + or PbCl + ) has it been frequently suggested that the metal and the electrolyte anion adsorb simultaneously. A review of experimental data for the adsorption of Cd 2+ , Pb 2+ , Co 2+ , UO 2 2+ , Zn 2+ , Cu 2+ , Ba 2+ , Sr 2+ , and Ca 2+ onto quartz, silica, goethite, hydrous ferric oxide, corundum, γ-alumina, anatase, birnessite, and magnetite, from NaNO 3 , KNO 3 , NaCl, and NaClO 4 solutions over a wide range of ionic strengths (0.0001 M-1.0 M), reveals that transition and heavy metal adsorption behavior with ionic strength is a function of the type of electrolyte. In NaNO 3 solutions, metal adsorption exhibits little or no dependence on the ionic strength of the solution. However, in NaCl solutions, transition and heavy metal adsorption decreases strongly with increasing ionic strength. In NaClO 4 solutions, metal adsorption decreases strongly with increasing ionic strength. In NaClO 4 solutions, metal adsorption exhibits little dependence on ionic strength but is often suggestive of an increase in metal adsorption with increasing ionic strength. Analysis of selected adsorption edges was carried out using the extended triple-layer model and aqueous speciation models that included metal-nitrate, metal-chloride, and metal-hydroxide complexes

Anti-inflammatory drugs interacting with Zn(II), Cd(II) and Pt(II) metal ions.

Science.gov (United States)

Dendrinou-Samara, C; Tsotsou, G; Ekateriniadou, L V; Kortsaris, A H; Raptopoulou, C P; Terzis, A; Kyriakidis, D A; Kessissoglou, D P

1998-09-01

Complexes of Zn(II), Cd(II) and Pt(II) metal ions with the anti-inflammatory drugs, 1-methyl-5-(p-toluoyl)-1H-pyrrole-2-acetic acid (Tolmetin), alpha-methyl-4-(2-methylpropyl)benzeneacetic acid (Ibuprofen), 6-methoxy-alpha-methylnaphthalene-2-acetic acid (Naproxen) and 1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid (indomethacin) have been synthesized and characterized. In the structurally characterized Cd(naproxen)2 complex the anti-inflammatory drugs acts as bidentate chelate ligand coordinatively bound to metal ions through the deprotonated carboxylate group. Crystal data for 1: [C32H26O8Cd], orthorhombic, space group P22(1)2(1), a = 5.693(2) (A), b = 8.760(3) (A), c = 30.74(1) (A), V = 1533(1) A3, Z = 2. Antibacterial and growth inhibitory activity is higher than that of the parent ligands or the platinum(II) diamine compounds.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

Science.gov (United States)

Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. Copyright © 2015 Elsevier B.V. All rights reserved.

Alkaline earth metals

International Nuclear Information System (INIS)

Brown, Paul L.; Ekberg, Christian

2016-01-01

The beryllium ion has a relatively small ionic radius. As a consequence of this small size, its hydrolysis reactions begin to occur at a relatively low pH. To determine the stability and solubility constants, however, the Gibbs energy of the beryllium ion is required. In aqueous solution calcium, like the other alkaline earth metals, only exists as a divalent cation. The size of the alkaline earth cations increases with increasing atomic number, and the calcium ion is bigger than the magnesium ion. The hydrolysis of barium(II) is weaker than that of strontium(II) and also occurs in quite alkaline pH solutions, and similarly, only the species barium hydroxide has been detected. There is only a single experimental study on the hydrolysis of radium. As with the stability constant trend, it would be expected that the enthalpy of radium would be lower than that of barium due to the larger ionic radius.

Mechanistic studies on E. coli DNA topoisomerase I: Divalent ion effects

International Nuclear Information System (INIS)

Domanico, P.L.; Tse-Dinh, Y.C.

1991-01-01

E. coli DNA topoisomerase I catalyzes the hydrolysis of short, single stranded oligodeoxynucleotides. It also forms a covalent protein-DNA complex with negatively supercoiled DNA in the absence of Mg2+ but requires Mg2+ for the relaxation of negatively supercoiled DNA. In this paper we investigate the effects of various divalent metals on catalysis. For the relaxation reaction, maximum enzyme activity plateaus after 2.5 mM Mg2+. However, the rate of cleavage of short oligodeoxynucleotide increased linearly between 0 and 15 mM Mg2+. In the oligodeoxynucleotide cleavage reaction, Ca2+, Mn2+, Co2+, and Zn2+ inhibit enzymatic activity. When these metals are coincubated with Mg2+ at equimolar concentrations, the normal effect of Mg2+ is not detectable. Of these metals, only Ca2+ can be substituted for Mg2+ as a metal cofactor in the relaxation reaction. And when Mg2+ is coincubated with Mn2+, Co2+, or Zn2+ at equimolar concentrations, the normal effect of Mg2+ on relaxation is not detectable. The authors propose that Mg2+ allows the protein-DNA complex to assume a conformation necessary for strand passage and enhance the rate of enzyme turnover

Lead (II) and nickel (II) adsorption kinetics from aqueous metal ...

African Journals Online (AJOL)

This paper discusses the kinetics of lead (II) and Nickel (II) ions adsorption from aqueous solutions using chemically modified and unmodified agricultural adsorbents at 28°C, pH 6.2 and 0.01M NaCl ionic strength. The removal of the two metals were found to increase with increase in chemical modification, the sequence ...

Thermodynamics of binding interactions between extracellular polymeric substances and heavy metals by isothermal titration microcalorimetry.

Science.gov (United States)

Yan, Peng; Xia, Jia-Shuai; Chen, You-Peng; Liu, Zhi-Ping; Guo, Jin-Song; Shen, Yu; Zhang, Cheng-Cheng; Wang, Jing

2017-05-01

Extracellular polymeric substances (EPS) play a crucial role in heavy metal bio-adsorption using activated sludge, but the interaction mechanism between heavy metals and EPS remains unclear. Isothermal titration calorimetry was employed to illuminate the mechanism in this study. The results indicate that binding between heavy metals and EPS is spontaneous and driven mainly by enthalpy change. Extracellular proteins in EPS are major participants in the binding process. Environmental conditions have significant impact on the adsorption performance. Divalent and trivalent cations severely impeded the binding of heavy metal ions to EPS. Electrostatic interaction mainly attributed to competition between divalent cations and heavy metal ions; trivalent cations directly competed with heavy metal ions for EPS binding sites. Trivalent cations were more competitive than divalent cations for heavy metal ion binding because they formed complexing bonds. This study facilitates a better understanding about the interaction between heavy metals and EPS in wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparative sensitivity of rat cerebellar neurons to dysregulation of divalent cation homeostasis and cytotoxicity caused by methylmercury

International Nuclear Information System (INIS)

Edwards, Joshua R.; Marty, M. Sue; Atchison, William D.

2005-01-01

The objective of the present study was to determine the relative effectiveness of methylmercury (MeHg) to alter divalent cation homeostasis and cause cell death in MeHg-resistant cerebellar Purkinje and MeHg-sensitive granule neurons. Application of 0.5-5 μM MeHg to Purkinje and granule cells grown in culture caused a concentration- and time-dependent biphasic increase in fura-2 fluorescence. At 0.5 and 1 μM MeHg, the elevations of fura-2 fluorescence induced by MeHg were biphasic in both cell types, but significantly delayed in Purkinje as compared to granule cells. Application of the heavy-metal chelator, TPEN, to Purkinje cells caused a precipitous decline in a proportion of the fura-2 fluorescence signal, indicating that MeHg causes release of Ca 2+ and non-Ca 2+ divalent cations. Purkinje cells were also more resistant than granule cells to the neurotoxic effects of MeHg. At 24.5 h after-application of 5 μM MeHg, 97.7% of Purkinje cells were viable. At 3 μM MeHg there was no detectable loss of Purkinje cell viability. In contrast, only 40.6% of cerebellar granule cells were alive 24.5 h after application of 3 μM MeHg. In conclusion, Purkinje neurons in primary cultures appear to be more resistant to MeHg-induced dysregulation of divalent cation homeostasis and subsequent cell death when compared to cerebellar granule cells. There is a significant component of non-Ca 2+ divalent cation released by MeHg in Purkinje neurons

Binding of Divalent Cations to Polygalacturonate: A Mechanism Driven by the Hydration Water.

Science.gov (United States)

Huynh, Uyen T D; Lerbret, Adrien; Neiers, Fabrice; Chambin, Odile; Assifaoui, Ali

2016-02-11

We have investigated the interactions between polygalacturonate (polyGal) and four divalent cations (M(2+) = Ba(2+), Ca(2+), Mg(2+), Zn(2+)) that differ in size and affinity for water. Our results evidence that M(2+)-polyGal interactions are intimately linked to the affinity of M(2+) for water. Mg(2+) interacts so strongly with water that it remains weakly bound to polyGal (polycondensation) by sharing water molecules from its first coordination shell with the carboxylate groups of polyGal. In contrast, the other cations form transient ionic pairs with polyGal by releasing preferentially one water molecule (for Zn(2+)) or two (for Ca(2+) and Ba(2+)), which corresponds to monodentate and bidentate binding modes with carboxylates, respectively. The mechanism for the binding of these three divalent cations to polyGal can be described by two steps: (i) monocomplexation and formation of point-like cross-links between polyGal chains (at low M(2+)/Gal molar ratios, R) and (ii) dimerization (at higher R). The threshold molar ratio, R*, between these two steps depends on the nature of divalent cations and is lower for calcium ions (R* 0.3). This difference may be explained by the intermediate affinity of Ca(2+) for water with respect to those of Zn(2+) and Ba(2+), which may induce the formation of cross-links of intermediate flexibility. By comparison, the lower and higher flexibilities of the cross-links formed by Zn(2+) and Ba(2+), respectively, may shift the formation of dimers to higher molar ratios (R*).

Manganese(II), iron(II), and mixed-metal metal-organic frameworks based on chains with mixed carboxylate and azide bridges: magnetic coupling and slow relaxation.

Science.gov (United States)

Wang, Yan-Qin; Yue, Qi; Qi, Yan; Wang, Kun; Sun, Qian; Gao, En-Qing

2013-04-15

Mn(II) and Fe(II) compounds derived from azide and the zwitterionic 1-carboxylatomethylpyridinium-4-carboxylate ligand are isomorphous three-dimensional metal-organic frameworks (MOFs) with the sra net, in which the metal ions are connected into anionic chains by mixed (μ-1,1-azide)bis(μ-carboxylate) triple bridges and the chains are cross-linked by the cationic backbones of the zwitterionic ligands. The Mn(II) MOFs display typical one-dimensional antiferromagnetic behavior. In contrast, with one more d electron per metal center, the Fe(II) counterpart shows intrachain ferromagnetic interactions and slow relaxation of magnetization attributable to the single-chain components. The activation energies for magnetization reversal in the infinite- and finite-chain regimes are Δτ1 = 154 K and Δτ2 = 124 K, respectively. Taking advantage of the isomorphism between the Mn(II) and Fe(II) MOFs, we have prepared a series of mixed-metal Mn(II)(1-x)Fe(II)(x) MOFs with x = 0.41, 0.63, and 0.76, which intrinsically feature random isotropic/anisotropic sites and competing antiferromagnetic-ferromagnetic interactions. The materials show a gradual antiferromagnetic-to-ferromagnetic evolution in overall behaviors as the Fe(II) content increases, and the Fe-rich materials show complex relaxation processes that may arise for mixed SCM and spin-glass mechanisms. A general trend is that the activation energy and the blocking temperature increase with the Fe(II) content, emphasizing the importance of anisotropy for slow relaxation of magnetization.

Progress and prospect of adsorptive removal of heavy metal ions from aqueous solution using metal-organic frameworks: A review of studies from the last decade.

Science.gov (United States)

Wen, Jia; Fang, Ying; Zeng, Guangming

2018-06-01

The efficient removal of heavy metals (HMs) from the environment has become an important issue from both biological and environmental perspectives. Recently, porous metal-organic frameworks (MOFs), combining central metals and organic ligands, have been proposed as promising materials in the capture of various toxic substances, including HMs, due to their unique characteristics. Here we review recent progress in the field of water remediation from the perspective of primary HMs (including divalent metals and variable-valent metals) in water pollution and the corresponding MOFs (including virgin and modified MOFs, magnetic MOFs composites and so on) that can remove these metals from water. The reported values of various MOFs for adsorption of heavy metal ions were 8.40-313 mg Pb(II) g -1 , 0.65-2173 mg Hg(II) g -1 , 3.63-145 mg Cd(II) g -1 , 14.0-127 mg Cr(III) g -1 , 15.4-145 mg Cr(VI) g -1 , 49.5-123 mg As(III) g -1 , and 12.3-303 mg As(V) g -1 . The main adsorption mechanisms associated with these processes are chemical (including coordination interaction, chemical bonding and acid-base interactions) and physical (including electrostatic interaction, diffusion and van der Waals force) adsorption, which were discussed in detailed. Further efforts should be made towards expanding the repertoire of MOFs that effectively remove multiple targeted HMs, as well as exploring possible applications of MOFs in the removal of HMs from non-aqueous environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

A High Sensitivity Micro Format Chemiluminescence Enzyme Inhibition Assay for Determination of Hg(II

Directory of Open Access Journals (Sweden)

Kanchanmala Deshpande

2010-06-01

Full Text Available A highly sensitive and specific enzyme inhibition assay based on alcohol oxidase (AlOx and horseradish peroxidase (HRP for determination of mercury Hg(II in water samples has been presented. This article describes the optimization and miniaturization of an enzymatic assay using a chemiluminescence reaction. The analytical performance and detection limit for determination of Hg(II was optimized in 96 well plates and further extended to 384 well plates with a 10-fold reduction in assay volume. Inhibition of the enzyme activity by dissolved Hg(II was found to be linear in the range 5–500 pg.mL−1 with 3% CVin inter-batch assay. Due to miniaturization of assay in 384 well plates, Hg(II was measurable as low as 1 pg.mL−1 within15 min. About 10-fold more specificity of the developed assay for Hg(II analysis was confirmed by challenging with interfering divalent metal ions such as cadmium Cd(II and lead Pb(II. Using the proposed assay we could successfully demonstrate that in a composite mixture of Hg(II, Cd(II and Pb(II, inhibition by each metal ion is significantly enhanced in the presence of the others. Applicability of the proposed assay for the determination of the Hg(II in spiked drinking and sea water resulted in recoveries ranging from 100–110.52%.

EPR study of manganese(II) binding to 55'-ATP, hemoglobin, and hemocyanin

Energy Technology Data Exchange (ETDEWEB)

Chang, S.S. (Duquesne Univ., Pittsburgh); Li, N.C.; Pratt, D.W.

1975-01-01

Several divalent metal ions affect the oxygen affinity of hemoglobin and hemocyanin. It is important, therefore, to understand the nature of metal-ion binding to these proteins. By comparing the EPR spectra of Mn(II), 0.001 M, in the absence and presence of carboxyhemoglobin or Limulus oxyhemocyanin (pH 7.3, Trizma buffer), the number of Mn binding sites, n, and the binding constant, K, can be determined. For carboxyhemoglobin, HbCO, we find 0.5 Mn binding sites per heme, K = 450 M/sup -1/. Each hemoglobin tetramer therefore binds two manganous ions suggesting that Mn(II), like Cu(II), may bind preferentially to one of the two types of subunits in hemoglobin. For hemocyanin, HcO/sub 2/, we find n = 5.8, K = 1.55 x 10/sup 3/ M/sup -1/. Each oxyhemocyanine therefore binds approximately six manganous ions, and the binding constant is three times larger than that for HbCO. We have also carried out similar experiments on 5'-ATP, and on solutions of HbCO and ATP containing McCl/sub 2/ or ZnCl/sub 2/. Zn(II) effectively competes with Mn(II) in binding hemoglobin and ATP, whereas Mg(II) does not, in accord with expectations from data on oxygen affinity of hemoglobin. (auth)

Synthesis and Structural Studies on Transition Metal Complexes Derived from 4-Hydroxy-4-methyl–2-pentanone-1H-benzimidazol-2-yl-hydrazone

Directory of Open Access Journals (Sweden)

M. Neelamma

2011-01-01

Full Text Available Transition metal complexes of Cr(III, Fe(III, Mn(II, Co(II, Ni(II, Cu(II and Zn(II with a tridentate ligand, 4-hydroxy-4-methyl-2-pentanone-1H-benzimidazole-2yl-hydrazone (H-HPBH derived from the condensation of 2-hydrazinobenzimidazole and diacetone alcohol was synthesized. Characterization has been done on the basis of analytical, conductance, thermal and magnetic data, infrared, 1H NMR, electronic, mass and ESR spectral data. From analytical and thermal data, the stoichiometry of the complexes has been found to be 1:1 (metal: ligand. Divalent complexes have the general formula [M(HPBHCl(H2O2] in octahedral geometry, [M(HPBHCl] in tetrahedral and square planar stereochemistries and trivalent complexes [M(HPBHCl2(H2O] in octahedral disposition. Infrared spectral data suggest that the ligand HPBH behaves as a monobasic tridentate ligand with N: N: O donor sequence towards the metal ions. On the basis of the above physicochemical data, octahedral, tetrahedral and square planar geometries were assigned for the complexes. The ligand and metal complexes were screened for their physiological activities against E. coli and S. aureus. The order of physiological activity has been found to be Cu(II > Ni(II > Zn(II > Co(II > Cr(III > Mn(II > Fe (III > ligand against E.coli and Ni(II > Cu(II > Zn(II > Mn(II > Cr(III > Fe(III > Co(II > ligand against S. aureus.

Metal Chelation in Asymmetric Diels-Alder Reaction (II)

International Nuclear Information System (INIS)

Chung, Kyoo Hyun; Chu, Chan Kook; Chang, Min Ho

2004-01-01

In the reaction, the inverse asymmetric induction has been observed by the use of either monovalent Lewis acids or divalent Lewis acids. The reaction of the acrylate of (S)-ethyl lactate with cyclopentadiene proceeded with 86% endo-S selectivity in the presence of TiCl 4 , divalent Lewis acid, whereas did with 32% endo-R selectivity in the presence of BF 3 ·Et 2 O, monovalent Lewis acid. When a chiral dienophile which was prepared from benzyl ester of (S)-proline or methyl ester of (S)-indoline-2-carboxylic acid was employed in the reaction, a similar diastereofacial selectivity was also observed. Recently, we reported the similar selectivity in the reaction of methyl (2S,5S)-(5-t-butyldimethylsilyloxypiperidin- 2-yl)ethanoatewith cyclopentadiene.

Stability constants for some divalent metal ion/crown ether complexes in methanol determined by polarography and conductometry

NARCIS (Netherlands)

Chen, L.; Bos, M.; Grootenhuis, P.D.J.; Christenhusz, A.; Hoogendam, E.; Reinhoudt, David; van der Linden, W.E.

1987-01-01

Stability constants in methanol at 25.0°C were evaluated for the complexes of the divalent cations Ca2+, Ni2+, Zn2+, Pb2+, Mg2+, Co2+ and Cu2+ with the macrocyclic polyethers 15-crown-5 (15C5), 18-crown-6 (18C6), dicyclohexyl-18-crown-6 (DC18C6) and dibenzo-24-crown-8 (DB24C8). The log K values of

Thermal, spectral, magnetic and biological studies of thiosemicarbazones complexes with metal ions: Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO2(VI)

International Nuclear Information System (INIS)

Mashaly, M.M.; Seleem, H.S.; El-Behairy, M.A.; Habib, H.A.

2004-01-01

Thiosemicarbazones ligands, isatin-3-thiosemicarbazone(HIT) and N-acetylisatin-3-thiosemicarbazone (HAIT), which have tridentate ONN coordinating sites were prepared. The complexes of both ligands with Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO 2 (VI) ions were isolated. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis and mass spectra, also by conductance, magnetic moment and TG-DSC measurements. All the transition metal complexes have octahedral configurations, except Cu-complexes which have planar geometry and the UO 2 (VI) complexes which have coordination number 8 and may acquire the distorted dodecahedral geometry. Thermal studies explored the possibility of obtaining new complexes. Inversion from octahedral to square-planar configuration occurred upon heating the parent Ni-HIAT complex to form the corresponding pyrolytic product. The antifungal activity against the tested organisms showed that some metal complexes enhanced the activity with respect to the parent ligands. (author)

Adsorptive behaviour of mercury on algal biomass: Competition with divalent cations and organic compounds

International Nuclear Information System (INIS)

Carro, Leticia; Barriada, Jose L.; Herrero, Roberto; Sastre de Vicente, Manuel E.

2011-01-01

Highlights: → Native and protonated macroalga S. muticum are good materials for mercury removal. → Fast kinetic process and high mercury uptakes have been found for those materials. → Diffusion control is the rate limiting step of the process. → Competition effects by organic compounds, inorganic salts and divalent cations were analyzed. → Continuous flow experiments allowed identification of mercury reduction during metal removal. - Abstract: Biosorption processes constitute an effective technique for mercury elimination. Sorption properties of native and acid-treated Sargassum muticum have been studied. Effect of pH, initial mercury concentration and contact time studies provided fundamental information about the sorption process. This information was used as the reference values to analyse mercury sorption under competition conditions. Saline effect has shown little influence in sorption, when only electrostatic modifications took place upon salt addition. On the contrary, if mercury speciation dramatically changed owing to the addition of an electrolyte, such as in the case of chloride salt, very large modifications in mercury sorption were observed. Competition with other divalent cations or organic compounds has shown little or none effect on mercury, indicating that a different mechanism is taking place during the removal of these pollutants. Finally, continuous flow experiments have clearly shown that a reduction process is also taking place during mercury removal. This fact is not obvious to elucidate under batch sorption experiments. Scanning Electron Microscopy analysis of the surface of the materials show deposits of mercury(I) and metallic mercury which is indicative of the reduction process proposed.

Reaction of N,N'-dimethylformamide and divalent viologen molecule to generate an organic dopant for molybdenum disulfide

Science.gov (United States)

Fukui, A.; Miura, K.; Ichimiya, H.; Tsurusaki, A.; Kariya, K.; Yoshimura, T.; Ashida, A.; Fujimura, N.; Kiriya, D.

2018-05-01

Tuning the carrier concentration is essential for semiconducting materials to apply optoelectronic devices. Molybdenum disulfide (MoS2) is a semiconducting material composed of atomically thin (˜0.7 nm thickness) layers. To dope thin MoS2, instead of using conventional atom/ion injection processes, a surface charge transfer method was successfully applied. In this study, we report a simple preparation method of a molecular dopant applicable to the doping process. The method follows a previous report for producing a molecular dopant, benzyl viologen (BV) which shows electron doping to MoS2. To prepare dopant BV molecules, a reduction process with a commercially available divalent BV by sodium borohydride (NaBH4) is required; however, the reaction requires a large consumption of NaBH4. NaBH4 drastically reacts with the solvent water itself. We found a reaction process of BV in an organic solvent, N,N'-dimethylformamide (DMF), by adding a small amount of water dissolving the divalent BV. The reaction is mild (at room temperature) and is autonomous once DMF comes into contact with the divalent BV aqueous solution. The reaction can be monitored with a UV-Vis spectrometer, and kinetic analysis indicates two reaction steps between divalent/monovalent/neutral viologen isomers. The product was soluble in toluene and did not dissolve in water, indicating it is similar to the reported dopant BV. The synthesized molecule was found to act as a dopant for MoS2 by applying a metal-oxide-semiconductor field-effect-transistor (MOSFET) structure. The process is a general method and applicable to other viologen-related dopants to tune the electronic structure of 2D materials to facilitate generating atomically thin devices.

Reaction of N,N’-dimethylformamide and divalent viologen molecule to generate an organic dopant for molybdenum disulfide

Directory of Open Access Journals (Sweden)

A. Fukui

2018-05-01

Full Text Available Tuning the carrier concentration is essential for semiconducting materials to apply optoelectronic devices. Molybdenum disulfide (MoS2 is a semiconducting material composed of atomically thin (∼0.7 nm thickness layers. To dope thin MoS2, instead of using conventional atom/ion injection processes, a surface charge transfer method was successfully applied. In this study, we report a simple preparation method of a molecular dopant applicable to the doping process. The method follows a previous report for producing a molecular dopant, benzyl viologen (BV which shows electron doping to MoS2. To prepare dopant BV molecules, a reduction process with a commercially available divalent BV by sodium borohydride (NaBH4 is required; however, the reaction requires a large consumption of NaBH4. NaBH4 drastically reacts with the solvent water itself. We found a reaction process of BV in an organic solvent, N,N’-dimethylformamide (DMF, by adding a small amount of water dissolving the divalent BV. The reaction is mild (at room temperature and is autonomous once DMF comes into contact with the divalent BV aqueous solution. The reaction can be monitored with a UV-Vis spectrometer, and kinetic analysis indicates two reaction steps between divalent/monovalent/neutral viologen isomers. The product was soluble in toluene and did not dissolve in water, indicating it is similar to the reported dopant BV. The synthesized molecule was found to act as a dopant for MoS2 by applying a metal-oxide-semiconductor field-effect-transistor (MOSFET structure. The process is a general method and applicable to other viologen-related dopants to tune the electronic structure of 2D materials to facilitate generating atomically thin devices.

The Formation of Metal (M=Co(II), Ni(II), and Cu(II)) Complexes by Aminosilanes Immobilized within Mesoporous Molecular Sieves

International Nuclear Information System (INIS)

Park, Dong Ho; Park, Sung Soo; Choe, Sang Joon

1999-01-01

The immobilization of APTMS(3-(2-aminoethylamino)propyltrimethoxysilane) and AAPTMS(3-(2-(2-aminoethyl) aminoethylamino)propyltrimethoxysilane) on the surface of high quality mesoporous molecular sieves MCM-41 and MCM-48 have been confirmed by F.T.-IR spectroscopy, Raman spectroscopy, 29 Si solid state NMR, and a surface polarity measurement using Reichardt's dye. The formation of metal (Co(II), Ni(II), and Cu(II)) complexes by immobilized aminosilanes have been investigated by photoacoustic spectroscopy(PAS). The assignment of UV-Vis. PAS bands makes it possible to identify the structure of metal complexes within mesoporous molecular sieves. Co(II) ion may be coordinated mainly in a tetrahedral symmetry by two APTMS onto MCM-41, and in an octahedral one by two AAPTMS. Both Ni(II) and Cu(II) coordinated by aminosilanes within MCM-41 form possibly the octahedral complexes such as [Ni(APTMS) 2 (H 2 O) 2 ] 2+ , [Ni(AAPTMS) 2 ] 2+ , [Cu(APTMS) 2 (H 2 O) 2 ] 2+ , and [Cu(AAPTMS)(H 2 O) 3 ] 2+ , respectively. The PAS band shapes of complexes onto MCM-48 are similar to those of corresponding MCM-41 with the variation of PAS intensity. Most of metal ion(II) within MCM-41 and MCM-48 are coordinated by aminosilanes without the impregnation on the surface

SEPARATION OF Fe (III, Cr(III, Cu(II, Ni(II, Co(II, AND Pb(II METAL IONS USING POLY(EUGENYL OXYACETIC ACID AS AN ION CARRIER BY A LIQUID MEMBRANE TRANSPORT METHOD

Directory of Open Access Journals (Sweden)

La Harimu

2010-06-01

Full Text Available Fe (III, Cr(III, Cu(II, Ni(II, Co(II, and Pb(II  metal ions had been separated using poly(eugenyl oxyacetic acid as an ion carrier by bulk liquid membrane transport method. The effect of pH, polyeugenyl oxyacetic acid ion carrier concentration, nitric acid concentration in the stripping solution, transport time, and metal concentration were optimized. The result showed that the optimum condition for transport of metal ions was at pH 4 for ion Fe(III and at pH 5 for Cr(III, Cu(II, Ni(II, Co(II, and Pb(II ions. The carrier volumes were optimum with concentration of 1 x 10-3 M at 7.5 mL for Cr(III, Cu (II,  Ni(II, Co(II ions and at 8.5 mL for Fe(III and Pb(II ions. The concentration of HNO3 in stripping phase was optimum at 2 M for Fe(III and Cu(II ions, 1 M for Cr(III, Ni(II and Co(II ions, and 0.5 M for Pb(II ion. The optimum transport times were 36 h for Fe(III and Co(II ions, and 48 h for Cr(III, Cu (II, Ni(II, and Pb(II ions. The concentration of metal ions accurately transported were 2.5 x 10-4 M for Fe(III and Cr(III ions, and 1 M for Cu (II, Ni(II, Co(II, and Pb(II ions. Compared to other metal ions the transport of Fe(III was the highest with selectivity order of Fe(III > Cr(III > Pb(II > Cu(II > Ni(II > Co(II. At optimum condition, Fe(III ion was transported through the membrane at 46.46%.   Keywords: poly(eugenyl oxyacetic acid, transport, liquid membrane, Fe (III, Cr(III, Cu(II, Ni(II, Co(II, and Pb(II ions

Effect of Divalent Cations on RED Performance and Cation Exchange Membrane Selection to Enhance Power Densities.

Science.gov (United States)

Rijnaarts, Timon; Huerta, Elisa; van Baak, Willem; Nijmeijer, Kitty

2017-11-07

Reverse electrodialysis (RED) is a membrane-based renewable energy technology that can harvest energy from salinity gradients. The anticipated feed streams are natural river and seawater, both of which contain not only monovalent ions but also divalent ions. However, RED using feed streams containing divalent ions experiences lower power densities because of both uphill transport and increased membrane resistance. In this study, we investigate the effects of divalent cations (Mg 2+ and Ca 2+ ) on RED and demonstrate the mitigation of those effects using both novel and existing commercial cation exchange membranes (CEMs). Monovalent-selective Neosepta CMS is known to block divalent cations transport and can therefore mitigate reductions in stack voltage. The new multivalent-permeable Fuji T1 is able to transport divalent cations without a major increase in resistance. Both strategies significantly improve power densities compared to standard-grade CEMs when performing RED using streams containing divalent cations.

Investigation of radiation-chemical behaviour of divalent palladium in perchloric acid solutions

International Nuclear Information System (INIS)

Vladimirova, M.V.; Kalinina, S.V.

1988-01-01

Gamma-radiolysis of divalent palladium in perchloric acid solutions is studied. Absorption spectra of intermediate palladium compounds formed in the irradiated solution are taken. The analysis of literature data as well as comparative analysis of the absorption spectra obtained under irradiation of palladium (2) perchloric acid solutions with absorption spectra of palladium chlorocomplexes allows to suppose that the mentioned compounds are chlorocomplexes of palladium (2) of different composition depending on HClO 4 concentration in the initial solution and absorbed radiation dose. Radiation-chemical reduction of palladium (2) up to metal is stated to take place in the whole studied range of initial concentrations of components of the system and dose rates. Kinetic dependences of metallic palladium formation are obtained. Values of radiation-chemical yields of metallic palladium formation depending on the initial concentrations of palladium (2) and perchloric acid are given. A mechanism of radiolytic reduction of palladium (2) in the investigated system is suggested based on the experimental data, and a theoretical value of the radiation-chemical yield of palladium (2) reduction being in a good agreement with experimentally found values is calculated

Chemical studies on the distribution of some heavy metals between two immiscible solutions

International Nuclear Information System (INIS)

Rizk, S.E.M.

2011-01-01

Separation and recovery of divalent zinc and cobalt ions from mixed sulphate and thiocyanate solutions have been carried out using CYANEX 921 (trioctylphosphine oxide), CYANEX 923 (a mixture of straight chain alkylated phosphine oxides) and CYANEX 925 (a mixture of branched chain alkylated phosphine oxides) in kerosene. Different parameters affecting the extraction equilibrium of Zn(II) and Co(II) in addition to temperature, were studied and the stoichiometry of the extracted Zn(II) and Co(II) species were postulated based on slope analysis method. The respective loaded organic phases were stripped with different mineral acids. The extraction percent of metal ions was found to increase with increasing ph and zinc was preferentially extracted over cobalt in the different investigated systems. The highest separation factor was obtained when using 0.015 M CYANEX 925 as extractant. Based on the obtained results, application of the method was tested to separate Zn(II) and Co(II) from Nickel Metal Hydride batteries (Ni-MH batteries) leached by 2.0 M H 2 SO 4 and good results were obtained. The extraction of Zn(II) and Co(II) from aqueous mixed sulphate and thiocyanate medium through supported liquid membrane (SLM) using CYANEX 925 in kerosene as carrier supported on cellulose nitrate membrane was studied. The influence of different parameters on the permeation of the investigated metals such as ph, extractant concentration, sulphuric acid concentration, thiocyanate concentration and strip solution concentration were also studied. The selectivity of the used system for Zn / Co separation is evaluated.

Synthesis, spectral characterization thermal stability, antimicrobial studies and biodegradation of starch–thiourea based biodegradable polymeric ligand and its coordination complexes with [Mn(II, Co(II, Ni(II, Cu(II, and Zn(II] metals

Directory of Open Access Journals (Sweden)

Nahid Nishat

2016-09-01

Full Text Available A biodegradable polymer was synthesized by the modification reaction of polymeric starch with thiourea which is further modified by transition metals, Mn(II, Co(II, Ni(II, Cu(II and Zn(II. All the polymeric compounds were characterized by (FT-IR spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, UV–visible spectra, magnetic moment measurements, thermogravimetric analysis (TGA and antibacterial activities. Polymer complexes of Mn(II, Co(II and Ni(II show octahedral geometry, while polymer complexes of Cu(II and Zn(II show square planar and tetrahedral geometry, respectively. The TGA revealed that all the polymer metal complexes are more thermally stable than their parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM-D-5338-93 standards of biodegradable polymers by CO2 evolution method which says that coordination decreases biodegradability. The antibacterial activity was screened with the agar well diffusion method against some selected microorganisms. Among all the complexes, the antibacterial activity of the Cu(II polymer–metal complex showed the highest zone of inhibition because of its higher stability constant.

Influence of divalent metal on the decomposition products of hydrotalcite-like ternary systems M{sup II}-Al-Cr (M{sup II} = Zn, Cd)

Energy Technology Data Exchange (ETDEWEB)

Perez, M.R.; Crespo, I.; Ulibarri, M.A.; Barriga, C. [Departamento de Quimica Inorganica e Ingenieria Quimica, Campus de Rabanales, Universidad de Cordoba, Cordoba (Spain); Rives, V. [GIR-QUESCAT, Departamento de Quimica Inorganica, Universidad de Salamanca, Salamanca (Spain); Fernandez, J.M., E-mail: um1feroj@uco.es [Departamento de Quimica Inorganica e Ingenieria Quimica, Campus de Rabanales, Universidad de Cordoba, Cordoba (Spain)

2012-02-15

Highlights: Black-Right-Pointing-Pointer LDHs M{sup II}-Al-Cr (M = Zn, Cd) with Cr in the layer or interlayer have been prepared. Black-Right-Pointing-Pointer LDHs Zn-Al or Zn-Cr decompose by heating forming ZnO and ZnAl{sub 2}O{sub 4} or ZnO and ZnCr{sub 2}O{sub 4}. Black-Right-Pointing-Pointer LDHs Zn-Al-Cr give rise to the formation of ZnO and the mixed spinel ZnAl{sub 2-x}Cr{sub x}O{sub 4}. Black-Right-Pointing-Pointer LDH Cd-Al-Cr shows the formation of CdO, CdCr{sub 2-x}Al{sub x}O{sub 4}, and (Al, Cr){sub 2}O{sub 3} mixed oxide. Black-Right-Pointing-Pointer Calcination of the CdAl-CrO{sub 4} give rise to (Al, Cr){sub 2}O{sub 3} as the majority phase. - Abstract: Layered double hydroxides (LDHs) containing M{sup II}, Al{sup III}, and Cr{sup III} in the brucite-like layers (M = Cd, Zn) with different starting Al/Cr molar ratios and nitrate/carbonate as the interlayer anion have been prepared following the coprecipitation method at a constant pH: Zn{sup II}-Al{sup III}-Cr{sup III}-CO{sub 3}{sup 2-} at pH = 10, and Cd{sup II}-Al{sup III}-Cr{sup III}-NO{sub 3}{sup -} at pH = 8. Two additional M{sup II},Al{sup III}-LDH samples (M = Cd, Zn) with chromate ions (CrO{sub 4}{sup 2-}) in the interlayer have been prepared by ionic exchange at pH = 9 and 8, respectively, starting from M{sup II}-Al{sup III}-NO{sub 3}{sup -}. The samples have been characterised by absorption atomic spectrometry, powder X-ray diffraction (PXRD), FT-IR spectroscopy and transmission electron microscopy (TEM). Their thermal stability has been assessed by DTA-TG and mass spectrometric analysis of the evolved gases. The PXRD patterns of the solids calcined at 800 Degree-Sign C show diffraction lines corresponding to ZnO and ZnAl{sub 2-x}Cr{sub x}O{sub 4} for the Zn-containing samples, and diffraction lines attributed to CdO and CdCr{sub 2}O{sub 4} and (Al,Cr){sub 2}O{sub 3} for the Cd-containing ones. Additionally a minority oxide, Cd{sub 2}CrO{sub 5}, is observed to Cd{sup II}-Al{sup III

Structural, magnetic and electronic properties of rare earth ternary oxides Li Ln(II) 2 Ln(III)O4

International Nuclear Information System (INIS)

Malki, M.

1987-06-01

Properties of a new class of rare earth ternary oxides Li Ln(II) 2 Ln(III)O 4 where Ln(II) is a divalent metal (Sr, Eu) and Ln(III) a trivalent rare earth (Eu, Gd, Dy, Er and Y). These orthorhombic compounds (type Li Eu 3 O 4 ) allow the study of many magnetic phenomena and their evolution in function of the nature of Ln(II) and Ln(III): diamagnetic ions Sr 2+ , Y 3+ ; isotrope magnetic ions: Eu 2+ , Gd 3+ and anisotrope magnetic ions Dy 3+ , Er 3+ . Magnetic and electric properties are obtained by classical techniques and from hyperfine interaction by Moessbauer spectroscopy. The possibility to use several Moessbauer resonance (nuclei Eu 151, Gd 155, Dy 161 and Er 166) completes informations obtained by the macroscopic study [fr

Interfacial (o/w) properties of naphthetic acids and metal naphthenates, naphtenic acid characterization and metal naphthenate inhibition

Energy Technology Data Exchange (ETDEWEB)

Brandal, Oeystein

2005-07-01

Deposition of metal naphthenates in process facilities is becoming a huge problem for petroleum companies producing highly acidic crudes. In this thesis, the main focus has been towards the oil-water (o/w) interfacial properties of naphthenic acids and their ability to react with different divalent cations across the interface to form metal naphthenates. The pendant drop technique was utilized to determine dynamic interfacial tensions (IFT) between model oil containing naphthenic acid, synthetic as well as indigenous acid mixtures, and pH adjusted water upon addition of different divalent cations. Changes in IFT caused by the divalent cations were correlated to reaction mechanisms by considering two reaction steps with subsequent binding of acid monomers to the divalent cation. The results were discussed in light of degree of cation hydration and naphthenic acid conformation, which affect the interfacial conditions and thus the rate of formation of 2:1 complexes of acid and cations. Moreover, addition of non-ionic oil-soluble surfactants used as basis compounds in naphthenate inhibitors was found to hinder a completion of the reaction through interfacial dilution of the acid monomers. Formation and stability of metal naphthenate films at o/w interfaces were studied by means of Langmuir technique with a trough designed for liquid-liquid systems. The effects of different naphthenic acids, divalent cations, and pH of the subphase were investigated. The results were correlated to acid structure, cation hydration, and degree of dissociation, which all affect the film stability against compression. Naphthenic acids acquired from a metal naphthenate deposit were characterized by different spectroscopic techniques. The sample was found to consist of a narrow family of 4-protic naphthenic acids with molecular weights around 1230 g/mol. These acids were found to be very o/w interfacially active compared to normal crude acids, and to form Langmuir monolayers with stability

Outer Sphere Adsorption of Pb(II)EDTA on Goethite

Energy Technology Data Exchange (ETDEWEB)

Bargar, John R

1999-07-16

FTIR and EXAFS spectroscopic measurements were performed on Pb(II)EDTA adsorbed on goethite as functions of pH (4-6), Pb(II)EDTA concentration (0.11 {micro}M - 72 {micro}M), and ionic strength (16 {micro}M - 0.5M). FTIR measurements show no evidence for carboxylate-Fe(III) bonding or protonation of EDTA at Pb:EDTA = 1:1. Both FTIR and EXAFS measurements suggest that EDTA acts as a hexadentate ligand, with all four of its carboxylate and both amine groups bonded to Pb(II). No evidence was observed for inner-sphere Pb(II)-goethite bonding at Pb:EDTA = 1:1. Hence, the adsorbed complexes should have composition Pb(II)EDTA{sup 2{minus}}. Since substantial uptake of PbEDTA(II){sup 2{minus}} occurred in the samples, we infer that Pb(II)EDTA{sup 2{minus}} adsorbed as outer-sphere complexes and/or as complexes that lose part of their solvation shells and hydrogen bond directly to goethite surface sites. We propose the term ''hydration-sphere'' for the latter type of complexes because they should occupy space in the primary hydration spheres of goethite surface functional groups, and to distinguish this mode of sorption from common structural definitions of inner- and outer-sphere complexes. The similarity of Pb(II) uptake isotherms to those of other divalent metal ions complexed by EDTA suggests that they too adsorb by these mechanisms. The lack of evidence for inner-sphere EDTA-Fe(III) bonding suggests that previously proposed metal-ligand - promoted dissolution mechanisms should be modified, specifically to account for the presence of outer-sphere precursor species.

On the valence state of Yb and Ce in transition metal intermetallic compounds

International Nuclear Information System (INIS)

Boer, F.R. de; Dijkman, W.H.; Mattens, W.C.M.

1979-01-01

In the pure state Yb is a divalent metal, similar to Ca; in alloys it can become trivalent like the majority of the rare earth metals. Using a value of 38 kJ (mol Yb) -1 for the energy difference between divalent and trivalent Yb metal and using model calculations for the heat of formation of intermetallic compounds, the authors are able to account for the existing information on the valence state of Yb in transition metal compounds. A similar analysis of compounds of Ce with transition metals shows that a model in which the 4f electron is treated as a core electron, i.e. being absent in the tetravalent modification of Ce and present as a fully localized electron in trivalent Ce, does not apply. (Auth.)

Study of the heavy metal phytoextraction capacity of two forage species growing in an hydroponic environment.

Science.gov (United States)

Bonfranceschi, Barros A; Flocco, C G; Donati, E R

2009-06-15

Sorghum and alfalfa are two important forage crops. We studied their capacity for accumulating heavy metals in hydroponic experiments. Cadmium, nickel (as divalent cations) and chromium (trivalent and hexavalent) were added individually to the nutrient solution in a range of concentrations from 1 to 80 mg/l. Cr(III) was complexed with EDTA to increase its bioavailability. In alfalfa the increases in the concentration of Cr(III) and Cr(VI) favoured translocation of the metals to the upper parts of the plants, while with Ni(II) the level of translocated metal remained almost unchanged. In sorghum, both Cr(VI) and Ni(II) produced similar results to those in alfalfa, but increases in the concentrations of Cd(II) and Cr(III) in the solution lead to a higher accumulation of the metal at the root level. The concentrations referred to the dry biomass of alfalfa were 500 mg/kg (aerial parts) and 1500 mg/kg (roots) of Cr(III), simultaneously enhancing plant growth. Sorghum captured 500 and 1100 mg/kg (in aerial parts) and 300 and 2000 mg/kg (in roots) for Ni(II) and Cd(II) respectively, without significant damage to its biomass. The results show that alfalfa and sorghum can not only grow in the presence of high heavy metal concentration but also capture and translocate them to the aerial parts; because of these results special attention should be given to these crop plants for their possible use in phytoremediation of large contaminated areas but especially to avoid the possible introduction of the metals accumulated in aerial parts into the food chain when those plants grow in contaminated areas.

Study of the heavy metal phytoextraction capacity of two forage species growing in an hydroponic environment

Energy Technology Data Exchange (ETDEWEB)

Bonfranceschi, Barros A. [Centro de Investigacion y Desarrollo en Fermentaciones Industriales (CINDEFI, UNLP-CCT La Plata, CONICET), Facultad de Ciencias Exactas (UNLP), Calle 50 y 115, 1900 La Plata (Argentina); Flocco, C.G. [Consejo Nacional de Investigaciones Cientificas y Tecnologicas (CONICET), Buenos Aires (Argentina); Donati, E.R., E-mail: donati@quimica.unlp.edu.ar [Centro de Investigacion y Desarrollo en Fermentaciones Industriales (CINDEFI, UNLP-CCT La Plata, CONICET), Facultad de Ciencias Exactas (UNLP), Calle 50 y 115, 1900 La Plata (Argentina)

2009-06-15

Sorghum and alfalfa are two important forage crops. We studied their capacity for accumulating heavy metals in hydroponic experiments. Cadmium, nickel (as divalent cations) and chromium (trivalent and hexavalent) were added individually to the nutrient solution in a range of concentrations from 1 to 80 mg/l. Cr(III) was complexed with EDTA to increase its bioavailability. In alfalfa the increases in the concentration of Cr(III) and Cr(VI) favoured translocation of the metals to the upper parts of the plants, while with Ni(II) the level of translocated metal remained almost unchanged. In sorghum, both Cr(VI) and Ni(II) produced similar results to those in alfalfa, but increases in the concentrations of Cd(II) and Cr(III) in the solution lead to a higher accumulation of the metal at the root level. The concentrations referred to the dry biomass of alfalfa were 500 mg/kg (aerial parts) and 1500 mg/kg (roots) of Cr(III), simultaneously enhancing plant growth. Sorghum captured 500 and 1100 mg/kg (in aerial parts) and 300 and 2000 mg/kg (in roots) for Ni(II) and Cd(II) respectively, without significant damage to its biomass. The results show that alfalfa and sorghum can not only grow in the presence of high heavy metal concentration but also capture and translocate them to the aerial parts; because of these results special attention should be given to these crop plants for their possible use in phytoremediation of large contaminated areas but especially to avoid the possible introduction of the metals accumulated in aerial parts into the food chain when those plants grow in contaminated areas.

Study of the heavy metal phytoextraction capacity of two forage species growing in an hydroponic environment

International Nuclear Information System (INIS)

Bonfranceschi, Barros A.; Flocco, C.G.; Donati, E.R.

2009-01-01

Sorghum and alfalfa are two important forage crops. We studied their capacity for accumulating heavy metals in hydroponic experiments. Cadmium, nickel (as divalent cations) and chromium (trivalent and hexavalent) were added individually to the nutrient solution in a range of concentrations from 1 to 80 mg/l. Cr(III) was complexed with EDTA to increase its bioavailability. In alfalfa the increases in the concentration of Cr(III) and Cr(VI) favoured translocation of the metals to the upper parts of the plants, while with Ni(II) the level of translocated metal remained almost unchanged. In sorghum, both Cr(VI) and Ni(II) produced similar results to those in alfalfa, but increases in the concentrations of Cd(II) and Cr(III) in the solution lead to a higher accumulation of the metal at the root level. The concentrations referred to the dry biomass of alfalfa were 500 mg/kg (aerial parts) and 1500 mg/kg (roots) of Cr(III), simultaneously enhancing plant growth. Sorghum captured 500 and 1100 mg/kg (in aerial parts) and 300 and 2000 mg/kg (in roots) for Ni(II) and Cd(II) respectively, without significant damage to its biomass. The results show that alfalfa and sorghum can not only grow in the presence of high heavy metal concentration but also capture and translocate them to the aerial parts; because of these results special attention should be given to these crop plants for their possible use in phytoremediation of large contaminated areas but especially to avoid the possible introduction of the metals accumulated in aerial parts into the food chain when those plants grow in contaminated areas.

Divalent cations as modulators of neuronal excitability: Emphasis on copper and zinc

Directory of Open Access Journals (Sweden)

RICARDO DELGADO

2006-01-01

Full Text Available Based on indirect evidence, a role for synaptically released copper and zinc as modulators of neuronal activity has been proposed. To test this proposal directly, we studied the effect of copper, zinc, and other divalent cations on voltage-dependent currents in dissociated toad olfactory neurons and on their firing rate induced by small depolarizing currents. Divalent cations in the nanomolar range sped up the activation kinetics and increased the amplitude of the inward sodium current. In the micromolar range, they caused a dose dependent inhibition of the inward Na+ and Ca2+ currents (I Na and I Ca and reduced de amplitude of the Ca2+-dependent K+ outward current (I Ca-K. On the other hand, the firing rate of olfactory neurons increased when exposed to nanomolar concentration of divalent cations and decreased when exposed to micromolar concentrations. This biphasic effect of divalent cations on neuronal excitability may be explained by the interaction of these ions with high and low affinity sites in voltage-gated channels. Our results support the idea that these ions are normal modulators of neuronal excitability

Synthesis, characterization and biological studies of metal complexes of Co (II), Ni (II), Cu (II), Zn (II) with sulphadimidine-benzylidene

International Nuclear Information System (INIS)

Tahira, F.; Imran, M.; Iqbal, J.

2009-01-01

Some novel complexes of Co (II), Ni (II), Cu (II), and Zn (II) have been synthesized with a Schiff base ligand derived from sulphadimidine and benzaldehyde. The structural features of the complexes have been determined by elemental analysis, magnetic susceptibility, conductance measurement, UV/ Vis. and infrared spectroscopy. IR studies revealed that the Schiff base ligand Sulphadimidine-benzylidene has monoanionic bidendate nature and coordinate with metal ions through nitrogen atom of azomethine (>C = N) and deprotonated -NH group. All the complexes were assigned octahedral geometry on the basis of magnetic moment and electronic spectroscopic data. Low value of conductance supports their non-electrolytic nature. The ligand, as well as its complexes were checked for their in vitro antimicrobial activities against two gram positive bacterial strains, Bacillus subtillus. Staphylococcus aureus and one gram negative Salmonella typhae and five fungal strains, Nigrospora oryzae, Curvularia lunata, Drechslera rostrata, Aspergillus niger and Candida olbicans by disc diffusion method and agar plate technique, respectively. Both the antibacterial and antitungal activities of the synthesized metal complexes were found to be more as compared to parent drug and uncomplexed ligand. All the complexes contain coordinated water, which is lost at 141-160 degree C. (author)

Synthesis, characterization, in-vitro antimicrobial properties, molecular docking and DFT studies of 3-{(E-[(4,6-dimethylpyrimidin-2-ylimino]methyl} naphthalen-2-ol and Heteroleptic Mn(II, Co(II, Ni(II and Zn(II complexes

Directory of Open Access Journals (Sweden)

Chioma Festus

2018-03-01

Full Text Available Heteroleptic divalent metal complexes [M(L (bipy(Y]•nH2O (where M = Mn, Co, Ni, and Zn; L = Schiff base; bipy = 2,2’-bipyridine; Y = OAc and n = 0, 1 have been synthesized from pyrimidine Schiff base ligand 3-{(E-[(4,6-dimethylpyrimidin-2-ylimino]methyl} naphthalen-2-ol, 2,2’-bipyridine and metal(II acetate salts. The Schiff base and its complexes were characterized by analytical (CHN elemental analyses, solubility, melting point, conductivity measurements, spectral (IR, UV-vis, 1H and 13C-NMR and MS and magnetometry. The elemental analyses, Uv-vis spectra and room temperature magnetic moment data provide evidence of six coordinated octahedral geometry for the complexes. The metal complexes’ low molar conductivity values in dimethylsulphoxide suggested that they were non-ionic in nature. The compounds displayed moderate to good antimicrobial and antifungal activities against S. aureus, P. aeruginosa, E. coli, B. cereus, P. mirabilis, K. oxytoca, A. niger, A. flevus and R. Stolonifer. The compounds also exhibited good antioxidant potentials with ferrous ion chelation and, 1-diphenyl-2-picryl-hydrazyl (DPPH radical scavenging assays. Molecular docking studies showed a good interaction with drug targets used. The structural and electronic properties of complexes were further confirmed by density functional theory calculations.

Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

Science.gov (United States)

Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

2016-05-28

Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

Metal-ion exchange induced structural transformation as a way of forming novel Ni(II)− and Cu(II)−salicylaldimine structures

Energy Technology Data Exchange (ETDEWEB)

Wu, Jing-Yun, E-mail: jyunwu@ncnu.edu.tw; Tsai, Chi-Jou; Chang, Ching-Yun; Wu, Yung-Yuan

2017-02-15

A Zn(II)−salicylaldimine complex [Zn(L{sup salpyca})(H{sub 2}O)]{sub n} (1, where H{sub 2}L{sup salpyca}=4-hydroxy-3-(((pyridin-2-yl)methylimino)methyl)benzoic acid), with a one-dimensional (1D) chain structure, has been successfully converted to a discrete Ni(II)−salicylaldimine complex [Ni(L{sup salpyca})(H{sub 2}O){sub 3}] (2) and an infinite Cu(II)−salicylaldimine complex ([Cu(L{sup salpyca})]·3H{sub 2}O){sub n} (3) through a metal-ion exchange induced structural transformation process. However, such processes do not worked by Mn(II) and Co(II) ions. Solid-state structure analyses reveal that complexes 1–3 form comparable coordinative or supramolecular zigzag chains running along the crystallographic [201] direction. In addition, replacing Zn(II) ion by Ni(II) and Cu(II) ions caused changes in coordination environment and sphere of metal centers, from a 5-coordinate intermediate geometry of square pyramidal and trigonal bipyramidal in 1 to a 6-coordinate octahedral geometry in 2, and to a 4-coordiante square planar geometry in 3. This study shows that metal-ion exchange serves as a very efficient way of forming new coordination complexes that may not be obtained through direct synthesis. - Graphical abstract: A Zn(II)−salicylaldimine zigzag chain has been successfully converted to a Ni(II)−salicylaldimine supramolecular zigzag chain and a Cu(II)−salicylaldimine coordinative zigzag chain through metal-ion exchange induced structural transformations, which is not achieved by Mn(II) and Co(II) ions.

Removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution using rice husk-based activated carbon

Energy Technology Data Exchange (ETDEWEB)

Taha, Mohd F., E-mail: faisalt@petronas.com.my; Shaharun, Maizatul S. [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750, Perak Darul Ridzuan (Malaysia); Shuib, Anis Suhaila, E-mail: anisuha@petronas.com.my; Borhan, Azry [Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750, Perak Darul Ridzuan (Malaysia)

2014-10-24

An attempt was made to investigate the potential of rice husk-based activated carbon as an alternative low-cost adsorbent for the removal of Ni(II), Zn(II) and Pb(II) ions from single aqueous solution. Rice husk-based activated carbon was prepared via treatment of rice husk with NaOH followed by the carbonization process at 400°C for 2 hours. Three samples, i.e. raw rice husk, rice husk treated with NaOH and rice husk-based activated carbon, were analyzed for their morphological characteristics using field-emission scanning electron microscope/energy dispersive X-ray (FESEM/EDX). These samples were also analyzed for their carbon, hydrogen, nitrogen, oxygen and silica contents using CHN elemental analyzer and FESEM/EDX. The porous properties of rice husk-based activated carbon were determined by Brunauer-Emmett-Teller (BET) surface area analyzer, and its surface area and pore volume were 255 m{sup 2}/g and 0.17 cm{sup 2}/g, respectively. The adsorption studies for the removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution were carried out at a fixed initial concentration of metal ion (150 ppm) with variation amount of adsorbent (rice husk-based activated carbon) as a function of varied contact time at room temperature. The concentration of each metal ion was analyzed using atomic absorption spectrophotometer (AAS). The results obtained from adsorption studies indicate the potential of rice husk as an economically promising precursor for the preparation of activated carbon for removal of Ni(II), Zn(II) and Pb(II) ions from single aqueous solution. Isotherm and kinetic model analyses suggested that the experimental data of adsorption studies fitted well with Langmuir, Freundlich and second-order kinetic models.

(II) metal ions using phosphonate-functionalized polymer

Indian Academy of Sciences (India)

The metal binding was examined by the energy dispersive spectroscopy and scanning electron microscopy for the adsorbed Sr(II). Batch adsorption studies were performed by varying three parameters, namely initial pH, adsorbentdose and the contact time. The reaction kinetics was determined by the Langmuir, Freundlich, ...

Effects of polyamines on the DNA-reactive properties of dimeric mithramycin complexed with cobalt(II): implications for anticancer therapy.

Science.gov (United States)

Hou, Ming-Hon; Lu, Wen-Je; Huang, Chun-Yu; Fan, Ruey-Jane; Yuann, Jeu-Ming P

2009-06-09

Few studies have examined the effects of polyamines on the action of DNA-binding anticancer drugs. Here, a Co(II)-mediated dimeric mithramycin (Mith) complex, (Mith)(2)-Co(II), was shown to be resistant to polyamine competition toward the divalent metal ion when compared to the Fe(II)-mediated drug complexes. Surface plasmon resonance experiments demonstrated that polyamines interfered with the binding capacity and association rates of (Mith)(2)-Co(II) binding to DNA duplexes, while the dissociation rates were not affected. Although (Mith)(2)-Co(II) exhibited the highest oxidative activity under physiological conditions (pH 7.3 and 37 degrees C), polyamines (spermine in particular) inhibited the DNA cleavage activity of the (Mith)(2)-Co(II) in a concentration-dependent manner. Depletion of intracellular polyamines by methylglyoxal bis(guanylhydrazone) (MGBG) enhanced the sensitivity of A549 lung cancer cells to (Mith)(2)-Co(II), most likely due to the decreased intracellular effect of polyamines on the action of (Mith)(2)-Co(II). Our study suggests a novel method for enhancing the anticancer activity of DNA-binding metalloantibiotics through polyamine depletion.

Compounds of divalent thulium, neodymium, and dysprosium

International Nuclear Information System (INIS)

Bochkarev, M.N.; Fedushkin, I.L.; Trifonov, A.A.; Fagin, A.A.; Kirillov, E.N.

1998-01-01

Full text: Judging on the Ln(II)/Ln(III) potentials Tm, Nd, and Dy are the first candidates after Sm, Eu, and Yb for the preparation of Ln(II) compounds. The first molecular Tm(II) derivatives, TmI 2 (DME) 3 (I), has been obtained recently by the reduction of TmI 3 with thulium metal in DME (1,2-dimethoxyethane). The tetrahydrofuran (THF) analogue, TmI 2 (THF) 5 , was synthesized similarly. In the case of TmBI 3 and TmCl 3 the same reaction does not occur. The compound I is inert toward naphthalene, anthracene, phenylacetylene, CpH, (Me 3 Si) 2 NH, 2,4,6-t-Bu 3 C 6 H 2 OH, Cp 2 V, Cp 2 Fe, or Cp 3 Er. The reactions of I with PhOH, Ph 3 COH, 3,6-t-Bu 2 C 6 H 2 (OH) 2 -1,2 (Cat), and calixarene (Cal) produce, Ph 3 COTmI 2 (DME) 2 , (Cat)TmI(DME) 2 , and (Cal)TmI, correspondingly. The attempts to use I for preparation of the other Tm(II) complexes failed. In all cases (reactions with C 10 H 8 Li, CpK, [1,3-(Me 3 Si) 2 C 5 H 3 ]MgCl, and [Cp'-SiMe 2 -Ind']K 2 ) the Tm(III) derivatives (respectively, (C 10 H 8 Tm) 2 C 10 H 8 , Cp 3 Tm, [1,3-(Me 3 Si) 2 C 5 H 3 ] 2 TmCl, and Cp'-SiMe 2 -Ind')TmI) were obtained. The new stable Tm(II) complex, PhOTmI(DME) 2 (II), has been synthesized by the reduction of I with potassium metal in DME. The product was isolated as the green crystals with μ eff 4.6 BM. Unlike TmI 3 , NdI 3 and DyI 3 can not be reduced by metallic neodymium, dysprosium or sodium in DME or THF. Re-investigation of the product formed in the reaction of NdCl 3 with a lack of Li and naphthalene which was claimed before as NdCl 2 (THF) 2 has shown that this is a mixture of Nd(III) naphthalene complexes of the type [(NdCl 2 (THF) 2 ]nC 10 H 8 (n = 4- 7) (III). Nevertheless the product may be used instead of NdCl 2 for the preparation of RNdCl 2 type complexes. The reactions of III with t-BuNCH=CHNBu-t (DAD), PhCH=CHCH=CHPh (DBD), and PhCH=CHPh afford (DAD)NdCl 2 (THF) 2 , (DBD)[NdCl 2 (THF) 2 ] 2 , and (PhCHCHPh)[NdCl 2 ] 2 (THF) 3 , respectively. The iodides of Nd(II

Metal waste forms from treatment of EBR-II spent fuel

International Nuclear Information System (INIS)

Abraham, D. P.

1998-01-01

Demonstration of Argonne National Laboratory's electrometallurgical treatment of spent nuclear fuel is currently being conducted on irradiated, metallic driver fuel and blanket fuel elements from the Experimental Breeder Reactor-II (EBR-II) in Idaho. The residual metallic material from the electrometallurgical treatment process is consolidated into an ingot, the metal waste form (MWF), by employing an induction furnace in a hot cell. Scanning electron microscopy (SEM) and chemical analyses have been performed on irradiated cladding hulls from the driver fuel, and on samples from the alloy ingots. This paper presents the microstructures of the radioactive ingots and compares them with observations on simulated waste forms prepared using non-irradiated material. These simulated waste forms have the baseline composition of stainless steel - 15 wt % zirconium (SS-15Zr). Additions of noble metal elements, which serve as surrogates for fission products, and actinides are made to that baseline composition. The partitioning of noble metal and actinide elements into alloy phases and the role of zirconium for incorporating these elements is discussed in this paper

Adsorption of aqueous Cd(II) and Pb(II) on activated carbon nanopores prepared by chemical activation of doum palm shell.

Science.gov (United States)

Gaya, Umar Ibrahim; Otene, Emmanuel; Abdullah, Abdul Halim

2015-01-01

Non-uniformly sized activated carbons were derived from doum palm shell, a new precursor, by carbonization in air and activation using KOH, NaOH and ZnCl2. The activated carbon fibres were characterised by X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, particle size analysis and evaluated for Cd(II) and Pb(II) removal. The 40-50 nm size, less graphitic, mesoporous NaOH activated carbon yielded high adsorption efficiency, pointing largely to the influence surface area. The performance of the KOH based activated carbon was arguably explained for the first time in terms of crystallinity. The efficiencies of the mesoporous ZnCl2-formulated activated carbon diminished due to the presence of larger particles. Batch adsorption of divalent metals revealed dependence on adsorbent dose, agitation time, pH and adsorbate concentrations with high adsorption efficiencies at optimum operating parameters. The equilibrium profiles fitted Langmuir and Freundlich isotherms, and kinetics favoured pseudo-second order model. The study demonstrated the practicability of the removal of alarming levels of cadmium and lead ions from industrial effluents.

Template synthesis and characterization of biologically active transition metal complexes comprising 14-membered tetraazamacrocyclic ligand

Directory of Open Access Journals (Sweden)

DHARMPAL SINGH

2010-02-01

Full Text Available A novel series of complexes of the type [M(C28H24N4X2], whereM = Co(II, Ni(II, Cu(II, Zn(II and Cd(II, X = Cl–, NO3–, CH3COO– and (C28H24N4 corresponds to the tetradentate macrocyclic ligand, were synthe¬sized by template condensation of 1,8-diaminonaphthalene and diacetyl in the presence of divalent metal salts in methanolic medium. The complexes were characterized by elemental analyses, conductance and magnetic measurements, as well as by UV/Vis, NMR, IR and MS spectroscopy. The low values of the molar conductance indicate non-electrolyte type of complexes. Based on these spectral data, a distorted octahedral geometry may be proposed for all of these complexes. All the synthesized macrocyclic complexes were tested for in vitro antibacterial activity against some pathogenic bacterial strains, viz Bacillus cereus, Salmonella typhi, Escherichia coli and Staphylococcus aureus. The MIC values shown by the complexes against these bacterial strains were compared with the MIC shown by the standard antibiotics linezolid and cefaclor.

Abolition of Biofilm Formation in Urinary Tract Escherichia coli and Klebsiella Isolates by Metal Interference through Competition for Fur

DEFF Research Database (Denmark)

Hancock, Viktoria; Dahl, Malin; Klemm, Per

2010-01-01

Bacterial biofilms are associated with a large number of persistent and chronic infections. Biofilm-dwelling bacteria are particularly resistant to antibiotics and immune defenses, which makes it hard if not impossible to eradicate biofilm-associated infections. In the urinary tract, free iron...... is strictly limited but is critical for bacterial growth. Biofilm-associated Escherichia coli cells are particularly desperate for iron. An attractive way of inhibiting biofilm formation is to fool the bacterial regulatory system for iron uptake. Here, we demonstrate that biofilm formation can be impaired...... by the addition of divalent metal ions, such as Zn(II) and Co(II), which inhibit iron uptake by virtue of their higher-than-iron affinity for the master controller protein of iron uptake, Fur. Reduced biofilm formation of urinary tract-infectious E. coli strains in the presence of Zn(II) was observed...

Synthesis, spectral characterization thermal stability, antimicrobial studies and biodegradation of starch–thiourea based biodegradable polymeric ligand and its coordination complexes with [Mn(II), Co(II), Ni(II), Cu(II), and Zn(II)] metals

OpenAIRE

Nahid Nishat; Ashraf Malik

2016-01-01

A biodegradable polymer was synthesized by the modification reaction of polymeric starch with thiourea which is further modified by transition metals, Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). All the polymeric compounds were characterized by (FT-IR) spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, UV–visible spectra, magnetic moment measurements, thermogravimetric analysis (TGA) and antibacterial activities. Polymer complexes of Mn(II), Co(II) and Ni(II) show octahedral geometry, wh...

Trace Metal Requirements and Interactions in Symbiodinium kawagutii

Directory of Open Access Journals (Sweden)

Irene B. Rodriguez

2018-02-01

Full Text Available Photosynthetic organisms need trace metals for various biological processes and different groups of microalgae have distinctive obligate necessities due to their respective biochemical requirements and ecological niches. We have previously shown that the dinoflagellate Symbiodinium kawagutii requires high concentrations of bioavailable Fe to achieve optimum growth. Here, we further explored the trace metal requirements of S. kawagutii with intensive focus on the effect of individual metal and its interaction with other divalent metals. We found that low Zn availability significantly decreases growth rates and results in elevated intracellular Mn, Co, Ni, and Fe quotas in the dinoflagellate. The results highlight the complex interaction among trace metals in S. kawagutii and suggest either metal replacement strategy to counter low Zn availability or enhanced uptake of other metals by non-specific divalent metal transporters. In this work, we also examined the Fe requirement of S. kawagutii using continuous cultures. We validated that 500 pM of Fe′ was sufficient to support maximum cell density during steady state growth period either at 26 or 28°C. This study shows that growth of S. kawagutii was limited by metal availability in the following order, Fe > Zn > Mn > Cu > Ni > Co. The fundamental information obtained for the free-living Symbiodinium shall provide insights into how trace metal availability, either from ambient seawater or hosts, affects growth and proliferation of symbiotic dinoflagellates and the interaction between symbiont and their hosts.

Potentiometric studies on ternary complexes involving some divalent transition metal ions, gallic acid and biologically abundant aliphatic dicarboxylic acids in aqueous solutions

Directory of Open Access Journals (Sweden)

Abdelatty Mohamed Radalla

2015-06-01

Full Text Available Formation of binary and ternary complexes of the divalent transition metal ions, Cu2+, Ni2+, Co2+ and Zn2+ with gallic acid and the biologically important aliphatic dicarboxylic acids (adipic, succinic, malic, malonic, maleic, tartaric and oxalic acids were investigated by means of the potentiometric technique at 25 °C and I = 0.10 mol dm−3 NaNO3. The acid-base properties of the ligands were investigated and discussed. The acidity constants of gallic acid and aliphatic dicarboxylic acids were determined and used for determining the stability constants of the binary and ternary complexes formed in the aqueous medium under the above experimental conditions. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes are inferred from the corresponding potentiometric pH-metric titration curves. The ternary complex formation was found to occur in a stepwise manner. The stability constants of these binary and ternary systems were calculated. The values of Δ log K, percentage of relative stabilization (%R.S. and log X were evaluated and discussed. The concentration distribution of the various complex species formed in solution was evaluated and discussed. The mode of chelation of ternary complexes formed was ascertained by conductivity measurements.

CE of phytosiderophores and related metal species in plants.

Science.gov (United States)

Xuan, Yue; Scheuermann, Enrico B; Meda, Anderson R; Jacob, Peter; von Wirén, Nicolaus; Weber, Günther

2007-10-01

Phytosiderophores (PS) and the closely related substance nicotianamine (NA) are key substances in metal uptake into graminaceous plants. Here, the CE separation of these substances and related metal species is demonstrated. In particular, the three PS 2'-deoxymugineic acid (DMA), mugineic acid (MA), and 3-epi-hydroxymugineic acid (epi-HMA), and NA, are separated using MES/Tris buffer at pH 7.3. Moreover, three Fe(III) species of the different PS are separated without any stability problems, which are often present in chromatographic analyses. Also divalent metal species of Cu, Ni, and Zn with the ligands DMA and NA are separated with the same method. By using a special, zwitterionic CE capillary, even the separation of two isomeric Fe(III) chelates with the ligand ethylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid (EDDHA) is possible (i.e., meso-Fe(III)-EDDHA and rac-Fe(III)-EDDHA), and for fast separations of NA and respective divalent and trivalent metal species, a polymer CE microchip with suppressed EOF is described. The proposed CE method is applicable to real plant samples, and enables to detect changes of metal species (Cu-DMA, Ni-NA), which are directly correlated to biological processes.

Assessment of metal sorption mechanisms by aquatic macrophytes using PIXE analysis

Energy Technology Data Exchange (ETDEWEB)

Módenes, A.N., E-mail: anmodenes@yahoo.com.br [Department of Chemical Engineering-Postgraduate Program, West Parana State University, Campus of Toledo, rua da Faculdade 645, Jd. La Salle, 85903-000 Toledo, PR (Brazil); Espinoza-Quiñones, F.R.; Santos, G.H.F.; Borba, C.E. [Department of Chemical Engineering-Postgraduate Program, West Parana State University, Campus of Toledo, rua da Faculdade 645, Jd. La Salle, 85903-000 Toledo, PR (Brazil); Rizzutto, M.A. [Physics Institute, University of São Paulo, Rua do Matão s/n, Travessa R 187, 05508-900 São Paulo, SP (Brazil)

2013-10-15

Highlights: • Divalent metal ion removals by Egeria densa biosorbent. • Multielements concentrations in biosorbent samples by PIXE analysis. • Elements mass balance in liquid and solid phase before and after metal removals. • Assessment of the mechanisms involved in Cd{sup 2+} and Zn{sup 2+} removal by biosorbent. • Confirmation of the signature of ion exchange process in metal removal. -- Abstract: In this work, a study of the metal sorption mechanism by dead biomass has been performed. All batch metal biosorption experiments were performed using the aquatic macrophyte Egeria densa as biosorbent. Divalent cadmium and zinc solutions were used to assess the sorption mechanisms involved. Using a suitable equilibrium time of 2 h and a mixture of 300 mg biosorbent and 50 mL metal solution at pH 5, monocomponent sorption experiments were performed. In order to determine the residual amounts of metals in the aqueous solutions and the concentrations of removed metals in the dry biomass, Particle Induced X-ray Emission (PIXE) measurements in thin and thick target samples were carried out. Based on the strong experimental evidence from the mass balance among the major elements participating in the sorption processes, an ion exchange process was identified as the mechanism responsible for metal removal by the dry biomass.

Lightweight Metal RubberTM Sensors and Interconnects, Phase II

Data.gov (United States)

National Aeronautics and Space Administration — The objective of this NASA Phase II program is to develop and increase the Technology Readiness Level of multifunctional Metal RubberTM (MRTM) materials that can be...

Assessment of heavy metal tolerance and hexavalent chromium reducing potential of Corynebacterium paurometabolum SKPD 1204 isolated from chromite mine seepage

Directory of Open Access Journals (Sweden)

Amal Kanti Paul

2016-07-01

Full Text Available Corynebacterium paurometabolum SKPD 1204 (MTCC 8730, a heavy metal tolerant and chromate reducing bacterium isolated from chromite mine seepage of Odisha, India has been evaluated for chromate reduction under batch culture. The isolate was found to tolerate metals like Co(II, Cu(II, Ni(II, Mn(II, Zn(II, Fe(III and Hg(II along with Cr(VI and was resistant to different antibiotics as evaluated by disc-diffusion method. The isolate, SKPD 1204 was found to reduce 62.5% of 2 mM Cr(VI in Vogel Bonner broth within 8 days of incubation. Chromate reduction capability of SKPD 1204 decreased with increase in Cr(VI concentration, but increased with increase in cell density and attained its maximum at 1010 cells/mL. Chromate reducing efficiency of SKPD 1204 was promoted in the presence of glycerol and glucose, while the highest reduction was recorded at pH 7.0 and 35 °C. The reduction process was inhibited by divalent cations Zn(II, Cd(II, Cu(II, and Ni(II, but not by Mn(II. Anions like nitrate, phosphate, sulphate and sulphite was found to be inhibitory to the process of Cr(VI reduction. Similarly, sodium fluoride, carbonyl cyanide m-chlorophenylhydrazone, sodium azide and N, N,-Di cyclohexyl carboiimide were inhibitory to chromate reduction, while 2,4-dinitrophenol appeared to be neither promotive nor inhibitory to the process.

Micellar effect on metal-ligand complexes of Co(II, Ni(II, Cu(II and Zn(II with citric acid

Directory of Open Access Journals (Sweden)

Nageswara Rao Gollapalli

2009-12-01

Full Text Available Chemical speciation of citric acid complexes of Co(II, Ni(II, Cu(II and Zn(II was investigated pH-metrically in 0.0-2.5% anionic, cationic and neutral micellar media. The primary alkalimetric data were pruned with SCPHD program. The existence of different binary species was established from modeling studies using the computer program MINIQUAD75. Alkalimetric titrations were carried out in different relative concentrations (M:L:X = 1:2:5, 1:3:5, 1:5:3 of metal (M to citric acid. The selection of best chemical models was based on statistical parameters and residual analysis. The species detected were MLH, ML2, ML2H and ML2H2. The trend in variation of stability constants with change in mole fraction of the medium is explained on the basis of electrostatic and non-electrostatic forces. Distributions of the species with pH at different compositions of micellar media are also presented.

Adsorption of Cd(II) Metal Ion on Adsorbent beads from Biomass Saccharomycess cereviceae - Chitosan

Science.gov (United States)

Hasri; Mudasir

2018-01-01

The adsorbent beads that was preparation from Saccharomycess cereviceae culture strain FN CC 3012 and shrimp shells waste and its application for adsorption of Cd (II) metal ion has been studied. The study start with combination of Saccharomycess cereviceae biomass to chitosan (Sc-Chi), contact time, pH of solution and initial concentration of cations. Total Cd(II) metal ion adsorbed was calculated from the difference of metal ion concentration before and after adsorption by AAS. The results showed that optimum condition for adsorption of Cd(II) ions by Sc-Chi beads was achieved with solution pH of 4, contact time of 60 minutes and initial concentration adsorption 100mg/L. The hydroxyl (-OH) and amino (-NH2) functional groups were believed to be responsible for the adsorption of Cd(II) ions.

High pressure metallization of Mott Insulators: Magnetic, structural and electronic properties

International Nuclear Information System (INIS)

Pasternak, M.P.; Hearne, G.; Sterer, E.; Taylor, R.D.; Jeanloz, R.

1993-01-01

High pressure studies of the insulator-metal transition in the (TM)I 2 (TM = V, Fe, Co and Ni) compounds are described. Those divalent transition-metal iodides are structurally isomorphous and classified as Mott Insulators. Resistivity, X-ray diffraction and Moessbauer Spectroscopy were employed to investigate the electronic, structural, and magnetic properties as a function of pressure both on the highly correlated and on the metallic regimes

Heavy metal / polyacid interaction : an electrochemical study of the binding of Cd(II), Pb(II) and Zn(II) to polycarboxylic and humic acids

NARCIS (Netherlands)

Cleven, R.F.M.J.

1984-01-01

Polyelectrolyte effects in the interaction of heavy metal ions with model polycarboxylic acids have been described, in order to establish the relevance of these effects in the interaction of heavy metal ions with naturally occurring humic and fulvic acids. The model systems consisted of Cd(II),

Mixed ligand complexes of alkaline earth metals: Part XII. Mg(II, Ca(II, Sr(II and Ba(II complexes with 5-chlorosalicylaldehyde and salicylaldehyde or hydroxyaromatic ketones

Directory of Open Access Journals (Sweden)

MITHLESH AGRAWAL

2002-04-01

Full Text Available The reactions of alkaline earth metal chlorides with 5-chlorosalicylaldehyde and salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been carried out in 1 : 1 : 1 mole ratio and the mixed ligand complexes of the type MLL’(H2O2 (where M = Mg(II, Ca(II, Sr(II and Ba(II, HL = 5-chlorosalicylaldehyde and HL’ = salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been isolated. These complexes were characterized by TLC, conductance measurements, IR and 1H-NMR spectra.

Biologically active new Fe(II, Co(II, Ni(II, Cu(II, Zn(II and Cd(II complexes of N-(2-thienylmethylenemethanamine

Directory of Open Access Journals (Sweden)

C. SPÎNU

2008-04-01

Full Text Available Iron(II, cobalt(II, nickel (II, copper (II, zinc(II and cadmium(II complexes of the type ML2Cl2, where M is a metal and L is the Schiff base N-(2-thienylmethylenemethanamine (TNAM formed by the condensation of 2-thiophenecarboxaldehyde and methylamine, were prepared and characterized by elemental analysis as well as magnetic and spectroscopic measurements. The elemental analyses suggest the stoichiometry to be 1:2 (metal:ligand. Magnetic susceptibility data coupled with electronic, ESR and Mössbauer spectra suggest a distorted octahedral structure for the Fe(II, Co(II and Ni(II complexes, a square-planar geometry for the Cu(II compound and a tetrahedral geometry for the Zn(II and Cd(II complexes. The infrared and NMR spectra of the complexes agree with co-ordination to the central metal atom through nitrogen and sulphur atoms. Conductance measurements suggest the non-electrolytic nature of the complexes, except for the Cu(II, Zn(II and Cd(II complexes, which are 1:2 electrolytes. The Schiff base and its metal chelates were screened for their biological activity against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa and the metal chelates were found to possess better antibacterial activity than that of the uncomplexed Schiff base.

Acidic pH and divalent cation sensing by PhoQ are dispensable for systemic salmonellae virulence.

Science.gov (United States)

Hicks, Kevin G; Delbecq, Scott P; Sancho-Vaello, Enea; Blanc, Marie-Pierre; Dove, Katja K; Prost, Lynne R; Daley, Margaret E; Zeth, Kornelius; Klevit, Rachel E; Miller, Samuel I

2015-05-23

Salmonella PhoQ is a histidine kinase with a periplasmic sensor domain (PD) that promotes virulence by detecting the macrophage phagosome. PhoQ activity is repressed by divalent cations and induced in environments of acidic pH, limited divalent cations, and cationic antimicrobial peptides (CAMP). Previously, it was unclear which signals are sensed by salmonellae to promote PhoQ-mediated virulence. We defined conformational changes produced in the PhoQ PD on exposure to acidic pH that indicate structural flexibility is induced in α-helices 4 and 5, suggesting this region contributes to pH sensing. Therefore, we engineered a disulfide bond between W104C and A128C in the PhoQ PD that restrains conformational flexibility in α-helices 4 and 5. PhoQ(W104C-A128C) is responsive to CAMP, but is inhibited for activation by acidic pH and divalent cation limitation. phoQ(W104C-A128C) Salmonella enterica Typhimurium is virulent in mice, indicating that acidic pH and divalent cation sensing by PhoQ are dispensable for virulence.

Adiabatic differential scanning calorimetric study of divalent cation induced DNA - DPPC liposome formulation compacted for gene delivery

Directory of Open Access Journals (Sweden)

Erhan Süleymanoglu

2004-11-01

Full Text Available Complexes between nucleic acids and phospholipid vesicles have been developed as stable non-viral gene delivery vehicles. Currently employed approach uses positively charged lipid species and a helper zwitterionic lipid, the latter being applied for the stabilization of the whole complex. However, besides problematic steps during their preparation, cationic lipids are toxic for cells. The present work describes some energetic issues pertinent to preparation and use of neutral lipid-DNA self-assemblies, thus avoiding toxicity of lipoplexes. Differential scanning calorimetry data showed stabilization of polynucleotide helix upon its interaction with liposomes in the presence of divalent metal cations. It is thus possible to suggest this self-assembly as an improved formulation for use in gene delivery.

One-step synthesis of gold bimetallic nanoparticles with various metal-compositions

International Nuclear Information System (INIS)

Bratescu, Maria Antoaneta; Takai, Osamu; Saito, Nagahiro

2013-01-01

Highlights: ► Synthesis of bimetallic nanoparticles in an aqueous solution discharge. ► Alloying gold with divalent sp metals, trivalent sp metals, 3d or 4d metals. ► Formation mechanism of bimetallic nanoparticles by metal reduction and gold erosion. ► Blue and red shift of surface plasmon resonance. -- Abstract: A rapid, one-step process for the synthesis of bimetallic nanoparticles by simultaneous metal reduction and gold erosion in an aqueous solution discharge was investigated. Gold bimetallic nanoparticles were obtained by alloying gold with various types of metals belonging to one of the following categories: divalent sp metals, trivalent sp metals, 3d or 4d metals. The composition of the various gold bimetallic nanoparticles obtained depends on electrochemical factors, charge transfer between gold and other metal, and initial concentration of metal in solution. Transmission electron microscopy and energy dispersive spectroscopy show that the gold bimetallic nanoparticles were of mixed pattern, with sizes of between 5 and 20 nm. A red-shift of the surface plasmon resonance band in the case of the bimetallic nanoparticles Au–Fe, Au–Ga, and Au–In, and a blue-shift of the plasmon band of the Au–Ag nanoparticles was observed. In addition, the interaction of gold bimetallic nanoparticles with unpaired electrons, provided by a stable free radical molecule, was highest for those NPs obtained by alloying gold with a 3d metal

Solubility of hydrogen in transition metals

International Nuclear Information System (INIS)

Lee, H.M.

1976-01-01

Correlations exist between the heat of solution of hydrogen and the difference in energy between the lowest lying energy levels of the trivalent d/sup n-1/s electronic configuration and the divalent d/sup n-2/s 2 (or the tetravalent d/sup n/) configuration of the neutral gaseous atoms. The trends observed in the transition metal series are discussed in relation to the number of valence electrons per atom in the transition elements in their metallic and neutral states

Effect of divalent ions on the optical emission behavior of protein thin films

Energy Technology Data Exchange (ETDEWEB)

Bhowal, Ashim Chandra, E-mail: ashimbhowal111@gmail.com; Kundu, Sarathi [Physical Sciences Division, Institute of Advanced Study in Science and Technology, Vigyan Path, Paschim Boragaon, Garchuk, Guwahati, Assam 781035 (India)

2016-05-06

Photoluminescence behaviors of proteinthin film, bovine serum albumin (BSA) have been studied in the presence of three divalent ions (Mg{sup 2+}, Ca{sup 2+} and Ba{sup 2+}) at different temperatures using fluorescence spectroscopy. Film thickness and morphology have been studied using atomic force microscopy. Variation of different physicochemical parameters like temperature, solvent polarity, pH, ionic strength, substrate binding etc. can make conformational changes in the protein structure and hence influences the emission behavior.In thin film conformation of BSA, dynamic quenching behavior has beenidentified in the presence of all the three divalent ions at pH≈ 5.5. Depending upon the charge density of the divalent ions interaction with protein molecules modifies and as a result quenching efficiency varies. Also after heat treatment, conformation of the protein molecules changes and as a result the quenching efficiency enhances than that of the unheated films. Studies on such protein-ion interactions and conformational variation may explore various functions of protein when it will adsorb on soft surfaces like membranes, vesicles, etc.

Quantum Chemical Investigation on the Antioxidant Activity of Neutral and Anionic Forms of Juglone: Metal Chelation and Its Effect on Radical Scavenging Activity

Directory of Open Access Journals (Sweden)

Aymard Didier Fouegue Tamafo

2017-01-01

Full Text Available The chelation ability of divalent Mg, Ca, Fe, Co, Ni, Cu, Zn, and monovalent Cu ions by neutral and anionic forms of juglone has been investigated at DFT/B3LYP/6-31+G(d,p level of theory in gas and aqueous phases. It is noteworthy that only the 1 : 1 stoichiometry was considered herein. The effects of these metals on the radical scavenging activity of neutral juglone were evaluated via the usual descriptors of hydrogen atom transfer. According to our results, metal chelation by the two forms of juglone was spontaneous and exothermic in both media. Based on the binding energies, Cu(II ion showed the highest affinity for the ligands. QTAIM analyses identified the metal-ligand bonds as intermediate type interactions in all the chelates, except those of Ca and Mg. It was also found that the chelates were better radical scavengers than the ligands. In the gas phase, the scavenging activity of the compounds was found to be governed by direct hydrogen atom transfer, the Co(II chelate being the most reactive. In the aqueous phase also, the sequential proton loss electron transfer was preferred by all the molecules, while the Cu(II chelates were the most reactive.

Cross-sectional study of expression of divalent metal transporter-1, transferrin, and hepcidin in blood of smelters who are occupationally exposed to manganese

Directory of Open Access Journals (Sweden)

Qiyuan Fan

2016-09-01

Full Text Available Background Manganese (Mn is widely used in industries including the manufacture of Mn-iron (Fe alloy. Occupational Mn overexposure causes manganism. Mn is known to affect Fe metabolism; this study was designed to test the hypothesis that workers exposed to Mn may have an altered expression of mRNAs encoding proteins in Fe metabolism. Methods Workers occupationally exposed to Mn (n = 71 from a Mn–Fe alloy factory and control workers without Mn-exposure (n = 48 from a pig-iron plant from Zunyi, China, were recruited for this study. Blood samples were collected into Trizol-containing tubes. Total RNA was isolated, purified, and subjected to real-time RT-PCR analysis. Metal concentrations were quantified by atomic absorption spectrophotometry. Results Working environment and genetic background of both groups were similar except for marked differences in airborne Mn concentrations (0.18 mg/m3 in Mn–Fe alloy factory vs. 0.0022 mg/m3 in pig-Fe plant, and in blood Mn levels (34.3 µg/L vs. 10.4 µg/L. Mn exposure caused a significant decrease in the expression of divalent metal transporter-1 (DMT1, transferrin (Tf and hepcidin by 58.2%, 68.5% and 61.5%, respectively, as compared to controls, while the expression of transferrin receptor (TfR was unaltered. Linear regression analysis revealed that expressions of DMT1, Tf and hepcidin were inversely correlated with the accumulative Mn exposure; the correlation coefficients (r are −0.47, −0.54, and −0.49, respectively (p < 0.01. Conclusion The data suggest that occupational Mn exposure causes decreased expressions of DMT1, Tf and hepcidin in blood cells; the finding will help understand the mechanism underlying Mn exposure-associated alteration in Fe homeostasis among workers.

Indolenine meso-substituted dibenzotetraaza[14]annulene and its coordination chemistry toward the transition metal ions Mn(III), Fe(III), Co(II), Ni(II), Cu(II), and Pd(II).

Science.gov (United States)

Khaledi, Hamid; Olmstead, Marilyn M; Ali, Hapipah Mohd; Thomas, Noel F

2013-02-18

A new dibenzotetraaza[14]annulene bearing two 3,3-dimethylindolenine fragments at the meso positions (LH(2)), has been synthesized through a nontemplate method. X-ray crystallography shows that the whole molecule is planar. The basicity of the indolenine ring permits the macrocycle to be protonated external to the core and form LH(4)(2+)·2Cl(-). Yet another structural modification having strong C-H···π interactions was found in the chloroform solvate of LH(2). The latter two modifications are accompanied by a degree of nonplanar distortion. The antiaromatic core of the macrocycle can accommodate a number of metal ions, Mn(III), Fe(III), Co(II), Ni(II) and Cu(II), to form complexes of [Mn(L)Br], [Mn(L)Cl], [Fe(LH(2))Cl(2)](+)·Cl(-), [Co(L)], [Ni(L)], and [Cu(L)]. In addition, the reaction of LH(2) with the larger Pd(II) ion leads to the formation of [Pd(2)(LH(2))(2)(OAc)(4)] wherein the macrocycle acts as a semiflexible ditopic ligand to coordinate pairs of metal ions via its indolenine N atoms into dinuclear metallocycles. The compounds LH(2), [Co(L)], and [Ni(L)] are isostructural and feature close π-stacking as well as linear chain arrangements in the case of the metal complexes. Variable temperature magnetic susceptibility measurements showed thermally induced paramagnetism in [Ni(L)].

Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Stronthium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

Energy Technology Data Exchange (ETDEWEB)

Smith, Robert W.; Fujita, Yoshiko

2007-11-07

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers’ exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadose zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the

Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Strontium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

International Nuclear Information System (INIS)

Smith, Robert W.; Fujita, Yoshiko

2007-01-01

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadose zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the

Catalytic properties of lanthanide amide, imide and nitride formed by thermal degradation of liquid ammonia solutions of Eu and Yb metal

International Nuclear Information System (INIS)

Imamura, H.; Mizuno, K.; Ohishi, K.; Suda, E.; Kanda, K.; Sakata, Y.; Tsuchiya, S.

1998-01-01

The catalytic properties of lanthanide amide, imide and nitride prepared by the use of liquid ammonia solutions of lanthanide metals (Ln=Eu and Yb) were studied for catalytic hydrogenation. The reaction of Eu or Yb metal solutions in liquid ammonia with silica yielded SiO 2 -grafted lanthanide amide in the divalent state. The divalent amide showed catalytic activity for the selective hydrogenation of dienes and benzene. It was found that partial hydrogenation of benzene occurred with a very high selectivity for cyclohexene. Amides of calcium, strontium and barium were examined similarly in connection with catalytic studies on divalent amides. Imide and nitride, into which the lanthanide (Ln/AC) deposited by impregnation of active carbon (AC) with liquid ammonia solutions of lanthanide metals were converted thermally, were studied catalytically. It was concluded that imide or imide-like species generated during the thermal degradation of lanthanide amide to nitride were very active in the hydrogenation of ethene. Lanthanide nitride was virtually inactive, but the nitride highly dispersed on active carbon was activated when subjected to evacuation treatment above about 1000 K. (orig.)

Zn(II)- and Cu(II)-induced non-fibrillar aggregates of amyloid-beta (1-42) peptide are transformed to amyloid fibrils, both spontaneously and under the influence of metal chelators.

Science.gov (United States)

Tõugu, Vello; Karafin, Ann; Zovo, Kairit; Chung, Roger S; Howells, Claire; West, Adrian K; Palumaa, Peep

2009-09-01

Aggregation of amyloid-beta (Abeta) peptides is a central phenomenon in Alzheimer's disease. Zn(II) and Cu(II) have profound effects on Abeta aggregation; however, their impact on amyloidogenesis is unclear. Here we show that Zn(II) and Cu(II) inhibit Abeta(42) fibrillization and initiate formation of non-fibrillar Abeta(42) aggregates, and that the inhibitory effect of Zn(II) (IC(50) = 1.8 micromol/L) is three times stronger than that of Cu(II). Medium and high-affinity metal chelators including metallothioneins prevented metal-induced Abeta(42) aggregation. Moreover, their addition to preformed aggregates initiated fast Abeta(42) fibrillization. Upon prolonged incubation the metal-induced aggregates also transformed spontaneously into fibrils, that appear to represent the most stable state of Abeta(42). H13A and H14A mutations in Abeta(42) reduced the inhibitory effect of metal ions, whereas an H6A mutation had no significant impact. We suggest that metal binding by H13 and H14 prevents the formation of a cross-beta core structure within region 10-23 of the amyloid fibril. Cu(II)-Abeta(42) aggregates were neurotoxic to neurons in vitro only in the presence of ascorbate, whereas monomers and Zn(II)-Abeta(42) aggregates were non-toxic. Disturbed metal homeostasis in the vicinity of zinc-enriched neurons might pre-dispose formation of metal-induced Abeta aggregates, subsequent fibrillization of which can lead to amyloid formation. The molecular background underlying metal-chelating therapies for Alzheimer's disease is discussed in this light.

Development of an ELISA assay for screening inhibitors against divalent metal ion dependent alphavirus capping enzyme.

Science.gov (United States)

Kaur, Ramanjit; Mudgal, Rajat; Narwal, Manju; Tomar, Shailly

2018-06-26

Alphavirus non-structural protein, nsP1 has a distinct molecular mechanism of capping the viral RNAs than the conventional capping mechanism of host. Thus, alphavirus capping enzyme nsP1 is a potential drug target. nsP1 catalyzes the methylation of guanosine triphosphate (GTP) by transferring the methyl group from S-adenosylmethionine (SAM) to a GTP molecule at its N7 position with the help of nsP1 methyltransferase (MTase) followed by guanylylation (GT) reaction which involves the formation of m 7 GMP-nsP1 covalent complex by nsP1 guanylyltransferase (GTase). In subsequent reactions, m 7 GMP moiety is added to the 5' end of the viral ppRNA by nsP1 GTase resulting in the formation of cap0 structure. In the present study, chikungunya virus (CHIKV) nsP1 MTase and GT reactions were confirmed by an indirect non-radioactive colorimetric assay and western blot assay using an antibody specific for the m 7 G cap, respectively. The purified recombinant CHIKV nsP1 has been used for the development of a rapid and sensitive non-radioactive enzyme linked immunosorbent assay (ELISA) to identify the inhibitors of CHIKV nsP1. The MTase reaction is followed by GT reaction and resulted in m 7 GMP-nsP1 covalent complex formation. The developed ELISA nsP1 assay measures this m 7 GMP-nsP1 complex by utilizing anti-m 7 G cap monoclonal antibody. The mutation of a conserved residue Asp63 to Ala revealed its role in nsP1 enzyme reaction. Inductively coupled plasma mass spectroscopy (ICP-MS) was used to determine the presence of magnesium ions (Mg 2+ ) in the purified nsP1 protein. The divalent metal ion selectivity and investigation show preference for Mg 2+ ion by CHIKV nsP1. Additionally, using the developed ELISA nsP1 assay, the inhibitory effects of sinefungin, aurintricarboxylic acid (ATA) and ribavirin were determined and the IC 50 values were estimated to be 2.69 µM, 5.72 µM and 1.18 mM, respectively. Copyright © 2018. Published by Elsevier B.V.

Interaction of divalent minerals with liposoluble nutrients and phytochemicals during digestion and influences on their bioavailability - a review.

Science.gov (United States)

Corte-Real, Joana; Bohn, Torsten

2018-06-30

Several divalent minerals, including the macroelements calcium and magnesium, are essential nutrients for humans. However, their intake, especially via high-dose supplements, has been suspected to reduce the availability of lipophilic dietary constituents, including lipids, liposoluble vitamins, and several phytochemicals such as carotenoids. These constituents require emulsification in order to be bioavailable, and high divalent mineral concentrations may perturb this process, due to precipitations of free fatty acids or bile salt complexation, both pivotal for mixed micelle formation. Though in part based on in vitro or indirect evidence, it appears likely that high-dose supplements of divalent minerals around or even below their recommended dietary allowance perturb the availability of certain liposoluble miroconstituents, in addition to reducing absorption of dietary lipids/cholesterol. In this review, we investigate possible negative influences of divalent minerals, including trace elements (iron, zinc), on the digestion and intestinal uptake of lipophilic dietary constituents, with a focus on carotenoids. Copyright © 2018 Elsevier Ltd. All rights reserved.

TOLERANCE OF AGAVE TEQUILANA TO HIGH LEVELS OF DIVALENT METAL CATIONS

Directory of Open Access Journals (Sweden)

Elmi Roseida Cen-Cen

2015-11-01

Full Text Available Los agaves son plantas que pertenecen a un género constituido por numerosas especies, adaptadas para crecer en muy diversos hábitats, algunos con condiciones ambientales extremas. Distintas especies de agave crecen sobre distintos tipos de suelos, algunas en suelos con muy bajo contenido de nutrientes minerales y otras en suelos salinos o en suelos contaminados con iones metálicos. La relación planta-suelo ha sido escasamente estudiada en este género por lo que se desconoce, entre otras cuestiones, cuál es la capacidad de los agaves para absorber, transportar y almacenar nutrientes minerales, cuáles son los mecanismos celulares y bioquímicos que utilizan, o si poseen especial sensibilidad o tolerancia a los iones metálicos. Este estudio reporta el efecto de diversas concentraciones de sulfato de cadmio, cobalto, cobre, zinc o de manganeso sobre plántulas deAgave tequilana, bajo condiciones controladas de laboratorio; la concentración mínima de esos iones metálicos requerida para inducir un efecto tóxico visualmente detectable en tiempos cortos (ocho días; describimos los efectos tóxicos que estos metales generan sobre las plántulas de agave; y reportamos la cantidad de Cu2+, Cd2+ y Co2+ que se acumula en las hojas de plántulas de agave tratadas con altas concentraciones (milimolares de esos metales. Nuestros resultados muestran que, en experimentos de toxicidad aguda y bajo las condiciones aquí establecidas, elA. tequilanaposee una notable tolerancia a altas concentraciones de los distintos metales iónicos probados, incluyendo tanto micronutrientes como metales tóxicos, así como la capacidad de transportar en altas cantidades estos metales a tejido aéreo.

The synthesis and properties of some organometallic compounds containing group IV (Ge, Sn)-group II (Zn, Cd) metal---metal bonds

NARCIS (Netherlands)

Des Tombe, F.J.A.; Kerk, G.J.M. van der; Creemers, H.M.J.C.; Carey, N.A.D.; Noltes, J.G.

1972-01-01

The reactions of triphenylgermane and triphenyltin hydride with coordinatively saturated organozinc or organocadmium compounds give organometallic complexes containing Group IV (Ge, Sn)-Group II(Zn, Cd) metal---metal bonds. The 2,2′-bipyridine complexes show solvent-dependent charge-transfer

Hemolysis of human red blood cells induced by the combination of diethyldithiocarbamate (DDC) and divalent metals: modulation by anaerobiosis, certain antioxidants and oxidants.

Science.gov (United States)

Ginsburg, I; Sadovnic, M; Varani, J; Tirosh, O; Kohen, R

1999-08-01

The objective of the present communication is to describe the role played by combinations between diethydithiocarbamate (DDC) and divalent metals in hemolysis of human RBC. RBC which had been treated with DDC (10-50 microM) were moderately hemolyzed (about 50%) upon the addition of subtoxic amounts of Cu2+ (50 microM). However, a much stronger and a faster hemolysis occurred either if mixtures of RBC-DDC were immediately treated either by Co2+ (50 microM) or by a premixture of Cu2+ and Co2+ (Cu:Co) (50 microM). While Fe2+ and Ni2+, at 50 microM, initiated 30-50% hemolysis when combined with DDC (50 microM), on a molar basis, Cd2+ was at least 50 fold more efficient than any of the other metals in the initiation of hemolysis by DDC. On the other hand, neither Mn2+ nor Zn2+, had any hemolysis-initiating effects. Co2+ was the only metal which totally blocked hemolysis if added to DDC prior to the addition of the other metals. Hemolysis by mixtures of DDC + (Cu:Co) was strongly inhibited by anaerobiosis (flushing with nitrogen gas), by the reducing agents glutathione, N-acetyl cysteine, mercaptosuccinate, ascorbate, TEMPO, and alpha-tocopherol, by the PLA2 inhibitorbromophenacylbromide (BrPACBr), by tetracycline as well as by phosphatidyl choline, cholesterol and by trypan blue. However, TEMPO, BrPACBr and PC were the only agents which inhibited hemolysis induced by DDC: Cd2+ complexes. On the other hand, none of the classical scavengers of reactive oxygen species (ROS) employed e.g dimethylthiourea, catalase, histidine, mannitol, sodium benzoate, nor the metal chelators desferal and phenanthroline, had any appreciable inhibitory effects on hemolysis induced by DDC + (Cu:Co). DDC oxidized by H2O2 lost its capacity to act in concert either with Cu2+ or with Cd2+ to hemolyze RBC. While either heating RBC to temperatures greater than 37 degrees C or exposure of the cells to glucose-oxidase-generated peroxide diminished their susceptibility to hemolysis, exposure to the

Supported transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing

International Nuclear Information System (INIS)

Ho, T.C.; Chianelli, R.R.; Jacobson, A.J.; Young, A.R.

1987-01-01

A process is described for hydrotreating a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150 0 C and heating the composite at elevated temperature of at least about 150 0 C, in the presence of sulfur and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals which are chelated by at least one neutral, nitrogen-containing polydentate ligand L. The divalent promoter metal is selected from the group consisting of Ni, Co, Zn, Cu and mixture thereof. The contacting occurs for a time sufficient to hydrotreat at least a portion of the feed

High-energy-density, aqueous, metal-polyiodide redox flow batteries

Science.gov (United States)

Li, Bin; Nie, Zimin; Wang, Wei; Liu, Jun; Sprenkle, Vincent L.

2017-08-29

Improved metal-based redox flow batteries (RFBs) can utilize a metal and a divalent cation of the metal (M.sup.2+) as an active redox couple for a first electrode and electrolyte, respectively, in a first half-cell. For example, the metal can be Zn. The RFBs can also utilize a second electrolyte having I.sup.-, anions of I.sub.x (for x.gtoreq.3), or both in an aqueous solution, wherein the I.sup.- and the anions of I.sub.x (for x.gtoreq.3) compose an active redox couple in a second half-cell.

Electronic structure and superconductivity of divalent metals under very high pressure

International Nuclear Information System (INIS)

Bireckoven, B.

1987-05-01

A single crystal, high-pressure diamond cell has been developed for the study of superconductors under pressures to over 50 GPa. A high sensitivity AC-SQUID magnetometer has been employed to detect the diamagnetic response of the very small samples at T C . The T C (p)-dependence of the lead-manometer has been calibrated against the ruby-pressure-scale up to pressures of 30 GPa. In spite of the well-known fcc/hcp-transition at 13 GPa lead shows a smooth T C (p)-behaviour and thus is a very suitable manometer. Band structure calculations for the alkaline earth metals indicate an appreciable s-to-d transfer with increasing pressure. In fact, superconductivity was previously observed in the pressure induced d-transition metals Sr and Ba (however not yet in Ca). For the first time the author presents a quantitative investigation of T C as a function of p up to 50 GPa. Both elements turn out to be ''good'' superconductors featuring T C 's of about 7 K. The possibility of a generalized phase diagram for the alkaline earth metals will be critically discussed. At any rate, the occurrence of such high T C 's is rather strong evidence for a substantial d-transition metal character at high p. Investigations of very dilute BaEu-alloys up to 45 GPa reveal a strong monotonic increase of ΔT C = T C Ba -T C BaEu . (orig./GSCH)

Effects of mutagenesis of aspartic acid residues in the putative phosphoribosyl diphosphate binding site of Escherichia coli phosphoribosyl diphosphate synthetase on metal ion specificity and ribose-5-phosphate binding

DEFF Research Database (Denmark)

Willemoës, Martin; Nilsson, Dan; Hove-Jensen, Bjarne

1996-01-01

The three conserved aspartic acid residues of the 5-phospho-d-ribosyl a-1-diphosphate binding site (213-GRDCVLVDDMIDTGGT-228) of Escherichia coli phosphoribosyl diphosphate synthetase were studied by analysis of the mutant enzymes D220E, D220F, D221A, D224A, and D224S. The mutant enzymes showed...... enzymes were dependent on the metal ion present, suggesting a function of the investigated aspartic acid residues both in the binding of ribose 5-phosphate, possibly via a divalent metal ion, and in the interaction with a divalent metal ion during catalysis....

Nickel incorporation in Fe(II, III hydroxysulfate Green Rust: effect on crystal lattice spacing and oxidation products Incorporação de níquel em Fe (II-III Grenn Rust hidroxisulfato: efeito sobre a estrutura cristalina e produtos de oxidação

Directory of Open Access Journals (Sweden)

Lucia Helena Garófalo Chaves

2009-10-01

Full Text Available Ni(II-Fe(II-Fe(III layered double hydroxides (LDH or Ni-containing sulfate green rust (GR2 samples were prepared from Ni(II, Fe(II and Fe(III sulfate salts and analyzed with X ray diffraction. Nickel is readily incorporated in the GR2 structure and forms a solid solution between GR2 and a Ni(II-Fe(III LDH. There is a correlation between the unit cell a-value and the fraction of Ni(II incorporated into the Ni(II-GR2 structure. Since there is strong evidence that the divalent/trivalent cation ratio in GR2 is fixed at 2, it is possible in principle to determine the extent of divalent cation substitution for Fe(II in GR2 from the unit cell a-value. Oxidation forms a mixture of minerals but the LDH structure is retained if at least 20 % of the divalent cations in the initial solution are Ni(II. It appears that Ni(II is incorporated in a stable LDH structure. This may be important for two reasons, first for understanding the formation of LDHs, which are anion exchangers, in the natural environment. Secondly, this is important for understanding the fate of transition metals in the environment, particularly in the presence of reduced Fe compounds.Amostras de hidróxidos de dupla camada (HDC, ou "sulfate green rust" (GR2, contendo Ni foram preparadas utilizando-se sulfatos de Ni(II, Fe(II e Fe(III e analisadas por difração de raios X. O Ni está incorporado na estrutura do GR2 e forma um sólido entre GR2 e um HDC contendo Ni(II-Fe(III. Há correlação entre os valores de "a" da célula unitária e os da fração de Ni(II incorporado na estrutura do Ni(II-GR2. Desde que haja forte evidência de que a razão entre os cátions divalente/trivalente no GR2 seja igual a 2, é possível, a princípio, determinar a extensão da substituição do cátion divalente por Fe(II no GR2 a partir dos valores de "a" da célula unitária do cristal. Sob o efeito da oxidação, é formada uma mistura de minerais, porém a estrutura do HDC não é alterada se pelo menos

Synthesis and characterization of divalent metal complexes with ligand derived from the reaction of 3-aminopyridine and biacetyl

Directory of Open Access Journals (Sweden)

RAMESH KUMAR

2006-09-01

Full Text Available Divalent cobalt, nickel and copper salts reacted in situ with 3-aminopyridine and biacetyl to form complexes of the type: [M(Ap2biac2X2], where Ap2biac is the ligand and X=Cl, Br, NO3 or NCS. The complexes were analysed and characterized as distorted octahedral by conductance, molecular weight, magnetic, electronic and IR spectral studies. The electronic spectra were interpreted and tentative aassignments made. The infrared spectral studies revealed that two molecules of 3-aminopyridine were joined by molecules of biacetyl through a two carbon atom bridge and that the ligand coordinated through azomethine nitrogen atoms, whereas the pyridine nitrogen does not participate in the coordination. In the far infrared spectra, various metal–ligand vibrations were observed and are discussed.

Raman spectroscopy of DNA-metal complexes. II. The thermal denaturation of DNA in the presence of Sr2+, Ba2+, Mg2+, Ca2+, Mn2+, Co2+, Ni2+, and Cd2+.

Science.gov (United States)

Duguid, J G; Bloomfield, V A; Benevides, J M; Thomas, G J

1995-12-01

aggregation, reveals increased turbidity during the melting transition for all divalent DNA-metal complexes, except SrDNA and BaDNA. Turbidity was not observed for DNA in the absence of metal. A correlation was made between DNA melting, aggregation, and the ratio of Raman intensities I1335/I1374. At room temperature, DNA-metal interactions result in a pH drop of 1.2-2.2 units for alkaline earths and more than 2.5 units for transition metals. Sr2+, Ba2+, and Mg2+ cause protonated sites on the DNA to become thermally labile. These results lead to a model that describes DNA aggregation and denaturation during heating in the presence of divalent metal cations; 1) The cations initially interact with the DNA at phosphate and/or base sites, resulting in proton displacement. 2) A combination of metal-base interactions and heating disrupts the base pairing within the DNA duplex. This allows divalent metals and protons to bind to additional sites on the DNA bases during the aggregation/melting process. 3) Strands whose bases have swung open upon disruption are linked to neighboring strands by metal ion bridges. 4) Near the midpoint of the melting transition, thermal energy breaks up the aggregate. We have no evidence to indicate whether metal ion cross-bridges or direct base-base interactions rupture first. 5) Finally, all cross-links break, resulting in single-stranded DNA complexed with metal ions.

Removal of industrial dyes and heavy metals by Beauveria bassiana: FTIR, SEM, TEM and AFM investigations with Pb(II).

Science.gov (United States)

Gola, Deepak; Malik, Anushree; Namburath, Maneesh; Ahammad, Shaikh Ziauddin

2017-10-01

Presence of industrial dyes and heavy metal as a contaminant in environment poses a great risk to human health. In order to develop a potential technology for remediation of dyes (Reactive remazol red, Yellow 3RS, Indanthrene blue and Vat novatic grey) and heavy metal [Cu(II), Ni(II), Cd(II), Zn(II), Cr(VI) and Pb(II)] contamination, present study was performed with entomopathogenic fungi, Beauveria bassiana (MTCC no. 4580). High dye removal (88-97%) was observed during the growth of B. bassiana while removal percentage for heavy metals ranged from 58 to 75%. Further, detailed investigations were performed with Pb(II) in terms of growth kinetics, effect of process parameters and mechanism of removal. Growth rate decreased from 0.118 h -1 (control) to 0.031 h -1 , showing 28% reduction in biomass at 30 mg L -1 Pb(II) with 58.4% metal removal. Maximum Pb(II) removal was observed at 30 °C, neutral pH and 30 mg L -1 initial metal concentration. FTIR analysis indicated the changes induced by Pb(II) in functional groups on biomass surface. Further, microscopic analysis (SEM and atomic force microscopy (AFM)) was performed to understand the changes in cell surface morphology of the fungal cell. SEM micrograph showed a clear deformation of fungal hyphae, whereas AFM studies proved the increase in surface roughness (RSM) in comparison to control cell. Homogenous bioaccumulation of Pb(II) inside the fungal cell was clearly depicted by TEM-high-angle annular dark field coupled with EDX. Present study provides an insight into the mechanism of Pb(II) bioremediation and strengthens the significance of using entomopathogenic fungus such as B. bassiana for metal and dye removal.

Effect of illite clay and divalent cations on bitumen recovery

Energy Technology Data Exchange (ETDEWEB)

Ding, X. [SNC-Lavalin Inc., Calgary, AB (Canada); Repka, C. [Baker Petrolite Corp., Fort McMurray, AB (Canada); Xu, Z.; Masliyah, J. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering

2006-12-15

Nearly 35 per cent of Canada's petroleum needs can be met from the Athabasca oil sands, particularly as conventional sources of petroleum decline. The interactions between bitumen and clay minerals play a key role in the recovery process of bitumen because they affect bitumen aeration. The 2 clays minerals found in various oil sands extraction process streams are kaolinite and illite. In this study, doping flotation tests using deionized water and electrokinetic studies were performed to examine the effect of illite clays on bitumen recovery. The effect of magnesium ions was also examined and compared with calcium ions. This paper also discussed the effects of temperature and tailings water chemistry. The negative effect of illite clay on bitumen recovery was found to be associated with its acidity. Denver flotation cell measurements indicated that the addition of calcium or magnesium ions to the flotation deionized water had only a slight effect on bitumen recovery, but the co-addition of illite clay and divalent cations resulted in a dramatic reduction in bitumen recovery. The effect was more significant at lower process temperature and low pH values. Zeta potential distributions of illite suspensions and bitumen emulsions were measured individually and as a mixture to determine the effect of divalent cations on the interaction between bitumen and illite clay. The presence of 1 mM calcium or magnesium ions in deionized water had a pronounced effect on the interactions between bitumen and illite clay. Slime coating of illite onto bitumen was not observed in zeta potential distribution measurements performed in alkaline tailings water. When tests were conducted using plant recycle water, the combination of illite clay and divalent cations did not have an adverse effect on bitumen recovery. 25 refs., 3 tabs., 15 figs.

Oligo-m-phenyleneoxalamide copper(II) mesocates as electro-switchable ferromagnetic metal-organic wires.

Science.gov (United States)

Pardo, Emilio; Ferrando-Soria, Jesús; Dul, Marie-Claire; Lescouëzec, Rodrigue; Journaux, Yves; Ruiz-García, Rafael; Cano, Joan; Julve, Miguel; Lloret, Francesc; Cañadillas-Delgado, Laura; Pasán, Jorge; Ruiz-Pérez, Catalina

2010-11-15

Double-stranded copper(II) string complexes of varying nuclearity, from di- to tetranuclear species, have been prepared by the Cu(II)-mediated self-assembly of a novel family of linear homo- and heteropolytopic ligands that contain two outer oxamato and either zero (1 b), one (2 b), or two (3 b) inner oxamidato donor groups separated by rigid 2-methyl-1,3-phenylene spacers. The X-ray crystal structures of these Cu(II) (n) complexes (n=2 (1 d), 3 (2 d), and 4 (3 d)) show a linear array of metal atoms with an overall twisted coordination geometry for both the outer CuN(2)O(2) and inner CuN(4) chromophores. Two such nonplanar all-syn bridging ligands 1 b-3 b in an anti arrangement clamp around the metal centers with alternating M and P helical chiralities to afford an overall double meso-helicate-type architecture for 1 d-3 d. Variable-temperature (2.0-300 K) magnetic susceptibility and variable-field (0-5.0 T) magnetization measurements for 1 d-3 d show the occurrence of S=nS(Cu) (n=2-4) high-spin ground states that arise from the moderate ferromagnetic coupling between the unpaired electrons of the linearly disposed Cu(II) ions (S(Cu)=1/2) through the two anti m-phenylenediamidate-type bridges (J values in the range of +15.0 to 16.8 cm(-1)). Density functional theory (DFT) calculations for 1 d-3 d evidence a sign alternation of the spin density in the meta-substituted phenylene spacers in agreement with a spin polarization exchange mechanism along the linear metal array with overall intermetallic distances between terminal metal centers in the range of 0.7-2.2 nm. Cyclic voltammetry (CV) and rotating-disk electrode (RDE) electrochemical measurements for 1 d-3 d show several reversible or quasireversible one- or two-electron steps that involve the consecutive metal-centered oxidation of the inner and outer Cu(II) ions (S(Cu)=1/2) to diamagnetic Cu(III) ones (S(Cu)=0) at relatively low formal potentials (E values in the range of

Divalent metal transporter 1 (DMT1) in the brain: implications for a role in iron transport at the blood-brain barrier, and neuronal and glial pathology.

Science.gov (United States)

Skjørringe, Tina; Burkhart, Annette; Johnsen, Kasper Bendix; Moos, Torben

2015-01-01

Iron is required in a variety of essential processes in the body. In this review, we focus on iron transport in the brain and the role of the divalent metal transporter 1 (DMT1) vital for iron uptake in most cells. DMT1 locates to cellular membranes and endosomal membranes, where it is a key player in non-transferrin bound iron uptake and transferrin-bound iron uptake, respectively. Four isoforms of DMT1 exist, and their respective characteristics involve a complex cell-specific regulatory machinery all controlling iron transport across these membranes. This complexity reflects the fine balance required in iron homeostasis, as this metal is indispensable in many cell functions but highly toxic when appearing in excess. DMT1 expression in the brain is prominent in neurons. Of serious dispute is the expression of DMT1 in non-neuronal cells. Recent studies imply that DMT1 does exist in endosomes of brain capillary endothelial cells denoting the blood-brain barrier. This supports existing evidence that iron uptake at the BBB occurs by means of transferrin-receptor mediated endocytosis followed by detachment of iron from transferrin inside the acidic compartment of the endosome and DMT1-mediated pumping iron into the cytosol. The subsequent iron transport across the abluminal membrane into the brain likely occurs by ferroportin. The virtual absent expression of transferrin receptors and DMT1 in glial cells, i.e., astrocytes, microglia and oligodendrocytes, suggest that the steady state uptake of iron in glia is much lower than in neurons and/or other mechanisms for iron uptake in these cell types prevail.

BIOASSAY STUDIES OF METAL(II) COMPLEXES OF 2,2'-(ETHANE ...

African Journals Online (AJOL)

Preferred Customer

diyldiimino)diacetic acid (EDDA) were prepared and characterized. Coordination complexes of the EDDA ... corresponding amines with alkyl halide to bear diammines of the same class with different substituents. ... Bioassay studies of metal(II) complexes of 2,2'-(ethane-1,2-diyldiimino)diacetic acid. Bull. Chem. Soc. Ethiop.

Inter-DNA Attraction Mediated by Divalent Counterions

International Nuclear Information System (INIS)

Qiu Xiangyun; Andresen, Kurt; Kwok, Lisa W.; Lamb, Jessica S.; Park, Hye Yoon; Pollack, Lois

2007-01-01

Can nonspecifically bound divalent counterions induce attraction between DNA strands? Here, we present experimental evidence demonstrating attraction between short DNA strands mediated by Mg 2+ ions. Solution small angle x-ray scattering data collected as a function of DNA concentration enable model independent extraction of the second virial coefficient. As the [Mg 2+ ] increases, this coefficient turns from positive to negative reflecting the transition from repulsive to attractive inter-DNA interaction. This surprising observation is corroborated by independent light scattering experiments. The dependence of the observed attraction on experimental parameters including DNA length provides valuable clues to its origin

Heavy Metal Removal by Chitosan and Chitosan Composite

International Nuclear Information System (INIS)

Abdel-Mohdy, F.A.; El-Sawy, S.; Ibrahim, M.S.

2005-01-01

Radiation grafting of diethyl aminoethyl methacrylate (DEAEMA) on chitosan to impart ion exchange properties and to be used for the separation of metal ions from waste water, was carried out. The effect of experimental conditions such as monomer concentration and the radiation dose on grafting were studied. On using chitosan, grafted chitosan and some chitosan composites in metal ion removal they show high up-take capacity for Cu 2+ and lower uptake capacities for the other divalent metal ions used (Zn and Co). Competitive study, performed with solutions containing mixture of metal salts, showed high selectivity for Cu 2+ than the other metal ion. Limited grafting of DEAEMA polymer -containing specific functional groups-onto the chitosan backbone improves the sorption performance

Removal of Cu(II) metal ions from aqueous solution by amine functionalized magnetic nanoparticles

Science.gov (United States)

Kothavale, V. P.; Karade, V. C.; Waifalkar, P. P.; Sahoo, Subasa C.; Patil, P. S.; Patil, P. B.

2018-04-01

The adsorption behavior of Cu(II) metal cations was investigated on the amine functionalized magnetic nanoparticles (MNPs). TheMNPs were synthesized by thesolvothermal method and functionalized with (3-Aminopropyl)triethoxysilane (APTES). MNPs were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and vibrating sample magnetometer (VSM). The MNPs have pure magnetite phase with particle size around 10-12 nm. MNPs exhibits superparamagnetic behavior with asaturation magnetization of 68 emu/g. The maximum 38 % removal efficiency was obtained for Cu(II) metal ions from the aqueous solution.

Synthesis, structural characterization, electrochemical and biological studies on divalent metal chelates of a new ligand derived from pharmaceutical preservative, dehydroacetic acid, with 1,4-diaminobenzene

Directory of Open Access Journals (Sweden)

Sanaa M. Emam

2017-05-01

Full Text Available Cobalt(II, nickel(II, copper(II, zinc(II and cadmium(II complexes of new 3-acetyl-4-[(4-aminophenylamino]-6-methyl-2H-pyran-2-one (HL1 derived from dehydroacetic acid and 1,4-diaminobenzene were prepared and characterized. The structural features were determined from their elemental analyses, 1H, and 13C-NMR spectra, molar conductivities, magnetic moments, IR, UVvis. spectra, thermal analyses (D.T.A. and T.G.A. and E.S.R. measurements. Their magnetic susceptibility measurements and low conductance data provide evidence for the mono- or dimeric and non-electrolytic nature of the solid complexes. The E.S.R. spectra of copper(II complexes show axial type symmetry with covalent or ionic bond character. The electrochemical behavior of the complexes in DMF (dimethylformamide solvent at 298 K was studied. The biological activity of the ligand and its metal(II complexes was also studied. The obtained complexes showed higher activities than the free ligand in protecting the Egyptian cotton fields from Spodoptera littoralis larvae.

Crystal structure and properties of tetragonal EuAg4In8 grown by metal flux technique

International Nuclear Information System (INIS)

Subbarao, Udumula; Sarkar, Sumanta; Peter, Sebastian C.

2015-01-01

The compound EuAg 4 In 8 has been obtained as single crystals in high yield from reactions run in liquid indium. X-ray diffraction on single crystals suggests that EuAg 4 In 8 crystallizes in the CeMn 4 Al 8 structure type, tetragonal space group I4/mmm with lattice constants a=b=9.7937(2) Å and c=5.7492(2) Å. Crystal structure of EuAg 4 In 8 is composed of pseudo Frank–Kasper cages occupied by one europium atom in each ring, which are shared through the corner along the ab plane resulting in a three dimensional network. The magnetic susceptibility of EuAg 4 In 8 was measured in the temperature range 2–300 K, which obeyed Curie–Weiss law above 50 K. Magnetic moment value calculated from the fitting indicates the presence of divalent europium, which was confirmed by X-ray absorption near edge spectroscopy. Electrical resistivity measurements suggest that EuAg 4 In 8 is metallic in nature with a probable Fermi liquid behavior at low temperature. - Graphical abstract: The tetragonal EuAg 4 In 8 has been grown as single crystals from reactions run in liquid indium. Magnetic and XANES measurements suggest divalent nature of Eu and resistivity measurements suggest metallic nature. - Highlights: • EuAg 4 In 8 phase having tetragonal phase is grown by metal flux technique. • Magnetic and XANES measurements exhibit divalent nature of Eu in EuAg 4 In 8 . • Resistivity measurement suggests metallic nature and probable Fermi liquid behavior

Effect of Cu(II), Cd(II) and Zn(II) on Pb(II) biosorption by algae Gelidium-derived materials.

Science.gov (United States)

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2008-06-15

Biosorption of Pb(II), Cu(II), Cd(II) and Zn(II) from binary metal solutions onto the algae Gelidium sesquipedale, an algal industrial waste and a waste-based composite material was investigated at pH 5.3, in a batch system. Binary Pb(II)/Cu(II), Pb(II)/Cd(II) and Pb(II)/Zn(II) solutions have been tested. For the same equilibrium concentrations of both metal ions (1 mmol l(-1)), approximately 66, 85 and 86% of the total uptake capacity of the biosorbents is taken by lead ions in the systems Pb(II)/Cu(II), Pb(II)/Cd(II) and Pb(II)/Zn(II), respectively. Two-metal results were fitted to a discrete and a continuous model, showing the inhibition of the primary metal biosorption by the co-cation. The model parameters suggest that Cd(II) and Zn(II) have the same decreasing effect on the Pb(II) uptake capacity. The uptake of Pb(II) was highly sensitive to the presence of Cu(II). From the discrete model it was possible to obtain the Langmuir affinity constant for Pb(II) biosorption. The presence of the co-cations decreases the apparent affinity of Pb(II). The experimental results were successfully fitted by the continuous model, at different pH values, for each biosorbent. The following sequence for the equilibrium affinity constants was found: Pb>Cu>Cd approximately Zn.

Ion exchange equilibrium for some uni-univalent and uni-divalent ...

African Journals Online (AJOL)

The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Duolite A-102 D. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well ...

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag

International Nuclear Information System (INIS)

Xue Yongjie; Hou Haobo; Zhu Shujing

2009-01-01

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01 M NaNO 3 . In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84 mM in the single element system and 0.21 mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH 50 (the pH at which 50% adsorption occurs) was found to follow the sequence Zn > Cu > Pb > Cd in single-element systems, but Pb > Cu > Zn > Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag

Energy Technology Data Exchange (ETDEWEB)

Xue Yongjie [School of Resource and Environment Science, Wuhan University, Hubei, Wuhan (China); Wuhan Kaidi Electric Power Environmental Protection Co. Ltd., Hubei, Wuhan (China)], E-mail: xueyj@mail.whut.edu.cn; Hou Haobo; Zhu Shujing [School of Resource and Environment Science, Wuhan University, Hubei, Wuhan (China)

2009-02-15

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01 M NaNO{sub 3}. In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84 mM in the single element system and 0.21 mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH{sub 50} (the pH at which 50% adsorption occurs) was found to follow the sequence Zn > Cu > Pb > Cd in single-element systems, but Pb > Cu > Zn > Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag.

Science.gov (United States)

Xue, Yongjie; Hou, Haobo; Zhu, Shujing

2009-02-15

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.

Fluorescent Protein-Based Ca2+ Sensor Reveals Global, Divalent Cation-Dependent Conformational Changes in Cardiac Troponin C.

Directory of Open Access Journals (Sweden)

Myriam A Badr

Full Text Available Cardiac troponin C (cTnC is a key effector in cardiac muscle excitation-contraction coupling as the Ca2+ sensing subunit responsible for controlling contraction. In this study, we generated several FRET sensors for divalent cations based on cTnC flanked by a donor fluorescent protein (CFP and an acceptor fluorescent protein (YFP. The sensors report Ca2+ and Mg2+ binding, and relay global structural information about the structural relationship between cTnC's N- and C-domains. The sensors were first characterized using end point titrations to decipher the response to Ca2+ binding in the presence or absence of Mg2+. The sensor that exhibited the largest responses in end point titrations, CTV-TnC, (Cerulean, TnC, and Venus was characterized more extensively. Most of the divalent cation-dependent FRET signal originates from the high affinity C-terminal EF hands. CTV-TnC reconstitutes into skinned fiber preparations indicating proper assembly of troponin complex, with only ~0.2 pCa unit rightward shift of Ca2+-sensitive force development compared to WT-cTnC. Affinity of CTV-TnC for divalent cations is in agreement with known values for WT-cTnC. Analytical ultracentrifugation indicates that CTV-TnC undergoes compaction as divalent cations bind. C-terminal sites induce ion-specific (Ca2+ versus Mg2+ conformational changes in cTnC. Our data also provide support for the presence of additional, non-EF-hand sites on cTnC for Mg2+ binding. In conclusion, we successfully generated a novel FRET-Ca2+ sensor based on full length cTnC with a variety of cellular applications. Our sensor reveals global structural information about cTnC upon divalent cation binding.

Liquid metal blanket module testing and design for ITER/TIBER II

International Nuclear Information System (INIS)

Mattas, R.F.; Cha, Y.; Finn, P.A.; Majumdar, S.; Picologlou, B.; Stevens, H.; Turner, L.

1988-05-01

A major goal for ITER is the testing of nuclear components to demonstrate the integrated performance of the most attractive concepts that can lead to a commercial fusion reactor. As part of the ITER/TIBER II study, the test program and design of test models were examined for a number of blanket concepts. The work at Argonne National Laboratory focused on self-cooled liquid metal blankets. A test program for liquid metal blankets was developed based upon the ITER/TIBER II operating schedule and the specific data needs to resolve the key issues for liquid metals. Testing can begin early in reactor operation with liquid metal MHD tests to confirm predictive capability. Combined heat transfer/MHD tests can be performed during initial plasma operation. After acceptable heat transfer performance is verified, tests to determine the integrated high temperature performance in a neutron environment can begin. During the high availability phase operation, long term performance and reliability tests will be performed. It is envisioned that a companion test program will be conducted outside ITER to determine behavior under severe accident conditions and upper performance limits. A detailed design of a liquid metal test module and auxiliary equipment was also developed. The module followed the design of the TPSS blanket. Detailed analysis of the heat transfer and tritium systems were performed, and the overall layout of the systems was determined. In general, the blanket module appears to be capable of addressing most of the testing needs. 8 refs., 27 figs., 11 tabs

HIGH-RESOLUTION SPECTROSCOPY OF EXTREMELY METAL-POOR STARS IN THE LEAST EVOLVED GALAXIES: BOÖTES II

International Nuclear Information System (INIS)

Ji, Alexander P.; Frebel, Anna; Simon, Joshua D.; Geha, Marla

2016-01-01

We present high-resolution Magellan/MIKE spectra of the four brightest confirmed red giant stars in the ultra-faint dwarf galaxy Boötes II (Boo II). These stars all inhabit the metal-poor tail of the Boo II metallicity distribution function. The chemical abundance pattern of all detectable elements in these stars is consistent with that of the Galactic halo. However, all four stars have undetectable amounts of neutron-capture elements Sr and Ba, with upper limits comparable to the lowest ever detected in the halo or in other dwarf galaxies. One star exhibits significant radial velocity variations over time, suggesting it to be in a binary system. Its variable velocity has likely increased past determinations of the Boo II velocity dispersion. Our four stars span a limited metallicity range, but their enhanced α-abundances and low neutron-capture abundances are consistent with the interpretation that Boo II has been enriched by very few generations of stars. The chemical abundance pattern in Boo II confirms the emerging trend that the faintest dwarf galaxies have neutron-capture abundances distinct from the halo, suggesting the dominant source of neutron-capture elements in halo stars may be different than in ultra-faint dwarfs

Thermodynamics of complexes formation by ITC in methanol/water = 9/1 (v/v) solution: A case study

Energy Technology Data Exchange (ETDEWEB)

Fisicaro, Emilia, E-mail: emilia.fisicaro@unipr.it [University of Parma, Department of Pharmacy, Parco Area delle Scienze, 27/A, 43124 Parma (Italy); Compari, Carlotta; Bacciottini, Franco; Contardi, Laura [University of Parma, Department of Pharmacy, Parco Area delle Scienze, 27/A, 43124 Parma (Italy); Carcelli, Mauro; Rispoli, Gabriele; Rogolino, Dominga [University of Parma, Department of Chemistry, Parco Area delle Scienze, 17/A, 43124 Parma (Italy)

2014-06-01

Graphical abstract: Integrase strand transfert inhibitors chelate the metal ions in the active site of HIV integrase. - Highlights: • Development of inhibitors acting against those viral enzymes operating via a cooperative two-metal ion mechanism, such as HIV integrase (IN), requires optimizing the binding affinity to the target. • We have defined an experimental procedure for obtaining reliable thermodynamic data by ITC in methanol/water = 9/1 (v/v) as solvent. • Formation heats in mixed solvent of the complexes formed by a ligand, model of Raltegravir, with Mg(II), Mn(II), Co(II) and Zn(II) are here reported. - Abstract: Most enzymes that participate in the biochemistry of nucleic acids require divalent metal ion cofactors to promote activity. Development of potent inhibitors, acting against those viral enzymes operating via a cooperative two-metal ion mechanism, such as HIV integrase (IN) and RNase H, hepatitis C virus polymerase and influenza endonuclease, requires optimizing the binding affinity to the target, which is dictated by the binding free energy composed of both enthalpic and entropic contributions. They can be obtained by using isothermal titration microcalorimetry. We have defined an experimental procedure for obtaining reliable thermodynamic data in methanol/water = 9/1 0.1 M KCl as solvent, used to overcome solubility problems. In this way we have measured the heats of formation of the complexes formed by N-(4-fluorobenzyl)-5-hydroxy-2-isopropyl-1-methyl-6-oxo-1, 6-dihydroxypyrimidine-4-carboxylate (HL, a model of Raltegravir, the antiretroviral drug produced by Merck and Co.), and a series of divalent metal ions of biological interest (Mg(II), Mn(II), Co(II) and Zn(II)), whose speciation was previously determined by potentiometry.

The modulation of TRPM7 currents by nafamostat mesilate depends directly upon extracellular concentrations of divalent cations

Directory of Open Access Journals (Sweden)

Chen Xuanmao

2010-12-01

Full Text Available Abstract Concentrations of extracellular divalent cations (Ca2+ and Mg2+ fall substantially during intensive synaptic transmission as well as during some pathophysiological conditions such as epilepsy and brain ischemia. Here we report that a synthetic serine protease inhibitor, nafamostat mesylate (NM, and several of its analogues, block recombinant TRPM7 currents expressed in HEK293T cells in inverse relationship to the concentration of extracellular divalent cations. Lowering extracellular Ca2+ and Mg2+ also evokes a divalent-sensitive non-selective cation current that is mediated by TRPM7 expression in hippocampal neurons. In cultured hippocampal neurons, NM blocked these TRPM7-mediated currents with an apparent affinity of 27 μM, as well as the paradoxical Ca2+ influx associated with lowering extracellular Ca2+. Unexpectedly, pre-exposure to NM strongly potentiated TRPM7 currents. In the presence of physiological concentrations of extracellular divalent cations, NM activates TRPM7. The stimulating effects of NM on TRPM7 currents are also inversely related to extracellular Ca2+ and Mg2+. DAPI and HSB but not netropsin, blocked and stimulated TRPM7. In contrast, mono-cationic, the metabolites of NM, p-GBA and AN, as well as protease inhibitor leupeptin and gabexate failed to substantially modulate TRPM7. NM thus provides a molecular template for the design of putative modulators of TRPM7.

Synthesis, crystal structure, and magnetic properties of two-dimensional divalent metal glutarate/dipyridylamine coordination polymers, with a single crystal-to-single crystal transformation in the copper derivative

International Nuclear Information System (INIS)

Montney, Matthew R.; Supkowski, Ronald M.; Staples, Richard J.; LaDuca, Robert L.

2009-01-01

Hydrothermal reaction of divalent metal chlorides with glutaric acid and 4,4'-dipyridylamine (dpa) has afforded an isostructural family of coordination polymers with formulation [M(glu)(dpa)] n (M=Co (1), Ni (2), Cu (3); glu=glutarate). Square pyramidal coordination is seen in 1-3, with semi-ligation of a sixth donor to produce a '5+1' extended coordination sphere. Neighboring metal atoms are linked into 1D [M(glu)] n neutral chains through chelating/monodentate bridging glutarate moieties with a syn-anti binding mode, and semi-chelation of the pendant carboxylate oxygen. These chains further connect into 2D layers through dipodal dpa ligands. Neighboring layers stack into the pseudo 3D crystal structure of 1-3 through supramolecular hydrogen bonding between dpa amine units and the semi-chelated glutarate oxygen atoms. The variable temperature magnetic behavior of 1-3 was explored and modeled as infinite 1D Heisenberg chains. Notably, complex 3 undergoes a thermally induced single crystal-to-single crystal transformation between centric and acentric space groups, with a conformationally disordered unilayer structure at 293 K and an ordered bilayer structure at 173 K. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analyses. - Graphical abstract: The coordination polymers [M(glu)(dpa)] n (M=Co (1), Ni (2), Cu (3); glu=glutarate, dpa=4,4'-dipyridylamine) exhibit 2D layer structures based on 1D [M(glu)] n chains linked through dpa tethers. Antiferromagnetic coupling is observed for 2 and 3, while ferromagnetism is predominant in 1. Compound 3 undergoes a thermally induced single crystal-to-single crystal transformation from an acentric to a centrosymmetric space group

Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

Energy Technology Data Exchange (ETDEWEB)

Keates, Adam C. [School of Chemistry, University of Southampton, Southampton, Hampshire SO17 1B,. UK (United Kingdom); Wang, Qianlong [Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY (United Kingdom); Weller, Mark T., E-mail: m.t.weller@bath.ac.uk [Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY (United Kingdom)

2014-02-15

Single crystal and bulk polycrystalline forms of K{sub 2}MP{sub 2}O{sub 7} (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42{sub 1}m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP{sub 2}O{sub 7}]{sup 2−} with potassium cations situated between the layers. The MO{sub 4} tetrahedra share oxygen atoms with [P{sub 2}O{sub 7}]{sup 4−} diphosphate groups and the potassium ions have KO{sub 8} square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen, as a result of the Jahn–Teller (JT) effect for the high spin d{sup 6} Fe(II) and p-orbital mixing or a second order JT effect for d{sup 9} Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K{sub 2}MP{sub 2}O{sub 7}, M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP{sub 2}O{sub 7}]{sup 2−}, formed from linked pyrophosphate groups and MO{sub 4} tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d{sup 6} Fe(II) and p-orbital mixing and second-order JT effects for d{sup 9} Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d{sup 10} distorted coordinations.

Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

International Nuclear Information System (INIS)

Keates, Adam C.; Wang, Qianlong; Weller, Mark T.

2014-01-01

Single crystal and bulk polycrystalline forms of K 2 MP 2 O 7 (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42 1 m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP 2 O 7 ] 2− with potassium cations situated between the layers. The MO 4 tetrahedra share oxygen atoms with [P 2 O 7 ] 4− diphosphate groups and the potassium ions have KO 8 square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen, as a result of the Jahn–Teller (JT) effect for the high spin d 6 Fe(II) and p-orbital mixing or a second order JT effect for d 9 Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K 2 MP 2 O 7 , M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP 2 O 7 ] 2− , formed from linked pyrophosphate groups and MO 4 tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d 6 Fe(II) and p-orbital mixing and second-order JT effects for d 9 Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d 10 distorted coordinations

Transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing

International Nuclear Information System (INIS)

Jacobson, A.J.; Chianelli, R.R.; Pecoraro, T.A.

1987-01-01

A process is described for hydrorefining a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150 0 C and in the presence of hydrogen with a catalyst obtained by heating one or more precursor salts at elevated temperature of at least about 150 0 C, in the presence of sulfur or one or more sulfur-bearing compounds and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals which are chelated by at least one neutral, nitrogen-containing polydentate ligand. The divalent promoter metal is selected from the group consisting of Ni, Co, Zn, Cu and mixture thereof. The contacting occurs for a time sufficient to hydrorefine at least a portion of the feed

Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins

Energy Technology Data Exchange (ETDEWEB)

Matsubara, I. [Lab. of Chemistry, Tokyo Women' s Medical Univ. (Japan); Takeda, Y.; Ishida, K. [Lab. of Chemistry, Nippon Medical School, Kawasaki-shi, Kanagawa-ken (Japan)

2000-02-01

The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 {mu}g of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios. (orig.)

Structure of the Ni(II) complex of Escherichia coli peptide deformylase and suggestions on deformylase activities depending on different metal(II) centres.

Science.gov (United States)

Yen, Ngo Thi Hai; Bogdanović, Xenia; Palm, Gottfried J; Kühl, Olaf; Hinrichs, Winfried

2010-02-01

Crystal structures of polypeptide deformylase (PDF) of Escherichia coli with nickel(II) replacing the native iron(II) have been solved with chloride and formate as metal ligands. The chloro complex is a model for the correct protonation state of the hydrolytic hydroxo ligand and the protonated status of the Glu133 side chain as part of the hydrolytic mechanism. The ambiguity that recently some PDFs have been identified with Zn(2+) ion as the active-site centre whereas others are only active with Fe(2+) (or Co(2+), Ni(2+) is discussed with respect to Lewis acid criteria of the metal ion and substrate activation by the CD loop.

Study of surface modifications for improved selected metal (II-VI) semiconductor based devices

Science.gov (United States)

Blomfield, Christopher James

Metal-semiconductor contacts are of fundamental importance to the operation of all semiconductor devices. There are many competing theories of Schottky barrier formation but as yet no quantitative predictive model exists to adequately explain metal-semiconductor interfaces. The II-VI compound semiconductors CdTe, CdS and ZnSe have recently come to the fore with the advent of high efficiency photovoltaic cells and short wavelength light emitters. Major problems still exist however in forming metal contacts to these materials with the desired properties. This work presents results which make a significant contribution to the theory of metal/II-VI interface behaviour in terms of Schottky barriers to n-type CdTe, CdS and ZnSe.Predominantly aqueous based wet chemical etchants were applied to the surfaces of CdTe, CdS and ZnSe which were subsequently characterised by X-ray photoelectron spectroscopy. The ionic nature of these II-VI compounds meant that they behaved as insoluble salts of strong bases and weak acids. Acid etchants induced a stoichiometric excess of semiconductor anion at the surface which appeared to be predominantly in the elemental or hydrogenated state. Alkaline etchants conversely induced a stoichiometric excess of semiconductor cation at the surface which appeared to be in an oxidised state.Metal contacts were vacuum-evaporated onto these etched surfaces and characterised by current-voltage and capacitance-voltage techniques. The surface preparation was found to have a clear influence upon the electrical properties of Schottky barriers formed to etched surfaces. Reducing the native surface oxide produced near ideal Schottky diodes. An extended study of Au, Ag and Sb contacts to [mathematical formula] substrates again revealed the formation of several discrete Schottky barriers largely independent of the metal used; for [mathematical formula]. Deep levels measured within this study and those reported in the literature led to the conclusion that Fermi

Effects of Pop III to PopII transition on the lowest metallicity stars in dwarf galaxies

Science.gov (United States)

Zhang, Yimiao; Keres, Dusan; FIRE Team

2018-01-01

We examine the effects of the enrichments from Population III (Pop III) stars on the formation and properties of the first generation of the Population II (Pop II) stars. Pop III stars begin to transition towards Pop II stars when the metals dispersed in Pop III supernovae pollute the nearby gas. However, details of this transition are still largely unknown. We use dwarf galaxy simulations from the Feedback In Realistic Environments (FIRE) project to identify the star-forming gas that is likely to be pre-enriched by Pop III supernovae and follow the stars that form in such gas. This pre-enrichment will leave the signature in the lowest metallicity stars that can be used to better constrain the details of the Pop III-to-Pop II transition.

The removal of toxic metals from liquid effluents by ion exchange resins. Part II: cadmium(II/ sulphate/Lewatit TP260

Directory of Open Access Journals (Sweden)

Alguacil, F. J.

2002-10-01

Full Text Available The adsorption of cadmium (II, from aqueous sulphate solutions, on Lewatit TP260 resin has been investigated in batch equilibrium experiments. The influence of pH and temperature on metal adsorption capacity have also been examined. The kinetic performance of the resin has been assesed and the results have been correlated by the pore diffusion model. The resin has been used in mini-columns to study its performance under dynamics conditions. The desorption of metal ion is achieved using sulphuric acid (0.25M and 0.5M.

Se estudia la adsorción de cadmio(II, de disoluciones en medio sulfato, sobre la resina Lewatit TP260. La adsorción del metal se ha investigado en función del pH, la temperatura y el tiempo de contacto con la resina. Los estudios cinéticos permiten correlacionar el proceso de intercambio iónico con el modelo de difusión en poro. Se ha empleado el sistema en mini columnas para evaluar el comportamiento de la resina bajo condiciones dinámicas. La desorción del metal se lleva a cabo con disoluciones de ácido sulfúrico (0,25M y 0,5M.

Spectroscopic and thermal degradation behavior of Mg(II, Ca(II, Ba(II and Sr(II complexes with paracetamol drug

Directory of Open Access Journals (Sweden)

Moamen S. Refat

2017-05-01

Full Text Available Complexes of Mg(II, Ca(II, Ba(II and Sr(II with paracetamol drug were synthesized and characterized by elemental analysis, conductivity, UV–Vis, IR, and 1H NMR spectroscopy and thermal analysis, as well as screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as paracetamol behaves as a neutral bidentate ligand coordinated to the metal ions via the lone pair of electrons of nitrogen and carbonyl-O atoms of the amide group. From the microanalytical data, the stoichiometry of the complexes reacts with Mg(II, Ca(II, Ba(II and Sr(II by molar ratios (2:1 (paracetamol:metal ion. The thermal behavior (TG/DTG of the complexes was studied. The ligand and their metal complexes were screened against both of antibacterial and fungicidal activities.

Preparation of Schiff s base complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) and their spectroscopic, magnetic, thermal, and antifungal studies

International Nuclear Information System (INIS)

Parekh, H.M.; Patel, M.N.

2006-01-01

The potassium salt of salicylidene-DL-alanine (KHL), bis(benzylidene)ethylenediamine (A 1 ), thiophene-o-carboxaldene-p-toluidine (A 2 ), and its metal complexes of the formula [(M II (L)(A)(H 2 O)] (M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II); A = A 1 or A 2 ) are prepared. They are characterized by elemental analysis, magnetic susceptibility measurements, thermogravimetric analysis, and infrared and electronic spectral studies. The electronic spectral and magnetic moment data suggest an octahedral geometry for the complexes. All of these complexes, metal nitrates, fungicides (bavistin and emcarb), and ligands are screened for their antifungal activity against Aspergillus niger, Fusarium oxysporum, and Aspergillus flavus using a plate poison technique. The complexes show higher activity than those of the free ligands, metal nitrate, and the control (DMSO) and moderate activity against bavistin and emcarb [ru

The effects of monovalent and divalent cations on the stability of silver nanoparticles formed from direct reduction of silver ions by Suwannee River humic acid/natural organic matter

Energy Technology Data Exchange (ETDEWEB)

Akaighe, Nelson [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States); Depner, Sean W.; Banerjee, Sarbajit [Department of Chemistry, 410 Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY 14260-3000 (United States); Sharma, Virender K. [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States); Sohn, Mary, E-mail: msohn@fit.edu [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States)

2012-12-15

The formation and characterization of AgNPs (silver nanoparticles) formed from the reduction of Ag{sup +} by SRNOM (Suwannee River natural organic matter) is reported. The images of SRNOM-formed AgNPs and the selected area electron diffraction (SAED) were captured by high resolution transmission electron microscopy (HRTEM). The colloidal and chemical stability of SRNOM- and SRHA (Suwannee River humic acid)-formed AgNPs in different ionic strength solutions of NaCl, KCl, CaCl{sub 2} and MgCl{sub 2} was investigated in an effort to evaluate the key fate and transport processes of these nanoparticles in natural aqueous environments. The aggregation state, stability and sedimentation rate of the AgNPs were monitored by Dynamic Light Scattering (DLS), zeta potential, and UV-vis measurements. The results indicate that both types of AgNPs are very unstable in high ionic strength solutions. Interestingly, the nanoparticles appeared more unstable in divalent cation solutions than in monovalent cation solutions at similar concentrations. Furthermore, the presence of SRNOM and SRHA contributed to the nanoparticle instability at high ionic strength in divalent metallic cation solutions, most likely due to intermolecular bridging with the organic matter. The results clearly suggest that changes in solution chemistry greatly affect nanoparticle long term stability and transport in natural aqueous environments. Highlights: Black-Right-Pointing-Pointer Formation of SRNOM-AgNPs under environmentally relevant conditions Black-Right-Pointing-Pointer Influence of monovalent versus divalent cations on SRHA- and SRNOM-AgNP stability Black-Right-Pointing-Pointer Effect of AgNPs on organic matter removal from water columns.

Two-phase coexistence in the monovalent-to-divalent phase transition of dineopentylbiferrocene-fluorotetracyanoquinodimethane [npBifc-(F1TCNQ)3], charge-transfer salt

International Nuclear Information System (INIS)

Uruichi, Mikio; Yue, Yue; Yakushi, Kyuya; Mochida, Tomoyuki

2007-01-01

We present experimental findings showing that for npBifc-(F 1 TCNQ) 3 , two phases coexist over a wide temperature interval of 100-150 K near the monovalent-to-divalent phase transition temperature. Macroscopic domains of the high-temperature (monovalent) and low-temperature (divalent) phases were detected in the transition temperature region using X-ray diffraction and micro-Raman spectroscopy techniques. The volume fraction of the two domains continuously varied depending upon the temperature. A considerably large volume difference was found between the monovalent and divalent phases. The effect of volumetric strain due to this volume difference is discussed to understand this inhomogeneous state. (author)

Competitive adsorption of Pb(II), Cu(II), and Zn(II) ions onto hydroxyapatite-biochar nanocomposite in aqueous solutions

Science.gov (United States)

Wang, Yu-Ying; Liu, Yu-Xue; Lu, Hao-Hao; Yang, Rui-Qin; Yang, Sheng-Mao

2018-05-01

A hydroxyapatite-biochar nanocomposite (HAP-BC) was successfully fabricated and its physicochemical properties characterized. The analyses showed that HAP nanoparticles were successfully loaded on the biochar surface. The adsorption of Pb(II), Cu(II), and Zn(II) by HAP-BC was systematically studied in single and ternary metal systems. The results demonstrated that pH affects the adsorption of heavy metals onto HAP-BC. Regarding the adsorption kinetics, the pseudo-second-order model showed the best fit for all three heavy metal ions on HAP-BC. In both single and ternary metal ion systems, the adsorption isotherm of Pb(II) by HAP-BC followed Langmuir model, while those of Cu(II) and Zn(II) fitted well with Freundlich model. The maximum adsorption capacity for each tested metal by HAP-BC was higher than that of pristine rice straw biochar (especially for Pb(II)) or those of other reported adsorbents. Therefore, HAP-BC could explore as a new material for future application in heavy metal removal.

A metal-organic framework nanocomposite made from functionalized magnetite nanoparticles and HKUST-1 (MOF-199) for preconcentration of Cd(II), Pb(II), and Ni(II)

International Nuclear Information System (INIS)

Ghorbani-Kalhor, Ebrahim

2016-01-01

The author describes the preparation of a magnetic metal organic framework of type MOF-199 containing magnetite (Fe 3 O 4 ) nanoparticles carrying covalently immobilized 4-(thiazolylazo) resorcinol (Fe 3 O 4 -TAR). This material is shown to represent a viable sorbent for separation and preconcentration of Cd(II), Pb(II), and Ni(II) ions. Box-Behnken design was applied to optimize the parameters affecting preconcentration. Following elution with 0.6 mol L −1 EDTA, the ions were quantified by FAAS. The capacity of the sorbent ranged between 185 and 210 mg g −1 . The limits of detection are 0.15, 0.40, and 0.8 ng mL −1 for Cd(II), Ni(II), and Pb(II) ions, respectively. The relative standard deviations are <8.5 %. The method was successfully applied to the rapid extraction of trace amounts of these ions from sea food and agri food. (author)

Study of oxidation states of the transition metals in a series of Prussian blue analogs using x-ray absorption near edge structure (XANES) spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Adak, S. [Department of Physics, New Mexico State University, Las Cruces, NM, 88003 (United States); Hartl, M., E-mail: monika.hartl@esss.se [European Spallation Source ESS AB, 22100, Lund (Sweden); Manuel Lujan Jr. Neutron Scattering Center (LANSCE-LC), Los Alamos National Laboratory, Los Alamos, NM, 87545 (United States); Daemen, L. [Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN, 37830 (United States); Manuel Lujan Jr. Neutron Scattering Center (LANSCE-LC), Los Alamos National Laboratory, Los Alamos, NM, 87545 (United States); Fohtung, E.; Nakotte, H. [Department of Physics, New Mexico State University, Las Cruces, NM, 88003 (United States)

2017-01-15

Highlights: • Systematic XANES measurements on Prussian blue analogs shows oxidation state of transition metals. • Cobal-iron bimetallic hexacyanometallates show unexpected oxidation states. • Iron(II) ions in hexacyanometallates(III) show varying spin state depending on their bond to the “N” end or “C” end of the cyanide ligand. • Thermal expansion coefficients have been linked to the XANES results. - Abstract: There have been renewed interests in metal-organic framework classes of materials such as Prussian blue analogues (PBAs) due to their potential usage in energy storage applications. In particular, due to their high surface areas, controllable structures and excellent electrochemical properties, PBAs such as hexacyanometalates M{sup II}{sub 3}[A{sup III}(CN){sub 6}]{sub 2*}nH{sub 2}O (M = Mn, Fe, Co, Ni, Cu, Zn; A = Co, Fe, Cr; n = no. of water molecules present), M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}]{sub 2*}nH{sub 2}O (M = Mn, Co, Ni, Cu, Zn) and mixed hexacyanometalates(III) (Fe{sub 1-x}Co{sub x}){sub 3}[B{sup III}(CN){sub 6}]{sub 2}·nH{sub 2}O (x = 0.25, 0.5, 0.75; B = Co, Fe) could have possible usage as a new class of cathode and even anode materials for rechargeable batteries. Detailed knowledge of the oxidation states of the transition metals in PBAs is required to improve efficiency and durability of such devices. Furthermore, a link between the thermal expansion observed in these materials and the oxidation state of the transition metal is of interest to synthesize materials with a desired thermal expansion behavior, Here we demonstrate the use of Synchrotron based X-ray absorption near-edge structure (XANES) spectra to identify transition metal oxidation states. Our analysis reveals the presence of divalent, trivalent and/or mixed valence transition metals in the materials as well as high-spin and low-spin complexes.

The Lithium-, r- and s-Enhanced Metal-Poor Giant HK-II 17435-00532

International Nuclear Information System (INIS)

Roederer, Ian U.; Prieto, Carlos Allende; Sneden, Christopher; Frebel, Anna; Shetrone, Matthew; Rhee, Jaehyon; Gallino, Roberto; Bisterzo, Sara; Beers, Timothy C.; Cowan, John J.

2008-01-01

We present the first detailed abundance analysis of the metal-poor giant HK-II 17435-00532. This star was observed as part of the University of Texas Long-Term Chemical Abundances of Stars in the Halo (CASH) Project. A spectrum was obtained with the High Resolution Spectrograph (HRS) on the Hobby-Eberly Telescope with a resolving power of R∼15000. Our analysis reveals that this star may be located on the red giant branch, red horizontal branch, or early asymptotic giant branch. We find that this metal-poor ([Fe/H] = -2.2) star has an unusually high lithium abundance (logε(Li) = +2.1), mild carbon ([C/Fe] = +0.7) and sodium ([Na/Fe] = +0.6) enhancement, as well as enhancement of both s-process ([Ba/Fe] = +0.8) and r-process ([Eu/Fe] = +0.5) material. The high Li abundance can be explained by self-enrichment through extra mixing mechanisms that connect the convective envelope with the outer regions of the H-burning shell. If so, HK-II 17435-00532 is the most metal-poor starin which this short-lived phase of Li enrichment has been observed. The r- and s-process material was not produced in this star but was either present in the gas from which HK-II 17435-00532 formed or was transferred to it from a more massive binary companion. Despite the current non-detection of radial velocity variations (over a time span of ∼180 days), it is possible that HK-II 17435-00532 is in a long-period binary system, similar to other stars with both r and s enrichment

Divalent Cations Regulate the Ion Conductance Properties of Diverse Classes of Aquaporins

Directory of Open Access Journals (Sweden)

Mohamad Kourghi

2017-11-01

Full Text Available Aquaporins (AQPs are known to facilitate water and solute fluxes across barrier membranes. An increasing number of AQPs are being found to serve as ion channels. Ion and water permeability of selected plant and animal AQPs (plant Arabidopsis thaliana AtPIP2;1, AtPIP2;2, AtPIP2;7, human Homo sapiens HsAQP1, rat Rattus norvegicus RnAQP4, RnAQP5, and fly Drosophila melanogaster DmBIB were expressed in Xenopus oocytes and examined in chelator-buffered salines to evaluate the effects of divalent cations (Ca2+, Mg2+, Ba2+ and Cd2+ on ionic conductances. AtPIP2;1, AtPIP2;2, HsAQP1 and DmBIB expressing oocytes had ionic conductances, and showed differential sensitivity to block by external Ca2+. The order of potency of inhibition by Ca2+ was AtPIP2;2 > AtPIP2;1 > DmBIB > HsAQP1. Blockage of the AQP cation channels by Ba2+ and Cd2+ caused voltage-sensitive outward rectification. The channels with the highest sensitivity to Ca2+ (AtPIP2;1 and AtPIP2;2 showed a distinctive relief of the Ca2+ block by co-application of excess Ba2+, suggesting that divalent ions act at the same site. Recognizing the regulatory role of divalent cations may enable the discovery of other classes of AQP ion channels, and facilitate the development of tools for modulating AQP ion channels. Modulators of AQPs have potential value for diverse applications including improving salinity tolerance in plants, controlling vector-borne diseases, and intervening in serious clinical conditions involving AQPs, such as cancer metastasis, cardiovascular or renal dysfunction.

Induction of divalent cation permeability by heterologous expression of a voltage sensor domain.

Science.gov (United States)

Arima, Hiroki; Tsutsui, Hidekazu; Sakamoto, Ayako; Yoshida, Manabu; Okamura, Yasushi

2018-01-06

The voltage sensor domain (VSD) is a protein domain that confers sensitivity to membrane potential in voltage-gated ion channels as well as the voltage-sensing phosphatase. Although VSDs have long been considered to function as regulatory units acting on adjacent effectors, recent studies have revealed the existence of direct ion permeation paths in some mutated VSDs and in the voltage-gated proton channel. In this study, we show that calcium currents are evoked upon membrane hyperpolarization in cells expressing a VSD derived from an ascidian voltage-gated ion channel superfamily. Unlike the previously reported omega-pore in the Shaker K + channel and rNav1.4, mutations are not required. From electrophysiological experiments in heterologous expression systems, we found that the conductance is directly mediated by the VSD itself and is carried by both monovalent and divalent cations. This is the first report of divalent cation permeation through a VSD-like structure. Copyright © 2018 Elsevier B.V. All rights reserved.

Theoretical study of heavy metal Cd, Cu, Hg, and Ni(II) adsorption on the kaolinite(0 0 1) surface

Energy Technology Data Exchange (ETDEWEB)

Zhao, Jian, E-mail: zhaojian0209@aliyun.com [Institute of Applied Physics and Computational Mathematics, PO Box 8009, Beijing 100088 (China); State Key Laboratory of Geomechanics and Deep Underground Engineering, China University of Mining and Technology, Beijing 100083 (China); He, Man-Chao [State Key Laboratory of Geomechanics and Deep Underground Engineering, China University of Mining and Technology, Beijing 100083 (China)

2014-10-30

Highlights: • We investigated the adsorption of Cd, Cu, Hg, and Ni(II) on kaolinite(0 0 1) surface. • The adsorption capabilities of the kaolinite for HM atoms were Ni > Cu > Cd > Hg(II). • The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms. • The adsorption energy decreases with the coverage for Ni(II) atoms. - Abstract: Heavy metal pollution is currently of great concern because it has been recognized as a potential threat to air, water, and soil. Adsorption was one of the most popular methods for the removal of heavy metal. The adsorption of heavy metal Cd, Cu, Hg, and Ni(II) atoms on the hydroxylated (0 0 1) surface of kaolinite was investigated using density-functional theory within the generalized gradient approximation and a supercell approach. The coverage dependence of the adsorption structures and energetics were systematically studied for a wide range of coverage Θ [from 0.11 to 1.0 monolayers (ML)] and adsorption sites. The most stable among all possible adsorption sites for Cd(II) atom was the two-fold bridge site followed by the one-fold top site, and the top site was the most favorite adsorption site for Cu and Ni(II) atoms, while the three-fold hollow site was the most stable adsorption site for Hg(II) atom followed by the two-fold bridge site. The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms, thus indicating the higher stability of surface adsorption and a tendency to the formation of adsorbate islands (clusters) with increasing the coverage. However, the adsorption energy of Ni(II) atoms decreases when increasing the coverage. The adsorption capabilities of the kaolinite clay for the heavy metal atoms were in the order of Ni > Cu > Cd > Hg(II). The other properties of the Cd, Cu, Hg, and Ni(II)/kaolinite(0 0 1) system including the different charge distribution, the lattice relaxation, and the electronic density of states were also studied and discussed in detail.

Theoretical study of heavy metal Cd, Cu, Hg, and Ni(II) adsorption on the kaolinite(0 0 1) surface

International Nuclear Information System (INIS)

Zhao, Jian; He, Man-Chao

2014-01-01

Highlights: • We investigated the adsorption of Cd, Cu, Hg, and Ni(II) on kaolinite(0 0 1) surface. • The adsorption capabilities of the kaolinite for HM atoms were Ni > Cu > Cd > Hg(II). • The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms. • The adsorption energy decreases with the coverage for Ni(II) atoms. - Abstract: Heavy metal pollution is currently of great concern because it has been recognized as a potential threat to air, water, and soil. Adsorption was one of the most popular methods for the removal of heavy metal. The adsorption of heavy metal Cd, Cu, Hg, and Ni(II) atoms on the hydroxylated (0 0 1) surface of kaolinite was investigated using density-functional theory within the generalized gradient approximation and a supercell approach. The coverage dependence of the adsorption structures and energetics were systematically studied for a wide range of coverage Θ [from 0.11 to 1.0 monolayers (ML)] and adsorption sites. The most stable among all possible adsorption sites for Cd(II) atom was the two-fold bridge site followed by the one-fold top site, and the top site was the most favorite adsorption site for Cu and Ni(II) atoms, while the three-fold hollow site was the most stable adsorption site for Hg(II) atom followed by the two-fold bridge site. The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms, thus indicating the higher stability of surface adsorption and a tendency to the formation of adsorbate islands (clusters) with increasing the coverage. However, the adsorption energy of Ni(II) atoms decreases when increasing the coverage. The adsorption capabilities of the kaolinite clay for the heavy metal atoms were in the order of Ni > Cu > Cd > Hg(II). The other properties of the Cd, Cu, Hg, and Ni(II)/kaolinite(0 0 1) system including the different charge distribution, the lattice relaxation, and the electronic density of states were also studied and discussed in detail

Synthesis and characterization of heterobimetallic complexes of the type [Cu(pn2][MCl4] where M = Co(II, Ni(II, Cu(II, Zn(II, Cd(II, and Hg(II

Directory of Open Access Journals (Sweden)

Seema Yadav

2016-11-01

Full Text Available A series of new bimetallic transition metal complexes of the type [Cu(pn2] [MCl4] have been synthesized (where M = Co(II, Ni(II, Cu(II, Zn(II, Cd(II and Hg(II, pn = 1,3-diaminopropane and characterized by elemental analysis, molar conductance, TGA, IR and electronic spectra. All the compounds are 1:1 electrolyte in DMF. The Cu(II ion is square-planar while metal ions in the anionic moiety acquire their usual tetrahedral arrangement. On the basis of these studies it is concluded that anionic moiety is electrically stabilized by its cationic counterpart.

Higher cytotoxicity of divalent antibody-toxins than monovalent antibody-toxins

International Nuclear Information System (INIS)

Won, JaeSeon; Nam, PilWon; Lee, YongChan; Choe, MuHyeon

2009-01-01

Recombinant antibody-toxins are constructed via the fusion of a 'carcinoma-specific' antibody fragment to a toxin. Due to the high affinity and high selectivity of the antibody fragments, antibody-toxins can bind to surface antigens on cancer cells and kill them without harming normal cells [L.H. Pai, J.K. Batra, D.J. FitzGerald, M.C. Willingham, I. Pastan, Anti-tumor activities of immunotoxins made of monoclonal antibody B3 and various forms of Pseudomonas exotoxin, Proc. Natl. Acad. Sci. USA 88 (1991) 3358-3362]. In this study, we constructed the antibody-toxin, Fab-SWn-PE38, with SWn (n = 3, 6, 9) sequences containing n-time repeated (G 4 S) between the Fab fragment and PE38 (38 kDa truncated form of Pseudomonas exotoxin A). The SWn sequence also harbored one cysteine residue that could form a disulfide bridge between two Fab-SWn-PE38 monomers. We assessed the cytotoxicity of the monovalent (Fab-SWn-PE38), and divalent ([Fab-SWn-PE38] 2 ) antibody-toxins. The cytotoxicity of the dimer against the CRL1739 cell line was approximately 18.8-fold higher than that of the monomer on the ng/ml scale, which was approximately 37.6-fold higher on the pM scale. These results strongly indicate that divalency provides higher cytotoxicity for an antibody-toxin.

Fluorimetric determination of copper(II) in aqueous solution using lucifer yellow CH as selective metal reagent

Energy Technology Data Exchange (ETDEWEB)

Mayr, T.; Wencel, D.; Werner, T. [Univ. of Regensburg (Germany) Inst. of Analytical Chemistry, Chemo- and Biosensors

2001-09-01

Lucifer yellow CH is shown to be a highly selective fluorescent reagent for the determination of Cu(II) in the {mu}g L{sup -1} concentration range. The fluorophore is statically quenched by Cu(II); the carbohydrazide group was assigned as the complexing part of the dye molecule. A total range of Cu(II) determination from 0.06 mg L{sup -1} (1 {mu}mol L{sup -1}) to 6.3 mg L{sup -1} (100 {mu}mol L{sup -1}) with a limit of detection of 0.019 mg L{sup -1} (0.3 {mu}mol L{sup -1}) was obtained, along with surprisingly high selectivity. There was no interference from alkaline and earth alkaline metal ions. The cross sensitivity to heavy metal ions was evaluated by the separate solution method and by competitive binding experiments. Calibration plots are shown for Cu(II) determination at different pH and the dissociation constant was determined. The application of the reagent was demonstrated by the determination of the Cu(II) content of tap water samples. (orig.)

Synthesis and Characterization of Acyclic and Cyclic Azabridged Ligands Incorporating 2,2'-Bipyridine Subunits and Their Complexes With Copper(II, Cobalt(II, and Nickel(II

Directory of Open Access Journals (Sweden)

Andrea Pappalardo

2003-07-01

Full Text Available The synthesis of a series of N,N'-disubstituted acyclic (AL and cyclic (CL aza-bridged ligands incorporating 2,2-pipryidine subunits is described. 1H-NMR and IR spectral data support the proposed ligand structures. Dynamic 1H-NMR studies on diurea and diamide derivatives point to the presence of slowly interconverting conformers on the 1H-NMR time-scale, owing to N−H···N hydrogen bonding and/or a restricted rotation around the amide bonds. The ligands synthesized form 1:1 complexes with divalent transition metal ions. Upon complexation, bis-ester derivatives AL5 and CL5 undergo a metal-induced hydrolysis of the ester groups to carboxyl functions, which act as additional binding sites for the metal ion, as well as hydrogen-bonding donor-acceptor binding site to produce dimeric complexes.

Immobilization of radionuclides and heavy metals through anaerobic bio-oxidation of Fe(II)

International Nuclear Information System (INIS)

Lack, J.G.; Chaudhuri, S.K.; Kelly, S.D.; Kemner, K.M.; O'Connor, S.M.; Coates, J.D.

2002-01-01

Adsorption of heavy metals and radionuclides (HMR) onto iron and manganese oxides has long been recognized as an important reaction for the immobilization of these compounds. However, in environments containing elevated concentrations of these HMR the adsorptive capacity of the iron and manganese oxides may well be exceeded, and the HMR can migrate as soluble compounds in aqueous systems. Here we demonstrate the potential of a bioremediative strategy for HMR stabilization in reducing environments based on the recently described anaerobic nitrate-dependent Fe(II) oxidation by Dechlorosoma species. Bio-oxidation of 10 mM Fe(II) and precipitation of Fe(III) oxides by these organisms resulted in rapid adsorption and removal of 55 μM uranium and 81 μM cobalt from solution. The adsorptive capacity of the biogenic Fe(III) oxides was lower than that of abiotically produced Fe(III) oxides (100 μM for both metals), which may have been a result of steric hindrance by the microbial cells on the iron oxide surfaces. The binding capacity of the biogenic oxides for different heavy metals was indirectly correlated to the atomic radius of the bound element. X-ray absorption spectroscopy indicated that the uranium was bound to the biogenically produced Fe(III) oxides as U(VI) and that the U(VI) formed bidentate and tridentate inner-sphere complexes with the Fe(III) oxide surfaces. Dechlorosoma suillum oxidation was specific for Fe(II), and the organism did not enzymatically oxidize U(IV) or Co(II). Small amounts (less than 2.5 μM) of Cr(III) were reoxidized by D. suillum; however, this appeared to be inversely dependent on the initial concentration of the Cr(III). The results of this study demonstrate the potential of this novel approach for stabilization and immobilization of HMR in the environment.

Complexes of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and dioxouranium(II) with thiophene-2-aldehydethiosemicarbazone

International Nuclear Information System (INIS)

Singh, Balwan; Misra, Harihar

1986-01-01

Metal complexes of thiosemicarbazides have been known for their pharmacological applications. Significant antitubercular, fungicidal and antiviral activities have been reported for thiosemicarbazides and their derivatives. The present study describes the systhesis and characterisation of complexes of Co II , Cu II , Zn II ,Cd II and UO II with thiosemicarbazone obtained by condensing thiophene-2-aldehyde with thiosemicarbazide. 17 refs., 2 tables. (author)

Translocation of metal phosphate via the phosphate inorganic transport system of Escherichia coli

NARCIS (Netherlands)

van Veen, H.W; Abee, T.; Kortstee, G.J J; Konings, W.N; Zehnder, A.J B

1994-01-01

P-i transport via the phosphate inorganic transport system (Pit) of Escherichia coil was studied in natural and artificial membranes. P-i uptake via Pit is dependent on the presence of divalent cations, like Mg2+, Ca2+, Co2+, or Mn2+, which form a soluble, neutral metal phosphate (MeHPO(4)) complex.

Neutralization by metal ions of the toxicity of sodium selenide.

Directory of Open Access Journals (Sweden)

Marc Dauplais

Full Text Available Inert metal-selenide colloids are found in animals. They are believed to afford cross-protection against the toxicities of both metals and selenocompounds. Here, the toxicities of metal salt and sodium selenide mixtures were systematically studied using the death rate of Saccharomyces cerevisiae cells as an indicator. In parallel, the abilities of these mixtures to produce colloids were assessed. Studied metal cations could be classified in three groups: (i metal ions that protect cells against selenium toxicity and form insoluble colloids with selenide (Ag⁺, Cd²⁺, Cu²⁺, Hg²⁺, Pb²⁺ and Zn²⁺, (ii metal ions which protect cells by producing insoluble metal-selenide complexes and by catalyzing hydrogen selenide oxidation in the presence of dioxygen (Co²⁺ and Ni²⁺ and, finally, (iii metal ions which do not afford protection and do not interact (Ca²⁺, Mg²⁺, Mn²⁺ or weakly interact (Fe²⁺ with selenide under the assayed conditions. When occurring, the insoluble complexes formed from divalent metal ions and selenide contained equimolar amounts of metal and selenium atoms. With the monovalent silver ion, the complex contained two silver atoms per selenium atom. Next, because selenides are compounds prone to oxidation, the stabilities of the above colloids were evaluated under oxidizing conditions. 5,5'-dithiobis-(2-nitrobenzoic acid (DTNB, the reduction of which can be optically followed, was used to promote selenide oxidation. Complexes with cadmium, copper, lead, mercury or silver resisted dissolution by DTNB treatment over several hours. With nickel and cobalt, partial oxidation by DTNB occurred. On the other hand, when starting from ZnSe or FeSe complexes, full decompositions were obtained within a few tens of minutes. The above properties possibly explain why ZnSe and FeSe nanoparticles were not detected in animals exposed to selenocompounds.

Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation.

Science.gov (United States)

Kitadai, Norio

2017-03-01

Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg 2+ ) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu 2+ ) are therefore not beneficial places for peptide bond formation on the primitive

Levels of Cd (II, Mn (II, Pb (II, Cu (II, and Zn (II in Common Buzzard (Buteo buteo from Sicily (Italy by Derivative Stripping Potentiometry

Directory of Open Access Journals (Sweden)

P. Licata

2010-01-01

Full Text Available The purpose of this study was to determine the concentrations of heavy metals (Cd, Pb, Cu, Mn, and Zn in different organs (liver, kidney, muscle, lung, skin, and feathers of buzzards (Buteo buteo, utilized as a “biological indicator” for environmental contamination, from different areas of Sicily and to investigate the relationships between birds sex, age, and weight and metal levels in these samples. All samples of common buzzards were collected at the “Recovery Center of Wild Fauna” of Palermo, through the Zooprophilactic Institute. Potentiometric stripping analysis (PSA was used to determine the content of Cd(II, Cu(II, Mn(II, Pb(II, and Zn(II in bird tissues. For toxic metals, the highest levels of Pb were in liver and those of Cd in lung; Zn levels were higher than Cu and Mn in all tissues analyzed. The concentrations in liver, lung, kidney, and muscle could be considered as an indicative of chronic exposure to metals while the presence of metals in skin could be consequential to storing and elimination processes. The found concentrations of metals in the studied matrices required a highly sensitive method for their determination and a simple sample preparation procedure, and the proposed method was well suited for this purpose.

Molecular cloning of a putative divalent-cation transporter gene as a new genetic marker for the identification of Lactobacillus brevis strains capable of growing in beer.

Science.gov (United States)

Hayashi, N; Ito, M; Horiike, S; Taguchi, H

2001-05-01

Random amplified polymorphic DNA (RAPD) PCR analysis of Lactobacillus brevis isolates from breweries revealed that one of the random primers could distinguish beer-spoilage strains of L. brevis from nonspoilage strains. The 1.1-kb DNA fragment amplified from all beer-spoilers included one open reading frame, termed hitA (hop-inducible cation transporter), which encodes an integral membrane protein with 11 putative trans-membrane domains and a binding protein-dependent transport signature of a non-ATP binding membrane transporter common to several prokaryotic and eukaryotic transporters. The hitA polypeptide is homologous to the natural resistance-associated macrophage protein (Nramp) family characterized as divalent-cation transport proteins in many prokaryotic and eukaryotic organisms. Northern blot analysis indicated that the hitA transcripts are expressed in cells cultivated in MRS broth supplemented with hop bitter compounds, which act as mobile-carrier ionophores, dissipating the trans-membrane pH gradient in bacteria sensitive to the hop bitter compounds by exchanging H+ for cellular divalent cations such as Mn2+. This suggests that the hitA gene products may play an important role in making the bacteria resistant to hop bitter compounds in beer by transporting metal ions such as Mn2+ into cells that no longer maintain the proton gradient.

Adsorption study of cadmium (II) and lead (II) on radish peels

International Nuclear Information System (INIS)

Anwar, J.; Shafique, U.; Salman, M.; Zaman, W.; Memoona, M.

2009-01-01

The removal efficiency of heavy metals like Cd(II) and Pb(II) from aqueous solutions by adsorption on Raphanus sativus (Radish peels) has been studied. The effects of time, pH, concentration of adsorbent and agitation speed on adsorption have been evaluated. It is found that radish peels powder has high removal efficiency for both the metals. Batch adsorption study has shown that Cd(II) and Pb(II) has been removed up to 88% and 86% respectively. Adsorption equilibriums for both metals have been described by the Langmuir isotherm. The maximum amount of heavy metals (Q ) adsorbed at max equilibrium were 7.5 and 1.23 mg/g for Cd(II) and Pb(II) respectively as evaluated by Langmuir isotherm. It is concluded that waste materials like radish peels can be used for removal of heavy metals from aqueous streams. (author)

Flame atomic absorption spectrometric determination of heavy metals in aqueous solution and surface water preceded by co-precipitation procedure with copper(II) 8-hydroxyquinoline

Science.gov (United States)

Ipeaiyeda, Ayodele Rotimi; Ayoade, Abisayo Ruth

2017-12-01

Co-precipitation procedure has widely been employed for preconcentration and separation of metal ions from the matrices of environmental samples. This is simply due to its simplicity, low consumption of separating solvent and short duration for analysis. Various organic ligands have been used for this purpose. However, there is dearth of information on the application of 8-hydroxyquinoline (8-HQ) as ligand and Cu(II) as carrier element. The use of Cu(II) is desirable because there is no contamination and background adsorption interference. Therefore, the objective of this study was to use 8-HQ in the presence of Cu(II) for coprecipitation of Cd(II), Co(II), Cr(III), Ni(II) and Pb(II) from standard solutions and surface water prior to their determinations by flame atomic absorption spectrometry (FAAS). The effects of pH, sample volume, amount of 8-HQ and Cu(II) and interfering ions on the recoveries of metal ions from standard solutions were monitored using FAAS. The water samples were treated with 8-HQ under the optimum experimental conditions and metal concentrations were determined by FAAS. The metal concentrations in water samples not treated with 8-HQ were also determined. The optimum recovery values for metal ions were higher than 85.0%. The concentrations (mg/L) of Co(II), Ni(II), Cr(III), and Pb(II) in water samples treated with 8-HQ were 0.014 ± 0.002, 0.03 ± 0.01, 0.04 ± 0.02 and 0.05 ± 0.02, respectively. These concentrations and those obtained without coprecipitation technique were significantly different. Coprecipitation procedure using 8-HQ as ligand and Cu(II) as carrier element enhanced the preconcentration and separation of metal ions from the matrix of water sample.

Henry's Law vaporization studies and thermodynamics of einsteinium-253 metal dissolved in ytterbium

International Nuclear Information System (INIS)

Kleinschmidt, P.D.; Ward, J.W.; Matlack, G.M.; Haire, R.G.

1984-01-01

The cohesive energy of metallic einsteinium determines whether einsteinium is a trivalent or divalent metal. The enthalpy of sublimation, a measure of the cohesive energy, is calculated from the partial pressures of einsteinium over an alloy. The partial pressure of 253 Es has been measured over the range 470--870 K, using combined target and mass spectrometric Knudsen effusion techniques. An alloy was prepared with einsteinium dissolved in a ytterbium solvent to produce a very dilute solution. Partial pressure measurements on the alloy were amenable to the experimental technique and a data analysis using a Henry's law treatment of the data. Vapor pressure data are combined with an estimated crystal entropy S 0 298 and ΔC 0 /sub p/ for ytterbium, to produce enthalpy, entropy, and free energy functions from 298 to 1300 K. The vapor pressure of einsteinium in a dilute einsteinium--ytterbium alloy is described by the equation log P(atm) = -(6815 +- 216)/T+2.576 +- 0.337, from which we calculate for the enthalpy of sublimation of pure einsteinium ΔH 0 298 (second law) = 31.76 kcal/mol. The value of the enthalpy of sublimation is consistent with the conclusion that Es is a divalent metal

Effects of metal ions on growth, β-oxidation system, and thioesterase activity of Lactococcus lactis.

Science.gov (United States)

Li, Liang; Ma, Ying

2014-10-01

The effects of divalent metal ions (Ca(2+), Mg(2+), Fe(2+), and Cu(2+)) on the growth, β-oxidation system, and thioesterase activity of Lactococcus lactis were investigated. Different metal ions significantly influenced the growth of L. lactis: Ca(2+) and Fe(2+) accelerated growth, whereas Cu(2+) inhibited growth. Furthermore, Mg(2+) inhibited growth of L. lactis at a low concentration but stimulated growth of L. lactis at a high concentration. The divalent metal ions had significant effects on activity of the 4 key enzymes of the β-oxidation system (acyl-CoA dehydrogenase, enoyl-CoA hydratase, L-3-hydroxyacyl-CoA dehydrogenase, and thiolase) and thioesterase of L. lactis. The activity of acyl-CoA dehydrogenases increased markedly in the presence of Ca(2+) and Mg(2+), whereas it decreased with 1 mmol/L Fe(2+) or 12 mmol/L Mg(2+). All the metal ions could induce activity of enoyl-CoA hydratase. In addition, 12 mmol/L Mg(2+) significantly stimulated activity of L-3-hydroxyacyl-CoA dehydrogenase, and all metal ions could induce activity of thiolase, although thiolase activity decreased significantly when 0.05 mmol/L Cu(2+) was added into M17 broth. Inhibition of thioesterase activity by all 4 metal ions could be reversed by 2 mmol/L Ca(2+). These results help us understand the effect of metal ions on the β-oxidation system and thioesterase activity of Lactococcus lactis. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

GLOBULAR CLUSTER ABUNDANCES FROM HIGH-RESOLUTION, INTEGRATED-LIGHT SPECTROSCOPY. II. EXPANDING THE METALLICITY RANGE FOR OLD CLUSTERS AND UPDATED ANALYSIS TECHNIQUES

Energy Technology Data Exchange (ETDEWEB)

Colucci, Janet E.; Bernstein, Rebecca A.; McWilliam, Andrew [The Observatories of the Carnegie Institution for Science, 813 Santa Barbara St., Pasadena, CA 91101 (United States)

2017-01-10

We present abundances of globular clusters (GCs) in the Milky Way and Fornax from integrated-light (IL) spectra. Our goal is to evaluate the consistency of the IL analysis relative to standard abundance analysis for individual stars in those same clusters. This sample includes an updated analysis of seven clusters from our previous publications and results for five new clusters that expand the metallicity range over which our technique has been tested. We find that the [Fe/H] measured from IL spectra agrees to ∼0.1 dex for GCs with metallicities as high as [Fe/H] = −0.3, but the abundances measured for more metal-rich clusters may be underestimated. In addition we systematically evaluate the accuracy of abundance ratios, [X/Fe], for Na i, Mg i, Al i, Si i, Ca i, Ti i, Ti ii, Sc ii, V i, Cr i, Mn i, Co i, Ni i, Cu i, Y ii, Zr i, Ba ii, La ii, Nd ii, and Eu ii. The elements for which the IL analysis gives results that are most similar to analysis of individual stellar spectra are Fe i, Ca i, Si i, Ni i, and Ba ii. The elements that show the greatest differences include Mg i and Zr i. Some elements show good agreement only over a limited range in metallicity. More stellar abundance data in these clusters would enable more complete evaluation of the IL results for other important elements.

Bile secretion of cadmium, silver, zinc and copper in the rat. Involvement of various transport systems.

NARCIS (Netherlands)

Havinga, R; Vonk, RJ; Kuipers, F

1996-01-01

In the present study we compared, in vivo in rats, the hepatobiliary transport of monovalent (silver:Ag) and divalent metals (zinc:Zn; cadmium:Cd) with that of copper (Cu). Cu can have two oxidation states in vivo, i.e. Cu(I) and Cu(II). Studies were performed in normal Wistar (NW) rats and mutant

Syntheses, structural characterization and spectroscopic studies of cadmium(II)-metal(II) cyanide complexes with 4-(2-aminoethyl)pyridine

Science.gov (United States)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Hökelek, Tuncer

2017-02-01

Three new cadmium(II)-metal(II) cyanide complexes, [Cd(4aepy)2(H2O)2][Ni(CN)4] (1), [Cd(4aepy)2(H2O)2][Pd(CN)4] (2) and [Cd(4aepy)2(H2O)2][Pt(CN)4] (3) [4aepy = 4-(2-aminoethyl)pyridine], have been synthesized and characterized by elemental, thermal, FT-IR and Raman spectral analyses. The crystal structures of 1 and 2 have been determined by single crystal X-ray diffraction technique, in which they crystallize in the monoclinic system and C2/c space group. The M(II) [M(II) = Ni(II), Pd(II) and Pt(II)] ions are coordinated with the carbon atoms of the four cyanide groups in the square planar geometries and the [M(CN)4]2- ions act as counter ions. The Cd(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. 3D supramolecular structures of 1 and 2 were occurred by M⋯π and hydrogen bonding (Nsbnd H⋯N and Osbnd H⋯N) interactions. Vibrational assignments of all the observed bands were given and the spectral properties were also supported the crystal structures of the complexes. A possible decompositions of the complexes were investigated in the temperature range 30-800 °C in the static atmosphere.

Solid phase extraction of Cd(II) and Pb(II) using a magnetic metal-organic framework, and their determination by FAAS

International Nuclear Information System (INIS)

Sohrabi, Mahmoud Reza; Matbouie, Zahra; Asgharinezhad, Ali Akbar; Dehghani, Ali

2013-01-01

We describe a novel magnetic metal-organic framework (MOF) for the preconcentration of Cd(II) and Pb(II) ions. The MOF was prepared from the Fe 3 O 4 -pyridine conjugate and the copper(II) complex of trimesic acid. The MOF was characterized by IR spectroscopy, elemental analysis, SEM and XRD. A Box-Behnken design through response surface methodology and experimental design was used to identify the optimal parameters for preconcentration. Extraction time, amount of magnetic MOF and pH value were found to be critical factors for uptake, while type, volume, concentration of eluent, and elution time are critical in the elution step. The ions were then determined by FAAS. The limits of detection are 0.2 and 1.1 μg L −1 for Cd(II), and Pb(II) ions, respectively, relative standard deviations are −1 of Cd(II) and Pb(II) ions), and the enrichment capacity of the MOF is at around 190 mg g −1 for both ions which is higher than the conventional Fe 3 O 4 -pyridine material. The magnetic MOF was successfully applied to the rapid extraction of trace quantities of Cd(II) and Pb(II) ions in fish, sediment, and water samples. (author)

Characteristic of metallic state preperties of mendelevium and other actinoids by thermochcomatography

International Nuclear Information System (INIS)

Hubener, S.; Zvara, I.

1982-01-01

The adsorption of the heavy actinoids Cf, Es, Fm, and Md on polycrystalline titanium and molybdenum has been studied by thermochromatography in comparison with several well-known metallic elements, in trace amounts. The data lead us to suggest that Es, Fm, and Md are divalent in the metallic state and, moreover, that the position of their f energy levels relativg to the Fermi-energy is lower than in the cases of Cf and Yb. A correlation was found between the experimental enthalpies of adsorption of the heavy actinoids and their predicted enthalpies of sublimation

Extraction behaviour of 2-octylaminopyridine towards lead(II) from succinate media and its separation from other toxic metals

International Nuclear Information System (INIS)

Mane, Chandrashekhar P.; Anuse, Mansing A.

2008-01-01

Liquid-liquid extraction of lead(II) from succinate media was carried out with 2-octylaminopyridine (2-OAP) in chloroform. Lead(II) was quantitatively extracted with 0.036 M 2-OAP in chloroform from 0.005-0.007 M sodium succinate when equilibrated for 5 min. Lead(II) from the organic phase was stripped with three 10 mL portions of 0.4 M acetic acid and determined titrimetrically with EDTA. The nature of extracted species was determined from the log-log plot. The optimum conditions have been evaluated based on a critical study of weak acid concentration, extractant concentration, period of equilibration and effect of diluents. The metal loading capacity of the reagent was found to be 8 mg of lead(II) with 10 mL 0.036 M of the extractant. The extraction of the lead(II) was carried out in presence of various ions to ascertain the tolerance limit of individual. Temperature dependence of the extraction equilibrium constants was examined to estimate the apparent thermodynamic functions (ΔH, ΔS and ΔG) for extraction reaction. Lead(II) was successfully separated from commonly associated metal ions such as Bi(III), Hg(II), Cr(VI), Cd(II), Zn(II), Al(III), Ca(II), Ba(II) and from binary and ternary mixtures. The method was extended for determination of lead(II) in real samples

Salinity-Dependent Contact Angle Alteration in Oil/Brine/Silicate Systems: the Critical Role of Divalent Cations.

Science.gov (United States)

Haagh, M E J; Siretanu, I; Duits, M H G; Mugele, F

2017-04-11

The effectiveness of water flooding oil recovery depends to an important extent on the competitive wetting of oil and water on the solid rock matrix. Here, we use macroscopic contact angle goniometry in highly idealized model systems to evaluate how brine salinity affects the balance of wetting forces and to infer the microscopic origin of the resultant contact angle alteration. We focus, in particular, on two competing mechanisms debated in the literature, namely, double-layer expansion and divalent cation bridging. Our experiments involve aqueous droplets with a variable content of chloride salts of Na + , K + , Ca 2+ , and Mg 2+ , wetting surfaces of muscovite and amorphous silica, and an environment of ambient decane containing small amounts of fatty acids to represent polar oil components. By diluting the salt content in various manners, we demonstrate that the water contact angle on muscovite, not on silica, decreases by up to 25° as the divalent cation concentration is reduced from typical concentrations in seawater to zero. Decreasing the ionic strength at a constant divalent ion concentration, however, has a negligible effect on the contact angle. We discuss the consequences for the interpretation of core flooding experiments and the identification of a microscopic mechanism of low salinity water flooding, an increasingly popular, inexpensive, and environment-friendly technique for enhanced oil recovery.

Bulk band gaps in divalent hexaborides: A soft x-ray emission study

International Nuclear Information System (INIS)

Denlinger, Jonathan D.; Gweon, Gey-Hong; Allen, James W.; Bianchi, Andrea D.; Fisk, Zachary

2001-01-01

Boron K-edge soft x-ray emission and absorption are used to address the fundamental question of whether divalent hexaborides are intrinsic semimetals or defect-doped bandgap insulators. These bulk sensitive measurements, complementary and consistent with surface-sensitive angle-resolved photoemission experiments, confirm the existence of a bulk band gap and the location of the chemical potential at the bottom of the conduction band

Disturbances to metal partitioning during toxicity testing of iron(II)-rich estuarine pore waters and whole sediments.

Science.gov (United States)

Simpson, Stuart L; Batley, Graeme E

2003-02-01

Metal partitioning is altered when suboxic estuarine sediments containing Fe(II)-rich pore waters are disturbed during collection, preparation, and toxicity testing. Experiments with model Fe(II)-rich pore waters demonstrated the rates at which adsorptive losses of Cd, Cu, Ni, Mn, Pb, and Zn occur upon exposure to air. Experiments with Zn-contaminated estuarine sediments demonstrated large and often unpredictable changes to metal partitioning during sediment storage, removal of organisms, and homogenization before testing. Small modifications to conditions, such as aeration of overlying waters, caused large changes to the metal partitioning. Disturbances caused by sediment collection required many weeks for reestablishment of equilibrium. Bioturbation by benthic organisms led to oxidation of pore-water Fe(II) and lower Zn fluxes because of the formation of Fe hydroxide precipitates that adsorb pore-water Zn. For five weeks after the addition of organisms to sediments, Zn fluxes increased slowly as the organisms established themselves in the sediments, indicating that the establishment of equilibrium was not rapid. The results are discussed in terms of the dynamic nature of suboxic, Fe(II)-rich estuarine sediments, how organisms perturb their environment, and the importance of understanding chemistry in toxicity testing with whole sediments or pore water. Recommendations are provided for the handling of sediments for toxicity testing.

Surface energy and work function of elemental metals

DEFF Research Database (Denmark)

Skriver, Hans Lomholt; Rosengaard, N. M.

1992-01-01

and noble metals, as derived from the surface tension of liquid metals. In addition, they give work functions which agree with the limited experimental data obtained from single crystals to within 15%, and explain the smooth behavior of the experimental work functions of polycrystalline samples......We have performed an ab initio study of the surface energy and the work function for six close-packed surfaces of 40 elemental metals by means of a Green’s-function technique, based on the linear-muffin-tin-orbitals method within the tight-binding and atomic-sphere approximations. The results...... are in excellent agreement with a recent full-potential, all-electron, slab-supercell calculation of surface energies and work functions for the 4d metals. The present calculations explain the trend exhibited by the surface energies of the alkali, alkaline earth, divalent rare-earth, 3d, 4d, and 5d transition...

Preparation and Spectral Properties of Mixed-Ligand Complexes of VO(IV, Ni(II, Zn(II, Pd(II, Cd(II and Pb(II with Dimethylglyoxime and N-acetylglycine

Directory of Open Access Journals (Sweden)

Shayma A. Shaker

2010-01-01

Full Text Available A number of mixed-ligand complexes of the general formula [M(D(G] where D=dimethylglyoximato monoanion, G=N-acetylglycinato and M=VO(IV, Ni(II, Zn(II, Pd(II, Cd(II and Pb(II were prepared. Each complex was characterized by elemental analysis, determination of metal, infrared spectra, electronic spectra, (1H and 13C NMR spectra, conductivity and magnetic moments. All these complexes were not soluble in some of the organic solvent but highly soluble in dimethylformamide. The conductivity data showed the non-electrolytic nature of the complexes. The electronic spectra exhibited absorption bands in the visible region caused by the d-d electronic transition such as VO(IV, Ni(II and Pd(II. The IR and (1H, 13C NMR spectra which have indicate that the dimethylglyoxime was coordinated with the metal ions through the N and O atoms of the oxime group and N-acetylglycine was coordinated with metal ions through the N atom and terminal carboxyl oxygen atom.

Divalent cations and the protein surface co-ordinate the intensity of human platelet adhesion and P-selectin surface expression.

Science.gov (United States)

Whiss, P A; Andersson, R G G

2002-07-01

At sites of blood vessel injury, platelets adhere to exposed vessel components, such as collagen, or immobilized fibrinogen derived from plasma or activated platelets. The divalent cations Mg(2+) and Ca(2+) are essential for platelet adhesion and activation, but Mg(2+) can also inhibit platelet activation. The present study evaluates, by an enzymatic method, the effects of various divalent cations on the adhesion of isolated human platelets to collagen, fibrinogen, albumin or plastic in vitro. By enzyme-linked immunosorbent assay, platelet surface expression of P-selectin was measured to estimate the state of activation on adherence. Mg(2+) increased platelet adhesion exclusively to collagen and fibrinogen at physiologically relevant concentrations. At higher concentrations, the adhesion declined. Ca(2+) induced a weak adhesion only to fibrinogen at physiological doses and a peak of increased adhesion to all protein-coated surfaces at 10 mmol/l. Mn(2+) elicited dose-dependent adhesion only to collagen and fibrinogen. Zn(2+), Ni(2+) and Cu(2+) increased the adhesion of platelets independently of the surface. Ca(2+) dose-dependently inhibited adhesion elicited by Mg(2+) to collagen and fibrinogen. No other combination of divalent cations elicited such an effect. Mg(2+)-dependent platelet adhesion to collagen and Ca(2+)-dependent adhesion to fibrinogen increased P-selectin expression. Thus, the present study shows that the outcome of the platelet adhesion depends on the surface and the access of divalent cations, which co-ordinate the intensity of platelet adhesion and P-selectin surface expression.

Influence of group II metals on Radium-226 concentration ratios in the native green plum (Buchanania obovata) from the Alligator Rivers Region, Northern Territory, Australia

International Nuclear Information System (INIS)

Medley, Peter; Bollhöfer, Andreas

2016-01-01

In this study, uptake of Ra from soil, and the influence of group II metals on Ra uptake, into the stones and edible flesh of the fruit of the wild green plum, Buchanania obovata, was investigated. Selective extraction of the exchangeable fraction of the soil samples was undertaken but was not shown to more reliably predict Ra uptake than total soil Ra activity concentration. Comparison of the group II metal to Ca ratios (i.e. Sr/Ca, Ba/Ca, Ra/Ca) in the flesh with exchangeable Ca shows that Ca outcompetes group II metals for root uptake and that the uptake pathway discriminated against group II metals relative to ionic radius, with uptake of Ca > Sr > Ba >> Ra. Flesh and stone analysis showed that movement of group II metals to these components of the plant, after root uptake, was strongly related. This supports the hypothesis that Sr, Ba and Ra are being taken up as analogue elements, and follow the same uptake and translocation pathways, with Ca. Comparison with previously reported data from a native passion fruit supports the use of total soil CRs on natural, undisturbed sites. As exchangeable CRs for Ra reach a saturation value it may be possible to make more precise predictions using selective extraction techniques for contaminated or disturbed sites. - Highlights: • We studied uptake of Ra-226 from soil into Buchanania obovata. • The influence of group II metals (Sr, Ba and Ca) on Ra uptake was investigated. • The exchangeable Ra fraction of the soil was not a more reliable predictor of Ra uptake than total soil Ra. • Ca outcompetes group II metals Sr, Ba and Ra for root uptake. • Uptake discriminated against group II metals relative to ionic radius, with uptake of Ca > Sr > Ba >> Ra.

Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

Science.gov (United States)

Mohamed, Gehad G.; El-Gamel, Nadia E. A.

2004-11-01

The ternary piroxicam (Pir; 4-hydroxy-2-methyl- N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA cheletes were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

EPR of divalent manganese in non-Kramers hosts

Energy Technology Data Exchange (ETDEWEB)

Lech, J.; Slezak, A. [Institute of Physics, Technical University of Czestochowa, Czestochowa (Poland)

1997-12-31

Various interactions which lead to the observation of sharp EPR spectra of the high half-integer spin impurity Mn{sup 2+} (S=5/2) in paramagnetic hosts with integer spins S=1 and S=2 have been studied. Studies have been carried out on the basis of data extracted from experimental EPR spectra of Mn{sup 2+} in single crystal of divalent nickel Ni{sup 2+} (S=1) and Fe{sup 2+} (S=1) perchlorate hexahydrates. It has been shown that dipolar host-host and host-guest couplings broaden resonance lines of Mn{sup 2+}. Narrowing of the lines in the both crystals can be mainly attributed to the host-guest exchange interactions and quenching of the host spins. 19 refs, 3 figs, 1 tab.

Crucial role of dynamic linker histone binding and divalent ions for DNA accessibility and gene regulation revealed by mesoscale modeling of oligonucleosomes

Science.gov (United States)

Collepardo-Guevara, Rosana; Schlick, Tamar

2012-01-01

Monte Carlo simulations of a mesoscale model of oligonucleosomes are analyzed to examine the role of dynamic-linker histone (LH) binding/unbinding in high monovalent salt with divalent ions, and to further interpret noted chromatin fiber softening by dynamic LH in monovalent salt conditions. We find that divalent ions produce a fiber stiffening effect that competes with, but does not overshadow, the dramatic softening triggered by dynamic-LH behavior. Indeed, we find that in typical in vivo conditions, dynamic-LH binding/unbinding reduces fiber stiffening dramatically (by a factor of almost 5, as measured by the elasticity modulus) compared with rigidly fixed LH, and also the force needed to initiate chromatin unfolding, making it consistent with those of molecular motors. Our data also show that, during unfolding, divalent ions together with LHs induce linker-DNA bending and DNA–DNA repulsion screening, which guarantee formation of heteromorphic superbeads-on-a-string structures that combine regions of loose and compact fiber independently of the characteristics of the LH–core bond. These structures might be important for gene regulation as they expose regions of the DNA selectively. Dynamic control of LH binding/unbinding, either globally or locally, in the presence of divalent ions, might constitute a mechanism for regulation of gene expression. PMID:22790986

Data in support of the negative influence of divalent cations on (?)-epigallocatechin-3-gallate (EGCG)-mediated inhibition of matrix metalloproteinase-2 (MMP-2)

OpenAIRE

Deb, Gauri; Batra, Sahil; Limaye, Anil M.

2015-01-01

In this data article we have provided evidence for the negative influence of divalent cations on (−)‐epigallocatechin-3-gallate (EGCG)-mediated inhibition of matrix metalloproteinase-2 (MMP-2) activity in cell-free experiments. Chelating agents, such as EDTA and sodium citrate alone, did not affect MMP-2 activity. While EDTA enhanced, excess of divalent cations interfered with EGCG-mediated inhibition of MMP-2.

Characteristics of separation of carnitine and metal ions in cheese whey model solution by loose reverse osmosis membrane

Energy Technology Data Exchange (ETDEWEB)

Xu, J.; Echizen, H.; Xing, X.; Yamamoto, S.; Unno, H. [Tokyo Institute of Technology, Tokyo (Japan)

1996-04-20

Aiming at recovering carnitine from cheese whey by using loose reverse osmosis membranes, rejection characteristics of several components in the whey were examined by using model solutions. An electroneutral membrane was found to be most effective for the separation. The rejection of carnitine was above 0.95 independent of the pH of solutions, while monovalent metal ions showed low rejections of 0.1-0.3. On the other hand, the rejections of divalent metal ions deceased with increase of the pH, and reached a minimum of about 0.5. As a result, mono-and divalent metal ions could be removed simultaneously by adjusting the pH of the feed solutions. To clarify the effect of pH on the rejection the permeate of MgCl2 aqueous solution was examined. The rejections of MgCl2 were greatly affected by the pH and showed the same tendency as the mixed station. The effect of the pH on permeation of electrolyte was considered to be caused mainly by the adsorption of ions on the membrane. 16 refs., 6 figs., 2 tabs.

Methanosarcina acetivorans C2A topoisomerase IIIα, an archaeal enzyme with promiscuity in divalent cation dependence.

Directory of Open Access Journals (Sweden)

Raymond Morales

Full Text Available Topoisomerases play a fundamental role in genome stability, DNA replication and repair. As a result, topoisomerases have served as therapeutic targets of interest in Eukarya and Bacteria, two of the three domains of life. Since members of Archaea, the third domain of life, have not been implicated in any diseased state to-date, there is a paucity of data on archaeal topoisomerases. Here we report Methanosarcina acetivorans TopoIIIα (MacTopoIIIα as the first biochemically characterized mesophilic archaeal topoisomerase. Maximal activity for MacTopoIIIα was elicited at 30-35°C and 100 mM NaCl. As little as 10 fmol of the enzyme initiated DNA relaxation, and NaCl concentrations above 250 mM inhibited this activity. The present study also provides the first evidence that a type IA Topoisomerase has activity in the presence of all divalent cations tested (Mg(2+, Ca(2+, Sr(2+, Ba(2+, Mn(2+, Fe(2+, Co(2+, Ni(2+, Cu(2+, Zn(2+ and Cd(2+. Activity profiles were, however, specific to each metal. Known type I (ssDNA and camptothecin and type II (etoposide, novobiocin and nalidixic acid inhibitors with different mechanisms of action were used to demonstrate that MacTopoIIIα is a type IA topoisomerase. Alignment of MacTopoIIIα with characterized topoisomerases identified Y317 as the putative catalytic residue, and a Y317F mutation ablated DNA relaxation activity, demonstrating that Y317 is essential for catalysis. As the role of Domain V (C-terminal domain is unclear, MacTopoIIIα was aligned with the canonical E. coli TopoI 67 kDa fragment in order to construct an N-terminal (1-586 and a C-terminal (587-752 fragment for analysis. Activity could neither be elicited from the fragments individually nor reconstituted from a mixture of the fragments, suggesting that native folding is impaired when the two fragments are expressed separately. Evidence that each of the split domains plays a role in Zn(2+ binding of the enzyme is also provided.

Mussel-inspired histidine-based transient network metal coordination hydrogels

Science.gov (United States)

Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.; Burghardt, Wesley R.; Messersmith, Phillip B.

2013-01-01

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants. PMID:23441102

Isolation Of PS II Nanoparticles And Oxygen Evolution Studies In Synechococcus Spp. PCC 7942 Under Heavy Metal Stress

Science.gov (United States)

Ahmad, Iffat Zareen; Sundaram, Shanthy; Tripathi, Ashutosh; Soumya, K. K.

2009-06-01

The effect of heavy metals was seen on the oxygen evolution pattern of a unicellular, non-heterocystous cyanobacterial strain of Synechococcus spp. PCC 7942. It was grown in a BG-11 medium supplemented with heavy metals, namely, nickel, copper, cadmium and mercury. Final concentrations of the heavy metal solution used in the culture were 0.1, 0.4 and 1 μM. All the experiments were performed in the exponential phase of the culture. Oxygen-evolving photosystem II (PS II) particles were purified from Synechococcus spp. PCC 7942 by a single-step Ni2+-affinity column chromatography after solubilization of thylakoid membranes with sucrose monolaurate. Oxygen evolution was measured with Clark type oxygen electrode fitted with a circulating water jacket. The light on the surface of the vessel was 10 w/m2. The cultures were incubated in light for 15 minutes prior to the measurement of oxygen evolution. Oxygen evolution was measured in assay mixture containing phosphate buffer (pH-7.5, 0.1 M) in the presence of potassium ferricyanide as the electron acceptor. The preparation from the control showed a high oxygen-evolving activity of 2, 300-2, 500 pmol O2 (mg Chl)-1 h-1 while the activity was decreased in the cultures grown with heavy metals. The inhibition of oxygen evolution shown by the organism in the presence of different metals was in the order Hg>Ni>Cd>Cu. Such heavy metal resistant strains will find application in the construction of PS II- based biosensors for the monitoring of pollutants.

Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some metal (II) complexes with ONO donor ligand containing benzo[b]thiophene and coumarin moieties

Science.gov (United States)

Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

2014-09-01

Schiff base ligand 3-chloro-N‧-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzo[b]thiophene-2-carbohydrazide and its Cu(II), Co(II), Ni(II) and Zn(II) complexes were synthesized, characterized by elemental analysis and various physico-chemical techniques like, IR, 1H NMR, ESI-mass, UV-Visible, thermogravimetry - differential thermal analysis, magnetic measurements and molar conductance. Spectral analysis indicates octahedral geometry for all the complexes. Cu(II) complex have 1:1 stoichiometry of the type [M(L)(Cl)(H2O)2], whereas Co(II), Ni(II) and Zn(II) complexes have 1:2 stoichiometric ratio of the type [M(L)2]. The bonding sites are the oxygen atom of amide carbonyl, nitrogen of azomethine function and phenolic oxygen of the Schiff base ligand via deprotonation. The thermogravimetry - differential thermal analysis studies gave evidence for the presence of coordinated water molecules in the composition of Cu(II) complex which was further supported by IR measurements. All the complexes were investigated for their electrochemical activity, but only the Cu(II) complex showed the redox property. In order to evaluate the effect of antimicrobial potency of metal ions upon chelation, ligand and its metal complexes along with their respective metal chlorides were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligand. Ligand and its complexes were screened for free radical scavenging activity by DPPH method and DNA cleavage activity using Calf-thymus DNA (Cat. No-105850).

Studies on nickel (II and palladium (II complexes with some tetraazamacrocycles containing tellurium

Directory of Open Access Journals (Sweden)

Rathee Nitu

2012-01-01

Full Text Available The synthesis of 10-membered and 12-membered tellurium containing tetraazamacrocyclic complexes of divalent nickel and palladium by template condensation of diaryltellurium dichlorides, (aryl = p-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, p-methoxyphenyl with 1,2-diaminoethane and 1,3-diaminopropane in the presence of metal dichloride is reported. The resulting complexes have been subjected to elemental analyses, magnetic measurements, electronic absorption, infra-red, and proton magnetic resonance spectral studies. The formation of proposed macrocyclic skeletons and their donor sites have been identified on the basis of spectral studies. Distorted octahedral structure for the nickel complexes in the solid state and squareplanar structure for the palladium complexes have been suggested.

Thermolysis synthesis of pure phase NiO from novel sonochemical synthesized Ni(II) nano metal-organic supramolecular architecture.

Science.gov (United States)

Hanifehpour, Younes; Morsali, Ali; Mirtamizdoust, Babak; Joo, Sang Woo; Soltani, Behzad

2017-07-01

Nano-structures of a new supramolecular coordination compound of divalent nickel with the pyrazol (pzH) containing the terminal azide anions, [Ni(pzH) 2 (N 3 ) 2 ] (1), with discrete molecular architecture (DMA) in solid state was synthesized via sonochemical method. The new nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, IR, and elemental analysis. Compound 1 was structurally characterized by single crystal X-ray diffraction and the single-crystal X-ray data shows that the coordination number of Ni (II) ions is six, (NiN 6 ), with four N-donor atoms from neutral "pzH" ligands and two N-donors from two terminal azide anions. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are consistent with the crystal structure. The NiO nanoparticles were obtained by thermolysis of 1 at 180°C with oleic acid as a surfactant. Copyright © 2017 Elsevier B.V. All rights reserved.

Computer augumented modelling studies of Pb(II, Cd(II, Hg(II, Co(II, Ni(II, Cu(II and Zn(II complexes of L-glutamic acid in 1,2-propanediol–water mixtures

Directory of Open Access Journals (Sweden)

MAHESWARA RAO VEGI

2008-12-01

Full Text Available Chemical speciation of Pb(II, Cd(II, Hg(II, Co(II, Ni(II, Cu(II and Zn(II complexes of L-glutamic acid was studied at 303 K in 0–60 vol. % 1,2-propanediol–water mixtures, whereby the ionic strength was maintained at 0.16 mol dm-3. The active forms of the ligand are LH3+, LH2 and LH–. The predominant detected species were ML, ML2, MLH, ML2H and ML2H2. The trend of the variation in the stability constants with changing dielectric constant of the medium is explained based on the cation stabilizing nature of the co-solvents, specific solvent–water interactions, charge dispersion and specific interactions of the co-solvent with the solute. The effect of systematic errors in the concentrations of the substances on the stability constants is in the order alkali > > acid > ligand > metal. The bioavailability and transportation of metals are explained based on distribution diagrams and stability constants.

Coloration of chromium-doped yttrium aluminum garnet single-crystal fibers using a divalent codopant

International Nuclear Information System (INIS)

Tissue, B.M.; Jia, W.; Lu, L.; Yen, W.M.

1991-01-01

We have grown single-crystal fibers of Cr:YAG and Cr,Ca:YAG under oxidizing and reducing conditions by the laser-heated-pedestal-growth method. The Cr:YAG crystals were light green due to Cr 3+ in octahedral sites, while the Cr,Ca:YAG crystals were brown. The presence of the divalent codopant was the dominant factor determining the coloration in these single-crystal fibers, while the oxidizing power of the growth atmosphere had little effect on the coloration. The Cr,Ca:YAG had a broad absorption band centered at 1.03 μm and fluoresced from 1.1 to 1.7 μm, with a room-temperature lifetime of 3.5 μs. The presence of both chromium and a divalent codopant were necessary to create the optically-active center which produces the near-infrared emission. Doping with only Ca 2+ created a different coloration with absorption in the blue and ultraviolet. The coloration in the Cr,Ca:YAG is attributed to Cr 4+ and is produced in as-grown crystals without irradiation or annealing, as has been necessary in previous work

Non-bonding interactions and non-covalent delocalization effects play a critical role in the relative stability of group 12 complexes arising from interaction of diethanoldithiocarbamate with the cations of transition metals Zn(II), Cd(II), and Hg(II): a theoretical study.

Science.gov (United States)

Bahrami, Homayoon; Farhadi, Saeed; Siadatnasab, Firouzeh

2016-07-01

The chelating properties of diethanoldithiocarbamate (DEDC) and π-electron flow from the nitrogen atom to the sulfur atom via a plane-delocalized π-orbital system (quasi ring) was studied using a density functional theory method. The molecular structure of DEDC and its complexes with Zn(II), Cd(II), and Hg(II) were also considered. First, the geometries of this ligand and DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) were optimized, and the formation energies of these complexes were then calculated based on the electronic energy, or sum of electronic energies, with the zero point energy of each species. Formation energies indicated the DEDC-Zn(II) complex as the most stable complex, and DEDC-Cd(II) as the least stable. Structural data showed that the N1-C2 π-bond was localized in the complexes rather than the ligand, and a delocalized π-bond over S7-C2-S8 was also present. The stability of DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) complexes increased in the presence of the non-specific effects of the solvent (PCM model), and their relative stability did not change. There was π-electron flow or resonance along N1-C2-S7 and along S7-C2-S8 in the ligand. The π-electron flow or resonance along N1-C2-S7 was abolished when the metal interacted with sulfur atoms. Energy belonging to van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand was calculated for each complex. The results of nucleus-independent chemical shift (NICS) indicated a decreasing trend as Zn(II) Hg(II) for the aromaticity of the quasi-rings. Finally, by ignoring van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand, the relative stability of the complexes was changed as follows:[Formula: see text] Graphical Abstract Huge electronic cloud localized on Hg(II) in the Hg(II)-DEDC complex.

A Versatile Dinucleating Ligand Containing Sulfonamide Groups

DEFF Research Database (Denmark)

Sundberg, Jonas; Witt, Hannes; Cameron, Lisa

2014-01-01

ligand can be prepared in aqueous solutions using only divalent metal ions. Two of the copper(II) complexes, [Cu2(psmp)(OH)] and [Cu2(psmp)(OAc)2]-, demonstrate the anticipated 1:2 ligand/metal stoichiometry and show that the dimetallic binding site created for exogenous ligands possesses high inherent...... of antiferromagnetic coupling. This is corroborated computationally by broken-symmetry density functional theory, which for isotropic modeling of the coupling predicts an antiferromagnetic coupling strength of J = 70.5 cm-1....

Biological low pH Mn(II) oxidation in a manganese deposit influenced by metal-rich groundwater

Science.gov (United States)

Bohu, Tsing; Akob, Denise M.; Abratis, Michael; Lazar, Cassandre S.; Küsel, Kirsten

2016-01-01

The mechanisms, key organisms, and geochemical significance of biological low-pH Mn(II) oxidation are largely unexplored. Here, we investigated the structure of indigenous Mn(II)-oxidizing microbial communities in a secondary subsurface Mn oxide deposit influenced by acidic (pH 4.8) metal-rich groundwater in a former uranium mining area. Microbial diversity was highest in the Mn deposit compared to the adjacent soil layers and included the majority of known Mn(II)-oxidizing bacteria (MOB) and two genera of known Mn(II)-oxidizing fungi (MOF). Electron X-ray microanalysis showed that romanechite [(Ba,H2O)2(Mn4+,Mn3+)5O10] was conspicuously enriched in the deposit. Canonical correspondence analysis revealed that certain fungal, bacterial, and archaeal groups were firmly associated with the autochthonous Mn oxides. Eight MOB within the Proteobacteria, Actinobacteria, and Bacteroidetes and one MOF strain belonging to Ascomycota were isolated at pH 5.5 or 7.2 from the acidic Mn deposit. Soil-groundwater microcosms demonstrated 2.5-fold-faster Mn(II) depletion in the Mn deposit than adjacent soil layers. No depletion was observed in the abiotic controls, suggesting that biological contribution is the main driver for Mn(II) oxidation at low pH. The composition and species specificity of the native low-pH Mn(II) oxidizers were highly adapted to in situ conditions, and these organisms may play a central role in the fundamental biogeochemical processes (e.g., metal natural attenuation) occurring in the acidic, oligotrophic, and metalliferous subsoil ecosystems.

Ab Initio Assessment of the Bonding in Disulfonates Containing Divalent Nitrogen and Phosphorus Atoms

DEFF Research Database (Denmark)

Andersen, Vinca Bonde; Berg, Rolf W.; Shim, Irene

2017-01-01

The iminodisulfonate, [N(SO3)2]3–, and phosphinodisulfonate, [P(SO3)2]3–, ions have been investigated by performing ab initio MP2/6-311+G**calculations. The nitrogen and phosphorus atoms as part of the ions are shown to be divalent with a negative charge and two lone pairs on the nitrogen...

Structure and reactivity of a mononuclear gold(II) complex

Science.gov (United States)

Preiß, Sebastian; Förster, Christoph; Otto, Sven; Bauer, Matthias; Müller, Patrick; Hinderberger, Dariush; Hashemi Haeri, Haleh; Carella, Luca; Heinze, Katja

2017-12-01

Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined. The gold atom adopts a 2+2 coordination mode in between those of gold(III) (four-coordinate square planar) and gold(I) (two-coordinate linear), owing to a second-order Jahn-Teller distortion enabled by the relativistically lowered 6s orbital of gold. The reactivity of this gold(II) complex towards dioxygen, nitrosobenzene and acids is discussed. This study provides insight on the ionic radius of gold(II), and allows it to be placed within the homologous series of nd9 Cu/Ag/Au divalent ions and the 5d8/9/10 Pt/Au/Hg 'relativistic' triad in the periodic table.

Synthesis of amino functionalized magnetic graphenes composite material and its application to remove Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II) from contaminated water

International Nuclear Information System (INIS)

Guo, Xiaoyao; Du, Bin; Wei, Qin; Yang, Jian; Hu, Lihua; Yan, Liangguo; Xu, Weiying

2014-01-01

Highlights: • Graphenes magnetic composite nanoparticles (Fe 3 O 4 -GS) were used to adsorb metal ions. • The adsorption of metal ions onto Fe 3 O 4 -GS could be well interpreted by the Freundlich equation. • The adsorption of metal ions onto Fe 3 O 4 -GS fit pseudo-second order kinetic model. • Thermodynamic studies illustrated that the adsorption process was endothermic and spontaneous in nature. - Abstract: In the present study, a kind of graphenes magnetic material (Fe 3 O 4 -GS) was prepared by compositing graphene sheet with ferroferric oxide, and shown to be effictive for removing Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II) ions from aqueous solution. The synthesized sorbent was characterized by SEM, TEM, FTIR, XRD, XPS and BET, respectively. The pH ZPC value of the sorbent was estimated to be 3.5 by alkaline-titration methods. Fe 3 O 4 -GS can be simply recovered from water with magnetic separation at low magnetic field within one minute. The sorption capacities of the metals were 17.29, 27.95, 23.03, 27.83 and 22.07 mg g −1 for Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II), respectively. Kinetic data showed good correlation with pseudo-second-order equation and the Freundlich model was found to fit for the isotherm data of all the heavy metal ions. It was found that the metals sorption was accomplished mainly via chelation or ion exchange. The results of thermodynamic studies illustrate that the adsorption process was endothermic and spontaneous in nature

Effect of the chelation of metal cation on the antioxidant activity of chondroitin sulfates.

Science.gov (United States)

Ajisaka, Katsumi; Oyanagi, Yutaka; Miyazaki, Tatsuo; Suzuki, Yasuhiro

2016-06-01

The antioxidant potencies of chondroitin sulfates (CSs) from shark cartilage, salmon cartilage, bovine trachea, and porcine intestinal mucosa were compared by three representative methods for the measurement of the antioxidant activity; DPPH radical scavenging activity, superoxide radical scavenging activity, and hydroxyl radical scavenging activity. CSs from salmon cartilage and bovine trachea showed higher potency in comparison with CSs from shark cartilage and porcine intestinal mucosa. Next, CS from salmon cartilage chelating with Ca(2+), Mg(2+), Mn(2+), or Zn(2+) were prepared, and their antioxidant potencies were compared. CS chelating with Ca(2+) or Mg(2+) ions showed rather decreased DPPH radical scavenging activity in comparison with CS of H(+) form. In contrast, CS chelating with Ca(2+) or Mg(2+) ion showed remarkably enhanced superoxide radical scavenging activity than CS of H(+) or Na(+) form. Moreover, CS chelating with divalent metal ions, Ca(2+), Mg(2+), Mn(2+), or Zn(2+), showed noticeably higher hydroxyl radical scavenging activity than CS of H(+) or Na(+) form. The present results revealed that the scavenging activities of, at least, superoxide radical and hydroxyl radical were enhanced by the chelation with divalent metal ions.

Enhancement of chitosan-graphene oxide SPR sensor with a multi-metallic layers of Au–Ag–Au nanostructure for lead(II) ion detection

Energy Technology Data Exchange (ETDEWEB)

Kamaruddin, Nur Hasiba [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Bakar, Ahmad Ashrif A., E-mail: ashrif@ukm.edu.my [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Yaacob, Mohd Hanif; Mahdi, Mohd Adzir [Wireless and Photonic Network Research Centre, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor (Malaysia); Zan, Mohd Saiful Dzulkefly [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Shaari, Sahbudin [Institute of Microengineering and Nanoelectronics, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia)

2016-01-15

Highlights: • Tri-metallic Au–Ag–Au CS-GO SPR sensor was fabricated for the first time. • The tri-metallic nanostructure provided an enhanced evanescent field. • Successful functionalization of the CS-GO sensing layer. • Superior performance for lead(II) ion detection. - Abstract: We demonstrate the enhancement of surface plasmon resonance (SPR) technique by implementing a multi-metallic layers of Au–Ag–Au nanostructure in the chitosan-graphene oxide (CS-GO) SPR sensor for lead(II) ion detection. The performance of the sensor is analyzed via SPR measurements, from which the sensitivity, signal-to-noise ratio and repeatability are determined. The nanostructure layers are characterized using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). We showed that the proposed structure has increased the shift in the SPR angle up to 3.5° within the range of 0.1–1 ppm due to the enhanced evanescent field at the sensing layer-analyte interface. This sensor also exhibits great repeatability which benefits from the stable multi-metallic nanostructure. The SNR value of 0.92 for 5 ppm lead(II) ion solution and reasonable linearity range up to that concentration shows that the tri-metallic CS-GO SPR sensor gives a good response towards the lead(II) ion solution. The CS-GO SPR sensor is also sensitive to at least a 10{sup −5} change in the refractive index. The results prove that our proposed tri-metallic CS-GO SPR sensor demonstrates a strong performance and reliability for lead(II) ion detection in accordance with the standardized lead safety level for wastewater.

Effects of thermal aging on the microstructure of Type-II boundaries in dissimilar metal weld joints

Science.gov (United States)

Yoo, Seung Chang; Choi, Kyoung Joon; Bahn, Chi Bum; Kim, Si Hoon; Kim, Ju Young; Kim, Ji Hyun

2015-04-01

In order to investigate the effects of long-term thermal aging on the microstructural evolution of Type-II boundary regions in the weld metal of Alloy 152, a representative dissimilar metal weld was fabricated from Alloy 690, Alloy 152, and A533 Gr.B. This mock-up was thermally aged at 450 °C to accelerate the effects of thermal aging in a nuclear power plant operation condition (320 °C). The microstructure of the Type-II boundary region of the weld root, which is parallel to and within 100 μm of the fusion boundary and known to be more susceptible to material degradation, was then characterized after different aging times using a scanning electron microscope equipped with an energy dispersive X-ray spectroscope for micro-compositional analysis, electron backscattered diffraction detector for grain and grain boundary orientation analysis, and a nanoindenter for measurement of mechanical properties. Through this, it was found that a steep compositional gradient and high grain average misorientation is created in the narrow zone between the Type-II and fusion boundaries, while the concentration of chromium and number of low-angle grain boundaries increases with aging time. A high average hardness was also observed in the same region of the dissimilar metal welds, with hardness peaking with thermal aging simulating an operational time of 15 years.

"Rocking-Chair"-Type Metal Hybrid Supercapacitors.

Science.gov (United States)

Yoo, Hyun Deog; Han, Sang-Don; Bayliss, Ryan D; Gewirth, Andrew A; Genorio, Bostjan; Rajput, Nav Nidhi; Persson, Kristin A; Burrell, Anthony K; Cabana, Jordi

2016-11-16

Hybrid supercapacitors that follow a "rocking-chair"-type mechanism were developed by coupling divalent metal and activated carbon electrodes in nonaqueous electrolytes. Conventional supercapacitors require a large amount of electrolyte to provide a sufficient quantity of ions to the electrodes, due to their Daniell-type mechanism that depletes the ions from the electrolyte while charging. The alternative "rocking-chair"-type mechanism effectively enhances the energy density of supercapacitors by minimizing the necessary amount of electrolyte, because the ion is replenished from the metal anode while it is adsorbed to the cathode. Newly developed nonaqueous electrolytes for Mg and Zn electrochemistry, based on bis(trifluoromethylsulfonyl)imide (TFSI) salts, made the metal hybrid supercapacitors possible by enabling reversible deposition on the metal anodes and reversible adsorption on an activated carbon cathode. Factoring in gains through the cell design, the energy density of the metal hybrid supercapacitors is projected to be a factor of 7 higher than conventional devices thanks to both the "rocking-chair"-type mechanism that minimizes total electrolyte volume and the use of metal anodes, which have substantial merits in capacity and voltage. Self-discharge was also substantially alleviated compared to conventional supercapacitors. This concept offers a route to build supercapacitors that meet dual criteria of power and energy densities with a simple cell design.

Antibacterial Co(II, Ni(II, Cu(II and Zn(II complexes with biacetyl-derived Schiff bases

Directory of Open Access Journals (Sweden)

MUHAMMAD IMRAN

2010-08-01

Full Text Available The condensation reactions of biacetyl with ortho-hydroxyaniline and 2-aminobenzoic acid to form bidendate NO donor Schiff bases were studied. The prepared Schiff base ligands were further utilized for the formation of metal chelates having the general formula [ML2(H2O2] where M = Co(II, Ni(II, Cu(II and Zn(II and L = HL1 and HL2. These new compounds were characterized by conductance measurements, magnetic susceptibility measurements, elemental analysis, and IR, 1H-NMR, 13C-NMR and electronic spectroscopy. Both Schiff base ligands were found to have a mono-anionic bidentate nature and octahedral geometry was assigned to all metal complexes. All the complexes contained coordinated water which was lost at 141–160 °C. These compounds were also screened for their in vitro antibacterial activity against four bacterial species, namely: Escherichia coli, Staphylococcus aureus, Salmonella typhi and Bacillus subtilis. The metal complexes were found to have greater antibacterial activity than the uncomplexed Schiff base ligands.

Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions.

Science.gov (United States)

Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry

2013-05-20

A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.

New fluorescent azo-Schiff base Cu(II) and Zn(II) metal chelates; spectral, structural, electrochemical, photoluminescence and computational studies

Science.gov (United States)

Purtas, Fatih; Sayin, Koray; Ceyhan, Gokhan; Kose, Muhammet; Kurtoglu, Mukerrem

2017-06-01

A new Schiff base containing azo chromophore group obtained by condensation of 2-hydroxy-4-[(E)-phenyldiazenyl]benzaldehyde with 3,4-dimethylaniline (HL) are used for the syntheses of new copper(II) and zinc(II) chelates, [Cu(L)2], and [Zn(L)2], and characterized by physico-chemical and spectroscopic methods such as 1H and 13C NMR, IR, UV.-Vis. and elemental analyses. The solid state structure of the ligand was characterized by single crystal X-ray diffraction study. X-ray diffraction data was then used to calculate the harmonic oscillator model of aromaticity (HOMA) indexes for the rings so as to investigate of enol-imine and keto-amine tautomeric forms in the solid state. The phenol ring C10-C15 shows a considerable deviation from the aromaticity with HOMA value of 0.837 suggesting the shift towards the keto-amine tautomeric form in the solid state. The analytical data show that the metal to ligand ratio in the chelates was found to be 1:2. Theoretical calculations of the possible isomers of the ligand and two metal complexes are performed by using B3LYP method. Electrochemical and photoluminescence properties of the synthesized azo-Schiff bases were also investigated.

Equilibrium and kinetic studies of Pb(II, Cd(II and Zn(II sorption by Lagenaria vulgaris shell

Directory of Open Access Journals (Sweden)

Mitić-Stojanović Dragana-Linda

2012-01-01

Full Text Available The sorption of lead, cadmium and zinc ions from aqueous solution by Lagenaria vulgaris shell biosorbent (LVB in batch system was investigated. The effect of relevant parameters such as contact time, biosorbent dosage and initial metal ions concentration was evaluated. The Pb(II, Cd(II and Zn(II sorption equilibrium (when 98% of initial metal ions were sorbed was attained within 15, 20 and 25 min, respectively. The pseudo first, pseudo-second order, Chrastil’s and intra-particle diffusion models were used to describe the kinetic data. The experimental data fitted the pseudo-second order kinetic model and intra-particle diffusion model. Removal efficiency of lead(II, cadmium(II and zinc(II ions rapidly increased with increasing biosorbent dose from 0.5 to 8.0 g dm-3. Optimal biosorbent dose was set to 4.0 g dm-3. An increase in the initial metal concentration increases the sorption capacity. The sorption data of investigated metal ions are fitted to Langmuir, Freundlich and Temkin isotherm models. Langmuir model best fitted the equilibrium data (r2 > 0.99. Maximal sorption capacities of LVB for Pb(II, Cd(II and Zn(II at 25.0±0.5°C were 0.130, 0.103 and 0.098 mM g-1, respectively. The desorption experiments showed that the LVB could be reused for six cycles with a minimum loss of the initial sorption capacity.

Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

KAUST Repository

Muralikrishna, S.; Ravishankar, T.N.; Ramakrishnappa, T.; Nagaraju, Doddahalli H.; Krishna Pai, Ranjith

2015-01-01

Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic

Solid-phase extraction of Mn(II), Co(II), Ni(II), Cu(II), Cd(II) and Pb(II) ions from environmental samples by flame atomic absorption spectrometry (FAAS)

Energy Technology Data Exchange (ETDEWEB)

Duran, Celal [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Gundogdu, Ali [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Bulut, Volkan Numan [Department of Chemistry, Giresun Faculty of Art and Science, Karadeniz Technical University, 28049 Giresun (Turkey); Soylak, Mustafa [Department of Chemistry, Faculty of Art and Science, Erciyes University, 38039 Kayseri (Turkey)]. E-mail: soylak@erciyes.edu.tr; Elci, Latif [Department of Chemistry, Faculty of Art and Science, Pamukkale University, 20020 Denizli (Turkey); Sentuerk, Hasan Basri [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Tuefekci, Mehmet [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey)

2007-07-19

A new method using a column packed with Amberlite XAD-2010 resin as a solid-phase extractant has been developed for the multi-element preconcentration of Mn(II), Co(II), Ni(II), Cu(II), Cd(II), and Pb(II) ions based on their complex formation with the sodium diethyldithiocarbamate (Na-DDTC) prior to flame atomic absorption spectrometric (FAAS) determinations. Metal complexes sorbed on the resin were eluted by 1 mol L{sup -1} HNO{sub 3} in acetone. Effects of the analytical conditions over the preconcentration yields of the metal ions, such as pH, quantity of Na-DDTC, eluent type, sample volume and flow rate, foreign ions etc. have been investigated. The limits of detection (LOD) of the analytes were found in the range 0.08-0.26 {mu}g L{sup -1}. The method was validated by analyzing three certified reference materials. The method has been applied for the determination of trace elements in some environmental samples.

Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands

Science.gov (United States)

Sumathi, S.; Tharmaraj, P.; Sheela, C. D.; Anitha, C.

2012-11-01

Transition metal complexes of various acetylacetone based ligands of the type ML [where M = Cu(II), Ni(II), Co(II); L = 3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, 1H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate).

Mitochondrial membranes with mono- and divalent salt: Changes induced by salt ions on structure and dynamics

NARCIS (Netherlands)

Pöyry, S.; Róg, T.; Karttunen, M.E.J.; Vattulainen, I.

2009-01-01

We employ atomistic simulations to consider how mono- (NaCl) and divalent (CaCl2) salt affects properties of inner and outer membranes of mitochondria. We find that the influence of salt on structural properties is rather minute, only weakly affecting lipid packing, conformational ordering, and

Synthesis and characterization of near-IR absorbing metal-free and zinc(II phthalocyanines modified with aromatic azo groups

Directory of Open Access Journals (Sweden)

Mukaddes Özçeşmeci

2015-05-01

Full Text Available Metal-free and zinc(II phthalocyanine complexes bearing peripheral (E-4-((2-hydroxynaphthalen-1-yldiazenyl units have been synthesized. Novel phthalonitrile derivative required for the preparation of phthalocyanine complexes was prepared by coupling 4-aminophthalonitrile and 2-naphthol. The structures of these new compounds were characterized by using elemental analyses, proton nuclear magnetic resonance, fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, fluorescence spectroscopy and mass spectrometry. In the UV-Vis spectra a broad absorption band appears for phthalocyanine complexes at around 450–500 nm resulting from azo-group introduced onto the phthalocyanine ring. The photophysical properties of metal-free and zinc(II phthalocyanines were studied in tetrahydrofuran.

Metal based biologically active compounds: Design, synthesis, DNA binding and antidiabetic activity of 6-methyl-3-formyl chromone derived hydrazones and their metal (II) complexes.

Science.gov (United States)

Philip, Jessica Elizabeth; Shahid, Muhammad; Prathapachandra Kurup, M R; Velayudhan, Mohanan Puzhavoorparambil

2017-10-01

Two chromone hydrazone ligands HL 1 and HL 2 were synthesized and characterized by elemental analyses, IR, 1 H NMR & 13 C NMR, electronic absorption and mass spectra. The reactions of the chromone hydrazones with transition metals such as Ni, Cu, and Zn (II) salts of acetate afforded mononuclear metal complexes. Characterization and structure elucidation of the prepared chromone hydrazone metal (II) complexes were done by elemental, IR, electronic, EPR spectra and thermo gravimetric analyses as well as conductivity and magnetic susceptibility measurements. The spectroscopic data showed that the ligand acts as a mono basic bidentate with coordination sites are azomethine nitrogen and hydrazonic oxygen, and they exhibited distorted geometry. The biological studies involved antidiabetic activity i.e. enzyme inhibition of α-amylase and α-glucosidase, Calf Thymus - DNA (CT-DNA) interaction and molecular docking. Potential capacity of synthesized compounds to inhibit the α-amylase and α-glucosidase activity was assayed whereas DNA interaction studies were carried out with the help UV-Vis absorption titration and viscosity method. The docking studies of chromone hydrazones show that they are minor groove binders. Complexes were found to be good DNA - intercalates. Chromone hydrazones and its transition metal complexes have shown comparable antidiabetic activity with a standard drug acarbose. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrothermal synthesis, crystal structures, and enantioselective adsorption property of bis(L-histidinato)nickel(II) monohydrate

Science.gov (United States)

Ramos, Christian Paul L.; Conato, Marlon T.

2018-05-01

Despite the numerous researches in metal-organic frameworks (MOFs), there are only few reports on biologically important amino acids, histidine in particular, on its use as bridging ligand in the construction of open-framework architectures. In this work, hydrothermal synthesis was used to prepare a compound based on Ni2+ and histidine. The coordination assembly of imidazole side chain of histidine with divalent nickel ions in aqueous condition yielded purple prismatic solids. Single crystal X-ray diffraction (XRD) analysis of the product revealed structure for Ni(C6H8N3O2)2 • H2O that has a monoclinic (C2) structure with lattice parameters, a = 29.41, b = 8.27, c = 6.31 Å, β = 90.01 ˚. Circular dichroism - optical rotatory dispersion (CD-ORD), Powder X-ray diffraction (PXRD) and Fourier transform - infrared spectroscopy (FT-IR) analyses are conducted to further characterize the crystals. Enantioselective adsorption analysis using racemic mixture of 2-butanol confirmed bis(L-histidinato)nickel(II) monohydrate MOF crystal's enantioselective property preferentially favoring the adsorption of (S)-2-butanol isomer.

Biosorption of cadmium (II) and lead (II) from aqueous solutions using mushrooms: A comparative study

Energy Technology Data Exchange (ETDEWEB)

Vimala, R., E-mail: vimararagu@yahoo.co.in [School of Biotechnology, Chemical and Biomedical Engineering, VIT University, Vellore 632014, Tamil Nadu (India); Das, Nilanjana [School of Biotechnology, Chemical and Biomedical Engineering, VIT University, Vellore 632014, Tamil Nadu (India)

2009-08-30

Sorption capacity of oyster mushroom (Pleurotus platypus), button mushroom (Agaricus bisporus) and milky mushroom (Calocybe indica) were evaluated on biosorption of heavy metals, viz. cadmium (II) and lead (II) from aqueous solutions. The optimum sorption conditions were studied for each metal separately. The desired pH of the aqueous solution was found to be 6.0 for the removal of cadmium (II) and 5.0 for removal of lead (II) for all the mushrooms. The percent removal of both the metals was found to increase with the increase in biosorbent dosage and contact time. The fitness of the biosorption data for Langmuir and Freundlich adsorption models was investigated. It was found that biosorption of cadmium (II) and lead (II) ions onto the biomass of the three mushrooms were better suitable to Langmuir than Freundlich adsorption model. P. platypus showed the highest metal uptake potential for cadmium (q{sub max} 34.96 mg/g) whereas A. bisporus exhibited maximum potential for lead (q{sub max} 33.78 mg/g). Milky mushroom showed the lowest metal uptake capacity for both the metals. The present data confirms that mushrooms may be used as efficient biosorbent for the removal of cadmium (II) and lead (II) ions from aqueous solution.

Preliminary screening of Ni(II metal tolerance and dye-decolorizing by Nocardiopsis sp. SD8

Directory of Open Access Journals (Sweden)

Ramasamy Thangaraj

2016-04-01

Full Text Available Objective: To reveal the screening of metal tolerance and dye-decolorizing of Nocardiopsis sp. Methods: NiSO4 and Congo red dye were used for evaluating the metal tolerance and dyedecolorizing of the randomly selected actinobacterial isolates. Results: Nocardiopsis sp. SD8 showed a better efficiency in Ni(II tolerance, though a longer lag phase was observed for this microorganism grown for 7 days in integrated mismatch negativity. Interestingly, we also found that Nocardiopsis sp. SD8 had dye-decolorizing, hemolytic, lipase and protease activity. Conclusions: The present results revealed the bioremediation of metal resistant and diverse properties of Nocardiopsis sp. SD8 and further investigations are needed to extract and identify the potent molecule.

Cd(II and Pb(II complexes of the polyether ionophorous antibiotic salinomycin

Directory of Open Access Journals (Sweden)

Tanabe Makoto

2011-09-01

Full Text Available Abstract Background The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II ions in in vivo experiments, despite so far no Pb(II-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II and lead(II. Results New metal(II complexes of the polyether ionophorous antibiotic salinomycin with Cd(II and Pb(II ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa undergoes a reaction with heavy metal(II ions to form [Cd(Sal2(H2O2] (1 and [Pb(Sal(NO3] (2, respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. Conclusion The formation of the salinomycin heavy metal(II complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock

Cd(II) and Pb(II) complexes of the polyether ionophorous antibiotic salinomycin

Science.gov (United States)

2011-01-01

Background The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II) ions in in vivo experiments, despite so far no Pb(II)-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II) and lead(II). Results New metal(II) complexes of the polyether ionophorous antibiotic salinomycin with Cd(II) and Pb(II) ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa) undergoes a reaction with heavy metal(II) ions to form [Cd(Sal)2(H2O)2] (1) and [Pb(Sal)(NO3)] (2), respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II) ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II) center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II) cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. Conclusion The formation of the salinomycin heavy metal(II) complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock farming

Fe (III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of schiff bases based-on glycine and phenylalanine: Synthesis, magnetic/thermal properties and antimicrobial activity

Science.gov (United States)

Sevgi, Fatih; Bagkesici, Ugur; Kursunlu, Ahmed Nuri; Guler, Ersin

2018-02-01

Zinc (II), copper (II), nickel (II), cobalt (II) and iron (III) complexes of Schiff bases (LG, LP) derived from 2-hydroxynaphthaldehyde with glycine and phenylalanine were reported and characterized by 1H NMR, 13C NMR, elemental analyses, melting point, FT-IR, magnetic susceptibility and thermal analyses (TGA). TGA data show that iron and cobalt include to the coordinated water and metal:ligand ratio is 1:2 while the complex stoichiometry for Ni (II), Cu (II) and Zn (II) complexes is 1:1. As expected, Ni (II) and Zn (II) complexes are diamagnetic; Cu (II), Co (II) and Fe (III) complexes are paramagnetic character due to a strong ligand of LG and LP. The LG, LP and their metal complexes were screened for their antimicrobial activities against five Gram-positive (Staphylococcus aureus, Methicillin resistant Staphylococcus aureus (MRSA), Bacillus cereus, Streptococcus mutans and Enterococcus faecalis) and three Gram-negative (Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa) and one fungi (Candida albicans) by using broth microdilution techniques. The activity data show that ligands and their metal complexes exhibited moderate to good activity against Gram-positive bacteria and fungi.

Extraterrestrial Metals Processing, Phase II

Data.gov (United States)

National Aeronautics and Space Administration — The Extraterrestrial Metals Processing (EMP) system produces iron, silicon, and light metals from Mars, Moon, or asteroid resources in support of advanced human...

Heavy metal extraction from PCB wastewater treatment sludge by sulfuric acid

International Nuclear Information System (INIS)

Kuan, Yu-Chung; Lee, I-Hsien; Chern, Jia-Ming

2010-01-01

Heavy metals contaminated wastewater sludge is classified as hazardous solid waste and needs to be properly treated to prevent releasing heavy metals to the environment. In this study, the wastewater treatment sludge from a printed circuit board manufacturing plant was treated in a batch reactor by sulfuric acid to remove the contained heavy metals. The effects of sulfuric acid concentration and solid to liquid ratio on the heavy metal removal efficiencies were investigated. The experimental results showed that the total and individual heavy metal removal efficiencies increased with increasing sulfuric acid concentration, but decreased with increasing solid to liquid ratio. A mathematical model was developed to predict the residual sludge weights at varying sulfuric concentrations and solid to liquid ratios. The trivalent heavy metal ions, iron and chromium were more difficult to be removed than the divalent ions, copper, zinc, nickel, and cadmium. For 5 g/L solid to liquid ratio, more than 99.9% of heavy metals can be removed from the sludge by treating with 0.5 M sulfuric acid in 2 h.

Metallic complexes with glyphosate: a review

OpenAIRE

Coutinho, Cláudia F. B.; Mazo, Luiz Henrique

2005-01-01

We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature.

Pb(II) and Hg(II) binding to $\\textit{de novo}$ designed proteins studied by $^{204m}$Pb- and $^{199m}$Hg-Perturbed Angular Correlation of $\\gamma$-rays (PAC) spectroscopy : Clues to heavy metal toxicity

CERN Multimedia

2002-01-01

$\\textit{De novo}$ design of proteins combined with PAC spectroscopy offers a unique and powerful approach to the study of fundamental chemistry of heavy metal-protein interactions, and thus of the mechanisms underlying heavy metal toxicity. In this project we focus on Pb(II) and Hg(II) binding to designed three stranded coiled coil proteins with one or two binding sites, mimicking a variety of naturally occurring thiolate-rich metal ion binding sites in proteins. The $^{204m}$Pb- and $^{199m}$Hg-PAC experiments will complement data already recorded with EXAFS, NMR, UV-Vis and CD spectroscopies.

Metallic complexes with glyphosate: a review

International Nuclear Information System (INIS)

Coutinho, Claudia F.B.; Mazo, Luiz Henrique

2005-01-01

We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

Zinc is the metal cofactor of Borrelia burgdorferi peptide deformylase.

Science.gov (United States)

Nguyen, Kiet T; Wu, Jen-Chieh; Boylan, Julie A; Gherardini, Frank C; Pei, Dehua

2007-12-15

Peptide deformylase (PDF, E.C. 3.5.1.88) catalyzes the removal of N-terminal formyl groups from nascent ribosome-synthesized polypeptides. PDF contains a catalytically essential divalent metal ion, which is tetrahedrally coordinated by three protein ligands (His, His, and Cys) and a water molecule. Previous studies revealed that the metal cofactor is a Fe2+ ion in Escherichia coli and many other bacterial PDFs. In this work, we found that PDFs from two iron-deficient bacteria, Borrelia burgdorferi and Lactobacillus plantarum, are stable and highly active under aerobic conditions. The native B. burgdorferi PDF (BbPDF) was purified 1200-fold and metal analysis revealed that it contains approximately 1.1 Zn2+ ion/polypeptide but no iron. Our studies suggest that PDF utilizes different metal ions in different organisms. These data have important implications in designing PDF inhibitors and should help address some of the unresolved issues regarding PDF structure and catalytic function.

The roles of EBR-II and TREAT [Transient Reactor Test] in establishing liquid metal reactor safety

International Nuclear Information System (INIS)

Sackett, J.I.; Lehto, W.K.; Solbrig, C.W.

1990-01-01

This paper examines the role of the Experimental Breeder Reactor II (EBR-II) and Transient Reactor Test (TREAT) facilities in contributing to the understanding and resolution of key safety issues in liquid metal reactor safety during the decade of the 80's. Fuels and materials testing has been carried out to address questions on fuels behavior during steady-state and upset conditions. In addition, EBR-II has conducted plant tests to demonstrate passive response to ATWS events and to develop control and diagnostic strategies for safe operation of advanced LMRs. TREAT and EBR-II complement each other and between them provide a transient testing capability that covers the whole range of concerns during overpower conditions. EBR-II, with use of the special Automatic Control Rod Drive System, can generate power change rates that overlap the lower end of the TREAT capability. 21 refs

Novel DOTA-based prochelator for divalent peptide vectorization: synthesis of dimeric bombesin analogues for multimodality tumor imaging and therapy.

Science.gov (United States)

Abiraj, Keelara; Jaccard, Hugues; Kretzschmar, Martin; Helm, Lothar; Maecke, Helmut R

2008-07-28

Dimeric peptidic vectors, obtained by the divalent grafting of bombesin analogues on a newly synthesized DOTA-based prochelator, showed improved qualities as tumor targeted imaging probes in comparison to their monomeric analogues.

Understanding the resistivity and absolute thermoelectric power of disordered metals and alloys

International Nuclear Information System (INIS)

Gasser, Jean-Georges

2008-01-01

We recall definitions of the electronic transport properties, direct coefficients like electrical and thermal transport conductivities and crossed thermoelectric coefficients like the Seebeck, Peltier and Thomson coefficients. We discuss the links between the different electronic transport coefficients and the experimental problems in measuring these properties in liquid metals. The electronic transport properties are interpreted in terms of the scattering of electrons by 'pseudo-atoms'. The absolute thermoelectric power (ATP), thermopower or Seebeck coefficient is known as the derivative of the electrical resistivity versus energy. The key is to understand the concept of resistivity versus energy. We show that the resistivity follows approximately a 1/E curve. The structure factor modulates this curve and, for a Fermi energy corresponding to noble and divalent metals, induces a positive thermopower when the free electron theory predicts a negative one. A second modulation is introduced by the pseudopotential squared form factor or equivalently by the squared t matrix of the scattering potential. This term sometimes introduces an anti-resonance (divalent metals) which lowers the resistivity, and sometimes a resonance having an important effect on the transition metals. Following the position of the Fermi energy, the thermopower can be positive or negative. For heavy semi-metals, the density of states splits into an s and a p band, themselves different from a free electron E 0.5 curve. The electrons available to be scattered enter the Ziman formula. Thus if the density of states is not a free electron one, a third modulation of the ρ ≅ 1/E curve is needed, which also can change the sign of the thermopower. For alloys, different contributions weighted by the concentrations are needed to explain the concentration dependent resistivity or thermopower. The formalism is the same for amorphous metals. It is possible that this mechanism can be extended to high

Liquid metal reactor deactivation as applied to the experimental breeder reactor - II

International Nuclear Information System (INIS)

Earle, O. K.; Michelbacher, J. A.; Pfannenstiel, D. F.; Wells, P. B.

1999-01-01

The Experimental Breeder Reactor-II (EBR-II) at Argonne National Laboratory-West (ANL-W) was shutdown in September, 1994. This sodium cooled reactor had been in service since 1964, and by the US Department of Energy (DOE) mandate, was to be placed in an industrially and radiologically safe condition for ultimate decommissioning. The deactivation of a liquid metal reactor presents unique concerns. The first major task associated with the project was the removal of all fueled assemblies. In addition, sodium must be drained from systems and processed for ultimate disposal. Residual quantities of sodium remaining in systems must be deactivated or inerted to preclude future hazards associated with pyrophoricity and generation of potentially explosive hydrogen gas. A Sodium Process Facility (SPF) was designed and constructed to react the elemental sodium from the EBR-II primary and secondary systems to sodium hydroxide for disposal. This facility has a design capacity to allow the reaction of the complete inventory of sodium at ANL-W in less than two years. Additional quantities of sodium from the Fermi-1 reactor are also being treated at the SPF

Synthesis and structural characterization of nickel(II), cobalt(II), Zinc(II), manganese(II), cadmium(II) and uranium(VI) complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazone

International Nuclear Information System (INIS)

Patel, P.S.; Patel, M.M.; Ray, R.M.

1993-01-01

A few metal complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazones (OAOATS)/(OAPATS) with Ni(II), Co(II), Zn(II), Mn(II), Hg(II), Cd(II) and UO 2 (II) have been prepared and characterized by elemental analyses, conductivity, differential scanning calorimetry study, thermogravimetric analyses and infrared and electronic spectral measurements in conjunction with magnetic susceptibility measurements at room temperature. They have also been tested for their antimicrobial activities. (author). 24 refs., 2 tabs

Metals from the ritual site of Shaitanskoye Ozero II (Sverdlovsk Oblast, Russia

Directory of Open Access Journals (Sweden)

Nikolaevna Korochkova, Olga

2010-12-01

Full Text Available The present article describes materials from the ritual site of Shaitanskoye Ozero II, Sverdlovsk Oblast. Few excavations carried out at the site measuring less than 240 sq. m in size, yielded more than 160 bronze artifacts: utensils, weapons, rolled copper ornaments, and abundant smelting and casting waste. Apart from Seima-Turbino (celts and laminar knives and Eurasian types (daggers with cast hilts, truncated knives with guards, fluted bracelets and rings, several metal artifacts were revealed manufactured in the style of the Samus-Kizhirovo tradition. Bronze artifacts, stone knives and scrapers, and numerous arrowheads are accompanied by ceramics of the Koptyaki type. Metals use mainly a copper-tin alloy. This assemblage is shown to be relevant to the local tradition of metalworking, which, in this particular region, was comparatively ancient having been left uninterrupted by the rapid migrations of the Seima-Turbino people. In addition, the assemblage indicates the sources from which post-Seima artifacts reached the Alakul people. These artifacts may also have been linked with a large metalworking center located in the Middle Urals.

Este artículo describe los materiales del sitio ritual de Shaitanskoye Ozero II, Provincia de Sverdlovsk. Las reducidas excavaciones emprendidas en el lugar con superficie inferior a los 240 m² han entregado más de 160 objetos de bronce: utensilios, armas, adornos en espiral de cobre y abundantes residuos de la fusión y el trabajo del metal. Además de tipos Seima-Turbino (hachas tubulares y cuchillos planos y Euroasiáticos (puñales de mango fundido, cuchillos con empuñadura de lengüeta, brazaletes y anillos acanalados, varios artefactos metálicos resultaron manufacturados según el estilo de la tradición Samus-Kizhirovo. Los artefactos de bronce, los líticos (cuchillos, raspadores y numerosas puntas de flecha están acompañados por cerámicos de tipo Koptyaki. El metal es

Controlling the oxidation of bis-tridentate cobalt(ii) complexes having bis(2-pyridylalkyl)amines: ligand vs. metal oxidation.

Science.gov (United States)

Anjana, S; Donring, S; Sanjib, P; Varghese, B; Murthy, Narasimha N

2017-08-22

Two bis-tridentate chelated cobalt(ii) complexes, which differ in the ligand structure by a methylene group, activate molecular oxygen (O 2 ), and give different oxidation products. The O 2 reaction of [Co II (pepma) 2 ] 2+ (1) with unsymmetrical 2-(2-pyridyl)-N-(2-pyridylmethyl)ethanamine (pepma) results in ligand oxidation, to the corresponding Co(ii) imine complex [Co II (pepmi) 2 ] 2+ (2). Contrastingly, the Co(ii) complex [Co II (bpma) 2 ] 2+ (3) of similar symmetrical bis(2-pyridylmethyl)amine (bpma), undergoes metal oxidation, yielding a cobalt(iii) complex, [Co III (bpma) 2 ] 2+ (4). The reversibility of the amine to imine conversion and the stability of the Co(ii) imine complex (2) are investigated. Furthermore, the solution dynamics of Co(ii) complexes are highlighted with the help of paramagnetic 1 H-NMR spectroscopy.

HIGH YIELD AND RAPID SYNTHESES METHODS FOR PRODUCING METALLO-ORGANIC SALTS

DEFF Research Database (Denmark)

2005-01-01

A new method for preparing salts of metal cations and organic acids, especially divalent salts of alkaline earth metal ions from group II of the periodic system and carboxylic acids. The method comprising the use of a high temperature (about 90° or more) and, optionally. high pressure, in order...... to obtain a higher yield, purity and faster reaction speed than obtained with known synthesis methods. In particular, the present invention relates to the production of strontium salts of carboxylic acids. Novel strontium salts are also provided by the present method....

Synthesis of high-surface-area γ-Al2O3 from aluminum scrap and its use for the adsorption of metals: Pb(II), Cd(II) and Zn(II)

International Nuclear Information System (INIS)

Asencios, Yvan J.O.; Sun-Kou, María R.

2012-01-01

Highlights: ► Aluminum hydroxide obtained from aluminum scrap led to the formation of gamma alumina. ► Acidic pH of precipitation favored the formation of small particles of high surface areas. ► Higher aging temperature favored the formation of large structures of large pore sizes. ► Higher aging temperature generated symmetrical solids of regular hexagonal prism forms. ► Aluminas of large pores adsorbed metals as following: Pb (1.75 Å) > Cd (1.54 Å) > Zn (1.38 Å). - Abstract: Several types of alumina were synthesized from sodium aluminate (NaAlO 2 ) by precipitation with sulfuric acid (H 2 SO 4 ) and subsequently calcination at 500 °C to obtain γ-Al 2 O 3 . The precursor aluminate was derived from aluminum scrap. The various γ-Al 2 O 3 synthesized were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), adsorption–desorption of N 2 (S BET ) and scanning electron microscopy (SEM). XRD revealed that distinct phases of Al 2 O 3 were formed during thermal treatment. Moreover, it was observed that conditions of synthesis (pH, aging time and temperature) strongly affect the physicochemical properties of the alumina. A high-surface-area alumina (371 m 2 g −1 ) was synthesized under mild conditions, from inexpensive raw materials. These aluminas were tested for the adsorption of Cd(II), Zn(II) and Pb(II) from aqueous solution at toxic metal concentrations, and isotherms were determined.

Androgen Receptor Antagonism By Divalent Ethisterone Conjugates In Castrate-Resistant Prostate Cancer Cells

Science.gov (United States)

Levine, Paul M.; Lee, Eugine; Greenfield, Alex; Bonneau, Richard; Logan, Susan K.; Garabedian, Michael J.; Kirshenbaum, Kent

2013-01-01

Sustained treatment of prostate cancer with Androgen Receptor (AR) antagonists can evoke drug resistance, leading to castrate-resistant disease. Elevated activity of the AR is often associated with this highly aggressive disease state. Therefore, new therapeutic regimens that target and modulate AR activity could prove beneficial. We previously introduced a versatile chemical platform to generate competitive and non-competitive multivalent peptoid oligomer conjugates that modulate AR activity. In particular, we identified a linear and a cyclic divalent ethisterone conjugate that exhibit potent anti-proliferative properties in LNCaP-abl cells, a model of castrate-resistant prostate cancer. Here, we characterize the mechanism of action of these compounds utilizing confocal microscopy, time-resolved fluorescence resonance energy transfer, chromatin immunoprecipitation, flow cytometry, and microarray analysis. The linear conjugate competitively blocks AR action by inhibiting DNA binding. In addition, the linear conjugate does not promote AR nuclear localization or co-activator binding. In contrast, the cyclic conjugate promotes AR nuclear localization and induces cell-cycle arrest, despite its inability to compete against endogenous ligand for binding to AR in vitro. Genome-wide expression analysis reveals that gene transcripts are differentially affected by treatment with the linear or cyclic conjugate. Although the divalent ethisterone conjugates share extensive chemical similarities, we illustrate that they can antagonize the AR via distinct mechanisms of action, establishing new therapeutic strategies for potential applications in AR pharmacology. PMID:22871957

Investigating the pharmacodynamic and magnetic properties of pyrophosphate-bridged coordination complexes

Science.gov (United States)

Ikotun, Oluwatayo (Tayo) F.

The multidentate nature of pyrophosphate makes it an attractive ligand for complexation of metal cations. The participation of pyrophosphate in a variety of biological pathways and its metal catalyzed hydrolysis has driven our investigation into its coordination chemistry. We have successfully synthesized a library of binuclear pyrophosphate bridge coordination complexes. The problem of pyrophosphate hydrolysis to phosphate in the presence of divalent metal ions was overcome by incorporating capping ligands such as 1,10-phenanthroline and 2,2'-bipyridine prior to the addition of the pyrophosphate. The magnetic properties of these complexes was investigated and magneto-structural analysis was conducted. The biological abundance of pyrophosphate and the success of metal based drugs such as cisplatin, prompted our investigation of the cytotoxic properties of M(II) pyrophosphate dimeric complexes (where M(II) is CoII, CuII, and NiII) in adriamycin resistant human ovarian cancer cells. Thess compounds were found to exhibit toxicity in the nanomolar to picomolar range. We conducted in vitro stability studies and the mechanism of cytoxicity was elucidated by performing DNA mobility and binding assays, enzyme inhibition assays, and in vitro oxidative stress studies.

Ca II triplet spectroscopy of RGB stars in NGC 6822: kinematics and metallicities

Science.gov (United States)

Swan, J.; Cole, A. A.; Tolstoy, E.; Irwin, M. J.

2016-03-01

We present a detailed analysis of the chemistry and kinematics of red giants in the dwarf irregular galaxy NGC 6822. Spectroscopy at ≈8500 Å was acquired for 72 red giant stars across two fields using FORS2 at the VLT. Line-of-sight extinction was individually estimated for each target star to accommodate the variable reddening across NGC 6822. The mean radial velocity was found to be = -52.8 ± 2.2 km s-1 with dispersion σv = 24.1 km s-1, in agreement with other studies. Ca II triplet equivalent widths were converted into [Fe/H] metallicities using a V magnitude proxy for surface gravity. The average metallicity was = -0.84 ± 0.04 with dispersion σ = 0.31 dex and interquartile range 0.48. Our assignment of individual reddening values makes our analysis more sensitive to spatial variations in metallicity than previous studies. We divide our sample into metal-rich and metal-poor stars; the former were found to cluster towards small radii with the metal-poor stars more evenly distributed across the galaxy. The velocity dispersion of the metal-poor stars was found to be higher than that of the metal-rich stars (σ _{v_MP}=27.4 km s-1; σ _{v_MR}=21.1 km s-1); combined with the age-metallicity relation this indicates that the older populations have either been dynamically heated during their lifetimes or were born in a less disc-like distribution than the younger stars.. The low ratio vrot/σv suggests that within the inner 10 arcmin, NGC 6822's stars are dynamically decoupled from the H I gas, and possibly distributed in a thick disc or spheroid structure.

Application of Local Adsorbant From Southeast Sulawesi Clay Immobilized Saccharomyces Cerevisiae Bread’s Yeast Biomass for Adsorption Of Mn(Ii) Metal Ion

Science.gov (United States)

R, Halimahtussaddiyah; Mashuni; Budiarni

2017-05-01

Southeast Sulawesi has a great stock of clay. It is probably to use as a source of adsorbent. The adsorbent capacity of clay can be largered with teratment using bread’s yeast as biomass. At this research, study of analysis adsorption of Mn(II) metal ion on clay immobilized Saccharomyces cerevisiae bread’s yeast biomass adsorbent has been conducted. The aims of this research were to determine the effects of contact time, pH and concentration of Mn(II) metal ion and to determine the adsorption capacity of clay immobilized S. cerevisiae biomass for adsorbtion of Mn(II) metal ion. Activated clay was synthesized by reaction of clay with KMnO4, H2SO4 and HCl. S. cerevisiae biomass was result by bread’s yeast mashed. Immobilization of S. cerevisiae biomass into clay was done by mixing of ratio of S. cerevisiae bread’s yeast biomass and clay equal to 1:3 (mass of biomassa : mass of clay). The adsorption capacity was determined by using Freundlich and Langmuir adsorption isoterms. The results of FTIR spectrums showed that the functional groups of clay immobilized S. cerevisiae biomass were Si-OH (wave number 1643 cm-1), Si-O-Si (wave number 1033 cm-1), N-H (wave number 2337 cm-1), O-H (wave number 3441cm-1), and C-H (wave number 2931 cm-1). The result of adsorption capacity from Mn(II) metal ion of contact time optimum 120 minutes, pH optimun at 7 and concentration optimum 50 mg/L were 1,816 mg/g; 0,509 mg/g and 2,624mg/g respectively. The adsorption capacity of Mn(II) metal ion with ratio 1:3 (biomass : clay) was 0,1045 mg/g. Type of isothermal adsorption followed the Freunlich adsorption.

The synthesis and characterization of 1,2-dihydroxyimino-3,6-di-aza-8,9-O-iso-butylidene nonane and its complexes with Ni(II), Cu(II), Zn(II) and Cd(II)

International Nuclear Information System (INIS)

Canpolat, E.; Kaya, M.; Gorgulu, A.O.

2002-01-01

1,2-dihydroxyimino-3,6-di-aza-8,9-O-iso-butylidene nonane (H 2 L) was synthesized starting from 1,2-O-iso-butylidene-4-aza-6-amino hexane (RNH 2 ) and antichloroglyoxime. Ni(II) and Cu(II) complexes of H 2 L have a metal:ligand ratio 1:2 and the ligand coordinates through two N atoms, as do most of the vic-dioximes. However, Zn(II) and Cd(II) complexes of H 2 L have a metal: ligand ratio 1:1 and one chloride ion and one water molecule are also coordinated to the metal ion. Structures of the ligand and its transition-metal complexes are proposed, according to elemental analysis, IR, 13 C and 1 H NMR spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA). (author)

Microbial Mineral Transformations at the Fe(II)/Fe(III) Redox Boundary for Solid Phase Capture of Strontium and Other Metal/Radionuclide Contaminants

International Nuclear Information System (INIS)

Ferris, F.G.; Roden, E.E.

2000-01-01

The migration of 90 Sr in groundwater is a significant environmental concern at former nuclear weapons production sites in the US and abroad. Although retardation of 90 Sr transport relative to mean groundwater velocity is known to occur in contaminated aquifers, Sr 2+ does not sorb as strongly to iron oxides and other mineral phases as do other metal-radionuclides contaminants. Thus, some potential exists for extensive 90 Sr migration from sources of contamination. Chemical or biological processes capable of retarding or immobilizing Sr 2+ in groundwater environments are of interest from the standpoint of understanding controls on subsurface Sr 2+ migration. In addition, it may be possible to exploit such processes for remediation of subsurface Sr contamination. In this study the authors examined the potential for the solid phase sorption and incorporation of Sr 2+ into carbonate minerals formed during microbial Fe(III) oxide reduction as a first step toward evaluating whether this process could be used to promote retardation of 90 Sr migrations in anaerobic subsurface environments. The demonstration of Sr 2+ capture in carbonate mineral phases formed during bacterial HFO reduction and urea hydrolysis suggests that microbial carbonate mineral formation could contribute to Sr 2+ retardation in groundwater environments. This process may also provide a mechanism for subsurface remediation of Sr 2+ and other divalent metal contaminants that form insoluble carbonate precipitates

Exploring 3D non-interpenetrated metal-organic framework with malonate-bridged Co(II) coordination polymer: structural elucidation and theoretical study

Science.gov (United States)

Hossain, Anowar; Mandal, Tripti; Mitra, Monojit; Manna, Prankrishna; Bauzá, Antonio; Frontera, Antonio; Seth, Saikat Kumar; Mukhopadhyay, Subrata

2017-12-01

A Co(II)-based coordination polymer with tetranuclear cobalt(II)-malonate cluster has been easily generated by aqueous medium self-assembly from Cobalt(II) chloride hexahydrate and malonic acid. The structure exhibits a non-interpenetrating, highly undulating two-dimensional (2D) bi-layer network with (4,4) topology. The crystal structure is composed of infinite interdigitated 2D metal-organic bi-layers which extended to an intricate 3D framework through the interbilayer hydrogen bonds. We have studied energetically by means of Density Functional Theory (DFT) calculations the H-bonding interactions that connect the 2D metal-organic bi-layers. The finite theoretical models have been used to compute conventional O‒H•••O and unconventional C‒H•••O interactions which plays a key role to build 3D architecture.

Enhanced desorption of cesium from collapsed interlayer regions in vermiculite by hydrothermal treatment with divalent cations

Energy Technology Data Exchange (ETDEWEB)

Yin, Xiangbiao, E-mail: yin.x.aa@m.titech.ac.jp [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Wang, Xinpeng [College of Resources and Metallurgy, Guangxi University, 100 Daxue East Road, Nanning 530004 (China); Wu, Hao; Ohnuki, Toshihiko; Takeshita, Kenji [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

2017-03-15

Highlights: • Desorption of Cs{sup +} fixed in collapsed interlayer region of vermiculite was studied. • Monovalent cations readily induced interlayer collapse inhibiting Cs{sup +} desorption. • Larger hydrous ionic radii of divalent cations greatly prevented Cs{sup +} desorption. • Effect of divalent cation on Cs{sup +} desorption changes depending on thermal treatment. • ∼100% removal of saturated Cs{sup +} was achieved by hydrothermal treatment at 250 °C. - Abstract: Adsorption of cesium (Cs) on phyllosilicates has been intensively investigated because natural soils have strong ability of immobilizing Cs within clay minerals resulting in difficulty of decontamination. The objectives of present study are to clarify how Cs fixation on vermiculite is influenced by structure change caused by Cs sorption at different loading levels and how Cs desorption is affected by various replacing cations induced at different treating temperature. As a result, more than 80% of Cs was readily desorbed from vermiculite with loading amount of 2% saturated Cs (5.49 × 10{sup −3} mmol g{sup −1}) after four cycles of treatment of 0.01 M Mg{sup 2+}/Ca{sup 2+} at room temperature, but less than 20% of Cs was desorbed from saturated vermiculite. These distinct desorption patterns were attributed to inhibition of Cs desorption by interlayer collapse of vermiculite, especially at high Cs loadings. In contrast, elevated temperature significantly facilitated divalent cations to efficiently desorb Cs from collapsed regions. After five cycles of treatment at 250 °C with 0.01 M Mg{sup 2+}, ∼100% removal of saturated Cs was achieved. X-ray diffraction analysis results suggested that Cs desorption was completed through enhanced diffusion of Mg{sup 2+} cations into collapsed interlayer space under hydrothermal condition resulting in subsequent interlayer decollapse and readily release of Cs{sup +}.

Competition from Cu(II), Zn(II) and Cd(II) in Pb(II) binding to Suwannee River Fulvic Acid

NARCIS (Netherlands)

Chakraborty, P.; Chakrabarti, C.L.

2008-01-01

This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration

Ni (II) and Cu(II) complexes of

African Journals Online (AJOL)

ADOWIE PERE

ABSTRACT: The objective of this study is to investigate the antimicrobial activity of novel. Schiff base metal complexes. The resistance of micro-organisms to classical antimicrobial compounds poses a challenge to effective management and treatment of some diseases. In line with this, copper (II), nickel (II) and cobalt (II) ...

Metal ion effects on enolase activity

International Nuclear Information System (INIS)

Lee, M.E.; Nowak, T.

1986-01-01

Most metal binding studies with yeast enolase suggest that two metals per monomer are required for catalytic activity. The functions of metal I and metal II have not been unequivocally defined. In a series of kinetic experiments where the concentration of MgII is kept constant at subsaturating levels (1mM), the addition of MnII or of ZnII gives a hyperbolic decrease in activity. The final velocity of these mixed metal systems is the same velocity obtained with either only MnII or ZnII respectively. The concentration of MnII (40 μM) or of Zn (2μM) which gives half maximal effect in the presence of (1mM) MgII is approximately the same as the Km' value for MnII (9μM) or ZnII (3μM) respectively. Direct binding of MnII to enolase in the absence and presence of MgII shows that MnII and MgII compete for the same metal site on enolase. In the presence of 2-phosphoglycerate (2-PGA) and MgII, only a single site is occupied by MnII. Results suggest MnII at site I and MgII at site II. PRR and high resolution 1 H and 31 P NMR studies of enzyme-ligand complexes containing MnII and MgII and MnII are consistent with this model. 31 P measurements allow a measure of the equilibrium constant (0.36) for enolase. Saturation transfer measurements yield net rate constants (k/sub f/ = 0.49s -1 ; k/sub r/ = 1.3s -1 ) for the overall reaction. These values are smaller than k/sub cat/ (38s -1 ) measured under analogous conditions. The cation at site I appears to determine catalytic activity

Metallicities for old stellar systems from Ca II triplet strengths in member giants

International Nuclear Information System (INIS)

Armandroff, T.E.; Da costa, G.S.

1991-01-01

The spectra of giants in six well-studied Galactic globulars spanning a wide range of abundance are used to investigate the utility of the Ca II triplet as an abundance indicator. The calibration resulting from these clusters is used to derive metal abundances from the spectra of giants in Eridanus, Pal 12, and the Carina dwarf spheroidal galaxy. The results obtained are compared with earlier determinations based on giant branch photometry. 37 refs

Glutamate Ligation in the Ni(II)- and Co(II)-Responsive Escherichia coli Transcriptional Regulator, RcnR

Energy Technology Data Exchange (ETDEWEB)

Carr, Carolyn E. [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003, United States; Musiani, Francesco [Laboratory; Huang, Hsin-Ting [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003, United States; Chivers, Peter T. [Departments of Biosciences and Chemistry, Durham University, Durham DH1 3LE, United Kingdom; Ciurli, Stefano [Laboratory; Maroney, Michael J. [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003, United States

2017-05-18

Escherichia coli RcnR (resistance to cobalt and nickel regulator, EcRcnR) is a metal-responsive repressor of the genes encoding the Ni(II) and Co(II) exporter proteins RcnAB by binding to PRcnAB. The DNA binding affinity is weakened when the cognate ions Ni(II) and Co(II) bind to EcRcnR in a six-coordinate site that features a (N/O)5S ligand donor-atom set in distinct sites: while both metal ions are bound by the N terminus, Cys35, and His64, Co(II) is additionally bound by His3. On the other hand, the noncognate Zn(II) and Cu(I) ions feature a lower coordination number, have a solvent-accessible binding site, and coordinate protein ligands that do not include the N-terminal amine. A molecular model of apo-EcRcnR suggested potential roles for Glu34 and Glu63 in binding Ni(II) and Co(II) to EcRcnR. The roles of Glu34 and Glu63 in metal binding, metal selectivity, and function were therefore investigated using a structure/function approach. X-ray absorption spectroscopy was used to assess the structural changes in the Ni(II), Co(II), and Zn(II) binding sites of Glu → Ala and Glu → Cys variants at both positions. The effect of these structural alterations on the regulation of PrcnA by EcRcnR in response to metal binding was explored using LacZ reporter assays. These combined studies indicate that while Glu63 is a ligand for both metal ions, Glu34 is a ligand for Co(II) but possibly not for Ni(II). The Glu34 variants affect the structure of the cognate metal sites, but they have no effect on the transcriptional response. In contrast, the Glu63 variants affect both the structure and transcriptional response, although they do not completely abolish the function of EcRcnR. The structure of the Zn(II) site is not significantly perturbed by any of the glutamic acid variations. The spectroscopic and functional data obtained on the mutants were used to calculate models of the metal-site structures of EcRcnR bound to Ni(II), Co(II), and Zn(II). The results are interpreted

Ion exchange equilibrium for some uni-univalent and uni-divalent reaction systems using strongly basic anion exchange resin Duolite A-102 D

Directory of Open Access Journals (Sweden)

R.S. Lokhande

2008-04-01

Full Text Available The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Duolite A-102 D. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems was observed to increase with rise in temperature, indicating the endothermic exchange reactions having enthalpy values of 13.7, 38.0, 23.9, 22.9 kJ/mol, respectively.

Multisite Ion Model in Concentrated Solutions of Divalent Cations (MgCl2 and CaCl2): Osmotic Pressure Calculations

Science.gov (United States)

2015-01-01

Accurate force field parameters for ions are essential for meaningful simulation studies of proteins and nucleic acids. Currently accepted models of ions, especially for divalent ions, do not necessarily reproduce the right physiological behavior of Ca2+ and Mg2+ ions. Saxena and Sept (J. Chem. Theor. Comput.2013, 9, 3538–3542) described a model, called the multisite-ion model, where instead of treating the ions as an isolated sphere, the charge was split into multiple sites with partial charge. This model provided accurate inner shell coordination of the ion with biomolecules and predicted better free energies for proteins and nucleic acids. Here, we expand and refine the multisite model to describe the behavior of divalent ions in concentrated MgCl2 and CaCl2 electrolyte solutions, eliminating the unusual ion–ion pairing and clustering of ions which occurred in the original model. We calibrate and improve the parameters of the multisite model by matching the osmotic pressure of concentrated solutions of MgCl2 to the experimental values and then use these parameters to test the behavior of CaCl2 solutions. We find that the concentrated solutions of both divalent ions exhibit the experimentally observed behavior with correct osmotic pressure, the presence of solvent separated ion pairs instead of direct ion pairs, and no aggregation of ions. The improved multisite model for (Mg2+ and Ca2+) can be used in classical simulations of biomolecules at physiologically relevant salt concentrations. PMID:25482831

A GMOS-N IFU study of the central H II region in the blue compact dwarf galaxy NGC 4449: kinematics, nebular metallicity and star formation

Science.gov (United States)

Kumari, Nimisha; James, Bethan L.; Irwin, Mike J.

2017-10-01

We use integral field spectroscopic (IFS) observations from the Gemini Multi-Object Spectrograph North (GMOS-N) to study the central H II region in a nearby blue compact dwarf (BCD) galaxy NGC 4449. The IFS data enable us to explore the variation of physical and chemical conditions of the star-forming region and the surrounding gas on spatial scales as small as 5.5 pc. Our kinematical analysis shows possible signatures of shock ionization and shell structures in the surroundings of the star-forming region. The metallicity maps of the region, created using direct Te and indirect strong line methods (R23, O3N2 and N2), do not show any chemical variation. From the integrated spectrum of the central H II region, we find a metallicity of 12 + log(O/H) = 7.88 ± 0.14 ({˜ }0.15^{+0.06}_{-0.04} Z⊙) using the direct method. Comparing the central H II region metallicity derived here with those of H II regions throughout this galaxy from previous studies, we find evidence of increasing metallicity with distance from the central nucleus. Such chemical inhomogeneities can be due to several mechanisms, including gas loss via supernova blowout, galactic winds or metal-poor gas accretion. However, we find that the localized area of decreased metallicity aligns spatially with the peak of star-forming activity in the galaxy, suggesting that gas accretion may be at play here. Spatially resolved IFS data for the entire galaxy are required to confirm the metallicity inhomogeneity found in this study and determine its possible cause.

Review of the SIMMER-II analyses of liquid-metal-cooled fast breeder reactor core-disruptive accident fuel escape

International Nuclear Information System (INIS)

DeVault, G.P.; Bell, C.R.

1985-01-01

Early fuel removal from the active core of a liquid-metal-cooled fast breeder reactor undergoing a core-disruptive accident may reduce the potential for large energetics resulting from recriticalities. This paper presents a review of analyses with the SIMMER-II computer program of the effectiveness of possible fuel escape paths. Where possible, how SIMMER-II compares with or is validated against experiments that simulated the escape paths also is discussed

Synthesis, spectral, thermal and antimicrobial studies on cobalt(II), nickel(II), copper(II), zinc(II) and palladium(II) complexes containing thiosemicarbazone ligand

Science.gov (United States)

El-Sawaf, Ayman K.; El-Essawy, Farag; Nassar, Amal A.; El-Samanody, El-Sayed A.

2018-04-01

The coordination characteristic of new N4-morpholinyl isatin-3-thiosemicarbazone (HL) towards Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) has been studies. The structures of the complexes were described by elemental analyses, molar conductivity, magnetic, thermal and spectral (IR, UV-Vis, 1H and 13C NMR and ESR) studies. On the basis of analytical and spectral studies the ligand behaves as monobasic tridentate ONS donor forming two five membered rings towards cobalt, copper and palladium and afforded complexes of the kind [M(L)X], (Mdbnd Co, Cu or Pd; Xdbnd Cl, Br or OAc). Whereas the ligand bound to NiCl2 as neutral tridentate ONS donor and with ZnCl2 as neutral bidentate NS donor. The newly synthesized thiosemicarbazone ligand and some of its complexes were examined for antimicrobial activity against 2 gram negative bacterial strains (Escherichia coli Pseudomonas and aeruginosa), 2 gram positive bacterial strains (Streptococcus pneumoniae and Staphylococcus aureus)} and two Pathogenic fungi (Aspergillus fumigatus and Candida albicans). All metal complexes possess higher antimicrobial activity comparing with the free thiosemicarbazone ligand. The high potent activities of the complexes may arise from the coordination and chelation, which tends to make metal complexes act as more controlling and potent antimicrobial agents, thus hindering the growing of the microorganisms. The antimicrobial results also show that copper bromide complex is better antimicrobial agent as compared to the Schiff base and its metal complexes.

Synthesis, Spectral and Antimicrobial Studies of Some Co(II, Ni(II and Cu(II Complexes Containing 2-Thiophenecarboxaldehyde Moiety

Directory of Open Access Journals (Sweden)

A. P. Mishra

2012-01-01

Full Text Available Some new Schiff base metal complexes of Co(II, Ni(II and Cu(II derived from 3-chloro-4-fluoroaniline (HL1 and 4-fluoroaniline (HL2 with 2-thiophenecarboxaldehyde have been synthesized and characterized by elemental analysis, FT-IR, FAB-mass, molar conductance, electronic spectra, ESR and magnetic susceptibility. The complexes exhibit coordination number 4 or 6. The complexes are colored and stable in air. Analytical data revealed that all the complexes exhibited 1:2 (metal: ligand ratio. FAB-mass data show degradation pattern of the complexes. The Schiff base and metal complexes show a good activity against the bacteria; B. subtilis, E. coli and S. aureus and fungi A. niger, A. flavus and C. albicans. The antimicrobial results also indicate that the metal complexes are better antimicrobial agents as compared to the Schiff bases.

SURVEY OF THE SPECTRA OF THE DIVALENT RARE EARTH IONS IN CUBIC CRYSTALS

Energy Technology Data Exchange (ETDEWEB)

McClure, Donald S. [Univ. of Chicago, IL (United States); Kiss, Zoltan J. [RCA Laboratories, Princeton, NJ (United States)

1963-04-15

The rare earth ions may exist in the divalent state in suitable host crystals such as CaF/sub 2/. All of the trivalent ions from La to Yb are reduced in situ to the divalent state in CaF/sub 2/ by gamma irradiation. The spectra of most of these ions show that the ground and first few excited states derive from f/sup n/ configurations, but the wesk absorption due to these is masked at higher energies by strong broad bands of the parity permitted f/sup n/ yields f/sup n-1/ d transitions. The excitation energy of these spectra have been calculated in a first approximation as the energy difference between the Hund Rule'' single determinant states of the configurations f/sup n -1/d and f/sup n/. This procedure satisfactorily accounts for the remarkable variations in the excitation energy in passing from one ion to the next in the series with the exception of Ge/ sup 2+/ Ce/sup 2+/, and Tb/sup 2+/, Ge/sup 2+/ probably has f/sup 7/d for its ground con figuration, while Ce/sup 2+/ and Tb/sup 2+/ are borderline cases. The spectral structure probably arises chiefly from the crystal field splitting of the d-orbital, since each ion in CaF/sub 2/ has a similar spectrum, and the spectra change drastically in sites of other than cubic symmetry. (auth)

Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

International Nuclear Information System (INIS)

Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo

2016-01-01

Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function. (paper)

Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

Science.gov (United States)

Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo

2016-02-01

Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function.

A plasmid containing the human metallothionein II gene can function as an antibody-assisted electrophoretic biosensor for heavy metals.

Science.gov (United States)

Wooten, Dennis C; Starr, Clarise R; Lyon, Wanda J

2016-01-01

Different forms of heavy metals affect biochemical systems in characteristic ways that cannot be detected with typical metal analysis methods like atomic absorption spectrometry. Further, using living systems to analyze interaction of heavy metals with biochemical systems can be laborious and unreliable. To generate a reliable easy-to-use biologically-based biosensor system, the entire human metallothionein-II (MT-II) gene was incorporated into a plasmid (pUC57-MT) easily replicated in Escherichia coli. In this system, a commercial polyclonal antibody raised against human metal-responsive transcription factor-1 protein (MTF-1 protein) could modify the electrophoretic migration patterns (i.e. cause specific decreases in agarose gel electrophoretic mobility) of the plasmid in the presence or absence of heavy metals other than zinc (Zn). In the study here, heavy metals, MTF-1 protein, and polyclonal anti-MTF-1 antibody were used to assess pUC57-MT plasmid antibody-assisted electrophoretic mobility. Anti-MTF-1 antibody bound both MTF-1 protein and pUC57-MT plasmid in a non-competitive fashion such that it could be used to differentiate specific heavy metal binding. The results showed that antibody-inhibited plasmid migration was heavy metal level-dependent. Zinc caused a unique mobility shift pattern opposite to that of other metals tested, i.e. Zn blocked the antibody ability to inhibit plasmid migration, despite a greatly increased affinity for DNA by the antibody when Zn was present. The Zn effect was reversed/modified by adding MTF-1 protein. Additionally, antibody inhibition of plasmid mobility was resistant to heat pre-treatment and trypsinization, indicating absence of residual DNA extraction-resistant bacterial DNA binding proteins. DNA binding by anti-DNA antibodies may be commonly enhanced by xenobiotic heavy metals and elevated levels of Zn, thus making them potentially effective tools for assessment of heavy metal bioavailability in aqueous solutions and

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

Science.gov (United States)

Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

2018-02-19

The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

Case study II: application of the divalent cation bridging theory to improve biofloc properties and industrial activated sludge system performance-using alternatives to sodium-based chemicals.

Science.gov (United States)

Higgins, Matthew J; Sobeck, David C; Owens, Steven J; Szabo, Lynn M

2004-01-01

The objective of this study was to investigate the application of the divalent cation bridging theory (DCBT) as a tool in the chemical selection process at an activated sludge plant to improve settling, dewatering, and effluent quality. According to the DCBT, to achieve improvements, the goal of chemical selection should be to reduce the ratio of monovalent-to-divalent (M/D) cations. A study was conducted to determine the effect of using magnesium hydroxide [Mg(OH)2] as an alternative to sodium hydroxide (NaOH) at a full-scale industrial wastewater treatment plant. Floc properties and treatment plant performance were measured for approximately one year during two periods of NaOH addition and Mg(OH)2 addition. A cost analysis of plant operation during NaOH and Mg(OH)2 use was also performed. During NaOH addition, the M/D ratio was 48, while, during Mg(OH)2 addition, this ratio was reduced to an average of approximately 0.1. During the Mg(OH)2 addition period, the sludge volume index, effluent total suspended solids, and effluent chemical oxygen demand were reduced by approximately 63, 31, and 50%, respectively, compared to the NaOH addition period. The alum and polymer dose used for clarification was reduced by approximately 50 and 60%, respectively, during Mg(OH)2 addition. The dewatering properties of the activated sludge improved dewatering as measured by decreased capillary suction time and specific resistance to filtration (SRF), along with an increase in cake solids from the SRF test. This corresponded to a reduction in the volume of solids thickened by centrifuges at the treatment plant, which reduced the disposal costs of solids. Considering the costs for chemicals and solids disposal, the annual cost of using Mg(OH)2 was approximately 30,000 dollars to 115,000 dollars less than using NaOH, depending on the pricing of NaOH. The results of this study confirm that the DCBT is a useful tool for assessing chemical-addition strategies and their potential effect

Extraction studies of Cd(II), Cu(II), Mn(II), Ni(II) and Zn(II) using N, N', N, N' -Bis((2-hydroxy-3,5-di-tert-butylbenzyl) (2-pyridylmethyl)) -ethylenediamine as a novel ligand

International Nuclear Information System (INIS)

Laus, R.; Anjos, A.D.; Naves, A.

2008-01-01

In the present study, the use of N,N',N,N'-bis((2-hydroxy-3,5-di-tert-butylbenzyl) (2- pyridylmethyl))-ethylenediamine (H2L) as ligand was evaluated in the liquid-liquid (water- chloroform) extraction of Cd(II), Cu(II), Mn(II), Ni(II) and Zn(II). Experiments were carried out to determine the pH for maximum extraction for each metal ion by ligand, maximum extraction capacity, extraction kinetics and extraction selectivity. The results revealed that the extraction of metal ions is dependent on the pH: maximum extraction maximum was obtained in the pH range of 4.5 - 6.0 for Cu(II) and 8.0 - 9.0 for Zn(II). Cd(II) and Mn(II) were best extracted at pH 9.0 and Ni(II) at 10.0. The ligand H2L was effective for the extraction of Cd(II), Cu(II) and Zn(II) (extraction efficient, %E equal 100%), whereas %E of 76% and 23.5% were observed for Mn(II) and Ni(II), respectively. The ligand presented high selectivity for the extraction of Cu(II) at pH 4.0. (author)

Metal-Chelate Immobilization of Lipase onto Polyethylenimine Coated MCM-41 for Apple Flavor Synthesis.

Science.gov (United States)

Sadighi, Armin; Motevalizadeh, Seyed Farshad; Hosseini, Morteza; Ramazani, Ali; Gorgannezhad, Lena; Nadri, Hamid; Deiham, Behnaz; Ganjali, Mohammad Reza; Shafiee, Abbas; Faramarzi, Mohammad Ali; Khoobi, Mehdi

2017-08-01

An enzyme immobilized on a mesoporous silica nanoparticle can serve as a multiple catalyst for the synthesis of industrially useful chemicals. In this work, MCM-41 nanoparticles were coated with polyethylenimine (MCM-41@PEI) and further modified by chelation of divalent metal ions (M = Co 2+ , Cu 2+ , or Pd 2+ ) to produce metal-chelated silica nanoparticles (MCM-41@PEI-M). Thermomyces lanuginosa lipase (TLL) was immobilized onto MCM-41, MCM-41@PEI, and MCM-41@PEI-M by physical adsorption. Maximum immobilization yield and efficiency of 75 ± 3.5 and 65 ± 2.7% were obtained for MCM@PEI-Co, respectively. The highest biocatalytic activity at extremely acidic and basic pH (pH = 3 and 10) values were achieved for MCM-PEI-Co and MCM-PEI-Cu, respectively. Optimum enzymatic activity was observed for MCM-41@PEI-Co at 75 °C, while immobilized lipase on the Co-chelated support retained 70% of its initial activity after 14 days of storage at room temperature. Due to its efficient catalytic performance, MCM-41@PEI-Co was selected for the synthesis of ethyl valerate in the presence of valeric acid and ethanol. The enzymatic esterification yield for immobilized lipase onto MCM-41@PEI-Co was 60 and 53%, respectively, after 24 h of incubation in n-hexane and dimethyl sulfoxide media. Graphical Abstract Divalent metal chelated polyethylenimine coated MCM-41 (MCM-41@PEI-M) was used for immobilization of Thermomyces lanuginosa lipase catalyzing green apple flavor preparation.

Selective Hg(II) adsorption from aqueous solutions of Hg(II) and Pb(II) by hydrolyzed acrylamide-grafted PET films.

Science.gov (United States)

Rahman, Nazia; Sato, Nobuhiro; Sugiyama, Masaaki; Hidaka, Yoshiki; Okabe, Hirotaka; Hara, Kazuhiro

2014-01-01

Selective Hg(II) adsorption from aqueous solutions of Hg(II) and Pb(II) using hydrolyzed acrylamide (AAm)-grafted polyethylene terephthalate (PET) films was examined to explore the potential reuse of waste PET materials. Selective recovery of Hg(II) from a mixture of soft acids with similar structure, such as Hg(II) and Pb(II), is important to allow the reuse of recovered Hg(II). An adsorbent for selective Hg(II) adsorption was prepared by γ-ray-induced grafting of AAm onto PET films followed by partial hydrolysis through KOH treatment. The adsorption capacity of the AAm-grafted PET films for Hg(II) ions increased from 15 to 70 mg/g after partial hydrolysis because of the reduction of hydrogen bonding between -CONH2 groups and the corresponding improved access of metal ions to the amide groups. The prepared adsorbent was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The absorbent film showed high selectivity for the adsorption of Hg(II) over Pb(II) throughout the entire initial metal concentration range (100-500 mg/L) and pH range (2.2-5.6) studied. The high selectivity is attributed to the ability of Hg(II) ions to form covalent bonds with the amide groups. The calculated selectivity coefficient for the adsorbent binding Hg(II) over Pb(II) was 19.2 at pH 4.5 with an initial metal concentration of 100 mg/L. Selective Hg(II) adsorption equilibrium data followed the Langmuir model and kinetic data were well fitted by a pseudo-second-order equation. The adsorbed Hg(II) and Pb(II) ions were effectively desorbed from the adsorbent film by acid treatment, and the regenerated film showed no marked loss of adsorption capacity upon reuse for selective Hg(II) adsorption.

Tetra- and octa-[4-(2-hydroxyethyl)phenoxy bearing novel metal-free and zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysicochemical properties

Energy Technology Data Exchange (ETDEWEB)

Köksoy, Baybars [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, 41400 Gebze, Kocaeli (Turkey); Bulut, Mustafa, E-mail: mbulut@marmara.edu.tr [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey)

2015-05-15

In this study, four novel phthalonitriles (1–4) and their corresponding metal-free (5–8) and zinc(II) phthalocyanine derivatives (9–12) bearing 4-(hydroxyethyl)phenoxy groups were synthesized. These novel compounds were characterized by IR, elemental analyses, {sup 1}H-NMR, UV–vis, and MALDI-TOF spectral data. Furthermore, photophysical (fluorescence quantum yields and lifetimes) and photochemical properties (singlet oxygen generation and photodegradation quantum yields) of these phthalocyanines were investigated in dimethylsulfoxide. The studied zinc(II) phthalocyanines generated highly singlet oxygen which is very important for the photodynamic therapy (PDT) of cancer. The fluorescence quenching behaviour of the newly synthesized phthalocyanine compounds were also investigated using 1,4-benzoquinone. - Highlights: • Octa and tetra 4-(hydroxyethyl)phenoxy substituted metal-free and zinc(II) phthalocyanines. • Study of photophysicochemical properties of eight new phthalocyanines. • Highly singlet oxygen generation for novel zinc(II) phthalocyanine photosensitizers.

Divalent phosphate is a counterion for carboxyatractyloside-insensitive adenine nucleotide transport in rat liver mitochondria

International Nuclear Information System (INIS)

Nosek, M.T.; Aprille, J.R.

1986-01-01

Unidirectional, carboxyatractyloside(CAT)-insensitive adenine nucleotide (AdN) fluxes have been studied in isolated rat liver mitochondria (mito). Previous work has shown that ATP x Mg transport in one direction is coupled to ATP x Mg or P/sub i/ transport in the opposite direction. The purpose of this study was to determine whether divalent HPO 4 2- or monovalent H 2 PO 4 - is the transported phosphate species. The authors used the monofluorophosphate (PO 3 F 2- ) and difluorophosphate (PO 2 F 2 - ) analogues as potential counterions forAdN efflux. After a preincubation on ice with 14 C-ADP to label the matrix AdN, efflux was measured at 30 0 C, pH 7.4, in 225mM sucrose, 10mM KCl, 5mM MgCl 2 , 5mM glutamate, 5mM malate, 10mM Tris, 0.5mM P/sub i/, 1mM ATP, and 5μM CAT. With no other additions efflux was -0.62 +/- 0.20 nmole/minute/mg protein. The data supports the hypothesis that divalent but not monovalent phosphate can act as a counterion for ATPx Mg transport over this CAT-insensitive carrier

Metal homeostasis in Hypogymnia physodes is controlled by lichen substances.

Science.gov (United States)

Hauck, Markus

2008-05-01

The hypothesis was tested that the lichen substances produced by the epiphytic lichen Hypogymnia physodes control the intracellular uptake of divalent transition metals. Incubating lichen thalli with and without their natural content of lichen substances with metal solutions showed that the lichen substances of H. physodes selectively inhibit the uptake of Cu(2+) and Mn(2+), but not of Fe(2+) and Zn(2+). Such behavior is ecologically beneficial, as ambient concentrations of Cu(2+) and Mn(2+) in precipitation and bark are known to limit the abundance of H. physodes, whereas limiting effects of Fe(2+) or Zn(2+) have never been found. This suggests that increasing the Cu(2+) and Mn(2+) tolerance stimulated the evolution of lichen substances in H. physodes. The depsidone physodalic acid is apparently most effective at reducing Cu(2+) and Mn(2+) uptake among the seven lichen substances produced by H. physodes. Probably lichen substances play a general role in the metal homeostasis of lichens.

A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence

International Nuclear Information System (INIS)

Eliseeva, Svetlana V.; Golovach, Iurii P.; Liasotskyi, Valerii S.; Antonovich, Valery P.; Petoud, Stéphane; Meshkova, Svetlana B.

2016-01-01

Most of the existing optical methods for Cu II detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a "turn-on" lanthanide(III)-based molecular probe for the specific detection of Cu II ions based on both visible (Tb III , Eu III ) and near-infrared (Nd III , Yb III ) emission. Quantum yields of the characteristic Ln III emission signals increases by at least two-orders of magnitude upon addition of Cu II into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of Cu II ions does not significantly affect the energy positions of the singlet (32,260 cm −1 ) and triplet (25,640–25,970 cm −1 ) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce Cu II to Cu I has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards Cu II over other transition metal ions: the addition of divalent Zn II , Cd II , Pd II , Ni II , Co II or trivalent Fe III , Ga III , In III ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of Cu II results in a 20- to 30-times lanthanide luminescence enhancement. This new strategy results in a versatile and selective optical platform for the

Pecan nutshell as biosorbent to remove Cu(II), Mn(II) and Pb(II) from aqueous solutions.

Science.gov (United States)

Vaghetti, Julio C P; Lima, Eder C; Royer, Betina; da Cunha, Bruna M; Cardoso, Natali F; Brasil, Jorge L; Dias, Silvio L P

2009-02-15

In the present study we reported for the first time the feasibility of pecan nutshell (PNS, Carya illinoensis) as an alternative biosorbent to remove Cu(II), Mn(II) and Pb(II) metallic ions from aqueous solutions. The ability of PNS to remove the metallic ions was investigated by using batch biosorption procedure. The effects such as, pH, biosorbent dosage on the adsorption capacities of PNS were studied. Four kinetic models were tested, being the adsorption kinetics better fitted to fractionary-order kinetic model. Besides that, the kinetic data were also fitted to intra-particle diffusion model, presenting three linear regions, indicating that the kinetics of adsorption should follow multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm model. The maximum biosorption capacities of PNS were 1.35, 1.78 and 0.946mmolg(-1) for Cu(II), Mn(II) and Pb(II), respectively.

Optical characterization and blu-ray recording properties of metal(II) azo barbituric acid complex films

Energy Technology Data Exchange (ETDEWEB)

Li, X.Y. [Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China)], E-mail: xyli@siom.ac.cn; Wu, Y.Q. [Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Key Lab of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, Haerbin 150080 (China)], E-mail: yqwu@siom.ac.cn; Gu, D.D.; Gan, F.X. [Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China)

2009-02-25

Smooth thin films of nickel(II), cobalt(II) and zinc(II) complexes with azo barbituric acid were prepared by the spin-coating method. Absorption spectra of the thin films on K9 glass substrates in 300-700 nm wavelength region were measured. Optical constants (complex refractive index N = n + ik) of the thin films prepared on single-crystal silicon substrates in 275-695 nm wavelength region were investigated on rotating analyzer-polarizer type of scanning ellipsometer, and dielectric constant {epsilon} ({epsilon} = {epsilon}{sub 1} + i{epsilon}{sub 2}) as well as absorption coefficient {alpha} of thin films were calculated at 405 nm. In addition, static optical recording properties of the cobalt(II) complex thin film with an Ag reflective layer was carried out using a 406.7 nm blue-violet laser and a high numerical aperture (NA) of 0.90. Clear recording marks with high reflectivity contrast (>60%) at proper laser power and pulse width were obtained, and the size of recording mark was as small as 250 nm. The results indicate that these metal(II) complexes are promising organic recording medium for the blu-ray optical storage system.

Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues

International Nuclear Information System (INIS)

Guezel, Fuat; Yakut, Hakan; Topal, Giray

2008-01-01

In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (k ads ) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (E a ) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (q m and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy (ΔH), free energy (ΔG), and entropy (ΔS) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures

Synthesis and Characterization of Multimetallic Fe(II) and Mn(II ...

African Journals Online (AJOL)

Iron(II) and Manganese(II) complexes of the resulting ligand were obtained from its reactions with Fe(II) and Mn(II) salts in absolute methanol for the metal to ligand ratio 2:3. These complexes were characterized by Solubility, Conductivity, IR and UV-VIS spectrometry, elemental analysis and mass spectrometry. Keywords: ...

Recovery of Cd(II), Co(II) and Ni(II) from Chloride Medium by Solvent Extraction Using CYANEX 923 and CYANEX 272 I

International Nuclear Information System (INIS)

Ahmed, M.; El Dessouky, S.I.; El-Nadi, Y.A.; Daoud, J.A.; Saad, E.A.

2008-01-01

The paper aims to study the extraction and separation of Cd(II), Co(II) and Ni(II) from their mixtures in hydrochloric acid medium with CYANEX 923 in kerosene. Preliminary investigations showed that only Cd(II) is extracted with CYANEX 923 while Co(II) and Ni(II) are not extracted. Different parameters affecting the extraction of Cd(II) with CYANEX 923 such as hydrochloric acid, hydrogen ion, extractant and metal concentrations, temperature investigations were also investigated. The stoichiometry of the extracted metal species investigated was found to be HCdCl 3 . 2 CYANEX 923. The stripping of the extracted Cd(II) species is obtained with 0.1 M HCl solution. Co(II) was found to be extracted with CYANEX 272 at ph 5.8 leaving Ni(II) in the solution. A developed process for the sequential of Cd(II), Co(II) and Ni(II) from their mixture in hydrochloric acid medium is proposed

Complexes in polyvalent metal - Alkali halide melts

International Nuclear Information System (INIS)

Akdeniz, Z.; Tosi, M.P.

1991-03-01

Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

Composite materials with metal oxide attached to lead chalcogenide nanocrystal quantum dots with linkers

Science.gov (United States)

Fuke, Nobuhiro; Koposov, Alexey Y; Sykora, Milan; Hoch, Laura

2014-12-16

Composite materials useful for devices such as photoelectrochemical solar cells include a substrate, a metal oxide film on the substrate, nanocrystalline quantum dots (NQDs) of lead sulfide, lead selenide, and lead telluride, and linkers that attach the NQDs to the metal oxide film. Suitable linkers preserve the 1s absorption peak of the NQDs. A suitable linker has a general structure A-B-C where A is a chemical group adapted for binding to a MO.sub.x and C is a chemical group adapted for binding to a NQD and B is a divalent, rigid, or semi-rigid organic spacer moiety. Other linkers that preserve the 1s absorption peak may also be used.

Zeolite-encapsulated Co(II), Mn(II), Cu(II) and Cr(III) salen complexes as catalysts for efficient selective oxidation of benzyl alcohol

Science.gov (United States)

Li, F. H.; Bi, H.; Huang, D. X.; Zhang, M.; Song, Y. B.

2018-01-01

Co(II), Mn(II), Cu(II) and Cr(III) salen type complexes were synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. Data of characterization indicates the formation of metal salen complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activity results show that Cosalcyen Y exhibited higher catalytic activity in the water phase selective oxidation of benzyl alcohol, which could be attributed to their geometry and the steric environment of the metal actives sites.

Cr(III,Mn(II,Fe(III,Co(II,Ni(II,Cu(II and Zn(II Complexes with Diisobutyldithiocarbamato Ligand

Directory of Open Access Journals (Sweden)

Mohammad Tarique

2011-01-01

Full Text Available The synthesis of sulphur and nitrogen containing dithiocarbamato ligand derived from diisobutylamine as well as its coordination compounds with 3d series transition metals is presented. These synthesized compounds were characterized on the basis of elemental analysis, conductometric measurements and IR spectral studies. The analytical data showed the stoichiometry 1:2 and 1:3 for the compounds of the types ML2 {M=Mn(II, Co(II, Ni(II, Cu(II and Zn(II} and M'L3{M'=Cr(III and Fe(III} respectively. The conductometric measurements proved the non-electrolytic behaviour of all the compounds. The bidentate nature of dithiocarbamato moiety was confirmed on the basis of IR spectral data.

Metallicity Variations in the Type II Globular Cluster NGC 6934

Science.gov (United States)

Marino, A. F.; Yong, D.; Milone, A. P.; Piotto, G.; Lundquist, M.; Bedin, L. R.; Chené, A.-N.; Da Costa, G.; Asplund, M.; Jerjen, H.

2018-06-01

The Hubble Space Telescope photometric survey of Galactic globular clusters (GCs) has revealed a peculiar “chromosome map” for NGC 6934. In addition to a typical sequence, similar to that observed in Type I GCs, NGC 6934 displays additional stars on the red side, analogous to the anomalous Type II GCs, as defined in our previous work. We present a chemical abundance analysis of four red giants in this GC. Two stars are located on the chromosome map sequence common to all GCs, and another two lie on the additional sequence. We find (i) star-to-star Fe variations, with the two anomalous stars being enriched by ∼0.2 dex. Because of our small-size sample, this difference is at the ∼2.5σ level. (ii) There is no evidence for variations in the slow neutron-capture abundances over Fe, at odds with what is often observed in anomalous Type II GCs, e.g., M 22 and ω Centauri (iii) no large variations in light elements C, O, and Na, compatible with locations of the targets on the lower part of the chromosome map where such variations are not expected. Since the analyzed stars are homogeneous in light elements, the only way to reproduce the photometric splits on the sub-giant (SGB) and the red giant (RGB) branches is to assume that red RGB/faint SGB stars are enhanced in [Fe/H] by ∼0.2. This fact corroborates the spectroscopic evidence of a metallicity variation in NGC 6934. The observed chemical pattern resembles only partially the other Type II GCs, suggesting that NGC 6934 might belong either to a third class of GCs, or be a link between normal Type I and anomalous Type II GCs. Based on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by AURA, Inc., under NASA contract NAS 5-26555. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile, and Gemini Telescope at Canada–France–Hawaii Telescope.

Competitive metal sorption and desorption onto Kappaphycus alvarezii, seaweed waste biomass

International Nuclear Information System (INIS)

Lee, K.O.; Nazaruddin Ramli; Mamot Said; Musa Ahmad; Suhaimi Mohd Yasir; Arbakariya Ariff

2011-01-01

Competitive metal sorption and desorption onto Kappaphycus alvarezii waste biomass were investigated. Metal sorption capacities were 0.82 mg Cr (III)/ g, 0.73 mg Ni (II)/ g, 0.67 mg Cd (II)/ g, 0.65 mg Cu( II)/ g and 0.64 mg Zn (II)/ g in multi metal system. Whereas, desorption efficiencies were 66.08 %, 71.50 % and 80.44 % using 0.1 M HNO 3 , 0.1 M HCl and 0.1 M H 2 SO 4 , respectively. The metal sorption sequence were Cr(III) > Ni(II) > Cd(II) > Cu(II) > Zn(II), while metal desorption sequence were Cd(II) > Zn(II) > Cu(II) > Ni(II) > Cr(III). Fourier transformed infrared spectroscopy (FTIR) technique was used to characterize the seaweed waste biomass. FTIR analysis shown that carbonyl (-C-O) and nitrile (-C≡N) groups interact with the metal ions. The experiments result revealed that Kappaphycus alvarezii waste biomass represent an attractive candidate to remove multi metal ions. (author)

Competitive metal sorption and desorption onto Kappaphycus alvarezii, seaweed waste biomass

Energy Technology Data Exchange (ETDEWEB)

Lee, K O; Ramli, Nazaruddin; Said, Mamot; Ahmad, Musa [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia (UKM), Bangi, selangor (Malaysia); Yasir, Suhaimi Mohd [School of Sciences and Technology, Universiti Malaysia Sabah (UMS), Sabah (Malaysia); Arbakariya Ariff, E-mail: naza@ukm.my [Faculty of Biotechnology and Biomolecular science, Universiti Putra Malaysia (UPM), Serdang, Selangor (Malaysia)

2011-07-15

Competitive metal sorption and desorption onto Kappaphycus alvarezii waste biomass were investigated. Metal sorption capacities were 0.82 mg Cr (III)/ g, 0.73 mg Ni (II)/ g, 0.67 mg Cd (II)/ g, 0.65 mg Cu( II)/ g and 0.64 mg Zn (II)/ g in multi metal system. Whereas, desorption efficiencies were 66.08 %, 71.50 % and 80.44 % using 0.1 M HNO{sub 3}, 0.1 M HCl and 0.1 M H{sub 2}SO{sub 4}, respectively. The metal sorption sequence were Cr(III) > Ni(II) > Cd(II) > Cu(II) > Zn(II), while metal desorption sequence were Cd(II) > Zn(II) > Cu(II) > Ni(II) > Cr(III). Fourier transformed infrared spectroscopy (FTIR) technique was used to characterize the seaweed waste biomass. FTIR analysis shown that carbonyl (-C-O) and nitrile (-C{identical_to}N) groups interact with the metal ions. The experiments result revealed that Kappaphycus alvarezii waste biomass represent an attractive candidate to remove multi metal ions. (author)

Combinatorial screening of potentiometric Pb(II) sensors from polysulfoaminoanthraquinone solid ionophore.

Science.gov (United States)

Huang, Mei-Rong; Ding, Yong-Bo; Li, Xin-Gui

2014-03-10

A potentiometric Pb(II)-selective sensor was fabricated by a combinatorial screening of electrically conducting polysulfoaminoanthraquinone (PSA) nanoparticles as a solid ionophore, ion exchangers (oleic acid (OA) and NaTPB), plasticizers in a polyvinyl chloride (PVC) matrix, membrane thickness, inner filling ion species, and concentration. The membrane sensor with the composition of PSA/PVC/DOP (dioctyl phthalate)/OA (1.0:33:61:5.0) exhibited the best performance, including a slope of 29.3 mV decade(-1) in the concentration range 10(-6.3)-10(-1.6) M, detection limit of 1.6 × 10(-7) M, response time of 16 s, lifetime of five months, and good response reversibility. The proposed sensor has demonstrated good selectivity for Pb(II) over other monovalent, divalent and trivalent interfering ions, and could be used in a pH range of 3.62-5.22. The Pb(II) sensor has been successfully applied for the determination of Pb(II) concentration in real-world samples and also as an indicator electrode for potentiometric titration of lead ions.

Removal of Zn(II) and Hg(II) from aqueous solution on a carbonaceous sorbent chemically prepared from rice husk

International Nuclear Information System (INIS)

El-Shafey, E.I.

2010-01-01

A carbonaceous sorbent was prepared from rice husk via sulfuric acid treatment. Sorption of Zn(II) and Hg(II) from aqueous solution was studied varying time, pH, metal concentration, temperature and sorbent status (wet and dry). Zn(II) sorption was found fast reaching equilibrium within ∼2 h while Hg(II) sorption was slow reaching equilibrium within ∼120 h with better performance for the wet sorbent than for the dry. Kinetics data for both metals were found to follow pseudo-second order model. Sorption rate of both metals was enhanced with temperature rise. Activation energy, E a , for Zn(II) sorption, was ∼13.0 kJ/mol indicating a diffusion-controlled process ion exchange process, however, for Hg(II) sorption, E a was ∼54 kJ/mol indicating a chemically controlled process. Sorption of both metals was low at low pH and increased with pH increase. Sorption was much higher for Hg(II) than for Zn(II) with higher uptake for both metals by rising the temperature. Hg(II) was reduced to Hg(I) on the sorbent surface. This was confirmed from the identification of Hg 2 Cl 2 deposits on the sorbent surface by scanning electron microscopy and X-ray diffraction. However, no redox processes were observed in Zn(II) sorption. Sorption mechanism is discussed.

Kinetic study on adsorption of Cr(VI), Ni(II), Cd(II) and Pb(II) ions from aqueous solutions using activated carbon prepared from Cucumis melo peel

Science.gov (United States)

Manjuladevi, M.; Anitha, R.; Manonmani, S.

2018-03-01

The adsorption of Cr(VI), Ni(II), Cd(II) and Pb(II), ions from aqueous solutions by Cucumis melo peel-activated carbon was investigated under laboratory conditions to assess its potential in removing metal ions. The adsorption behavior of metal ions onto CMAC was analyzed with Elovich, intra-particle diffusion rate equations and pseudo-first-order model. The rate constant of Elovich and intra-particle diffusion on CMAC increased in the sequence of Cr(VI) > Ni(II) > Cd(II) > Pb(II). According to the regression coefficients, it was observed that the kinetic adsorption data can fit better by the pseudo-first-order model compared to the second-order Lagergren's model with R 2 > 0.957. The maximum adsorption of metal ions onto the CMAC was found to be 97.95% for Chromium(VI), 98.78% for Ni(II), 98.55% for Pb(II) and 97.96% for Cd(II) at CMAC dose of 250 mg. The adsorption capacities followed the sequence Ni(II) ≈ Pb(II) > Cr(VI) ≈ Cd(II) and Ni(II) > Pb(II) > Cd(II) > Cr(VI). The optimum adsorption conditions selected were adsorbent dosage of 250 mg, pH of 3.0 for Cr(VI) and 6.0 for Ni(II), Cd(II) and Pb(II), adsorption concentration of 250 mg/L and contact time of 180.

Radial velocities and metallicities from infrared Ca ii triplet spectroscopy of open clusters. II. Berkeley 23, King 1, NGC 559, NGC 6603, and NGC 7245

Science.gov (United States)

Carrera, R.; Casamiquela, L.; Ospina, N.; Balaguer-Núñez, L.; Jordi, C.; Monteagudo, L.

2015-06-01

Context. Open clusters are key to studying the formation and evolution of the Galactic disc. However, there is a deficiency of radial velocity and chemical abundance determinations for open clusters in the literature. Aims: We intend to increase the number of determinations of radial velocities and metallicities from spectroscopy for open clusters. Methods: We acquired medium-resolution spectra (R ~ 8000) in the infrared region Ca ii triplet lines (~8500 Å) for several stars in five open clusters with the long-slit IDS spectrograph on the 2.5 m Isaac Newton Telescope (Roque de los Muchachos Observatory, Spain). Radial velocities were obtained by cross-correlation fitting techniques. The relationships available in the literature between the strength of infrared Ca ii lines and metallicity were also used to derive the metallicity for each cluster. Results: We obtain ⟨Vr⟩ = 48.6 ± 3.4, -58.4 ± 6.8, 26.0 ± 4.3, and -65.3 ± 3.2 km s-1 for Berkeley 23, NGC 559, NGC 6603, and NGC 7245, respectively. We found [ Fe/H ] = -0.25 ± 0.14 and -0.15 ± 0.18 for NGC 559 and NGC 7245, respectively. Berkeley 23 has low metallicity, [ Fe/H ] = -0.42 ± 0.13, which is similar to other open clusters in the outskirts of the Galactic disc. In contrast, we derived high metallicity ([ Fe/H ] = +0.43 ± 0.15) for NGC 6603, which places this system among the most metal-rich known open clusters. To our knowledge, this is the first determination of radial velocities and metallicities from spectroscopy for these clusters, except NGC 6603, for which radial velocities had been previously determined. We have also analysed ten stars in the line of sight to King 1. Because of the large dispersion obtained in both radial velocity and metallicity, we cannot be sure that we have sampled true cluster members. Based on observations made with the 2.5 m Isaac Newton Telescope operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the

Beryllium(II), manganese(II) and uranyl(VI)-salicylamide complexes

Energy Technology Data Exchange (ETDEWEB)

Maurya, P L; Agarwala, B V; Dey, A K [Allahabad Univ. (India)

1977-01-01

The preparation, composition, general properties and i.r. absorption spectra of the solid chelates formed by salicylamide with beryllium(II), manganese(II) and uranyl(VI) are described. The complexes have been synthesized by refluxing a mixture of ethanolic solutions of the reactants (metal:ligand :: 1:2) for several hours in the presence of alkali. Attempts to isolate the complexes by the interaction of ethanolic solutions of the metal salts and the ligand in the absence of alkali did not succeed.

New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

Energy Technology Data Exchange (ETDEWEB)

Bartsch, Richard A.

2012-06-04

The project objective was the discovery of new ligands for performing metal ion separations. The research effort entailed the preparation of new metal ion complexing agents and polymers and their evaluation in metal ion separation processes of solvent extraction, synthetic liquid membrane transport, and sorption. Structural variations in acyclic, cyclic, and bicyclic organic ligands were used to probe their influence upon the efficiency and selectivity with which metal ion separations can be performed. A unifying feature of the ligand structures is the presence of one (or more) side arm with a pendent acidic function. When a metal ion is complexed within the central cavity of the ligand, ionization of the side arm(s) produces the requisite anion(s) for formation of an overall electroneutral complex. This markedly enhances extraction/transport efficiency for separations in which movement of aqueous phase anions of chloride, nitrate, or sulfate into an organic medium would be required. Through systematic structural variations, new ligands have been developed for efficient and selective separations of monovalent metal ions (e.g., alkali metal, silver, and thallium cations) and of divalent metal ion species (e.g., alkaline earth metal, lead, and mercury cations). Research results obtained in these fundamental investigations provide important insight for the design and development of ligands suitable for practical metal ion separation applications.

Stability Constants of Mixed Ligand Complexes of Transition Metal(II Ions with Salicylidene-4-methoxyaniline as Primary Ligand and 5-Bromosalicylidene-4-nitroaniline as Secondary Ligand

Directory of Open Access Journals (Sweden)

N. G. Nadkarni

2011-01-01

Full Text Available Binary and ternary complexes of the type M-Y and M-X-Y [M = Mn(II, Ni(II, Cu(II and Zn(II; X = salicylidene-4-methoxyaniline and Y=5-bromosalicylidene-4-nitroaniline] have been examined pH-metrically at 27±0.5 °C and at constant ionic strength, μ= 0.1 M (KCl in 75 : 25(v/v 1,4-dioxne-water medium. The stability constants for binary (M-Y and ternary (M-X-Y systems were calculated. The relative stability (Δ log KT values of the ternary complexes with corresponding binary complexes for all the metal(II ions in the present study found to be negative indicating that ternary 1:1:1 (M-X-Y complexes are less stable than binary 1:1 (M-Y complexes. In the ternary system studied, the order of stability constants of mixed ligand complexes with respect to the metal ions was found to be Cu(II > NI(II > Mn(II > Zn(II; which is same as in the corresponding binary (M-Y systems.

Low iron stores are related to higher blood concentrations of manganese, cobalt and cadmium in non-smoking, Norwegian women in the HUNT 2 study

International Nuclear Information System (INIS)

Margrete Meltzer, Helle; Lise Brantsaeter, Anne; Borch-Iohnsen, Berit; Ellingsen, Dag G.; Alexander, Jan; Thomassen, Yngvar; Stigum, Hein; Ydersbond, Trond A.

2010-01-01

Low iron (Fe) stores may influence absorption or transport of divalent metals in blood. To obtain more knowledge about such associations, the divalent metal ions cadmium (Cd), manganese (Mn), cobalt (Co), copper (Cu), zinc (Zn) and lead (Pb) and parameters of Fe metabolism (serum ferritin, haemoglobin (Hb) and transferrin) were investigated in 448 healthy, menstruating non-smoking women, age 20-55 years (mean 38 years), participating in the Norwegian HUNT 2 study. The study population was stratified for serum ferritin: 257 were iron-depleted (serum ferritin 2 for the models were 0.28, 0.48 and 0.34, respectively. Strong positive associations between blood concentrations of Mn, Co and Cd were observed, also when controlled for their common association with ferritin. Apart from these associations, the models showed no significant interactions between the six divalent metals studied. Very mild anaemia (110≤Hb<120 g/L) did not seem to have any effect independent of low ferritin. Approximately 26% of the women with iron deficiency anaemia had high concentrations of all of Mn, Co and Cd as opposed to 2.3% of iron-replete subjects. The results confirm that low serum ferritin may have an impact on body kinetics of certain divalent metal ions, but not all. Only a fraction of women with low iron status exhibited an increased blood concentration of divalent metals, providing indication of complexities in the body's handling of these metals.

Spectroscopic and thermal degradation behavior of Mg(II), Ca(II), Ba(II) and Sr(II) complexes with paracetamol drug

OpenAIRE

Moamen S. Refat; Gehad G. Mohamed; Mohamed Y. El-Sayed; Hamada M.A. Killa; Hammad Fetooh

2017-01-01

Complexes of Mg(II), Ca(II), Ba(II) and Sr(II) with paracetamol drug were synthesized and characterized by elemental analysis, conductivity, UV–Vis, IR, and 1H NMR spectroscopy and thermal analysis, as well as screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as paracetamol behaves as a neutral bidentate ligand coordinated to the metal ions via the lone pair of electrons of nitrogen and carbonyl-O atoms of the amide group. From the microanalytical dat...

Synthesis, characterization and biological studies of 2-(4-nitrophenylamino-carbonyl)benzoic acid and its complexes with Cr(III), Co(II), Ni(II), Cu(II) and Zn(II)

International Nuclear Information System (INIS)

Imran, M; Nazir, S.; Latif, S.; Mahmood, Z.

2010-01-01

Cr(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of 2-(4-Nitrophenyl aminocarbonyl)benzoic acid were synthesized and characterized on the basis of physical, analytical and spectroscopic data. The ligands, as well as its metal complexes were checked for their in-vitro antimicrobial activity against three bacterial strains, Mycobacterium smegmatis, Escherichia coli, Pseudomonas aeuroginosa, and three fungal strains, Nigrospora oryzae, Aspergillus niger and Candida albicans. Disc diffusion method and Tube diffusion test were used for antibacterial and antifungal activities, respectively. The synthesized complexes only show significant antifungal activity but inactive for antibacterial, however, in general, the metal complexes were found to be more active against antimicrobial activities as compared to their un complexed ligand. (author)

Synthesis and characterization of polychelates of Cu(II), Ni(II), Co(II), Mn(II), Zn(II), oxovanadium(IV) and dioxouranium(VI) with 2,4-dihydroxybenzaldehyde-urea-formaldehyde polymer

International Nuclear Information System (INIS)

Patel, G.C.; Pancholi, H.B.; Patel, M.M.

1991-01-01

Polychelates of Cu(II), Ni(II), Co(II), Mn(II), Zn(II), oxovandium(IV) and dioxouranium(VI) with 2,4-dihydroxybenzaldehyde (2,4-DB)-urea(U)-formaldehyde(F) polymer (2,4-DBUF) have been prepared. Elemental analyses of the polychelates indicate a metal:ligand ratio of 1:2. The structures of the polychelates have been assigned on the basis of their elemental analyses, IR, reflectance spectra, magnetic moment, thermal data and their electrical conductivity behaviour. (author). 1 tab., 18 refs

Cooperative adsorption of critical metal ions using archaeal poly-γ-glutamate.

Science.gov (United States)

Hakumai, Yuichi; Oike, Shota; Shibata, Yuka; Ashiuchi, Makoto

2016-06-01

Antimony, beryllium, chromium, cobalt (Co), gallium (Ga), germanium, indium (In), lithium, niobium, tantalum, the platinoids, the rare-earth elements (including dysprosium, Dy), and tungsten are generally regarded to be critical (rare) metals, and the ions of some of these metals are stabilized in acidic solutions. We examined the adsorption capacities of three water-soluble functional polymers, namely archaeal poly-γ-glutamate (L-PGA), polyacrylate (PAC), and polyvinyl alcohol (PVA), for six valuable metal ions (Co(2+), Ni(2+), Mn(2+), Ga(3+), In(3+), and Dy(3+)). All three polymers showed apparently little or no capacity for divalent cations, whereas L-PGA and PAC showed the potential to adsorb trivalent cations, implying the beneficial valence-dependent selectivity of anionic polyelectrolytes with multiple carboxylates for metal ions. PVA did not adsorb metal ions, indicating that the crucial role played by carboxyl groups in the adsorption of crucial metal ions cannot be replaced by hydroxyl groups under the conditions. In addition, equilibrium studies using the non-ideal competitive adsorption model indicated that the potential for L-PGA to be used for the removal (or collection) of water-soluble critical metal ions (e.g., Ga(3+), In(3+), and Dy(3+)) was far superior to that of any other industrially-versatile PAC materials.

Study of physicochemical parameters for cadmium (II) and mercury (II) phytoremediation using the specie Eichhornia Crassipes (water hyacinth)

International Nuclear Information System (INIS)

Poma Llantoy, Victor R.; Valderrama Negron, Ana C.

2014-01-01

In this work, the studies were performed to measure the sorption capacity of metal ions Cd (II) and Hg (II) using the specie Eichhornia crassipes (water hyacinth). This study includes assays where the nutrient concentration, the pH and the metal ion concentration were optimized. These tests were carried out at room temperature and with aqueous solutions of Cd (II), Hg (II), in which the samples of Eichhornia crassipes were placed. To confirm the removal of these metals, the waste solutions after the treatment with the Water Hyacinth species were treated using the method APHA 3030-e. However, Eichhornia crassipes samples were treated using the EPA 200.3 method. The concentration of Cd (II) was determined by an ICP-OES spectrometer and Hg (II), by an atomic absorption spectrophotometer. The results showed: Optimal dosage 1 mL of A and 0,5 mL of B, optimum pH 5, optimum concentration of Cd (II) and Hg (II) 5 mg/L for each ion. With these parameters, it was started the removal of 5 mg/L of the metal ions contained in 1 L of solution. Being the percentages of sorption 16,56% for Cd (II) and 15,6% for Hg (II) after a period of 7 days. (author)

Accumulation of metal ions by pectinates

Science.gov (United States)

Deiana, S.; Deiana, L.; Palma, A.; Premoli, A.; Senette, C.

2009-04-01

The knowledge of the mechanisms which regulate the interactions of metal ions with partially methyl esterified linear polymers of α-1,4 linked D-galacturonic acid units (pectinates), well represented in the root inner and outer apoplasm, is of great relevance to understand the processes which control their accumulation at the soil-root interface as well as their mobilization by plant metabolites. Accumulation of a metal by pectinates can be affected by the presence of other metals so that competition or distribution could be expected depending on the similar or different affinity of the metal ions towards the binding sites, mainly represented by the carboxylate groups. In order to better understand the mechanism of accumulation in the apoplasm of several metal ions, the sorption of Cd(II), Zn(II), Cu(II), Pb(II) and Cr(III) by a Ca-polygalacturonate gel, used as model of the soil-root interface, with a degree of esterification of 18% (PGAE1) and 65% (PGAE2) was studied at pH 3.0, 4.0, 5.0 and 6.0 in the presence of CaCl2 2.5 mM.. The results show that sorption increases with increasing both the initial metal concentration and pH. A similar sorption trend was evidenced for Cu(II) and Pb(II) and for Zn(II) and Cd(II), indicating that the mechanism of sorption for these two ionic couples is quite different. As an example, at pH 6.0 and an initial metal concentration equal to 2.0 mM, the amount of Cu(II) and Pb(II) sorbed was about 1.98 mg-1 of PGAE1 while that of Cd(II) and Zn(II) was about 1.2 mg-1. Cr(III) showed a rather different sorption trend and a much higher amount (2.8 mg-1of PGAE1 at pH 6.0) was recorded. The higher affinity of Cr(III) for the polysaccharidic matrix is attributable to the formation of Cr(III) polynuclear species in solution, as shown by the distribution diagrams obtained through the MEDUSA software. On the basis of these findings, the following affinity towards the PGAE1 can be assessed: Cr(III) > Cu(II) ? Pb(II) > Zn (II) ? Cd(II

Strong room-temperature ultraviolet to red excitons from inorganic organic-layered perovskites, (MX4 (M=Pb, Sn, Hg; X=I-, Br-)

Science.gov (United States)

Ahmad, Shahab; Prakash, G. Vijaya

2014-01-01

Many varieties of layered inorganic-organic (IO) perovskite of type (MX4 (where R: organic moiety, M: divalent metal, and X: halogen) were successfully fabricated and characterized. X-ray diffraction data suggest that these inorganic and organic structures are alternatively stacked up along c-axis, where inorganic mono layers are of extended corner-shared MX6 octahedra and organic spacers are the bi-layers of organic entities. These layered perovskites show unusual room-temperature exciton absorption and photoluminescence due to the quantum and dielectric confinement-induced enhancement in the exciton binding energies. A wide spectral range of optical exciton tunability (350 to 600 nm) was observed experimentally from systematic compositional variation in (i) divalent metal ions (M=Pb, Sn, Hg), (ii) halides (X=I and Br-), and (iii) organic moieties (R). Specific photoluminescence features are due to the structure of the extended MX42- network and the eventual electronic band structure. The compositionally dependent photoluminescence of these IO hybrids could be useful in various photonic and optoelectronic devices.

Application of Carrier Element-Free Co-precipitation Method for Ni(II), Cu(II) and Zn(II) Ions Determination in Water Samples Using Chrysin

International Nuclear Information System (INIS)

Layth Imad Abd Ali; Wan Aini Wan Ibrahim; Azli Sulaiman; Mohd Marsin Sanagi

2015-01-01

A co-precipitation method was developed to separate and pre-concentrate Ni(II), Cu(II) and Zn(II) ions using an organic co precipitant, chrysin without adding any carrier element termed as carrier element-free co-precipitation (CEFC). Analytes were determined using flame atomic absorption spectrometry (FAAS). The influence of analytical conditions, such as pH of the solution, quantity of co-precipitant, standing time, centrifugation rate and time, sample volume, and interference of concomitant ions were investigated over the recovery yields of the trace metals. The limit of detection, the limit of quantification and linearity range obtained from the FAAS measurements were found to be in the range of 0.64 to 0.86 μg L -1 , 2.13 to 2.86 μg L -1 and 0.9972 to 0.9989 for Ni(II), Cu(III) and Zn(II) ions, respectively. The precision of the method, evaluated as the relative standard deviation (RSD) obtained after analyzing a series of 10 replicates, was between 2.6 % to 3.9 % for the trace metal ions. The proposed procedure was applied and validated by analyzing river water reference material for trace metals (SLRS-5) and spiking trace metal ions in some water samples. The recoveries of the analyte metal ions were between 94.7-101.2 %. (author)

Synthesis and spectroscopic studies of biologically active tetraazamacrocyclic complexes of Mn(II, Co(II, Ni(II, Pd(II and Pt(II

Directory of Open Access Journals (Sweden)

Monika Tyagi

2014-01-01

Full Text Available Complexes of Mn(II, Co(II, Ni(II, Pd(II and Pt(II were synthesized with the macrocyclic ligand, i.e., 2,3,9,10-tetraketo-1,4,8,11-tetraazacycoletradecane. The ligand was prepared by the [2 + 2] condensation of diethyloxalate and 1,3-diamino propane and characterized by elemental analysis, mass, IR and 1H NMR spectral studies. All the complexes were characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, IR, electronic and electron paramagnetic resonance spectral studies. The molar conductance measurements of Mn(II, Co(II and Ni(II complexes in DMF correspond to non electrolyte nature, whereas Pd(II and Pt(II complexes are 1:2 electrolyte. On the basis of spectral studies an octahedral geometry has been assigned for Mn(II, Co(II and Ni(II complexes, whereas square planar geometry assigned for Pd(II and Pt(II. In vitro the ligand and its metal complexes were evaluated against plant pathogenic fungi (Fusarium odum, Aspergillus niger and Rhizoctonia bataticola and some compounds found to be more active as commercially available fungicide like Chlorothalonil.

Metal components analysis of metallothionein-III in the brain sections of metallothionein-I and metallothionein-II null mice exposed to mercury vapor with HPLC/ICP-MS

Energy Technology Data Exchange (ETDEWEB)

Kameo, Satomi; Nakai, Kunihiko; Kurokawa, Naoyuki; Satoh, Hiroshi [Tohoku University, Graduate School of Medicine, Aoba-ku, Sendai (Japan); Kanehisa, Tomokazu; Naganuma, Akira [Tohoku University, Graduate School of Pharmaceutical Sciences, Sendai (Japan)

2005-04-01

Mercury vapor is effectively absorbed via inhalation and easily passes through the blood-brain barrier; therefore, mercury poisoning with primarily central nervous system symptoms occurs. Metallothionein (MT) is a cysteine-rich metal-binding protein and plays a protective role in heavy-metal poisoning and it is associated with the metabolism of trace elements. Two MT isoforms, MT-I and MT-II, are expressed coordinately in all mammalian tissues, whereas MT-III is a brain-specific member of the MT family. MT-III binds zinc and copper physiologically and is seemed to have important neurophysiological and neuromodulatory functions. The MT functions and metal components of MTs in the brain after mercury vapor exposure are of much interest; however, until now they have not been fully examined. In this study, the influences of the lack of MT-I and MT-II on mercury accumulation in the brain and the changes of zinc and copper concentrations and metal components of MTs were examined after mercury vapor exposure by using MT-I, II null mice and 129/Sv (wild-type) mice as experimental animals. MT-I, II null mice and wild-type mice were exposed to mercury vapor or an air stream for 2 h and were killed 24 h later. The brain was dissected into the cerebral cortex, the cerebellum, and the hippocampus. The concentrations of mercury in each brain section were determined by cold vapor atomic absorption spectrometry. The concentrations of mercury, copper, and zinc in each brain section were determined by inductively coupled plasma mass spectrometry (ICP-MS). The mercury accumulated in brains after mercury vapor exposure for MT-I, II null mice and wild-type mice. The mercury levels of MT-I, II null mice in each brain section were significantly higher than those of wild-type mice after mercury vapor exposure. A significant change of zinc concentrations with the following mercury vapor exposure for MT-I, II null mice was observed only in the cerebellum analyzed by two-way analysis of

Rhodium thioacetate complexes

International Nuclear Information System (INIS)

Baranovskij, I.B.; Golubnichaya, M.A.; Mazo, G.Ya.

1976-01-01

Thioacetato-complexes of rhodium(II) were prepared by the reaction of thioacetic acid with rhodium(II) carboxylates. Diamagnetic compounds of the type Rh 2 (CH 3 COS) 4 2A, where A=H 2 O, Py, N 2 H 4 .HCl, Thio, KNCS, DMSO, CH 3 CN, CsCl, or CH 3 COSH, were isolated. Their infrared spectra were recorded, and the principal vibrational wavenumbers assigned. The X-ray electron spectra confirm that rhodium is divalent. The thioacetato-complexes are dimeric, with a metal-metal bond. [Rh(NH 3 ) 5 (CH 3 COS)]I 2 was prepared, and its properties studied. The significant decrease in the strength of the bonds formed by the axial ligands with rhodium is due to the strong trans-influence of the covalent rhodium-rhodium sigma-bond

Synthesis, spectroscopic and antimicrobial properties of Co(II), Ni (II ...

African Journals Online (AJOL)

The objective of this study is to investigate the antimicrobial activity of novel Schiff base metal complexes. The resistance of micro-organisms to classical antimicrobial compounds poses a challenge to effective management and treatment of some diseases. In line with this, copper (II), nickel (II) and cobalt (II) complexes of ...

Biosorption kinetics of Cd (II, Cr (III and Pb (II in aqueous solutions by olive stone

Directory of Open Access Journals (Sweden)

M. Calero

2009-06-01

Full Text Available A by-product from olive oil production, olive stone, was investigated for the removal of Cd (II, Cr (III and Pb (II from aqueous solutions. The kinetics of biosorption are studied, analyzing the effect of the initial concentration of metal and temperature. Pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models have been used to represent the kinetics of the process and obtain the main kinetic parameters. The results show that the pseudo-second order model is the one that best describes the biosorption of the three metal ions for all the range of experimental conditions investigated. For the three metal ions, the maximum biosoption capacity and the initial biosorption rate increase when the initial metal concentration rises. However, the kinetic constant decreases when the initial metal concentration increases. The temperature effect on biosorption capacity for Cd (II and Cr (III is less significant; however, for Pb (II the effect of temperature is more important, especially when temperature rises from 25 to 40ºC. The biosorption capacity at mmol/g of olive stone changes in the following order: Cr>Cd>Pb. Thus, for an initial concentration of 220 mg/ℓ, a maximum sorption capacity of 0.079 mmol/g for Cr (III, 0.065 mmol/g for Cd (II and 0.028 mmol/g for Pb (II has been obtained.

The role of metals in production and scavenging of reactive oxygen species in photosystem II.

Science.gov (United States)

Pospíšil, Pavel

2014-07-01

Metal ions play a crucial role in enzymatic reactions in all photosynthetic organisms such as cyanobacteria, algae and plants. It well known that metal ions maintain the binding of substrate in the active site of the metalloenzymes and control the redox activity of the metalloenzyme in the enzymatic reaction. A large pigment-protein complex, PSII, known to serve as a water-plastoquinone oxidoreductase, contains three metal centers comprising non-heme iron, heme iron of Cyt b559 and the water-splitting manganese complex. Metal ions bound to PSII proteins maintain the electron transport from water to plastoquinone and regulate the pro-oxidant and antioxidant activity in PSII. In this review, attention is focused on the role of PSII metal centers in (i) the formation of superoxide anion and hydroxyl radicals by sequential one-electron reduction of molecular oxygen and the formation of hydrogen peroxide by incomplete two-electron oxidation of water; and (ii) the elimination of superoxide anion radical by one-electron oxidation and reduction (superoxide dismutase activity) and of hydrogen peroxide by two-electron oxidation and reduction (catalase activity). The balance between the formation and elimination of reactive oxygen species by PSII metal centers is discussed as an important aspect in the prevention of photo-oxidative damage of PSII proteins and lipids. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Copper(II) and zinc(II) as metal-carboxylate coordination complexes based on (1-methyl-1H-benzo[d]imidazol-2-yl) methanol derivative: Synthesis, crystal structure, spectroscopy, DFT calculations and antioxidant activity

Science.gov (United States)

Benhassine, Anfel; Boulebd, Houssem; Anak, Barkahem; Bouraiou, Abdelmalek; Bouacida, Sofiane; Bencharif, Mustapha; Belfaitah, Ali

2018-05-01

This work presents a combined experimental and theoretical study of two new metal-carboxylate coordination compounds. These complexes were prepared from (1-methyl-1H-benzimidazol-2-yl)methanol under mild conditions. The structures of the prepared compounds were characterized by single-crystal X-ray analysis, FTIR and UV-Vis spectroscopy. In the Cupper complex, the Cu(II) ion is coordinated by two ligands, which act as bidentate chelator through the non-substituted N and O atoms, and two carboxylicg oxygen atoms, displaying a hexa-coordinated compound in a distorted octahedral geometry, while in the Zinc complex the ligand is ligated to the Zn(II) ion in monodentate fashion through the N atom, and the metal ion is also bonded to carboxylic oxygen atoms. The tetra-coordinated compound displays a distorted tetrahedral shape. The density functional theory calculations are carried out for the determination of the optimized structures. The electronic transitions and fundamental vibrational wave numbers are calculated and are in good agreement with experimental. In addition, the ligand and its Cu(II) and Zn(II) complexes were screened and evaluated for their potential as DPPH radical scavenger.

Recovery of high-purity metallic Pd from Pd(II)-sorbed biosorbents by incineration.

Science.gov (United States)

Won, Sung Wook; Lim, Areum; Yun, Yeoung-Sang

2013-06-01

This work reports a direct way to recover metallic palladium with high purity from Pd(II)-sorbed polyethylenimine-modified Corynebacterium glutamicum biosorbent using a combined method of biosorption and incineration. This study is focused on the incineration part which affects the purity of recovered Pd. The incineration temperature and the amount of Pd loaded on the biosorbent were considered as major factors in the incineration process, and their effects were examined. The results showed that both factors significantly affected the enhancement of the recovery efficiency and purity of the recovered Pd. SEM-EDX and XRD analyses were used to confirm that Pd phase existed in the ash. As a result, the recovered Pd was changed from PdO to zero-valent Pd as the incineration temperature was increased from 600 to 900°C. Almost 100% pure metallic Pd was recovered with recovery efficiency above 99.0% under the conditions of 900°C and 136.9 mg/g. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis, Characterization, and Biological Activity of Mn(II, Fe(II, Co(II, Ni(II, Cu(II, Zn(II, and Cd(II Complexes of N-Thiophenoyl-N′-Phenylthiocarbohydrazide

Directory of Open Access Journals (Sweden)

M. Yadav

2013-01-01

Full Text Available Mn(II, Fe(II, Co(II, Ni(II, Cu(II, Zn(II, and Cd(II complex of N-thiophenoyl -N′-phenylthiocarbohydrazide (H2 TPTH have been synthesized and characterized by elemental analysis, magnetic susceptibility measurements, infrared, NMR, electronic, and ESR spectral studies. The complexes were found to have compositions [Mn(H TPTH2], [Co(TPTH (H2O2], [Ni(TPTH (H2O2], [Cu(TPTH], [Zn(H TPTH], [Cd(H TPTH2], and [Fe(H TPTH2(EtOH]. The magnetic and electronic spectral studies suggest square planar geometry for [Cu(TPTH], tetrahedral geometry for [Zn(TPTH] and [Cd(H TPTH2], and octahedral geometry for rest of the complexes. The infrared spectral studies of the 1 : 1 deprotonated complexes suggest bonding through enolic oxygen, thiolato sulfur, and both the hydrazinic nitrogens. Thus, H2TPTH acts as a binegative tetradentate ligand. H2 TPTH and its metal complexes have been screened against several bacteria and fungi.

Structural basis of Zn(II induced metal detoxification and antibiotic resistance by histidine kinase CzcS in Pseudomonas aeruginosa.

Directory of Open Access Journals (Sweden)

Dan Wang

2017-07-01

Full Text Available Pseudomonas aeruginosa (P. aeruginosa is a major opportunistic human pathogen, causing serious nosocomial infections among immunocompromised patients by multi-determinant virulence and high antibiotic resistance. The CzcR-CzcS signal transduction system in P. aeruginosa is primarily involved in metal detoxification and antibiotic resistance through co-regulating cross-resistance between Zn(II and carbapenem antibiotics. Although the intracellular regulatory pathway is well-established, the mechanism by which extracellular sensor domain of histidine kinase (HK CzcS responds to Zn(II stimulus to trigger downstream signal transduction remains unclear. Here we determined the crystal structure of the CzcS sensor domain (CzcS SD in complex with Zn(II at 1.7 Å resolution. This is the first three-dimensional structural view of Zn(II-sensor domain of the two-component system (TCS. The CzcS SD is of α/β-fold in nature, and it senses the Zn(II stimulus at micromole level in a tetrahedral geometry through its symmetry-related residues (His55 and Asp60 on the dimer interface. Though the CzcS SD resembles the PhoQ-DcuS-CitA (PDC superfamily member, it interacts with the effector in a novel domain with the N-terminal α-helices rather than the conserved β-sheets pocket. The dimerization of the N-terminal H1 and H1' α-helices is of primary importance for the activity of HK CzcS. This study provides preliminary insight into the molecular mechanism of Zn(II sensing and signaling transduction by the HK CzcS, which will be beneficial to understand how the pathogen P. aeruginosa resists to high levels of heavy metals and antimicrobial agents.

Metal-poor dwarf galaxies in the SIGRID galaxy sample. I. H II region observations and chemical abundances

International Nuclear Information System (INIS)

Nicholls, David C.; Dopita, Michael A.; Sutherland, Ralph S.; Jerjen, Helmut; Kewley, Lisa J.; Basurah, Hassan

2014-01-01

In this paper we present the results of observations of 17 H II regions in thirteen galaxies from the SIGRID sample of isolated gas-rich irregular dwarf galaxies. The spectra of all but one of the galaxies exhibit the auroral [O III] 4363 Å line, from which we calculate the electron temperature, T e , and gas-phase oxygen abundance. Five of the objects are blue compact dwarf galaxies, of which four have not previously been analyzed spectroscopically. We include one unusual galaxy which exhibits no evidence of the [N II] λλ 6548,6584 Å lines, suggesting a particularly low metallicity (< Z ☉ /30). We compare the electron temperature based abundances with those derived using eight of the new strong-line diagnostics presented by Dopita et al. Using a method derived from first principles for calculating total oxygen abundance, we show that the discrepancy between the T e -based and strong-line gas-phase abundances have now been reduced to within ∼0.07 dex. The chemical abundances are consistent with what is expected from the luminosity-metallicity relation. We derive estimates of the electron densities and find them to be between ∼5 and ∼100 cm –3 . We find no evidence for a nitrogen plateau for objects in this sample with metallicities 0.5 > Z ☉ > 0.15.

Metal-poor dwarf galaxies in the SIGRID galaxy sample. I. H II region observations and chemical abundances

Energy Technology Data Exchange (ETDEWEB)

Nicholls, David C.; Dopita, Michael A.; Sutherland, Ralph S.; Jerjen, Helmut; Kewley, Lisa J. [Research School of Astronomy and Astrophysics, Australian National University, Cotter Road, Weston ACT 2611 (Australia); Basurah, Hassan, E-mail: David.Nicholls@anu.edu.au [Astronomy Department, King Abdulaziz University, P.O. Box 80203 Jeddah (Saudi Arabia)

2014-05-10

In this paper we present the results of observations of 17 H II regions in thirteen galaxies from the SIGRID sample of isolated gas-rich irregular dwarf galaxies. The spectra of all but one of the galaxies exhibit the auroral [O III] 4363 Å line, from which we calculate the electron temperature, T{sub e} , and gas-phase oxygen abundance. Five of the objects are blue compact dwarf galaxies, of which four have not previously been analyzed spectroscopically. We include one unusual galaxy which exhibits no evidence of the [N II] λλ 6548,6584 Å lines, suggesting a particularly low metallicity (< Z {sub ☉}/30). We compare the electron temperature based abundances with those derived using eight of the new strong-line diagnostics presented by Dopita et al. Using a method derived from first principles for calculating total oxygen abundance, we show that the discrepancy between the T{sub e} -based and strong-line gas-phase abundances have now been reduced to within ∼0.07 dex. The chemical abundances are consistent with what is expected from the luminosity-metallicity relation. We derive estimates of the electron densities and find them to be between ∼5 and ∼100 cm{sup –3}. We find no evidence for a nitrogen plateau for objects in this sample with metallicities 0.5 > Z {sub ☉} > 0.15.

A study on adsorption of Pb(II), Cr(Ш) and Cu(II) from aqueous ...

African Journals Online (AJOL)

Peanut husk has been used in this work for removing Pb(II), Cr(Ш) and Cu(II) from aqueous solution. Batch adsorption studies were carried out under different pH, initial concentration of metal ions, interfering metal ions, time and temperature. Adsorption was poor in strongly acidic solution but was improved in alkaline ...

A NEW SCALING RELATION FOR H II REGIONS IN SPIRAL GALAXIES: UNVEILING THE TRUE NATURE OF THE MASS-METALLICITY RELATION

Energy Technology Data Exchange (ETDEWEB)

Rosales-Ortega, F. F.; Diaz, A. I. [Departamento de Fisica Teorica, Universidad Autonoma de Madrid, E-28049 Madrid (Spain); Sanchez, S. F.; Iglesias-Paramo, J.; Vilchez, J. M.; Mast, D. [Instituto de Astrofisica de Andalucia (CSIC), Camino Bajo de Huetor s/n, Aptdo. 3004, E-18080 Granada (Spain); Bland-Hawthorn, J. [Sydney Institute for Astronomy, School of Physics A28, University of Sydney, NSW 2006 (Australia); Husemann, B., E-mail: frosales@cantab.net [Leibniz-Institut fuer Astrophysik Potsdam (AIP), An der Sternwarte 16, D-14482 Potsdam (Germany)

2012-09-10

We demonstrate the existence of a local mass, metallicity, star formation relation using spatially resolved optical spectroscopy of H II regions in the local universe. One of the projections of this distribution-the local mass-metallicity relation-extends over a wide range in this parameter space: three orders of magnitude in mass and a factor of eight in metallicity. We explain the new relation as the combined effect of the differential distributions of mass and metallicity in the disks of galaxies, and a selective star formation efficiency. We use this local relation to reproduce-with a noticeable agreement-the mass-metallicity relation seen in galaxies, and conclude that the latter is a scale-up integrated effect of a local relation, supporting the inside-out growth and downsizing scenarios of galaxy evolution.

A NEW SCALING RELATION FOR H II REGIONS IN SPIRAL GALAXIES: UNVEILING THE TRUE NATURE OF THE MASS-METALLICITY RELATION

International Nuclear Information System (INIS)

Rosales-Ortega, F. F.; Díaz, A. I.; Sánchez, S. F.; Iglesias-Páramo, J.; Vílchez, J. M.; Mast, D.; Bland-Hawthorn, J.; Husemann, B.

2012-01-01

We demonstrate the existence of a local mass, metallicity, star formation relation using spatially resolved optical spectroscopy of H II regions in the local universe. One of the projections of this distribution—the local mass-metallicity relation—extends over a wide range in this parameter space: three orders of magnitude in mass and a factor of eight in metallicity. We explain the new relation as the combined effect of the differential distributions of mass and metallicity in the disks of galaxies, and a selective star formation efficiency. We use this local relation to reproduce—with a noticeable agreement—the mass-metallicity relation seen in galaxies, and conclude that the latter is a scale-up integrated effect of a local relation, supporting the inside-out growth and downsizing scenarios of galaxy evolution.

Synthesis, characterization and anti-fungal evaluation of Ni(II and Cu(II complexes with a derivative of 4-aminoantipyrine

Directory of Open Access Journals (Sweden)

Monika Tyagi

2017-01-01

Full Text Available Transition metal complexes of Ni(II and Cu(II metal ions with the general stoichiometry [M(LX]X and [M(LSO4], where M = Ni(II and Cu(II, L = (1E-N-((5-((E-(2,3-dimethyl-1-phenyl-4-pyrazolineiminomethylthiophen-2-ylmethylene-2,3-dimethyl-1-phenyl-4-pyrazolineamine and X = Cl−, NO3− and SO42−, have been synthesized and characterized. The synthesized ligand and metal complexes were characterized by 1H NMR, IR, mass spectrometry, UV–Vis spectra and EPR. In molecular modelling, the geometries of the Schiff's base and metal complexes were fully optimized with respect to the energy using the 6-31g(d,p basis set. The nickel(II complexes were found to have octahedral geometry, whereas the copper(II complexes were of tetragonal geometry. The covalency factor (β and orbital reduction factor (k suggest the covalent nature of the complexes. To develop broad spectrum new molecules against seed-borne fungi, the minimum inhibitory concentration (MIC of the ligand and its metal complexes was evaluated by the serial dilution method.

The removal of toxic metals from liquid effluents by ion exchange resins. Part VI: Manganese(II/H+/Lewatit K2621

Directory of Open Access Journals (Sweden)

Francisco J. Alguacil

2018-05-01

Full Text Available In this sixth part of the series, Manganese(II was removed from aqueous solutions by the cationic exchange resin Lewatit K2621. The investigation was performed under various experimental conditions such as the stirring speed associated with the system, aqueous pH, temperature, resin dosage and the ionic strength of the solution. The performance of the resin against the loading of metals from metal-binary solutions as well as the removal of Manganese(II from the solutions using multiwalled carbon nanotubes and functionalized (carboxylic groups multiwalled carbon nanotubes, were also investigated. Experimental results fit well with the pseudo-first kinetic order model, whereas fit of the data show that at 20 °C the process responded well to the diffusion controlled model, and that at 60 °C, the system is controlled by the moving boundary model. Adsorption data is better related to the Freundlich isotherm. Elution of the Manganese(II loaded onto the resin was investigated using acidic (H2SO4 or HCl solutions.

Oxidation of cyclohexane catalyzed by metal-ion-exchanged zeolites.

Science.gov (United States)

Sökmen, Ilkay; Sevin, Fatma

2003-08-01

The ion-exchange rates and capacities of the zeolite NaY for the Cu(II), Co(II), and Pb(II) metal ions were investigated. Ion-exchange equilibria were achieved in approximately 72 h for all the metal ions. The maximum ion exchange of metal ions into the zeolite was found to be 120 mg Pb(II), 110 mg Cu(II), and 100 mg Co(II) per gram of zeolite NaY. It is observed that the exchange capacity of a zeolite varies with the exchanged metal ion and the amount of metal ions exchanged into zeolite decreases in the sequence Pb(II) > Cu(II) > Co(II). Application of the metal-ion-exchanged zeolites in oxidation of cyclohexane in liquid phase with visible light was examined and it is observed that the order of reactivity of the zeolites for the conversion of cyclohexane to cyclohexanone and cyclohexanol is CuY > CoY > PbY. It is found that conversion increases by increase of the empty active sites of a zeolite and the formation of cyclohexanol is favored initially, but the cyclohexanol is subsequently converted to cyclohexanone.

Metal complex derivatives of hydrogen uranyl phosphate

International Nuclear Information System (INIS)

Grohol, D.; Blinn, E.L.

1994-01-01

Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

SPECIATION AND STABILITY OF METHYLENE BLUE-METAL ...

African Journals Online (AJOL)

a

With thiocyanate, zinc(II), cobalt(II) and copper(II) ions form stable anion, ... For a typical determination of metal ion, a suitable aliquot of the metal ion .... As the various reviews imply, a number of kinetic based analytical methods for photometric.

Extended metal–organic solids based on benzenepolycarboxylic ...

Indian Academy of Sciences (India)

2016-08-26

Aug 26, 2016 ... This article describes the recent results obtained in our laboratory on the interaction of polyfunctional ligands with divalent alkaline earth metal ions and a few divalent transition metal ions. Treatment of MCl2 ⋅ H2O (M = Mg, Ca, Sr or Ba) with 2-amino benzoic acid leads to the formation of complexes ...

Metal-poor dwarf galaxies in the SIGRID galaxy sample. II. The electron temperature-abundance calibration and the parameters that affect it

Energy Technology Data Exchange (ETDEWEB)

Nicholls, David C.; Dopita, Michael A.; Sutherland, Ralph S.; Jerjen, Helmut; Kewley, Lisa J., E-mail: David.Nicholls@anu.edu.au [Research School of Astronomy and Astrophysics, Australian National University, Cotter Rd., Weston ACT 2611 (Australia)

2014-07-20

In this paper, we use the Mappings photoionization code to explore the physical parameters that impact on the measurement of electron temperature and abundance in H II regions. In our previous paper, we presented observations and measurements of physical properties from the spectra of 17 H II regions in 14 isolated dwarf irregular galaxies from the SIGRID sample. Here, we analyze these observations further, together with three additional published data sets. We explore the effects of optical thickness, electron density, ionization parameter, ionization source, and non-equilibrium effects on the relation between electron temperature and metallicity. We present a standard model that fits the observed data remarkably well at metallicities between one-tenth and 1 solar. We investigate the effects of optically thin H II regions, and show that they can have a considerable effect on the measured electron temperature, and that there is evidence that some of the observed objects are optically thin. We look at the role of the ionization parameter and find that lower ionization parameter values give better fits at higher oxygen abundance. We show that higher pressures combined with low optical depth, and also κ electron energy distributions at low κ values, can generate the apparent high electron temperatures in low-metallicity H II regions, and that the former provides the better fit to observations. We examine the effects of these parameters on the strong line diagnostic methods. We extend this to three-dimensional diagnostic grids to confirm how well the observations are described by the grids.

Influence of metal doping of a MOF-74 framework on hydrogen adsorption

Energy Technology Data Exchange (ETDEWEB)

Botas, J.A.; Calleja, G.; Orcajo, M.G. [Rey Juan Carlos Univ., Madrid (Spain). Dept. of Chemical and Energy Technology; Sanchez-Sanchez, M. [CSIC, Madrid (Spain). Inst. de Catalisis y Petroleoquimica

2010-07-01

Microporous Metal-Organic Framework (MOF) adsorbents are considered an interesting option for hydrogen storage. Due to their porous nature and unusually high surface areas, these materials show an exceptional H{sub 2} uptake. Unfortunately, their interaction with H{sub 2} molecules is weak, so cryogenic temperatures are required to reach competitive H{sub 2} storage capacities. In this sense, the presence of coordinatively unsaturated and exposed metal centers in some MOF frameworks could increase the affinity for H{sub 2} through stronger metal-H{sub 2} interactions. In this preliminary work, the effect of doping a Zn{sup 2+}-MOF-74 framework with Co{sup 2+}, Cu{sup 2+} and Mg{sup 2+} on its adsorption properties for H{sub 2} has been studied. Characterization studies suggest that the samples prepared have actually the MOF-74 structure, in which the different tested heteroatom ions have been successfully incorporated. The differences in H{sub 2} adsorption at 77 K and 87 K between the MOF-74 samples doped with the mentioned divalent metal ions were discussed as a function of their free pore volume and amount of metal incorporation. (orig.)

Effect of divalent impurities on some physical properties of LiF and NaF

International Nuclear Information System (INIS)

Laj, C.

1969-05-01

The ionic thermo-currents technique is applied to the study of impurity vacancy dipoles in LiF and NaF doped with several divalent cations. In LiF only one ITC band is observed whatever the impurity studied. In NaF on the contrary two ITC bands are present, one corresponding to the one observed in LiF, the other one, intense in the case of small impurities, at lower temperature. A parallel EPR study in the case of Mn 2+ doped samples shows that the band observed in LiF and the corresponding one in NaF are due to the relaxation of dipoles formed by the association of an impurity and a vacancy in the next nearest position. The knowledge of the properties of the dipoles allows to show that the room temperature ionic conductivity of LiF is conditioned by the equilibrium: M ++ □+ → M ++ + □+. It is also shown that the isolated cation vacancy originating from this dissociation is responsible for the enhancement of γ-ray coloration of LiF doped with divalent cation impurities. A paramagnetic center ascribed to the presence of Mn 0 isolated in the lattice is also studied. The value of the hyperfine interaction and its temperature dependence are in good agreement with both the theory and the other experimental results. Finally it is shown that the disappearance of dipoles by annealing is related to the formation of complexes involving OH - ions, probably of the M(OH) 2 type, with the two OH - ions occupying a single fluorine site. (author) [fr

Competitive sorption of heavy metals by water hyacinth roots.

Science.gov (United States)

Zheng, Jia-Chuan; Liu, Hou-Qi; Feng, Hui-Min; Li, Wen-Wei; Lam, Michael Hon-Wah; Lam, Paul Kwan-Sing; Yu, Han-Qing

2016-12-01

Heavy metal pollution is a global issue severely constraining aquaculture practices, not only deteriorating the aquatic environment but also threatening the aquaculture production. One promising solution is adopting aquaponics systems where a synergy can be established between aquaculture and aquatic plants for metal sorption, but the interactions of multiple metals in such aquatic plants are poorly understood. In this study, we investigated the absorption behaviors of Cu(II) and Cd(II) in water by water hyacinth roots in both single- and binary-metal systems. Cu(II) and Cd(II) were individually removed by water hyacinth roots at high efficiency, accompanied with release of protons and cations such as Ca 2+ and Mg 2+ . However, in a binary-metal arrangement, the Cd(II) sorption was significantly inhibited by Cu(II), and the higher sorption affinity of Cu(II) accounted for its competitive sorption advantage. Ionic exchange was identified as a predominant mechanism of the metal sorption by water hyacinth roots, and the amine and oxygen-containing groups are the main binding sites accounting for metal sorption via chelation or coordination. This study highlights the interactive impacts of different metals during their sorption by water hyacinth roots and elucidates the underlying mechanism of metal competitive sorption, which may provide useful implications for optimization of phytoremediation system and development of more sustainable aquaculture industry. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catena-poly[[bis(1H-benzotriazole-kappaN3)cobalt(II)]-di-mu-tricyanomethanido-kappa2N:N'] and catena-poly[[bis(3,5-dimethyl-1H-pyrazole-kappaN2)manganese(II)]-di-mu-tricyanomethanido-kappa2N:N'].

Science.gov (United States)

Shao, Ze-Huai; Luo, Jun; Cai, Rui-Fang; Zhou, Xi-Geng; Weng, Lin-Hong; Chen, Zhen-Xia

2004-06-01

Two new one-dimensional coordination polymers, viz. the title compounds, [Co[C(CN)(3)](2)(C(6)H(5)N(3))(2)](n), (I), and [Mn[C(CN)(3)](2)(C(5)H(8)N(2))(2)](n), (II), have been synthesized and characterized by X-ray diffraction. Both complexes consist of linear chains with double 1,5-tricyanomethanide bridges between neighbouring divalent metal ions. The Co and Mn atoms are located on centres of inversion. In (I), the coordination environment of the Co(II) atom is that of an elongated octahedron. The Co(II) atom is coordinated in the equatorial plane by four nitrile N atoms of four bridging tricyanomethanide ions, with Co-N distances of 2.106 (2) and 2.110 (2) A, and in the apical positions by two N atoms from the benzotriazole ligands, with a Co-N distance of 2.149 (2) A. The [Co[C(CN)(3)](2)(C(6)H(5)N(3))(2)] units form infinite chains extending along the a axis. These chains are crosslinked via a hydrogen bond between the uncoordinated nitrile N atom of a tricyanomethanide anion and the H atom on the uncoordinated N atom of a benzotriazole ligand from an adjacent chain, thus forming a three-dimensional network structure. In (II), the Mn(II) atom also adopts a slightly distorted octahedral geometry, with four nitrile N atoms of tricyanomethanide ligands [Mn-N = 2.226 (2) and 2.227 (2) A] in equatorial positions and two N atoms of the monodentate 3,5-dimethylpyrazole ligands [Mn-N = 2.231 (2) A] in the axial sites. In (II), one-dimensional polymeric chains extending along the b axis are formed, with tricyanomethanide anions acting as bidentate bridging ligands. A hydrogen bond between the uncoordinated nitrile N atom of the tricyanomethanide ligand and the H atom on the uncoordinated N atom of a 3,5-dimethylpyrazole group from a neighbouring chain links the molecule into a two-dimensional layered structure.

Synthesis and Spectral Investigations of Manganese(II, Cobalt(II, Nickel(II, Copper(II and Zinc(II Complexes of New Polydentate Ligands Containing a 1,8-Naphthyridine Moiety

Directory of Open Access Journals (Sweden)

Sunkari Jyothi

2006-12-01

Full Text Available 2-(o-Hydroxyphenyl-1,8-naphthyridine (HN, 2-(4-hydroxy-6-methylpyran-2-one-3-yl-1,8-naphthyridine (HMPN and 2-(benzimidazol-2-yl-1,8-naphthyridine(BN react with acetates of Mn(II, Co(II, Ni(II, Cu(II and Zn(II to yield metal ioncomplexes of definite composition. These compounds were characterized by elementalanalyses, molar conductivity, magnetic susceptibility measurements, thermal studies, IR,UV-visible, NMR and mass spectral investigations. The complexes are found to have theformulae [M(HN2(H2O2], [M(HMPN2(H2O2] and [M(BN2(OAc2], respectively.

The Compact and Biologically Relevant Structure of Inter-α-inhibitor Is Maintained by the Chondroitin Sulfate Chain and Divalent Cations.

Science.gov (United States)

Scavenius, Carsten; Nikolajsen, Camilla Lund; Stenvang, Marcel; Thøgersen, Ida B; Wyrożemski, Łukasz; Wisniewski, Hans-Georg; Otzen, Daniel E; Sanggaard, Kristian W; Enghild, Jan J

2016-02-26

Inter-α-inhibitor is a proteoglycan of unique structure. The protein consists of three subunits, heavy chain 1, heavy chain 2, and bikunin covalently joined by a chondroitin sulfate chain originating at Ser-10 of bikunin. Inter-α-inhibitor interacts with an inflammation-associated protein, tumor necrosis factor-inducible gene 6 protein, in the extracellular matrix. This interaction leads to transfer of the heavy chains from the chondroitin sulfate of inter-α-inhibitor to hyaluronan and consequently to matrix stabilization. Divalent cations and heavy chain 2 are essential co-factors in this transfer reaction. In the present study, we have investigated how divalent cations in concert with the chondroitin sulfate chain influence the structure and stability of inter-α-inhibitor. The results showed that Mg(2+) or Mn(2+), but not Ca(2+), induced a conformational change in inter-α-inhibitor as evidenced by a decrease in the Stokes radius and a bikunin chondroitin sulfate-dependent increase of the thermodynamic stability. This structure was shown to be essential for the ability of inter-α-inhibitor to participate in extracellular matrix stabilization. In addition, the data revealed that bikunin was positioned adjacent to both heavy chains and that the two heavy chains also were in close proximity. The chondroitin sulfate chain interacted with all protein components and inter-α-inhibitor dissociated when it was degraded. Conventional purification protocols result in the removal of the Mg(2+) found in plasma and because divalent cations influence the conformation and affect function it is important to consider this when characterizing the biological activity of inter-α-inhibitor. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of N'-(furan-3-ylmethylene)-2-(4-methoxyphenylamino)acetohydrazide.

Science.gov (United States)

Emam, Sanaa M; El-Saied, Fathy A; Abou El-Enein, Saeyda A; El-Shater, Heba A

2009-03-01

Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of furan-2-carbaldehyde 4-methoxy-N-anilinoacetohydrazone were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and (1)H NMR spectra as well as magnetic moment and molar conductivity. Mononuclear complexes are obtained with 1:1 molar ratio except complexes 3 and 9 which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a neutral bidentate one and coordination occurs via the carbonyl oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the enolic oxygen atom, azomethine nitrogen atom and the oxygen atom of furan ring. Moreover, the ligand behaves as a neutral tridentate and coordination occurs via the carbonyl oxygen, azomethine nitrogen and furan oxygen atoms as well as a monobasic bidentate and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complex 10 possesses a square planar geometry. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes.

Batch adsorptive removal of Fe(III), Cu(II) and Zn(II) ions in aqueous and aqueous organic–HCl media by Dowex HYRW2-Na Polisher resin as adsorbents

OpenAIRE

Aboul-Magd, Abdul-Aleem Soliman; Al-Husain, Salwa Al-Rashed; Al-Zahrani, Salma Ahmed

2016-01-01

Of the metal ions in tap, Nile, waste and sea water samples and some ores were carried out. Removal of heavy metal ions such as Fe(III), Cd(II), Zn(II), Cu(II), Mn(II), Mg(II), and Pb(II) from water and wastewater is obligatory in order to avoid water pollution. Batch shaking adsorption experiments to evaluate the performance of nitric and hydrochloric acid solutions in the removal of metal ions by cation exchange resin at the same conditions for both, such as the effect of initial metal ion ...

Applications of RIGAKU Dmax Rapid II micro-X-ray diffractometer in the analysis of archaeological metal objects

Science.gov (United States)

Mozgai, Viktória; Szabó, Máté; Bajnóczi, Bernadett; Weiszburg, Tamás G.; Fórizs, István; Mráv, Zsolt; Tóth, Mária

2017-04-01

During material analysis of archaeological metal objects, especially their inlays or corrosion products, not only microstructure and chemical composition, but mineralogical composition is necessary to be determined. X-ray powder diffraction (XRD) is a widely-used method to specify the mineralogical composition. However, when sampling is not or limitedly allowed due to e.g. the high value of the object, the conventional XRD analysis can hardly be used. Laboratory micro-XRD instruments provide good alternatives, like the RIGAKU Dmax Rapid II micro-X-ray diffractometer, which is a unique combination of a MicroMax-003 third generation microfocus, sealed tube X-ray generator and a curved 'image plate' detector. With this instrument it is possible to measure as small as 10 µm area in diameter on the object. Here we present case studies for the application of the micro-XRD technique in the study of archaeological metal objects. In the first case niello inlay of a Late Roman silver augur staff was analysed. Due to the high value of the object, since it is the only piece known from the Roman Empire, only non-destructive analyses were allowed. To reconstruct the preparation of the niello, SEM-EDX analysis was performed on the niello inlays to characterise their chemical composition and microstructure. Two types of niello are present: a homogeneous, silver sulphide niello (acanthite) and an inhomogeneous silver-copper sulphide niello (exsolution of acanthite and jalpaite or jalpaite and stromeyerite). The micro-X-ray diffractometer was used to verify the mineralogical composition of the niello, supposed on the base of SEM results. In the second case corrosion products of a Late Roman copper cauldron with uncertain provenance were examined, since they may hold clues about the burial conditions (pH, Eh, etc.) of the object. A layer by layer analysis was performed in cross sections of small metal samples by using electron microprobe and micro-X-ray diffractometer. The results

Synchronous determination of mercury (II) and copper (II) based on quantum dots-multilayer film

International Nuclear Information System (INIS)

Ma Qiang; Ha Enna; Yang Fengping; Su Xingguang

2011-01-01

Graphical abstract: We developed a sensitive sensor for synchronous detection of Hg (II) and Cu (II) based on the quenchedand recovered PL intensity of QDs-multilayer films. Solutions containing Hg (II) or Cu (II) were used to quench the fluorescence of the QDs-multilayer films firstly. Then, glutathione (GSH) was used to remove Hg (II) or Cu (II) from the QDs-multilayer films due to stronger affinity of GSH-metal ions than that of QDs metal ions. Thus, the fluorescence of QDs-multilayer films was recovered. Highlights: → QDs-multilayer films were developed for synchronous detection of Hg (II) and Cu (II). → Hg (II) and Cu (II) could quench the photoluminescence of the QDs-multilayer films. → Glutathione was used to remove metal ions and recovery photoluminescence of QDs-multilayer films. - Abstract: A sensitive sensor for mercury (II) and copper (II) synchronous detection was established via the changed photoluminescence of CdTe quantum dots (QDs) multilayer films in this work. QDs were deposited on the quartz slides to form QDs-multilayer films by electrostatic interactions with poly(dimethyldiallyl ammonium chloride) (PDDA). Hg 2+ or Cu 2+ could quench the photoluminescence of the QDs-multilayer films, and glutathione (GSH) was used to remove Hg 2+ or Cu 2+ from QDs-multilayer films due to strong affinity of GSH-metal ions, which resulted in the recovered photoluminescence of QDs-multilayer films. There are good linear relationships between the metal ions concentration and the photoluminescence intensity of QDs in the quenched and recovered process. It was found that the Stern-Volmer constants for Hg 2+ are higher than that for Cu 2+ . Based on different quenching and recovery constant between Hg 2+ and Cu 2+ , the synchronous detection of Hg 2+ and Cu 2+ can be achieved. The linear ranges of this assay were obtained from 0.005 to 0.5 μM for Hg 2+ and from 0.01 to 1 μM for Cu 2+ , respectively. And the artificial water samples were determined by this

A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence

Energy Technology Data Exchange (ETDEWEB)

Eliseeva, Svetlana V., E-mail: svetlana.eliseeva@cnrs-orleans.fr [Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2 (France); Le Studium, Loire Valley Institute for Advanced Studies, 1 Rue Dupanloup, 45000 Orléans (France); Golovach, Iurii P.; Liasotskyi, Valerii S. [I.I.Mechnikov Odessa National University, 2 Dvoryanska street, 65082 Odessa (Ukraine); Antonovich, Valery P. [A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa (Ukraine); Petoud, Stéphane, E-mail: stephane.petoud@inserm.fr [Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2 (France); Meshkova, Svetlana B., E-mail: s_meshkova@ukr.net [A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa (Ukraine)

2016-03-15

Most of the existing optical methods for Cu{sup II} detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a 'turn-on' lanthanide(III)-based molecular probe for the specific detection of Cu{sup II} ions based on both visible (Tb{sup III}, Eu{sup III}) and near-infrared (Nd{sup III}, Yb{sup III}) emission. Quantum yields of the characteristic Ln{sup III} emission signals increases by at least two-orders of magnitude upon addition of Cu{sup II} into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of Cu{sup II} ions does not significantly affect the energy positions of the singlet (32,260 cm{sup −1}) and triplet (25,640–25,970 cm{sup −1}) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce Cu{sup II} to Cu{sup I} has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards Cu{sup II} over other transition metal ions: the addition of divalent Zn{sup II}, Cd{sup II}, Pd{sup II}, Ni{sup II}, Co{sup II} or trivalent Fe{sup III}, Ga{sup III}, In{sup III} ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of Cu{sup II} results in a 20- to 30-times

Improving the Performance of Lithium Manganese Phosphate Through Divalent Cation Substitution

Energy Technology Data Exchange (ETDEWEB)

Chen, Guoying; Richardson, Thomas J.

2008-03-03

Highly crystalline samples of LiMnPO{sub 4} and its analogs with partial substitution of Mn by divalent Mg, Cu, Zn, and Ni were prepared by hydrothermal synthesis and characterized by x-ray diffraction and infrared spectroscopy. Chemical oxidation produced two-phase mixtures of the initial phases LiMn{sub (1-y)}M{sub y}PO{sub 4} and the delithiated forms, Li{sub y}Mn{sub (1-y)}M{sub y}PO{sub 4}, all with the olivine structure. The extent of oxidation depended upon the quantity of oxidizing agent used and on the identity of the substituent ions. Mg, Ni and Cu were found to increase the level of delithation relative to that in pure LiMnPO{sub 4}. Mg was also shown to reduce the tendency of the oxidized phase to absorb water.

DNA incision evaluation, binding investigation and biocidal screening of Cu(II), Ni(II) and Co(II) complexes with isoxazole Schiff bases.

Science.gov (United States)

Ganji, Nirmala; Chityala, Vijay Kumar; Marri, Pradeep Kumar; Aveli, Rambabu; Narendrula, Vamsikrishna; Daravath, Sreenu; Shivaraj

2017-10-01

Two new series of binary metal complexes [M(L 1 ) 2 ] and [M(L 2 ) 2 ] where, M=Cu(II), Ni(II) & Co(II) and L 1 =4-((3,4-dimethylisoxazol-5-ylimino)methyl)benzene-1,3-diol; L 2 =2-((3,4-dimethylisoxazol-5-ylimino)methyl)-5-methoxyphenol were synthesized and characterized by elemental analysis, 1 H NMR, 13 C NMR, FT-IR, ESI mass, UV-Visible, magnetic moment, ESR, SEM and powder XRD studies. Based on these results, a square planar geometry is assigned for all the metal complexes where the Schiff base acts as uninegatively charged bidentate chelating agent via the hydroxyl oxygen and azomethine nitrogen atoms. DNA binding studies of all the complexes with calf thymus DNA have been comprehensively investigated using electronic absorption spectroscopy, fluorescence quenching and viscosity studies. The oxidative and photo cleavage affinity of metal complexes towards supercoiled pBR322 DNA has been ascertained by agarose gel electrophoresis assay. From the results, it is observed that all the metal complexes bind effectively to CT-DNA via an intercalative mode of binding and also cleave pBR322 DNA in a promising manner. Further the Cu(II) complexes have shown better binding and cleavage properties towards DNA. The antimicrobial activities of the Schiff bases and their metal complexes were studied on bacterial and fungal strains and the results denoted that the complexes are more potent than their Schiff base ligands. Copyright © 2017 Elsevier B.V. All rights reserved.

Nuclear Magnetic Resonance and Elastic Wave Velocity of Chalk Saturated with Brines Containing Divalent Ions

DEFF Research Database (Denmark)

Katika, Konstantina; Alam, Mohammad Monzurul; Fabricius, Ida Lykke

divided into groups of three and each group was saturated either with deionized water, calcite equilibrated water, or sodium chloride, magnesium chloride and calcium chloride solutions of the same ionic strength. Saturation with solutions that contain divalent ions caused major shifts in the distribution...... of the relaxation time. Core samples saturated with calcium chloride solution relaxed slower and those saturated with magnesium chloride solution relaxed faster than the rest of the samples. Along with the changes in relaxation the samples experienced smaller velocities of elastic waves when saturated with MgCl2...

Composition dependence of glow peak temperature in KCl1-xBrx doped with divalent cations

International Nuclear Information System (INIS)

Perez-Salas, R; Aceves, R; RodrIguez-Mijangos, R; Riveros, H G; Duarte, C

2004-01-01

Thermoluminescence measurements of β-irradiated Eu 2+ - and Ca 2+ - doped KCl 1-x KBr x solid solutions excited at room temperature have been carried out to identify the effect of composition on the glow peaks. A typical glow peak has been distinguished for each composition. A linear dependence of its temperature on the composition x has been found. These results indicate that for divalent impurity-doped alkali halide solid solutions these glow peak temperatures are mostly dependent on the lattice constant of the host than on the size of the anion or impurity cation

Emodin (1,3,8-trihydroxy-6-methylanthraquinone): a spectrophotometric reagent for the determination of beryllium(II), magnesium(II) and calcium(II)

International Nuclear Information System (INIS)

Pal, T.; Jana, N.R.

1993-01-01

The individual determination of Be II , Mg II or Ca II by conventional spectrophotometry and simultaneous determination of Mg II and Ca II in mixtures by first-derivative spectrophotometry are possible at trace levels, using emodin (1,3,8-trihydroxy-6-methylanthraquinone) as spectrophotometric reagent. Interference from other metal species, application of these methods to rock samples and statistical analysis of the results are discussed. (author)

Metal-ion retention properties of water-soluble amphiphilic block copolymer in double emulsion systems (w/o/w) stabilized by non-ionic surfactants.

Science.gov (United States)

Palencia, Manuel; Rivas, Bernabé L

2011-11-15

Metal-ion retention properties of water-soluble amphiphilic polymers in presence of double emulsion were studied by diafiltration. Double emulsion systems, water-in-oil-in-water, with a pH gradient between external and internal aqueous phases were prepared. A poly(styrene-co-maleic anhydride) (PSAM) solution at pH 6.0 was added to the external aqueous phase of double emulsion and by application of pressure a divalent metal-ion stream was continuously added. Metal-ions used were Cu(2+) and Cd(2+) at the same pH of polymer solution. According to our results, metal-ion retention is mainly the result of polymer-metal interaction. Interaction between PSMA and reverse emulsion globules is strongly controlled by amount of metal-ions added in the external aqueous phase. In addition, as metal-ion concentration was increased, a negative effect on polymer retention capacity and promotion of flocculation phenomena were produced. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis, characterisation and catalytic activity of 4, 5-imidazoledicarboxylate ligated Co(II) and Cd(II) metal-organic coordination complexes

Science.gov (United States)

Gangu, Kranthi Kumar; Maddila, Suresh; Mukkamala, Saratchandra Babu; Jonnalagadda, Sreekantha B.

2017-09-01

Two mono nuclear coordination complexes, namely, [Co(4,5-Imdc)2 (H2O)2] (1) and [Cd(4,5-Imdc)2(H2O)3]·H2O (2) were constructed using Co(II) and Cd(II) metal salts with 4,5-Imidazoledicarboxylic acid (4,5-Imdc) as organic ligand. Both 1, 2 were structurally characterized by single crystal XRD and the results reveal that 1 belongs to P21/n space group with unit cell parameters [a = 5.0514(3) Å, b = 22.5786(9) Å, c = 6.5377(3) Å, β = 111.5°] whereas, 2 belongs to P21/c space group with unit cell parameters [a = 6.9116(1) Å, b = 17.4579(2) Å, c = 13.8941(2) Å, β = 97.7°]. While Co(II) in 1 exhibited a six coordination geometry with 4,5-Imdc and water molecules, Cd(II) ion in 2 showed a seven coordination with the same ligand and solvent. In both 1 and 2, the hydrogen bond interactions with mononuclear unit generated 3D-supramolecular structures. Both complexes exhibit solid state fluorescent emission at room temperature. The efficacy of both the complexes as heterogeneous catalysts was examined in the green synthesis of six pyrano[2,3,c]pyrazole derivatives with ethanol as solvent via one-pot reaction between four components, a mixture of aromatic aldehyde, malononitrile, hydrazine hydrate and dimethyl acetylenedicarboxylate. Both 1 and 2 have produced pyrano [2,3,c]pyrazoles in impressive yields (92-98%) at room temperature in short interval of times (<20 min), with no need for any chromatographic separations. With good stability, ease of preparation and recovery plus reusability up to six cycles, both 1 and 2 prove to be excellent environmental friendly catalysts for the value-added organic transformations using green principles.

Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline