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

PubMed Central

Aldawsari, Abdullah; 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. PMID:28910368

Synthesis, spectroscopic characterization, first order nonlinear optical properties and DFT calculations of novel Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with 1,3-diphenyl-4-phenylazo-5-pyrazolone ligand

NASA Astrophysics Data System (ADS)

Abdel-Latif, Samir A.; Mohamed, Adel A.

2018-02-01

Novel Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) metal ions with 1,3-diphenyl-4-phenylazo-5-pyrazolone (L) have been prepared and characterized using different analytical and spectroscopic techniques. 1:1 Complexes of Mn(II), Co(II) and Zn(II) are distorted octahedral whereas Ni(II) complex is square planar and Cu(II) is distorted trigonal bipyramid. 1:2 Complexes of Mn(II), Co(II), Cu(II) and Zn(II) are distorted trigonal bipyramid whereas Ni(II) complex is distorted tetrahedral. All complexes behave as non-ionic in dimethyl formamide (DMF). The electronic structure and nonlinear optical parameters (NLO) of the complexes were investigated theoretically at the B3LYP/GEN level of theory. Molecular stability and bond strengths have been investigated by applying natural bond orbital (NBO) analysis. The geometries of the studied complexes are non-planner. DFT calculations have been also carried out to calculate the global properties; hardness (η), global softness (S) and electronegativity (χ). The calculated small energy gap between HOMO and LUMO energies shows that the charge transfer occurs within the complexes. The total static dipole moment (μtot), the mean polarizability (<α>), the anisotropy of the polarizability (Δα) and the mean first-order hyperpolarizability (<β>) were calculated and compared with urea as a reference material. The complexes show implying optical properties.

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

PubMed

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.

Synthesis, characterization and antimicrobial studies of Schiff base complexes

NASA Astrophysics Data System (ADS)

Zafar, Hina; Ahmad, Anis; Khan, Asad U.; Khan, Tahir Ali

2015-10-01

The Schiff base complexes, MLCl2 [M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by the template reaction of respective metal ions with 2-acetylpyrrole and 1,3-diaminopropane in 1:2:1 M ratio. The complexes have been characterized by elemental analyses, ESI - mass, NMR (1H and 13C), IR, XRD, electronic and EPR spectral studies, magnetic susceptibility and molar conductance measurements. These studies show that all the complexes have octahedral arrangement around the metal ions. The molar conductance measurements of all the complexes in DMSO indicate their non-electrolytic nature. The complexes were screened for their antibacterial activity in vitro against Gram-positive (Streptococcus pyogenes) and Gram-negative (Klebsiella pneumoniae) bacteria. Among the metal complexes studied the copper complex [CuLCl2], showed highest antibacterial activity nearly equal to standard drug ciprofloxacin. Other complexes also showed considerable antibacterial activity. The relative order of activity against S. Pyogenes is as Cu(II) > Zn(II) > Co(II) = Fe(II) > Ni(II) and with K. Pneumonia is as Cu(II) > Co(II) > Zn(II) > Fe(II) > Ni(II).

Removal of some metal ions by activated carbon prepared from Phaseolus aureus hulls.

PubMed

Rao, M Madhava; Ramana, D K; Seshaiah, K; Wang, M C; Chien, S W Chang

2009-07-30

Removal of lead [Pb(II)], zinc [Zn(II)], copper [Cu(II)], and cadmium [Cd(II)] from aqueous solutions using activated carbon prepared from Phaseolus aureus hulls (ACPAH), an agricultural waste was studied. The influence of various parameters such as effect of pH, contact time, adsorbent dose, and initial concentration of metal ions on the removal was evaluated by batch method. The removal of metal ions by ACPAH was pH dependent and the optimum pH values were 7.0, 8.0, 7.0 and 6.0 for Cu(II), Cd(II), Zn(II), and Pb(II), respectively. The sorption isotherms were studied using Langmuir, Freundlich, Dubinin-Radushkevich (D-R), and Temkin isotherm models. The maximum adsorption capacity values of ACPAH for metal ions were 21.8 mg g(-1) for Pb(II), 21.2 mg g(-1) for Zn(II), 19.5 mg g(-1) for Cu(II), and 15.7 mg g(-1) for Cd(II). The experiments demonstrated that the removal of metal ions followed the pseudo-second-order kinetic model. Desorption experiments were carried out using HCl solution with a view to regenerate the spent adsorbent and to recover the adsorbed metal ions.

Production and Isomeric Distribution of Xanthylium Cation Pigments and Their Precursors in Wine-like Conditions: Impact of Cu(II), Fe(II), Fe(III), Mn(II), Zn(II), and Al(III).

PubMed

Guo, Anque; Kontoudakis, Nikolaos; Scollary, Geoffrey R; Clark, Andrew C

2017-03-22

This study establishes the influence of Cu(II), Fe(II), Fe(III), Zn(II), Al(III), and Mn(II) on the oxidative production of xanthylium cations from (+)-catechin and either tartaric acid or glyoxylic acid in model wine systems. The reaction was studied at 25 °C using UHPLC and LC-HRMS for the analysis of phenolic products and their isomeric distribution. In addition to the expected products, a colorless product, tentatively assigned as a lactone, was detected for the first time. The results show the importance of Fe ions and a synergistic influence of Mn(II) in degrading tartaric acid to glyoxylic acid, whereas the other metal ions had minimal activity in this mechanistic step. Fe(II) and Fe(III) were shown to mediate the (+)-catechin-glyoxylic acid addition reaction, a role previously attributed to only Cu(II). Importantly, the study demonstrates that C-8 addition products of (+)-catechin are promoted by Cu(II), whereas C-6 addition products are promoted by Fe ions.

Nanoscale zero-valent iron for metal/metalloid removal from model hydraulic fracturing wastewater.

PubMed

Sun, Yuqing; Lei, Cheng; Khan, Eakalak; Chen, Season S; Tsang, Daniel C W; Ok, Yong Sik; Lin, Daohui; Feng, Yujie; Li, Xiang-Dong

2017-06-01

Nanoscale zero-valent iron (nZVI) was tested for the removal of Cu(II), Zn(II), Cr(VI), and As(V) in model saline wastewaters from hydraulic fracturing. Increasing ionic strength (I) from 0.35 to 4.10 M (Day-1 to Day-90 wastewaters) increased Cu(II) removal (25.4-80.0%), inhibited Zn(II) removal (58.7-42.9%), slightly increased and then reduced Cr(VI) removal (65.7-44.1%), and almost unaffected As(V) removal (66.7-75.1%) by 8-h reaction with nZVI at 1-2 g L -1 . The removal kinetics conformed to pseudo-second-order model, and increasing I decreased the surface area-normalized rate coefficient (k sa ) of Cu(II) and Cr(VI), probably because agglomeration of nZVI in saline wastewaters restricted diffusion of metal(loid)s to active surface sites. Increasing I induced severe Fe dissolution from 0.37 to 0.77% in DIW to 4.87-13.0% in Day-90 wastewater; and Fe dissolution showed a significant positive correlation with Cu(II) removal. With surface stabilization by alginate and polyvinyl alcohol, the performance of entrapped nZVI in Day-90 wastewater was improved for Zn(II) and Cr(VI), and Fe dissolution was restrained (3.20-7.36%). The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in removal trends from Day-1 to Day-90 wastewaters was attributed to: (i) distinctive removal mechanisms of Cu(II) and Cr(VI) (adsorption, (co-)precipitation, and reduction), compared to Zn(II) (adsorption) and As(V) (bidentate inner-sphere complexation); and (ii) changes in solution speciation (e.g., from Zn 2+ to ZnCl 3 - and ZnCl 4 2- ; from CrO 4 2- to CaCrO 4 complex). Bare nZVI was susceptible to variations in wastewater chemistry while entrapped nZVI was more stable and environmentally benign, which could be used to remove metals/metalloids before subsequent treatment for reuse/disposal. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pb, Cu, and Zn distributions at humic acid-coated metal-oxide surfaces

DOE PAGES

Wang, Yingge; Michel, F. Marc; Choi, Yongseong; ...

2016-05-09

Here, mineral surfaces are often coated by natural organic matter (NOM), which has a major influence on metal-ion sorption and sequestration because of the abundance of binding sites in such coatings and the changes they cause in local nanoscale environments. The effects of NOM coatings on mineral surfaces are, however, still poorly understood at the molecular level due to the complexity of these systems. In this study, we have applied long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy to measure the partitioning of naturally present Cu(II) (0.0226%), Zn(II) (0.009%), and Pb(II) ( 0.0004%) between Elliott Soil Humic Acid (ESHA) coatings andmore » three model single-crystal metal-oxide substrates: α-Al 2O 3 (0 0 0 1), α-Al 2O 3 (1 1 0 2), and α-Fe 2O 3 (0 0 0 1). The competitive sorption effects among these metal ions for binding sites in the ESHA coatings and on the metal-oxide surfaces were investigated as a function of reaction time, calcium content, and solution pH. Pb(II) ions present in the ESHA coatings were found to redistribute to reactive α-Al 2O 3 (1 1 0 2) and α-Fe 2O 3 (0 0 0 1) surfaces after 3 h of reaction (pH = 6.0, [Ca(II)] = 2 mM). Pb(II) partitioning onto these reactive metal-oxide surfaces increased with increasing reaction time (up to 7 d). In addition, the partitioning of Cu(II) and Zn(II) from the ESHA coating to the α-Fe 2O 3 (0 0 0 1) substrate increased slightly with reaction time (2.4% and 3.7% for Cu(II) and Zn(II), respectively, after 3 h and 6.4% and 7.7% for Cu(II) and Zn(II), respectively, after 72 h of reaction time).« less

Combined EXAFS and DFT Structure Calculations Provide Structural Insights into the 1:1 Multi-Histidine Complexes of CuII, CuI and ZnII with the Tandem Octarepeats of the Mammalian Prion Protein

PubMed Central

Pushie, M. Jake; Nienaber, Kurt H.; McDonald, Alex; Millhauser, Glenn L.; George, Graham N.

2014-01-01

The metal coordinating properties of the prion protein (PrP) have been the subject of intense focus and debate since the first reports of copper interaction with PrP just before the turn of the century. The picture of metal coordination to PrP has been improved and refined over the past decade, and yet the structural details of the various metal coordination modes have not been fully elucidated in some cases. Herein we employ X-ray absorption near edge spectroscopy as well as extended X-ray absorption fine structure (EXAFS) spectroscopy to structurally characterize the dominant 1:1 coordination modes for CuII, CuI and ZnII with an N-terminal fragment of PrP. The PrP fragment constitutes four tandem repeats representative of the mammalian octarepeat domain, designated OR4, which is also the most studied PrP fragment for metal interactions, making our findings applicable to a large body of previous work. Density functional theory (DFT) calculations provide additional structural and thermodynamic data, and candidate structures are used to inform EXAFS data analysis. The optimized geometries from DFT calculations are used to identify potential coordination complexes for multi-histidine coordination of CuII, CuI and ZnII in an aqueous medium, modeled using 4-methylimidazole to represent the histidine side chain. Through a combination of in silico coordination chemistry as well as rigorous EXAFS curve fitting, using full multiple scattering on candidate structures from DFT calculations, we have characterized the predominant coordination modes for the 1:1 complexes of CuII, CuI and ZnII with the OR4 peptide at pH 7.4 at atomic resolution, which are best represented as a square planar [CuII(His)4]2+, digonal [CuI(His)2]+ and tetrahedral [ZnII(His)3(OH2)]2+, respectively. PMID:25042361

Whole-genome sequence of Cupriavidus sp. strain BIS7, a heavy-metal-resistant bacterium.

PubMed

Hong, Kar Wai; Thinagaran, Dinaiz al; Gan, Han Ming; Yin, Wai-Fong; Chan, Kok-Gan

2012-11-01

Cupriavidus sp. strain BIS7 is a Malaysian tropical soil bacterium that exhibits broad heavy-metal resistance [Co(II), Zn(II), Ni(II), Se(IV), Cu(II), chromate, Co(III), Fe(II), and Fe(III)]. It is particularly resistant to Fe(II), Fe(III), and Zn(II). Here we present the assembly and annotation of its genome.

Pb, Cu, and Zn distributions at humic acid-coated metal-oxide surfaces

NASA Astrophysics Data System (ADS)

Wang, Yingge; Michel, F. Marc; Choi, Yongseong; Eng, Peter J.; Levard, Clement; Siebner, Hagar; Gu, Baohua; Bargar, John R.; Brown, Gordon E.

2016-09-01

Mineral surfaces are often coated by natural organic matter (NOM), which has a major influence on metal-ion sorption and sequestration because of the abundance of binding sites in such coatings and the changes they cause in local nanoscale environments. The effects of NOM coatings on mineral surfaces are, however, still poorly understood at the molecular level due to the complexity of these systems. In this study, we have applied long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy to measure the partitioning of naturally present Cu(II) (0.0226%), Zn(II) (0.009%), and Pb(II) (∼0.0004%) between Elliott Soil Humic Acid (ESHA) coatings and three model single-crystal metal-oxide substrates: α-Al2O3 (0 0 0 1), α-Al2O3 (1 -1 0 2), and α-Fe2O3 (0 0 0 1). The competitive sorption effects among these metal ions for binding sites in the ESHA coatings and on the metal-oxide surfaces were investigated as a function of reaction time, calcium content, and solution pH. Pb(II) ions present in the ESHA coatings were found to redistribute to reactive α-Al2O3 (1 -1 0 2) and α-Fe2O3 (0 0 0 1) surfaces after 3 h of reaction (pH = 6.0, [Ca(II)] = 2 mM). Pb(II) partitioning onto these reactive metal-oxide surfaces increased with increasing reaction time (up to 7 d). In addition, the partitioning of Cu(II) and Zn(II) from the ESHA coating to the α-Fe2O3 (0 0 0 1) substrate increased slightly with reaction time (2.4% and 3.7% for Cu(II) and Zn(II), respectively, after 3 h and 6.4% and 7.7% for Cu(II) and Zn(II), respectively, after 72 h of reaction time). However, no changes in the partitioning of Cu(II) and Zn(II) onto the α-Al2O3 (1 -1 0 2) surface were observed with increasing reaction time, suggesting that these ions strongly complex with functional groups in the ESHA coatings. Similar results were obtained for Cu(II) and Zn(II) on the ESHA-coated α-Al2O3 (1 -1 0 2) surfaces in samples without the addition of calcium. However, the amounts of Pb(II) mobilized from the ESHA coatings onto the α-Al2O3 (1 -1 0 2) surfaces increased from 40% (no added Ca) to 58% (with 2 mM Ca) after 72 h of reaction time, possibly due to displacement of Pb(II) by Ca(II) from binding sites in the ESHA coatings. In contrast, Pb(II), Cu(II), and Zn(II) present in the ESHA coatings were found to be unreactive with the α-Al2O3 (0 0 0 1) surface. The observed reactivities of the three ESHA-coated metal-oxide surfaces with respect to metal-ion sorption are consistent with the trend observed for the uncoated metal-oxide surfaces: α-Fe2O3 (0 0 0 1) > α-Al2O3 (1 -1 0 2) > α-Al2O3 (0 0 0 1). In addition, Pb(II) partitioning onto α-Al2O3 (1 -1 0 2) surfaces increased with increasing pH from 4.0 to 9.0 as a result of the increasingly negative surface charge. These results show that intrinsic properties (nature of binding sites, binding affinities, and surface charge) of the ESHA coatings and metal-oxide surfaces, as well as external parameters such as pH and competing ions, are key factors governing the distribution and speciation of metal ions at complex NOM/mineral interfaces.

Two novel macroacyclic schiff bases containing bis-N 2O 2 donor set and their binuclear complexes: synthesis, spectroscopic and magnetic properties

NASA Astrophysics Data System (ADS)

Karaoglu, Kaan; Baran, Talat; Serbest, Kerim; Er, Mustafa; Degirmencioglu, Ismail

2009-03-01

Herein, we report two novel macroacyclic Schiff bases derived from tetranaphthaldehyde derivative compound and their binuclear Mn(II), Ni(II), Cu(II) and Zn(II) complexes. The structures of the compounds have been proposed by elemental analyses, spectroscopic data i.e. IR, 1H and 13C NMR, UV-Vis, electrospray ionisation mass spectra, molar conductivities and magnetic susceptibility measurements. The stoichiometries of the complexes derived from mass and elemental analysis correspond to the general formula [M 2L(ClO 4) n](ClO 4) 4-n, (where M is Mn(II), Ni(II), Cu(II), Zn(II) and L represents the Schiff base ligands).

Whole-Genome Sequence of Cupriavidus sp. Strain BIS7, a Heavy-Metal-Resistant Bacterium

PubMed Central

Hong, Kar Wai; Thinagaran, Dinaiz a/l; Gan, Han Ming; Yin, Wai-Fong

2012-01-01

Cupriavidus sp. strain BIS7 is a Malaysian tropical soil bacterium that exhibits broad heavy-metal resistance [Co(II), Zn(II), Ni(II), Se(IV), Cu(II), chromate, Co(III), Fe(II), and Fe(III)]. It is particularly resistant to Fe(II), Fe(III), and Zn(II). Here we present the assembly and annotation of its genome. PMID:23115161

Synthesis, characterization, and ligand exchange reactivity of a series of first row divalent metal 3-hydroxyflavonolate complexes.

PubMed

Grubel, Katarzyna; Rudzka, Katarzyna; Arif, Atta M; Klotz, Katie L; Halfen, Jason A; Berreau, Lisa M

2010-01-04

A series of divalent metal flavonolate complexes of the general formula [(6-Ph(2)TPA)M(3-Hfl)]X (1-5-X; X = OTf(-) or ClO(4)(-); 6-Ph(2)TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II); 3-Hfl = 3-hydroxyflavonolate) were prepared and characterized by X-ray crystallography, elemental analysis, FTIR, UV-vis, (1)H NMR or EPR, and cyclic voltammetry. All of the complexes have a bidentate coordinated flavonolate ligand. The difference in M-O distances (Delta(M-O)) involving this ligand varies through the series, with the asymmetry of flavonolate coordination increasing in the order Mn(II) approximately Ni(II) < Cu(II) < Zn(II) < Co(II). The hypsochromic shift of the absorption band I (pi-->pi*) of the coordinated flavonolate ligand in 1-5-OTf (relative to that in free anion) increases in the order Ni(II) < Mn(II) < Cu(II) < Zn(II), Co(II). Previously reported 3-Hfl complexes of divalent metals fit well with this ordering. (1)H NMR studies indicate that the 3-Hfl complexes of Co(II), Ni(II), and Zn(II) exhibit a pseudo-octahedral geometry in solution. EPR studies suggest that the Mn(II) complex 1-OTf may form binuclear structures in solution. The mononuclear Cu(II) complex 4-OTf has a distorted square pyramidal geometry. The oxidation potential of the flavonolate ligand depends on the metal ion present and/or the solution structure of the complex, with the Mn(II) complex 1-OTf exhibiting the lowest potential, followed by the pseudo-octahedral Ni(II) and Zn(II) 3-Hfl complexes, and the distorted square pyramidal Cu(II) complex 4-OTf. The Mn(II) complex [(6-Ph(2)TPA)Mn(3-Hfl)]OTf (1-OTf) is unique in the series in undergoing ligand exchange reactions in the presence of M(ClO(4))(2).6H(2)O (M = Co, Ni, Zn) in CD(3)CN to produce [(6-Ph(2)TPA)M(CD(3)CN)(n)](X)(2), [Mn(3-Hfl)(2).0.5H(2)O], and MnX(2) (X = OTf(-) or ClO(4)(-)). Under similar conditions, the 3-Hfl complexes of Co(II), Ni(II), and Cu(II) undergo flavonolate ligand exchange to produce [(6-Ph(2)TPA)M(CD(3)CN)(n)](X)(2) (M = Co, Ni, Cu; n = 1 or 2) and [Zn(3-Hfl)(2).2H(2)O]. An Fe(II) complex of 3-Hfl, [(6-Ph(2)TPA)Fe(3-Hfl)]ClO(4) (8), was isolated and characterized by elemental analysis, FTIR, UV-vis, (1)H NMR, cyclic voltammetry, and a magnetic moment measurement. This complex reacts with O(2) to produce the diiron(III) mu-oxo compound [(6-Ph(2)TPAFe(3Hfl))(2)(mu-O)](ClO(4))(2) (6).

Bimetallic Metal-Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion.

PubMed

Zou, Ruyi; Li, Pei-Zhou; Zeng, Yong-Fei; Liu, Jia; Zhao, Ruo; Duan, Hui; Luo, Zhong; Wang, Jin-Gui; Zou, Ruqiang; Zhao, Yanli

2016-05-01

A highly porous metal-organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn2 (COO)4 ) and tetrameric (Zn4 (O)(CO2 )6 ), is successfully assembled by the reaction of a tricarboxylate ligand with Zn(II) ion. Subsequently, single-crystal-to-single-crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu(II) and Co(II) ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation-exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu(II) and Co(II) exchanged samples exhibit comparable CO2 adsorption capability to the pristine Zn(II) -based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO2 with epoxides into related carbonates demonstrate that Zn(II) -based MOF affords the highest catalytic activity as compared with Cu(II) and Co(II) exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic and biological studies of new mononuclear metal complexes of a bidentate NN and NO hydrazone-oxime ligand derived from egonol

NASA Astrophysics Data System (ADS)

Babahan, Ilknur; Emirdağ-Öztürk, Safiye; Poyrazoğlu-Çoban, Esin

2015-04-01

A novel ligand, vicinal dioxime ligand (egonol-hydrazone glyoxime) (LH2) was synthesized and characterized using 1H NMR, 13C NMR, MS, AAS, infrared spectroscopy, and magnetic susceptibility measurements. Mononuclear nickel (II), copper (II) and cobalt (II) complexes with a metal:ligand ratio of 1:2 for LH2 were also synthesized. Zn(II) forms complex [Zn(LH)Cl2] with a metal to ligand ratio of 1:1. IR spectrum shows that the ligand act in a bidentate manner and coordinates N4 donor groups of the ligands to NiII, CuII, CoII and ZnII ions. The detection of H-bonding (Osbnd H⋯O) in the [M(LH)2] metal complexes by IR spectra supported the square-planar MN4 coordination of Ni(II), Cu(II) and Co(II) complexes. The antimicrobial activities of compounds LH2 and their Ni(II), Cu(II), Co(II) and Zn(II) complexes were evaluated using the disc diffusion method against 16 bacteria and 5 yeasts. The minimal inhibitory concentrations (MICs) against all the bacteria and yeasts were also determined. Among the attempted test compounds, it is showed that all the compounds (L, LH2, [Ni(LH)2], [Cu(LH)2], [Co(LH)2(H2O)2], [Zn(LH)Cl2]) were effective against used test microorganisms.

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

PubMed

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.

Synthesis, spectral characterization, structural investigation and antimicrobial studies of mononuclear Cu(II), Ni(II), Co(II), Zn(II) and Cd(II) complexes of a new potentially hexadentate N2O4 Schiff base ligand derived from salicylaldehyde

NASA Astrophysics Data System (ADS)

Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Elerman, Yalcin; Buyukgungor, Orhan

2013-01-01

A new potentially hexadentate N2O4 Schiff base ligand, H2L derived from condensation reaction of an aromatic diamine and salicylaldehyde, and its metal complexes were characterized by elemental analyses, IR, UV-Vis, EI-MS, 1H and 13C NMR spectra, as well as conductance measurements. It has been originated that the Schiff base ligand with Cu(II), Ni(II), Co(II), Cd(II) and Zn(II) ions form mononuclear complexes on 1:1 (metal:ligand) stoichiometry. The conductivity data confirm the non-electrolytic nature of the complexes. Also the crystal structures of the complexes [ZnL] and [CoL] have also been determined by using X-ray crystallographic technique. The Zn(II) and Co(II) complexes show a tetrahedral configuration. Electronic absorption spectra of the Cu(II) and Ni(II) complexes suggest a square-planar geometry around the central metal ion. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Bacillus cereus, Enterococcus faecalis and Listeria monocytogenes and also against the three Gram-negative bacteria: Salmonella paraB, Citrobacter freundii and Enterobacter aerogenes. The results showed that in some cases the antibacterial activity of complexes were more than nalidixic acid and amoxicillin as standards.

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

PubMed

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

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.

PubMed

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.

Spectroscopic (FT-IR, FT-Raman, 1H, 13C NMR, UV/VIS), thermogravimetric and antimicrobial studies of Ca(II), Mn(II), Cu(II), Zn(II) and Cd(II) complexes of ferulic acid

NASA Astrophysics Data System (ADS)

Kalinowska, M.; Piekut, J.; Bruss, A.; Follet, C.; Sienkiewicz-Gromiuk, J.; Świsłocka, R.; Rzączyńska, Z.; Lewandowski, W.

2014-03-01

The molecular structure of Mn(II), Cu(II), Zn(II), Cd(II) and Ca(II) ferulates (4-hydroxy-3-methoxycinnamates) was studied. The selected metal ferulates were synthesized. Their composition was established by means of elementary and thermogravimetric analysis. The following spectroscopic methods were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance (13C, 1H NMR) and ultraviolet-visible (UV/VIS). On the basis of obtained results the electronic charge distribution in studied metal complexes in comparison with ferulic acid molecule was discussed. The microbiological study of ferulic acid and ferulates toward Escherichia coli, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris was done.

Synthesis, characterization and anti-microbial activity of a novel macrocyclic ligand derived from the reaction of 2,6-pyridinedicarboxylic acid with homopiperazine and its Co(II), Ni(II), Cu(II), and Zn(II) complexes

NASA Astrophysics Data System (ADS)

Soleimani, Esmaiel

2011-05-01

The preparation of a novel macrocyclic ligand ( 1), N,N'-diethylhomopiperazinyl,2,6-pyridinedicarboxylate and its Co(II), Ni(II), Cu(II), and Zn(II) complexes are described. The ligand was prepared in EtOH from the reaction of dipotassium salt of 2,6-pyridinedicarboxylic acid with 1,2-dibromoethane in the presence of homopiperazine. Reaction of macrocyclic ligand ( 1) in EtOH with CoCl 2.6H 2O, NiCl 2.6H 2O, CuCl 2.2H 2O, and ZnCl 2·2H 2O yielded the complexes with the general formula [M(L)Cl 2] {where M = Co(II) ( 2), Ni(II) ( 3), Cu(II) ( 4), Zn ( 5), respectively}. The analysis of IR, 1H and 13C NMR spectral data of macrocyclic ligand ( 1) and its Zn(II) complex ( 5) together with their molar conductivity values, and the magnetic moments of the complexes suggest that the macrocyclic ligand ( 1) is bonded to metal(II) ions through two oxygen atoms of ester moiety and the two nitrogen atoms of homopiperazine ring. The electronic spectral data of these complexes in DMSO are in good agreement with the octahedral coordination of M(II) ions. The ligand field parameters for these complexes, i.e. splitting energy and Racah parameter were calculated to be 14,945 and 673 cm -1 for the Co(II) ( 2), 16,260 and 774 cm -1 for the Ni(II) ( 3) complexes respectively. The spliting energy of 17,262 cm -1 was obtained for the Cu(II) complex ( 4).

Copper and the oxidation of hemoglobin: a comparison of horse and human hemoglobins.

PubMed

Rifkind, J M; Lauer, L D; Chiang, S C; Li, N C

1976-11-30

Oxidation studies of hemoglobin by Cu(II) indicate that for horse hemoglobin, up to a Cu(II)/heme molar ratio of 0.5, all of the Cu(II) added is used to rapidly oxidize the heme. On the other hand, most of the Cu(II) added to human hemoglobin at low Cu(II)/heme molar ratios is unable to oxidize the heme. Only at Cu(II)/heme molar ratios greater than 0.5 does the amount of oxidation per added Cu(II) approach that of horse hemoglobin. At the same time, binding studies indicate that human hemoglobin has an additional binding site involving one copper for every two hemes, which has a higher copper affinity than the single horse hemoglobin binding site. The Cu(II) oxidation of human hemoglobin is explained utilizing this additional binding site by a mechanism where a transfer of electrons cannot occur between the heme and the Cu(II) bound to the high affinity human binding site. The electron transfer must involve the Cu(II) bound to the lower affinity human hemoglobin binding site, which is similar to the only horse hemoglobin site. The involvement of beta-2 histidine in the binding of this additional copper is indicated by a comparison of the amino acid sequences of various hemoglobins which possess the additional site, with the amino acid sequences of hemoglobins which do not possess the additional site. Zn(II), Hg(II), and N-ethylmaleimide (NEM) are found to decrease the Cu(II) oxidation of hemoglobin. The sulfhydryl reagents, Hg(II) and NEM, produce a very dramatic decrease in the rate of oxidation, which can only be explained by an effect on the rate for the actual transfer of electrons between the Cu(II) and the Fe(II). The effect of Zn(II) is much smaller and can, for the most part, be explained by the increased oxygen affinity, which affects the ligand dissociation process that must precede the electron transfer process.

Synthesis and application of Fe3O4@SiO2@TiO2 for photocatalytic decomposition of organic matrix simultaneously with magnetic solid phase extraction of heavy metals prior to ICP-MS analysis.

PubMed

Habila, Mohamed A; ALOthman, Zeid A; El-Toni, Ahmed Mohamed; Labis, Joselito Puzon; Soylak, Mustafa

2016-07-01

Interference of organic compounds in the matrix of heavy metal solution could suppress their pre-concentration and detection processes. Therefore, this work aimed to develop simple and facile methods for separation of heavy metals before ICP-MS analysis. Fe3O4@SiO2@TiO2 core-double shell magnetic adsorbent was prepared and characterized by TEM, SEM, FTIR, XRD and surface area, and tested for Magnetic Solid Phase Extraction (MSPE) of Cu(II), Zn(II), Cd(II) and Pb(II). TEM micrograph of Fe3O4@SiO2@TiO2 reveals the uniform coating of TiO2 layer of about 20nm onto the Fe3O4@SiO2 nanoparticles and indicates that all nanoparticles are monodispersed and uniform. The saturation magnetization from the room-temperature hysteresis loops of Fe3O4 and Fe3O4@SiO2@TiO2 was found to be 72 and 40emug(-1), respectively, suggesting good separability of the nanoparticles. The Fe3O4@SiO2@TiO2 showed maximum adsorption capacity of 125, 137, 148 and 160mgg(-1) for Cu(II), Zn(II), Cd(II) and Pb(II) respectively, and the process was found to fit with the second order kinetic model and Langmuir isotherm. Fe3O4@SiO2@TiO2 showed efficient photocatalytic decomposition for tartrazine and sunset yellow (consider as Interfering organic compounds) in aqueous solution under the irradiation of UV light. The maximum recovery% was achieved at pH 5, by elution with 10mL of 2M nitric acid solution. The LODs were found to be 0.066, 0.049, 0.041 and 0.082µgL(-1) for Cu(II), Zn(II), Cd(II) and Pb(II), respectively while the LOQs were found to be 0.20, 0.15, 0.12 and 0.25µgL(-1) for Cu(II), Zn(II), Cd(II) and Pb(II), respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, characterization of 1,2,4-triazole Schiff base derived 3d-metal complexes: Induces cytotoxicity in HepG2, MCF-7 cell line, BSA binding fluorescence and DFT study

NASA Astrophysics Data System (ADS)

Tyagi, Prateek; Tyagi, Monika; Agrawal, Swati; Chandra, Sulekh; Ojha, Himanshu; Pathak, Mallika

2017-01-01

Two novel Schiff base ligands H2L1 and H2L2 have been synthesized by condensation reaction of amine derivative of 1,2,4-triazole moiety with 2-hydroxy-4-methoxybenzaldehyde. Co(II), Ni(II), Cu(II) and Zn(II) of the synthesized Schiff bases were prepared by using a molar ratio of ligand:metal as 1:1. The structure of the Schiff bases and synthesized metal complexes were established by 1H NMR, UV-Vis, IR, Mass spectrometry and molar conductivity. The thermal stability of the complexes was study by TGA. Fluorescence quenching mechanism of metal complexes 1-4 show that Zn(II) and Cu(II) complex binds more strongly to BSA. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31 + g(d,p) basis set. The spectral data shows that the ligands behaves as binegative tridentate. On the basis of the spectral studies, TGA and DFT data an octahedral geometry has been assigned for Co(II), Ni(II), square planar for Cu(II) and tetrahedral for Zn(II) complexes. The anticancer activity were screened against human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2). Result indicates that metal complexes shows increase cytotoxicity in proliferation to cell lines as compared to free ligand.

Metal Ions Removal Using Nano Oxide Pyrolox™ Material

NASA Astrophysics Data System (ADS)

Gładysz-Płaska, A.; Skwarek, E.; Budnyak, T. M.; Kołodyńska, D.

2017-02-01

The paper presents the use of Pyrolox™ containing manganese nano oxides used for the removal of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions. Their concentrations were analyzed using the atomic absorption spectrometer SpectrAA 240 FS (Varian) as well as UV-vis method. For this purpose the static kinetic and equilibrium studies were carried out using the batch technique. The effect of solution pH, shaking time, initial metal ion concentrations, sorbent dosage, and temperature was investigated. The equilibrium data were analyzed using the sorption isotherm models proposed by Freundlich, Langmuir-Freundlich, Temkin, and Dubinin-Radushkevich. The kinetic results showed that the pseudo second order kinetic model was found to correlate the experimental data well. The results indicate that adsorption of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions is strongly dependent on pH. The value of pH 4-7 was optimal adsorption. The time to reach the equilibrium was found to be 24 h, and after this time, the sorption percentage reached about 70%. Kinetics of Cu(II), Zn(II), Cd(II), Pb(II), and U(VI) adsorption on the adsorbent can be described by the pseudo second order rate equation. Nitrogen adsorption/desorption, infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) measurements for adsorbent characterization were performed. Characteristic points of the double layer determined for the studied Pyrolox™ sample in 0.001 mol/dm3 NaCl solution are pHPZC = 4 and pHIEP < 2.

Synthesis, structural elucidation, biological, antioxidant and nuclease activities of some 5-Fluorouracil-amino acid mixed ligand complexes

NASA Astrophysics Data System (ADS)

Shobana, Sutha; Subramaniam, Perumal; Mitu, Liviu; Dharmaraja, Jeyaprakash; Arvind Narayan, Sundaram

2015-01-01

Some biologically active mixed ligand complexes (1-9) have been synthesized from 5-Fluorouracil (5-FU; A) and amino acids (B) such as glycine (gly), L-alanine (ala) and L-valine (val) with Ni(II), Cu(II) and Zn(II) ions. The synthesized mixed ligand complexes (1-9) were characterized by various physico-chemical, spectral, thermal and morphological studies. 5-Fluorouracil and its mixed ligand complexes have been tested for their in vitro biological activities against some pathogenic bacterial and fungal species by the agar well diffusion method. The in vitro antioxidant activities of 5-Fluorouracil and its complexes have also been investigated by using the DPPH assay method. The results demonstrate that Cu(II) mixed ligand complexes (4-6) exhibit potent biological as well as antioxidant activities compared to 5-Fluorouracil and Ni(II) (1-3) and Zn(II) (7-9) mixed ligand complexes. Further, the cleaving activities of CT DNA under aerobic conditions show moderate activity with the synthesized Cu(II) and Ni(II) mixed ligand complexes (1-6) while no activity is seen with Zn(II) complexes (7-9). Binding studies of CT DNA with these complexes show a decrease in intensity of the charge transfer band to the extent of 5-15% along with a minor red shift. The free energy change values (Δ‡G) calculated from intrinsic binding constants indicate that the interaction between mixed ligand complex and DNA is spontaneous.

A breakthrough biosorbent in removing heavy metals: Equilibrium, kinetic, thermodynamic and mechanism analyses in a lab-scale study.

PubMed

Abdolali, Atefeh; Ngo, Huu Hao; Guo, Wenshan; Lu, Shaoyong; Chen, Shiao-Shing; Nguyen, Nguyen Cong; Zhang, Xinbo; Wang, Jie; Wu, Yun

2016-01-15

A breakthrough biosorbent namely multi-metal binding biosorbent (MMBB) made from a combination of tea wastes, maple leaves and mandarin peels, was prepared to evaluate their biosorptive potential for removal of Cd(II), Cu(II), Pb(II) and Zn(II) from multi-metal aqueous solutions. FTIR and SEM were conducted, before and after biosorption, to explore the intensity and position of the available functional groups and changes in adsorbent surface morphology. Carboxylic, hydroxyl and amine groups were found to be the principal functional groups for the sorption of metals. MMBB exhibited best performance at pH 5.5 with maximum sorption capacities of 31.73, 41.06, 76.25 and 26.63 mg/g for Cd(II), Cu(II), Pb(II) and Zn(II), respectively. Pseudo-first and pseudo-second-order models represented the kinetic experimental data in different initial metal concentrations very well. Among two-parameter adsorption isotherm models, the Langmuir equation gave a better fit of the equilibrium data. For Cu(II) and Zn(II), the Khan isotherm describes better biosorption conditions while for Cd(II) and Pb(II), the Sips model was found to provide the best correlation of the biosorption equilibrium data. The calculated thermodynamic parameters indicated feasible, spontaneous and exothermic biosorption process. Overall, this novel MMBB can effectively be utilized as an adsorbent to remove heavy metal ions from aqueous solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis, characterization and biological activity of complexes of 2-hydroxy-3,5-dimethylacetophenoneoxime (HDMAOX) with copper(II), cobalt(II), nickel(II) and palladium(II)

NASA Astrophysics Data System (ADS)

Singh, Bibhesh K.; Jetley, Umesh K.; Sharma, Rakesh K.; Garg, Bhagwan S.

2007-09-01

A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML 2 composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.

Synthesis, characterization and biological activity of complexes of 2-hydroxy-3,5-dimethylacetophenoneoxime (HDMAOX) with copper(II), cobalt(II), nickel(II) and palladium(II).

PubMed

Singh, Bibhesh K; Jetley, Umesh K; Sharma, Rakesh K; Garg, Bhagwan S

2007-09-01

A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML(2) composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.

Synthesis, spectroscopy, and binding constants of ketocatechol-containing iminodiacetic acid and its Fe(III), Cu(II), and Zn(II) complexes and reaction of Cu(II) complex with H₂O₂ in aqueous solution.

PubMed

Gao, Jiaojiao; Xing, Feifei; Bai, Yueling; Zhu, Shourong

2014-06-07

A new neuromelanin-like ketocatechol-containing iminodiacetic acid ligand, (N-(3,4-dihydroxyl)phenacylimino)diacetic acid (H4L), which is also quite similar to compounds found in insect cuticle, has been synthesized and characterized. The X-ray crystal structure of H4L has been successfully determined. Proton binding and coordination with Fe(III), Cu(II), and Zn(II) have been studied by potentiometric titrations and UV-vis spectrophotometry in aqueous solution. UV spectra of H4L in the absence and presence of different metal ions indicate complexes formed with the catechol moiety of H4L in aqueous solution. Visible spectra and NMR reveal that H4L with Fe(III), Cu(II), and Zn(II) can all give stable mono-(ML) and dinuclear complexes [M(ML)]. Fe(III) can also form {Fe(FeL)2} and {Fe(FeL)3} species with sufficient base. The process is accompanied by a drastic color change from light blue to deep-blue to wine-red. The Fe(III)-Cu(II) heteronuclear complex also exists in aqueous solution whose spectra are similar to the homonuclear Fe(III) complex. However, the spectra of {Fe(CuL)} shifted to a longer wavelength and {Fe(CuL)2} and {Fe(CuL)3} shifted to a shorter wavelength. Keto-enol tautomerism was observed in weak basic aqueous solution as indicated by (1)H NMR spectra. The reaction products of Cu(II) complex with H2O2 depend on the H2O2 concentration and pH value. Low concentrations of H2O2 oxidize H4L to a series of semiquinone and quinone compounds with absorption maxima at 314-400 nm, while a high concentration of H2O2 oxidizes H4L to colorless muconic acid derivatives. NaIO4 gives different oxidase products, but no 2,4,5-trihydroxyphenylalanine quinone (TPQ)-like hydroxyquinone can be found.

Coordination Polymer: Synthesis, Spectral Characterization and Thermal Behaviour of Starch-Urea Based Biodegradable Polymer and Its Polymer Metal Complexes

PubMed Central

Malik, Ashraf; Parveen, Shadma; Ahamad, Tansir; Alshehri, Saad M.; Singh, Prabal Kumar; Nishat, Nahid

2010-01-01

A starch-urea-based biodegradable coordination polymer modified by transition metal Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) was prepared by polycondensation of starch and urea. All the synthesized polymeric compounds were characterized by Fourier transform-infrared spectroscopy (FT-IR), 1H-NMR spectroscopy, 13C-NMR spectroscopy, UV-visible spectra, magnetic moment measurements, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). The results of electronic spectra and magnetic moment measurements indicate that Mn(II), Co(II), and Ni(II) complexes show octahedral geometry, while Cu(II) and Zn(II) complexes show square planar and tetrahedral geometry, respectively. The thermogravimetric analysis revealed that all the polymeric metal complexes are more thermally stable than the parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM standards of biodegradable polymers by CO2 evolution method. PMID:20414461

Synthesis and Spectral Evaluation of Some Unsymmetrical Mesoporphyrinic Complexes

PubMed Central

Boscencu, Rica; Oliveira, Anabela Sousa; Ferreira, Diana P.; Ferreira, Luís Filipe Vieira

2012-01-01

Synthesis and spectral evaluation of new zinc and copper unsymmetrical mesoporphyrinic complexes are reported. Zn(II)-5-(4-acetoxy-3-methoxyphenyl)-10,15,20- tris-(4-carboxymethylphenyl)porphyrin, Zn(II)-5-[(3,4-methylenedioxy)phenyl]-10,15,20- tris-(4-carboxymethylphenyl)porphyrin, Cu(II)-5-(4-acetoxy-3-methoxyphenyl)-10,15,20- tris-(4-carboxymethylphenyl)porphyrin and Cu(II)-5-[(3,4-methylenedioxy)phenyl]-10,15,20- tris-(4-carboxymethylphenyl)porphyrin were synthesized using microwave-assisted synthesis. The complexes were characterized by elemental analysis, FT-IR, UV-Vis, EPR and NMR spectroscopy, which fully confirmed their structure. The spectral absorption properties of the porphyrinic complexes were studied in solvents with different polarities. Fluorescence emission and singlet oxygen formation quantum yields were evaluated for the compounds under study, revealing high yields for the zinc derivatives. The copper complexes are not emissive and only display residual capacity for singlet oxygen formation. PMID:22942693

Synthesis, characterization, photoluminescence, and electrochemical studies of novel mononuclear Cu(II) and Zn(II) complexes with the 1-benzylimidazolium ligand

NASA Astrophysics Data System (ADS)

Bibi, Sherino; Mohammad, Sharifah; Manan, Ninie Suhana Abdul; Ahmad, Jimmy; Kamboh, Muhammad Afzal; Khor, Sook Mei; Yamin, Bohari M.; Abdul Halim, Siti Nadiah

2017-08-01

Two new mononuclear coordination complexes [Cu(bim)4Cl2]ṡ2H2O (1) and [Zn(bim)2Cl2] (2) containing the 1-benzylimidazole (bim) ligand were successfully synthesized. Both complexes were characterized by IR, UV-vis, and fluorescence spectroscopies, single crystal and powder X-ray diffraction measurements, and thermogravimetric analysis. Self-assembly during the recrystallization process resulted in the formation of octahedral and tetrahedral Cu(II) and Zn(II) complexes, respectively. The single crystals obtained are representative of the bulk material, as shown by the powder X-ray diffraction patterns. Cyclic voltammetry measurements showed that complex 1 undergoes a quasi-reversible redox reaction, while complex 2 undergoes reduction alone, and no oxidation peak was observed; this is due to the stability of the reduced form of complex 2.

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion.

PubMed

Shipley, Heather J; Engates, Karen E; Grover, Valerie A

2013-03-01

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.

Co(II), Ni(II), Cu(II) and Zn(II) complexes of tridentate ONO donor Schiff base ligand: Synthesis, characterization, thermal, non-isothermal kinetics and DFT calculations

NASA Astrophysics Data System (ADS)

Kusmariya, Brajendra S.; Mishra, A. P.

2017-02-01

We report here four mononuclear Co(II), Ni(II), Cu(II) and Zn(II) coordination compounds of general formula [M(L)2] {L = dcp; M = CoII, CuII & ZnII} and [M(L)(H2O)]·H2O {L = dcp; M = NiII} derived from tridentate 2,4-dichloro-6-{[(3-chloro-2-hydroxy-5-nitrophenyl)imino]methyl}phenol (dcp) ligand. These compounds were synthesized and characterized by elemental analysis, FT-IR, uv-vis, 1H NMR, molar conductance, magnetic moment, thermal, PXRD and SEM-EDX. The Powder X-ray Diffraction patterns and SEM analyses showed the crystalline nature of synthesized compounds. The peak broadening was explained in terms of crystallite size and the lattice strain using Scherrer and Williamson-Hall method. Thermogravimetric analysis was performed to determine the thermal stability of synthesized compounds under nitrogen atmosphere up to 820 K at 10 Kmin-1 heating rate. The kinetic and thermodynamic parameters of thermal decomposition were calculated using Coats-Redfern (C-R), Piloyan-Novikova (P-N) and Horowitz-Metzger (H-M) methods assuming first order degradation. The calculated optical band gap values of complexes were found to be in semiconducting range. To support the experimental findings, and derive some fruitful information viz. frequency calculations, HOMO-LUMO, energy gap (ΔE), molecular electrostatic potential (MEP), spin density, absorption spectra etc.; theoretical calculations by means of DFT and TD-DFT at B3LYP level were incorporated.

Agricultural solid waste for sorption of metal ions, part II: competitive assessment in multielemental solution and lake water.

PubMed

Milani, Priscila Aparecida; Consonni, João Luiz; Labuto, Geórgia; Carrilho, Elma Neide Vasconcelos Martins

2018-03-20

Sugarcane bagasse and hydroponic lettuce roots were used as biosorbents for the removal of Cu(II), Fe(II), Mn(II), and Zn(II) from multielemental solutions and lake water, in batch processes. These biomasses were studied in natura (lettuce roots, NLR, and sugarcane bagasse, NSB) and chemically modified with HNO 3 (lettuce roots, MLR, and sugarcane bagasse, MSB). The results showed higher adsorption efficiency for MSB and either NLR or MLR. The maximum adsorption capacities (q max ) in multielemental solution for Cu(II), Fe(II), Mn(II), and Zn(II) were 35.86, 31.42, 3.33, and 24.07 mg/g for NLR; 25.36, 27.95, 14.06, and 6.43 mg/g for MLR; 0.92, 3.94, 0.03, and 0.18 mg/g for NSB; and 54.11, 6.52, 16.7, and 1.26 mg/g for MSB, respectively. The kinetic studies with chemically modified biomasses indicated that sorption was achieved in the first 5 min and reached equilibrium around 30 min. Sorption of Cu(II), Fe(II), Mn(II), and Zn(II) in lake water by chemically modified biomasses was 24.31, 14.50, 8.03, and 8.21 mg/g by MLR, and 13.15, 10.50, 6.10, and 5.14 mg/g by MSB, respectively. These biosorbents are promising and low costs agricultural residues, and as for lettuce roots, these showed great potential even with no chemical modification.

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

PubMed

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.

Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: synthesis, characterization, fluorescence and corrosion inhibitors of ligands.

PubMed

Ali, Omyma A M

2014-11-11

Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans. Copyright © 2014 Elsevier B.V. All rights reserved.

Accumulation of metal ions by pectinates

NASA Astrophysics Data System (ADS)

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). Surprisingly, simultaneous sorption tests and SEM analyses indicate that a different mechanism regulates the sorption of Cu(II) and Pb(II) by PGAE1. In fact, the amount of Pb(II) sorbed (0.92 moles mg-1of PGAE1) by PGAE1 was nearly independent by the presence of Cu(II) ions, at least at the three different concentrations tested, that indicates a higher affinity of Pb(II). Such an aspect was further confirmed by exchange experiments. Samples of PGAE1 saturated with 1.96 moles mg-1of Cu(II) or 2.01 moles mg-1of Pb(II) were put in contact with 100 mL of solutions containing 97.3 moles of Pb(II) or 99.4 moles Cu(II), respectively. The exchange kinetics show that about 80% of Cu(II) was stochiometrically exchanged by Pb(II). In contrast, only about 10% of Pb(II) complexed by PGAE1 was exchanged by Cu(II). The kinetics of simultaneous sorption of all the metal ions tested indicate that Pb(II) is selectively sorbed by the PGAE1 gels. Cd(II) and Zn(II) show a similar affinity towards PGAE1. Thus, in the simultaneous presence of these ions, their selectivity towards this matrix follows the order: Pb > Cu > Cd ? Zn. Sorption of Cr(III) in the presence of the ions considered was not possible to carry out due to interference phenomena. The sorption of the same ions by 50 mg of PGAE2 evidences that the amount of Cu(II), Pb(II), and Cr(III) sorbed is markedly lower than that found for PGAE1. By considering that two carboxylic groups are involved in the complexation of a metal ion, the data show that such a stoichiometry is respected only for Pb(II). The amount of Cu(II) sorbed is about 50% lower than that of Pb(II) at all the pH values tested whereas those of Zn(II) and Cd(II) are negligible whereas that of Cr(III) is the highest. The different behaviour of Cu(II) compared to Pb(II) can be explained taking into account for both hydrophobic and steric effects of the methyl groups as well as to their different charge density. Thus, it can be concluded that the accumulation of metals at the soil-root interface strictly depends on the esterification degree of the root pectinates which, even highly esterified, do not loose the ability to accumulate metals, mainly Pb(II) and Cr(III).

Transition metal complexes of a new 15-membered [N5] penta-azamacrocyclic ligand with their spectral and anticancer studies

NASA Astrophysics Data System (ADS)

El-Boraey, Hanaa A.; Serag El-Din, Azza A.

2014-11-01

Novel penta-azamacrocyclic 15-membered [N5] ligand [L] i.e. 1,5,8,12-tetetraaza-3,4: 9,10-dibenzo-6-ethyl-7-methyl-1,12-(2,6-pyrido)cyclopentadecan-5,7 diene-2,11-dione and its transition metal complexes with Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and structurally characterized by elemental analysis, spectral, thermal as well as magnetic and molar conductivity measurements. On basis of IR, MS, UV-Vis 1H NMR and EPR spectral studies an octahedral geometry has been proposed for all complexes except Co(II), Cu(II) nitrate complexes and Pd(II) chloride complex that adopt tetrahedral, square pyramidal and square planar geometries, respectively. The antitumor activity of the synthesized ligand and some complexes against human breast cancer cell lines (MCF-7) and human hepatocarcinoma cell lines (HepG2) has been studied. The complexes (IC50 = 2.04-9.7, 2.5-3.7 μg/mL) showed potent antitumor activity comparable with their ligand (IC50 = 11.7, 3.45 μg/mL) against the above mentioned cell lines, respectively. The results evidently show that the activity of the ligand becomes more pronounced and significant when coordinated to the metal ion.

Polymeric material prepared from Schiff base based on O-carboxymethyl chitosan and its Cu(II) and Pd(II) complexes

NASA Astrophysics Data System (ADS)

Baran, Talat; Menteş, Ayfer

2016-07-01

In this study, a new eco-friendly Schiff base based on O-carboxymethyl chitosan ([OCMCS-7a]) and its copper(II) and palladium(II) complexes were synthesized. Characterizations of [OCMCS-7a] and its metal complexes were conducted using FTIR, 1H NMR, 13C NMR, TG/DTG, XRD, SEM-EDAX, ICP, UV-VIS, GC-MS, elemental analysis, magnetic moment and molar conductivity measurements. The degree of substitution (DS) of [OCMCS-7a] was determined by elemental analysis to be 0.44. It was shown by the solubility test that [OCMCS-7a] was completely soluble in water. Surface images of chitosan, [OCMCS-7a] and its Cu(II) and Pd(II) complexes were investigated using the SEM-EDAX technique. Their thermal behaviors and crystallinities of the synthesized complexes were determined by TG/DTG and X-ray powder diffraction techniques, respectively. The metal contents of the obtained complexes were determined using an ICP-OES instrument. From the analyses, it was noted that the thermal stabilities and crystallinities of [OCMCS-7a] and its complexes decreased compared to chitosan. As a consequence of surface screening, it was also noted that the surface structure of the chitosan was smoother than that of the obtained compounds.

Retention of heavy metal ions on comb-type hydrogels based on acrylic acid and 4-vinylpyridine, synthesized by gamma radiation

NASA Astrophysics Data System (ADS)

González-Gómez, Roberto; Ortega, Alejandra; Lazo, Luz M.; Burillo, Guillermina

2014-09-01

Two novel comb-type hydrogels based on pH-sensitive monomers (acrylic acid (AAc) and 4-vinylpyridine (4VP) were synthesized by gamma radiation. The systems were as follows: a) comb-type hydrogels of an AAc network followed by grafting of 4VP ((net-PAAc)-g-4VP) and b) comb-type hydrogels of an AAc network grafted onto polypropylene (PP) followed by grafting of 4VP (net-(PP-g-AAc)-g-4VP). The equilibrium isotherms and kinetics were evaluated for copper and zinc ions in aqueous solutions. The Zn(II) retention obtained was 480 mg g-1 and 1086 mg g-1 for (net-PAAc)-g-4VP and net-(PP-g-AAc)-g-4VP, respectively. At concentrations as low as ppm, retention efficiencies of approximately 90% were achieved for Cu(II) on (net-PAAc)-g-4VP and for Zn(II) on net-(PP-g-AAc)-g-4VP. Desorption of the hydrogels was also studied, and the results indicated that they can be used repeatedly in aqueous solutions. For both systems, the adsorption of Cu(II) and Zn(II) obeyed the Freundlich model, indicating heterogeneous sorption, and the retention process occurred by chemisorption. The sorption process follows a pseudo-second-order model.

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

NASA Astrophysics Data System (ADS)

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.

In vitro DNA binding, pBR322 plasmid cleavage and molecular modeling study of chiral benzothiazole Schiff-base-valine Cu(II) and Zn(II) complexes to evaluate their enantiomeric biological disposition for molecular target DNA

NASA Astrophysics Data System (ADS)

Alizadeh, Rahman; Afzal, Mohd; Arjmand, Farukh

2014-10-01

Bicyclic heterocyclic compounds viz. benzothiazoles are key components of deoxyribonucleic acid (DNA) molecules and participate directly in the encoding of genetic information. Benzothiazoles, therefore, represent a potent and selective class of antitumor compounds. The design and synthesis of chiral antitumor chemotherapeutic agents of Cu(II) and Zn(II), L- and -D benzothiazole Schiff base-valine complexes 1a &b and 2a &b, respectively were carried out and thoroughly characterized by spectroscopic and analytical techniques. Interaction of 1a and b and 2a and b with CT DNA by employing UV-vis, florescence, circular dichroic methods and cleavage studies of 1a with pBR322 plasmid, molecular docking were done in order to demonstrate their enantiomeric disposition toward the molecular drug target DNA. Interestingly, these studies unambiguously demonstrated the greater potency of L-enantiomer in comparison to D-enantiomer.

Isostructural 1D coordination polymers of Zn(II), Cd(II) and Cu(II) with phenylpropynoic acid and DABCO as organic linkers

NASA Astrophysics Data System (ADS)

Saravanakumar, Rajendran; Varghese, Babu; Sankararaman, Sethuraman

2014-11-01

Using phenylpropynoic acid (PPA) and 1,4-diazabicyclo[2.2.2]octane (DABCO) as organic spacers, isostructural coordination polymers of Zn(II), Cd(II) and Cu(II) were synthesized by solvothermal method and structurally characterized using single crystal XRD, powder XRD, 13C CP-MAS NMR spectroscopy. Single crystal XRD data revealed four PPA units coordinating with two metal ions forming a paddle wheel secondary building unit (SBU). The paddle wheel units are connected through coordination of DABCO nitrogen to the metal centers from the axial positions leading to the formation of the 1D coordination polymers along the c axis. Intermolecular π stacking and Csbnd H…π interactions between the adjacent polymer chains convert the 1D coordination polymer into an interesting 3D network with the Csbnd H…π bonds running along the crystallographic a and b axes. Thermal and nitrogen adsorption studies of these coordination polymers are reported.

Structural characterization and antimicrobial activities of transition metal complexes of a hydrazone ligand

NASA Astrophysics Data System (ADS)

Bakale, Raghavendra P.; Naik, Ganesh N.; Machakanur, Shrinath S.; Mangannavar, Chandrashekhar V.; Muchchandi, Iranna S.; Gudasi, Kalagouda B.

2018-02-01

A hydrazone ligand has been synthesized by the condensation of 2-nitrobenzaldehyde and hydralazine, and its Co(II), Ni(II), Cu(II) and Zn(II) complexes have been reported. Structural characterization of the ligand and its metal complexes has been performed by various spectroscopic [IR, NMR, UV-Vis, Mass], thermal and other physicochemical methods. The structure of the ligand and its Ni(II) complex has been characterized by single crystal X-ray diffraction studies. All the synthesized compounds have been screened for in vitro antimicrobial activity. The antibacterial activity is tested against Gram-positive strains Enterococcus faecalis, Streptococcus mutans and Staphylococcus aureus and Gram-negative strains Escherichia coli, Pseudomonas aeruginosa and Klebsiella pneumoniae using ciprofloxacin as the reference standard. Antifungal activity is tested against Candida albicans, Aspergillus fumigatus and Aspergillus niger using ketoconazole as the reference standard. The minimum inhibitory concentration (MIC) was determined for test compounds as well as for reference standard. Ligand, Cu(II) and Zn(II) complexes have shown excellent activity against Candida albicans.

The use of a polymer inclusion membrane in flow injection analysis for the on-line separation and determination of zinc.

PubMed

Zhang, Lujia L; Cattrall, Robert W; Kolev, Spas D

2011-06-15

This paper reports the first use of a polymer inclusion membrane (PIM) for on-line separation in flow injection analysis (FIA) involving simultaneous extraction and back-extraction. The FIA system containing the PIM separation module was used for the determination of Zn(II) in aqueous samples in the presence of Mg(II), Ca(II), Cd(II), Co(II), Ni(II), Cu(II), and Fe(III). The Fe(III) and Cu(II) interferences were eliminated by off-line precipitation with phosphate and on-line complexation with chloride, respectively. The concentration of Zn(II) was determined spectrophotometrically using 4-(2-pyridylazo) resorcinol (PAR). The optimal composition of the PIM consisted of 40% (m/m) di(2-ethlyhexyl) phosphoric acid (D2EHPA) as carrier, 10% (m/m) dioctyl phthalate (DOP) as plasticizer and 50% (m/m) poly(vinyl chloride) (PVC) as the base polymer. The optimized FIA system was characterized by a linear calibration curve in the range from 1.0 to 30.0 mg L(-1) Zn(II), a detection limit of 0.05 mg L(-1) and a relative standard deviation of 3.4% with a sampling rate of 4h(-1). Reproducible results were obtained for 20 replicate injections over a 5h period which demonstrated a good membrane stability. The FIA system was applied to the determination of Zn(II) in pharmaceuticals and samples from the galvanizing industry and very good agreement with atomic absorption spectrometry was obtained. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

PubMed

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 chelates 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.

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

NASA Astrophysics Data System (ADS)

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.

TREATMENT OF ACID MINE DRAINAGE: I. EQUILIBRIUM BIOSORPTION OF ZINC AND COPPER ON NON-VIABLE ACTIVATED SLUDGE

EPA Science Inventory

Biosorption is potentially attractive technology for treament of acid mine drainage for separation/recovery of metal ions and mitigation of their toxicity to sulfate reducing bacteria. This study describes the equilibrium biosorptio of Zn(II) and CU(II) by nonviable activated slu...

1D cyanide complexes with 2-pyridinemethanol: Synthesis, crystal structures and spectroscopic properties

NASA Astrophysics Data System (ADS)

Sayın, Elvan; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; Hökelek, Tuncer

2015-12-01

Two new one-dimensional coordination polymers, [Cu(hmpH)2Pd(μ-CN)2(CN)2]n (1) and [Cu(hmpH)2Pt(μ-CN)2(CN)2]n (2), (hmpH = 2-pyridinemethanol), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. Single crystal X-ray diffraction analysis indicates that complexes 1 and 2 are isomorphous and isostructural, and crystallize in the triclinic system and P-1 space group. The Pd(II) or Pt(II) ions are four coordinated with four cyanide-carbon atoms in a square planar geometry. Cu(II) ion displays a distorted octahedral coordination by two N-atoms and two O-atoms of hmpH ligands, two bridging cyanide groups. In one dimensional structure of the complexes, [M(CN)4]2- (M = Pd(II) or Pt(II)) anions and [Cu(hmpH)2]2+ cations are linked via bridging cyanide ligands. In the complexes, the presence of intramolecular C-H⋯M (M = Pd(II) or Pt(II)) interactions with distance values of 3.00-2.95 Å are established, respectively.

Quantum, characterization and spectroscopic studies on Cu(II), Pd(II) and Pt(II) complexes of 1-(benzo[d]thiazol-2-yl)-3-phenylthiourea and its biological application as antimicrobial and antioxidant

NASA Astrophysics Data System (ADS)

Jambi, M. S.

2017-09-01

Divalent platinum, palladium and copper chelates of H2PhT have been isolated and identified. Their structures have been elucidated by partial elemental analyses, magnetic susceptibilities and spectroscopic estimations and additionally mass spectra. The FTIR and 1H NMR studies illustrated that H2PhT performs as mono-negative bi-dentate in Cu(II) and Pd(II) complexes while it behaves as neutral bi-dentate in both Pt(II) complexes. Both magnetic moments and spectral studies suggests a tetrahedral coordination geometry for [Cu(HPhT)(H2O)Cl] complex, a square planar geometry for both [Pd(HPhT)2] and [Pt(H2PhT)2Cl2] complexes and octahedral geometry for [Pt(H2PhT)2Cl2] complex. The molecular modeling are drawn and demonstrated both bond lengths and angles, chemical reactivity, MEP, NLO, Mulliken atomic charges, and binding energy (kcal/mol) for the investigated compounds. Theoretical infrared intensities and 1H NMR of H2PhT was computed utilizing DFT technique. An examination of the experimental and hypothetical spectra can be extremely valuable in making right assignments and analyzing the main chemical shift. DNA bioassay, antibacterial and antifungal activities of the investigated compounds have been determined.

Synthesis of first row transition metal selenomaltol complexes.

PubMed

Spiegel, Michael T; Hoogerbrugge, Amanda; Truksa, Shamus; Smith, Andrew G; Shuford, Kevin L; Klausmeyer, Kevin K; Farmer, Patrick J

2018-06-21

We report an efficient, one-step synthesis of the chelator 3-hydroxy-2-methyl-4-selenopyrone (selenomaltol). Complexes of selenomaltol with Fe(iii), Ni(ii), Cu(ii) and Zn(ii) have been prepared and studied by NMR, X-ray crystallography, cyclic voltammetry, EPR and electronic absorption. The Ni(ii) and Cu(ii) complexes show chemically reversible oxidations which are suggested to be ligand-based. Nuclear independent chemical shifts (NICS) analysis is used to compare aromaticity of the heterocyclic rings of selenomaltol and its chelates. The compounds described here should significantly expand the scope and utility of unusual O,Se-donor chelates.

Metal dependent motif transition in a self-assembled monolayer of bipyridine derivatives via coordination: An STM study.

PubMed

Wang, Yi; Yuan, Qunhui; Xu, Hongbo; Zhu, Xuefeng; Gan, Wei

2016-07-21

Low-dimensional molecular motifs with diversity developed via the on-surface chemistry are attracting growing interest for their potential in advanced nanofabrication. In this work, scanning tunneling microscopy was employed to investigate the in situ and ex situ metal coordinations between 4,4'-ditetradecyl-2,2'-bipyridine (bpy) and Zn(ii) or Cu(ii) ions at a highly oriented pyrolytic graphite (HOPG)/1-phenyloctane interface under ambient conditions. The results demonstrate that the bpy adopts a flat-lying orientation with its substituted alkyl chains in a tail-to-tail arrangement in a bpy monolayer. For the in situ coordination, the bpy/Zn(ii) and bpy/Cu(ii) complexes are aligned in edge-on fashions, wherein the bpy stands vertically on the HOPG surface and interdigitates at the alkyl chains. In the two-dimensional arrays of ex situ coordinated complexes, metal dependent motifs have been observed with Zn(ii) and Cu(ii), wherein the bipyridine moieties are parallel to the graphite surface. These results suggest that the desired on-surface coordination architectures may be achieved by the intentional selection of the metal centers.

Structural characterization of 1,8-naphthalimides and in vitro microbiological activity of their Cu(II) and Zn(II) complexes

NASA Astrophysics Data System (ADS)

Grabchev, Ivo; Yordanova, Stanislava; Bosch, Paula; Vasileva-Tonkova, Evgenia; Kukeva, Rositsa; Stoyanov, Stanimir; Stoyanova, Radostina

2017-02-01

Two new 1,8-naphthalimide derivatives (NI1 and NI2) have been synthesized and characterized. The photophysical properties of the new compounds have been investigated in organic solvents of different polarity. It has been shown that both compounds are solvent depended. Cu(II) and Zn(II) complexes of NI2 were obtained and characterized by IR-NMR, fluorescence and EPR spectroscopy. The influence of different metal cations on the fluorescence intensity has been investigated in acetonitrile solution. Antimicrobial composite PLA-metal complexes materials have been obtained for the first time. Microbiological activity of both metal complexes has been investigated in vitro against different Gram-positive and Gram-negative bacteria and two yeasts. The various antimicrobial activities and the minimum inhibitory concentrations (MICs) of both complexes have been determined. The microbiological activity of composite materials PLA-metal complexes in thin polymeric film has also been investigated. The results suggest that the new metal complexes could find application in designing new antimicrobial preparations to control the spread of infections.

In vitro DNA binding, pBR322 plasmid cleavage and molecular modeling study of chiral benzothiazole Schiff-base-valine Cu(II) and Zn(II) complexes to evaluate their enantiomeric biological disposition for molecular target DNA.

PubMed

Alizadeh, Rahman; Afzal, Mohd; Arjmand, Farukh

2014-10-15

Bicyclic heterocyclic compounds viz. benzothiazoles are key components of deoxyribonucleic acid (DNA) molecules and participate directly in the encoding of genetic information. Benzothiazoles, therefore, represent a potent and selective class of antitumor compounds. The design and synthesis of chiral antitumor chemotherapeutic agents of Cu(II) and Zn(II), L- and -D benzothiazole Schiff base-valine complexes 1a &b and 2a &b, respectively were carried out and thoroughly characterized by spectroscopic and analytical techniques. Interaction of 1a and b and 2a and b with CT DNA by employing UV-vis, florescence, circular dichroic methods and cleavage studies of 1a with pBR322 plasmid, molecular docking were done in order to demonstrate their enantiomeric disposition toward the molecular drug target DNA. Interestingly, these studies unambiguously demonstrated the greater potency of L-enantiomer in comparison to D-enantiomer. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and spectral characterization of Schiff base complexes of Cu(II), Co(II), Zn(II) and VO(IV) containing 4-(4-aminophenyl)morpholine derivatives: Antimicrobial evaluation and anticancer studies

NASA Astrophysics Data System (ADS)

Dhahagani, K.; Mathan Kumar, S.; Chakkaravarthi, G.; Anitha, K.; Rajesh, J.; Ramu, A.; Rajagopal, G.

2014-01-01

Metal(II) chelates of Schiff bases derived from the condensation of 4-morpholinoaniline with substituted salicylaldehyde have been prepared and characterized by 1H NMR, IR, electronic, EPR, and magnetic measurement studies. The complexes are of the type M(X-MPMP)2 [where M = Cu(II), Co(II)), Zn(II), or VO(IV); MPMP = 2-[(4 morpholinophenyl imino) methyl] 4-X-phenol, X = Cl, (L1H), X = Br (L2H)]. Single crystal X-ray crystallography studies confirm the structure of newly synthesized Schiff bases. The Schiff bases act as bidentate monobasic ligands, coordinating through deprotonated phenolic oxygen and azomethine nitrogen atoms. The free ligands and metal complexes are screened for their biopotency. Metal complexes exhibit better activity than ligands. Anticancer activity of ligands and their metal complexes are evaluated in human heptocarcinoma(HepG2) cells. The preliminary bioassay indicates that the Schiff base and its zinc complex exhibit inhibitory activity against the human gastric cancer cell lines.

Nanomolar Copper Enhances Mercury Methylation by Desulfovibrio desulfuricans ND132

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Xia; Johs, Alexander; Zhao, Linduo

Methylmercury (MeHg) is produced by certain anaerobic microorganisms, such as the sulfate-reducing bacterium Desulfovibrio desulfuricans ND132, but environmental factors affecting inorganic mercury [Hg(II)] uptake and methylation remain unclear. We report that the presence of a small amount of copper ions [Cu(II), <100 nM] enhances Hg(II) uptake and methylation by washed cells of ND132, while Hg(II) methylation is inhibited at higher Cu(II) concentrations because of the toxicity of copper to the microorganism. The enhancement or inhibitory effect of Cu(II) is dependent on both time and concentration. The presence of nanomolar concentrations of Cu(II) facilitates rapid uptake of Hg(II) (within minutes) andmore » doubles MeHg production within a 24 h period, but micromolar concentrations of Cu(II) completely inhibit Hg(II) methylation. Metal ions such as zinc [Zn(II)] and nickel [Ni(II)] also inhibit but do not enhance Hg(II) methylation under the same experimental conditions. Furthermore, these observations suggest a synergistic effect of Cu(II) on Hg(II) uptake and methylation, possibly facilitated by copper transporters or metallochaperones in this organism, and highlight the fact that complex environmental factors affect MeHg production in the environment.« less

Nanomolar Copper Enhances Mercury Methylation by Desulfovibrio desulfuricans ND132

DOE PAGES

Lu, Xia; Johs, Alexander; Zhao, Linduo; ...

2018-05-29

Methylmercury (MeHg) is produced by certain anaerobic microorganisms, such as the sulfate-reducing bacterium Desulfovibrio desulfuricans ND132, but environmental factors affecting inorganic mercury [Hg(II)] uptake and methylation remain unclear. We report that the presence of a small amount of copper ions [Cu(II), <100 nM] enhances Hg(II) uptake and methylation by washed cells of ND132, while Hg(II) methylation is inhibited at higher Cu(II) concentrations because of the toxicity of copper to the microorganism. The enhancement or inhibitory effect of Cu(II) is dependent on both time and concentration. The presence of nanomolar concentrations of Cu(II) facilitates rapid uptake of Hg(II) (within minutes) andmore » doubles MeHg production within a 24 h period, but micromolar concentrations of Cu(II) completely inhibit Hg(II) methylation. Metal ions such as zinc [Zn(II)] and nickel [Ni(II)] also inhibit but do not enhance Hg(II) methylation under the same experimental conditions. Furthermore, these observations suggest a synergistic effect of Cu(II) on Hg(II) uptake and methylation, possibly facilitated by copper transporters or metallochaperones in this organism, and highlight the fact that complex environmental factors affect MeHg production in the environment.« less

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

NASA Astrophysics Data System (ADS)

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).

Characterization of a novel chelating resin of enhanced hydrophilicity and its analytical utility for preconcentration of trace metal ions.

PubMed

Islam, Aminul; Laskar, Mohammad Asaduddin; Ahmad, Akil

2010-06-15

A stable extractor of metal ions was synthesized through azo linking of p-hydroxybenzoic acid with Amberlite XAD-4 and was characterized by elemental analyses, infrared spectral and thermal studies. Its water regain value and hydrogen ion capacity were found to be 15.80 and 7.52mmolg(-1), respectively. Both batch and column methods were employed to study the sorption behavior for the metal ions which were subsequently determined by flame atomic absorption spectrophotometry. The optimum pH range for Co(II), Ni(II), Cu(II), Zn(II), and Pb(II) ions were 10.0, 8.0-9.0, 7.0, 7.0-8.0 and 7.0-8.0, respectively. The half-loading time, t(1/2), are 6.0, 8.0, 8.0, 8.0 and 4.0min, respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>75%). The breakthrough capacities for Co(II), Ni(II), Cu(II), Zn(II), and Pb(II) ions were found to be 0.46, 0.43, 0.42, 0.09 and 0.06mmolg(-1) with the corresponding preconcentration factor of 460, 460, 460, 360 and 260, respectively. The limit of preconcentration was in the range of 4.3-7.6microgL(-1). The detection limit for Co(II), Ni(II), Cu(II), Zn(II) and Pb(II) were found to be 0.47, 0.45, 0.50, 0.80, and 1.37microgL(-1), respectively. The Student's t (t-test) values for the analysis of standard reference materials were found to be less than the critical Student's t values at 95% confidence level. The AXAD-4-HBA has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil and fish.

Fluorescence Lifetime Imaging of Physiological Free Cu(II) Levels in Live Cells with a Cu(II)-Selective Carbonic Anhydrase-Based Biosensor

PubMed Central

McCranor, Bryan J.; Szmacinski, Henryk; Zeng, Hui Hui; Stoddard, A.K.; Hurst, Tamiika; Fierke, Carol A.; Lakowicz, J.R.

2014-01-01

Copper is a required trace element that plays key roles in a number of human enzymes, such that copper deficiency or genetic defects in copper transport lead to serious or fatal disease. Rae, et al., had famously predicted that free copper ion levels in the cell cytoplasm were extremely low, typically too low to be observable. We recently developed a variant of human apocarbonic anhydrase II for sensing metal ions that exhibits 25-fold better selectivity for Cu(II) over Zn(II) than the wild type protein, enabling us to accurately measure Cu(II) in the presence of ordinary cellular (picomolar) concentrations of free zinc. We inserted a fluorescent labeled Cu(II)-specific variant of human apocarbonic anhydrase into PC-12 cells and found that the levels are indeed extremely low (in the femtomolar range). We imaged the free Cu(II) levels in living cells by means of frequency-domain fluorescence lifetime microscopy. Implications of this finding are discussed. PMID:24671220

Coordination Chemistry of Linear Oligopyrrolic Fragments Inspired by Heme Metabolites

NASA Astrophysics Data System (ADS)

Gautam, Ritika

Linear oligopyrroles are degradation products of heme, which is converted in the presence of heme oxygenase to bile pigments, such as biliverdin and bilirubin. These tetrapyrrolic oligopyrroles are ubiquitously present in biological systems and find applications in the fields of catalysis and sensing. These linear tetrapyrrolic scaffolds are further degraded into linear tripyrrolic and dipyrrolic fragments. Although these lower oligopyrroles are abundantly present, their coordination chemistry requires further characterization. This dissertation focuses mainly on two classes of bioinspired linear oligopyrroles, propentdyopent and tripyrrindione, and their transition metal complexes, which present a rich ligand-based redox chemistry. Chapter 1 offers an overview of heme degradation to different classes of linear oligopyrroles and properties of their transition metal complexes. Chapter 2 is focused on the tripyrrin-1,14-dione scaffold of the urinary pigment uroerythrin, which coordinates divalent transition metals palladium and copper with square planar geometry. Specifically, the tripyrrin-1, 14-dione ligand binds Cu(II) and Pd(II) as a dianionic organic radical under ambient conditions. The electrochemical study confirms the presence of ligand based redox chemistry, and one electron oxidation or reduction reactions do not alter the planar geometry around the metal center. The X-Ray analysis and the electron paramagnetic resonance (EPR) studies of the complexes in the solid and solution phase reveals intermolecular interactions between the ligand based unpaired electrons and therefore formation of neutral pi-pi dimers. In Chapter 3, the antioxidant activity and the fluorescence sensor properties of the tripyrrin-1,14-dione ligand in the presence of superoxide are described. We found that the tripyrrindione ligand undergoes one-electron reduction in the presence of the superoxide radical anion (O2•- ) to form highly fluorescent H3TD1•- radical anion, which emits at 635 nm. This reaction also explains the antioxidant properties of the linear tripyrrin-1,14-dione ligand, which acts as a scavenger of O2•-. In Chapter 4, the zinc binding properties of the tripyrrin-1,14-dione ligand are described. The tripyrrolic ligand coordinates as a dianionic ligand with the divalent Zn(II) ion in both organic and aqueous buffered conditions. The complex formed is highly fluorescent with a long wavelength emission band at 648 nm. The X-Ray crystallography analysis indicates the existence of dinuclear complex [Zn(TD1•)(H2O)]2, featuring a distorted square planar geometry around the Zn(II) center. In Chapter 5, the coordination chemistry of the dipyrrin-1,9-dione fragment of propentdyopent ligand is shown with a series of transition metals like (e.g., Co(II), Ni(II), Cu(II) and Zn(II)), which form homoleptic tetrahedral complexes. The spectroscopic and electrochemical characterization confirms that the complexes shows ligand-based redox chemistry and acts as reservoirs for unpaired electrons. Chapter 6 describes the formation of the fluorescent BODIPY complex of propentdyopent ligand. The dipyrrin-1,9-dione scaffold of heme metabolite propendyopent undergoes a one-pot reaction with borontrifluoride etherate in toluene to form a green fluorescent [(pdp)BF2] complex. Spectroscopic studies reveal that the meso-unsubstituted [(pdp)BF2] complex is stable in tetrahydrofuran and has a quantum yield of 0.13. Electrochemical studies confirm that the complex undergoes ligand-based reduction and acts as a host for an unpaired electron.

Synthesis, characterization and biological activity of Cu(II), Ni(II) and Zn(II) complexes of biopolymeric Schiff bases of salicylaldehydes and chitosan.

PubMed

de Araújo, Eliene Leandro; Barbosa, Hellen Franciane Gonçalves; Dockal, Edward Ralph; Cavalheiro, Éder Tadeu Gomes

2017-02-01

Schiff bases have been prepared from biopolymer chitosan and salicylaldehyde, 5-methoxysalicylaldehyde, and 5-nitrosalicylaldehyde. Ligands were synthesized in a 1:1.5mol ratio, and their Cu(II), Ni(II) and Zn(II) complexes in a 1:1mol ratio (ligand:metal). Ligands were characterized by 1 H NMR and FTIR, resulting in degrees of substitution from 43.7 to 78.7%. Complexes were characterized using FTIR, electronic spectra, XPRD. The compounds were confirmed by the presence of an imine bond stretching in the 1630-1640cm -1 and νMetal-N and νMetal-O at <600cm -1 . Electronic spectra revealed that both Cu(II) and Ni(II) complexes present a square plane geometry. The crystallinity values were investigated by X-ray powder diffraction. Thermal behavior of all compounds was evaluated by TGA/DTG and DTA curves with mass losses related to dehydration and decomposition, with characteristic events for ligand and complexes. Schiff base complexes presented lower thermal stability and crystallinity than the starting chitosan. Residues were the metallic oxides as confirmed by XPRD, whose amounts were used in the calculation of the percentage of complexed metal ions. Surface morphologies were analyzed with SEM-EDAX. Preliminary cytotoxicity tests were performed using MTT assay with HeLa cells. Despite the differences in solubility, the free bases presented relatively low toxicity. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, characterization and anti-microbial evaluation of Cu(II), Ni(II), Pt(II) and Pd(II) sulfonylhydrazone complexes; 2D-QSAR analysis of Ni(II) complexes of sulfonylhydrazone derivatives

NASA Astrophysics Data System (ADS)

Özbek, Neslihan; Alyar, Saliha; Alyar, Hamit; Şahin, Ertan; Karacan, Nurcan

2013-05-01

Copper(II), nickel(II), platinum(II) and palladium(II) complexes with 2-hydroxy-1-naphthaldehyde-N-methylpropanesulfonylhydrazone (nafpsmh) derived from propanesulfonic acid-1-methylhydrazide (psmh) were synthesized, their structure were identified, and antimicrobial activity of the compounds was screened against three Gram-positive and three Gram-negative bacteria. The results of antimicrobial studies indicate that Pt(II) and Pd(II) complexes showed the most activity against all bacteria. The crystal structure of 2-hydroxy-1-naphthaldehyde-N-methylpropanesulfonylhydrazone (nafpsmh) was also investigated by X-ray analysis. A series of Ni(II) sulfonyl hydrazone complexes (1-33) was synthesized and tested in vitro against Escherichia coli and Staphylococcus aureus. Their antimicrobial activities were used in the QSAR analysis. Four-parameter QSAR models revealed that nucleophilic reaction index for Ni and O atoms, and HOMO-LUMO energy gap play key roles in the antimicrobial activity.

Palladium(II)-Catalyzed Annulation between ortho-Alkenylphenols and Allenes. Key Role of the Metal Geometry in Determining the Reaction Outcome.

PubMed

Casanova, Noelia; Del Rio, Karina P; García-Fandiño, Rebeca; Mascareñas, José L; Gulías, Moisés

2016-05-06

2-Alkenylphenols react with allenes, upon treatment with catalytic amounts of Pd(II) and Cu(II), to give benzoxepine products in high yields and with very good regio- and diastereoselectivities. This contrasts with the results obtained with Rh catalysts, which provided chromene-like products through a pathway involving a β-hydrogen elimination step. Computational studies suggest that the square planar geometry of the palladium is critical to favor the reductive elimination process required for the formation of the oxepine products.

Composition, Characterization and Antibacterial activity of Mn(II), Co(II),Ni(II), Cu(II) Zn(II) and Cd(II) mixed ligand complexes Schiff base derived from Trimethoprim with 8-Hydroxy quinoline

NASA Astrophysics Data System (ADS)

Numan, Ahmed T.; Atiyah, Eman M.; Al-Shemary, Rehab K.; Ulrazzaq, Sahira S. Abd

2018-05-01

New Schiff base ligand 2-((4-amino-5-(3, 4, 5-trimethoxybenzyl) pyrimidin-2-ylimino) (phenyl)methyl)benzoic acid] = [HL] was synthesized using microwave irradiation trimethoprim and 2-benzoyl benzoic acid. Mixed ligand complexes of Mn((II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) are reacted in ethanol with Schiff base ligand [HL] and 8-hydroxyquinoline [HQ] then reacted with metal salts in ethanol as a solvent in (1:1:1) ratio. The ligand [HL] is characterized by FTIR, UV-Vis, melting point, elemental microanalysis (C.H.N), 1H-NMR, 13C-NMR, and mass spectra. The mixed ligand complexes are characterized by infrared spectra, electronic spectra, (C.H.N), melting point, atomic absorption, molar conductance and magnetic moment measurements. These measurements indicate that the ligand [HL] coordinates with metal (II) ion in a tridentate manner through the oxygen and nitrogen atoms of the ligand, octahedral structures are suggested for these complexes. Antibacterial activity of the ligands [HL], [HQ] and their complexes are studied against (gram positive) and (gram negative) bacteria.

Removal of heavy metals from fly ash leachate using combined bioelectrochemical systems and electrolysis.

PubMed

Tao, Hu-Chun; Lei, Tao; Shi, Gang; Sun, Xiao-Nan; Wei, Xue-Yan; Zhang, Li-Juan; Wu, Wei-Min

2014-01-15

Based on environmental and energetic analysis, a novel combined approach using bioelectrochemical systems (BES) followed by electrolysis reactors (ER) was tested for heavy metals removal from fly ash leachate, which contained high detectable levels of Zn, Pb and Cu according to X-ray diffraction analysis. Acetic acid was used as the fly ash leaching agent and tested under various leaching conditions. A favorable condition for the leaching process was identified to be liquid/solid ratio of 14:1 (w/w) and leaching duration 10h at initial pH 1.0. It was confirmed that the removal of heavy metals from fly ash leachate with the combination of BESs and ER is feasible. The metal removal efficiency was achieved at 98.5%, 95.4% and 98.1% for Cu(II), Zn(II), and Pb(II), respectively. Results of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) indicated that Cu(II) was reduced and recovered mainly as metal Cu on cathodes related to power production, while Zn(II) and Pb(II) were not spontaneously reduced in BESs without applied voltage and basically electrolyzed in the electrolysis reactors. Copyright © 2013 Elsevier B.V. All rights reserved.

Electron Spin Resonance Studies of Carbonic Anhydrase: Transition Metal Ions and Spin-Labeled Sulfonamides*

PubMed Central

Taylor, June S.; Mushak, Paul; Coleman, Joseph E.

1970-01-01

Electron spin resonance (esr) spectra of Cu(II) and Co(II) carbonic anhydrase, and a spin-labeled sulfonamide complex of the Zn(II) enzyme, are reported. The coordination geometry of Cu(II) bound in the enzyme appears to have approximately axial symmetry. Esr spectra of enzyme complexes with metal-binding anions also show axial symmetry and greater covalency, in the order ethoxzolamide < SH- < N3- ≤ CN-. Well-resolved superhyperfine structure in the spectrum of the cyanide complex suggests the presence of two, and probably three, equivalent nitrogen ligands from the protein. Esr spectra of the Co(II) enzyme and its complexes show two types of Co(II) environment, one typical of the native enzyme and the 1:1 CN- complex, and one typical of a 2:1 CN- complex. Co(II) in the 2:1 complex appears to be low-spin and probably has a coordination number of 5. Binding of a spin-labeled sulfonamide to the active center immobilizes the free radical. The similarity of the esr spectra of spin-labeled Zn(II) and Co(II) carbonic anhydrases suggests that the conformation at the active center is similar in the two metal derivatives. PMID:4320976

Titania-Coated Silica Alone and Modified by Sodium Alginate as Sorbents for Heavy Metal Ions

NASA Astrophysics Data System (ADS)

Kołodyńska, D.; Gęca, M.; Skwarek, E.; Goncharuk, O.

2018-04-01

The novel organic-inorganic biohybrid composite adsorbent was synthesized based on nanosized silica-titania modified with alginate within the development of effective adsorbent for heavy metal ions. Effects of metal species Cu(II), Zn(II), Cd(II), and Pb(II); concentrations; pH; temperature; and adsorption onto titania-coated silica (ST20) initial or modified by sodium alginate (ST20-ALG) were studied. The equilibrium and kinetic data of metal ions adsorption were analyzed using Langmuir and Freundlich adsorption models and kinetic models: pseudo first order, pseudo second order, intraparticle kinetic model, and Elovich. The maximum sorption capacities observed were higher for the ST20-ALG composite compared to the initial ST20 oxide for all studied metal ions, namely their values for ST20-ALG were 22.44 mg g- 1 for Cu(II) adsorption, 19.95 mg g- 1 for Zn(II), 18.85 mg g- 1 for Cd(II), and 32.49 mg g- 1 for Pb(II). Structure and properties of initial silica-titania ST20 and modified by sodium alginate ST20-ALG adsorbents were analyzed using nitrogen adsorption/desorption isotherms, ATR-FTIR, SEM-EDS, and pHpzc techniques.

Antimicrobial and mutagenic activity of some carbono- and thiocarbonohydrazone ligands and their copper(II), iron(II) and zinc(II) complexes.

PubMed

Bacchi, A; Carcelli, M; Pelagatti, P; Pelizzi, C; Pelizzi, G; Zani, F

1999-06-15

Several mono- and bis- carbono- and thiocarbonohydrazone ligands have been synthesised and characterised; the X-ray diffraction analysis of bis(phenyl 2-pyridyl ketone) thiocarbonohydrazone is reported. The coordinating properties of the ligands have been studied towards Cu(II), Fe(II), and Zn(II) salts. The ligands and the metal complexes were tested in vitro against Gram positive and Gram negative bacteria, yeasts and moulds. In general, the bisthiocarbonohydrazones possess the best antimicrobial properties and Gram positive bacteria are the most sensitive microorganisms. Bis(ethyl 2-pyridyl ketone) thiocarbonohydrazone, bis(butyl 2-pyridyl ketone)thiocarbonohydrazone and Cu(H2nft)Cl2 (H2nft, bis(5-nitrofuraldehyde)thiocarbonohydrazone) reveal a strong activity with minimum inhibitory concentrations of 0.7 microgram ml-1 against Bacillus subtilis and of 3 micrograms ml-1 against Staphylococcus aureus. Cu(II) complexes are more effective than Fe(II) and Zn(II) ones. All bisthiocarbono- and carbonohydrazones are devoid of mutagenic properties, with the exception of the compounds derived from 5-nitrofuraldehyde. On the contrary a weak mutagenicity, that disappears in the copper complexes, is exhibited by monosubstituted thiocarbonohydrazones.

Al(III), Pd(II), and Zn(II) phthalocyanines for inactivation of dental pathogen Aggregatibacter actinomycetemcomitans as planktonic and biofilm-cultures

NASA Astrophysics Data System (ADS)

Kussovski, V.; Mantareva, V.; Angelov, I.; Avramov, L.; Popova, E.; Dimitrov, S.

2012-06-01

The Gram-negative, oral bacterium Aggregatibacter actinomycetemcomitans has been implicated as the causative agent of several forms of periodontal disease in humans. The new periodontal disease treatments are emergence in order to prevent infection progression. Antimicrobial photodynamic therapy (a-PDT) can be a useful tool for this purpose. It involves the use of light of specific wavelength to activate a nontoxic photosensitizing agent in the presence of oxygen for eradication of target cells, and appears effective in photoinactivation of microorganisms. The phthalocyanine metal complexes of Pd(II)- (PdPcC) and Al(III)- (AlPc1) were evaluated as photodynamic sensitizers towards a dental pathogen A. actinomycetemcomitans in comparison to the known methylpyridyloxy-substituted Zn(II) phthalocyanine (ZnPcMe). The planktonic and biofilm-cultivated species of A. actinomycetemcomitans were treated. The photophysical results showed intensive and far-red absorbance with high tendency of aggregation for Pd(II)-phthalocyanine. The dark toxicities of both photosensitizers were negligible at concentrations used (< 0.5 log decrease of viable cells). The photodynamic response for planktonic cultured bacteria was full photoinactivation after a-PDT with ZnPcMe. In case of the newly studied complexes, the effect was lower for PdPcC (4 log) as well as for AlPc1 (1.5-2 log). As it is known the bacterial biofilms were more resistant to a-PDT, which was confirmed for A. actinomycetemcomitans biofilms with 3 log reductions of viable cells after treatment with ZnPcMe and approximately 1 log reduction of biofilms after PdPcC and AlPc1. The initial results suggest that a-PDT can be useful for effective inactivation of dental pathogen A. actinomycetemcomitans.

Adsorption of transition metal ions from aqueous solutions onto a novel silica gel matrix inorganic-organic composite material.

PubMed

Yin, Ping; Xu, Qiang; Qu, Rongjun; Zhao, Guifang; Sun, Yanzhi

2010-01-15

A novel inorganic-organic composite material silica gel microspheres encapsulated by imidazole functionalized polystyrene (SG-PS-azo-IM) has been synthesized and characterized. This composite material was used to investigate the adsorption of Cr(III), Mn(II), Fe(III), Ni(II), Cu(II), Zn(II), Hg(II), Pb(II), Pd(II), Pt(II), Ag(I), and Au(III) from aqueous solutions, and the research results displayed that SG-PS-azo-IM has the highest adsorption capacity for Au(III). Langmuir and Freundlich isotherm models were applied to analyze the experimental data, the best interpretation for the experimental data was given by the Langmuir isotherm equation, and the maximum adsorption capacity for Au(III) is 1.700 mmol/g. The adsorption selectivity, the dynamic adsorption and desorption properties of SG-PS-azo-IM for Au(III) have also been studied. The results showed that SG-PS-azo-IM had excellent adsorption for Au(III) in four binary ions system, especially in the systems of Au(III)-Zn(II) and Au(III)-Cu(II), and almost Au(III) could be desorbed with the eluent solution of 0.5% thiourea in 1 mol/L HCl. Moreover, this novel composite material was used to preconcentrate Au(III) before its determination by flame atomic adsorption spectrometry. In the initial concentration range of 0.10-0.20 microg/mL, multiple of enrichment could reach 5.28. Thus, silica gel encapsulated by polystyrene coupling with imidazole (SG-PS-azo-IM) is favorable and useful for the removal of transition metal ions, and the high adsorption capacity makes it a good promising candidate material for Au(III) removal.

Spectral, optical and cytotoxicity studies on 2-isonicotinoyl-N-phenylhydrazine-1-carboxamide(H3L) and some of its metal complexes

NASA Astrophysics Data System (ADS)

Hosny, Nasser M.; Hassan, Nader Y.; Mahmoud, Heba M.; Abdel-Rhman, Mohamed H.

2018-03-01

The ligand 2-isonicotinoyl-N-phenylhydrazine-1-carboxamide (H3L) and its metal complexes with Co(II), Ni(II), Cu(II) and Zn(II) acetates have been synthesized. The isolated compounds have been characterized by elemental analyses, FT-IR, 1H NMR, 13C NMR, ESR, mass, electronic spectra, electrical conductivity, effective magnetic moments and thermal analyses. The free organic ligand exists in the keto form, but in the metal complexes, it coordinates in the enol form. Four coordinated species were suggested for all the isolated metal complexes. The measured optical band gap values confirmed the presence of direct electronic transition and the semi-conductivity of the compounds. The ligand and its Zn(II) complex were examined as cytotoxic agent against HCT-116 and HePG-2. The ligand showed very strong cytotoxic effect against HePG-2, but moderate cytotoxicity against HCT-116. Zn(II) complex showed weak cytotoxicity against the two cell lines.

Synthesis, Characterization and Antibacterial Activity of 1,4-di[ aminomethylene carboxyl] phenylene (H2L) and its Complexes Co(II), Cu (II), Zn(II) and Cd (II)

NASA Astrophysics Data System (ADS)

Sultan, J. S.; Fezea, S. M.; Mousa, F. H.

2018-05-01

A binucleating tetradentate Schiff base ligand, 1,4- di[amino methylene carboxylic] phenylene (H2L) and its forth new binuclear complexes [Co(II), Cu(II), Zn(II) and Cd(II)] were prepared via reaction metal (II) chloride with ligand (H2L) using 2:1 (M:L) in ethanol solvent. The new ligand (H2L) and its complexes were characterized by elemental microanalysis (C.H.N), atomic absorption, chloride content, molar conductance’s magnetic susceptibility, FTIR UV- Vis spectral and, 1H, 13 C- NMR (for H2L). The antibacterial activity with bacteria activity with bacteria, Staphylococcus aureus, Bacillus and Esccherichia Coli were studied.

Binaphthyl-containing Schiff base complexes with carboxyl groups for dye sensitized solar cell: An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Tsaturyan, Arshak; Machida, Yosuke; Akitsu, Takashiro; Gozhikova, Inna; Shcherbakov, Igor

2018-06-01

We report on synthesis and characterization of binaphthyl containing Schiff base Ni(II), Cu(II), and Zn(II) complexes as promising photosensitizers for dye-sensitized solar cells (DSSC). Based on theoretical and experimental data, the possibility of their application in DSSC was confirmed. To our knowledge, we find dye performance of complex is steric and rigid structure widely spread to efficiency. The spatial and electronic structures of the complexes were studied by means of the quantum chemical modeling using DFT and TD-DFT approaches. The adsorption energies of the complexes on TiO2 cluster were calculated and appeared to be very close in value. The Zn(II) complex has the biggest value of molar extinction.

Dithizone modified magnetic nanoparticles for fast and selective solid phase extraction of trace elements in environmental and biological samples prior to their determination by ICP-OES.

PubMed

Cheng, Guihong; He, Man; Peng, Hanyong; Hu, Bin

2012-01-15

A fast and simple method for analysis of trace amounts of Cr(III), Cu(II), Pb(II) and Zn(II) in environmental and biological samples was developed by combining magnetic solid phase extraction (MSPE) with inductively coupled plasma-optical emission spectrometry (ICP-OES) detection. Dithizone modified silica-coated magnetic Fe(3)O(4) nanoparticles (H(2)Dz-SCMNPs) were prepared and used for MSPE of trace amounts of Cr(III), Cu(II), Pb(II) and Zn(II). The prepared magnetic nanoparticles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). The factors affecting the extraction of the target metal ions such as pH, sample volume, eluent, and interfering ions had been investigated and the adsorption mechanism of the target metals on the self-prepared H(2)Dz-SCMNPs was investigated by FT-IR and X-ray photo electron spectroscopy (XPS). Under the optimized conditions, the detection limits of the developed method for Cr(III), Cu(II), Pb(II) and Zn(II) were 35, 11, 62, and 8ngL(-1), respectively, with the enrichment factor of 100. The relative standard deviations (RSDs, c=10μgL(-1), n=7) were in the range of 1.7-3.1% and the linear range was 0.1-100μgL(-1). The proposed method had been validated by two certified reference materials (GSBZ50009-88 environmental water and GBW07601 human hair), and the determined values were in good agreement with the certified values. The method was also applied for the determination of trace metals in real water and human hair samples with recoveries in the range of 85-110% for the spiked samples. The developed MSPE-ICP-OES method has the advantages of simplicity, rapidity, selectivity, high extraction efficiency and is suitable for the analysis of samples with large volume and complex matrix. Copyright © 2011 Elsevier B.V. All rights reserved.

New tailored substituted benzothiazole Schiff base Cu(II)/Zn(II) antitumor drug entities: effect of substituents on DNA binding profile, antimicrobial and cytotoxic activity.

PubMed

Zehra, Siffeen; Shavez Khan, Mohammad; Ahmad, Iqbal; Arjmand, Farukh

2018-05-07

New tailored Cu(II) & Zn(II) metal-based antitumor drug entities were synthesized from substituted benzothiazole o‒vanillin Schiff base ligands. The complexes were thoroughly characterized by elemental analysis, spectroscopic studies {IR, 1 H & 13 C NMR, ESI-MS, EPR} and magnetic susceptibility measurements. The structure activity relationship (SAR) studies of benzothiazole Cu(II) & Zn(II) complexes having molecular formulas [C 30 H 22 CuN 5 O 7 S 2 ], [C 30 H 20 Cl 2 CuN 5 O 7 S 2 ], [C 30 H 20 CuF 2 N 5 O 7 S 2 ], [C 30 H 22 N 4 O 4 S 2 Zn], [C 30 H 20 Cl 2 N 4 O 4 S 2 Zn], and [C 30 H 20 F 2 N 5 O 7 S 2 Zn], with CT‒DNA were performed by employing absorption, emission titrations, and hydrodynamic measurements. The DNA binding affinity was quantified by K b and K sv values which gave higher binding propensity for chloro-substituted Cu(II) [C 30 H 20 Cl 2 CuN 5 O 7 S 2 ] complex, suggestive of groove binding mode with subtle partial intercalation. Molecular properties and drug likeness profile were assessed for the ligands and all the Lipinski's rules were found to be obeyed. The antimicrobial potential of ligands and their Cu(II) & Zn(II) complexes were screened against some notably important pathogens viz., E. coli, S. aureus, P. aeruginosa, B. subtilis, and C. albicans. The cytotoxicity of the complexes [C 30 H 20 Cl 2 CuN 5 O 7 S 2 ], [C 30 H 20 CuF 2 N 5 O 7 S 2 ], [C 30 H 20 Cl 2 N 4 O 4 S 2 Zn], and [C 30 H 20 F 2 N 5 O 7 S 2 Zn] were evaluated against five human cancer cell lines viz., MCF‒7 (breast), MIA‒PA‒CA‒2 (pancreatic), HeLa (cervix) and Hep‒G2 (Hepatoma) and A498 (Kidney) by SRB assay which revealed that chloro-substituted [C 30 H 20 Cl 2 CuN 5 O 7 S 2 ] complex, exhibited pronounced specific cytotoxicity with GI 50 value of 4.8 μg/ml against HeLa cell line. Molecular docking studies were also performed to explore the binding modes and orientation of the complexes in the DNA helix.

Multiply Intercalator-Substituted Cu(II) Cyclen Complexes as DNA Condensers and DNA/RNA Synthesis Inhibitors.

PubMed

Hormann, Jan; Malina, Jaroslav; Lemke, Oliver; Hülsey, Max J; Wedepohl, Stefanie; Potthoff, Jan; Schmidt, Claudia; Ott, Ingo; Keller, Bettina G; Brabec, Viktor; Kulak, Nora

2018-05-07

Many drugs that are applied in anticancer therapy such as the anthracycline doxorubicin contain DNA-intercalating 9,10-anthraquinone (AQ) moieties. When Cu(II) cyclen complexes were functionalized with up to three (2-anthraquinonyl)methyl substituents, they efficiently inhibited DNA and RNA synthesis resulting in high cytotoxicity (selective for cancer cells) accompanied by DNA condensation/aggregation phenomena. Molecular modeling suggests an unusual bisintercalation mode with only one base pair between the two AQ moieties and the metal complex as a linker. A regioisomer, in which the AQ moieties point in directions unfavorable for such an interaction, had a much weaker biological activity. The ligands alone and corresponding Zn(II) complexes (used as redox inert control compounds) also exhibited lower activity.

Structural, theoretical and corrosion inhibition studies on some transition metal complexes derived from heterocyclic system

NASA Astrophysics Data System (ADS)

Gupta, Shraddha Rani; Mourya, Punita; Singh, M. M.; Singh, Vinod P.

2017-06-01

A Schiff base, (E)-N‧-((1H-indol-3-yl)methylene)-2-aminobenzohydrazide (Iabh) and its Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. These compounds have been characterized by different physico-chemical and spectroscopic tools (UV-Vis, IR, NMR and ESI-Mass). The molecular structure of Iabh is determined by single crystal X-ray diffraction technique. The ligand Iabh displays E-configuration about the >Cdbnd N- bond. The structure of ligand is stabilized by intra-molecular H-bonding. In all the metal complexes the ligand coordinates through azomethine-N and carbonyl-O resulting a distorted octahedral geometry for Mn(II), Co(II) and Cu(II) complexes in which chloride ions occupy axial positions. Ni(II) and Zn(II) complexes, however, form 4-coordinate distorted square planer and tetrahedral geometry around metal ion, respectively. The structures of the complexes have been satisfactorily modeled by calculations based on density functional theory (DFT) and time dependent-DFT (TD-DFT). The corrosion inhibition study of the compounds have been performed against mild steel in 0.5 M H2SO4 solution at 298 K by using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). They show appreciable corrosion inhibition property.

Chitosan film loaded with silver nanoparticles-sorbent for solid phase extraction of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II).

PubMed

Djerahov, Lubomir; Vasileva, Penka; Karadjova, Irina; Kurakalva, Rama Mohan; Aradhi, Keshav Krishna

2016-08-20

The present study describes the ecofriendly method for the preparation of chitosan film loaded with silver nanoparticles (CS-AgNPs) and application of this film as efficient sorbent for separation and enrichment of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II). The stable CS-AgNPs colloid was prepared by dispersing the AgNPs sol in chitosan solution at appropriate ratio and further used to obtain a cast film with very good stability under storage and good mechanical strength for easy handling in aqueous medium. The incorporation of AgNPs in the structure of CS film and interaction between the polymer matrix and nanoparticles were confirmed by UV-vis and FTIR spectroscopy. The homogeneously embedded AgNPs (average diameter 29nm, TEM analysis) were clearly observed throughout the film by SEM. The CS-AgNPs nanocomposite film shows high sorption activity toward trace metals under optimized chemical conditions. The results suggest that the CS-AgNPs nanocomposite film can be feasibly used as a novel sorbent material for solid-phase extraction of metal pollutants from surface waters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Using SEM-EDX and ICP-OES to investigate the elemental composition of green macroalga Vaucheria sessilis.

PubMed

Michalak, Izabela; Marycz, Krzysztof; Basińska, Katarzyna; Chojnacka, Katarzyna

2014-01-01

The biomass of Vaucheria sessilis forms algal mats in many freshwaters. There is a need to find the method of algal biomass utilization. Vaucheria sessilis is a rich source of micro- and macronutrients and can be used as a soil amendment. In the paper, the elemental composition of enriched, via bioaccumulation process, macroalga was investigated. For this purpose, two independent techniques were used: scanning electron microscopy with an energy dispersive X-ray analytical system (SEMEDX) and inductively coupled plasma optical emission spectroscopy (ICP-OES). The biomass was exposed to two microelemental solutions, with Cu(II) and Zn(II) ions. After two weeks of the experiment, macroalga accumulated 98.5 mg of Zn(II) ions in 1 g of dry biomass and 68.9 mg g(-1) of Cu(II) ions. Micrographs performed by SEM proved that bioaccumulation occurred. Metal ions were bound on the surface and in the interior of cells. Mappings of all cations showed that in the case of the surface of biomass (biosorption), the elements constituted aggregations and in the case of the cross section (bioaccumulation) they were evenly distributed. The algal biomass with permanently bound microelements can find an application in many branches of the industry (feed, natural fertilizers, etc.).

Determination of Zinc, Cadmium, Lead, Copper and Silver Using a Carbon Paste Electrode and a Screen Printed Electrode Modified with Chromium(III) Oxide

PubMed Central

Koudelkova, Zuzana; Syrovy, Tomas; Ambrozova, Pavlina; Moravec, Zdenek; Kubac, Lubomir; Hynek, David; Adam, Vojtech

2017-01-01

In this study, the preparation and electrochemical application of a chromium(III) oxide modified carbon paste electrode (Cr-CPE) and a screen printed electrode (SPE), made from the same material and optimized for the simple, cheap and sensitive simultaneous determination of zinc, cadmium, lead, copper and the detection of silver ions, is described. The limits of detection and quantification were 25 and 80 µg·L−1 for Zn(II), 3 and 10 µg·L−1 for Cd(II), 3 and 10 µg·L−1 for Pb(II), 3 and 10 µg·L−1 for Cu(II), and 3 and 10 µg·L−1 for Ag(I), respectively. Furthermore, this promising modification was transferred to the screen-printed electrode. The limits of detection for the simultaneous determination of zinc, cadmium, copper and lead on the screen printed electrodes were found to be 350 µg·L−1 for Zn(II), 25 µg·L−1 for Cd(II), 3 µg·L−1 for Pb(II) and 3 µg·L−1 for Cu(II). Practical usability for the simultaneous detection of these heavy metal ions by the Cr-CPE was also demonstrated in the analyses of wastewaters. PMID:28792450

Determination of Zinc, Cadmium, Lead, Copper and Silver Using a Carbon Paste Electrode and a Screen Printed Electrode Modified with Chromium(III) Oxide.

PubMed

Koudelkova, Zuzana; Syrovy, Tomas; Ambrozova, Pavlina; Moravec, Zdenek; Kubac, Lubomir; Hynek, David; Richtera, Lukas; Adam, Vojtech

2017-08-09

In this study, the preparation and electrochemical application of a chromium(III) oxide modified carbon paste electrode (Cr-CPE) and a screen printed electrode (SPE), made from the same material and optimized for the simple, cheap and sensitive simultaneous determination of zinc, cadmium, lead, copper and the detection of silver ions, is described. The limits of detection and quantification were 25 and 80 µg·L -1 for Zn(II), 3 and 10 µg·L -1 for Cd(II), 3 and 10 µg·L -1 for Pb(II), 3 and 10 µg·L -1 for Cu(II), and 3 and 10 µg·L -1 for Ag(I), respectively. Furthermore, this promising modification was transferred to the screen-printed electrode. The limits of detection for the simultaneous determination of zinc, cadmium, copper and lead on the screen printed electrodes were found to be 350 µg·L -1 for Zn(II), 25 µg·L -1 for Cd(II), 3 µg·L -1 for Pb(II) and 3 µg·L -1 for Cu(II). Practical usability for the simultaneous detection of these heavy metal ions by the Cr-CPE was also demonstrated in the analyses of wastewaters.

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

NASA Astrophysics Data System (ADS)

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.

Using SEM-EDX and ICP-OES to Investigate the Elemental Composition of Green Macroalga Vaucheria sessilis

PubMed Central

Michalak, Izabela; Marycz, Krzysztof; Basińska, Katarzyna; Chojnacka, Katarzyna

2014-01-01

The biomass of Vaucheria sessilis forms algal mats in many freshwaters. There is a need to find the method of algal biomass utilization. Vaucheria sessilis is a rich source of micro- and macronutrients and can be used as a soil amendment. In the paper, the elemental composition of enriched, via bioaccumulation process, macroalga was investigated. For this purpose, two independent techniques were used: scanning electron microscopy with an energy dispersive X-ray analytical system (SEMEDX) and inductively coupled plasma optical emission spectroscopy (ICP-OES). The biomass was exposed to two microelemental solutions, with Cu(II) and Zn(II) ions. After two weeks of the experiment, macroalga accumulated 98.5 mg of Zn(II) ions in 1 g of dry biomass and 68.9 mg g−1 of Cu(II) ions. Micrographs performed by SEM proved that bioaccumulation occurred. Metal ions were bound on the surface and in the interior of cells. Mappings of all cations showed that in the case of the surface of biomass (biosorption), the elements constituted aggregations and in the case of the cross section (bioaccumulation) they were evenly distributed. The algal biomass with permanently bound microelements can find an application in many branches of the industry (feed, natural fertilizers, etc.). PMID:25180212

Synthesis, spectroscopic, thermal and DFT calculations of 2-(3-amino-2-hydrazono-4-oxothiazolidin-5-yl) acetic acid binuclear metal complexes

NASA Astrophysics Data System (ADS)

Hassan, Walid M. I.; Badawy, M. A.; Mohamed, Gehad G.; Moustafa, H.; Elramly, Salwa

2013-07-01

The binuclear complexes of 2-(3-amino-2-hydrazono-4-oxothiazolidin-5-yl) acetic acid ligand (HL) with Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) ions were prepared and their stoichiometry was determined by elemental analysis. The stereochemistry of the studied series of metal complexes was established by analyzing their infrared, 1H NMR spectra and the magnetic moment measurements. According to the elemental analysis data, the complexes were found to have the formulae [Fe2L(H2O)8]Cl5 and [M2L(H2O)8]Cl3 (M = Co(II), Ni(II), Cu(II) and Zn(II)). The present analyses demonstrate that all metal ions coordinated to the ligand via O(9), O(11), N(16) and N(18) atoms. Thermal decomposition studies of the ligand-metal complexes have been performed to verify the status of water molecules present in these metal complexes and their general decomposition pattern. Density Functional Theory (DFT) calculations at the B3LYP/6-31G* level of theory have been carried out to investigate the equilibrium geometry of the ligand and complexes. Moreover, charge density distribution, extent of distortion from regular geometry, dipole moment and orientation have been performed and discussed.

Potentiometric and spectroscopic study of the interaction of 3d transition metal ions with inositol hexakisphosphate

NASA Astrophysics Data System (ADS)

Veiga, Nicolás; Macho, Israel; Gómez, Kerman; González, Gabriel; Kremer, Carlos; Torres, Julia

2015-10-01

Among myo-inositol phosphates, the most abundant in nature is the myo-inositol hexakisphosphate, InsP6. Although it is known to be vital to cell functioning, the biochemical research into its metabolism needs chemical and structural analysis of all the protonation, complexation and precipitation processes that it undergoes in the biological media. In view of its high negative charge at physiological level, our group has been leading a thorough research into the InsP6 chemical and structural behavior in the presence of the alkali and alkaline earth metal ions essential for life. The aim of this article is to extend these studies, dealing with the chemical and structural features of the InsP6 interaction with biologically relevant 3d transition metal ions (Fe(II), Fe(III), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)), in a non-interacting medium and under simulated physiological conditions. The metal-complex stability constants were determined by potentiometry, showing under ligand-excess conditions the formation of mononuclear species in different protonation states. Under metal ion excess, polymetallic species were detected for Fe(II), Fe(III), Zn(II) and Cu(II). Additionally, the 31P NMR and UV-vis spectroscopic studies provided interesting structural aspects of the strong metal ion-InsP6 interaction.

Synthesis and spectroscopic studies on the new Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transition metal complexes. Influence on biologically active peptides-regulating aminopeptidases.

PubMed

Hueso-Ureña, Francisco; Illán-Cabeza, Nuria A; Moreno-Carretero, Miguel N; Martínez-Martos, José M; Ramírez-Expósito, María J

2003-04-01

The synthesis, spectroscopic (IR, 1H and 13C NMR, UV-Vis-NIR, EPR), magnetic measurements and biological studies of a number of complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Au(III) and Hg(II) of the Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol and 5-aminouracil, ((5-[[(3-[[(2,4-dioxopyrimidin-5(1H,3H)-yl)imino]methyl]-2-hydroxy-5-methylphenyl)methylene]amino]pyrimidine-2,4(1H,3H)-dione, hereafter denoted as BDF5AU) are reported. In all cases, the complexes appear to be monomeric. The deprotonated ligand in the phenolic oxygen atom shows a tridentate coordination mode through the two azomethine nitrogen atoms and the phenolic oxygen atom. The coordination of the neutral ligand takes place through the phenolic oxygen atom and one azomethine nitrogen atom and the carbonylic oxygen atom in fourth position of one uracil ring. The biological properties of some perchlorate complexes on the activity of some neutral, acid, basic and omega aminopeptidases (AP) are assayed, demonstrating a general inhibitory effect. Neutral and basic AP are mainly inhibited by Cu(II), Ni(II) and Cd(II) complexes, although tyrosyl-AP is activated by Zn(II) complex. Glutamyl-AP but not aspartyl-AP is inhibited by all the complexes assayed excepting Zn(II) complex. Finally, omega AP is inhibited by Ni(II) and Cd(II) complexes. Copyright 2003 Elsevier Science Inc.

Synthesis, characterization and electrochemical studies of heterometallic manganese(IV)-zinc(II) and manganese(IV)-copper(II) complexes derived from bis(2-hydroxy-1-naphthaldehyde)oxaloyldihydrazone

NASA Astrophysics Data System (ADS)

Koch, Angira; Phukan, Arnab; Chanu, Oinam B.; Kumar, A.; Lal, R. A.

2014-02-01

Five manganese(IV) complexes [Mn(L)(bpy)] (1) and heterobimetallic complexes [MMn(L)Cl2(H2O)4]·1.5H2O (M = ZnII(2), CuII(3)) and [MnM(L)(bpy)Cl2] (M = ZnII(4), CuII(5)] have been synthesized from bis(2-hydroxy-1-naphthaldehyde)oxaloyldihydrazone (H4L) in methanol medium. The composition of the complexes have been established based on the data obtained from analytical, thermoanalytical and mass spectral studies. The structures of the complexes have been discussed in the light of molar conductance, magnetic moment, electronic, EPR, IR, FT-IR spectroscopic studies and transmission electron microscopies. The molar conductance values of these complexes in DMSO suggest their non-electrolytic nature. The μeff value for the complexes (1), (2) and (4) fall in the range 3.82-4.12 BM characteristic of the presence of the manganese(IV) in them. The complex (3) has μeff value of 3.70 BM at RT indicating considerable antiferromagnetic interaction between Mn(IV) and Cu(II). The μeff value of 4.72 BM for complex (5) is slightly lower than 4.90 BM for S = 2 ground state. In the complex (1) to (3), the ligand is coordinated to the metal centres as tetradentate ligand while in the complexes (4) and (5) as hexadentate ligand. Manganese(IV) has distorted octahedral stereochemistry in all complexes. Copper(II) has distorted octahedral and square planar stereochemistry in complexes (3) and (5) while zinc has distorted octahedral and tetrahedral stereochemistry, respectively. EPR studies of the complexes are also reported. The electron transfer reactions of the complexes have also been investigated by cyclic voltammetry.

Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some binuclear transition metal complexes of bicompartmental ONO donor ligands containing benzo[b]thiophene moiety

NASA Astrophysics Data System (ADS)

Mahendra Raj, K.; Vivekanand, B.; Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

2014-02-01

A series of new binucleating Cu(II), Co(II), Ni(II) and Zn(II) complexes of bicompartmental ligands with ONO donor were synthesized. The ligands were obtained by the condensation of 3-chloro-6-substituted benzo[b]thiophene-2-carbohydrazides and 4,6-diacetylresorcinol. The synthesized ligands and their complexes were characterized by elemental analysis and various spectroscopic techniques. Elemental analysis, IR, 1H NMR, ESI-mass, UV-Visible, TG-DTA, magnetic measurements, molar conductance and powder-XRD data has been used to elucidate their structures. The bonding sites are the oxygen atom of amide carbonyl, azomethine nitrogen and phenolic oxygen for ligands 1 and 2. The binuclear nature of the complexes was confirmed by ESR spectral data. TG-DTA studies for some complexes showed the presence of coordinated water molecules and the final product is the metal oxide. All the complexes were investigated for their electrochemical activity, only the Cu(II) complexes showed the redox property. Cu(II) complexes were square planar, whereas Co(II), Ni(II) and Zn(II) complexes were octahedral. Powder-XRD pattern have been studied in order to test the degree of crystallinity of the complexes and unit cell calculations were made. In order to evaluate the effect of antimicrobial activity of metal ions upon chelation, both the ligands and their metal complexes 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 ligands. The DNA cleaving capacities of all the complexes were analyzed by agarose gel electrophoresis method against supercoiled plasmid DNA. Among the compounds tested for antioxidant capacity, ligand 1 displayed excellent activity than its metal complexes.

Synthesis, spectroscopic properties, molecular docking, anti-colon cancer and anti-microbial studies of some novel metal complexes for 2-amino-4-phenylthiazole derivative

NASA Astrophysics Data System (ADS)

Al-Harbi, Sami A.; Bashandy, Mahmoud S.; Al-Saidi, Hammed M.; Emara, Adel A. A.; Mousa, Tarek A. A.

2015-06-01

This article describes the synthesis of novel bidentate Schiff base (H2L) from condensation of 2-amino-4-phenylthiazole (APT) with 4,6-diacetylresorcinol (DAR) in the molar ratio 2:1. We studied interaction of ligand (H2L) with transition metal ions such as Cr(III), Fe(III), Cu(II), Zn(II) and Cd(II). The ligand (H2L) has two bidentate sets of (N-O) units which can coordinate with two metal ions to afford novel binuclear metal complexes. The directions of coordinate bonds are from nitrogen atoms of azomethine groups and oxygen atoms of the phenolic groups. Structures of the newly synthesized complexes were confirmed by elemental analysis, IR, UV, 1H NMR, ESR, TGA and mass spectral data. All of the newly synthesized complexes were evaluated for their antibacterial and anti-fungal activities. They were also evaluated for their in vitro anticancer activity against human colon carcinoma cells (HCT-116) and mammalian cells of African green monkey kidney (VERO). The Cu(II) complex with selectivity index (S.I.) = 21.26 exhibited better activity than methotrexate (MTX) as a reference drug with S.I. value = 13.30, while Zn(II) complex with S.I. value = 10.24 was found to be nearly as active as MTX. Molecular docking studies further helped in understanding the mode of action of the compounds through their various interactions with active sites of dihydrofolate reductase (DHFR) enzyme. The observed activity of Fe(III) and Cu(II) complexes gave rise to the conclusion that they might exert their action through inhibition of the DHFR enzyme.

Synthesis, spectroscopic properties, molecular docking, anti-colon cancer and anti-microbial studies of some novel metal complexes for 2-amino-4-phenylthiazole derivative.

PubMed

Al-Harbi, Sami A; Bashandy, Mahmoud S; Al-Saidi, Hammed M; Emara, Adel A A; Mousa, Tarek A A

2015-06-15

This article describes the synthesis of novel bidentate Schiff base (H2L) from condensation of 2-amino-4-phenylthiazole (APT) with 4,6-diacetylresorcinol (DAR) in the molar ratio 2:1. We studied interaction of ligand (H2L) with transition metal ions such as Cr(III), Fe(III), Cu(II), Zn(II) and Cd(II). The ligand (H2L) has two bidentate sets of (N-O) units which can coordinate with two metal ions to afford novel binuclear metal complexes. The directions of coordinate bonds are from nitrogen atoms of azomethine groups and oxygen atoms of the phenolic groups. Structures of the newly synthesized complexes were confirmed by elemental analysis, IR, UV, (1)H NMR, ESR, TGA and mass spectral data. All of the newly synthesized complexes were evaluated for their antibacterial and anti-fungal activities. They were also evaluated for their in vitro anticancer activity against human colon carcinoma cells (HCT-116) and mammalian cells of African green monkey kidney (VERO). The Cu(II) complex with selectivity index (S.I.)=21.26 exhibited better activity than methotrexate (MTX) as a reference drug with S.I. value=13.30, while Zn(II) complex with S.I. value=10.24 was found to be nearly as active as MTX. Molecular docking studies further helped in understanding the mode of action of the compounds through their various interactions with active sites of dihydrofolate reductase (DHFR) enzyme. The observed activity of Fe(III) and Cu(II) complexes gave rise to the conclusion that they might exert their action through inhibition of the DHFR enzyme. Copyright © 2015 Elsevier B.V. All rights reserved.

Cellulose-lanthanum hydroxide nanocomposite as a selective marker for detection of toxic copper

PubMed Central

2014-01-01

In this current report, a simple, reliable, and rapid method based on modifying the cellulose surface by doping it with different percentages of lanthanum hydroxide (i.e., 1% La(OH)3-cellulose (LC), 5% La(OH)3-cellulose (LC2), and 10% La(OH)3-cellulose (LC3)) was proposed as a selective marker for detection of copper (Cu(II)) in aqueous medium. Surface properties of the newly modified cellulose phases were confirmed by Fourier transform infrared spectroscopy, field emission scanning electron microscope, energy dispersive X-ray spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopic analysis. The effect of pH on the adsorption of modified cellulose phases for Cu(II) was evaluated, and LC3 was found to be the most selective for Cu(II) at pH 6.0. Other parameters, influencing the maximum uptake of Cu(II) on LC3, were also investigated for a deeper mechanistic understanding of the adsorption phenomena. Results showed that the adsorption capacity for Cu(II) was improved by 211% on the LC3 phase as compared to diethylaminoethyl cellulose phase after only 2 h contact time. Adsorption isotherm data established that the adsorption process nature was monolayer with a homogeneous adsorbent surface. Results displayed that the adsorption of Cu(II) onto the LC3 phase obeyed a pseudo-second-order kinetic model. Selectivity studies toward eight metal ions, i.e., Cd(II), Co(II), Cr(III), Cr(VI), Cu(II), Fe(III), Ni(II), and Zn(II), were further performed at the optimized pH value. Based on the selectivity study, it was found that Cu(II) is highly selective toward the LC3 phase. Moreover, the efficiency of the proposed method was supported by implementing it to real environmental water samples with adequate results. PMID:25258599

Aging effects on chemical transformation and metal(loid) removal by entrapped nanoscale zero-valent iron for hydraulic fracturing wastewater treatment.

PubMed

Sun, Yuqing; Lei, Cheng; Khan, Eakalak; Chen, Season S; Tsang, Daniel C W; Ok, Yong Sik; Lin, Daohui; Feng, Yujie; Li, Xiang-Dong

2018-02-15

In this study, alginate and polyvinyl alcohol (PVA)-alginate entrapped nanoscale zero-valent iron (nZVI) was tested for structural evolution, chemical transformation, and metals/metalloids removal (Cu(II), Cr(VI), Zn(II), and As(V)) after 1-2month passivation in model saline wastewaters from hydraulic fracturing. X-ray diffraction analysis confirmed successful prevention of Fe 0 corrosion by polymeric entrapment. Increasing ionic strength (I) from 0 to 4.10M (deionized water to Day-90 fracturing wastewater (FWW)) with prolonged aging time induced chemical instability of alginate due to dissociation of carboxyl groups and competition for hydrogen bonding with nZVI, which caused high Na (7.17%) and total organic carbon (24.6%) dissolution from PVA-alginate entrapped nZVI after 2-month immersion in Day-90 FWW. Compared to freshly-made beads, 2-month aging of PVA-alginate entrapped nZVI in Day-90 FWW promoted Cu(II) and Cr(VI) uptake in terms of the highest removal efficiency (84.2% and 70.8%), pseudo-second-order surface area-normalized rate coefficient k sa (2.09×10 -1 Lm -2 h -1 and 1.84×10 -1 Lm -2 h -1 ), and Fe dissolution after 8-h reaction (13.9% and 8.45%). However, the same conditions inhibited Zn(II) and As(V) sequestration in terms of the lowest removal efficiency (31.2% and 39.8%) by PVA-alginate nZVI and k sa (4.74×10 -2 Lm -2 h -1 and 6.15×10 -2 Lm -2 h -1 ) by alginate nZVI. The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in metals/metalloids removal by entrapped nZVI after aging was attributed to distinctive removal mechanisms: (i) enhanced Cu(II) and Cr(VI) removal by nZVI reduction with accelerated electron transfer after pronounced dissolution of non-conductive polymeric immobilization matrix; (ii) suppressed Zn(II) and As(V) removal by nZVI adsorption due to restrained mass transfer after blockage of surface-active micropores. Entrapped nZVI was chemically fragile and should be properly stored and regularly replaced for good performance. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, characterization, molecular modeling and biological activity of metal complexes derived from (E)-N'-(furan-2-ylmethylene)morpholine-4-carbothiohydrazide

NASA Astrophysics Data System (ADS)

El-Samanody, El-Sayed A.; Emam, Sanaa M.; Emara, Esam M.

2017-10-01

A new series of some biologically active Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes was synthesized from the novel thiosemicarbazone ligand; (E)-N'-(furan-2-ylmethylene)morpholine-4-carbothiohydrazide (HL). Elemental, spectral, thermal analyses, magnetic susceptibility and molar conductivity measurements were used to elucidate the structure of separated compounds. The data prove that the ligand reacts with all metal ions in a neutral thione form. The electrolytic tetra-coordinate Cu(II); Zn(II) complexes (5, 6; 10) bind through the thione sulfur, furfural oxygen and azomethine nitrogen atoms of the ligand (NSO type) to construct fused five membered rings. However, the rest non-electrolyte octahedral complexes chelate via the furfural oxygen and azomethine nitrogen atoms of the ligand (NO type). Molecular modeling was conducted for the ligand and two representative complexes (1, 5) in order to substantiate their chemical structures. Thermal analyses are compatible with molecular modeling studies to support the proposed thermal decomposition pathways of metal complexes which start with the rupture of the long and weak N-NH bond. The thermal stability of metal complexes varies according to the number of solvents of crystallization, ionic radii and steric effect of anions. The ESR spectra of Cu(II) complexes are compatible with a primarily (dx2-y2)1 ground state with axial symmetry. The ligand and its Co(II); Cu(II); Cd(II) complexes (1; 5, 8; 11) along with their mixtures with metaldehyde were screened in vitro for their molluscicidal activity against Eobania vermiculata. Combination with metaldehyde enhances the toxicity effect of the tested compounds through reducing the period required for mortality and increasing the percentage of mortality after 24 h of treatments. The tested compounds gathered with metaldehyde are strongly affecting on the activity of ACP and ALP enzymes and TP content which are very important factors in the mucous secretion of Eobania vermiculata. These effects lead to excess mucous secretion, causing dryness and death for the snails.

Synthesis and Biological Evaluation of New Hydrazone Derivatives of Quinoline and Their Cu(II) and Zn(II) Complexes against Mycobacterium tuberculosis

PubMed Central

Mandewale, Mustapha C.; Thorat, Bapu; Shelke, Dnyaneshwar; Yamgar, Ramesh

2015-01-01

A new series of quinoline hydrazone derivatives and their metal complexes have been synthesized and their biological properties have been evaluated against Mycobacterium tuberculosis (H37 RV strain). Most of the newly synthesized compounds displayed 100% inhibitory activity at a concentration of 6.25–25 μg/mL, against Mycobacterium tuberculosis. Fluorescence properties of all the synthesized compounds have been studied. PMID:26759537

Impregnated multiwalled carbon nanotubes as efficient sorbent for the solid phase extraction of trace amounts of heavy metal ions in food and water samples.

PubMed

Gouda, Ayman A; Al Ghannam, Sheikha M

2016-07-01

A new, sensitive and simple solid phase extraction (SPE), separation and preconcentration method of some heavy metal ions, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) at trace levels using multiwalled carbon nanotubes (MWCNTs) impregnated with 2-(2-benzothiazolylazo)orcinol (BTAO) from food and water samples were investigated. The effect of analytical parameters was examined. The metals retained on the nanotubes at pH 7.0 were eluted by 5.0mL HNO3 (2.0molL(-1)). The influence of matrix ions on the proposed method was evaluated. The preconcentration factor was calculated and found to be 100. The detection limits (LODs) for Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) were found at 0.70, 1.2, 0.80, 2.6 and 2.2μgL(-1), respectively. The relative standard deviation (RSD) and the recoveries of the standard addition method were lower than 5.0% and 95-102%, respectively. The new procedure was successfully applied to the determination of trace amounts of the studied metal ions in various food and water samples and validated using certified reference materials SRM 1570A (spinach leaves) with satisfactory and compatible results. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis, spectroscopic, molecular structure, antioxidant, antimicrobial and antitumor behavior of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of O2N type tridentate chromone-2-carboxaldehyde Schiff's base ligand

NASA Astrophysics Data System (ADS)

Ammar, Reda A.; Alaghaz, Abdel-Nasser M. A.; Zayed, Mohamed E.; Al-Bedair, Lamia A.

2017-08-01

Tridentate Schiff's base (HL) ligand was synthesized via condensation of salicylaldehyde and 3-hydroxypyridin-2-yliminomethyl-4H-chromen-4-one and their corresponding Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. The isolated solid complexes were characterized by elemental analyses, molar conductance, spectral (IR, UV-Vis, 1H NMR), magnetic moment, EPR, and thermal measurements. The IR spectra showed that HL was coordinated to the metal ions in tridentate manner with O2N donor sites of the azomethine N, deprotonated phenolic-OH and carbonyl-O. The activation of thermodynamic parameters are calculated using Coast-Redfern and Horowitz-Metzger (HM). The octahedral geometry of the complexes is confirmed using DFT method from DMOL3 calculations, UV-Vis and magnetic moment measurements, ESR and ligand field parameters. Antioxidant activities have also been performed for all the compounds. The investigated ligand and metal complexes were screened for their in-vitro antimicrobial activities against different types of fungal and bacterial strains. The resulting data assert on the inspected compounds as a highly promising bactericides and fungicides. The antitumor activities of all inspected compounds were evaluated towards human liver Carcinoma (HepG2) cell line.

Syntheses, spectroscopic and thermal analyses of cyanide bridged heteronuclear polymeric complexes: [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine or N-ethylethylenediamine; Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II))

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla

2016-02-01

Polymeric tetracyanonickelate(II) complexes of the type [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine (men) or N-ethylethylenediamine (neen); Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II)) have been prepared and characterized by FT-IR, Raman spectroscopy, thermal and elemental analysis techniques. Additionally, FT-IR and Raman spectral analyses of men and neen have experimentally and theoretically investigated in the range of 4000-250 cm-1. The corresponding vibration assignments of men and neen are performed by using B3LYP density functional theory (DFT) method together with 6-31 G(d) basis set. The spectral features of the complexes suggest that the coordination environment of the M(II) ions are surrounded by the two symmetry related men and neen ligands and the two symmetry related N atom of cyanide groups, whereas the Ni(II) atoms are coordinated with a square-planar to four C atoms of the cyanide groups. Polymeric structures of the complexes consist of one dimensional alternative chains of [M(L)2]2+ and [Ni(CN)4]2- moieties. The thermal decompositions in the temperature range 30-700 °C of the complexes were investigated in the static air atmosphere.

Functionalization of magnetic hollow porous oval shape NiFe2O4 as a highly selective sorbent for the simultaneous determination of five heavy metals in real samples.

PubMed

Liu, Mingyang; Yang, Lijun; Zhang, Lei

2016-12-01

In this study, a functionalized magnetic hollow porous oval-shape NiFe 2 O 4 (MHPO-NiFe 2 O 4 ) was designed by a facile synthesis procedure, and employed as magnetic solid phase extraction (MSPE) material to extract several heavy metal ions. As-prepared MHPO-NiFe 2 O 4 exhibited superior adsorption capacities of 20.17, 16.64, 16.82, 9.69 and 16.58mgg -1 , for Cu(II), Cd(II), Cr(III), Co(II) and Zn(II), and was then used to detect these heavy metals elements in real samples by combining with inductively coupled plasma optical emission spectroscopy (ICP-OES). The possible mechanism of the enrichment of heavy metals ions on MHPO-NiFe 2 O 4 was proposed, which involved the dominant adsorption and desorption. The detection limits were as low as 0.015, 0.13, 0.062, 0.035 and 0.46μgL -1 for Cu(II), Cd(II), Cr(III), Co(II) and Zn(II), respectively. A good repeatability was obtained with the relative standard deviation (RSD) of 3.87%. Moreover, the method was successfully utilized for the analysis of five heavy metals in real samples (cabbage, lettuce, apple, seawater), with satisfactory recoveries in the range of 92-108%. Copyright © 2016 Elsevier B.V. All rights reserved.

A Bispidol Chelator with a Phosphonate Pendant Arm: Synthesis, Cu(II) Complexation, and 64Cu Labeling.

PubMed

Gillet, Raphaël; Roux, Amandine; Brandel, Jérémy; Huclier-Markai, Sandrine; Camerel, Franck; Jeannin, Olivier; Nonat, Aline M; Charbonnière, Loïc J

2017-10-02

Here we present the synthesis and characterization of a new bispidine (3,7-diazabicyclo[3.3.1]nonane) ligand with N-methanephosphonate substituents (L 2 ). Its physicochemical properties in water, as well as those of the corresponding Cu(II) and Zn(II) complexes, have been evaluated by using UV-visible absorption spectroscopy, potentiometry, 1 H and 31 P NMR, and cyclic voltammetry. Radiolabeling experiments with 64 Cu II have been carried out, showing excellent radiolabeling properties. Quantitative complexation was achieved within 60 min under stoichiometric conditions, at room temperature and in the nanomolar concentration range. It was also demonstrated that the complexation occurred below pH 2. Properties have been compared to those of the analogue bispidol bearing a N-methanecarboxylate substituent (L 1 ). Although both systems meet the required criteria to be used as new chelator for 64/67 Cu in terms of the kinetics of formation, thermodynamic stability, selectivity for Cu(II), and kinetic inertness regarding redox- or acid-assisted decomplexation processes, substitution of the carboxylic acid function by the phosphonic moiety is responsible for a significant increase in the thermodynamic stability of the Cu(II) complex (+2 log units for pCu) and also leads to an increase in the radiochemical yields with 64 Cu II which is quantitative for L 2 .

Structurally related hydrazone-based metal complexes with different antitumor activities variably induce apoptotic cell death.

PubMed

Megger, Dominik A; Rosowski, Kristin; Radunsky, Christian; Kösters, Jutta; Sitek, Barbara; Müller, Jens

2017-04-05

Three new complexes bearing the tridentate hydrazone-based ligand 2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)pyridine (L) were synthesized and structurally characterized. Biological tests indicate that the Zn(ii) complex [ZnCl 2 (L)] is of low cytotoxicity against the hepatocellular carcinoma cell line HepG2. In contrast, the Cu(ii) and Mn(ii) complexes [CuCl 2 (L)] and [MnCl 2 (L)] are highly cytotoxic with EC 50 values of 1.25 ± 0.01 μM and 20 ± 1 μM, respectively. A quantitative proteome analysis reveals that treatment of the cells with the Cu(ii) complex leads to a significantly altered abundance of 102 apoptosis-related proteins, whereas 38 proteins were up- or down-regulated by the Mn(ii) complex. A closer inspection of those proteins regulated only by the Cu(ii) complex suggests that the superior cytotoxic activity of this complex is likely to be related to an initiation of the caspase-independent cell death (CICD). In addition, an increased generation of reactive oxygen species (ROS) and a strong up-regulation of proteins responsive to oxidative stress suggest that alterations of the cellular redox metabolism likely contribute to the cytotoxicity of the Cu(ii) complex.

Synthesis, spectral characterization and DNA binding of Schiff-base metal complexes derived from 2-amino-3-hydroxyprobanoic acid and acetylacetone

NASA Astrophysics Data System (ADS)

Hosny, Nasser Mohammed; Hussien, Mostafa A.; Radwan, Fatima M.; Nawar, Nagwa

2014-11-01

Four new metal complexes derived from the reaction of Cu(II), Co(II), Ni(II) and Zn(II) acetates with the Schiff-base ligand (H3L) resulted from the condensation of the amino acid 2-amino-3-hydroxyprobanoic acid (serine) and acetylacetone have been synthesized and characterized by, elemental analyses, ES-MS, IR, UV-Vis., 1H NMR, 13C NMR, ESR, thermal analyses (TGA and DTG) and magnetic measurements. The results showed that the Schiff-base ligand acts as bi-negative tridentate through the azomethine nitrogen, the deprotonated carboxylate oxygen and the enolic carbonyl oxygen. The optical band gaps measurements indicated the semi-conducting nature of these complexes. Molecular docking was used to predict the binding between the Schiff base ligand with the receptor of prostate cancer mutant H874Y. The interactions between the Cu(II) complex and calf thymus DNA (CT-DNA) have been studied by UV spectra. The results confirm that the Cu(II) complex binds to CT-DNA in an intercalative mode.

Synthesis, characterization and anticancer activity of new Schiff bases bearing neocryptolepine

NASA Astrophysics Data System (ADS)

Emam, Sanaa M.; El Sayed, Ibrahim E. T.; Ayad, Mohamed I.; Hathout, Heba M. R.

2017-10-01

The synthesis of new Shiff base ligands denoted L1, HL2 and HL3 starting from the appropriate aminoneocryptolepine and salicaldehyde were described. The chelation abilities of L1, HL2 and HL3 ligands towards Co(II), Ni(II), Cu(II) and Pd(II) salts have been studied. A series of square planar complexes containing Cu(II) salts, PdCl2 and octahedral chelates containing NiCl2, CoCl2 salts (2 and 7) have been isolated. Also, the pentacoordinated Co(II) complex [Co(L1)2Cl]·Cl.0.5H2O·1.25EtOH (1) has been prepared. The mode of bonding and geometrical structure of complexes has been confirmed by elemental analyses and different spectroscopic methods together with thermal, magnetic moment studies, molecular modeling and X-ray diffraction. Furthermore, the synthesized ligands, in comparison to some of their metal complexes were screened for their anticancer activity against colorectal adenocarcinoma (HT-29) cells. The results showed that Co(II) complexes (1 and 7) exhibited higher anticancer activity when compared to the corresponding ligands.

Electrochemical, spectral, and computational studies of metalloporphyrin dimers formed by cation complexation of crown ether cavities.

PubMed

Chitta, Raghu; Rogers, Lisa M; Wanklyn, Amber; Karr, Paul A; Kahol, Pawan K; Zandler, Melvin E; D'Souza, Francis

2004-11-01

The effect on the electrochemical oxidation and reduction potentials of 5,10,15,20-tetrakis(benzo-15-crown-5)porphyrin (TCP) and its metal derivatives (MTCP; M = Mg(II), VO(IV), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II)) upon potassium ion induced dimerization of the porphyrins was systematically performed in benzonitrile containing 0.1 M (TBA)ClO(4) by differential pulse voltammetry technique. The HOMO--LUMO energy level diagram constructed from the electrochemical data revealed destabilization of the HOMO level and stabilization of the LUMO level upon dimer formation while such a perturbation was larger for the HOMO level than the LUMO level. The geometry and electronic structure of a representative ZnTCP and its dimer, K(4)(ZnTCP)(2), were evaluated by the ab initio B3LYP method utilizing a mixed basis set of 3-21G(*) for Zn, K, O, and N and STO-3G for C and H. The inter-porphyrin ring distance of the dimer calculated from the optimized geometry agreed with the spectroscopically determined one, and the calculated HOMO and LUMO frontier orbitals revealed delocalization on both of the porphyrins rings. The metal-metal distances calculated from the triplet ESR spectra of the K(+) induced porphyrin dimers bearing paramagnetic metal ions in the cavity followed the trend Cu--Cu < VO--VO < Ag--Ag. However, the spectral shifts resulting from the exciton coupling of the interacting porphyrin pi-systems revealed no specific trend with respect to the metal ion in the porphyrin cavity. Additionally, linear trends in the electrochemically measured HOMO--LUMO gap and the energy corresponding to the most intense visible band of both MTCP and K(4)(MTCP)(2) were observed. A reduced HOMO--LUMO gap predicted for the dimer by B3LYP/(3-21G(), STO-3G) calculations was confirmed by the results of optical absorption and electrochemical studies.

Spectral Characterization and 3D Molecular Modeling Studies of Metal Complexes Involving the O, N-Donor Environment of Quinazoline-4(3H)-one Schiff Base and Their Biological Studies

PubMed Central

Siddappa, Kuruba; Mane, Sunilkumar B.

2014-01-01

A simple condensation of 3-amino-2-methylquinazoline-4-one with 2-hydroxy-1-naphthaldehyde produced new tridentate ONO donor Schiff base ligand with efficient yield. The structural characterization of ligand and its Cu(II), Ni(II), Co(II), Mn(II), Zn(II), and Cd(II) complexes were achieved by the aid of elemental analysis, spectral characterization such as (UV-visible, IR, NMR, mass, and ESR), and magnetic data. The analytical and spectroscopic studies suggest the octahedral geometries of Cu(II), Co(II), Ni(II) and Mn(II) complexes and tetrahedral geometry of Zn(II) and Cd(II) complexes with the tridentate ONO Schiff base ligand. Furthermore, the conclusions drawn from these studies afford further support to the mode of bonding discussed on the basis of their 3D molecular modeling studies by considering different bond lengths, bond angles, and bond distance. The ligand and its metal complexes evaluated for their antimicrobial activity against Staphylococcus aureus (MTCC number 7443), Bacillus subtilis (MTCC number 9878), Escherichia coli (MTCC number 1698), Aspergillus niger (MTCC number 281), and Aspergillus flavus (MTCC number 277). The MIC of these compounds was found to be most active at 10 μg/mL concentration in inhibiting the growth of the tested organisms. The DNA cleavage activity of all the complexes was studied by gel electrophoresis method. PMID:24678278

Natural Minerals Coated by Biopolymer Chitosan: Synthesis, Physicochemical, and Adsorption Properties

NASA Astrophysics Data System (ADS)

Budnyak, T. M.; Yanovska, E. S.; Kichkiruk, O. Yu.; Sternik, D.; Tertykh, V. A.

2016-11-01

Natural minerals are widely used in treatment technologies as mineral fertilizer, food additive in animal husbandry, and cosmetics because they combine valuable ion-exchanging and adsorption properties together with unique physicochemical and medical properties. Saponite (saponite clay) of the Ukrainian Podillya refers to the class of bentonites, a subclass of layered magnesium silicate montmorillonite. Clinoptilolits are aluminosilicates with carcase structure. In our work, we have coated biopolymer chitosan on the surfaces of natural minerals of Ukrainian origin — Podilsky saponite and Sokyrnitsky clinoptilolite. Chitosan mineral composites have been obtained by crosslinking of adsorbed biopolymer on saponite and clinoptilolite surface with glutaraldehyde. The obtained composites have been characterized by the physicochemical methods such as thermogravimetric/differential thermal analyses (DTA, DTG, TG), differential scanning calorimetry, mass analysis, nitrogen adsorption/desorption isotherms, scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy to determine possible interactions between the silica and chitosan molecule. The adsorption of microquantities of cations Cu(II), Zn(II), Fe(III), Cd(II), and Pb(II) by the obtained composites and the initial natural minerals has been studied from aqueous solutions. The sorption capacities and kinetic adsorption characteristics of the adsorbents were estimated. It was found that the obtained results have shown that the ability of chitosan to coordinate heavy metal ions Zn(II), Cu(II), Cd(II), and Fe(III) is less or equal to the ability to retain ions of these metals in the pores of minerals without forming chemical bonds.

New metal phthalocyanines/metal simple hydroxide multilayers: experimental evidence of dipolar field-driven magnetic behavior.

PubMed

Bourzami, Riadh; Eyele-Mezui, Séraphin; Delahaye, Emilie; Drillon, Marc; Rabu, Pierre; Parizel, Nathalie; Choua, Sylvie; Turek, Philippe; Rogez, Guillaume

2014-01-21

A series of new hybrid multilayers has been synthesized by insertion-grafting of transition metal (Cu(II), Co(II), Ni(II), and Zn(II)) tetrasulfonato phthalocyanines between layers of Cu(II) and Co(II) simple hydroxides. The structural and spectroscopic investigations confirm the formation of new layered hybrid materials in which the phthalocyanines act as pillars between the inorganic layers. The magnetic investigations show that all copper hydroxide-based compounds behave similarly, presenting an overall antiferromagnetic behavior with no ordering down to 1.8 K. On the contrary, the cobalt hydroxide-based compounds present a ferrimagnetic ordering around 6 K, regardless of the nature of the metal phthalocyanine between the inorganic layers. The latter observation points to strictly dipolar interactions between the inorganic layers. The amplitude of the dipolar field has been evaluated from X-band and Q-band EPR spectroscopy investigation (Bdipolar ≈ 30 mT).

Synthesis, spectroscopic and thermal studies of transition metal complexes derived from benzil and diethylenetriamine

NASA Astrophysics Data System (ADS)

Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.

2007-10-01

A macrocyclic ligand, bdta (where bdta = 3,6,9,12,15,18-hexaaza-1,2,10,11-tetraphenyl-2,9,11,18-tetraenecyclododecane) has been prepared by cyclocondensation of benzil with diethylenetriamine which efficiently encapsulates transition as well as pseudo-transition metal ions leading to the formation of M(bdta)Cl 2 type complexes [where M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)]. The analytical, spectroscopic and magnetic moment data suggests an octahedral geometry for all the complexes. EPR spectra of Mn(II) and Cu(II) show considerable exchange interaction in the complex. They are non-conducting in DMSO. The TGA profile of the ligand and its complexes are identical and consists of two discreet stages. The voltammogram of Cu-complex exhibits a quasi-reversible one-electron transfer wave for Cu(II)/Cu(I) couple.

Synthesis, spectroscopic and thermal studies of transition metal complexes derived from benzil and diethylenetriamine.

PubMed

Khan, Sadaf; Nami, Shahab A A; Siddiqi, K S

2007-10-01

A macrocyclic ligand, bdta (where bdta=3,6,9,12,15,18-hexaaza-1,2,10,11-tetraphenyl-2,9,11,18-tetraenecyclododecane) has been prepared by cyclocondensation of benzil with diethylenetriamine which efficiently encapsulates transition as well as pseudo-transition metal ions leading to the formation of M(bdta)Cl2 type complexes [where M=Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)]. The analytical, spectroscopic and magnetic moment data suggests an octahedral geometry for all the complexes. EPR spectra of Mn(II) and Cu(II) show considerable exchange interaction in the complex. They are non-conducting in DMSO. The TGA profile of the ligand and its complexes are identical and consists of two discreet stages. The voltammogram of Cu-complex exhibits a quasi-reversible one-electron transfer wave for Cu(II)/Cu(I) couple.

Synthesis, spectroscopic characterization, DNA interaction and antibacterial study of metal complexes of tetraazamacrocyclic Schiff base

NASA Astrophysics Data System (ADS)

Shakir, Mohammad; Khanam, Sadiqa; Firdaus, Farha; Latif, Abdul; Aatif, Mohammad; Al-Resayes, Saud I.

The template condensation reaction between benzil and 3,4-diaminotoulene resulted mononuclear 12-membered tetraimine macrocyclic complexes of the type, [MLCl2] [M = Co(II), Ni(II), Cu(II) and Zn(II)]. The synthesized complexes have been characterized on the basis of the results of elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz. FT-IR, 1H and 13C NMR, FAB mass, UV-vis and EPR. An octahedral geometry has been envisaged for all these complexes, while a distorted octahedral geometry has been noticed for Cu(II) complex. Low conductivity data of all these complexes suggest their non-ionic nature. The interactive studies of these complexes with calf thymus DNA showed that the complexes are avid binders of calf thymus DNA. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria proved them as growth inhibiting agents.

Neuroprotective Effects and Mechanisms of Curcumin-Cu(II) and -Zn(II) Complexes Systems and Their Pharmacological Implications.

PubMed

Yan, Fa-Shun; Sun, Jian-Long; Xie, Wen-Hai; Shen, Liang; Ji, Hong-Fang

2017-12-28

Alzheimer's disease (AD) is the main form of dementia and has a steadily increasing prevalence. As both oxidative stress and metal homeostasis are involved in the pathogenesis of AD, it would be interesting to develop a dual function agent, targeting the two factors. Curcumin, a natural compound isolated from the rhizome of Curcuma longa , is an antioxidant and can also chelate metal ions. Whether the complexes of curcumin with metal ions possess neuroprotective effects has not been evaluated. Therefore, the present study was designed to investigate the protective effects of the complexes of curcumin with Cu(II) or Zn(II) on hydrogen peroxide (H₂O₂)-induced injury and the underlying molecular mechanisms. The use of rat pheochromocytoma (PC12) cells, a widely used neuronal cell model system, was adopted. It was revealed that curcumin-Cu(II) complexes systems possessed enhanced O₂ ·- -scavenging activities compared to unchelated curcumin. In comparison with unchelated curcumin, the protective effects of curcumin-Cu(II) complexes systems were stronger than curcumin-Zn(II) system. Curcumin-Cu(II) or -Zn(II) complexes systems significantly enhanced the superoxide dismutase, catalase, and glutathione peroxidase activities and attenuated the increase of malondialdehyde levels and caspase-3 and caspase-9 activities, in a dose-dependent manner. The curcumin-Cu(II) complex system with a 2:1 ratio exhibited the most significant effect. Further mechanistic study demonstrated that curcumin-Cu(II) or -Zn(II) complexes systems inhibited cell apoptosis via downregulating the nuclear factor κB (NF-κB) pathway and upregulating Bcl-2/Bax pathway. In summary, the present study found that curcumin-Cu(II) or -Zn(II) complexes systems, especially the former, possess significant neuroprotective effects, which indicates the potential advantage of curcumin as a promising agent against AD and deserves further study.

Genetic and physiological responses of Bacillus subtilis to metal ion stress.

PubMed

Moore, Charles M; Gaballa, Ahmed; Hui, Monica; Ye, Rick W; Helmann, John D

2005-07-01

Metal ion homeostasis is regulated principally by metalloregulatory proteins that control metal ion uptake, storage and efflux genes. We have used transcriptional profiling to survey Bacillus subtilis for genes that are rapidly induced by exposure to high levels of metal ions including Ag(I), Cd(II), Cu(II), Ni(II) and Zn(II) and the metalloid As(V). Many of the genes affected by metal stress were controlled by known metalloregulatory proteins (Fur, MntR, PerR, ArsR and CueR). Additional metal-induced genes are regulated by two newly defined metal-sensing ArsR/SmtB family repressors: CzrA and AseR. CzrA represses the CadA efflux ATPase and the cation diffusion facilitator CzcD and this repression is alleviated by Zn(II), Cd(II), Co(II), Ni(II) and Cu. CadA is the major determinant for Cd(II) resistance, while CzcD protects the cell against elevated levels of Zn(II), Cu, Co(II) and Ni(II). AseR negatively regulates itself and AseA, an As(III) efflux pump which contributes to arsenite resistance in cells lacking a functional ars operon. Our results extend the range of identified effectors for the As(III)-sensor ArsR to include Cd(II) and Ag(I) and for the Cu-sensor CueR to include Ag(I) and, weakly, Cd(II) and Zn(II). In addition to systems dedicated to metal homeostasis, specific metal stresses also strongly induced pathways related to cysteine, histidine and arginine metabolism.

Selective solid phase extraction of copper using a new Cu(II)-imprinted polymer and determination by inductively coupled plasma optical emission spectroscopy (ICP-OES).

PubMed

Yilmaz, Vedat; Arslan, Zikri; Hazer, Orhan; Yilmaz, Hayriye

2014-05-01

This work reports the preparation of a novel Cu(II)-ion imprinted polymer using 2-thiozylmethacrylamide (TMA) for on-line preconcentration of Cu(II) prior to its determination by inductively coupled optical emission spectroscopy (ICP-OES). Cu(II)-TMA monomer (complex) was synthesized and copolymerized via bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was washed with 5% (v/v) HNO 3 to remove Cu(II) ions and then with water until a neutral pH. The ion imprinted polymer was characterized by FT-IR and scanning electron microscopy. The experimental conditions were optimized for on-line preconcentration of Cu(II) using a minicolumn of ion imprinted polymer (IIP). Quantitative retention was achieved between pH 5.0 and 6.0, whereas the recoveries for the non-imprinted polymer (NIP) were about 61%. The IIP showed about 30 times higher selectivity to Cu(II) in comparison to NIP. The IIP also exhibited excellent selectivity for Cu(II) against the competing transition and heavy metal ions, including Cd, Co, Cr, Fe, Mn, Ni, Pb and Zn. Computational calculations revealed that the selectivity of IIP was mediated by the stability of Cu(II)-TMA complex which was far more stable than those of Co(II), Ni(II) and Zn(II) that have similar charge and ionic radii to Cu(II). A volume of 10 mL sample solution was loaded onto the column at 4.0 mL min -1 by using a sequential injection system (FIALab 3200) followed by elution with 1.0 mL of 2% (v/v) HNO 3 . The relative standard deviation (RSD) and limit of detection (LOD, 3s) of the method were 3.2% and 0.4 μg L -1 , respectively. The method was successfully applied to determination of Cu(II) in fish otoliths (CRM 22), bone ash (SRM 1400) and coastal seawater and estuarine water samples.

Selective solid phase extraction of copper using a new Cu(II)-imprinted polymer and determination by inductively coupled plasma optical emission spectroscopy (ICP-OES)

PubMed Central

Yilmaz, Vedat; Arslan, Zikri; Hazer, Orhan; Yilmaz, Hayriye

2014-01-01

This work reports the preparation of a novel Cu(II)-ion imprinted polymer using 2-thiozylmethacrylamide (TMA) for on-line preconcentration of Cu(II) prior to its determination by inductively coupled optical emission spectroscopy (ICP-OES). Cu(II)-TMA monomer (complex) was synthesized and copolymerized via bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was washed with 5% (v/v) HNO3 to remove Cu(II) ions and then with water until a neutral pH. The ion imprinted polymer was characterized by FT-IR and scanning electron microscopy. The experimental conditions were optimized for on-line preconcentration of Cu(II) using a minicolumn of ion imprinted polymer (IIP). Quantitative retention was achieved between pH 5.0 and 6.0, whereas the recoveries for the non-imprinted polymer (NIP) were about 61%. The IIP showed about 30 times higher selectivity to Cu(II) in comparison to NIP. The IIP also exhibited excellent selectivity for Cu(II) against the competing transition and heavy metal ions, including Cd, Co, Cr, Fe, Mn, Ni, Pb and Zn. Computational calculations revealed that the selectivity of IIP was mediated by the stability of Cu(II)-TMA complex which was far more stable than those of Co(II), Ni(II) and Zn(II) that have similar charge and ionic radii to Cu(II). A volume of 10 mL sample solution was loaded onto the column at 4.0 mL min−1 by using a sequential injection system (FIALab 3200) followed by elution with 1.0 mL of 2% (v/v) HNO3. The relative standard deviation (RSD) and limit of detection (LOD, 3s) of the method were 3.2% and 0.4 μg L−1, respectively. The method was successfully applied to determination of Cu(II) in fish otoliths (CRM 22), bone ash (SRM 1400) and coastal seawater and estuarine water samples. PMID:24511158

The use of a polymer inclusion membrane in a paper-based sensor for the selective determination of Cu(II).

PubMed

Jayawardane, B Manori; Coo, Lilibeth dlC; Cattrall, Robert W; Kolev, Spas D

2013-11-25

A disposable paper-based sensor (PBS) is described for the determination of Cu(II) in natural and waste waters at approximately 2 cents per measurement. The device makes use of a polymer inclusion membrane (PIM) to provide the selectivity for Cu(II). The PIM consists of 40 wt% di(2-ethlyhexyl) phosphoric acid (D2EHPA) as the carrier, 10 wt% dioctyl phthalate (DOP) as a plasticizer, 49.5 wt% poly(vinyl chloride) (PVC) as the base polymer and 0.5 wt% (mm(-1)) 1-(2'-pyridylazo)-2-naphthol (PAN) as the colourimetric reagent. High selectivity under mildly acidic conditions (HCl, pH 2.0) is achieved for Cu(II) in the presence of frequently encountered metal ions in natural and waste waters such as Fe(III), Al(III), Zn(II), Cd(II), Pb(II), Ca(II), Mg(II), and Ni(II). The laminated PBS consists of a PIM sensing disc (2mm in diameter) attached to the centre of a circular hydrophilic zone (7 mm in diameter) pretreated with 0.01 M HCl. This hydrophilic zone separates the sample port (a circular hole in the plastic cover) from the PIM sensing disc. After introducing 19.2 μL of a sample/standard solution to the sample port, Cu(II) diffuses across the hydrophilic zone and is extracted into the PIM disc as the Cu(II)-D2EHPA complex which subsequently reacts with PAN to produce the red-purple coloured Cu(II)-PAN complex. The colour intensity of the PIM disc is measured 15 min after sample/standard introduction by scanning using a flatbed scanner. Under optimal conditions the device is characterized by a limit of detection (LOD) and limit of quantitation (LOQ) of 0.06 and 0.21 mg L(-1) Cu(II), respectively, with two linear ranges together covering the Cu(II) concentration range from 0.1 to 30.0 mg L(-1). The PBS was successfully applied to the determination of Cu(II) in hot tap water and mine tailings water. Copyright © 2013 Elsevier B.V. All rights reserved.

Role of the Ca-pectates on the accumulation of heavy metals in the root apoplasm.

PubMed

Castaldi, Paola; Lauro, Giampaolo; Senette, Caterina; Deiana, Salvatore

2010-12-01

In order to better understand the processes that regulate the accumulation in the apoplasm of heavy metals and their mobilization by the plant metabolites it is essential to study the mechanisms that regulate the interactions between metal ions and pectins. In such a context, the sorption of Cd(II), Zn(II), Cu(II) and Pb(II) from single and multi-metal solutions, by a Ca-polygalacturonate gel with a degree of esterification of 18.0 (PGAM(1)) and 65.5% (PGAM(2)) was studied in the 3.0-6.0 pH range in the presence of CaCl(2) 2.5mM. The sorption of Cr(III) from single metal solution was also considered. The results show that the amount of each metal ion sorbed increases with increasing the initial metal ion concentration and pH. The data from the single metal solution tests show that at pH 6.0 the affinity of the metal ions towards the PGAM(1) matrix follows the order: Cr(III)>Cu(II)≅Pb(II)≫Zn(II)≅Cd(II). The simultaneous sorption of the bivalent metal ions by the PGAM(1) gels indicates that Pb(II) is selectively sorbed. The FT-IR spectra show that the carboxylate groups are mainly responsible for the metal ion coordination. The ability of PGAM(2) to accumulate Cr(III), Cu(II), and Pb(II) was lower than that found in the PGAM(1) systems whereas the sorption of Zn(II) and Cd(II) was negligible. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

Synthesis of Optode Thin Layer using Sol Gel Hybrid of Trietoxysiloxane monomer and 3-(Trimethoxysilyl) Propilamine with Ionophore 4-(2-Pyridilazo)-1,3-Benzenadiol (PAR)

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Rahmawati, F.; Kamal, S.; Slamet, S.; Yunianto, M.; Rahmawati, P.; Aini, F. N.

2018-03-01

Optode (Optical sensors) is one of the modern chemical sensors in the field of analytical chemistry that has utilized of inorganic polymers. The optode based on MLCT (Metal to Ligand Charge Transfer) (or MMLL’CT, Mixing Metal-Ligand to Ligand Charge Transfer) or LMCT (Ligand to Metal Charge Transfer) phenomenons have beed generated from oktyltrietxysilane, aminopropyltrimethoxysilane and 4-(2-pyrydilazo) resorcinol (abbreviated as OTES-APTS-PAR) for Cu(II), Cr(III), Ni(II), Fe(III), Cd(II), and Zn(II) ions target. The syntheses of thin layer optode were performed by sol gel method followed by evaporation in glass substrat. The formation of 4-(2-pyrydilazo) resorcinol complexes with ions target have gained strong absorption spectras in visible region because of charge transfer phenomenons. The optical sensor of OTES-APTS-PAR was analysed thermal properties using Differential Thermal Analysis (DTA). DTA thermogram showed a glass transition peaks at a temperature of 315.5 °C. Fourier transform Infrared (FTIR) spectras have showed that the optode materials consisted NH aryl groups indicated IR absorption at 1577.7 cm-1 and also –CH aromatic at 1469.0 cm-1. Synthesized optode materials have strong broad visible absorption with the maximum wavelengths (λmax) = 405 nm and 508.5 nm, respectively. This material have excellent optical responds to several metal ions such as Cu(II), Cr(III), Ni(II), Fe(III), Cd(II), and Zn(II) that was showed from huge Δλmax and the increase of Ktotal

Polyamidoamine dendrimers as sweeping agent and stationary phase for rapid and sensitive open-tubular capillary electrophoretic determination of heavy metal ions.

PubMed

Ge, Ying; Guo, Yujun; Qin, Weidong

2014-04-01

Polyamidoamine (PAMAM) dendrimer generation 2.5 was synthesized and evaluated as sweeping agent for in-column enrichment and as stationary phase for capillary electrochromatographic separation of heavy metal ions, viz., Pb(II), Cu(II), Hg(II), Zn(II) and Co(II), in a running buffer containing 4-(2-pyridylazo)resorcinol (PAR) as a chromogenic reagent. During experiment, a plug of aqueous PAMAM generation 2.5 solution was first introduced to the capillary, followed by electrokinetic injection of the heavy metal ions under a positive voltage. In this step, PAMAM acted as a sweeping agent, stacking the metal ions on the analyte/PAMAM boundary by forming metal ion-PAMAM complexes. The second preconcentration process occurred when PAR, a stronger ligand, moving toward the injection end under the electric field, reached and re-swept the metal ion-PAMAM zone, forming metal ion-PAR complexes. During separation, the neutral PAMAM moved toward the detector with the electroosmotic flow, dynamically coating the capillary wall, forming stationary phases that affected the separation of the metal ions. Due to the function of PAMAM, the detection sensitivity and resolution of the heavy metal ions improved significantly. Under the optimum conditions, the detection limits were 0.299, 0.184, 0.774, 0.182 and 0.047 μg/L for Pb(II), Cu(II), Hg(II), Zn(II) and Co(II), respectively. The method was successfully applied to the determination of heavy metals in snow, tap and rain water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic and DNA binding ability of CoII, NiII, CuII and ZnII complexes of Schiff base ligand (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol. X-ray crystal structure determination of cobalt (II) complex.

PubMed

Yarkandi, Naeema H; El-Ghamry, Hoda A; Gaber, Mohamed

2017-06-01

A novel Schiff base ligand, (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol (HL), has been designed and synthesized in addition to its metal chelates [Co(L) 2 ]·l2H 2 O, [Ni(L)Cl·(H 2 O) 2 ].5H 2 O, [Cu(L)Cl] and [Zn(L)(CH 3 COO)]. The structures of the isolated compounds have been confirmed and identified by means of different spectral and physicochemical techniques including CHN analysis, 1 H & 13 C NMR, mass spectral analysis, molar conductivity measurement, UV-Vis, infrared, magnetic moment in addition to TGA technique. The infrared spectral results ascertained that the ligand acts as monobasic tridentate binding to the metal centers via deprotonated hydroxyl oxygen, azomethine and imidazole nitrogen atoms. The UV-Vis, magnetic susceptibility and molar conductivity data implied octahedral geometry for Co(II) & Ni(II) complexes, tetrahedral for Zn(II) complex and square planar for Cu(II) complex. X-ray structural analysis of Co(II) complex 1 has been reported and discussed. Moreover, the type of interaction between the ligand & its complexes towards salmon sperm DNA (SS-DNA) has been examined by the measurement of absorption spectra and viscosity which confirmed that the ligand and its complexes interact with DNA via intercalation interaction as concluded from the values of binding constants (K b ). Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, characterization, nucleic acid interactions and photoluminescent properties of methaniminium hydrazone Schiff base and its Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes

NASA Astrophysics Data System (ADS)

Sennappan, M.; Murali Krishna, P.; Hosamani, Amar A.; Hari Krishna, R.

2018-07-01

An environmental benign and efficient reaction was carried out via amine exchange and condensation reaction in water and methanol mixture (3:1) and absence of catalyst between 1-[3-(2-hydroxy benzylidene)amine)phenyl]ethanone and benzhydrazide yields methaniminium hydrazone Schiff base in high yield. The prepared ligand was structurally characterized by using single crystal XRD, elemental analysis and spectroscopy (UV-Vis, FT-IR, LC-MS and NMR) techniques. The crystal data indicates the ligand crystallizes in orthorhombic system with Pna21 space group. Further, the ligand was used in synthesis of mononuclear Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes and were characterized by elemental analysis, magnetic moment and spectroscopy (UV-Vis, FT-IR and ESR) studies. The spectral data showed that ligand is coordinated to the metal ion through azomethine nitrogen and methaniminium nitrogen. The DNA binding absorption titrations reveals that, ligand, L and its metal complexes, 1-6 are avid binders to CT- DNA. The apparent binding constant values of compounds are in the order of 106 M-1. The nuclease activity of ligand, L and its metal complexes, 1-6 were investigated by gel electrophoresis method using pUC18 DNA. The photoluminescent properties of the methaniminium hydrazone ligand, L and its various metal complexes, 1-6 were investigated. The emission spectra of both ligand (L) and metal complexes (1-6) exhibits emission in the range of blue to red.

Synthesis, spectroscopic characterization, electrochemical behaviour, reactivity and antibacterial activity of some transition metal complexes with 2-(N-salicylideneamino)-3-carboxyethyl-4,5-dimethylthiophene.

PubMed

Daniel, Varughese P; Murukan, B; Kumari, B Sindhu; Mohanan, K

2008-07-01

Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with a potentially tridentate Schiff base, formed by condensation of 2-amino-3-carboxyethyl-4,5-dimethylthiophene with salicylaldehyde were synthesized and characterized on the basis of elemental analyses, molar conductance values, magnetic susceptibility measurements, UV-vis, IR, EPR and NMR spectral data, wherever possible and applicable. Spectral studies reveal that the free ligand exists in a bifunctionally hydrogen bonded manner and coordinates to the metal ion in a tridentate fashion through the deprotonated phenolate oxygen, azomethine nitrogen and ester carbonyl group. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry has been proposed for each complex. The EPR spectral data of the Cu(II) complex showed that the metal-ligand bonds have considerable covalent character. The Ni(II) complex has undergone facile transesterification reaction when refluxed in methanol for a lengthy period. X-ray diffraction studies of Cu(II) complex showed that the complex has an orthorhombic crystal lattice. In view of the biological activity of thiophene derivatives, the ligand and the complexes were subjected to antibacterial screening. It has been observed that the antibacterial activity of the ligand increased on chelation with metal ion.

Determination of copper binding in Pseudomonas putida CZ1 by chemical modifications and X-ray absorption spectroscopy.

PubMed

Chen, XinCai; Shi, JiYan; Chen, YingXu; Xu, XiangHua; Chen, LiTao; Wang, Hui; Hu, TianDou

2007-03-01

Previously performed studies have shown that Pseudomonas putida CZ1 biomass can bind an appreciable amount of Cu(II) and Zn(II) ions from aqueous solutions. The mechanisms of Cu- and Zn-binding by P. putida CZ1 were ascertained by chemical modifications of the biomass followed by Fourier transform infrared and X-ray absorption spectroscopic analyses of the living or nonliving cells. A dramatic decrease in Cu(II)- and Zn(II)-binding resulted after acidic methanol esterification of the nonliving cells, indicating that carboxyl functional groups play an important role in the binding of metal to the biomaterial. X-ray absorption spectroscopy was used to determine the speciation of Cu ions bound by living and nonliving cells, as well as to elucidate which functional groups were involved in binding of the Cu ions. The X-ray absorption near-edge structure spectra analysis showed that the majority of the Cu was bound in both samples as Cu(II). The fitting results of Cu K-edge extended X-ray absorption fine structure spectra showed that N/O ligands dominated in living and nonliving cells. Therefore, by combining different techniques, our results indicate that carboxyl functional groups are the major ligands responsible for the metal binding in P. putida CZ1.

Metal complexes of diisopropylthiourea: synthesis, characterization and antibacterial studies.

PubMed

Ajibade, Peter A; Zulu, Nonkululeko H

2011-01-01

Co(II), Cu(II), Zn(II) and Fe(III) complexes of diisopropylthiourea have been synthesized and characterized by elemental analyses, molar conductivity, magnetic susceptibility, FTIR and electronic spectroscopy. The compounds are non-electrolytes in solution and spectroscopic data of the complexes are consistent with 4-coordinate geometry for the metal(II) complexes and six coordinate octahedral for Fe(III) complex. The complexes were screened for their antibacterial activities against six bacteria: Escherichia coli, Pseudomonas auriginosa, Klebsiella pneumoniae, Bacillus cereus, Staphylococcus aureus and Bacillus pumilus. The complexes showed varied antibacterial activities and their minimum inhibitory concentrations (MICs) were determined.

Ternary metal complexes of guaifenesin drug: Synthesis, spectroscopic characterization and in vitro anticancer activity of the metal complexes.

PubMed

Mahmoud, W H; Mahmoud, N F; Mohamed, G G; El-Sonbati, A Z; El-Bindary, A A

2015-01-01

The coordination behavior of a series of transition metal ions named Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a mono negative tridentate guaifenesin ligand (GFS) (OOO donation sites) and 1,10-phenanthroline (Phen) is reported. The metal complexes are characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, UV-vis spectral studies, mass spectroscopy, ESR, XRD and thermal analysis (TG and DTG). The ternary metal complexes were found to have the formulae of [M(GFS)(Phen)Cl]Cl·nH2O (M=Cr(III) (n=1) and Fe(III) (n=0)), [M(GFS)(Phen)Cl]·nH2O (M=Mn(II) (n=0), Zn(II) (n=0) and Cu(II) (n=3)) and [M(GFS)(Phen)(H2O)]Cl·nH2O (M=Co(II) (n=0), Ni(II) (n=0) and Cd(II) (n=4)). All the chelates are found to have octahedral geometrical structures. The ligand and its ternary chelates are subjected to thermal analyses (TG and DTG). The GFS ligand, in comparison to its ternary metal complexes also was screened for their antibacterial activity on gram positive bacteria (Bacillus subtilis and Staphylococcus aureus), gram negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and for in vitro antifungal activity against (Candida albicans). The activity data show that the metal complexes have antibacterial and antifungal activity more than the parent GFS ligand. The complexes were also screened for its in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity. Copyright © 2015 Elsevier B.V. All rights reserved.

Pharmacologically significant complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) of novel Schiff base ligand, (E)-N-(furan-2-yl methylene) quinolin-8-amine: Synthesis, spectral, XRD, SEM, antimicrobial, antioxidant and in vitro cytotoxic studies

NASA Astrophysics Data System (ADS)

Shakir, M.; Hanif, Summaiya; Sherwani, Mohd. Asif; Mohammad, Owais; Al-Resayes, Saud I.

2015-07-01

A novel series of metal complexes of the types, [ML2(H2O)2]Cl2 and [ML2]Cl2 [M = Mn(II), 1; Co(II), 2; Ni(II), 3; Cu(II), 4; and Zn(II), 5] were synthesized by the interaction of ligand, L (E)-N-(furan-2-yl methylene) quinolin-8-amine, derived from the condensation of 2-furaldehyde and 8-aminoquinoline. The synthesized ligand and its metal complexes were characterized on the basis of results obtained from elemental analysis, ESI-MS, XRD, SEM, TGA/DTA, FT-IR, UV-Vis, magnetic moment and 1H and 13C NMR spectroscopic studies. EPR parameters were recorded in case of complex 4. The comparative in-vitro antimicrobial activities against various pathogens with reference to known antibiotics and antioxidant activity against standard control at variable concentrations revealed that the metal complexes show enhanced antimicrobial and free radical scavenging activities in general as compared to free ligand. However, the complexes 1 and 5 have shown best antioxidant activity among all the metal complexes. Furthermore, comparative in-vitro antiproliferative activity on ligand and its metal chelates performed on MDA-MB-231 (breast carcinoma), KCL22 (blood lymphoid carcinoma), HeLa (cervical carcinoma) cell lines and normal cells (PBMC) revealed that metal chelates show moderate to good activity as compared to ligand where as complex 1 seems to be the most promising one possessing a broad spectrum of activity against all the selected cancer cell lines with IC50 < 2.10 μM.

Structural, physicochemical characterization, theoretical studies of carboxamides and their Cu(II), Zn(II) complexes having antibacterial activities against E. coli

NASA Astrophysics Data System (ADS)

Aktan, Ebru; Gündüzalp, Ayla Balaban; Özmen, Ümmühan Özdemir

2017-01-01

The carboxamides; N,N‧-bis(thiophene-2-carboxamido)-1,3-diaminopropanol (L1) and N,N‧-bis(furan-2-carboxamido)-1,3-diaminopropanol (L2) were synthesized and characterized using 1H NMR, 13C NMR, LC-MS and FT-IR spectrum. The molecular geometries of these molecules were optimized by DFT/B3LYP method with 6-311G(d,p) basis set in Gaussian 09 software. The geometrical parameters, frontier molecular orbitals (FMOs) and molecular electrostatic potential (MEP) mapped surfaces were calculated by the same basis set. Dinuclear Cu(II) and Zn(II) complexes having general formula as [MLCl]2Cl2.nH2O (in which M = Cu(II),Zn(II); n = 0,2) were also synthesized and characterized using LC-MS and FT-IR spectrum, thermogravimetric analysis (TGA/DTA curves), magnetic moments and molar conductivities. Coordination was found to be through carbonyl oxygen and two chlorine atoms as bridging in distorted tetrahedral geometry. The optimized structures, geometrical parameters, frontier molecular orbitals (FMOs) and dipole moments of metal complexes were also obtained by DFT/B3LYP method with LanL2DZ basis set. Antibacterial activities of the compounds were screened against E. coli using microdilution method (MIC's in μg/mL). The activity results show that the corresponding compounds exhibit good to moderate antibacterial effects when compared with sulfamethoxazole and sulfisoxazole antibiotics as positive controls. Also, metal complexes have remarkable increase in their activities than parent ligands against E. coli which is mostly effected by [Cu(L2)Cl]2Cl2 complex as potential antibacterial agent.

The role of ligand covalency in the selective activation of metalloenediynes for Bergman cyclization

PubMed Central

Porter, Meghan R.; Zaleski, Jeffrey M.

2017-01-01

One of the key concerns with the development of radical-generating reactive therapeutics is the ability to control the activation event within a biological environment. To that end, a series of quinoline-metal-loenediynes of the form M(QuiED)·2Cl (M = Cu(II), Fe(II), Mg(II), or Zn(II)) and their independently synthesized cyclized analogs have been prepared in an effort to elucidate Bergman cyclization (BC) reactivity differences in solution. HRMS(ESI) establishes a solution stoichiometry of 1:1 metal to ligand with coordination of one chloride counter ion to the metal center. EPR spectroscopy of Cu(QuiED)·2Cl and Cu (QuiBD)·2Cl denotes an axially-elongated tetragonal octahedron (g║ > g⊥ > 2.0023) with a dx2–y2 ground state, while the electronic absorption spectrum reveals a pπ Cl→Cu(II) LMCT feature at 19,000 cm −1, indicating a solution structure with three nitrogens and a chloride in the equatorial plane with the remaining quinoline nitrogen and solvent in the axial positions. Investigations into the BC activity reveal formation of the cyclized product from the Cu(II) and Fe(II) complexes after 12 h at 45 °C in solution, while no product is observed for the Mg(II) or Zn(II) complexes under identical conditions. The basis of this reactivity difference has been found to be a steric effect leading to metal–ligand bond elongation and thus, a retardation of solution reactivity. These results demonstrate how careful consideration of ligand and complex structure may allow for a degree of control and selective activation of these reactive agents. PMID:28931964

The role of ligand covalency in the selective activation of metalloenediynes for Bergman cyclization.

PubMed

Porter, Meghan R; Zaleski, Jeffrey M

2016-01-08

One of the key concerns with the development of radical-generating reactive therapeutics is the ability to control the activation event within a biological environment. To that end, a series of quinoline-metal-loenediynes of the form M( QuiED )·2Cl (M = Cu(II), Fe(II), Mg(II), or Zn(II)) and their independently synthesized cyclized analogs have been prepared in an effort to elucidate Bergman cyclization (BC) reactivity differences in solution. HRMS(ESI) establishes a solution stoichiometry of 1:1 metal to ligand with coordination of one chloride counter ion to the metal center. EPR spectroscopy of Cu( QuiED )·2Cl and Cu ( QuiBD )·2Cl denotes an axially-elongated tetragonal octahedron ( g ║ > g ⊥ > 2.0023) with a d x 2 - y 2 ground state, while the electronic absorption spectrum reveals a pπ Cl→Cu(II) LMCT feature at 19,000 cm -1 , indicating a solution structure with three nitrogens and a chloride in the equatorial plane with the remaining quinoline nitrogen and solvent in the axial positions. Investigations into the BC activity reveal formation of the cyclized product from the Cu(II) and Fe(II) complexes after 12 h at 45 °C in solution, while no product is observed for the Mg(II) or Zn(II) complexes under identical conditions. The basis of this reactivity difference has been found to be a steric effect leading to metal-ligand bond elongation and thus, a retardation of solution reactivity. These results demonstrate how careful consideration of ligand and complex structure may allow for a degree of control and selective activation of these reactive agents.

Adsorption of divalent metals to metal oxide nanoparicles: Competitive and temperature effects

NASA Astrophysics Data System (ADS)

Grover, Valerie Ann

The presence of metals in natural waters is becoming a critical environmental and public health concern. Emerging nanotechnology and the use of metal oxide nanoparticles has been identified as a potential remediation technique in removing metals from water. However, practical applications are still being explored to determine how to apply their unique chemical and physical properties for full scale remediation projects. This thesis investigates the sorption properties of Cd(II), Cu(II), Pb(II) and Zn(II) to hematite (alpha-Fe2O3) and titanium dioxide (TiO2) nanoparticles in single- and binary-adsorbate systems. Competitive sorption was evaluated in 1L batch binary-metal systems with 0.05g/L nano-hematite at pH 8.0 and pH 6.0. Results indicate that the presence of a secondary metal can affect the sorption process depending upon the molar ratios, such as increased or reduced adsorption. Thermodynamic properties were also studied in order to better understand the effects of temperature on equilibrium and kinetic adsorption capabilities. Understanding the thermodynamic properties can also give insight to determine if the sorption process is a physical, chemical or ion exchange reaction. Thermodynamic parameters such as enthalpy (DeltaH), entropy (DeltaS), and Gibbs free energy (DeltaG) were evaluated as a function of temperature, pH, and metal concentration. Results indicate that Pb(II) and Cu(II) adsorption to nano-hematite was an endothermic and physical adsorption process, while Zn(II) and Cd(II) adsorption was dependent upon the adsorbed concentration evaluated. However, metal adsorptions to nano-titanium dioxide were all found to be endothermic and physical adsorption processes; the spontaneity of metal adsorption was temperature dependent for both metal oxide nanoparticles.

Spectroscopic characteristic (FT-IR, 1H, 13C NMR and UV-Vis) and theoretical calculations (MEP, DOS, HOMO-LUMO, PES, NBO analysis and keto-enol tautomerism) of new tetradentate N,N‧-bis(4-hydroxysalicylidene)-1,4-phenylenediamine ligand as chelating agent for the synthesis of dinuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes

NASA Astrophysics Data System (ADS)

Rajaei, Iman; Mirsattari, Seyed Nezamoddin

2018-07-01

The synthesis and characterization of a novel symmetrical Schiff base ligand N,Nʹ-bis(4-hydroxysalicylidene)-1,4-phenylenediamine (BHSP) was presented in this study and characterized by FT-IR, NMR (1H and 13C) and UV-Vis spectroscopy experimentally and theoretically. Also a series of binuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes of BHSP ligand have been synthesized by conventional sequential route in 1:1 equivalent of L:M ratio and characterized by routine physicochemical characterizations. The molecular geometry and vibrational frequencies of the BHSP in the ground state were calculated by using density functional theory (DFT) B3LYP method invoking 6-31G(d,p) and 6-31++G(d,p) basis sets. To study different conformations of the molecule, potential energy surface (PES) scan investigations were performed. The energetic behavior of the ligand compound (BHSP) in solvent media has been examined using B3LYP method with the 6-31G(d,p) and 6-31++G(d,p) basis sets by applying the polarized continuum model (PCM). In addition, DFT calculations of the BHSP ligand, molecular electrostatic potential (MEP), contour map, natural bond orbital (NBO) analysis, frontier molecular orbitals (FMO) analysis, NMR analysis and TD-DFT calculations were conducted. The calculated properties are in agreement with the available experimental data and closely related molecule BSP. The calculated results show that the optimized geometry can well reproduce the crystal structural parameters.

Preparation, spectral, X-ray powder diffraction and computational studies and genotoxic properties of new azo-azomethine metal chelates

NASA Astrophysics Data System (ADS)

Bitmez, Şirin; Sayin, Koray; Avar, Bariş; Köse, Muhammet; Kayraldız, Ahmet; Kurtoğlu, Mükerrem

2014-11-01

A new tridentate azo-azomethine ligand, N‧-[{2-hydroxy-5-[(4-nitrophenyl)diazenyl]phenyl}methylidene]benzohydrazidemonohydrate, (sbH·H2O) (1), is prepared by condensation of benzohydrazide and 2-hydroxy-5-[(4-nitrophenyl)diazenyl]benzaldehyde (a) with treatment of a solution of diazonium salt of p-nitroaniline and 2-hydroxybenzaldehyde in EtOH. The five coordination compounds, [Co(sb)2]·4H2O (2), [Ni(sb)2]·H2O (3), [Cu(sb)2]·4H2O (4), [Zn(sb)2]·H2O (5) and [Cd(sb)2]·H2O (6) are prepared by reacting the Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with the ligand. The structures of the compounds are elucidated from the elemental analyses data and spectroscopic studies. It is found the ligand acts as a tridentate bending through phenolic and carbonyl oxygens and nitrogen atom of the Cdbnd Nsbnd group similar to the most of salicylaldimines. Comparison of the infrared spectra of the ligand and its metal complexes confirm that azo-Schiff base behaves as a monobasic tridentate ligand towards the central metal ion with an ONO donor sequence. Upon complexation with the ligand, the Cd(II), and Zn(II) ions form monoclinic structures, while Co(II), Cu(II) and Ni(II) ions form orthorhombic structures. Quantum chemical calculations are performed on tautomers and its metal chelates by using DFT/B3LYP method. Most stable tautomer is determined as tautomer (1a). The geometrical parameters of its metal chelates are obtained as theoretically. The NLO properties of tautomer (1a) and its metal complexes are investigated. Finally, the ligand and its metal complexes are assessed for their genotoxicity.

Synthesis, characterization and properties of some divalent metal(II) complexes: Their electrochemical, catalytic, thermal and antimicrobial activity studies

NASA Astrophysics Data System (ADS)

Tümer, Mehmet; Ekinci, Duygu; Tümer, Ferhan; Bulut, Akif

2007-07-01

In this study, we synthesized the amine compound 2-(2-aminoethyliminomethyl)phenol (H 3A) as the starting material, and then we prepared the polydentate Schiff base ligands from the reactions of the amine compound (H 3A) with phtaldialdehyde (H 2L), 4-methyl-2,6-di-formlyphenol (H 3L 1) and 4- t-butyl-2,6-di-formylphenol (H 3L 2) in the ethanol solution. Moreover, the complexes Cd(II), Cu(II), Co(II), Ni(II), Zn(II) and Sn(II) of the ligands H 2L, H 3L 1 and H 3L 2 have been prepared. All compounds have been characterized by the analytical and spectroscopic methods. In addition, the magnetic susceptibility and molar conductance measurements have been made. The catalytic properties of the mono- and binuclear Co(II) and Cu(II) complexes have been studied on the 3,5-di- tert-butylcatechol (3,5-DTBC) and ascorbic acid (aa) as a substrate. The oxidative C-C coupling properties of the Co(II) and Cu(II) complexes have been investigated on the sterically hindered 2,6-di- tert-butylphenol (dtbp). The antimicrobial activity properties of the ligands and their mono- and binuclear complexes have been studied against the bacteria and fungi. The results have been compared to the antibacterial and fungi drugs. The TGA curves show that the decomposition takes place in three steps for all complexes. Electrochemical properties of the complexes Cu(II) and Ni(II) have been investigated for the first time in acetonitrile by cyclic voltammetry.

Effects of toxic metals and chemicals on biofilm and biocorrosion.

PubMed

Fang, Herbert H P; Xu, Li-Chong; Chan, Kwong-Yu

2002-11-01

Microbes in marine biofilms aggregated into clusters and increased the production of extracellular polymeric substances (EPS), by over 100% in some cases, when the seawater media containing toxic metals and chemicals, such as Cd(II), Cu(II), Pb(II), Zn(II), AI(III), Cr(III), glutaraldehyde, and phenol. The formation of microbial cluster and the increased production of EPS, which contained 84-92% proteins and 8-16% polysaccharides, accelerated the corrosion of the mild steel. However, there was no quantitative relationship between the degree of increased corrosion and the toxicity of metals/chemicals towards sulfate-reducing bacteria, or the increased EPS production.

Studies on Some Biologically Cobalt(II), Copper(II) and Zinc(II) Complexes With ONO, NNO and SNO Donor Pyrazinoylhydrazine-Derived Ligands

PubMed Central

Praveen, Marapaka; Sherazi, Syed K. A.

1998-01-01

Biologically active complexes of Co(II), Ni(II), Cu(II) and Zn(II) with novel ONO, NNO and SNO donor pyrazinoylhydrazine-derived compounds have been prepared and characterized on the basis of analytical data and various physicochemical studies. Distorted octahedral structures for all the complexes have been proposed. The synthesized ligands and their complexes have been screened for their antibacterial activity against bacterial species Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Klebsiella pneumonae. The activity data show the metal complexes to be more active than the parent free ligands against one or more bacterial species. PMID:18475857

Synthesis, Characterization and Biological Evaluation of Transition Metal Complexes Derived from N, S Bidentate Ligands

PubMed Central

Md Yusof, Enis Nadia; Ravoof, Thahira Begum S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhimanyu; Crouse, Karen Anne; Mohamed Tahir, Mohamed Ibrahim; Ahmad, Haslina

2015-01-01

Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC) with 2-methoxybenzaldehyde (2MB) and 3-methoxybenzaldehyde (3MB). The ligands were reacted separately with acetates of Cu(II), Ni(II) and Zn(II) yielding 1:2 (metal:ligand) complexes. The metal complexes formed were expected to have a general formula of [M(NS)2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1) and S2M3MBH (2) were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7) and estrogen receptor-negative (MDA-MB-231) breast cancer cell lines. Only the Cu(II) complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II) complexes have a strong DNA binding affinity. PMID:25988384

Ligational behaviour of lomefloxacin drug towards Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO(2)(VI) ions: synthesis, structural characterization and biological activity studies.

PubMed

Abd el-Halim, Hanan F; Mohamed, Gehad G; el-Dessouky, Maher M I; Mahmoud, Walaa H

2011-11-01

Nine new mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO(2)(VI) complexes of lomefloxacin drug were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, XRD, UV-vis, (1)H NMR as well as conductivity and magnetic susceptibility measurements and thermal analyses. The dissociation constants of lomefloxacin and stability constants of its binary complexes have been determined spectrophotometrically in aqueous solution at 25±1°C and at 0.1 M KNO(3) ionic strength. The discussion of the outcome data of the prepared complexes indicate that the lomefloxacin ligand behaves as a neutral bidentate ligand through OO coordination sites and coordinated to the metal ions via the carbonyl oxygen and protonated carboxylic oxygen with 1:1 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The powder XRD study reflects the crystalline nature for the investigated ligand and its complexes except Mn(II), Zn(II) and UO(2)(II). The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first steps followed by decomposition of the anions, coordinated water and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. A comparative study of the inhibition zones of the ligand and its metal complexes indicates that metal complexes exhibit higher antibacterial effect against one or more bacterial species than the free LFX ligand. The antifungal and anticancer activities were also tested. The antifungal effect of almost metal complexes is higher than the free ligand. LFX, [Co(LFX)(H(2)O)(4)]·Cl(2) and [Zn(LFX)(H(2)O)(4)]·Cl(2) were found to be very active with IC50 values 14, 11.2 and 43.1, respectively. While, other complexes had been found to be inactive at lower concentration than 100 μg/ml. Copyright © 2011 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic characterization, biological studies and DFT calculations on some transition metal complexes of NO donor ligand

NASA Astrophysics Data System (ADS)

Zordok, W. A.; Sadeek, S. A.

2018-04-01

Seven new complexes of2-oxo-4,6-diphenyl-1,2-dihyropyridine-3-carbonitrile (L) with Fe(III), Co(II), Cu(II), Zn(II), Y(III), Zr(IV) and La(III) were synthesized. The isolated solid compounds were elucidated from micro analytical, IR, electronic, mass, 1H NMR, magnetic susceptibility measurements and TG/DTG, DTA analyses. The intensity of ν(Ctbnd N) was changed to strong and shifted to around 2200 cm-1. Also, the ν(Cdbnd O) was shifted to higher frequency value (1644 cm-1). The spectra of the complexes indicate that the free ligand is coordinated to the metal ions via nitrogen of carbonitrile group and oxygen of keto group. From DFT calculations the Cu(II) and Fe(III) complexes behave as regular octahedral, while other complexes are distorted octahedral. The value of energy gap of the free ligand (ΔE = 0.3343 eV) is greater than all new complexes, so they are more reactive than free ligand, also the Fe(III) complex (ΔE = 0.0985 eV) is the most reactive complex, while Cu(II) complex (ΔE = 0.3219 eV) is the least reactive complex. The LMCT in case of Zr(IV) complex was resulted from transitions from HOMO-2 (62%), HOMO-1 (16%)and HOMO (25%), while the d-d transition in Fe(III) complex was resulted from HOMO-1(30%), HOMO-2(62%) and HOMO(30%). Also, the metal complexes exhibit antibacterial activity for Gram-positive and Gram-negative and antifungal activity. The Y(III) and Cu(II) complexes are highly significant for Escherichia coli and salmonella typhimurium.

Spectral studies, thermal investigation and biological activity of some metal complexes derived from (E)-N‧-(1-(4-aminophenyl)ethylidene)morpholine-4-carbothiohydrazide

NASA Astrophysics Data System (ADS)

El-Samanody, El-Sayed A.; Polis, Magdy W.; Emara, Esam M.

2017-09-01

A new series of biologically active Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes derived from the novel thiosemicarbazone ligand; (E)-N‧-(1-(4-aminophenyl)ethylidene)morpholine-4-carbothiohydrazide (HL) were synthesized. The mode of bonding of the ligand and the geometrical structures of its metal complexes were achieved by different analytical and spectral methods. The ligand coordinated with metal ions in a neutral bidentate fashion through the thione sulfur and azomethine nitrogen atoms. All metal complexes adopted octahedral geometry, except Cu(II) complexes (3, 6, 7) which have a square planar structure. The general thermal decomposition pathways of the ligand along with its metal complexes were explained. The thermal stability of the complexes is controlled by the number of outer and inner sphere water molecules, ionic radii and the steric hindrance. The activation thermodynamic parameters; (activation energy (E*), enthalpy of activation (ΔH*), entropy of activation (ΔS*) and Gibbs free energy (ΔG*)) along with order of reaction (n) were estimated from DTG curves. The ESR spectra of Cu(II) complexes indicated that (dx2-y2)1 is the ground state with covalence character of metal-ligand bonds. The molluscicidal and biochemical effects of the ligand and its Ni(II); Cu(II) complexes (2; 3, 5, 7) along with their combinations with metaldehyde were screened in vitro on the mucous gland of Eobania vermiculata. The tested compounds exhibited a significant toxicity against the tested animals and have almost the same toxic effect of metaldehyde which increases the mucous secretion of the snails and leads to death.

Dinuclear complexes containing linear M-F-M [M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)] bridges: trends in structures, antiferromagnetic superexchange interactions, and spectroscopic properties.

PubMed

Reger, Daniel L; Pascui, Andrea E; Smith, Mark D; Jezierska, Julia; Ozarowski, Andrew

2012-11-05

The reaction of M(BF(4))(2)·xH(2)O, where M is Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II), with the new ditopic ligand m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (L(m)*) leads to the formation of monofluoride-bridged dinuclear metallacycles of the formula [M(2)(μ-F)(μ-L(m)*)(2)](BF(4))(3). The analogous manganese(II) species, [Mn(2)(μ-F)(μ-L(m)*)(2)](ClO(4))(3), was isolated starting with Mn(ClO(4))(2)·6H(2)O using NaBF(4) as the source of the bridging fluoride. In all of these complexes, the geometry around the metal centers is trigonal bipyramidal, and the fluoride bridges are linear. The (1)H, (13)C, and (19)F NMR spectra of the zinc(II) and cadmium(II) compounds and the (113)Cd NMR of the cadmium(II) compound indicate that the metallacycles retain their structure in acetonitrile and acetone solution. The compounds with M = Mn(II), Fe(II), Co(II), Ni(II), and Cu(II) are antiferromagnetically coupled, although the magnitude of the coupling increases dramatically with the metal as one moves to the right across the periodic table: Mn(II) (-6.7 cm(-1)) < Fe(II) (-16.3 cm(-1)) < Co(II) (-24.1 cm(-1)) < Ni(II) (-39.0 cm(-1)) ≪ Cu(II) (-322 cm(-1)). High-field EPR spectra of the copper(II) complexes were interpreted using the coupled-spin Hamiltonian with g(x) = 2.150, g(y) = 2.329, g(z) = 2.010, D = 0.173 cm(-1), and E = 0.089 cm(-1). Interpretation of the EPR spectra of the iron(II) and manganese(II) complexes required the spin Hamiltonian using the noncoupled spin operators of two metal ions. The values g(x) = 2.26, g(y) = 2.29, g(z) = 1.99, J = -16.0 cm(-1), D(1) = -9.89 cm(-1), and D(12) = -0.065 cm(-1) were obtained for the iron(II) complex and g(x) = g(y) = g(z) = 2.00, D(1) = -0.3254 cm(-1), E(1) = -0.0153, J = -6.7 cm(-1), and D(12) = 0.0302 cm(-1) were found for the manganese(II) complex. Density functional theory (DFT) calculations of the exchange integrals and the zero-field splitting on manganese(II) and iron(II) ions were performed using the hybrid B3LYP functional in association with the TZVPP basis set, resulting in reasonable agreement with experiment.

Single crystal EPR and optical studies of paramagnetic ions doped zinc potassium phosphate hexahydrate—Part I: Cu(II)—a case of orthorhombic symmetry

NASA Astrophysics Data System (ADS)

Sambasiva Rao, P.; Rajendiran, T. M.; Venkatesan, R.; Madhu, N.; Chandrasekhar, A. V.; Reddy, B. J.; Reddy, Y. P.; Ravikumar, R. V. S. S. N.

2001-12-01

Single crystal electron paramagnetic resonance (EPR) studies on Cu(II) doped zinc potassium phosphate hexahydrate (ZPPH) were carried out at room temperature. The angular variation spectra in the three orthogonal planes indicate that the paramagnetic impurity has entered the lattice substitutionally in place of Zn(II) and the spin Hamiltonian parameters calculated from these spectra are gxx=2.188, gyy=2.032, gzz=2.373, Axx=50 G, Ayy=65.0 G and Azz=80 G. The g and A tensors were coincident and these values matched fairly well with the values obtained from powder spectrum. The bonding parameters have also been calculated.

Synthesis, spectroscopic characterization and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with Schiff bases derived from 5-bromo-salicylaldehyde

NASA Astrophysics Data System (ADS)

Kursunlu, Ahmed Nuri; Guler, Ersin; Sevgi, Fatih; Ozkalp, Birol

2013-09-01

In this study, the new Schiff base ligands derived from condensation of amine and 5-bromo-salicylaldehyde were characterized. All compounds, the Schiff bases and the metal complexes, were characterized by elemental analyzes, FT-IR, 1H NMR, 13C NMR and magnetic susceptibility measurements. The synthesized ligands, along with their metal (II) complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa and Salmonella enteritidis) and four Gram-positive (Streptococcus pyogones, Bacillus cereus, Staphylococcus aureus and Methicillin-resistant S. aureus) bacterial strains by using disc diffusion and broth microdilution techniques.

Preparation of Palladium(II) Ion-Imprinted Polymeric Nanospheres and Its Removal of Palladium(II) from Aqueous Solution

NASA Astrophysics Data System (ADS)

Tao, Hu-Chun; Gu, Yi-Han; Liu, Wei; Huang, Shuai-Bin; Cheng, Ling; Zhang, Li-Juan; Zhu, Li-Li; Wang, Yong

2017-11-01

Three kinds of functional monomers, 4-vinylpridine(4-VP), 2-(allylthio)nicotinic acid(ANA), and 2-Acetamidoacrylic acid(AAA), were used to synthetize palladium(II) ion-imprinted polymeric nanospheres (Pd(II) IIPs) via precipitation-polymerization method in order to study the effects of different functional monomers on the adsorption properties of ion-imprinted materials. The results of UV spectra in order to study the interaction between template ion PdCl4 2- and functional monomers showed that there were great differences in structure after the template reacted with three functional monomers, 4-VP and ANA caused a large structural change, while AAA basically did not change. Further results on the adsorption performance of Pd(II) IIPs on Pd(II) confirmed 4-VP was the most promising candidate for the synthesis of Pd(II) IIPs with an adsorption capacity of 5.042 mg/g as compared with ANA and AAA. The influence of operating parameters on Pd(II) IIP's performance on Pd(II) adsorption was investigated. There was an increase in the adsorption capacity of Pd(II) IIPs at higher pH, temperature, and initial concentration of Pd(II). The results of multi-metal competitive adsorption experiments showed that Pd(II) IIPs had selectivity for Pd(II). An adsorption equilibrium could be reached at 180 min. Kinetic analysis showed that the adsorption test data fitted best to the pseudo-second order kinetic model, and the theoretical equilibrium adsorption capacity was about 5.085 mg/g. The adsorption isotherms of Pd(II) by Pd(II) IIPs agreed well with the Freundlich equation, suggesting a favorable adsorption reaction under optimal conditions. These results showed that Pd(II) IIPs have potential application in the removal of Pd(II) from aqueous solutions and may provide some information for the selection of functional monomers in the preparation of Pd(II) IIPs.

Functionalisation of mesoporous silica gel with 2-[(phosphonomethyl)-amino]acetic acid functional groups. Characterisation and application

NASA Astrophysics Data System (ADS)

Caldarola, Dario; Mitev, Dimitar P.; Marlin, Lucile; Nesterenko, Ekaterina P.; Paull, Brett; Onida, Barbara; Bruzzoniti, Maria Concetta; Carlo, Rosa Maria De; Sarzanini, Corrado; Nesterenko, Pavel N.

2014-01-01

A new complexing adsorbent was prepared by chemical modification of mesoporous silica Kieselgel 60 (dp = 37-63 μm, average pore size 6 nm, specific surface area 425 m2 g-1) with 3-glycidoxypropyltrimethoxysilane and 2-[(phosphonomethyl)amino]acetic acid (PMA), commonly known as glyphosate. The prepared adsorbent was fully characterised using elemental analysis, thermal gravimetric analysis (TGA), acid-base potentiometric titration, Fourier Transform Infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption isotherms at 77 K (BET), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). The concentration of bonded PMA groups calculated from the nitrogen content was 0.38 mmol per gram. The adsorption of transition metal ions on PMA functionalised silica (HEPMAS) was studied from aqueous solutions having different pH and the following selectivity was established, Zn(II) < Co(II) < Cd(II) < Mn(II) < Ni(II) < Cu(II). The calculated values of distribution coefficients D for the adsorption of ecotoxic metal ions on HEPMAS are 5.0 × 104, 4.9 × 105 and 2.6 × 104 for Zn(II), Pb(II) and Cd(II), respectively.

Structure and mechanism of Cu- and Ni-substituted analogs of metallo-β-lactamase L1

PubMed Central

Hu, Zhenxin; Spadafora, Lauren J.; Hajdin, Christine E.; Bennett, Brian; Crowder, Michael W.

2009-01-01

In an effort to further probe metal binding to metallo-β-lactamase L1 (mβl L1), Cu- (Cu-L1) and Ni-substituted (Ni-L1) L1 were prepared and characterized by kinetic and spectroscopic studies. Cu-L1 bound 1.7 equivalents of Cu and small amounts of Zn(II) and Fe. The EPR spectrum of Cu-L1 exhibited two overlapping, axial signals, indicative of type 2 sites with distinct affinities for Cu(II). Both signals indicated multiple nitrogen ligands. Despite the expected proximity of the Cu(II) ions, however, only indirect evidence was found for spin-spin coupling. Cu-L1 exhibited higher kcat (96 s−1) and Km (224 μM) values, as compared to the values of dinuclear Zn(II)-containing L1, when nitrocefin was used as substrate. The Ni-L1 bound 1 equivalent of Ni and 0.3 equivalents of Zn(II). Ni-L1 was EPR-silent, suggesting that the oxidation state of nickel was +2; this suggestion was confirmed by 1H NMR spectra, which showed relatively sharp proton resonances. Stopped-flow kinetic studies showed that ZnNi-L1 stabilized significant amounts of the nitrocefin-derived intermediate and that the decay of intermediate is rate-limiting. 1H NMR spectra demonstrate that Ni(II) binds in the Zn2 site and that the ring-opened product coordinates Ni(II). Both Cu-L1 and ZnNi-L1 hydrolyze cephalosporins and carbapenems, but not penicillins, suggesting that the Zn2 site modulates substrate preference in mβ1 L1. These studies demonstrate that the Zn2 site in L1 is very flexible and can accommodate a number of different transition metal ions; this flexibility could possibly offer an organism that produces L1 an evolutionary advantage when challenged with β-lactam containing antibiotics. PMID:19228020

Investigating Langmuir films at the air-water interface using a planar array infrared reflection-absorption spectrograph

NASA Astrophysics Data System (ADS)

Kim, Young Shin

In this work, a new planar array infrared reflection-absorption spectrograph (PA-IRRAS) was developed to investigate a broad range of Langmuir films at the air-water interface. This instrument is capable of recording sample and reference spectra simultaneously with an optical setup that is the same as that of a single-beam instrument but splits the incident infrared beam into two sections on a plane mirror (H) or a water trough. With this design, the instrument could accommodate large infrared accessories, such as a water trough. In addition, water bands were subtracted to obtain a high quality spectrum for a poly(lactic acid) (PLA) Langmuir film on the water subphase with a resolution of about 8 cm-1 in 10.8 sec. With this instrument, two types of monolayer systems were studied; polymeric and lipid Langmuir films at the air-water interface. For the polymeric monolayer system, PA-IRRAS was used as a probe to follow the real-time conformational changes associated with intermolecular interactions of the polymer chains during the compression of the monolayers. It was found that the mixture of poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) (D/L) formed a stereocomplex when the mixed solution developed the two-dimensional monolayer at the air-water interface. The stereocomplexation occurred before film compression, indicating that there is no direct correlation between film compression and stereocomplexation. For the lipid monolayer system, PA-IRRAS was also used as a probe to investigate the origin of the disruption of a lipid monolayer upon protein adsorption at the air-water interface. Analysis of the time-resolved PA-IRRAS spectra revealed that Cu(II) ion-chelated DSIDA lipid monolayer (Cu 2+-DSIDA) was readily disrupted by myoglobin adsorption as demonstrated by a blue shift of 1.7 cm-1 and a lower intensity in the vas(CH2) stretch mode of the lipid monolayer over a period of five hours. To find the origin of the disruption of the lipid monolayer, a postulated model, employing a DSIDA monolayer-deposited ZnSe window, was investigated. An FT-IR spectroscopic study demonstrated that the Cu(II) ion formed stronger chelation with an iminodiacetatic acid (IDA) lipid head group than that formed with a Zn(II) ion. In addition, no distinct difference was observed in the secondary structures of myoglobin as myoglobin was adsorbed to Cu2+-DSIDA over a period of five hours. Dynamic light scattering (DLS) data revealed that, by the addition of Cu(II) or Zn(II) ion, lysozyme was rapidly aggregated and readily precipitated. However, the hydrodynamic volume of myoglobin was not responsive to the addition of Zn(II) ion. When Cu(II) ion was added, aggregation of myoglobin was sustained without precipitation over a period of five hours. Therefore, these results strongly suggest that the disruption of Cu2+-DSIDA lipid monolayer upon myoglobin adsorption is due to myoglobin aggregation, mediated by the chelated Cu(II) ion, rather than a conformational change in adsorbed myoglobin. Besides the above monolayer systems, PA-IRRAS is used for the rapid detection of a low concentration of aqueous species. The previous designs for a PA-IR spectrograph were not applicable to detect a low concentration of aqueous species due to the contribution from a stray light and high relative humidity (in the vicinity of 25-40%). To overcome this problem, newly designed PA-IRRAS optical setup was purged with dry nitrogen gas to keep the relative humidity at approximately 15%. In addition, baffles constructed from corrugated cardboard were placed throughout the optical setup to prevent any stray light from reaching the detector. The PA-IRRAS results obtained from poly(N-isopropylacrylamide) (PNIPAM) revealed that solutions down to a concentration of 0.005% w/w could be successfully studied. These results are quite remarkable, given the acquisition time of only 10 seconds and the direct overlap of the Amide I band of PNIPAM and the H-O-H stretch of H2O. (Abstract shortened by UMI.)

Synthesis, spectroscopic, biological activity and thermal characterization of ceftazidime with transition metals

NASA Astrophysics Data System (ADS)

Masoud, Mamdouh S.; Ali, Alaa E.; Elasala, Gehan S.; Kolkaila, Sherif A.

2018-03-01

Synthesis, physicochemical characterization and thermal analysis of ceftazidime complexes with transition metals (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)) were discussed. It's obtained that ceftazidime act as bidentate ligand. From magnetic measurement and spectral data, octahedral structures were proposed for all complexes except for cobalt, nickel and mercury had tetrahedral structural. Hyper chemistry program confirmed binding sites of ceftazidime. Ceftazidime complexes show higher activity than ceftazidime for some strains. From TG and DTA curves the thermal decomposition mechanisms of ceftazidime and their metal complexes were suggested. The thermal decomposition of the complexes ended with the formation of metal oxides as a final product except in case of Hg complex.

Single crystal EPR and optical studies of paramagnetic ions doped zinc potassium phosphate hexahydrate--part I: Cu(II)--a case of orthorhombic symmetry.

PubMed

Sambasiva Rao, P; Rajendiran, T M; Venkatesan, R; Madhu, N; Chandrasekhar, A V; Reddy, B J; Reddy, Y P; Ravikumar, R V

2001-12-01

Single crystal electron paramagnetic resonance (EPR) studies on Cu(II) doped zinc potassium phosphate hexahydrate (ZPPH) were carried out at room temperature. The angular variation spectra in the three orthogonal planes indicate that the paramagnetic impurity has entered the lattice substitutionally in place of Zn(II) and the spin Hamiltonian parameters calculated from these spectra are g(xx) = 2.188, g(yy) = 2.032, g(zz) = 2.373, Axx = 50 G, Ayy = 65.0 G and Azz = 80 G. The g and A tensors were coincident and these values matched fairly well with the values obtained from powder spectrum. The bonding parameters have also been calculated.

Bivalent transition metal complexes of o-hydroxyacetophenone [N-(3-hydroxy-2-naphthoyl)] hydrazone: Spectroscopic, antibacterial, antifungal activity and thermogravimetric studies

NASA Astrophysics Data System (ADS)

Zaky, R. R.; Ibrahim, K. M.; Gabr, I. M.

2011-10-01

Schiff base complexes of Cu(II), Ni(II) and Zn(II) with the o-hydroxyacetophenone [N-(3-hydroxy-2-naphthoyl)] hydrazone (H 2o-HAHNH) containing N and O donor sites have been synthesized. Both ligand and its metal complexes were characterized by different physicochemical methods, elemental analysis, molar conductivity ( 1H NMR, 13C NMR, IR, UV-visible, ESR, MS spectra) and also thermal analysis (TG and DTG) techniques. The discussion of the outcome data of the prepared complexes indicates that the ligand behave as a bidentate and/or tridentate ligand. The electronic spectra of the complexes as well as their magnetic moments suggest octahedral geometries for all isolated complexes. The room temperature solid state ESR spectrum of the Cu(II) complex shows d x2- y2 as a ground state, suggesting tetragonally distorted octahedral geometry around Cu(II) centre. The molar conductance measurements proved that the complexes are non-electrolytes. The kinetic thermodynamic parameters such as: E#, Δ H#, Δ G#, Δ S# are calculated from the DTG curves, for the [Ni(H O-HAHNH) 2] and [Zn(H 2 O-HAHNH)(OAc) 2]·H 2O complexes using the Coats-Redfern equation. Also, the antimicrobial properties of all compounds were studied using a wide spectrum of bacterial and fungal strains. The [Cu(H o-HAHNH)(OAc)(H 2O) 2] complex was the most active against all strains, including Aspergillus sp., Stemphylium sp. and Trichoderma sp. Fungi; E. coli and Clostridium sp. Bacteria.

Effect of Jahn-Teller ion in zinc sodium sulphate hexahydrate: a case of low hyperfine coupling constant for Cu(II) ion

NASA Astrophysics Data System (ADS)

Naidu, K. C.; Shiyamala, C.; Mithira, S.; Natarajan, B.; Venkatesan, R.; Rao, P. S.

2005-06-01

Single crystal electron paramagnetic resonance (EPR) studies of Cu(II) doped zinc sodium sulphate hexahydrate are carried out from room temperature (RT) to 123 K. The RT spectra show unresolved hyperfine lines and hence angular variation studies are also carried out at 123 K to obtain spin Hamiltonian parameters. The spin Hamiltonian parameters calculated from the 123 K spectra are: g(11)=2.039, g(22)=2.232, g(33)=2.394, A(11)=5.64 mT, A(22)=4.20 mT, and A(33)=7.94 mT. The g-matrix values at RT and 123 K have matched fairly well with each other. The low hyperfine value (A(33)), obtained at 123 K, has been explained by considering considerable admixture of d(x 2-y 2) ground state with d(z 2) excited state and the delocalization of the unpaired spin density onto the ligands. The admixture coefficients of ground state wave function are: a=0.346, b=0.935, c=0.055, d=0.040, e=-0.040, where a and b correspond to admixture coefficients for d(z 2) and d(x 2-y 2), respectively. Angular variation of Cu(II) resonances in the three orthogonal axes shows that the impurity has entered a substitutional site in the host lattice in place of Zn(II). Bonding parameters, kappa=0.295, P=245.4x10(-4), alpha(2)=0.709, alpha=0.8421 and alpha'=0.6034, have also been calculated to fully characterize the EPR.

Screening and production of a potent extracellular Arthrobacter creatinolyticus urease for determination of heavy metal ions.

PubMed

Ramesh, Rajendran; Aarthy, Mayilvahanan; Gowthaman, Marichetti Kuppuswami; Gabrovska, Katya; Godjevargova, Tzonka; Kamini, Numbi Ramudu

2014-04-01

This paper describes the isolation of a potent extracellular urease producing microorganism, identified by 16S rRNA as Arthrobacter creatinolyticus MTCC 5604 and its medium optimization by classical one-factor-at-a-time method and central composite rotatable design (CCRD), a tool of response surface methodology (RSM). An optimal activity of 9.0 U ml(-1) was obtained by classical method and statistical optimization of the medium resulted in an activity of 17.35 U ml(-1) at 48 h and 30 °C. This activity was 4.91 times greater than the initial activity (3.53 U ml(-1) ) from the basal medium and the enzyme showed maximum activity at pH 8.0 and 60 °C and was stable at pH 7.0-9.0 and temperatures up to 50 °C. Furthermore, the enzyme was assessed for its activity reduction by determining the inhibitory concentration (IC50 ) of heavy metal ions and the inhibition of urease was in the order of Cu(II) > Cd(II) > Zn(II) > Ni(II). Urease was highly sensitive to Cu(II) and its inhibition was 94% and 100% in model solutions containing a mixture of Cu(II) with heavy metal ions Cd(II) and Zn(II), respectively. The results of these studies suggested that the enzyme could be utilized as sensors to determine the levels of Cu(II) ions in industrial effluents, contaminated soil and ground water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrospray ionization mass spectrometric investigations of the complexation behavior of macrocyclic thiacrown ethers with bivalent transitional metals (Cu, Co, Ni and Zn).

PubMed

Tsybizova, Alexandra; Tarábek, Ján; Buchta, Michal; Holý, Petr; Schröder, Detlef

2012-10-15

Heavy metals are both a problem for the environment and an important resource for industry. Their selective extraction by means of organic ligands therefore is an attractive topic. The coordination of three thiacrown ethers to late 3d-metal ions was investigated by a combination of electrospray ionization mass spectrometry (ESI-MS) and electron paramagnetic resonance (EPR). The mass spectrometric experiments were carried out in an ion trap mass spectrometer with an ESI source. Absolute binding constants were estimated by comparison with data for 18-crown-6/Na(+). EPR spectroscopy was used as a complementary method for investigating the Cu(I) /Cu(II) redox couple. The study found that thiacrown ethers preferentially bind traces of copper even at an excess of other metal ions (Co(II), Ni(II), and Zn(II)). The absolute association constants of the Cu(I) complexes were about 10(8) M(-1), and about two orders of magnitude lower for the other 3d-metal cations. The EPR spectra demonstrated that the reduction from Cu(II) to Cu(I) upon formation of the [(thiacrown)Cu](+) species takes place in solution. ESI-MS demonstrated that the three thiacrown ligands examined had high binding constants as well as good selectivities for copper(I) at low concentrations, and in the presence of other metal ions. By a combination of ESI-MS and EPR spectrometry it was shown that the reduction from Cu(II) to Cu(I) occurred in solution. Copyright © 2012 John Wiley & Sons, Ltd.

Synthesis, interaction with DNA and bovine serum albumin of the transition metal complexes of demethylcantharate and 2-aminobenzothiazole

NASA Astrophysics Data System (ADS)

Zhang, Fan; Lin, Qiu-Yue; Li, Shi-Kun; Zhao, Yu-Ling; Wang, Peng-Peng; Chen, Miao-Miao

2012-12-01

Four new transition metal complexes (Habtz)2[M(DCA)2]·6H2O (M = Co(II) (1), Ni(II) (2), Cu(II) (3), Zn(II) (4); DCA = demethylcantharate, 7-oxabicyclo [2.2.1]heptane-2,3-dicarboxylate, C8H8O5; Habtz = 2-aminobenzothiazole acid, C7H7N2S) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra and thermogravimetric analysis. The coordination number of complex was six. The X-ray diffraction analysis indicated that complex 3 crystallized in the triclinic crystal system with P1¯ space group. The DNA-binding properties of the complexes were investigated by electronic absorption spectra, fluorescence spectra, viscosity measurements. Title complexes could bind to DNA via partial intercalative mode. The Kb of the complexes were 5.33 × 104 (1), 7.04 × 104 (2), 9.91 × 104 (3) and 5.03 × 104 L mol-1 (4). The results of agarose gel electrophoresis showed that Cu(II) complex could cleave pBR322 plasmid DNA via radical-based mechanism. The complexes could quench the intrinsic fluorescence of bovine serum albumin (BSA) through a static quenching with the binding constants Ka of 1.11 × 104 (1), 1.24 × 106 (2), 8.42 × 105 (3) and 1.75 × 104 L mol-1 (4). The complexes had intense antiproliferative activities against human hepatoma cell lines (SMMC7721) and human gastric cancer cells (MGC80-3) lines in vitro. Cu(II) complex had the strongest activity against human gastric cancer cells.

Rapid detection of protein phosphatase activity using Zn(II)-coordinated gold nanosensors based on His-tagged phosphopeptides.

PubMed

Lee, Jin Oh; Kim, Eun-Ji; Lim, Butaek; Kim, Tae-Wuk; Kim, Young-Pil

2015-01-20

We report a rapid colorimetric assay to detect protein phosphatase (PP) activity based on the controlled assembly and disassembly of gold nanoparticles (AuNPs) via Zn(II)-specific coordination in the presence of His6-tagged phosphopeptides. Among divalent metal ions including Ni(II), Cu(II), Co(II), Mg(II), Mn(II), and Zn(II), only Zn(II) triggered a strong association between phosphopeptides with hexahistidine at a single end and nitrilotriacetic acid (NTA)-modified AuNPs (21.3 nm in core diameter), leading to the self-assembly of AuNPs and consequently changes in color of the AuNP solution. In contrast, unphosphorylated peptides and His6-deficient phosphopeptides did not change the color of the AuNP solution. As a result, protein phosphatase 1 (PP1) activity and its inhibition were easily quantified with high sensitivity by determining the extinction ratio (E520/E700) of colloidal AuNPs. Most importantly, this method was capable of detecting protein phosphatase 2A (PP2A) activity in immunoprecipitated plant extracts. Because PPs play pivotal roles in mediating diverse signal transduction pathways as primary effectors of protein dephosphorylation, we anticipate that our method will be applied as a rapid format method to analyze the activities of various PPs and their inhibition.

Possible steric control of the relative strength of chelation enhanced fluorescence for zinc(II) compared to cadmium(II): metal ion complexing properties of tris(2-quinolylmethyl)amine, a crystallographic, UV-visible, and fluorometric study.

PubMed

Williams, Neil J; Gan, Wei; Reibenspies, Joseph H; Hancock, Robert D

2009-02-16

The idea is examined that steric crowding in ligands can lead to diminution of the chelation enhanced fluorescence (CHEF) effect in complexes of the small Zn(II) ion as compared to the larger Cd(II) ion. Steric crowding is less severe for the larger ion and for the smaller Zn(II) ion leads to Zn-N bond length distortion, which allows some quenching of fluorescence by the photoinduced electron transfer (PET) mechanism. Some metal ion complexing properties of the ligand tris(2-quinolylmethyl)amine (TQA) are presented in support of the idea that more sterically efficient ligands, which lead to less M-N bond length distortion with the small Zn(II) ion, will lead to a greater CHEF effect with Zn(II) than Cd(II). The structures of [Zn(TQA)H(2)O](ClO(4))(2).1.5 H(2)O (1), ([Pb(TQA)(NO(3))(2)].C(2)H(5)OH) (2), ([Ag(TQA)(ClO(4))]) (3), and (TQA).C(2)H(5)OH (4) are reported. In 1, the Zn(II) is 5-coordinate, with four N-donors from the ligand and a water molecule making up the coordination sphere. The Zn-N bonds are all of normal length, showing that the level of steric crowding in 1 is not sufficient to cause significant Zn-N bond length distortion. This leads to the observation that, as expected, the CHEF effect in the Zn(II)/TQA complex is much stronger than that in the Cd(II)/TQA complex, in contrast to similar but more sterically crowded ligands, where the CHEF effect is stronger in the Cd(II) complex. The CHEF effect for TQA with the metal ions examined varies as Zn(II) > Cd(II) > Ni(II) > Pb(II) > Hg(II) > Cu(II). The structure of 2 shows an 8-coordinate Pb(II), with evidence of a stereochemically active lone pair, and normal Pb-N bond lengths. In 3, the Ag(I) is 5-coordinate, with four N-donors from the TQA and an oxygen from the perchlorate. The Ag(I) shows no distortion toward linear 2-coordinate geometry, and the Ag-N bonds fall slightly into the upper range for Ag-N bonds in 5-coordinate complexes. The structure of 4 shows the TQA ligand to be involved in pi-stacking between quinolyl groups from adjacent TQA molecules. Formation constants determined by UV-visible spectroscopy are reported in 0.1 M NaClO(4) at 25 degrees C for TQA with Zn(II), Cd(II), and Pb(II). When compared with other similar ligands, one sees that, as the level of steric crowding increases, the stability decreases most with the small Zn(II) ion and least with the large Pb(II) ion. This is in accordance with the idea that TQA has a moderate level of steric crowding and that steric crowding increases for TQA analogs tris(2-pyridylmethyl)amine (TPyA) < TQA < tris(6-methyl-2-pyridyl)amine (TMPyA).

Antioxidant, electrochemical, thermal, antimicrobial and alkane oxidation properties of tridentate Schiff base ligands and their metal complexes

NASA Astrophysics Data System (ADS)

Ceyhan, Gökhan; Çelik, Cumali; Uruş, Serhan; Demirtaş, İbrahim; Elmastaş, Mahfuz; Tümer, Mehmet

2011-10-01

In this study, two Schiff base ligands (HL 1 and HL 2) and their Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) metal complexes were synthesized and characterized by the analytical and spectroscopic methods. Alkane oxidation activities of the metal complexes were studied on cyclohexane as substrate. The ligands and their metal complexes were evaluated for their antimicrobial activity against Corynebacterium xerosis, Bacillus brevis, Bacillus megaterium, Bacillus cereus, Mycobacterium smegmatis, Staphylococcus aureus, Micrococcus luteus and Enterococcus faecalis (as Gram-positive bacteria) and Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Yersinia enterocolitica, Klebsiella fragilis, Saccharomyces cerevisiae, and Candida albicans (as Gram-negative bacteria). The antioxidant properties of the Schiff base ligands were evaluated in a series of in vitro tests: 1,1-diphenyl-2-picrylhydrazyl (DPPH rad ) free radical scavenging and reducing power activity of superoxide anion radical generated non-enzymatic systems. Electrochemical and thermal properties of the compounds were investigated.

Interaction of curcumin with Zn(II) and Cu(II) ions based on experiment and theoretical calculation

NASA Astrophysics Data System (ADS)

Zhao, Xue-Zhou; Jiang, Teng; Wang, Long; Yang, Hao; Zhang, Sui; Zhou, Ping

2010-12-01

Curcumin and its complexes with Zn 2+ and Cu 2+ ions were synthesized and characterized by elemental analysis, mass spectroscopy, IR spectroscopy, UV spectroscopy, solution 1H and solid-state 13C NMR spectroscopy, EPR spectroscopy. In addition, the density functional theory (DFT)-based UV and 13C chemical shift calculations were also performed to view insight into those compound structures and properties. The results show that curcumin easily chelate the metal ions, such as Zn 2+ and Cu 2+, and the Cu(II)-curcumin complex has an ability to scavenge free-radicals. We demonstrated the differences between Zn(II)-curcumin and Cu(II)-curcumin complexes in structure and properties, enhancing the comprehensions about the curcumin roles in the Alzhermer's disease treatment.

Synthesis, spectroscopic characterization, antimicrobial and antitumor studies of mono-, bi- and tri-nuclear metal complexes of a new Schiff base ligand derived from o-acetoacetylphenol

NASA Astrophysics Data System (ADS)

Adly, Omima M. I.; Shebl, Magdy; El-Shafiy, Hoda F.; Khalil, Saied M. E.; Taha, A.; Mahdi, Mohammed A. N.

2017-12-01

New mono-, bi- and trinuclear metal complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and UO2(VI) with a new Schiff base ligand H3L; ((E)-2-hydroxy-N‧-(4-(2-hydroxyphenyl)-4-oxobutan-2-ylidene)) benzohydrazide (H3L) have been synthesized. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The metal complexes exhibited octahedral and tetrahedral geometrical arrangements. Kinetic parameters (Ea, A, ΔH, ΔS and ΔG) of the thermal decomposition stages have been evaluated using Coats-Redfern equations. Structural parameters of the synthesized compounds were calculated on the basis of DFT level implemented in the Gaussian 09 program and Hyperchem 7.52 and correlated with the experimental data. The antimicrobial activity of the present compounds was screened against Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Salmonella typhimurium and Escherichia coli), yeast (Candida albicans) and fungus (Aspergillus fumigatus). The antitumor activity of the ligand and its Ni(II) and Cu(II) complexes was investigated against HepG2 cell line.

Non-enzymatic palladium recovery on microbial and synthetic surfaces.

PubMed

Rotaru, Amelia-Elena; Jiang, Wei; Finster, Kai; Skrydstrup, Troels; Meyer, Rikke Louise

2012-08-01

The use of microorganisms as support for reduction of dissolved Pd(II) to immobilized Pd(0) nanoparticles is an environmentally friendly approach for Pd recovery from waste. To better understand and engineer Pd(0) nanoparticle synthesis, one has to consider the mechanisms by which Pd(II) is reduced on microbial surfaces. Escherichia coli, Shewanella oneidensis, and Pseudomonas putida were used as model organisms in order to elucidate the role of microbial cells in Pd(II) reduction under acidic conditions. Pd(II) was reduced by formate under acidic conditions, and the process occurred substantially faster in the presence of cells as compared to cell-free controls. We found no difference between native (untreated) and autoclaved cells, and could demonstrate that even a non-enzymatic protein (bovine serum albumin) stimulated Pd(II) reduction as efficiently as bacterial cells. Amine groups readily interact with Pd(II), and to specifically test their role in surface-assisted Pd(II) reduction by formate, we replaced bacterial cells with polystyrene microparticles functionalized with amine or carboxyl groups. Amine-functionalized microparticles had the same effect on Pd(II) reduction as bacterial cells, and the effect could be hampered if the amine groups were blocked by acetylation. The interaction with amine groups was confirmed by infrared spectroscopy on whole cells and amine-functionalized microparticles. In conclusion, bio-supported Pd(II) reduction on microbial surfaces is possibly mediated by a non-enzymatic mechanism. We therefore suggest the use of amine-rich biomaterials rather than intact cells for Pd bio-recovery from waste. Copyright © 2012 Wiley Periodicals, Inc.

Nucleoside-2',3'/3',5'-bis(thio)phosphate antioxidants are also capable of disassembly of amyloid beta42-Zn(ii)/Cu(ii) aggregates via Zn(ii)/Cu(ii)-chelation.

PubMed

Hevroni, Bosmat Levi; Major, Dan Thomas; Dixit, Mudit; Mhashal, Anil Ranu; Das, Susanta; Fischer, Bilha

2016-05-18

Currently, there is an urgent need for biocompatible metal-ion chelators capable of antioxidant activity and disassembly of amyloid beta (Aβ)-aggregates as potential therapeutics for Alzheimer's disease (AD). We recently demonstrated the promising antioxidant activity of adenine/guanine 2',3' or 3',5'-bis(thio)phosphate analogues, 2'-dA/G3'5'PO/S and A2'3'PO/S, and their affinity to Zn(ii)-ions. These findings encouraged us to evaluate them as agents for the dissolution of Aβ42-Zn(ii)/Cu(ii) aggregates. Specifically, we explored their ability to bind Cu(ii)/Zn(ii)-ions, the geometry and stoichiometry of these complexes, Cu(ii)/Zn(ii)-binding-sites and binding mode, and the ability of these analogues to dissolve Aβ42-Zn(ii)/Cu(ii) aggregates, as well as their effect on the secondary structure of those aggregates. Finally, we identified the most promising agents for dissolution of Aβ42-Zn(ii)/Cu(ii) aggregates. Specifically, we observed the formation of a 1 : 1 complex between 2'-dG3'5'PO and Cu(ii), involving O4 ligands. Zn(ii) was coordinated by both thiophosphate groups of 2'-dA3'5'PS and A2'3'PS involving O2S2 ligands in a 1 : 1 stoichiometry. A2'3'PS dissolves Aβ42-Zn(ii) and Aβ42-Cu(ii) aggregates as effectively as, and 2.5-fold more effectively than EDTA, respectively. Furthermore, 2'-dG3'5'PS and A2'3'PS reverted the Aβ42-M(ii) structure, back to that of the free Aβ42. Finally, cryo-TEM and TEM images confirmed the disassembly of Aβ42 and Aβ42-M(ii) aggregates by A2'3'PS. Hence, 2'-dG3'5'PS and A2'3'PS may serve as promising scaffolds for new AD therapeutics, acting as both effective antioxidants and agents for solubilization of Aβ42-Cu(ii)/Zn(ii) aggregates.

Synthesis, characterization and biological activity of some transition metals with Schiff base derived from 2-thiophene carboxaldehyde and aminobenzoic acid

NASA Astrophysics Data System (ADS)

Mohamed, Gehad G.; Omar, M. M.; Hindy, Ahmed M. M.

2005-12-01

Metal complexes of Schiff base derived from 2-thiophene carboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The ligand dissociation as well as the metal-ligand stability constants were calculated pH metrically at 25 °C and ionic strength μ = 0.1 (1 M NaCl). The complexes are found to have the formulae [M(HL) 2](X) n· yH 2O (where M = Fe(III) (X = Cl, n = 3, y = 3), Co(II) (X = Cl, n = 2, y = 1.5), Ni(II) (X = Cl, n = 2, y = 1) and UO 2(II) (X = NO 3, n = 2, y = 0)) and [M(L) 2] (where M = Cu(II) (X = Cl) and Zn(II) (X = AcO)). The molar conductance data reveal that Fe(III) and Co(II), Ni(II) and UO 2(II) chelates are ionic in nature and are of the type 3:1 and 2:1 electrolytes, respectively, while Cu(II) and Zn(II) complexes are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a terdentate manner with ONS donor sites of the carboxylate O, azomethine N and thiophene S. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, Δ H*, Δ S* and Δ G* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.

A series of coordination polymers constructed from R-isophthalic acid (R=-SO3H, -NO2, and -OH) and N-donor ligands: Syntheses, structures and fluorescence properties

NASA Astrophysics Data System (ADS)

Zhou, Yong-Hong; Zhou, Xu-Wan; Zhou, Su-Rong; Tian, Yu-Peng; Wu, Jie-Ying

2017-01-01

Six novel Zn(II), Cd(II), and Cu(II) mixed-ligand coordination complexes, namely, [Zn2Na(sip)2(bpp)3(Hbpp)(H2O)2]·8H2O (1), [Cd3(sip)2(nbi)6(H2O)2]·7H2O (2), [Zn(sip)(nbi)2(H2O)]·Hnbi·3H2O (3), [Cd(hip)(nbi)2(H2O)]·nbi·5H2O (4), [Cd2(nip)2(nbi)2(H2O)2]·DMF (5), and [Cu(nip)(nbi)(H2O)2]·H2O (6) (H3sip=5-sulfoisophthalic acid, H2hip=5-hydroxylisophthalic acid, H2nip=5-nitroisophthalic acid, bpp=1,3-bis(4-pyridyl)propane, and nbi=6-nitrobenzimidazole) have been synthesized hydrothermally by the self-assembly of R-isophthalic acid (R=-SO3H, -NO2, and -OH) and N-donor ligands. Single crystal X-ray analyses reveal that two Zn(II) ions and one Na(I) ion of complex 1 are linked through O atoms to generate a 1D linear chain. Then the 2D supramolecular architectures are constructed via intermolecular interactions. In complex 2, the Cd1 ions are connected by bridging carboxyl groups from sip3- anions to form 1D double chain, which are further connected by Cd2 ions to afford 2D layer structure. The adjacent 2D layers are further linked via hydrogen-bonding interactions to give 3D supramolecular network. Compounds 3-5 show 1D chain structures, which are assembled into 2D or 3D supramolecular frameworks via weak interactions. In compound 6, the Cu(II) ions are bridged by the nip2- ligands to form 48-membered ring, which is assembled into 1Dchain via the π-π stacking interaction. In addition, the thermal stabilities and fluorescence properties of these compounds have also been studied.

Extraction behaviour and mechanism of Pt(iv) and Pd(ii) by liquid-liquid extraction with an ionic liquid [HBBIm]Br.

PubMed

Liu, Wenhui; Wang, Qi; Zheng, Yan; Wang, Shubin; Yan, Yan; Yang, Yanzhao

2017-06-06

In this study, a method of one-step separation and recycling of high purity Pd(ii) and Pt(iv) using an ionic liquid, 1-butyl-3-benzimidazolium bromate ([HBBIm]Br), was investigated. The effects of [HBBIm]Br concentration, initial metal concentration, and loading capacity of [HBBIm]Br were examined in detail. It was observed that [HBBIm]Br was a very effective extractant for selectively extracting Pd(ii) and precipitating Pt(iv). Through selectively extracting Pd(ii) and precipitating Pt(iv), each metal with high purity was separately obtained from mixed Pd(ii) and Pt(iv) multi-metal solution. The method of one-step separation of Pd(ii) and Pt(iv) is simple and convenient. The anion exchange mechanism between [HBBIm]Br and Pt(iv) was proven through Job's method and FTIR and 1 H NMR spectroscopies. The coordination mechanism between [HBBIm]Br and Pd(ii) was demonstrated via single X-ray diffraction and was found to be robust and distinct, as supported by the ab initio quantum-chemical studies. The crystals of the [PdBr 2 ·2BBIm] complex were formed first. Moreover, the influence of the concentrations of hydrochloric acid, sodium chloride, and sodium nitrate on the precipitation of Pt(iv) and extraction of Pd(ii) was studied herein. It was found that only the concentration of H + could inhibit the separation of Pt(iv) because H + could attract the anion PtCl 6 2- ; thus, the exchange (anion exchange mechanism) between the anions PtCl 6 2- and Br - was prevented. However, both the concentration of H + and Cl - can obviously inhibit the extraction of Pd(ii) because H + and Cl - are the reaction products and increasing their concentration can inhibit the progress of the reaction (coordination mechanism).

Spectral and in vitro antimicrobial properties of 2-oxo-4-phenyl-6-styryl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid transition metal complexes

NASA Astrophysics Data System (ADS)

Dhankar, Raksha P.; Rahatgaonkar, Anjali M.; Chorghade, Mukund S.; Tiwari, Ashutosh

2-oxo-4-phenyl-6-styryl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid (ADP) was complexed with acetates of Mn(II), Ni(II), Cu(II) and Zn(II). The structures of the ligand and its metal complexes were characterized by microanalysis, IR, NMR, UV-vis spectroscopy, magnetic susceptibility and TGA-DTA analyses. Octahedral and square planar geometries were suggested for the complexes in which the central metal ion coordinated with sbnd O donors of ligand and acetate ions. Each ligand binds the metal using carboxylate oxygens. The ligand and complexes were evaluated for their antimicrobial activities against different species of pathogenic bacteria and fungi. The present novel pyrimidine containing complexes could constitute a new group of antibacterial and antifungal agents.

Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

NASA Astrophysics Data System (ADS)

Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

2016-05-01

We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

QM/MM Calculation of the Enzyme Catalytic Cycle Mechanism for Copper- and Zinc-Containing Superoxide Dismutase.

PubMed

Lintuluoto, Masami; Yamada, Chiaki; Lintuluoto, Juha M

2017-08-03

The entire enzyme catalytic mechanism including the electron and the proton transfers of the copper- and zinc-containing extracellular superoxide dismutase (SOD3) was investigated by using QM/MM method. In the first step, the electron transfer from O 2 ·- to SOD3 occurred without the bond formation between the donor and the acceptor and formed the triplet oxygen molecule and reduced SOD3. In the reduced SOD3, the distorted tetrahedral structure of Cu(I) atom was maintained. The reduction of Cu(II) atom induced the protonation of His113, which bridges between the Cu(II) and Zn(II) atoms in the resting state. Since the protonation of His113 broke the bond between Cu(I) and His113, three-coordinated Cu(I) was formed. Further, we suggest the binding of O 2 ·- formed hydrogen peroxide and the resting state after both the Cu reduction and the protonation of His113. The protonation of His113 caused the conformational change of Arg186 located at the entrance of the reactive site. The electrostatic potential surface around the reactive site showed that Arg186 plays an important role as electrostatic guidance for the negatively charged substrates only after the protonation of His113. The rotation of Arg186 switched the proton supply routes via Glu108 or Glu179 for transferring two protons from the bulk solvent.

New 15-membered tetraaza (N4) macrocyclic ligand and its transition metal complexes: Spectral, magnetic, thermal and anticancer activity

NASA Astrophysics Data System (ADS)

El-Boraey, Hanaa A.; EL-Gammal, Ohyla A.

2015-03-01

Novel tetraamidemacrocyclic 15-membered ligand [L] i.e. naphthyl-dibenzo[1,5,9,12]tetraazacyclopentadecine-6,10,11,15-tetraoneand its transition metal complexes with Fe(II), Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and characterized by elemental analysis, spectral, thermal as well as magnetic and molar conductivity measurements. On the basis of analytical, spectral (IR, MS, UV-Vis, 1H NMR and EPR) and thermal studies distorted octahedral or square planar geometry has been proposed for the complexes. The antitumor activity of the synthesized ligand and some complexes against human breast cancer cell lines (MCF-7) and human hepatocarcinoma cell lines (HepG2) has been studied. The complexes (IC50 = 2.27-2.7, 8.33-31.1 μg/mL, respectively) showed potent antitumor activity, towards the former cell lines comparable with their ligand (IC50 = 13, 26 μg/mL, respectively). The results show that the activity of the ligand towards breast cancer cell line becomes more pronounced and significant when coordinated to the metal ion.

Optical studies on phthalocyanines substituted with phenylazonaphthoxy groups

NASA Astrophysics Data System (ADS)

Özçeşmeci, İbrahim; Sorar, Idris; Gül, Ahmet

2016-10-01

The synthesis and characterization of peripherally ({1-[(Z or E)-phenylazo]-2-naphthyl} oxy) tetra-substituted metal-free and metallo (Zn(II), Co(II) and Cu(II)) phthalocyanines are described in this study. Aggregation properties of these compounds were investigated in the concentration range of 20-1 μM in tetrahydrofuran. Spectroscopic and photophysical properties of these phthalocyanines have been investigated in tetrahydrofuran. Thin films of metallophthalocyanines were prepared by spin coating technique. Results show that transmittance values of the films change with respect to the metal ions in the visible and Q absorptions regions. Films were also annealed at 100, 200 and 300 °C and their optical properties were investigated as a function of annealing temperature. The spectrophotometric measurements of transmittance spectra were carried out in the wavelength range 200-1000 nm. Results showed that transmittance values of ZnPc thin films were increased as a result of heat treatment.

Synthesis, characterization, antimicrobial, DNA-cleavage and antioxidant activities of 3-((5-chloro-2-phenyl-1H-indol-3-ylimino)methyl)quinoline-2(1H)-thione and its metal complexes

NASA Astrophysics Data System (ADS)

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

2015-01-01

Schiff base 3-((5-chloro-2-phenyl-1H-indol-3-ylimino)methyl)quinoline-2(1H)-thione and its Cu(II), Co(II), Ni(II), Zn(II) and Fe(III), complexes have been synthesized and characterized by elemental analysis, UV-Visible, IR, 1H NMR, 13C NMR and mass spectra, molar conductance, magnetic susceptibility, ESR and TGA data. The ligand and its metal complexes have been screened for their antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa, antifungal activity against Aspergillus niger and Aspergillus flavus in minimum inhibition concentration (MIC) by cup plate method respectively, antioxidant activity using 1,1-diphenyl-2-picryl hydrazyl (DPPH), which was compared with that of standard drugs vitamin-C and vitamin-E and DNA cleavage activity using calf-thymus DNA.

Pyrazole bridged dinuclear Cu(II) and Zn(II) complexes as phosphatase models: Synthesis and activity

NASA Astrophysics Data System (ADS)

Naik, Krishna; Nevrekar, Anupama; Kokare, Dhoolesh Gangaram; Kotian, Avinash; Kamat, Vinayak; Revankar, Vidyanand K.

2016-12-01

Present work describes synthesis of dibridged dinuclear [Cu2L2(μ2-NN pyr)(NO3)2(H2O)2] and [Zn2L(μ-OH)(μ-NNpyr)(H2O)2] complexes derived from a pyrazole based ligand bis(2-hydroxy-3-methoxybenzylidene)-1H-pyrazole-3,5-dicarbohydrazide. The ligand shows dimeric chelate behaviour towards copper against monomeric for zinc counterpart. Spectroscopic evidences affirm octahedral environment around the metal ions in solution state and non-electrolytic nature of the complexes. Both the complexes are active catalysts towards phosphomonoester hydrolysis with first order kcat values in the range of 2 × 10-3s-1. Zinc complex exhibited promising catalytic efficiency for the hydrolysis. The dinuclear complexes hydrolyse via Lewis acid activation, whereby the phosphate esters are preferentially bound in a bidentate bridging fashion and subsequent nucleophilic attack to release phosphate group.

Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes.

PubMed

Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M Arif

2016-05-15

We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and characterization of ligational behavior of curcumin drug towards some transition metal ions: Chelation effect on their thermal stability and biological activity

NASA Astrophysics Data System (ADS)

Refat, Moamen S.

2013-03-01

Complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with curcumin ligand as antitumor activity were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-Vis, IR, Raman, ESR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a monobasic bidentate ligand towards the central metal ion with an oxygen's donor atoms sequence of both sbnd OH and Cdbnd O groups under keto-enol structure. From the microanalytical data, the stoichiometry of the complexes 1:2 (metal:ligand) was found. The ligand and their metal complexes were screened for antibacterial activity against Escherichia Coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa and fungicidal activity against Aspergillus flavus and Candida albicans.

Synthesis of some metallophthalocyanines with dimethyl 5-(phenoxy)-isophthalate substituents and evaluation of their antioxidant-antibacterial activities

NASA Astrophysics Data System (ADS)

Salih Ağırtaş, M.; Karataş, Ceyhun; Özdemir, Sadin

2015-01-01

The synthesis, characterization, spectral, antioxidant and antibacterial properties of dimethyl 5-(phenoxy)-isophthalate substituted Zinc, Cobalt, Copper, and Nickel phthalocyanines are reported. The novel compounds have been characterized by using electronic absorption, nuclear magnetic resonance spectroscopy, infrared, elemental analysis and mass spectrometry. The antioxidant and antibacterial activities of newly synthesized phthalocyanines and its starting material are tested. The DPPH free radical scavenging ability of phthalocyanine Co(II) and Zn(II) complexes on DPPH are 44.8% and 40.1% at 100 mg/L concentration, respectively. The phthalocyanine Co(II) and Cu(II) complexes show very strong ferrous ion chelating activity of 91.2% and 89.3% at concentration of 100 mg/L, respectively. Compound 3 displays strong reducing power like α-tocopherol. Antibacterial activities of phthalocyanine Co(II) and Amikacin (30 μg/disk) against Micrococcus luteus (ATCC 9341) are 16 mm in diameter.

Anchoring plant metallothioneins to the inner face of the plasma membrane of Saccharomyces cerevisiae cells leads to heavy metal accumulation.

PubMed

Ruta, Lavinia Liliana; Lin, Ya-Fen; Kissen, Ralph; Nicolau, Ioana; Neagoe, Aurora Daniela; Ghenea, Simona; Bones, Atle M; Farcasanu, Ileana Cornelia

2017-01-01

In this study we engineered yeast cells armed for heavy metal accumulation by targeting plant metallothioneins to the inner face of the yeast plasma membrane. Metallothioneins (MTs) are cysteine-rich proteins involved in the buffering of excess metal ions, especially Cu(I), Zn(II) or Cd(II). The cDNAs of seven Arabidopsis thaliana MTs (AtMT1a, AtMT1c, AtMT2a, AtMT2b, AtMT3, AtMT4a and AtMT4b) and four Noccaea caerulescens MTs (NcMT1, NcMT2a, NcMT2b and NcMT3) were each translationally fused to the C-terminus of a myristoylation green fluorescent protein variant (myrGFP) and expressed in Saccharomyces cerevisiae cells. The myrGFP cassette introduced a yeast myristoylation sequence which allowed directional targeting to the cytosolic face of the plasma membrane along with direct monitoring of the intracellular localization of the recombinant protein by fluorescence microscopy. The yeast strains expressing plant MTs were investigated against an array of heavy metals in order to identify strains which exhibit the (hyper)accumulation phenotype without developing toxicity symptoms. Among the transgenic strains which could accumulate Cu(II), Zn(II) or Cd(II), but also non-canonical metal ions, such as Co(II), Mn(II) or Ni(II), myrGFP-NcMT3 qualified as the best candidate for bioremediation applications, thanks to the robust growth accompanied by significant accumulative capacity.

A series of coordination polymers constructed from R-isophthalic acid (R=–SO{sub 3}H, –NO{sub 2}, and –OH) and N-donor ligands: Syntheses, structures and fluorescence properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Yong-Hong, E-mail: zhou21921@sina.com; Zhou, Xu-Wan; Zhou, Su-Rong

Six novel Zn(II), Cd(II), and Cu(II) mixed-ligand coordination complexes, namely, [Zn{sub 2}Na(sip){sub 2}(bpp){sub 3}(Hbpp)(H{sub 2}O){sub 2}]·8H{sub 2}O (1), [Cd{sub 3}(sip){sub 2}(nbi){sub 6}(H{sub 2}O){sub 2}]·7H{sub 2}O (2), [Zn(sip)(nbi){sub 2}(H{sub 2}O)]·Hnbi·3H{sub 2}O (3), [Cd(hip)(nbi){sub 2}(H{sub 2}O)]·nbi·5H{sub 2}O (4), [Cd{sub 2}(nip){sub 2}(nbi){sub 2}(H{sub 2}O){sub 2}]·DMF (5), and [Cu(nip)(nbi)(H{sub 2}O){sub 2}]·H{sub 2}O (6) (H{sub 3}sip=5-sulfoisophthalic acid, H{sub 2}hip=5-hydroxylisophthalic acid, H{sub 2}nip=5-nitroisophthalic acid, bpp=1,3-bis(4-pyridyl)propane, and nbi=6-nitrobenzimidazole) have been synthesized hydrothermally by the self-assembly of R-isophthalic acid (R=–SO{sub 3}H, –NO{sub 2}, and –OH) and N-donor ligands. Single crystal X-ray analyses reveal that two Zn(II) ions and one Na(I) ion of complex 1 are linked through Omore » atoms to generate a 1D linear chain. Then the 2D supramolecular architectures are constructed via intermolecular interactions. In complex 2, the Cd1 ions are connected by bridging carboxyl groups from sip{sup 3−} anions to form 1D double chain, which are further connected by Cd2 ions to afford 2D layer structure. The adjacent 2D layers are further linked via hydrogen-bonding interactions to give 3D supramolecular network. Compounds 3–5 show 1D chain structures, which are assembled into 2D or 3D supramolecular frameworks via weak interactions. In compound 6, the Cu(II) ions are bridged by the nip{sup 2−} ligands to form 48-membered ring, which is assembled into 1Dchain via the π-π stacking interaction. In addition, the thermal stabilities and fluorescence properties of these compounds have also been studied. - Graphical abstract: A series of Cd(II)/Zn(II)/ Cu(II) coordination polymers based on R-isophthalic acid (R=–SO{sub 3}H, –NO{sub 2}, and –OH) and N-donor ligands have been synthesized under hydrothermal conditions and structurally characterized. Photoluminescent properties have been discussed. - Highlights: • Six coordination polymers were synthesized based on mixed-ligand strategy. • The polycarboxylate acids play a crucial role in determining the final structures. • Each complex shows diverse structures and different supramolecular interactions.« less

Exploring the Effect of Surface Functionality on the Self-Assembly of Polyoxopalladate Macroions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haso, Fadi; Yang, Peng; Gao, Yunyi

2015-05-12

The solution behavior of the two polyoxo-13-palladates(II) ([Pd(II) 13 As(V) 8 O34 (OH)6 ](8-) and [Pd(II) 13 (As(V) Ph)8 O32 ](6-) ) was studied in detail. We discovered that the countercation-mediated attraction is the driving force for their self-assembly into larger architectures. However, the presence of phenyl groups in the periphery of [Pd(II) 13 (As(V) Ph)8 O32 ](6-) results in an enhanced attraction among these polyanions through hydrophobic interactions, which leads to completely different trends of assembly size for these two very similar clusters when decreasing solvent polarity. An increase of assembly size with increasing solvent polarity was observed formore » [Pd(II) 13 (As(V) Ph)8 O32 ](6-) , whereas for [Pd(II) 13 As (V) 8 O34 (OH)6 ](8-) it was the opposite, due to the absence of hydrophobic interactions.« less

Synthesis, spectral and thermal studies of some transition metal mixed ligand complexes: Modeling of equilibrium composition and biological activity

NASA Astrophysics Data System (ADS)

Neelakantan, M. A.; Sundaram, M.; Nair, M. Sivasankaran

2011-09-01

Several mixed ligand Ni(II), Cu(II) and Zn(II) complexes of 2-amino-3-hydroxypyridine (AHP) and imidazoles viz., imidazole (him), benzimidazole (bim), histamine (hist) and L-histidine (his) have been synthesized and characterized by elemental and spectral (vibrational, electronic, 1H NMR and EPR) data as well as by magnetic moment values. On the basis of elemental analysis and molar conductance values, all the complexes can be formulated as [MAB]Cl except histidine complexes as MAB. Thermogravimetric studies reveal the presence of coordinated water molecules in most of the complexes. From the magnetic measurements and electronic spectral data, octahedral structure was proposed for Ni(II) and Cu(II)-AHP-his, tetrahedral for Cu(II)-AHP-him/bim/hist, but square planar for the Cu(II)-AHP complex. The g∥/ A∥ calculated supports tetrahedral environment around the Cu(II) in Cu(II)-AHP-him/bim/hist and distorted octahedral for Cu(II)-AHP-his complexes. The morphology of the reported metal complexes was investigated by scanning electron micrographs (SEM). The potentiometric study has been performed in aqueous solution at 37 °C and I = 0.15 mol dm -3 NaClO 4. MABH, MAB and MAB 2 species has been identified in the present systems. Proton dissociation constants of AHP and stability constants of metal complexes were determined using MINIQUAD-75. The most probable structure of the mixed ligand species is discussed based upon their stability constants. The in vitro biological activity of the complexes was tested against the Gram positive and Gram negative bacteria, fungus and yeast. The oxidative DNA cleavage studies of the complexes were performed using gel electrophoresis method. Cu(II) complexes have been found to promote DNA cleavage in presence of biological reductant such as ascorbate and oxidant like hydrogen peroxide.

Adsorption of Pd(II) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Zhang, Yongjian; Wang, Jinchao; Guo, Zhanchen

2010-05-01

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Pd(II) contained in the chloride solution obtained from the dry chlorination process, thermodynamic and kinetics studies for adsorption of Pd(II) complexes from the chloride solutions on anionic exchange resin Diaion WA21J were carried out. It was found that Pd, Pt, Rh, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The isothermal adsorption of Pd(II) was found to fit Freundlich, Langmuir and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The adsorption of Pd(II) on the resin was favorable according to the values of 1/n and R(L) from Freundlich and Langmuir adsorption isotherms, respectively. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 5.70, 4.84 and 4.05 mg/g and the corresponding value X(m) based on Dubinin-Kaganer-Radushkevich were 5.55, 4.69 and 4.01 mg/g at temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. The apparent adsorption energies (E(ad)) based on Dubinin-Kaganer-Radushkevich isotherm were -15.43, -16.22 and -23.57 kJ/mol for the temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. Chemical adsorption was a main mechanism involved in the adsorption process. Pd(II) adsorption on the resin could be accelerated by increasing the adsorption temperature. The adsorption of Pd(II) from the chloride solution on the resin underwent pseudo-first order kinetic process and the apparent adsorption activation energy E(a) was 15.0 kJ/mol. The intra-particle diffusion was a main rate controlling step in the Pd(II) adsorption process under the adsorption conditions. Copyright 2010 Elsevier Inc. All rights reserved.

Functionalization of Magnetic Chitosan Particles for the Sorption of U(VI), Cu(II) and Zn(II)—Hydrazide Derivative of Glycine-Grafted Chitosan

PubMed Central

Hamza, Mohammed F.; Aly, Mohsen M.; Abdel-Rahman, Adel A.-H.; Ramadan, Samar; Raslan, Heba; Wang, Shengye; Vincent, Thierry; Guibal, Eric

2017-01-01

A new magnetic functionalized derivative of chitosan is synthesized and characterized for the sorption of metal ions (environmental applications and metal valorization). The chemical modification of the glycine derivative of chitosan consists of: activation of the magnetic support with epichlorohydrin, followed by reaction with either glycine to produce the reference material (i.e., Gly sorbent) or glycine ester hydrochloride, followed by hydrazinolysis to synthesize the hydrazide functionalized sorbent (i.e., HGly sorbent). The materials are characterized by titration, elemental analysis, FTIR analysis (Fourrier-transform infrared spectrometry), TGA analysis (thermogravimetric analysis) and with SEM-EDX (scanning electron microscopy coupled to energy dispersive X-ray analysis). The sorption performances for U(VI), Cu(II), and Zn(II) are tested in batch systems. The sorption performances are compared for Gly and HGly taking into account the effect of pH, the uptake kinetics (fitted by the pseudo-second order rate equation), and the sorption isotherms (described by the Langmuir and the Sips equations). The sorption capacities of the modified sorbent reach up to 1.14 mmol U g−1, 1.69 mmol Cu g−1, and 0.85 mmol Zn g−1. In multi-metal solutions of equimolar concentration, the chemical modification changes the preferences for given metal ions. Metal ions are desorbed using 0.2 M HCl solutions and the sorbents are re-used for five cycles of sorption/desorption without significant loss in performances. PMID:28772896

Synthesis and thermal characterization of new ternary chelates of piroxicam and tenoxicam with glycine and DL-phenylalanine and some transition metals.

PubMed

Zayed, M A; El-Dien, F A Nour; Mohamed, Gehad G; El-Gamel, Nadia E A

2006-05-01

The ternary chelates of piroxicam (Pir) and tenoxicam (Ten) with Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) in the presence of various amino acids such as glycine (Gly) or dl-phenylalanine (PhA) were prepared and characterized with different physicochemical methods. IR spectra confirm that Pir and Ten behave 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 deprotonated carboxylic group. In addition, PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its deprotonated carboxylic and amino groups. The solid reflectance spectra and magnetic moment measurements confirm that all the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. Thermal behaviour of the complexes is extensively studied using TG and DTA techniques. TG results show that water molecules (hydrated and coordinated) and anions are removed in the first and second steps while Gly, PhA, Pir and Ten are decomposed in the next and subsequent steps. The pyrolyses of the chelates into different gases are observed in the DTA curves as exo- or endothermic peaks. Also, phase transition states are observed in some chelates. Different thermodynamic parameters are calculated using Coats-Redfern method and the results are interpreted.

Synthesis and thermal characterization of new ternary chelates of piroxicam and tenoxicam with glycine and DL-phenylalanine and some transition metals

NASA Astrophysics Data System (ADS)

Zayed, M. A.; El-Dien, F. A. Nour; Mohamed, Gehad G.; El-Gamel, Nadia E. A.

2006-05-01

The ternary chelates of piroxicam (Pir) and tenoxicam (Ten) with Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) in the presence of various amino acids such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized with different physicochemical methods. IR spectra confirm that Pir and Ten behave 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 deprotonated carboxylic group. In addition, PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its deprotonated carboxylic and amino groups. The solid reflectance spectra and magnetic moment measurements confirm that all the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. Thermal behaviour of the complexes is extensively studied using TG and DTA techniques. TG results show that water molecules (hydrated and coordinated) and anions are removed in the first and second steps while Gly, PhA, Pir and Ten are decomposed in the next and subsequent steps. The pyrolyses of the chelates into different gases are observed in the DTA curves as exo- or endothermic peaks. Also, phase transition states are observed in some chelates. Different thermodynamic parameters are calculated using Coats-Redfern method and the results are interpreted.

Design, spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

NASA Astrophysics Data System (ADS)

Hanif, Muhammad; Chohan, Zahid H.

2013-03-01

A new series of three biologically active triazole derived Schiff base ligands L1-L3 have been synthesized in equimolar reaction of 3-amino-1H-1,2,4-triazole with pyrrol-2-carboxaldehyde, 4-bromo-thiophene-2-carboxaldehyde, and 5-iodo-2-hydroxy benzaldehyde. The prepared Schiff bases were used for further complex formation reaction with different metal elements like Co(II), Ni(II), Cu(II) and Zn(II) as chlorides by using a molar ratio of ligand:metal as 2:1. The structure and bonding nature of all the compounds were identified by their physical, spectral and analytical data. All the metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which showed a distorted octahedral geometry. All the synthesized compounds, were studied for their in vitro antibacterial, and antifungal activities, against four Gram-negative (Escherichia coli, Shigella sonnei, Pseudomonas aeruginosa and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and against six fungal strains (Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata) by using agar-well diffusion method. It has been shown that all the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. In vitro Brine Shrimp bioassay was also carried out to investigate the cytotoxic properties of these compounds. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.

Microwave assisted synthesis of biarlys by Csbnd C coupling reactions with a new chitosan supported Pd(II) catalyst

NASA Astrophysics Data System (ADS)

Baran, Talat; Menteş, Ayfer

2016-10-01

In this study a new type chitosan-based support has been produced for Pd(II) catalyst and its catalytic performance in Suzuki Csbnd C reactions has been studied under microwave irradiation without using any solvent. The chemical identification of the catalyst was performed using TG/DTG, FTIR, UV-Vis ICP-OES, SEM/EDAX, 13C NMR, molar conductivity, XRD and magnetic moment techniques. The performance of this new Pd(II) catalyst was studied in Suzuki Csbnd C reactions. The Pd(II) catalyst exhibited a good catalytic performance in very short time (4 min) by giving high TONs and TOFs with low amount of the catalyst (0.015 mol%). The catalyst also had reusability and did not lose its activity until six runs.

Metal bacteriochlorins which act as dual singlet oxygen and superoxide generators.

PubMed

Fukuzumi, Shunichi; Ohkubo, Kei; Zheng, Xiang; Chen, Yihui; Pandey, Ravindra K; Zhan, Riqiang; Kadish, Karl M

2008-03-06

A series of stable free-base, Zn(II) and Pd(II) bacteriochlorins containing a fused six- or five-member diketo- or imide ring have been synthesized as good candidates for photodynamic therapy sensitizers, and their electrochemical, photophysical, and photochemical properties were examined. Photoexcitation of the palladium bacteriochlorin affords the triplet excited state without fluorescence emission, resulting in formation of singlet oxygen with a high quantum yield due to the heavy atom effect of palladium. Electrochemical studies revealed that the zinc bacteriochlorin has the smallest HOMO-LUMO gap of the investigated compounds, and this value is significantly lower than the triplet excited-state energy of the compound in benzonitrile. Such a small HOMO-LUMO gap of the zinc bacteriochlorin enables intermolecular photoinduced electron transfer from the triplet excited state to the ground state to produce both the radical cation and the radical anion. The radical anion thus produced can transfer an electron to molecular oxygen to produce superoxide anion which was detected by electron spin resonance. The same photosensitizer can also act as an efficient singlet oxygen generator. Thus, the same zinc bacteriochlorin can function as a sensitizer with a dual role in that it produces both singlet oxygen and superoxide anion in an aprotic solvent (benzonitrile).

Controlled intracellular generation of reactive oxygen species in human mesenchymal stem cells using porphyrin conjugated nanoparticles

NASA Astrophysics Data System (ADS)

Lavado, Andrea S.; Chauhan, Veeren M.; Alhaj Zen, Amer; Giuntini, Francesca; Jones, D. Rhodri E.; Boyle, Ross W.; Beeby, Andrew; Chan, Weng C.; Aylott, Jonathan W.

2015-08-01

Nanoparticles capable of generating controlled amounts of intracellular reactive oxygen species (ROS), that advance the study of oxidative stress and cellular communication, were synthesized by functionalizing polyacrylamide nanoparticles with zinc(ii) porphyrin photosensitisers. Controlled ROS production was demonstrated in human mesenchymal stem cells (hMSCs) through (1) production of nanoparticles functionalized with varying percentages of Zn(ii) porphyrin and (2) modulating the number of doses of excitation light to internalized nanoparticles. hMSCs challenged with nanoparticles functionalized with increasing percentages of Zn(ii) porphyrin and high numbers of irradiations of excitation light were found to generate greater amounts of ROS. A novel dye, which is transformed into fluorescent 7-hydroxy-4-trifluoromethyl-coumarin in the presence of hydrogen peroxide, provided an indirect indicator for cumulative ROS production. The mitochondrial membrane potential was monitored to investigate the destructive effect of increased intracellular ROS production. Flow cytometric analysis of nanoparticle treated hMSCs suggested irradiation with excitation light signalled controlled apoptotic cell death, rather than uncontrolled necrotic cell death. Increased intracellular ROS production did not induce phenotypic changes in hMSC subcultures.Nanoparticles capable of generating controlled amounts of intracellular reactive oxygen species (ROS), that advance the study of oxidative stress and cellular communication, were synthesized by functionalizing polyacrylamide nanoparticles with zinc(ii) porphyrin photosensitisers. Controlled ROS production was demonstrated in human mesenchymal stem cells (hMSCs) through (1) production of nanoparticles functionalized with varying percentages of Zn(ii) porphyrin and (2) modulating the number of doses of excitation light to internalized nanoparticles. hMSCs challenged with nanoparticles functionalized with increasing percentages of Zn(ii) porphyrin and high numbers of irradiations of excitation light were found to generate greater amounts of ROS. A novel dye, which is transformed into fluorescent 7-hydroxy-4-trifluoromethyl-coumarin in the presence of hydrogen peroxide, provided an indirect indicator for cumulative ROS production. The mitochondrial membrane potential was monitored to investigate the destructive effect of increased intracellular ROS production. Flow cytometric analysis of nanoparticle treated hMSCs suggested irradiation with excitation light signalled controlled apoptotic cell death, rather than uncontrolled necrotic cell death. Increased intracellular ROS production did not induce phenotypic changes in hMSC subcultures. Electronic supplementary information (ESI) available: Materials and experimental methods for the synthesis of (1) positively charged alkyne functionalized nanoparticles (2) Zn(ii) and Cu(ii) centred porphyrin (3); conjugating porphyrins to alkyne-functionalized nanoparticles via click chemistry (4) nanoparticle characterisation (size charge and fluorescence), (5) synthesis of BPTFMC (6) hMSC collection, storage and preparation (7) delivery of porphyrin functionalized nanoparticles (8) staining mitochondria, cumulative ROS production and determination of nanoparticles subcellular localisation (9) fluorescence microscopy and controlled irradiation of hMSCs (10) flow cytometry and controlled irradiation using a custom built irradiator. In addition, results highlighting: (1) nanoparticles emission spectra, size and charge, (2) BPTFMC fluorescence response and (3) hMSCs following light irradiation using flow cytometry. See DOI: 10.1039/c5nr00795j

Zn(II), Ni(II), Cu(II) and Pb(II) complexes of tridentate asymmetrical Schiff base ligands: Synthesis, characterization, properties and biological activity

NASA Astrophysics Data System (ADS)

Şahin, Mustafa; Koçak, Nuriye; Erdenay, Damla; Arslan, Uğur

2013-02-01

New asymmetrical tridentate Schiff base ligands were synthesized using 1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-hydroxy-1-napthaldehyde, 9-anthracenecarboxaldehyde. Schiff base ligands and their metal complexes were synthesised and characterized by using FT-IR, 1H NMR, 13C NMR, UV-Vis, XRD, ESR, elemental analysis and fluorescence studies. The antimicrobial activity of the ligands and their metal complexes were studied against Staphylococcus aureus ATCC 29213, S. aureus ATCC 25923, Streptococcus mutans RSHM 676, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853. The determination of the antibacterial activity was done using the broth microdilution methods. In general, it has been determined that the studied compounds have MIC values similar to Gram-positive and Gram-negative bacteria. It has been found that Ni, Pb, Zn derivatives of HL1A and ZnL2A has lower MIC values than ampicillin for P. aeruginosa ATCC 27853 strain.

Portable Multispectral Colorimeter for Metallic Ion Detection and Classification

PubMed Central

Jaimes, Ruth F. V. V.; Borysow, Walter; Gomes, Osmar F.; Salcedo, Walter J.

2017-01-01

This work deals with a portable device system applied to detect and classify different metallic ions as proposed and developed, aiming its application for hydrological monitoring systems such as rivers, lakes and groundwater. Considering the system features, a portable colorimetric system was developed by using a multispectral optoelectronic sensor. All the technology of quantification and classification of metallic ions using optoelectronic multispectral sensors was fully integrated in the embedded hardware FPGA ( Field Programmable Gate Array) technology and software based on virtual instrumentation (NI LabView®). The system draws on an indicative colorimeter by using the chromogen reagent of 1-(2-pyridylazo)-2-naphthol (PAN). The results obtained with the signal processing and pattern analysis using the method of the linear discriminant analysis, allows excellent results during detection and classification of Pb(II), Cd(II), Zn(II), Cu(II), Fe(III) and Ni(II) ions, with almost the same level of performance as for those obtained from the Ultravioled and visible (UV-VIS) spectrophotometers of high spectral resolution. PMID:28788082

Spectroscopic, and thermal studies of some new binuclear transition metal(II) complexes with hydrazone ligands containing acetoacetanilide and isoxazole.

PubMed

Chen, Zhimin; Wu, Yiqun; Gu, Donghong; Gan, Fuxi

2007-11-01

A new chelating ligand, 2-(2-(5-tert-butylisoxazol-3-yl)hydrazono)-N-(2,4-dimethylphenyl)-3-oxobutanamide (HL), and its four binuclear transition metal complexes, M(2)(L)(2) (micro-OCH(3))(2) [M=Ni(II), Co(II), Cu(II), Zn(II)], were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, (1)H NMR, MALDI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using the spin-coating method and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Different thermodynamic and kinetic parameters namely activation energy (E*), enthalpy of activation (DeltaH*), entropy of activation (DeltaS*) and free energy change of activation (DeltaG*) are calculated using Coats-Redfern (CR) equation.

Investigation of complexes tannic acid and myricetin with Fe(III)

NASA Astrophysics Data System (ADS)

Sungur, Şana; Uzar, Atike

2008-01-01

The pH dependence of the complexes was determined by both potentiometric and spectrophotometric studies. Stability constants and stoichiometries of the formed complexes were determined using slope ratio method. Fe(III) was formed complexes with tannic acid of various stoichiometries, which in the 1:1 molar ratio at pH < 3, in the 2:1 molar ratio at pH 3-7 and in the 4:1 molar ratio at pH > 7. Fe(III) was formed complexes with myricetin in the 1:2 molar ratio at pH 4 and 5 and in the 1:1 molar ratio at pH 6. Stability constant values were found to be 10 5 to 10 17 and 10 5 to 10 9 for Fe(III)-tannic acid complexes and Fe(III)-myricetin complexes. Both tannic acid and myricetin were possessed minimum affinities to Cu(II) and Zn(II). They had less affinity for Al(III) than for Fe(III).

Multiple heavy metal removal using an entomopathogenic fungi Beauveria bassiana.

PubMed

Gola, Deepak; Dey, Priyadarshini; Bhattacharya, Arghya; Mishra, Abhishek; Malik, Anushree; Namburath, Maneesh; Ahammad, Shaikh Ziauddin

2016-10-01

Towards the development of a potential remediation technology for multiple heavy metals [Zn(II), Cu(II), Cd(II), Cr(VI) and Ni(II)] from contaminated water, present study examined the growth kinetics and heavy metal removal ability of Beauveria bassiana in individual and multi metals. The specific growth rate of B. bassiana varied from 0.025h(-1) to 0.039h(-1) in presence of individual/multi heavy metals. FTIR analysis indicated the involvement of different surface functional groups in biosorption of different metals, while cellular changes in fungus was reflected by various microscopic (SEM, AFM and TEM) analysis. TEM studies proved removal of heavy metals via sorption and accumulation processes, whereas AFM studies revealed increase in cell surface roughness in fungal cells exposed to heavy metals. Present study delivers first report on the mechanism of bioremediation of heavy metals when present individually as well as multi metal mixture by entomopathogenic fungi. Copyright © 2016 Elsevier Ltd. All rights reserved.

Simultaneous spectrophotometric determination of four metals by two kinds of partial least squares methods

NASA Astrophysics Data System (ADS)

Gao, Ling; Ren, Shouxin

2005-10-01

Simultaneous determination of Ni(II), Cd(II), Cu(II) and Zn(II) was studied by two methods, kernel partial least squares (KPLS) and wavelet packet transform partial least squares (WPTPLS), with xylenol orange and cetyltrimethyl ammonium bromide as reagents in the medium pH = 9.22 borax-hydrochloric acid buffer solution. Two programs, PKPLS and PWPTPLS, were designed to perform the calculations. Data reduction was performed using kernel matrices and wavelet packet transform, respectively. In the KPLS method, the size of the kernel matrix is only dependent on the number of samples, thus the method was suitable for the data matrix with many wavelengths and fewer samples. Wavelet packet representations of signals provide a local time-frequency description, thus in the wavelet packet domain, the quality of the noise removal can be improved. In the WPTPLS by optimization, wavelet function and decomposition level were selected as Daubeches 12 and 5, respectively. Experimental results showed both methods to be successful even where there was severe overlap of spectra.

Metal based pharmacologically active complexes of Cu(II), Ni(II) and Zn(II): synthesis, spectral, XRD, antimicrobial screening, DNA interaction and cleavage investigation.

PubMed

Raman, Natarajan; Mahalakshmi, Rajkumar; Arun, T; Packianathan, S; Rajkumar, R

2014-09-05

The present contribution reports a thorough characterization of newly obtained metallointercalators incorporating Schiff bases, formed by the condensation of N-acetoacetyl-o-toluidine with 1-amino-4-nitrobenzene (L(1))/1-amino-4-chlorobenzene (L(2)) as main ligand and 1,10-phenanthroline as co-ligand respectively. The characterization of newly formed metallointercalators has been done by (1)H NMR, UV-Vis, IR, EPR spectroscopy and molar conductivity studies. X-ray powder diffraction illustrates that they are crystalline nature. Binding interaction of these complexes with calf thymus (CT-DNA) has been investigated by emission, absorption, viscosity, cyclic voltammetry and differential pulse voltammetry. DNA binding experiments results reveal that the synthesized complexes interact with DNA through intercalative mode. The in vitro antibacterial and antifungal assay indicate that these complexes are good antimicrobial agents against various pathogens. The DNA cleavage exhibits that they act as efficient cleaving agents. Copyright © 2014 Elsevier B.V. All rights reserved.

Portable Multispectral Colorimeter for Metallic Ion Detection and Classification.

PubMed

Braga, Mauro S; Jaimes, Ruth F V V; Borysow, Walter; Gomes, Osmar F; Salcedo, Walter J

2017-07-28

This work deals with a portable device system applied to detect and classify different metallic ions as proposed and developed, aiming its application for hydrological monitoring systems such as rivers, lakes and groundwater. Considering the system features, a portable colorimetric system was developed by using a multispectral optoelectronic sensor. All the technology of quantification and classification of metallic ions using optoelectronic multispectral sensors was fully integrated in the embedded hardware FPGA ( Field Programmable Gate Array) technology and software based on virtual instrumentation (NI LabView ® ). The system draws on an indicative colorimeter by using the chromogen reagent of 1-(2-pyridylazo)-2-naphthol (PAN). The results obtained with the signal processing and pattern analysis using the method of the linear discriminant analysis, allows excellent results during detection and classification of Pb(II), Cd(II), Zn(II), Cu(II), Fe(III) and Ni(II) ions, with almost the same level of performance as for those obtained from the Ultravioled and visible (UV-VIS) spectrophotometers of high spectral resolution.

Application of laboratory prepared and commercially available biochars to adsorption of cadmium, copper and zinc ions from water.

PubMed

Bogusz, Aleksandra; Oleszczuk, Patryk; Dobrowolski, Ryszard

2015-11-01

The goal of the presented work was the evaluation and comparison of two biochars (produced from Sida hermaphrodita - BCSH/laboratory produced and from wheatstraw - BCS/commercial available) to adsorb heavy metal ions (Cd(II), Cu(II) and Zn(II)) from water. Kinetics of the sorption as well as sorption isotherms, the influence of solution pH and interfering ions were investigated. Different physico-chemical properties of biochars had the great influence on adsorption capacity. The greater adsorption efficiency was observed for BCSH than for BCS in the case of all investigated metals. The adsorption efficiency of BCSH was correlated with higher content of carbon and oxygen, what is equal with higher content of polar-groups on the BCSH surface e.g., -COOH. Furthermore, the molar ratio of O/C as well as polarity index (which was higher for BCSH) was also important parameters. Copyright © 2015 Elsevier Ltd. All rights reserved.

Spectroscopic studies of porphyrin functionalized multiwalled carbon nanotubes and their interaction with TiO2 nanoparticles surface

NASA Astrophysics Data System (ADS)

Zannotti, Marco; Giovannetti, Rita; D'Amato, Chiara Anna; Rommozzi, Elena

2016-01-01

UV-vis and fluorescence investigations about the non-covalent interaction, in ethanolic solutions, of multi-wall carbon nanotube (MWCNT) with Coproporphyrin-I, and its Cu(II) and Zn(II) complexes (MCPIs) have been reported. Evidence of binding between MWCNTs and porphyrins was discovered from spectral adsorption decrease with respect to free porphyrins and by the exhibition of photoluminescence quenching with respect to free porphyrins demonstrating that MWCNT@MCPIs are potential donor-acceptor complexes. Equilibrium and kinetic aspects in the interactions with monolayer transparent TiO2 thin films with the obtained MWCNT@MCPIs are clarified showing their effective adsorption by porphyrin links on the TiO2 monolayer support, with respect to not only MWCNTs, according to the Langmuir model and with pseudo-first-order kinetics. Morphological description of the adsorption of MWCNT@MCPIs on TiO2 with scanning electron microscopy has been reported. The obtained experimental evidences describe therefore MWCNT@MCPIs as potential sensitizers in the DSSC (Dye-Sensitized Solar Cell) applications.

Spectroscopic, thermal analysis and DFT computational studies of salen-type Schiff base complexes.

PubMed

Ebrahimi, Hossein Pasha; Hadi, Jabbar S; Abdulnabi, Zuhair A; Bolandnazar, Zeinab

2014-01-03

A new series of metal(II) complexes of Co(II), Ni(II), Cu(II), Zn(II), and Pb(II) have been synthesized from a salen-type Schiff base ligand derived from o-vanillin and 4-methyl-1,2-phenylenediamine and characterized by elemental analysis, spectral (IR, UV-Vis, (1)H NMR, (13)C NMR and EI-mass), molar conductance measurements and thermal analysis techniques. Coats-Redfern method has been utilized to calculate the kinetic and thermodynamic parameters of the metal complexes. The molecular geometry, Mulliken atomic charges of the studied compounds were investigated theoretically by performing density functional theory (DFT) to access reliable results to the experimental values. The theoretical (13)C chemical shift results of the studied compounds have been calculated at the B3LYP, PBEPBE and PW91PW91 methods and standard 6-311+G(d,p) basis set starting from optimized geometry. The comparison of the results indicates that B3LYP/6-311+G(d,p) yields good agreement with the observed chemical shifts. The measured low molar conductance values in DMF indicate that the metal complexes are non-electrolytes. The spectral and thermal analysis reveals that all complexes have octahedral geometry except Cu(II) complex which can attain the square planner arrangement. The presence of lattice and coordinated water molecules are indicated by thermograms of the complexes. The thermogravimetric (TG/DTG) analyses confirm high stability for all complexes followed by thermal decomposition in different steps. Copyright © 2013 Elsevier B.V. All rights reserved.

Design, spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases.

PubMed

Hanif, Muhammad; Chohan, Zahid H

2013-03-01

A new series of three biologically active triazole derived Schiff base ligands L(1)-L(3) have been synthesized in equimolar reaction of 3-amino-1H-1,2,4-triazole with pyrrol-2-carboxaldehyde, 4-bromo-thiophene-2-carboxaldehyde, and 5-iodo-2-hydroxy benzaldehyde. The prepared Schiff bases were used for further complex formation reaction with different metal elements like Co(II), Ni(II), Cu(II) and Zn(II) as chlorides by using a molar ratio of ligand:metal as 2:1. The structure and bonding nature of all the compounds were identified by their physical, spectral and analytical data. All the metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which showed a distorted octahedral geometry. All the synthesized compounds, were studied for their in vitro antibacterial, and antifungal activities, against four Gram-negative (Escherichia coli, Shigella sonnei, Pseudomonas aeruginosa and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and against six fungal strains (Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata) by using agar-well diffusion method. It has been shown that all the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. In vitro Brine Shrimp bioassay was also carried out to investigate the cytotoxic properties of these compounds. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination. Copyright © 2012 Elsevier B.V. All rights reserved.

Nano sponge Mn₂O ₃ as a new adsorbent for the preconcentration of Pd(II) and Rh(III) ions in sea water, wastewater, rock, street sediment and catalytic converter samples prior to FAAS determinations.

PubMed

Yavuz, Emre; Tokalıoğlu, Serife; Sahan, Halil; Patat, Saban

2014-10-01

In this study, a nano sponge Mn2O3 adsorbent was synthesized and was used for the first time. Various parameters affecting the recovery values of Pd(II) and Rh(III) were examined. The tolerance limits (≥ 90 %) for both Pd(II) and Rh(III) ions were found to be 75,000 mg L(-1) Na(I), 75,000 mg L(-1) K(I), 50,000 mg L(-1) Mg(II) and 50,000 mg L(-1) Ca(II). A 30s contact time was enough for both adsorption and elution. A preconcentration factor of 100 was obtained by using 100mg of the nano sponge Mn2O3. The reusability of the adsorbent was 120 times. Adsorption capacities for Pd(II) and Rh(III) were found to be 42 and 6.2 mg g(-1), respectively. The detection limits were 1.0 µg L(-1) for Pd(II) and 0.37 µg L(-1) for Rh(III) and the relative standard deviations (RSD, %) were found to be ≤ 2.5%. The method was validated by analyzing the standard reference material, SRM 2556 (Used Auto Catalyst Pellets) and spiked real samples. The optimized method was applied for the preconcentration of Pd(II) and Rh(III) ions in water (sea water and wastewater), rock, street sediment and catalytic converter samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis of symmetrical tetrameric conjugates of the radiolanthanide chelator DOTPI for application in endoradiotherapy by means of click chemistry

NASA Astrophysics Data System (ADS)

Wurzer, Alexander; Vágner, Adrienn; Horváth, Dávid; Fellegi, Flóra; Wester, Hans-Jürgen; Kálmán, Ferenc K.; Notni, Johannes

2018-04-01

Due to its 4 carbonic acid groups being available for bioconjugation, the cyclen tetraphosphinate chelator DOTPI, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis[methylene(2-carboxyethylphosphinic acid)], represents an ideal scaffold for synthesis of tetrameric bioconjugates for labeling with radiolanthanides, to be applied as endoradiotherapeuticals. We optimized a protocol for bio-orthogonal DOTPI conjugation via Cu(I)-catalyzed Huisgen-cycloaddition of terminal azides and alkynes (CuAAC), based on the building block DOTPI(azide)4. A detailed investigation of kinetic properties of Cu(II)-DOTPI complexes aimed at optimization of removal of DOTPI-bound copper by transchelation. Protonation and equilibrium properties of Ca(II)-, Zn(II) and Cu(II)-complexes of DOTPI and its tetra-cyclohexylamide DOTPI(Chx)4 (a model for DOTPI conjugates) as well as kinetic inertness (transchelation challenge in the presence of 20 to 40-fold excess of EDTA) were investigated by pH-potentiometry and spectrophotometry. Similar stability constants of CaII-, ZnII and CuII-complexes of DOTPI (logK(CaL)=8.65, logK(ZnL=15.40, logK(CuL)=20.30) and DOTPI(Chx)4 (logK(CaL)=8.99, logK(ZnL)=15.13, logK(CuL)=20.42) were found. Transchelation of CuII-complexes occurs via proton-assisted dissociation, whereafter released Cu(II) is scavenged by EDTA. The corresponding dissociation rates (kd=25×10‑7 and 5×10‑7 s‑1 for Cu(DOTPI) and Cu(DOTPI(Chx)4), respectively, at pH 4 and 298 K) indicate that conjugation increases the kinetic inertness by a factor of 5. However demetallation is completed within 4.5 and 7.2 hours at pH 2 and 25 °C, respectively, indicating that CuII removal after formation of CuAAC can be achieved in an uncomplicated manner by addition of excess H4EDTA. For proof-of-principle, tetrameric DOTPI conjugates of the prostate-specific membrane antigen (PSMA) targeting motif Lys-urea-Glu (KuE) were synthesized via CuAAC as well as dibenzo-cyclooctine (DBCO) based, strain-promoted click chemistry (SPAAC), which were labeled with Lu-177 and subsequently evaluated in vitro and in SCID mice bearing subcutaneous LNCaP tumor (PSMA+ human prostate carcinoma) xenografts. High affinities (3.4 and 1.4 nM, respectively) and persistent tumor uptakes (approx. 3.5% 24 h after injection) confirm suitability of DOTPI-based tetramers for application in targeted radionuclide therapy.

Synthesis of Symmetrical Tetrameric Conjugates of the Radiolanthanide Chelator DOTPI for Application in Endoradiotherapy by Means of Click Chemistry

PubMed Central

Wurzer, Alexander; Vágner, Adrienn; Horváth, Dávid; Fellegi, Flóra; Wester, Hans-Jürgen; Kálmán, Ferenc K.; Notni, Johannes

2018-01-01

Due to its 4 carbonic acid groups being available for bioconjugation, the cyclen tetraphosphinate chelator DOTPI, 1,4,7,10-tetraazacyclododecane-1,4,7, 10-tetrakis[methylene(2-carboxyethylphosphinic acid)], represents an ideal scaffold for synthesis of tetrameric bioconjugates for labeling with radiolanthanides, to be applied as endoradiotherapeuticals. We optimized a protocol for bio-orthogonal DOTPI conjugation via Cu(I)-catalyzed Huisgen-cycloaddition of terminal azides and alkynes (CuAAC), based on the building block DOTPI(azide)4. A detailed investigation of kinetic properties of Cu(II)-DOTPI complexes aimed at optimization of removal of DOTPI-bound copper by transchelation. Protonation and equilibrium properties of Ca(II)-, Zn(II), and Cu(II)-complexes of DOTPI and its tetra-cyclohexylamide DOTPI(Chx)4 (a model for DOTPI conjugates) as well as kinetic inertness (transchelation challenge in the presence of 20 to 40-fold excess of EDTA) were investigated by pH-potentiometry and spectrophotometry. Similar stability constants of CaII-, ZnII, and CuII-complexes of DOTPI (logK(CaL) = 8.65, logK(ZnL = 15.40, logK(CuL) = 20.30) and DOTPI(Chx)4 (logK(CaL) = 8.99, logK(ZnL) = 15.13, logK(CuL) = 20.42) were found. Transchelation of Cu(II)-complexes occurs via proton-assisted dissociation, whereafter released Cu(II) is scavenged by EDTA. The corresponding dissociation rates [kd = 25 × 10−7 and 5 × 10−7 s−1 for Cu(DOTPI) and Cu(DOTPI(Chx)4), respectively, at pH 4 and 298 K] indicate that conjugation increases the kinetic inertness by a factor of 5. However, demetallation is completed within 4.5 and 7.2 h at pH 2 and 25°C, respectively, indicating that Cu(II) removal after formation of CuAAC can be achieved in an uncomplicated manner by addition of excess H4EDTA. For proof-of-principle, tetrameric DOTPI conjugates of the prostate-specific membrane antigen (PSMA) targeting motif Lys-urea-Glu (KuE) were synthesized via CuAAC as well as dibenzo-azacyclooctine (DBCO) based, strain-promoted click chemistry (SPAAC), which were labeled with Lu-177 and subsequently evaluated in vitro and in SCID mice bearing subcutaneous LNCaP tumor (PSMA+ human prostate carcinoma) xenografts. High affinities (3.4 and 1.4 nM, respectively) and persistent tumor uptakes (approx. 3.5% 24 h after injection) confirm suitability of DOTPI-based tetramers for application in targeted radionuclide therapy. PMID:29692987

One-step synthesis of fluorescein modified nano-carbon for Pd(II) detection via fluorescence quenching.

PubMed

Panchompoo, Janjira; Aldous, Leigh; Baker, Matthew; Wallace, Mark I; Compton, Richard G

2012-05-07

Carbon black (CB) nanoparticles modified with fluorescein, a highly fluorescent molecule, were prepared using a facile and efficient methodology. Simply stirring CB in aqueous solution containing fluorescein resulted in the strong physisorption of fluorescein onto the CB surface. The resulting Fluorescein/CB was then characterised by means of X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), fluorescence microscopy and fluorescence spectroscopy. The optimum experimental conditions for fluorescence of Fluorescein/CB viz. fluorescence excitation and emission wavelengths, O(2) removal and the amount of Fluorescein/CB used, were investigated. The Fluorescein/CB was used as a fluorescent probe for the sensitive detection of Pd(II) in water, based on fluorescence quenching. The results demonstrated that the fluorescence intensity of Fluorescein/CB decreased with increasing Pd(II) concentration, and the fluorescence quenching process could be described by the Stern-Volmer equation. The limit of detection (LOD) for the fluorescence quenching of Fluorescein/CB by Pd(II) in aqueous solution was found to be 1.07 μM (based on 3σ). Last, approaches were studied for the removal of Fe(III) which interferes with the fluorescence quenching of Fluorescein/CB. Complexation of Fe(III) with salicylic acid was used to enhance and control the selectivity of Fluorescein/CB sensor towards Pd(II) in the presence of Fe(III).

Syntheses, structures, and properties of imidazolate-bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) dinuclear complexes of a single macrocyclic ligand with two hydroxyethyl pendants.

PubMed

Li, Dongfeng; Li, Shuan; Yang, Dexi; Yu, Jiuhong; Huang, Jin; Li, Yizhi; Tang, Wenxia

2003-09-22

The imidazolate-bridged homodinuclear Cu(II)-Cu(II) complex, [(CuimCu)L]ClO(4).0.5H(2)O (1), and heterodinuclear Cu(II)-Zn(II) complex, [(CuimZnL(-)(2H))(CuimZnL(-)(H))](ClO(4))(3) (2), of a single macrocyclic ligand with two hydroxyethyl pendants, L (L = 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)tricyclo[22,2,2,2(11,14)]triaconta-1,11,13,24,27,29-hexaene), have been synthesized as possible models for copper-zinc superoxide dismutase (Cu(2),Zn(2)-SOD). Their crystal structures analyzed by X-ray diffraction methods have shown that the structures of the two complexes are markedly different. Complex 1 crystallizes in the orthorhombic system, containing an imidazolate-bridged dicopper(II) [Cu-im-Cu](3+) core, in which the two copper(II) ions are pentacoordinated by virtue of an N4O environment with a Cu.Cu distance of 5.999(2) A, adopting the geometry of distorted trigonal bipyramid and tetragonal pyramid, respectively. Complex 2 crystallizes in the triclinic system, containing two similar Cu-im-Zn cores in the asymmetric unit, in which both the Cu(II) and Zn(II) ions are pentacoordinated in a distorted trigonal bipyramid geometry, with the Cu.Zn distance of 5.950(1)/5.939(1) A, respectively. Interestingly, the macrocyclic ligand with two arms possesses a chairlike (anti) conformation in complex 1, but a boatlike (syn) conformation in complex 2. Magnetic measurements and ESR spectroscopy of complex 1 have revealed the presence of an antiferromagnetic exchange interaction between the two Cu(II) ions. The ESR spectrum of the Cu(II)-Zn(II) heterodinuclear complex 2 displayed a typical signal for mononuclear trigonal bipyramidal Cu(II) complexes. From pH-dependent ESR and electronic spectroscopic studies, the imidazolate bridges in the two complexes have been found to be stable over broad pH ranges. The cyclic voltammograms of the two complexes have been investigated. Both of the two complexes can catalyze the dismutation of superoxide and show rather high activity.

Metal complexes of a new potentially heptadentate(N 7) tripodal Schiff base ligand. Synthesis, NMR studies and ab initio calculations

NASA Astrophysics Data System (ADS)

Salehzadeh, Sadegh; Javarsineh, Seyed Amrollah; Keypour, Hassan

2006-03-01

Tris(3-aminopropyl)amine, 2-pyridinecarboxaldehyde and a number of metal ions were used to prepare metal complexes of a new fully condensed potentially heptadentate(N 7) tripodal Schiff base ligand (L 333). The resulting complexes, [M(L 333)](ClO 4) 2 {M= Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II); L 333=[N(CH 2CH 2CH 2N dbnd6 CH(C 5H 4N)) 3]}, were characterized by microanalysis, IR and electronic spectra in all cases and by NMR spectra in the case of Zn(II) and Cd(II) complexes: these two are both seven-co-ordinate. The 1H NMR, COSY and HMQC spectra of these complexes show two kinds of protons for each methylene group. The COSY spectrum confirms the geminal coupling of the two protons of each methylene group, indicating that the protons are diastereotopic in rigid six-membered rings. In the 1H NMR spectrum of the cadmium complex the signal of the imine proton has two clear satellites peaks ( 3J=41.9 Hz) with intensities in the ratio 1:6:1 due to coupling with neighbouring 111/113Cd. This coupling constant was confirmed by 113Cd NMR spectroscopy. Ab initio studies on [Fe(L 333)] 2+, [Zn(L 333)] 2+ and [Cd(L 333)] 2+ and also on the previously known complex, [Cd(L Me333)] 2+ are also reported. The results show that the shortest bonding interaction between the metal ion and the bridging tertiary nitrogen atom of the ligand is occurs in the Cd(II) complexes.

Interaction between transition metals and phenylalanine: a combined experimental and computational study.

PubMed

Elius Hossain, Md; Mahmudul Hasan, Md; Halim, M E; Ehsan, M Q; Halim, Mohammad A

2015-03-05

Some transition metal complexes of phenylalanine of general formula [M(C9H10NO2)2]; where M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) are prepared in aqueous medium and characterized by spectroscopic, thermo-gravimetric (TG) and magnetic susceptibility analysis. Density functional theory (DFT) has been employed calculating the equilibrium geometries and vibrational frequencies of those complexes at B3LYP level of theory using 6-31G(d) and SDD basis sets. In addition, frontier molecular orbital and time-dependent density functional theory (TD-DFT) calculations are performed with CAM-B3LYP/6-31+G(d,p) and B3LYP/SDD level of theories. Thermo-gravimetric analysis confirms the composition of the complexes by comparing the experimental and calculated data for C, H, N and metals. Experimental and computed IR results predict a significant change in vibrational frequencies of metal-phenylalanine complexes compared to free ligand. DFT calculation confirms that Mn, Co, Ni and Cu complexes form square planar structure whereas Zn adopts distorted tetrahedral geometry. The metal-oxygen bonds in the optimized geometry of all complexes are shorter compared to the metal-nitrogen bonds which is consistent with a previous study. Cation-binding energy, enthalpy and Gibbs free energy indicates that these complexes are thermodynamically stable. UV-vis and TD-DFT studies reveal that these complexes demonstrate representative metal-to-ligand charge transfer (MLCT) and d-d transitions bands. TG analysis and IR spectra of the metal complexes strongly support the absence of water in crystallization. Magnetic susceptibility data of the complexes exhibits that all except Zn(II) complex are high spin paramagnetic. Copyright © 2014 Elsevier B.V. All rights reserved.

Recovery of palladium(II) by methanogenic granular sludge.

PubMed

Pat-Espadas, Aurora M; Field, James A; Otero-Gonzalez, Lila; Razo-Flores, Elías; Cervantes, Francisco J; Sierra-Alvarez, Reyes

2016-02-01

This is the first report that demonstrates the ability of anaerobic methanogenic granular sludge to reduce Pd(II) to Pd(0). Different electron donors were evaluated for their effectiveness in promoting Pd reduction. Formate and H2 fostered both chemically and biologically mediated Pd reduction. Ethanol only promoted the reduction of Pd(II) under biotic conditions and the reduction was likely mediated by H2 released from ethanol fermentation. No reduction was observed in biotic or abiotic assays with all other substrates tested (acetate, lactate and pyruvate) although a large fraction of the total Pd was removed from the liquid medium likely due to biosorption. Pd(II) displayed severe inhibition towards acetoclastic and hydrogenotrophic methanogens, as indicated by 50% inhibiting concentrations as low as 0.96 and 2.7 mg/L, respectively. The results obtained indicate the potential of utilizing anaerobic granular sludge bioreactor technology as a practical and promising option for Pd(II) reduction and recovery offering advantages over pure cultures. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis, spectroscopic, fluorescence properties and biological evaluation of novel Pd(II) and Cd(II) complexes of NOON tetradentate Schiff bases.

PubMed

Ali, Omyma A M

2014-01-01

The solid complexes of Pd(II) and Cd(II) with N,N/bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H2L(1)), and N,N/bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H2L(2)) have been synthesized and characterized by several techniques using elemental analysis (CHN), FT-IR, (1)H NMR, UV-Vis spectra and thermal analysis. Elemental analysis data proved 1:1 stoichiometry for the reported complexes while spectroscopic data indicated square planar and octahedral geometries for Pd(II) and Cd(II) complexes, respectively. The prepared ligands, Pd(II) and Cd(II) complexes exhibited intraligand (π-π(∗)) fluorescence and can potentially serve as photoactive materials. Thermal behavior of the complexes was studied and kinetic parameters were determined by Coats-Redfern method. Both the ligands and their complexes have been screened for antimicrobial activities. Copyright © 2013 Elsevier B.V. All rights reserved.

Development of luminescent sensors based on transition metal complexes for the detection of nitroexplosives.

PubMed

Sathish, Veerasamy; Ramdass, Arumugam; Velayudham, Murugesan; Lu, Kuang-Lieh; Thanasekaran, Pounraj; Rajagopal, Seenivasan

2017-12-12

The detection of chemical explosives is a major area of research interest and is essential for the military as well as homeland security to counter the catastrophic effects of global terrorism. In recent years, tremendous effort has been devoted to the development of luminescent materials for the detection of explosives in the vapor, solution, and solid states with a high degree of selectivity and sensitivity and a rapid response time. Apart from the wide range of organic fluorescent chemosensors, transition metal complexes play a prominent role in the sensing of nitroaromatic explosives owing to their rich photophysical characteristics. This review briefly summarizes the salient features of the design and preparation of transition metal (Zn(ii), Ir(iii), Pd(ii), Pt(ii), Re(i) and Ru(ii)) complexes/metallacycles/metallosupramolecules with emphasis on their photophysical properties, sensing behavior, mechanism of action, and the driving forces for detecting explosives and future prospects and challenges. Most of the probes that have been reported to date act as "turn-off" luminescent sensors because their emission (intensity, lifetime, and quantum yield) is eventually quenched upon sensing with nitroaromatic compounds (NACs) through photo-induced electron or energy transfer. These unique properties of transition metal complexes in response to explosives open up new vistas for the development of real world applications such as on-site detection, in-field security, forensic research, etc.

Recovery of Elemental Palladium by Shewanella putrefaciens

NASA Astrophysics Data System (ADS)

Akasaka, S.; Xia, X.; Sawada, K.; Enokida, Y.; Yamamoto, I.; Ohnuki, T.

2006-12-01

Microbial reduction of metals plays an important role in environmental behavior and provides a technique for the recovery of metals from industrial wastewater. Recently, demand for platinum group metals (PGMs) increases by their catalytic properties. The extreme rarity of PGMs have led to a growing interest in their recovery. Palladium, one of PGMs, has different oxidation states of Pd(II) and Pd(0). The oxidized form of Pd(II) is soluble, while the reduced form of Pd(0) is insoluble. In this study, microbial reduction of palladium by Fe(III)- reducing bacterium, Shewanella putrefaceins was conducted. This bacterium is known to be capable of reducing metals, such as Mn(IV), U(VI), or Tc(VII) with organic C or H2 as an electron donor. In order to investigate the potential of S. putrefaciens to reduce Pd(II) in solution, resting cells or heat-killed cells were suspended under anaerobic conditions with lactate or H2 as an electron donor. The cells of S. putrefaciens (NBRC3908) were grown in aerobic medium, harvested by centrifugation, and then washed with 25 mmol/dm3 HEPES and 100 mmol/dm3 NaCl (HEPES-NaCl) solution (pH 7.0). The heat-killed cells were autoclaved for 20 min at 121 degrees C. The cell suspension (21.5 mg in dry weight) was resuspended in the HEPES-NaCl solution which contained 1.0 mmol/dm3 Na2PdCl4 (Wako Pure chemical Industries, Ltd). The suspensions were bubbled with N2 for 15 min before 10 mmol/dm3 lactate or 4.8 v/v% H2 was added. The suspensions were then incubated at 30 degrees C. Redox potential (Eh) and pH of the solutions were measured in an inert glove box with Ar gas. Concentration of Pd(II) was measured by Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES). Deposited Pd and cells were analyzed by X-ray powder diffraction (XRD) and Scanning Electron Microscope (SEM) with Energy-Dispersive Spectroscopy (EDS). Approximately 86% of Pd(II) of the initial concentration was removed from solution by the resting cells within 24 h when lactate was used as an electron donor. A black precipitates were observed in the solution, that was confirmed as Pd(0) by XRD analysis. SEM and EDS analyses identified that Pd bearing precipitates were present on and/or in the cells. The size of the precipitates associated with cells was approximately 100 nm in diameter. Approximately 23% of Pd(II) was removed by the heat-killed cells within 24 h. The precipitates between 200 and 300 nm in diameter were observed to be associated with the heat-killed cells by SEM and EDS analyses. No removal of Pd(II) was obtained without cells. On the contrary, complete removal of Pd(II) was occurred within 4 h after exposure of the resting cells to Pd(II) solution when H2 was used as an electron donor. Approximately 88 and 80% of Pd(II) was removed within 4 h with the heat-killed cells and without cells, respectively. The measured Eh and pH values were plotted in the Eh-pH diagram calculated for Pd-Cl-H2O system indicated that chemical conditions in the solutions were saturated with respect to Pd(0) at 24 or 4 h of incubation regardless the electron donor. These findings indicate that S. putrefaciens is capable to enhance the precipitation of palladium from solution by reducing Pd(II) to Pd(0) with lactate or H2 as an electron donor.

From atactic to isotactic CO/p-methylstyrene copolymer by proper modification of Pd(II) catalysts bearing achiral alpha-diimines.

PubMed

Binotti, Barbara; Carfagna, Carla; Zuccaccia, Cristiano; Macchioni, Alceo

2005-01-07

Cationic Pd(II) complexes modified with achiral C(2v)-symmetric alpha-diimine ligands allow preparation of atactic or isotactic stereoblock CO/p-methylstyrene copolymers; both catalyst activity and polyketone microstructure depend on the choice of alpha-diimine substituents and counterion.

Synthesis, structural, optical and anti-rheumatic activity of metal complexes derived from (E)-2-amino-N-(1-(2-aminophenyl)ethylidene)benzohydrazide (2-AAB) with Ru(III), Pd(II) and Zr(IV)

NASA Astrophysics Data System (ADS)

Hosny, Nasser Mohammed; Sherif, Yousery E.

2015-02-01

Three new metal complexes derived from Pd(II), Ru(III) and Zr(IV) with (E)-2-amino-N-(1-(2-aminophenyl)ethylidene)benzohydrazide (2-AAB) have been synthesized. The isolated complexes were characterized by elemental analyses, FT-IR, UV-Vis, ES-MS, 1H NMR, XRD, thermal analyses (TGA and DTA) and conductance. The morphology and the particle size were determined by transmittance electron microscope (TEM). The results showed that, the ligand coordinates to Pd(II) in the enol form, while it coordinates to Ru(III) and Zr(IV) in the keto form. A square planar geometry is suggested for Pd(II) complex and octahedral geometries are suggested for Ru(III) and Zr(IV) complexes. The optical band gaps of the isolated complexes were measured and indicated the semi-conductivity nature of the complexes. The anti-inflammatory and analgesic activities of the ligand and its complexes showed that, Ru(III) complex has higher effect than the well known drug "meloxicam".

Extraction of Ni (II) from Spent Hydrodesulfurization HDS Catalyst Through Leaching and Electroless Precipitation of Ni(OH)2

NASA Astrophysics Data System (ADS)

Pradhan, Sangita R.; Dash, Barsha; Sanjay, Kali; Subbaiah, T.

2013-04-01

The extraction of nickel (II) from a spent hydro-desulfurization catalyst containing 11.6 pct Ni was carried out through sulfuric acid leaching. Variations of parameters such as the concentration of acid, temperature, and time, were studied and optimized. Nickel hydroxide was precipitated from the leach liquor via neutralization with 1 M sodium hydroxide up to pH 12 in three different methods: normal neutralization precipitation, and then neutralization precipitation followed by aging at 353 K (80 °C) for 4 hours and neutralization of the leach liquor with 10 pct (v/v) of 0.1 N sodium lauryl sulfate. X-ray diffraction (XRD) and transmission electron microscopy (TEM) microanalysis shows a difference in crystallinity with the method of precipitation. The nickel hydroxide contains Cu(II), Co(II), Zn(II), and Mn(II) as trace impurities. The discharge capacities of the precipitated nickel hydroxides were 120 mAhg-1, 140.72 mAhg-1, and 145.2 mAhg-1 for aged sample, sample without surfactant, and with surfactant respectively.

Coordination Polymers Containing 1,3-Phenylenebis-((1H-1,2,4-triazol-1-yl)methanone) Ligand: Synthesis and ε-Caprolactone Polymerization Behavior.

PubMed

Bello-Vieda, Nestor J; Murcia, Ricardo A; Muñoz-Castro, Alvaro; Macías, Mario A; Hurtado, John J

2017-11-10

The reaction of isophthaloyl dichloride with 1 H -1,2,4-triazole afforded the new ligand 1,3-phenylenebis(1,2,4-triazole-1-yl)methanone ( 1 ). A series of Co(II), Cu(II), Zn(II) and Ni(II) complexes were synthesized using 1 and then characterized by melting point analysis, elemental analysis, theoretical calculations, thermogravimetric analysis, X-ray powder diffraction, nuclear magnetic resonance, infrared and Raman spectroscopy. Experimental and computational studies predict the formation of coordination polymers (CPs). The cobalt and copper CPs and zinc(II) complex were found to be good initiators for the ring-opening polymerization of ε-caprolactone (CL) under solvent-free conditions. ¹H-NMR analysis showed that the obtained polymers of CL were mainly linear and had terminal hydroxymethylene groups. Differential scanning calorimetry showed that the obtained polycaprolactones had high crystallinity, and TGA showed that they had decomposition temperatures above 400 °C. These results provide insight and guidance for the design of metal complexes with potential applications in the polymerization of CL.

Chitin nanofibrils for rapid and efficient removal of metal ions from water system.

PubMed

Liu, Dagang; Zhu, Yi; Li, Zehui; Tian, Donglin; Chen, Lei; Chen, Peng

2013-10-15

Joint mechanical defibrillation was successfully used to downsize chitin micro-particles (CMP) into nanofibrils without changing its chemical or crystalline structure. The fine chitin nanofibrils (CNF) bearing width of about 50 nm and length of more than 1 μm were then developed as heavy metal ion sorbents. The uptake performance of CNF dependent on pH, ionic concentration, time, and temperature was investigated. Results show that fixation amount of Cd(II), Ni(II), Cu(II), Zn(II), Pb(II), Cr(III) on CNF was up to 2.94, 2.30, 2.22, 2.06, 1.46, and 0.31 mmol/g, respectively, much higher than CMP due to high specific surface area and widely distributed pores of CNF. Adsorption kinetics of CMP and CNF followed pseudo-second-order model and Freundlich isotherm although CNF exhibited higher rate constant and sorption capacity than that of CMP. The defibrillated CNF is renewable, feasible, easily recyclable, and is thought as good candidate for heavy metal ion treatment due to their low sorption energy, rapid and efficient uptake capacity. Copyright © 2013 Elsevier Ltd. All rights reserved.

Exploration of cellular DNA lesion, DNA-binding and biocidal ordeal of novel curcumin based Knoevenagel Schiff base complexes incorporating tryptophan: Synthesis and structural validation

NASA Astrophysics Data System (ADS)

Chandrasekar, Thiravidamani; Raman, Natarajan

2016-07-01

A few novel Schiff base transition metal complexes of general formula [MLCl] (where, L = Schiff base, obtained by the condensation reaction of Knoevenagel condensate of curcumin, L-tryptophan and M = Cu(II), Ni(II), Co(II), and Zn(II)), were prepared by stencil synthesis. They were typified using UV-vis, IR, EPR spectral techniques, micro analytical techniques, magnetic susceptibility and molar conductivity. Geometry of the metal complexes was examined and recognized as square planar. DNA binding and viscosity studies revealed that the metal(II) complexes powerfully bound via an intercalation mechanism with the calf thymus DNA. Gel-electrophoresis technique was used to investigate the DNA cleavage competence of the complexes and they establish to approve the cleavage of pBR322 DNA in presence of oxidant H2O2. This outcome inferred that the synthesized complexes showed better nuclease activity. Moreover, the complexes were monitored for antimicrobial activities. The results exposed that the synthesized compounds were forceful against all the microbes under exploration.

Sorption of heavy metal ions by the nonliving biomass of freshwater macrophytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schneider, I.A.H.; Rubio, J.

1999-07-01

The removal of heavy metal ions by the nonliving biomass of aquatic macrophytes was investigated. The work involved studies of physical and biochemical properties of the materials, batch sorption experiments carried out in agitation flasks, and continuous runs in a packed bed column at laboratory scale. Results showed that the dried biomass of Potamogeton lucens, Salvinia herzogii, and Eichhornia crassipes were excellent biosorbents for Cr(III), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II). The sorption mechanism by these biomaterials was found to proceed mainly by ion exchange reactions between the metal ions and the cationic weak exchanger groups present on the plantmore » surface. Sorption followed the Langmuir isotherm, and maximum metal uptakes values (independent of the metal ion species) were attained at about 1.5 mequiv g{sup {minus}1} for P. lucens, 0.9 mequiv g{sup {minus}1} for S. herzogii, and 0.7 mequiv g{sup {minus}1} for E. crassipes. Advantages and disadvantages found in the use of these natural adsorbents for heavy metals ions present in industrial wastewaters are envisaged.« less

Synthesis, spectral, thermal and optical properties of Schiff-base complexes derived from 2(E)-2-((z)-4-hydroxypent-3-en-2-ylideneamino)-5-guanidinopentanoic acid and acetylacetone

NASA Astrophysics Data System (ADS)

Hosny, Nasser Mohammed; Hussien, Mostafa A.; Radwan, Fatima M.; Nawar, Nagwa

2017-09-01

New metal complexes derived from the in situ reaction of Cu(II), Co(II), Ni(II) and Zn(II) acetates with the Schiff-base ligand (H2L) resulted from the condensation of 2-amino-5-guanidinopentanoic acid (arginine) and acetylacetone have been synthesized. The resulting complexes have been characterized by, elemental analyses, ES-MS, IR, Raman spectra, UV-Vis., 1HNMR, ESR, thermal analyses (TGA and DTG) and magnetic measurements. The results showed that, The Schiff-base ligand acts as bi-negative tridentate coordinating via azomethine nitrogen, enolic carbonyl oxygen and carboxylate oxygen after displacement of hydrogen. The thermodynamic parameters E∗, ΔH, ΔG and ΔS of the isolated complexes have been calculated. The optical band gap (Eg) values of Cu, Co, Ni and Zn were found to be 3.3, 3.4, 3.7 and 4.3 eV, respectively, arising from direct transitions. Optical band gap measurements indicate the semi-conductivity nature of these complexes.

Contribution of tertiary amino groups to Re(VII) biosorption on modified corn stalk: competitiveness and regularity.

PubMed

Lou, Zhenning; Zhao, Ziyi; Li, Yexia; Shan, Weijun; Xiong, Ying; Fang, Dawei; Yue, Shuang; Zang, Shuliang

2013-04-01

The effects of basic strength and steric hindrance of gels modified by dimethylamine, diethylamine, di-n-octylamine and di-2-ethylhexylamine, respectively, on rhenium (Re(VII)) adsorption capacity and selectivity were discussed. By comparing with the adsorption of other coexisting metals, such as Mo(VI), Cu(II), Pb(II), Fe(III), Zn(II), Mn(VII) and Ni(II), the gel modified by di-n-octylamine (DNOA-OCS) showed a high affinity for Re(VII) at higher hydrochloric acid concentration (C(H)(+)≥1.0 mol L(-1)), and the maximum adsorption capacity was 98.69 mg g(-1). This article not only described the adsorption behavior but also suggested isotherms, kinetics and thermodynamics of Re(VII) onto the DNOA-OCS gel in an aqueous medium using several models. Further study on adsorption of rhenium in a fixed-bed column packed with the DNOA-OCS gel under continuous and recirculating modes could confirm that the corn stalk gel modified by di-n-octylamine could be used as the adsorbent of Re(VII) from Mo-containing wastewater. Copyright © 2013 Elsevier Ltd. All rights reserved.

Spectroscopic studies and antibacterial activities of some new 16-membered octaazamacrocyclic complexes derived from thiocarbohydrazide and pentane-2,4-dione

NASA Astrophysics Data System (ADS)

Singh, D. P.; Kumar, Krishan; Chopra, Rimpi Mehani ne'e.

2011-02-01

A series of macrocyclic complexes of the type [M(C 12H 20N 8S 2)X 2]; where M = Co(II), Ni(II), Cu(II), Zn(II); X = Cl -, NO 3-, CH 3COO - has been synthesized by template condensation of thiocarbohydrazide and pentane-2,4-dione in the presence of divalent metal salts in methanolic medium. The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic measurements, electronic, NMR, IR, EPR and MS spectral studies. The low value of molar conductance indicates them to be non-electrolytes. On the basis of various studies a distorted octahedral geometry may be proposed for all of these complexes. These metal complexes were also tested for their in vitro antibacterial activities against some Gram-positive bacterial strains, i.e., Bacillus subtilis, Bacillus stearothermophilus and two Gram-negative bacterial strains, i.e., Escherichia coli, Pseudomonas putida. The results obtained were compared with standard antibiotics, Chloramphenicol and Streptomycin and found that some of the synthesized complexes show good antibacterial activities as compared to the standard antibiotics.

New 14-membered octaazamacrocyclic complexes of divalent transition metal ions with their antimicrobial and spectral studies

NASA Astrophysics Data System (ADS)

Singh, D. P.; Kumar, Krishan; Sharma, Chetan

2010-01-01

A novel series of macrocyclic complexes of the type [M(C 18H 14N 10S 2)X 2]; where M = Co(II), Ni(II), Cu(II), Zn(II) and Cd(II); X = Cl -, NO 3-, CH 3COO - has been synthesized by [2+2] condensation of thiocarbohydrazide and isatin in the presence of divalent metal salts in methanolic medium. The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic measurements, electronic, NMR and infrared spectral studies. The low value of molar conductance indicates them to be non-electrolytes. On the basis of various studies a distorted octahedral geometry may be proposed for all of these complexes. These metal complexes were also tested for their in vitro antimicrobial activities against some Gram-positive bacteria viz. Staphylococcus aureus, Bacillus subtilis, and some Gram-negative bacteria Escherichia coli, Pseudomonas aeruginosa and some fungal strains Aspergillus niger, Aspergillus flavus (molds), Candida albicans, Saccharomyces cerevisiae (yeasts). The results obtained were compared with standard antibiotic: Ciprofloxacin and the standard antifungal drug: Amphotericin-B.

Simulation of the influence of EDTA on the sorption of heavy metals by humic acids

NASA Astrophysics Data System (ADS)

Kropacheva, T. N.; Didik, M. V.; Kornev, V. I.

2015-04-01

The results of mathematical simulation of sorption equilibria with the participation of divalent cations of heavy metals (HMs), chelant (EDTA), and insoluble forms of humic acids (HAs) are discussed. It is shown that the formation of chelates of metals with EDTA in solutions results in the decreasing sorption of the metals by humic acids. We also analyzed the effect of the acidity of the medium and the HM: EDTA: HA ratio (in a wide range) on the desorption of metals. The desorbing effect of EDTA on the metals is the highest at pH 3-5 and increases with an increase in the concentration of EDTA and a decrease in the concentration of HAs. With respect to the remobilization of metals under the impact of EDTA, the metal cations can be arranged into the following sequence: Cu(II) > Ni(II) > Pb(II) ≫ Cd(II) > Co(II) > Zn(II). The obtained data have been used to analyze the remobilization / extraction of HMs from soils with a high content of humic substances.

SOD activity and DNA binding properties of a new symmetric porphyrin Schiff base ligand and its metal complexes.

PubMed

Çay, Sevim; Köse, Muhammet; Tümer, Ferhan; Gölcü, Ayşegül; Tümer, Mehmet

2015-12-05

4-Methoxy-2,6-bis(hydroxymethyl)phenol (1) was prepared from the reaction of 4-methoxyphenol and formaldehyde. The compound (1) was then oxidized to the 4-methoxy-2,6-diformylphenol (2) compound. Molecular structure of compound (2) was determined by X-ray diffraction method. A new symmetric porphyrin Schiff base ligand 4-methoxy-2,6-bis[5-(4-iminophenyl)-10,15,20-triphenylporphyrin]phenol (L) was prepared from the reaction of the 5-(4-aminophenyl)-10,15,20-triphenylporphyrin (TTP-NH2) and the compound (2) in the toluene solution. The metal complexes (Cu(II), Fe(III), Mn(III), Pt(II) and Zn(II)) of the ligand (L) were synthesized and characterized by the spectroscopic and analytical methods. The DNA (fish sperm FSdsDNA) binding studies of the ligand and its complexes were performed using UV-vis spectroscopy. Additionally, superoxide dismutase activities of the porphyrin Schiff base metal complexes were investigated. Additionally, electrochemical, photoluminescence and thermal properties of the compounds were investigated. Copyright © 2015 Elsevier B.V. All rights reserved.

Enhanced selective metal adsorption on optimised agroforestry waste mixtures.

PubMed

Rosales, Emilio; Ferreira, Laura; Sanromán, M Ángeles; Tavares, Teresa; Pazos, Marta

2015-04-01

The aim of this work is to ascertain the potentials of different agroforestry wastes to be used as biosorbents in the removal of a mixture of heavy metals. Fern (FE), rice husk (RI) and oak leaves (OA) presented the best removal percentages for Cu(II) and Ni(II), Mn(II) and Zn(II) and Cr(VI), respectively. The performance of a mixture of these three biosorbents was evaluated, and an improvement of 10% in the overall removal was obtained (19.25mg/g). The optimum mixture proportions were determined using simplex-centroid mixture design method (FE:OA:RI=50:13.7:36.3). The adsorption kinetics and isotherms of the optimised mixture were fit by the pseudo-first order kinetic model and Langmuir isotherm. The adsorption mechanism was studied, and the effects of the carboxylic, hydroxyl and phenolic groups on metal-biomass binding were demonstrated. Finally, the recoveries of the metals using biomass were investigated, and cationic metal recoveries of 100% were achieved when acidic solutions were used. Copyright © 2015 Elsevier Ltd. All rights reserved.

Separation of macromolecular proteins and rejection of toxic heavy metal ions by PEI/cSMM blend UF membranes.

PubMed

Kanagaraj, P; Nagendran, A; Rana, D; Matsuura, T; Neelakandan, S

2015-01-01

The charged surface modifying macromolecule (cSMM) was blended into the casting solution of poly(ether imide) (PEI) to prepare surface modified ultrafiltration membranes by phase inversion technique. The separation of proteins including bovine serum albumin, egg albumin, pepsin and trypsin was investigated by the fabricated membranes. On increasing cSMM content, solute rejection decreases whereas membrane flux increases. The pore size and surface porosity of the 5 wt% cSMM blend PEI membranes increases to 41.4 Å and 14.8%, respectively. Similarly, the molecular weight cut-off of the membranes ranged from 20 to 45 kDa, depending on the various compositions of the prepared membranes. The toxic heavy metal ions Cu(II), Cr(III), Zn(II) and Pb(II) from aqueous solutions were subjected to rejection by the prepared blended membrane with various concentration of polyethyleneimine (PETIM) as water soluble polymeric ligand. It was found that the rejection behavior of metal ion depends on the PETIM concentration and the stability complexation of metal ion with ligand. Copyright © 2014 Elsevier B.V. All rights reserved.

Biologically active and thermally stable polymeric Schiff base and its metal polychelates: Their synthesis and spectral aspects

NASA Astrophysics Data System (ADS)

Rasool, Raza; Hasnain, Sumaiya

2015-09-01

New metal polychelates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) obtained by the interaction of metal acetates with polymeric Schiff base containing formaldehyde and piperazine, have been investigated. Structural and spectroscopic properties have been evaluated by elemental analysis, FT-IR and 1H-NMR. Geometry of the chelated polymers was confirmed by magnetic susceptibility measurements, UV-Visible spectroscopy and Electron Spin Resonance. The molecular weight of the polymer was determined by gel permeation chromatography (GPC). Thermogravimetric analysis indicated that metal polychelates were more thermally stable than their corresponding ligand. All compounds were screened for their antimicrobial activities against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, (bacteria) and Candida albicans, Microsporum canis, Cryptococcus neoformans (fungi) by agar well diffusion method. Interestingly, the polymeric Schiff base was found to be antimicrobial in nature but less effective as compared to the metal polychelates. On the basis of thermal and antimicrobial behavior, these polymers hold potential applications as thermally resistant antimicrobial and antifouling coating materials as well as antimicrobial packaging materials.

Simultaneous Automatic Electrochemical Detection of Zinc, Cadmium, Copper and Lead Ions in Environmental Samples Using a Thin-Film Mercury Electrode and an Artificial Neural Network

PubMed Central

Kudr, Jiri; Nguyen, Hoai Viet; Gumulec, Jaromir; Nejdl, Lukas; Blazkova, Iva; Ruttkay-Nedecky, Branislav; Hynek, David; Kynicky, Jindrich; Adam, Vojtech; Kizek, Rene

2015-01-01

In this study a device for automatic electrochemical analysis was designed. A three electrodes detection system was attached to a positioning device, which enabled us to move the electrode system from one well to another of a microtitre plate. Disposable carbon tip electrodes were used for Cd(II), Cu(II) and Pb(II) ion quantification, while Zn(II) did not give signal in this electrode configuration. In order to detect all mentioned heavy metals simultaneously, thin-film mercury electrodes (TFME) were fabricated by electrodeposition of mercury on the surface of carbon tips. In comparison with bare electrodes the TMFEs had lower detection limits and better sensitivity. In addition to pure aqueous heavy metal solutions, the assay was also performed on mineralized rock samples, artificial blood plasma samples and samples of chicken embryo organs treated with cadmium. An artificial neural network was created to evaluate the concentrations of the mentioned heavy metals correctly in mixture samples and an excellent fit was observed (R2 = 0.9933). PMID:25558996

Synthesis and Spectral Characterization of Antifungal Sensitive Schiff Base Transition Metal Complexes

PubMed Central

Sakthivel, A.; Rajasekaran, K.

2007-01-01

New N2O2 donor type Schiff base has been designed and synthesized by condensing acetoacetanilido-4-aminoantipyrine with 2-aminobenzoic acid in ethanol. Solid metal complexes of the Schiff base with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, fast atom bombardment (FAB) mass, IR, UV-Vis, and 1H NMR spectral studies. The data show that the complexes have the composition of ML type. The UV-Vis. and magnetic susceptibility data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The in vitro antifungal activities of the compounds were tested against fungi such as Aspergillus niger, Aspergillus flavus, Rhizopus stolonifer, Candida albicans, Rhizoctonia bataicola and Trichoderma harizanum. All the metal complexes showed stronger antifungal activities than the free ligand. The minimum inhibitory concentrations (MIC) of the metal complexes were found in the range of 10~31 µg/ml. PMID:24015086

Intracellular Zn(II) Intoxication Leads to Dysregulation of the PerR Regulon Resulting in Heme Toxicity in Bacillus subtilis

PubMed Central

2016-01-01

Transition metal ions (Zn(II), Cu(II)/(I), Fe(III)/(II), Mn(II)) are essential for life and participate in a wide range of biological functions. Cellular Zn(II) levels must be high enough to ensure that it can perform its essential roles. Yet, since Zn(II) binds to ligands with high avidity, excess Zn(II) can lead to protein mismetallation. The major targets of mismetallation, and the underlying causes of Zn(II) intoxication, are not well understood. Here, we use a forward genetic selection to identify targets of Zn(II) toxicity. In wild-type cells, in which Zn(II) efflux prevents intoxication of the cytoplasm, extracellular Zn(II) inhibits the electron transport chain due to the inactivation of the major aerobic cytochrome oxidase. This toxicity can be ameliorated by depression of an alternate oxidase or by mutations that restrict access of Zn(II) to the cell surface. Conversely, efflux deficient cells are sensitive to low levels of Zn(II) that do not inhibit the respiratory chain. Under these conditions, intracellular Zn(II) accumulates and leads to heme toxicity. Heme accumulation results from dysregulation of the regulon controlled by PerR, a metal-dependent repressor of peroxide stress genes. When metallated with Fe(II) or Mn(II), PerR represses both heme biosynthesis (hemAXCDBL operon) and the abundant heme protein catalase (katA). Metallation of PerR with Zn(II) disrupts this coordination, resulting in depression of heme biosynthesis but continued repression of catalase. Our results support a model in which excess heme partitions to the membrane and undergoes redox cycling catalyzed by reduced menaquinone thereby resulting in oxidative stress. PMID:27935957

A Method for Selective Depletion of Zn(II) Ions from Complex Biological Media and Evaluation of Cellular Consequences of Zn(II) Deficiency

PubMed Central

Richardson, Christopher E. R.; Cunden, Lisa S.; Butty, Vincent L.; Nolan, Elizabeth M.; Lippard, Stephen J.; Shoulders, Matthew D.

2018-01-01

We describe the preparation, evaluation, and application of an S100A12 protein-conjugated solid support, hereafter the “A12-resin,” that can remove 99% of Zn(II) from complex biological solutions without significantly perturbing the concentrations of other metal ions. The A12-resin can be applied to selectively deplete Zn(II) from diverse tissue culture media and from other biological fluids, including human serum. To further demonstrate the utility of this approach, we investigated metabolic, transcriptomic, and metallomic responses of HEK293 cells cultured in medium depleted of Zn(II) using S100A12. The resulting data provide insight into how cells respond to acute Zn(II) deficiency. We expect that the A12-resin will facilitate interrogation of disrupted Zn(II) homeostasis in biological settings, uncovering novel roles for Zn(II) in biology. PMID:29334734

Selective determination of gold(III) ion using CuO microsheets as a solid phase adsorbent prior by ICP-OES measurement.

PubMed

Rahman, Mohammed M; Khan, Sher Bahadar; Marwani, Hadi M; Asiri, Abdullah M; Alamry, Khalid A; Al-Youbi, Abdulrahman O

2013-01-30

We have prepared calcined CuO microsheets (MSs) by a wet-chemical process using reducing agents in alkaline medium and characterized by UV/vis., fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), and field-emission scanning electron microscopy (FESEM) etc. The detailed structural, compositional, and optical characterizations of the MSs were evaluated by XRD pattern, FT-IR, X-ray photoelectron spectroscopy (XPS), and UV-vis spectroscopy, respectively which confirmed that the obtained MSs are well-crystalline CuO and possessed good optical properties. The CuO MSs morphology was investigated by FESEM, which confirmed that the calcined nanomaterials were sheet-shaped and grown in large-quantity. Here, the efficiency of the CuO MS was applied for a selective adsorption of gold(III) ion prior to its detection by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of CuO MSs towards various metal ions, including Au(III), Cd(II), Co(II), Cr(III), Fe(III), Pd(II), and Zn(II) was analyzed. Based on the adsorption isotherm study, it was confirmed that the selectivity of MSs phase was mostly towards Au(III) ion. The static adsorption capacity for Au(III) was calculated to be 57.0 mg g(-1). From Langmuir adsorption isotherm, it was confirmed that the adsorption process was mainly monolayer-adsorption onto a surface containing a finite number of adsorption sites. Copyright © 2012 Elsevier B.V. All rights reserved.

Recovery of precious metals from space

NASA Technical Reports Server (NTRS)

Freiser, Henry

1991-01-01

The overall objective is to develop efficient and economical separation and recovery methods for the platinum group and other precious metals. The separation of Pd(II) from Pt(II), Ir(III), and Rh(III) with trioctylphosphine oxide (TOPO) in heptane using centrifugal partition chromatography (CPC) was investigated. Activities to achieve this objective focussed on selection and evaluation of extraction systems for the PGM and modification of selected systems for multistage operation with a view to scaling up to desired macro levels. On the basis of preliminary evaluation of a series of simple metal complexing agents and chelating agents, the TOPO in heptane was selected as a likely system for isolating of Pd(II) and Pt(II) from the other PGM. A multistage apparatus capable of configuration as a simple rugged device, a centrifugal partition chromatograph (CPC), was shown to be effective. The extraction of Pd(II) was studied by CPC and batch solvent extraction. The distribution ratios for Pd(II) determined by both methods agree well. In low HCl concentrations (less than 0.1 M), the extracted species was PdCl2.(TOPO)2, irrespective of the chloride concentration, while at acid concentrations above 0.1 M, the Pd was extracted as the ion pair, 2(TOPO.H+).(PdCl4)2-. Base line separation of Pd(II) and Pt(II) in CPC was obtained under a variety of chloride and HCl concentration. It was demonstrated that the efficiency of CPC for metal separation was limited by chemical kinetic factors rather than instrumental factors, strongly suggesting that dramatic improvements can be achieved by studying reaction kinetics of formation and dissociation of the extractable metal complex.

Symmetrical and unsymmetrical pincer complexes with group 10 metals: synthesis via aryl C-H activation and some catalytic applications.

PubMed

Niu, Jun-Long; Hao, Xin-Qi; Gong, Jun-Fang; Song, Mao-Ping

2011-05-21

Aryl-based pincer metal complexes with anionic terdentate ligands have been widely applied in organic synthesis, organometallic catalysis and other related areas. Synthetically, the most simple and convenient method for the construction of these complexes is the direct metal-induced C(aryl)-H bond activation, which can be fulfilled by choosing the appropriate functional donor groups in the two side arms of the aryl-based pincer preligands. In this perspective, we wish to summarize some results achieved by our group in this context. Successful examples include symmetrical chiral bis(imidazoline) NCN pincer complexes with Ni(II), Pd(II) and Pt(II), bis(phosphinite) and bis(phosphoramidite) PCP pincer Pd(II) complexes, unsymmetrical (pyrazolyl)phosphinite, (amino)phosphinite and (imino)phosphinite PCN pincer Pd(II) complexes, chiral (imidazolinyl)phosphinite and (imidazolinyl)phosphoramidite PCN pincer complexes with Ni(II) and Pd(II) as well as unsymmetrical (oxazolinyl)amine and (oxazolinyl)pyrazole NCN' pincer Pd(II) complexes. Among them, the P-donor containing complexes are efficiently synthesized by the "one-pot phosphorylation/metalation" method. The obtained symmetrical and unsymmetrical pincer complexes have been used as catalysts in Suzuki-Miyaura reaction (Pd), asymmetric Friedel-Crafts alkylation of indole with trans-β-nitrostyrene (Pt) as well as in asymmetric allylation of aldehyde and sulfonimine (Pd). In the Suzuki couplings conducted at 40-50 °C, some unsymmetrical Pd complexes exhibit much higher activity than the related symmetrical ones which can be attributed to their faster release of active Pd(0) species resulting from the hemilabile coordination of the ligands. Literature results on the synthesis of some related pincer complexes as well as their activities in the above catalytic reactions are also presented.

Oxidative removal of aqueous steroid estrogens by manganese oxides.

PubMed

Xu, Lei; Xu, Chao; Zhao, Meirong; Qiu, Yuping; Sheng, G Daniel

2008-12-01

This study investigated the oxidative removal of steroid estrogens from water by synthetic manganese oxide (MnO2) and the factors influencing the reactions. Using 1 x 10(-5)M MnO2 at pH 4, estrone (E1), 17beta-estradiol (E2), estriol (E3) and 17alpha-ethinylestradiol (EE2), all at 4 x 10(-6)M, were rapidly removed within 220 min, indicating the effectiveness of MnO2 as an oxidizing agent towards estrogens. E2 removal increased with decreasing pH over the tested range of 4-8, due most likely to increased oxidizing power of MnO2 and a cleaner reactive surface in acidic solutions. Coexisting metal ions of 0.01 M (Cu(II), Zn(II), Fe(III) and Mn(II)) and Mn(II) released from MnO2 reduction competed with E2 for reactive sites leading to reduced E2 removal. Observed differential suppression on E2 removal may be related to different speciations of metals, as suggested by the MINTEQ calculations, and hence their different adsorptivities on MnO2. By suppressing the metal effect, humic acid substantially enhanced E2 removal. This was attributed to complexation of humic acid with metal ions. With 0.01 M ZnCl2 in solutions containing 1 mg l(-1) humic acid, the binding of humic acid for Zn(II) was determined at 251 mmol g(-1). An in vitro assay using human breast carcinoma MCF-7 cells indicated a near elimination of estrogenic activities without secondary risk of estrogen solutions treated with MnO2. Synthetic MnO2 is therefore a promising chemical agent under optimized conditions for estrogen removal from water. Metal chelators recalcitrant to MnO2 oxidation may be properly used to further enhance the MnO2 performance.

Mono- and dinuclear bioxazoline-palladium complexes for the stereocontrolled synthesis of CO/styrene polyketones.

PubMed

Scarel, Alessandro; Durand, Jérôme; Franchi, Davide; Zangrando, Ennio; Mestroni, Giovanni; Carfagna, Carla; Mosca, Luca; Seraglia, Roberta; Consiglio, Giambattista; Milani, Barbara

2005-10-07

The coordination chemistry of the chiral bioxazoline ligand (4S,4'S)-2,2'-bis(4-isopropyl-4,5-dihydrooxazole) to Pd(II) provides evidence that the ligand bonding can occur either through chelation of one Pd(II) ion leading to a mononuclear species with the expected cis geometry, or by double bridging of two Pd(II) ions giving a dinuclear complex with trans geometry. The species in solution are identified by 1H NMR spectroscopy. Both the mononuclear and the dinuclear complexes promote the CO/styrene copolymerization, yielding the corresponding polyketone with a fully or a predominantly isotactic microstructure, depending on the reaction medium. The nature of the anion present in the palladium precatalysts affects the polyketone stereochemistry. MALDI-TOF analysis of the copolymers synthesized reveals the presence of p-hydroxyphenolic end-groups, thus confirming and explaining the role of 1,4-hydroquinone as a molecular weight regulator.

Palladium(II) complexes with highly basic imidazolin-2-imines and their reactivity toward small bio-molecules.

PubMed

Bogojeski, Jovana; Volbeda, Jeroen; Freytag, Matthias; Tamm, Matthias; Bugarčić, Živadin D

2015-10-21

A series of novel Pd(ii) complexes with chelating mono(imidazolin-2-imine) and bis(imidazolin-2-imine) ligands were synthesized. The crystal structures of [Pd(DMEAIm(iPr))Cl2] and [Pd(DPENIm(iPr))Cl2] were determined by X-ray diffraction analysis. The reactivity of the six Pd(ii) complexes, namely, [Pd(en)Cl2], [Pd(EAIm(iPr))Cl2], [Pd(DMEAIm(iPr))Cl2], [Pd(DPENIm(iPr))Cl2], [Pd(BL(iPr))Cl2] and [Pd(DACH(Im(iPr))2)Cl2], were investigated. Spectrophotometric acid-base titrations were performed to determine the pKa values of the coordinated water molecules in [Pd(en)(H2O)2](2+), [Pd(EAIm(iPr))(H2O)2](2+), [Pd(DMEAIm(iPr))(H2O)2](2+), [Pd(DPENIm(iPr))(H2O)2](2+), [Pd(BL(iPr))(H2O)2](2+) and [Pd(DACH(Im(iPr))2)(H2O)2](2+). The substitution of the chloride ligands in these complexes by TU, l-Met, l-His and Gly was studied under pseudo-first-order conditions as a function of the nucleophile concentration and temperature using stopped-flow techniques; the sulfur-donor nucleophiles have shown better reactivity than nitrogen-donor nucleophiles. The obtained results indicate that there is a clear correlation between the nature of the imidazolin-2-imine ligands and the acid-base characteristics and reactivity of the resulting Pd(ii) complexes; the order of reactivity of the investigated Pd(ii) complexes is: [Pd(en)Cl2] > [Pd(EAIm(iPr))Cl2] > [Pd(DMEAIm(iPr))Cl2] > [Pd(DPENIm(iPr))Cl2] > [Pd(BL(iPr))Cl2] > [Pd(DACH(Im(iPr))2)Cl2]. The solubility measurements revealed good solubility of the studied imidazolin-2-imine complexes in water, despite the fact that these Pd(ii) complexes are neutral complexes. Based on the performed studies, three unusual features of the novel imidazolin-2-imine Pd(ii) complexes are observed, that is, good solubility in water, very low reactivity and high pKa values. The coordination geometries around the palladium atoms are distorted square-planar; the [Pd(DMEAIm(iPr))Cl2] complex displays Pd-N distances of 2.013(2) and 2.076(2) Å, while the [Pd(DPENIm(iPr))Cl2] complex displays similar Pd-N distances of 2.034(4) and 2.038(3) Å. The studied systems are of interest because little is known about the substitution behavior of imidazolin-2-imine Pd(ii) complexes with bio-molecules under physiological conditions.

Laser-ignited frontal polymerization of shape-controllable poly(VI-co-AM) hydrogels based on 3D templates toward adsorption of heavy metal ions

NASA Astrophysics Data System (ADS)

Fan, Suzhen; Liu, Sisi; Wang, Xiao-Qiao; Wang, Cai-Feng; Chen, Su

2016-06-01

Given the increasing heavy metal pollution issue, fast preparation of polymeric hydrogels with excellent adsorption property toward heavy metal ions is very attractive. In this work, a series of poly( N-vinylimidazole-co-acrylamide) (poly(VI-co-AM)) hydrogels were synthesized via laser-ignited frontal polymerization (LIFP) for the first time. The dependence of frontal velocity and temperature on two factors monomer ratios and initiator concentrations was systematically investigated. Poly(VI-co-AM) hydrogels with any self-supporting shapes can be synthesized by a one-step LIFP in seconds through the application of 3D templates. These shape-persistent hydrogels are pH-responsive and exhibit excellent adsorption/desorption characteristics toward Mn(II), Zn(II), Cd(II), Ni(II), Cu(II) and Co(II) ions, and the adsorption conformed to the pseudo-second-order kinetic model. The reusability of the hydrogels toward mental ions adsorption was further researched, which suggested that the hydrogels can be reused without serious decrease in adsorption capacity. This work might open a promising strategy to facilely prepare shape-controllable hydrogels and expand the application of LIFP.

An automated system for liquid-liquid extraction in monosegmented flow analysis

PubMed Central

Facchin, Ileana; Pasquini, Celio

1997-01-01

An automated system to perform liquid-liquid extraction in monosegmented flow analysis is described. The system is controlled by a microcomputer that can track the localization of the aqueous monosegmented sample in the manifold. Optical switches are employed to sense the gas-liquid interface of the air bubbles that define the monosegment. The logical level changes, generated by the switches, are flagged by the computer through a home-made interface that also contains the analogue-to-digital converter for signal acquisition. The sequence of operations, necessary for a single extraction or for concentration of the analyte in the organic phase, is triggered by these logical transitions. The system was evaluated for extraction of Cd(II), Cu(II) and Zn(II) and concentration of Cd(II) from aqueous solutions at pH 9.9 (NH3/NH4Cl buffer) into chloroform containing PAN (1-(2-pyridylazo)-2-naphthol) . The results show a mean repeatability of 3% (rsd) for a 2.0 mg l-1 Cd(II) solution and a linear increase of the concentration factor for a 0.5mg l-1 Cd(II) solution observed for up to nine extraction cycles. PMID:18924792

Synthesis and characterization of poly(maleic acid)-grafted crosslinked chitosan nanomaterial with high uptake and selectivity for Hg(II) sorption.

PubMed

Ge, Huacai; Hua, Tingting

2016-11-20

Chitosan-poly(maleic acid) nanomaterial (PMACS) with the size of 400-900nm was synthesized by grafting poly(maleic acid) onto chitosan and then crosslinking with glutaraldehyde. The synthesis conditions were optimized. The structure and morphology of PMACS were characterized by FT-IR, XRD, SEM and TGA. PMACS was used to adsorb some heavy metal ions such as Hg(II), Pb(II), Cu(II), Cd(II), Co(II), and Zn(II). The results indicated that PMACS had selectivity for Hg(II) sorption. The effects of various variables for sorption of Hg(II) were further explored. The maximum capacity for Hg(II) sorption was found to be 1044mgg(-1) at pH 6.0, which could compare with the maximal value of the recently reported other sorbents. The sorption followed the pseudo-second-order kinetics and Langmuir isotherm models. The rising of temperature benefited the uptake and the sorption was a spontaneous chemical process. The sorbent could be reused with EDTA. Hence, the nanomaterial would be used as a selective and high uptake sorbent in the removal of Hg(II) from effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determination of some metal ions in various meat and baby food samples by atomic spectrometry.

PubMed

Daşbaşı, Teslima; Saçmacı, Şerife; Ülgen, Ahmet; Kartal, Şenol

2016-04-15

In this paper, we report a simple and rapid solid phase extraction system for the separation/preconcentration and determination of Cd(II), Co(II), Cu(II), Fe(III), Cr(III), Pb(II), and Zn(II) ions by flame atomic absorption spectrometry (FAAS). This method is based upon the retention of metal ions on a column packed with poly[N-(3-methyl-1H-indole-1-yl)]-2-methacrylamide-co-2-acrylamido-2-methyl-1-propane sulphonic acid-co divinylbenzene] (MMAD) resin as a solid-phase extraction (SPE) sorbent at pH 8. At the optimized conditions, the limits of detection (3 s/b) between 0.12 and 1.6 μg L(-1), preconcentration factor of 100, and the relative standard deviation of ⩽1.8% were achieved (n=10). The accuracy of the method was verified by analyzing certified reference materials (CRMs) and performing recovery experiments. The developed method was successfully applied to the various natural water, meat products and baby food samples. The recoveries of analyte ions were found in added real samples and CRMs from 95% to 102%. Copyright © 2015 Elsevier Ltd. All rights reserved.

Spectral, biological screening of metal chelates of chalcone based Schiff bases of N-(3-aminopropyl) imidazole.

PubMed

Kalanithi, M; Rajarajan, M; Tharmaraj, P; Sheela, C D

2012-02-15

Tridentate chelate complexes of Co(II), Ni(II), Cu(II) and Zn(II) have been synthesized from the chalcone based ligands 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-(phenylallyl)]phenol(HL(1)), 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-p-tolylallyl]phenol(HL(2)), 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-4-nitrophenylallyl]phenol(HL(3)). Microanalytical data, UV-vis spectrophotometric method, magnetic susceptibility measurements, IR, 1H NMR, Mass, and EPR techniques were used to characterize the structure of chelates. The electronic absorption spectra and magnetic susceptibility measurements suggest a distorted square planar geometry for the copper(II) ion. The other metal complexes show distorted tetrahedral geometry. The coordination of the ligands with metal(II) ions was further confirmed by solution fluorescence spectrum. The antimicrobial activity of the ligands and metal(II) complexes against the species Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albigans and Aspergillus niger has been carried out and compared. The electrochemical behavior of copper(II) complex is studied by cyclic voltammetry. Copyright © 2011 Elsevier B.V. All rights reserved.

Synthesis, spectral characterization, molecular modeling, biological activity and potentiometric studies of 4-amino-5-mercapto-3-methyl-S-triazole Schiff's base complexes

NASA Astrophysics Data System (ADS)

Alaghaz, Abdel-Nasser M. A.; Zayed, Mohamed E.; Alharbi, Suliman A.

2015-03-01

The Schiff's base derived from condensation of s-triazole (4-amino-5-mercapto-3-methyl-S-triazole) with pyridine-2-aldehyde and their corresponding Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. The isolated solid complexes were characterized by elemental analyses, molar conductance, spectral (IR, UV-Vis, 1H NMR, mass), magnetic moment and thermal measurements. The IR spectral data suggest that the ligand coordinate in a tridentate manner (SNN) via the one thiol (SH), one pyridine ring and the azomethine (Cdbnd N) groups. The data show that the complexes have composition of ML2 type. The activation of thermodynamic parameters are calculated using Coats-Redfern, Horowitz-Metzger (HM), and Piloyan-Novikova (PN). The octahedral geometry of the complexes is confirmed using DFT method from DMOL3 calculations and ligand field parameters. Protonation constants of Schiff base and stability constants of their binary metal complexes have been determined potentiometrically in 50% DMSO-water media at 25 °C and ionic strength 0.10 M potassium nitrate. The biological activity of these compounds against various fungi has been investigated.

Synthesis, characterization and application of a new chelating resin for solid phase extraction, preconcentration and determination of trace metals in some dairy samples by flame atomic absorption spectrometry.

PubMed

Daşbaşı, Teslima; Saçmacı, Şerife; Çankaya, Nevin; Soykan, Cengiz

2016-11-15

In this study, a simple and rapid solid phase extraction/preconcentration procedure was developed for determination of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Pb(II), and Zn(II) trace metals by flame atomic absorption spectrometry (FAAS). A new chelating resin, poly(N-cyclohexylacrylamide-co-divinylbenzene-co-2-acrylamido-2-methyl-1-propanesulfonic acid) (NCA-co-DVB-co-AMPS) (hereafter CDAP) was synthesized and characterized. The influences of the analytical parameters such as pH of the sample solution, type and concentration of eluent, flow rates of the sample and eluent, volume of the sample and eluent, amount of chelating resin, and interference of ions were examined. The limit of detection (LOD) of analytes were found (3s) to be in the range of 0.65-1.90μgL(-1). Preconcentration factor (PF) of 200 and the relative standard deviation (RSD) of ⩽2% were achieved (n=11). The developed method was applied for determination of analytes in some dairy samples and certified reference materials. Copyright © 2016 Elsevier Ltd. All rights reserved.

One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Şahin, Onur

2016-11-01

Two new one dimensional (1D) cyanide complexes, namely [M(4-aepy)2(H2O)2][Pt(CN)4], (4-aepy = 4-(2-aminoethyl)pyridine M = Cu(II) (1) or Zn(II) (2)), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. The crystallographic analyses reveal that 1 and 2 are isomorphous and isostructural, and crystallize in the monoclinic system and C2 space group. The Pt(II) ions are coordinated by four cyanide-carbon atoms in the square-planar geometry and the [Pt(CN)4]2- ions act as a counter ion. The M(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4-aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. The crystal structures of 1 and 2 are similar each other and linked via intermolecular hydrogen bonding, Pt⋯π interactions to form 3D supramolecular network. Vibration assignments of all the observed bands are given and the spectral features also supported to the crystal structures of the complexes.

Exploring DNA binding and nucleolytic activity of few 4-aminoantipyrine based amino acid Schiff base complexes: A comparative approach

NASA Astrophysics Data System (ADS)

Raman, N.; Sakthivel, A.; Pravin, N.

A series of novel Co(II), Cu(II), Ni(II) and Zn(II) complexes were synthesized from Schiff base(s), obtained by the condensation of 4-aminoantipyrine with furfural and amino acid (glycine(L1)/alanine(L2)/valine(L3)) and respective metal(II) chloride. Their structural features and other properties were explored from the analytical and spectral methods. The binding behaviors of the complexes to calf thymus DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The intrinsic binding constants for the above synthesized complexes are found to be in the order of 102 to 105 indicating that most of the synthesized complexes are good intercalators. The binding constant values (Kb) clearly indicate that valine Schiff-base complexes have more intercalating ability than alanine and glycine Schiff-base complexes. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens. The IC50 values of [Ni(L1)2] and [Zn(L1)2] complexes imply that these complexes have preferable ability to scavenge hydroxyl radical.

A dip-and-read test strip for the determination of mercury(II) ion in aqueous samples based on urease activity inhibition.

PubMed

Shi, Guo-Qing; Jiang, Guibin

2002-11-01

A sensitive dip-and-read test strip for the determination of mercury in aqueous samples based on the inhibition of urease reaction by the ion has been developed. The strip has a circular sensing zone that containing two layers: the top layer is a cellulose acetate membrane where urease is immobilized on it; the bottom layer is a pH indicator wafer that is impregnated with urea. The principle of the measurement is based on the disappearance of a yellow spot on the pH indicator wafer. The elapsing time until the disappearance of the spot which depends on the concentration of mercury(II) ion is measured with a stopwatch. Under the experimental conditions, as low as 0.2 ng/ml mercury can be observed with the detection range from 0.2 to 200 ng/ml in water. Organomercury compounds give essentially the same response as inorganic mercury. Heavy-metal ions such as Ag(I), Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) as well as other sample matrixes basically do not interfere with the mercury measurement.

Interferences in electrochemical hydride generation of hydrogen selenide

NASA Astrophysics Data System (ADS)

Bolea, E.; Laborda, F.; Belarra, M. A.; Castillo, J. R.

2001-12-01

Interferences from Cu(II), Zn(II), Pt(IV), As(III) and nitrate on electrochemical hydride generation of hydrogen selenide were studied using a tubular flow-through generator, flow injection sample introduction and quartz tube atomic absorption spectrometry. Comparison with conventional chemical generation using tetrahydroborate was also performed. Lead and reticulated vitreous carbon (RVC), both in particulate form, were used as cathode materials. Signal supressions up to 60-75%, depending on the cathode material, were obtained in the presence of up to 200 mg l-1 of nitrate due to the competitive reduction of the anion. Interference from As(III) was similar in electrochemical and chemical generation, being related to the quartz tube atomization process. Zinc did not interfere up to Se/Zn ratios 1:100, whereas copper and platinum showed suppression levels up to 50% for Se/interferent ratios 1:100. Total signal suppression was observed in presence of Se/Cu ratios 1:100 when RVC cathodes were used. No memory effects were observed in any case. Scanning electron microscopy and squared wave voltametry studies supported the interference mechanism based on the decomposition of the hydride on the dispersed particles of the reduced metal.

Synthesis, characterization and anti-microbial activity of phenylurea-formaldehyde resin (PUF) and its polymer metal complexes (PUF-Mn(II)

NASA Astrophysics Data System (ADS)

Ahamad, Tansir; Alshehri, Saad M.

2012-10-01

Phenylurea-formaldehyde polymer (PUF) was synthesized via polycondensation of phenylurea and formaldehyde in basic medium, its polymer-metal complexes [PUF-M(II)] were prepared with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) ions. PUF and PUF-M(II) were characterized with magnetic moment measurements, elemental and spectral (UV-visible, FTIR, 1H-NMR, 13C-NMR and ESR) analysis. The thermal behaviors of all the synthesized polymers were carried out using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The thermal data revealed that all of the PUF-M(II) showed higher thermal stabilities than the PUF and also ascribed that the PUF-Cu(II) showed better thermal stability than the other PUF-M(II). The kinetic parameters such as activation energy, pre-exponential factor etc., were evaluated for these polymer metal complexes using Coats-Redfern equation. In addition, the antimicrobial activity of the synthesized polymers was tested against several microorganisms using agar well diffusion methods. Among all of the PUF-M(II), the antimicrobial activity of the PUF-Cu(II) showed the highest zone of inhibition because of its higher stability constant and may be used in biomedical applications.

Spectral characterization, thermal and biological activity studies of Schiff base complexes derived from 4,4‧-Methylenedianiline, ethanol amine and benzil

NASA Astrophysics Data System (ADS)

Emam, Sanaa Moustafa

2017-04-01

Some new metal(II) complexes of asymmetric Schiff base ligand were prepared by template technique. The shaped complexes are in binuclear structures and were explained through elemental analysis, molar conductivity, various spectroscopic methods (IR, U.V-Vis, XRD, ESR), thermal (TG) and magnetic moment measurements. The IR spectra were done demonstrating that the Schiff base ligand acts as neutral tetradentate moiety in all metal complexes. The electronic absorption spectra represented octahedral geometry for all complexes, while, the ESR spectra for Cu(II) complex showed axially symmetric g-tensor parameter with g׀׀ > g⊥ > 2.0023 indicating to 2B1g ground state with (dx2-y2)1 configuration. The nature of the solid residue created from TG estimations was affirmed utilizing IR and XRD spectra. The biological activity of the prepared complexes was studied against Land Snails. Additionally, the in vitro antitumor activity of the synthesized complexes with Hepatocellular Carcinoma cell (Hep-G2) was examined. It was observed that Zn(II) complex (5), exhibits a high inhibition of growth of the cell line with IC50 of 7.09 μg/mL.

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

NASA Astrophysics Data System (ADS)

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.

Zn(II)-coordination modulated ligand photophysical processes – the development of fluorescent indicators for imaging biological Zn(II) ions

PubMed Central

Yuan, Zhao; Simmons, J. Tyler; Sreenath, Kesavapillai

2014-01-01

Molecular photophysics and metal coordination chemistry are the two fundamental pillars that support the development of fluorescent cation indicators. In this article, we describe how Zn(II)-coordination alters various ligand-centered photophysical processes that are pertinent to developing Zn(II) indicators. The main aim is to show how small organic Zn(II) indicators work under the constraints of specific requirements, including Zn(II) detection range, photophysical requirements such as excitation energy and emission color, temporal and spatial resolutions in a heterogeneous intracellular environment, and fluorescence response selectivity between similar cations such as Zn(II) and Cd(II). In the last section, the biological questions that fluorescent Zn(II) indicators help to answer are described, which have been motivating and challenging this field of research. PMID:25071933

Synthesis, Characterization and Cytotoxicity Studies of Palladium(II)-Proflavine Complexes

PubMed Central

Polyanskaya, Tatyana V.; Kazhdan, Irene; Motley, D. Michelle; Walmsley, Judith A.

2010-01-01

An investigation of the reaction of Pd(II) complexes with proflavine (3,6-diaminoacridine) resulted in the isolation of the compounds [Pd(terpy)(proflavine)](NO3)(HSO4)·3H2O, 1, (terpy = 2,2’:6’,2”-terpyridine), [Pd(en)(proflavineH))](NO3)(SO4), 2, (en = ethylenediamine), and [Pd(proflavineH)Cl2](SO4)0.5 ·H2O, 3. They have been isolated and characterized by NMR, IR, and electrospray ionization mass spectrometry techniques and by elemental analyses. The proflavine was bonded to the Pd(II) through the endocyclic nitrogen in 1, but through the proflavine NH2 in 2. Compound 3 appeared to be polymeric in the solid state with a 1:1 mole ratio of Pd(II):proflavine. Upon solution of 3 in DMSO, two unique species were formed. In one species the Pd(II) was bonded to Two proflavines through the endocyclic nitrogen (1:2 mole ratio) and in the other species, a Pd(II) was bonded to each NH2 group of a single proflavine (2:1 mole ratio). Molecular modeling of the equilibrium geometry by Spartan 8 produced structures which were consistent with the experimental data on the solutions of the three compounds. In vitro cytotoxicity testing against two breast cancer cell lines and one ovarian cancer cell line showed that compounds 1 and 3 had significant activity. PMID:20709409

Synthesis and spectroscopic characterization of 3,4-difluoroacetophenone-thiosemicarbazone and its palladium(II) complex: Evaluation of antimicrobial and antitumour activity

NASA Astrophysics Data System (ADS)

Jagadeesh, M.; Rashmi, H. K.; Subba Rao, Y.; Sreenath Reddy, A.; Prathima, B.; Uma Maheswari Devi, P.; Reddy, A. Varada

2013-11-01

A new cis-palladium(II)diaqua(3,4-difluoroacetophenonethiosemicarbazone complex (Pd(II) complex) is synthesized using 3,4-difluoroacetophenonethiosemicarbazone(L). The L and its Pd(II) complex are characterized and confirmed by elemental analyses, electrochemical analyses, FT-IR, FT-Raman, UV-Vis, HRMS and LC-MS techniques. Ligand L is further characterized by 1H, 13C and 19F NMR spectroscopy. The crystal structure of L is unambiguously characterized by single X-ray crystallography. The ligand (L) belongs to monoclinic system with P2(1)/C space group and the unit cell parameters are a(Å) = 9.1144(7), b(Å) = 13.7928(7), c(Å) = 8.4174(5), α(°) = 90, β(°) = 100.715, γ(°) = 90 and volume V(A3) = 1039.73(11). The Raman bands observed for the L and its Pd(II) complex are in good agreement with the FT-IR spectral data. The Pd(II) complex is found to be highly efficient in inhibiting the growth of human pathogens like Salmonella typhimurium and Klebsiella pneumonia with MIC value 10.0 μg/mL whose inhibition zones are almost comparable with the standard antibiotic. The synthesized compounds have shown antiproliferative activity against the human breast cancer cell lines MDA-MB231 by intermitting the regular pathway of ribonucleotidereductase.

Study on separation of platinum group metals from high level liquid waste using macroporous (MOTDGA-TOA)/SiO{sub 2}-P silica-based absorbent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ito, Tatsuya; Japan Atomic Energy Agency, Tokai-mura Naka-gun, Ibarak319-1195; Kim, Seong-Yun

2013-07-01

The recovery of platinum group metals (PGMs) from high level liquid waste (HLLW) by macroporous silica-based adsorbent, (MOTDGA-TOA)/SiO{sub 2}-P has been developed by impregnating two extractants of N,N'-dimethyl-N,N'-di-n-octyl-thio-diglycolamide (MOTDGA) and tri-n-octylamine (TOA) into a silica/polymer composite support (SiO{sub 2}-P). The adsorption of Ru(III), Rh(III) and Pd(II) have been investigated in simulated HLLW by batch method. The adsorbent has shown good uptake property for Pd(II). In addition, the combined use of MOTDGA and TOA improved the adsorption of Ru(III) and Rh(III) better than the individual use of them. The usability of adsorbent in radiation fields was further confirmed by irradiation experiments.more » The adsorbent remained to have the uptake capability for PGMs over the absorbed dose of 100 kGy, corresponding with one really adsorbed by the adsorbent, and showed good retention capability for Pd(II) even at the absorbed dose of 800 kGy. The chromatographic separation of metal ions was demonstrated with the adsorbent packed column, there is no influence of Re(VII) (instead of Tc) on the excellent separation behavior of Pd(II). (authors)« less

Zinc-sensitive MRI contrast agent detects differential release of Zn(II) ions from the healthy vs. malignant mouse prostate.

PubMed

Clavijo Jordan, M Veronica; Lo, Su-Tang; Chen, Shiuhwei; Preihs, Christian; Chirayil, Sara; Zhang, Shanrong; Kapur, Payal; Li, Wen-Hong; De Leon-Rodriguez, Luis M; Lubag, Angelo J M; Rofsky, Neil M; Sherry, A Dean

2016-09-13

Many secretory tissues release Zn(II) ions along with other molecules in response to external stimuli. Here we demonstrate that secretion of Zn(II) ions from normal, healthy prostate tissue is stimulated by glucose in fasted mice and that release of Zn(II) can be monitored by MRI. An ∼50% increase in water proton signal enhancement is observed in T1-weighted images of the healthy mouse prostate after infusion of a Gd-based Zn(II) sensor and an i.p. bolus of glucose. Release of Zn(II) from intracellular stores was validated in human epithelial prostate cells in vitro and in surgically exposed prostate tissue in vivo using a Zn(II)-sensitive fluorescent probe known to bind to the extracellular surface of cells. Given the known differences in intracellular Zn(II) stores in healthy versus malignant prostate tissues, the Zn(II) sensor was then evaluated in a transgenic adenocarcinoma of the mouse prostate (TRAMP) model in vivo. The agent proved successful in detecting small malignant lesions as early as 11 wk of age, making this noninvasive MR imaging method potentially useful for identifying prostate cancer in situations where it may be difficult to detect using current multiparametric MRI protocols.

Small-Molecule Fluorescent Sensors for Investigating Zinc Metalloneurochemistry

PubMed Central

Nolan, Elizabeth M.; Lippard, Stephen J.

2008-01-01

Conspectus Metal ions are involved in many neurobiological processes relevant to human health and disease. The metalloneurochemistry of Zn(II) is of substantial current interest. Zinc is the second most abundant d-block metal ion in the human brain and its distribution varies, with relatively high concentrations found in the hippocampus. Brain zinc is generally divided into two categories: protein-bound and loosely-bound. The latter pool is also referred to as histochemically observable, chelatable, labile, or mobile zinc. The neurophysiological and neuropathological significance of such mobile Zn(II) remains enigmatic. Studies of Zn(II) distribution, translocation, and function in vivo require tools for its detection. Because Zn(II) has a closed-shell d10 configuration and no convenient spectroscopic signature, fluorescence is a suitable method for monitoring Zn(II) in biological contexts. This Account summarizes work by our laboratory addressing the design, preparation, characterization, and use of small-molecule fluorescent sensors for imaging mobile Zn(II) in living cells and samples of brain tissue. These sensors provide “turn-on” or ratiometric Zn(II) detection in aqueous solution at neutral pH. By making alterations to the Zn(II)-binding unit and fluorophore platform, we have devised sensors with varied photophysical and metal-binding properties. We used several of these probes to image Zn(II) distribution, uptake, and mobilization in a variety of cell types, including neuronal cultures. Goals for the future include developing strategies for multi-color imaging, further defining the quenching and turn-on mechanisms of the sensors, and employing the probes to elucidate the functional significance of Zn(II) in neurobiology. PMID:18989940

Ap4A is not an efficient Zn(II) binding agent. A concerted potentiometric, calorimetric and NMR study.

PubMed

Wszelaka-Rylik, Małgorzata; Witkiewicz-Kucharczyk, Aleksandra; Wójcik, Jacek; Bal, Wojciech

2007-05-01

Diadenosine 5',5''-P(1)P(4) tetraphosphate (Ap(4)A) has been considered as an intracellular partner for Zn(II). We applied potentiometry, ITC and NMR to study protonation equilibria of Ap(4)A and Zn(II) complexation by this dinucleotide. The values of binding constants obtained by these three techniques under various experimental conditions coherently demonstrated that Ap(4)A binds Zn(II) weakly, with an apparent binding constant of ca. 10(4) at neutral pH. Such a low stability of Zn(II) complexes with Ap(4)A excludes a possibility for interactions between these two agents in vivo.

Comparative effects of zinc oxide nanoparticles and dissolved zinc on zebrafish embryos and eleuthero-embryos: importance of zinc ions.

PubMed

Brun, Nadja Rebecca; Lenz, Markus; Wehrli, Bernhard; Fent, Karl

2014-04-01

The increasing use of zinc oxide nanoparticles (nZnO) and their associated environmental occurrence make it necessary to assess their potential effects on aquatic organisms. Upon water contact, nZnO dissolve partially to zinc (Zn(II)). To date it is not yet completely understood, whether effects of nZnO are solely or partly due to dissolved Zn(II). Here we compare potential effects of 0.2, 1 and 5mg/L nZnO and corresponding concentrations of released Zn(II) by water soluble ZnCl2 to two development stages of zebrafish, embryos and eleuthero-embryos, by analysing expressional changes by RT-qPCR. Another objective was to assess uptake and tissue distribution of Zn(II). Laser ablation-ICP-MS analysis demonstrated that uptake and tissue distribution of Zn(II) were identical for nZnO and ZnCl2 in eleuthero-embryos. Zn(II) was found particularly in the retina/pigment layer of eyes and brain. Both nZnO and dissolved Zn(II) derived from ZnCl2 had similar inhibiting effects on hatching, and they induced similar expressional changes of target genes. At 72hours post fertilization (hpf), both nZnO and Zn(II) delayed hatching at all doses, and inhibited hatching at 1 and 5 mg/L at 96 hpf. Both nZnO and Zn(II) lead to induction of metallothionein (mt2) in both embryos and eleuthero-embryos at all concentrations. Transcripts of oxidative stress related genes cat and Cu/Zn sod were also altered. Moreover, we show for the first time that nZnO exposure results in transcriptional changes of pro-inflammatory cytokines IL-1β and TNFα. Overall, transcriptional alterations were higher in embryos than eleuthero-embryos. The similarities of the effects lead to the conclusion that effects of nZnO are mainly related to the release of Zn(II). Copyright © 2014 Elsevier B.V. All rights reserved.

Batch and fixed-bed column studies for biosorption of Zn(II) ions onto pongamia oil cake (Pongamia pinnata) from biodiesel oil extraction.

PubMed

Shanmugaprakash, M; Sivakumar, V

2015-12-01

The present work, analyzes the potential of defatted pongamia oil cake (DPOC) for the biosorption of Zn(II) ions from aqueous solutions in the both batch and column mode. Batch experiments were conducted to evaluate the optimal pH, effect of adsorbent dosage, initial Zn(II) ions concentration and contact time. The biosorption equilibrium and kinetics data for Zn(II) ions onto the DPOC were studied in detail, using several models, among all it was found to be that, Freundlich and the second-order model explained the equilibrium data well. The calculated thermodynamic parameters had shown that the biosorption of Zn(II) ions was exothermic and spontaneous in nature. Batch desorption studies showed that the maximum Zn(II) recovery occurred, using 0.1 M EDTA. The Bed Depth Service Time (BDST) and the Thomas model was successfully employed to evaluate the model parameters in the column mode. The results indicated that the DPOC can be applied as an effective and eco-friendly biosorbent for the removal of Zn(II) ions in polluted wastewater. Copyright © 2015 Elsevier Ltd. All rights reserved.

A new chitosan Schiff base supported Pd(II) complex for microwave-assisted synthesis of biaryls compounds

NASA Astrophysics Data System (ADS)

Baran, Talat

2017-08-01

In this study, a new heterogeneous palladium (II) catalyst that contains O-carboxymethyl chitosan Schiff base has been designed for Suzuki coupling reactions. The chemical structures of the synthesized catalyst were characterized with the FTIR, TG/DTG, ICP-OES, SEM/EDAX, 1H NMR, 13C NMR, GC/MS, XRD, and magnetic moment techniques. The reusability and catalytic behavior of heterogeneous catalyst was tested towards Suzuki reactions. As a result of the tests, excellent selectivity was obtained, and by-products of homo coupling were not seen in the spectra. The biaryls products were identified on a GC/MS. In addition, it was determined in the reusability tests that the catalysts could be used several times (seven runs). More importantly, with very low catalyst loading (6 × 10-3 mol %) in very short reaction time (5 min), chitosan Schiff base supported Pd(II) complex gave high TON and TOF values. These findings showed that Schiff base supported Pd(II) catalyst is suitable for Suzuki cross coupling reactions.

Engineering Porous Polymer Hollow Fiber Microfluidic Reactors for Sustainable C-H Functionalization.

PubMed

He, Yingxin; Rezaei, Fateme; Kapila, Shubhender; Rownaghi, Ali A

2017-05-17

Highly hydrophilic and solvent-stable porous polyamide-imide (PAI) hollow fibers were created by cross-linking of bare PAI hollow fibers with 3-aminopropyl trimethoxysilane (APS). The APS-grafted PAI hollow fibers were then functionalized with salicylic aldehyde for binding catalytically active Pd(II) ions through a covalent postmodification method. The catalytic activity of the composite hollow fiber microfluidic reactors (Pd(II) immobilized APS-grafted PAI hollow fibers) was tested via heterogeneous Heck coupling reaction of aryl halides under both batch and continuous-flow reactions in polar aprotic solvents at high temperature (120 °C) and low operating pressure. X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) analyses of the starting and recycled composite hollow fibers indicated that the fibers contain very similar loadings of Pd(II), implying no degree of catalyst leaching from the hollow fibers during reaction. The composite hollow fiber microfluidic reactors showed long-term stability and strong control over the leaching of Pd species.

Recognition of thymine in DNA bulges by a Zn(II) macrocyclic complex.

PubMed

del Mundo, Imee Marie A; Fountain, Matthew A; Morrow, Janet R

2011-08-14

A Zn(II) macrocyclic complex with appended quinoline is a bifunctional recognition agent that uses both the Zn(II) center and the pendent aromatic group to bind to thymine in bulges with good selectivity over DNA containing G, C or A bulges. Spectroscopic studies show that the stem containing the bulge stays largely intact in a DNA hairpin with the Zn(II) complex bound to the thymine bulge. This journal is © The Royal Society of Chemistry 2011

A convenient method for determination of quizalofop-p-ethyl based on the fluorescence quenching of eosin Y in the presence of Pd(II)

NASA Astrophysics Data System (ADS)

Wu, Huan; Zhao, Yanmei; Tan, Xuanping; Zeng, Xiaoqing; Guo, Yuan; Yang, Jidong

2017-03-01

A convenient fluorescence quenching method for determination of Quizalofop-p-ethyl(Qpe) was proposed in this paper. Eosin Y(EY) is a red dye with strong green fluorescence (λex/λem = 519/540 nm). The interaction between EY, Pd(II) and Qpe was investigated by fluorescence spectroscopy, resonance Rayleigh scattering(RRS) and UV-Vis absorption. Based on changes in spectrum, Pd(II) associated with Qpe giving a positively charged chelate firstly, then reacted with EY through electrostatic and hydrophobic interaction formed ternary chelate could be demonstrated. Under optimum conditions, the fluorescence intensity of EY could be quenched by Qpe in the presence of Pd(II) and the RRS intensity had a remarkable enhancement, which was directly proportional to the Qpe concentration within a certain concentration range, respectively. Based on the fluorescence quenching of EY-Pd(II) system by Qpe, a novel, convenient and specific method for Qpe determination was developed. To our knowledge, this is the first fluorescence method for determination of Qpe was reported. The detection limit for Qpe was 20.3 ng/mL and the quantitative determination range was 0.04-1.0 μg/mL. The method was highly sensitive and had larger detection range compared to other methods. The influence of coexisting substances was investigated with good anti-interference ability. The new analytical method has been applied to determine of Qpe in real samples with satisfactory results.

Synthesis, characterization and cytotoxicity studies of palladium(II)-proflavine complexes.

PubMed

Polyanskaya, Tatyana V; Kazhdan, Irene; Motley, D Michelle; Walmsley, Judith A

2010-11-01

An investigation of the reaction of Pd(II) complexes with proflavine (3,6-diaminoacridine) resulted in the isolation of the compounds [Pd(terpy)(proflavine)](NO(3))(HSO(4))*3H(2)O, 1, (terpy = 2,2':6',2″-terpyridine), [Pd(en)(proflavineH))](NO(3))(SO(4)), 2, (en = ethylenediamine), and [Pd(proflavineH)Cl(2)](SO(4))(0.5)*H(2)O, 3. They have been isolated and characterized by NMR, IR, and electro-spray ionization mass spectrometry techniques and by elemental analyses. The proflavine was bonded to the Pd(II) through the endocyclic nitrogen in 1, but through the proflavine NH(2) in 2. Compound 3 appeared to be polymeric in the solid state with a 1:1 mole ratio of Pd(II):proflavine. Upon solution of 3 in DMSO, two unique species were formed. In one species the Pd(II) was bonded to two proflavines through the endocyclic nitrogen (1:2 mole ratio) and in the other species, a Pd(II) was bonded to each NH(2) group of a single proflavine (2:1 mole ratio). Molecular modeling of the equilibrium geometry by Spartan 8 produced structures which were consistent with the experimental data on the solutions of the three compounds. In vitro cytotoxicity testing against two breast cancer cell lines and one ovarian cancer cell line showed that compounds 1 and 3 had significant activity. Copyright © 2010 Elsevier Inc. All rights reserved.

Characterization of sophorolipid biosurfactant produced by Cryptococcus sp. VITGBN2 and its application on Zn(II) removal from electroplating wastewater.

PubMed

Basak, Geetanjali; Das, Nilanjana

2014-11-01

The present study aimed at elucidating the role of biosurfactant produced by yeast for the removal of Zn(II) ions from electroplating wastewater. The yeast species isolated from CETP, Vellore, Tamilnadu was identified as Cryptococcus sp.VITGBN2, based on molecular techniques, and was found to be potent producer of biosurfactant in mineral salt media containing vegetable oil as additional carbon source. Chemical structure of the purified biosurfactant was identified as acidic diacetate sophorolipid through GC-MS analysis. Interaction of Zn(II) ions with biosurfactant was monitored using FT-IR, SEM and EDS analysis. Zn (II) removal at 100 mg l(-1) concentration was 84.8% compared were other synthetic surfactants (Tween 80 and sodium dodecyl sulphate), yeast mediated biosurfactant showed enhanced Zn (II) removal in batch mode. The role of biosurfactant on Zn(II) removal was evaluated in column mode packed with biosurfactant entrapped in sodium alginate beads. At a flow rate of 1 ml min(-1) and bed height of 12 cm, immobilized biosurfactant showed 94.34% Zn(II) removal from electroplating wastewater. The present study confirmed that Zn(II) removal was biosurfactant mediated. This is the first report establishing the involvement of yeast mediated biosurfactant in Zn(II) removal from wastewater.

Intercalation of a Zn(II) complex containing ciprofloxacin drug between DNA base pairs.

PubMed

Shahabadi, Nahid; Asadian, Ali Ashraf; Mahdavi, Mryam

2017-11-02

In this study, an attempt has been made to study the interaction of a Zn(II) complex containing an antibiotic drug, ciprofloxacin, with calf thymus DNA using spectroscopic methods. It was found that Zn(II) complex could bind with DNA via intercalation mode as evidenced by: hyperchromism in UV-Vis spectrum; these spectral characteristics suggest that the Zn(II) complex interacts with DNA most likely through a mode that involves a stacking interaction between the aromatic chromophore and the base pairs of DNA. DNA binding constant (K b = 1.4 × 10 4 M -1 ) from spectrophotometric studies of the interaction of Zn(II) complex with DNA is comparable to those of some DNA intercalative polypyridyl Ru(II) complexes 1.0 -4.8 × 10 4 M -1 . CD study showed stabilization of the right-handed B form of DNA in the presence of Zn(II) complex as observed for the classical intercalator methylene blue. Thermodynamic parameters (ΔH < 0 and ΔS < 0) indicated that hydrogen bond and Van der Waals play main roles in this binding prose. Competitive fluorimetric studies with methylene blue (MB) dye have shown that Zn(II) complex exhibits the ability of this complex to displace with DNA-MB, indicating that it binds to DNA in strong competition with MB for the intercalation.

Imaging free zinc levels in vivo - what can be learned?

PubMed

De Leon-Rodriguez, Luis; Lubag, Angelo Josue M; Sherry, A Dean

2012-12-01

Our ever-expanding knowledge about the role of zinc in biology includes its role in redox modulation, immune response, neurotransmission, reproduction, diabetes, cancer, and Alzheimers disease is galvanizing interest in detecting and monitoring the various forms of Zn(II) in biological systems. This paper reviews reported strategies for detecting and tracking of labile or "free" unchelated Zn(II) in tissues. While different bound structural forms of Zn(II) have been identified and studied in vitro by multiple techniques, very few molecular imaging methods have successfully tracked the ion in vivo. A number of MRI and optical strategies have now been reported for detection of free Zn(II) in cells and tissues but only a few have been applied successfully in vivo. A recent report of a MRI sensor for in vivo tracking of Zn(II) released from pancreatic β-cells during insulin secretion exemplifies the promise of rational design of new Zn(II) sensors for tracking this biologically important ion in vivo. Such studies promise to provide new insights into zinc trafficking in vivo and the critical role of this ion in many human diseases.

Elimination of Cu(II) toxicity by powdered waste sludge (PWS) addition to an activated sludge unit treating Cu(II) containing synthetic wastewater.

PubMed

Pamukoglu, M Yunus; Kargi, Fikret

2007-09-05

Copper(II) ion toxicity onto activated sludge organisms was eliminated by addition of powdered waste sludge (PWS) to the feed wastewater for removal of Cu(II) ions by biosorption before biological treatment. The synthetic feed wastewater containing 14 or 22 mgl(-1) Cu(II) was mixed with PWS in a mixing tank where Cu(II) ions were adsorbed onto PWS and the mixture was fed to a sedimentation tank to separate Cu(II) containing PWS from the feed wastewater. The activated sludge unit fed with the effluent of the sedimentation tank was operated at a hydraulic residence time (HRT) of 10h and sludge age (SRT) of 10 days. To investigate Cu(II), COD and toxicity removal performance of the activated sludge unit at different PWS loadings, the system was operated at different PWS loading rates (0.1-1 gPWSh(-1)) while the Cu(II) loading rate was constant throughout the operation. Percent copper, COD and toxicity removals increased with increasing PWS loading rate due to increased adsorption of Cu(II) onto PWS yielding low Cu(II) contents in the feed. Biomass concentration in the aeration tank increased and the sludge volume index (SVI) decreased with increasing PWS loading rate due to elimination of Cu(II) from the feed wastewater by PWS addition. PWS addition to the Cu(II) containing wastewater was proven to be effective for removal of Cu(II) by biosorption before biological treatment. Approximately, 1 gPWSh(-1) should be added for 28 mgCuh(-1) loading rate for complete removal of Cu(II) from the feed wastewater to obtain high COD removals in the activated sludge unit.

A mechanistic investigation on copolymerization of ethylene with polar monomers using a cyclophane-based Pd(II) alpha-diimine catalyst.

PubMed

Popeney, Chris S; Guan, Zhibin

2009-09-02

A detailed mechanistic investigation of the copolymerization of ethylene and methyl acrylate (MA) by a Pd(II) cyclophane-based alpha-diimine catalyst is reported. Our previous observations of unusually high incorporations of acrylates in copolymerization using this catalyst (J. Am. Chem. Soc. 2007, 129, 10062) prompted us to conduct a full mechanistic study on ethylene/MA copolymerization, which indicates a dramatic departure from normal Curtin-Hammett kinetic behavior as observed in copolymerization using the normal Brookhart type of Pd(II) alpha-diimine catalysts. Further investigation reveals that this contrasting behavior originates from the axial blocking effect of the cyclophane ligand hindering olefin substitution and equilibration. In equilibrium studies of ethylene with nitriles, the cyclophane catalyst was found to more strongly favor the linearly binding nitrile ligands as compared to the standard acyclic Pd(II) alpha-diimine catalysts. Ethylene exchange rates in the complexes [(N--N)PdMe(C(2)H(4))](+) (N--N = diimine) were measured by 2D EXSY NMR spectroscopy and found to be over 100 times slower in the cyclophane case. Measurement of the slow equilibration of ethylene, methyl acrylate, and 4-methoxystyrene in cyclophane-based Pd(II) olefin complexes by (1)H NMR and fitting of the obtained kinetic plots allowed for the estimation of exchange rates and equilibrium constants of the olefins. After extrapolation to typical polymerization temperature, DeltaG(double dagger) = 20.6 and 16.4 kcal/mol for ethylene-methyl acrylate exchange in the forward (ethylene displacement by methyl acrylate) and reverse directions, respectively. These values are of similar magnitude to the previously determined migratory insertion barriers of ethylene (DeltaG(double dagger) = 18.9 kcal/mol) and methyl acrylate (DeltaG(double dagger) = 16.3 kcal/mol) under equivalent conditions, but contrast strongly to the rapid olefin exchange seen in the Brookhart acyclic catalyst. The large barrier to olefin exchange hinders olefin pre-equilibrium, decreasing the cyclophane catalyst's ability to preferentially incorporate one monomer (in this case ethylene) over the other, thus giving rise to high comonomer incorporations.

Generating a Metal-responsive Transcriptional Regulator to Test What Confers Metal Sensing in Cells*

PubMed Central

Osman, Deenah; Piergentili, Cecilia; Chen, Junjun; Chakrabarti, Buddhapriya; Foster, Andrew W.; Lurie-Luke, Elena; Huggins, Thomas G.; Robinson, Nigel J.

2015-01-01

FrmR from Salmonella enterica serovar typhimurium (a CsoR/RcnR-like transcriptional de-repressor) is shown to repress the frmRA operator-promoter, and repression is alleviated by formaldehyde but not manganese, iron, cobalt, nickel, copper, or Zn(II) within cells. In contrast, repression by a mutant FrmRE64H (which gains an RcnR metal ligand) is alleviated by cobalt and Zn(II). Unexpectedly, FrmR was found to already bind Co(II), Zn(II), and Cu(I), and moreover metals, as well as formaldehyde, trigger an allosteric response that weakens DNA affinity. However, the sensory metal sites of the cells' endogenous metal sensors (RcnR, ZntR, Zur, and CueR) are all tighter than FrmR for their cognate metals. Furthermore, the endogenous metal sensors are shown to out-compete FrmR. The metal-sensing FrmRE64H mutant has tighter metal affinities than FrmR by approximately 1 order of magnitude. Gain of cobalt sensing by FrmRE64H remains enigmatic because the cobalt affinity of FrmRE64H is substantially weaker than that of the endogenous cobalt sensor. Cobalt sensing requires glutathione, which may assist cobalt access, conferring a kinetic advantage. For Zn(II), the metal affinity of FrmRE64H approaches the metal affinities of cognate Zn(II) sensors. Counter-intuitively, the allosteric coupling free energy for Zn(II) is smaller in metal-sensing FrmRE64H compared with nonsensing FrmR. By determining the copies of FrmR and FrmRE64H tetramers per cell, then estimating promoter occupancy as a function of intracellular Zn(II) concentration, we show how a modest tightening of Zn(II) affinity, plus weakened DNA affinity of the apoprotein, conspires to make the relative properties of FrmRE64H (compared with ZntR and Zur) sufficient to sense Zn(II) inside cells. PMID:26109070

Dipotassium tetra­kis­(thio­cyanato-κS)palladate(II)–(2,2′-bipyrimidine-κ2 N 1,N 1′)bis­(thio­cyanato-κS)palladium(II) (1/2)

PubMed Central

Ha, Kwang

2012-01-01

The asymmetric unit of the title compound, K2[Pd(NCS)4]·2[Pd(NCS)2(C8H6N4)], contains two crystallographically independent half-mol­ecules of the anionic PdII complex, two K+ cations and two independent neutral PdII complexes; an inversion centre is located at the centroid of each anionic complex. In the anionic complexes, each PdII ion is four-coordinated in an almost regular square-planar environment by four S atoms from four SCN− anions, and the PdS4 unit is exactly planar. In the neutral complexes, the PdII ion has a slightly distorted square-planar coordination environment defined by two pyrimidine N atoms derived from a chelating 2,2′-bipyrimidine ligand and two mutually cis S atoms from two SCN− anions. Both 2,2′-bipyrimidine ligands are almost planar [dihedral angle between the rings = 3.98 (16) and 4.57 (17)°] and also chelate to a potassium ion from their other two N atoms. In the crystal, the K+ ions inter­act with various S and N atoms of the ligands, forming a three-dimensional polymeric network, in which the shortest K⋯K contacts between the KN7S polyhedra are 4.4389 (17) and 4.4966 (18) Å. Intra- and inter­molecular C—H⋯S and C—H⋯N hydrogen bonds are also observed. PMID:22590117

Flame Atomic Absorption Spectrometric Determination of Trace Metal Ions in Environmental and Biological Samples After Preconcentration on a Newly Developed Amberlite XAD-16 Chelating Resin Containing p-Aminobenzene Sulfonic Acid.

PubMed

Islam, Aminul; Ahmad, Akil; Laskar, Mohammad Asaduddin

2015-01-01

Amberlite® XAD-16 was functionalized with p-aminobenzene sulfonic acid via an azo spacer in order to prepare a new chelating resin, which was then characterized by water regain value, hydrogen ion capacity, elemental analyses, and IR spectral and thermal studies. The maximum uptake of Cu(II), Ni(II), Zn(II), Co(II), Cr(III), Fe(III), and Pb(II) ions was observed in the pH range 4.0-6.0 with the corresponding half-loading times of 6.5, 7.0, 8.0, 9.0, 11.0, 8.5, and 16.5 min. The sorption data followed Langmuir isotherms and a pseudo-second-order model. Thermodynamic quantities, ΔH and ΔS, based on the variation of the distribution coefficient with temperature were also evaluated. High preconcentration factors of 60-100 up to a low preconcentration limit of 4.0-6.6 μg/L have been achieved for the metal ions. The validity of the method was checked by analyzing standard reference materials and recoveries of trace metals after spiking. The analytical applications of the method were explored by analyzing natural water, mango pulp, mint leaves, and fish.

beta-Citryl-L-glutamate is an endogenous iron chelator that occurs naturally in the developing brain.

PubMed

Hamada-Kanazawa, Michiko; Kouda, Makiko; Odani, Akira; Matsuyama, Kaori; Kanazawa, Kiyoka; Hasegawa, Tatsuya; Narahara, Masanori; Miyake, Masaharu

2010-01-01

The compound beta-citryl-L-glutamate (beta-CG) was initially isolated from developing brains, while it has also been found in high concentrations in testes and eyes. However, its functional roles are unclear. To evaluate its coordination with metal ions, we performed pH titration experiments. The stability constant, logbeta(pqr) for M(p)(beta-CG)(q)H(r) was calculated from pH titration data, which showed that beta-CG forms relatively strong complexes with Fe(III), Cu(II), Fe(II) and Zn(II). beta-CG was also found able to solubilize Fe more effectively from Fe(OH)(2) than from Fe(OH)(3). Therefore, we examined the effects of beta-CG on Fe-dependent reactive oxygen species (ROS)-generating systems, as well as the potential ROS-scavenging activities of beta-CG and metal ion-(beta-CG) complexes. beta-CG inhibited the Fe-dependent degradation of deoxyribose and Fe-dependent damage to DNA or plasmid DNA in a dose-dependent manner, whereas it had no effect on Cu-mediated DNA damage. In addition, thermodynamic data showed that beta-CG in a physiological pH solution is an Fe(II) chelator rather than an Fe(III) chelator. Taken together, these findings suggest that beta-CG is an endogenous low molecular weight Fe chelator.

[Preparation of Pb2+ imprinted acrylic acid-co-styrene and analysis of its adsorption properties by FAAS].

PubMed

Shawket, Abliz; Abdiryim, Supahun; Wang, Ji-De; Ismayil, Nurulla

2011-06-01

With lead ion template, acrylic acid as functional monomer, potassium persulfate as initiator, strytrene as framework monomer, lead ion imprinted polymers (Pb(II)-IIPs) were prepared using free emulsion polymerization method. The structure and morphology of the polymers were analyzed by UV-spectra, FTIR and scanning electron microscopy. The adsorption/ desorption and selectivity for Pb2+ were investigated by flame atomic absorption spectrometry (FAAS) as the detection means. The results show that compared with non-imprinted polymers(NIPs), the Pb(II)-IIPs had higher specific adsorption properties and selective recognition ability for Pb(II). The relative selectivity coefficient of Pb(II)-IIPs for Pb(II) was 6.25, 6.18, 6.25 and 6.38 in the presence of Cd(II), Cu(II), Mn(II) and Zn(II) interferences, respectively. The absorption rate was the best at the pH of adsorbent solution of 6, Adsorption rate reached 96% during the 2.5 h static adsorption time. Using 3.0 mol x L(-1) HCI as the best desorption solvent to desorb the adsorbents, the desorbtion rate reached 98%. Under the best adsorption conditions, the adsorption capacity of Pb(II)-IIPs for Pb(II) was found to be 40. mg x g(-1).

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

NASA Astrophysics Data System (ADS)

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.

Transition metal ion capture using functional mesoporous carbon made with 1,10-phenanthroline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chouyyok, Wilaiwan; Yantasee, Wassana; Shin, Yongsoon

2009-11-01

Functional mesoporous carbon has been built using 1,10-phenanthroline as the fundamental building block, resulting in a nanoporous, high surface area sorbent capable of selectively binding transition metal ions. This material had a specific surface area of 870 m2/g, an average pore size of about 30Å, and contained as much as 8.2 weight percent N. Under acidic conditions, where the 1,10-phenanthroline ligand is protonated, this material was found to be an effective anion exchange material for transition metal anions like PdCl4-2 and H2VO4-1. 1,10-phenanthroline functionalized mesoporous carbon (“Phen-FMC”) was found to have a high affinity for Cu(II), even down to amore » pH of 1. At pHs above 5, Phen-FMC was found to bind a variety of transition metal cations (e.g. Co(II), Ni(II), Zn(II), etc.) from filtered ground water, river water and seawater. Phen-FMC displayed rapid sorption kinetics with Co(II) in filtered river water, reaching equilibrium in less than an hour, and easily lowering the [Co(II)] to sub-ppb levels. Phen-FMC was found to be more effective for transition metal ion capture than ion exchange resin or activated carbon.« less

Novel kinetic model of the removal of divalent heavy metal ions from aqueous solutions by natural clinoptilolite.

PubMed

Jovanovic, Mina; Rajic, Nevenka; Obradovic, Bojana

2012-09-30

Removal of heavy metal ions from aqueous solutions using zeolites is widely described by pseudo-second order kinetics although this model may not be valid under all conditions. In this work, we have extended approaches used for derivation of this model in order to develop a novel kinetic model that is related to the ion exchange mechanism underlying sorption of metal ions in zeolites. The novel model assumed two reversible steps, i.e. release of sodium ions from the zeolite lattice followed by bonding of the metal ion. The model was applied to experimental results of Cu(II) sorption by natural clinoptilolite-rich zeolitic tuff at different initial concentrations and temperatures and then validated by predictions of ion exchange kinetics of other divalent heavy metal ions (i.e. Mn(II), Zn(II) and Pb(II)). Model predictions were in excellent agreements with experimental data for all investigated systems. In regard to the proposed mechanism, modeling results implied that the sodium ion release rate was constant for all investigated metals while the overall rate was mainly determined by the rate of heavy metal ion bonding to the lattice. In addition, prediction capabilities of the novel model were demonstrated requiring one experimentally determined parameter, only. Copyright © 2012 Elsevier B.V. All rights reserved.

Exploiting differential electrochemical stripping behaviors of Fe3O4 nanocrystals toward heavy metal ions by crystal cutting.

PubMed

Yao, Xian-Zhi; Guo, Zheng; Yuan, Qing-Hong; Liu, Zhong-Gang; Liu, Jin-Huai; Huang, Xing-Jiu

2014-08-13

This study attempts to understand the intrinsic impact of different morphologies of nanocrystals on their electrochemical stripping behaviors toward heavy metal ions. Two differently shaped Fe3O4 nanocrystals, i.e., (100)-bound cubic and (111)-bound octahedral, have been synthesized for the experiments. Electrochemical results indicate that Fe3O4 nanocrystals with different shapes show different stripping behaviors toward heavy metal ions. Octahedral Fe3O4 nanocrystals show better electrochemical sensing performances toward the investigated heavy metal ions such as Zn(II), Cd(II), Pb(II), Cu(II), and Hg(II), in comparison with cubic ones. Specifically, Pb(II) is found to have the best stripping performance on both the (100) and (111) facets. To clarify these phenomena, adsorption abilities of as-prepared Fe3O4 nanocrystals have been investigated toward heavy metal ions. Most importantly, combined with theoretical calculations, their different electrochemical stripping behaviors in view of facet effects have been further studied and enclosed at the level of molecular/atom. Finally, as a trial to find a disposable platform completely free from noble metals, the potential application of the Fe3O4 nanocrystals for electrochemical detection of As(III) in drinking water is demonstrated.

Synthesis and characterization of a series of transition metal complexes with a new symmetrical polyoxaaza macroacyclic Schiff base ligand: X-ray crystal structure of cobalt(II) and nickel(II) complexes and their antibacterial properties

NASA Astrophysics Data System (ADS)

Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Valencia, Laura

2013-01-01

A new symmetrical [N4O2] hexadentate Schiff base ligand, (E)-N-(pyridin-2-ylmethylene)-2-(3-(2-((E)-pyridin-2-lmethyleneamino)phenoxy)naphthalen-2-yloxy)benzenamine, abbreviated to L, and its complexes of Ni(II), Cu(II), Zn(II), Co(II), Cd(II) and Mn(II) have been synthesized in the presence of metal ions. The complexes were structurally characterized by elemental analyses, IR, UV-Vis, NMR and molar conductivity. The crystal structures of two complexes, [NiL(ONO2)2]·2H2O and [CoLCl2]CH3OH·0.5H2O, have been determined by a single crystal X-ray diffraction study. In these complexes, the ligand is coordinated in a neutral form via pyridine and azomethine nitrogen atoms. The metal ions complete their six coordination with two coordinated nitrate or chloride ions, forming a distorted octahedral geometry. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Enterococcus faecalis, Bacillus cereus and Staphylococcus epid and also against the three Gram-negative bacteria: Citrobacter freundii, Enterobacter aerogenes and Salmonella typhi. The activity data show that the complexes are more potent antibacterials than the parent Schiff base.

Structural, spectral and biological studies of binuclear tetradentate metal complexes of N 3O Schiff base ligand synthesized from 4,6-diacetylresorcinol and diethylenetriamine

NASA Astrophysics Data System (ADS)

Emara, Adel A. A.

2010-09-01

The binuclear Schiff base, H 2L, ligand was synthesized by reaction of 4,6-diacetylresorcinol with diethylenetriamine in the molar ratio 1:2. The coordination behavior of the H 2L towards Cu(II), Ni(II), Co(II), Zn(II), Fe(III), Cr(III), VO(IV) and UO 2(VI) ions has been investigated. The elemental analyses, magnetic moments, thermal studies and IR, electronic, 1H NMR, ESR and mass spectra were used to characterize the isolated ligand and its metal complexes. The ligand acts as dibasic with two N 3O-tetradentate sites and can coordinate with two metal ions to form binuclear complexes. The bonding sites are the nitrogen atoms of the azomethine and amine groups and the oxygen atoms of the phenolic groups. The metal complexes exhibit either square planar, tetrahedral, square pyramid or octahedral structures. The Schiff base ligand and its metal complexes were tested against four pathogenic bacteria ( Staphylococcus aureus and Streptococcus pyogenes) as Gram-positive bacteria, and ( Pseudomonas fluorescens and Pseudomonas phaseolicola) as Gram-negative bacteria and two pathogenic fungi ( Fusarium oxysporum and Aspergillus fumigatus) to assess their antimicrobial properties. Most of the complexes exhibit mild antibacterial and antifungal activities against these organisms.

Efficient adsorption of multiple heavy metals with tailored silica aerogel-like materials.

PubMed

Vareda, João P; Durães, Luisa

2017-11-10

Recently developed tailored adsorbents for heavy metal uptake are studied in batch tests with Cu, Pb, Cd, Ni, Cr and Zn, in order to decontaminate polluted environments where these heavy metals are found in solution - water courses and groundwater. The adsorbents feature mercapto or amine-mercapto groups that are capable of complexating the cations. Through the use of equilibrium tests it is found that a remarkably high heavy metal uptake is obtained for all metals (ranging from 84 to 140 mg/g). These uptake values are quite impressive when compared to other adsorbents reported in the literature, which is also due to the double functionalization present in one of the adsorbents. For the best adsorbent, adsorption capacities followed the order Cu(II) > Pb(II) > Zn(II) > Cr(III) > Cd(II) > Ni(II). With these adsorbents, the removal process was fast with most of the metals being removed in less than 1 h. Competitive sorption tests were performed in tertiary mixtures that were based on real world polluted sites. It was found that although competitive sorption occurs, affecting the individual removal of each metal, all the cations in solution still interact with the adsorbent, achieving removal values that make this type of material very interesting for its proposed application.

Synthesis, characterization and anti-microbial activity of phenylurea-formaldehyde resin (PUF) and its polymer metal complexes (PUF-Mn(II).

PubMed

Ahamad, Tansir; Alshehri, Saad M

2012-10-01

Phenylurea-formaldehyde polymer (PUF) was synthesized via polycondensation of phenylurea and formaldehyde in basic medium, its polymer-metal complexes [PUF-M(II)] were prepared with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) ions. PUF and PUF-M(II) were characterized with magnetic moment measurements, elemental and spectral (UV-visible, FTIR, 1H-NMR, 13C-NMR and ESR) analysis. The thermal behaviors of all the synthesized polymers were carried out using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The thermal data revealed that all of the PUF-M(II) showed higher thermal stabilities than the PUF and also ascribed that the PUF-Cu(II) showed better thermal stability than the other PUF-M(II). The kinetic parameters such as activation energy, pre-exponential factor etc., were evaluated for these polymer metal complexes using Coats-Redfern equation. In addition, the antimicrobial activity of the synthesized polymers was tested against several microorganisms using agar well diffusion methods. Among all of the PUF-M(II), the antimicrobial activity of the PUF-Cu(II) showed the highest zone of inhibition because of its higher stability constant and may be used in biomedical applications. Copyright © 2012 Elsevier B.V. All rights reserved.

Trace lead analysis based on carbon-screen-printed-electrodes modified via 4-carboxy-phenyl diazonium salt electroreduction.

PubMed

Bouden, Sarra; Chaussé, Annie; Dorbes, Stephane; El Tall, Omar; Bellakhal, Nizar; Dachraoui, Mohamed; Vautrin-Ul, Christine

2013-03-15

This paper describes the use of 4-carboxyphenyl-grafted screen-printed carbon electrodes (4-CP-SPEs) for trace lead analysis. These novel and simple use of electrodes were easily prepared by the electrochemical reduction of the corresponding diazonium salt. Pb detection was then performed by a three-steps method in order to avoid oxygen interference: (i) immersion of the grafted screen-printed electrode (SPE) in the sample and adsorption of Pb(II), (ii) reduction of adsorbed Pb(II) by chronoamperometry (CA), and (iii) oxidation of Pb by Anodic Square Wave Voltammetry (SWV). The reoxidation response was exploited for lead detection and quantification. In order to optimize the analytical responses, the influence of the adsorption medium pH and the adsorption time were investigated. Moreover, an interference study was carried out with Cu(II), Hg(II), Al(III), Mn(II), Zn(II), Cd(II) and no major interference can be expected to quantify Pb(II). The described method provided a limit of detection and a limit of quantification of 1.2 × 10(-9)M and 4.1 × 10(-9)M, respectively. These performances indicate that the 4-CP-SPE could be considered as an efficient tool for environmental analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

Cathodic stripping voltammetry of nickel: sonoelectrochemical exploitation of the Ni(III)/Ni(II) couple.

PubMed

Davis, James; Vaughan, D Huw; Stirling, David; Nei, Lembit; Compton, Richard G

2002-07-19

The exploitation of the Ni(III)/Ni(II) transition as a means of quantifying the concentration of nickel within industrial samples was assessed. The methodology relies upon the reagentless electrodeposition of Ni onto a glassy carbon electrode and the subsequent oxidative conversion of the metallic layer to Ni(III). The analytical signal is derived from a cathodic stripping protocol in which the reduction of the Ni(III) layer to Ni(II) is monitored through the use of square wave voltammetry. The procedure was refined through the introduction of an ultrasonic source which served to both enhance the deposition of nickel and to remove the nickel hydroxide layer that results from the measurement process. A well-defined stripping peak was observed at +0.7 V (vs. Agmid R:AgCl) with the response found to be linear over the range 50 nM to 1 muM (based on a 30 s deposition time). Other metal ions such as Cu(II), Mn(II), Cr(III), Pb(II), Cd(II), Zn(II), Fe(III) and Co(II) did not interfere with the response when present in hundred fold excess. The viability of the technique was evaluated through the determination of nickel within a commercial copper nickel alloy and validated through an independent comparison with a standard ICP-AES protocol.

Relative abundance of chemical forms of Cu(II) and Cd(II) on soybean roots as influenced by pH, cations and organic acids

PubMed Central

Zhou, Qin; Liu, Zhao-dong; Liu, Yuan; Jiang, Jun; Xu, Ren-kou

2016-01-01

Little information is available on chemical forms of heavy metals on integrate plant roots. KNO3 (1 M), 0.05M EDTA at pH6 and 0.01 M HCl were used sequentially to extract the exchangeable, complexed and precipitated forms of Cu(II) and Cd(II) from soybean roots and then to investigate chemical form distribution of Cu(II) and Cd(II) on soybean roots. Cu(II) and Cd(II) adsorbed on soybean roots were mainly exchangeable form, followed by complexed form, while their precipitated forms were very low under acidic conditions. Soybean roots had a higher adsorption affinity to Cu(II) than Cd(II), leading to higher toxic of Cu(II) than Cd(II). An increase in solution pH increased negative charge on soybean and thus increased exchangeable Cu(II) and Cd(II) on the roots. Ca2+, Mg2+ and NH4+ reduced exchangeable Cu(II) and Cd(II) levels on soybean roots and these cations showed greater effects on Cd(II) than Cu(II) due to greater adsorption affinity of the roots to Cu(II) than Cd(II). L-malic and citric acids decreased exchangeable and complexed Cu(II) on soybean roots. In conclusion, Cu(II) and Cd(II) mainly existed as exchangeable and complexed forms on soybean roots. Ca2+ and Mg2+ cations and citric and L-malic acids can potentially alleviate Cu(II) and Cd(II) toxicity to plants. PMID:27805020

A facile strategy for achieving high selective Zn(II) fluorescence probe by regulating the solvent polarity.

PubMed

Wang, Haoping; Kang, Tiantian; Wang, Xiaoju; Feng, Liheng

2018-07-01

A simple Schiff base comprised of tris(2-aminoethyl)amine and salicylaldehyde was designed and synthesized by one-step reaction. Although this compound has poor selectivity for metal ions in acetonitrile, it shows high selectivity and sensitivity detection for Zn(II) ions through adjusting the solvent polarity (the volume ratio of CH 3 CN/H 2 O). In other words, this work provides a facile way to realize a transformation from poor to excellent feature for fluorescent probes. The bonding mode of this probe with Zn(II) ions was verified by 1 H NMR and MS assays. The stoichiometric ratio of the probe with Zn(II) is 1:1 (mole), which matches with the Job-plot assay. The detection limitation of the probe for Zn(II) is up to 1 × 10 -8 mol/L. The electrochemical property of the probe combined with Zn(II) was investigated by cyclic voltammetry method, and the result agreed with the theoretical calculation by the Gaussian 09 software. The probe for Zn(II) could be applied in practical samples and biological systems. The main contribution of this work lies in providing a very simple method to realize the selectivity transformation for poor selective probes. The providing way is a simple, easy and low-cost method for obtaining high selectively fluorescence probes. Copyright © 2018 Elsevier B.V. All rights reserved.

Mononuclear Pd(II) complex as a new therapeutic agent: Synthesis, characterization, biological activity, spectral and DNA binding approaches

NASA Astrophysics Data System (ADS)

Saeidifar, Maryam; Mirzaei, Hamidreza; Ahmadi Nasab, Navid; Mansouri-Torshizi, Hassan

2017-11-01

The binding ability between a new water-soluble palladium(II) complex [Pd(bpy)(bez-dtc)]Cl (where bpy is 2,2‧-bipyridine and bez-dtc is benzyl dithiocarbamate), as an antitumor agent, and calf thymus DNA was evaluated using various physicochemical methods, such as UV-Vis absorption, Competitive fluorescence studies, viscosity measurement, zeta potential and circular dichroism (CD) spectroscopy. The Pd(II) complex was synthesized and characterized using elemental analysis, molar conductivity measurements, FT-IR, 1H NMR, 13C NMR and electronic spectra studies. The anticancer activity against HeLa cell lines demonstrated lower cytotoxicity than cisplatin. The binding constants and the thermodynamic parameters were determined at different temperatures (300 K, 310 K and 320 K) and shown that the complex can bind to DNA via electrostatic forces. Furthermore, this result was confirmed by the viscosity and zeta potential measurements. The CD spectral results demonstrated that the binding of Pd(II) complex to DNA induced conformational changes in DNA. We hope that these results will provide a basis for further studies and practical clinical use of anticancer drugs.

Synthesis, spectroscopic, thermal and anticancer studies of metal-antibiotic chelations: Ca(II), Fe(III), Pd(II) and Au(III) chloramphenicol complexes

NASA Astrophysics Data System (ADS)

Al-Khodir, Fatima A. I.; Refat, Moamen S.

2016-09-01

Four Ca(II), Fe(III), Pd(II) and Au(III) complexes of chloramphenicol drug have been synthesized and well characterized using elemental analyses, (infrared, electronic, and 1H-NMR) spectra, magnetic susceptibility measurement, and thermal analyses. Infrared spectral data show that the chloramphenicol drug coordinated to Ca(II), Pd(II) and Au(III) metal ions through two hydroxyl groups with 1:1 or 1:2 M ratios, but Fe(III) ions chelated towards chloramphenicol drug via the oxygen and nitrogen atoms of amide group with 1:2 ratio based on presence of keto↔enol form. The X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) techniques were used to identify the nano-size particles of both iron(III) and gold(III) chloramphenicol complexes. The antimicrobial assessments of the chloramphenicol complexes were scanned and collected the results against of some kind of bacteria and fungi. The cytotoxic activity of the gold(III) complex was tested against the human colon carcinoma (HCT-116) and human hepatocellular carcinoma (HepG-2) tumor cell lines.

Interdependence of free zinc changes and protein complex assembly - insights into zinc signal regulation.

PubMed

Kocyła, Anna; Adamczyk, Justyna; Krężel, Artur

2018-01-24

Cellular zinc (Zn(ii)) is bound with proteins that are part of the proteomes of all domains of life. It is mostly utilized as a catalytic or structural protein cofactor, which results in a vast number of binding architectures. The Zn(ii) ion is also important for the formation of transient protein complexes with a Zn(ii)-dependent quaternary structure that is formed upon cellular zinc signals. The mechanisms by which proteins associate with and dissociate from Zn(ii) and the connection with cellular Zn(ii) changes remain incompletely understood. In this study, we aimed to examine how zinc protein domains with various Zn(ii)-binding architectures are formed under free Zn(ii) concentration changes and how formation of the Zn(ii)-dependent assemblies is related to the protein concentration and reactivity. To accomplish these goals we chose four zinc domains with different Zn(ii)-to-protein binding stoichiometries: classical zinc finger (ZnP), LIM domain (Zn 2 P), zinc hook (ZnP 2 ) and zinc clasp (ZnP 1 P 2 ) folds. Our research demonstrated a lack of changes in the saturation level of intraprotein zinc binding sites, despite various peptide concentrations, while homo- and heterodimers indicated a concentration-dependent tendency. In other words, at a certain free Zn(ii) concentration, the fraction of a formed dimeric complex increases or decreases with subunit concentration changes. Secondly, even small or local changes in free Zn(ii) may significantly affect protein saturation depending on its architecture, function and subcellular concentration. In our paper, we indicate the importance of interdependence of free Zn(ii) availability and protein subunit concentrations for cellular zinc signal regulation.

Synthesis, characterization and biological activity of some transition metals with Schiff base derived from 2-thiophene carboxaldehyde and aminobenzoic acid.

PubMed

Mohamed, Gehad G; Omar, M M; Hindy, Ahmed M M

2005-12-01

Metal complexes of Schiff base derived from 2-thiophene carboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The ligand dissociation as well as the metal-ligand stability constants were calculated pH metrically at 25 degrees C and ionic strength mu=0.1 (1M NaCl). The complexes are found to have the formulae [M(HL)2](X)n.yH2O (where M=Fe(III) (X=Cl, n=3, y=3), Co(II) (X=Cl, n=2, y=1.5), Ni(II) (X=Cl, n=2, y=1) and UO2(II) (X=NO3, n=2, y=0)) and [M(L)2] (where M=Cu(II) (X=Cl) and Zn(II) (X=AcO)). The molar conductance data reveal that Fe(III) and Co(II), Ni(II) and UO2(II) chelates are ionic in nature and are of the type 3:1 and 2:1 electrolytes, respectively, while Cu(II) and Zn(II) complexes are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a terdentate manner with ONS donor sites of the carboxylate O, azomethine N and thiophene S. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.

Fluorescent probe based subcellular distribution of Cu(II) ions in living electrotrophs isolated from Cu(II)-reduced biocathodes of microbial fuel cells.

PubMed

Tao, Ye; Xue, Hua; Huang, Liping; Zhou, Peng; Yang, Wei; Quan, Xie; Yuan, Jinxiu

2017-02-01

Based on the four indigenous electrotrophs (Stenotrophomonas maltophilia JY1, Citrobacter sp. JY3, Pseudomonas aeruginosa JY5 and Stenotrophomonas sp. JY6) isolated from well adapted Cu(II)-reduced biocathodes of microbial fuel cells (MFCs), a rhodamine based Cu(II) fluorescent probe was used to imaginably and quantitatively track subcellular Cu(II) ions in these electrotrophs. Cathodic electrons led to more Cu(II) ions (14.3-30.1%) in the intracellular sites at operation time of 2-3h with Cu(II) removal rates of 2.90-3.64mg/Lh whereas the absence of cathodic electrons prolonged the appearance of more Cu(II) ions (16.6-22.5%) to 5h with Cu(II) removal rates of 1.96-2.28mg/Lh. This study illustrates that cathodic electrons directed more Cu(II) ions for quicker entrance into the electrotrophic cytoplasm, and gives an alternative approach for developing imaging and functionally tracking Cu(II) ions in the electrotrophs of MFCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis, characterization of Ag(I), Pd(II) and Pt(II) complexes of a triazine-3-thione and their interactions with bovine serum albumin

NASA Astrophysics Data System (ADS)

Zhang, Xiuying; Li, Shuyan; Yang, Lin; Fan, Changqing

2007-11-01

Ag(I), Pd(II) and Pt(II) complexes of 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]triazine-3-thione (LH 2OCH 3) have been synthesized and characterized by elemental analysis, molar conductance, 1H NMR, IR spectra, UV spectra and thermal analysis (TG-DTA). The components of the three complexes are [Ag(C 15H 10N 3S)] 6, Pd(C 15H 10N 3S) 2 and Pt(C 15H 10N 3S) 2·C 3H 6O·2H 2O, respectively. All the complexes are nonelectrolyte and have high thermodynamic stability. The ligand may act as bidentate NS donor for Pd(II) and Pt(II) complexes, while it seems to be bidentate NS bridging via sulphur atom for Ag(I) complex. A planar quadrangular structure is proposed for Pd(II) and Pt(II) complexes and Ag(I) complex may be a hexanuclear cluster. Their interactions with bovine serum albumin (BSA) are investigated using steady state fluorescence technology. It is observed that all of them can quench the intrinsic fluorescence of BSA through static quenching procedure. The binding constants ( KA) at different temperatures, thermodynamic parameters enthalpy changes (Δ H) and entropy changes (Δ S) between BSA and the compounds are calculated. Based on the values of Δ H and Δ S, it is judged that the main acting force of PtL 2·C 3H 6O·2H 2O with BSA may be electrostatic interaction, and for the LH 2OCH 3, Ag 6L 6 and PdL 2, hydrophobic and electrostatic interactions may be involved in their binding processes.

A novel polymer probe for Zn(II) detection with ratiometric fluorescence signal

NASA Astrophysics Data System (ADS)

Diao, Haipeng; Guo, Lixia; Liu, Wen; Feng, Liheng

2018-05-01

A conjugated polymer probe comprised of fluorene, quinolone and benzothiazole units was designed and synthesized by the Suzuki coupling reaction. Through the studies of photophysical and thermal properties, the polymer displays blue-emitting feature and good thermal stability. A ratiometric fluorescence signal of the probe for Zn(II) was observed in ethanol with a new emission peak at 555 nm. The probe possesses a high selectivity and sensitivity for Zn(II) during familiar metal ions in ethanol. The detection limit of the probe for Zn (II) is up to 10-8 mol/L. The electron distributions of the polymer before and after bonding with Zn (II) were investigated by the Gaussian 09 software, which agreed with the experimental results. Noticeably, based on the color property of the probe with Zn(II), a series of color test paper were developed for visual detecting Zn(II) ions. This work helps to provide a platform or pattern for the development of polymer fluorescence probe in the chemosensor field.

Evaluation of adsorption properties of sulphurised activated carbon for the effective and economically viable removal of Zn(II) from aqueous solutions.

PubMed

Anoop Krishnan, K; Sreejalekshmi, K G; Vimexen, V; Dev, Vinu V

2016-02-01

The prospective application of sulphurised activated carbon (SAC) as an ecofriendly and cost-effective adsorbent for Zinc(II) removal from aqueous phase is evaluated, with an emphasis on kinetic and isotherm aspects. SAC was prepared from sugarcane bagasse pith obtained from local juice shops in Sree Bhadrakali Devi Temple located at Ooruttukala, Neyyattinkara, Trivandrum, India during annual festive seasons. Activated carbon modified with sulphur containing ligands was opted as the adsorbent to leverage on the affinity of Zn(II) for sulphur. We report batch-adsorption experiments for parameter optimisations aiming at maximum removal of Zn(II) from liquid-phase using SAC. Adsorption of Zn(II) onto SAC was maximum at pH 6.5. For initial concentrations of 25 and 100mgL(-1), maximum of 12.3mgg(-1) (98.2%) and 23.7mgg(-1) (94.8%) of Zn(II) was adsorbed onto SAC at pH 6.5. Kinetic and equilibrium data were best described by pseudo-second-order and Langmuir models, respectively. A maximum adsorption capacity of 147mgg(-1) was obtained for the adsorption of Zn(II) onto SAC from aqueous solutions. The reusability of the spent adsorbent was also determined. Copyright © 2015 Elsevier Inc. All rights reserved.

Synthetic hydroxyapatites doped with Zn(II) studied by X-ray diffraction, infrared, Raman and thermal analysis

NASA Astrophysics Data System (ADS)

Guerra-López, José R.; Echeverría, Gustavo A.; Güida, Jorge A.; Viña, Raúl; Punte, Graciela

2015-06-01

Calcium hydroxyapatite (CaHap) formation when different amounts of Zn(II) are present in the mother solution has been investigated by atomic absorption, infrared and Raman spectroscopies, X-ray diffraction and thermal analysis (DTA and TG). The studied samples have been synthesized at T=95 °C and pH 9 in air. The analysis of the results have shown that the pure CaHap sample crystallizes in the monoclinic form P21/b. Concentrations up to 20% of Zn(II) in the mother solution, equivalent to smaller concentrations in solid (up to 9.1% in wt), favor the formation of the hexagonal apatite, P63/m, while Zn(II) concentrations higher than 20% in solution help an amorphous phase development where vibrational spectra indicated coexistence of two phases: an apatite and ZnNH4PO4·H2O. Infrared data of thermal treated samples endorse that HPO42- ion had not been incorporated in Zn(II) doped samples during the synthesis process. Present results also allow to conclude that Zn(II) cation exhibits a preference to occupy the Ca2 site of the apatite structure and induces water adsorption and a small quantity of CO32- cation incorporation, leading to formation of a less crystalline Ca deficient apatite.

Binding Modes of Phthalocyanines to Amyloid β Peptide and Their Effects on Amyloid Fibril Formation.

PubMed

Valiente-Gabioud, Ariel A; Riedel, Dietmar; Outeiro, Tiago F; Menacho-Márquez, Mauricio A; Griesinger, Christian; Fernández, Claudio O

2018-03-13

The inherent tendency of proteins to convert from their native states into amyloid aggregates is associated with a range of human disorders, including Alzheimer's and Parkinson's diseases. In that sense, the use of small molecules as probes for the structural and toxic mechanism related to amyloid aggregation has become an active area of research. Compared with other compounds, the structural and molecular basis behind the inhibitory interaction of phthalocyanine tetrasulfonate (PcTS) with proteins such as αS and tau has been well established, contributing to a better understanding of the amyloid aggregation process in these proteins. We present here the structural characterization of the binding of PcTS and its Cu(II) and Zn(II)-loaded forms to the amyloid β-peptide (Aβ) and the impact of these interactions on the peptide amyloid fibril assembly. Elucidation of the PcTS binding modes to Aβ 40 revealed the involvement of specific aromatic and hydrophobic interactions in the formation of the Aβ 40 -PcTS complex, ascribed to a binding mode in which the planarity and hydrophobicity of the aromatic ring system in the phthalocyanine act as main structural determinants for the interaction. Our results demonstrated that formation of the Aβ 40 -PcTS complex does not interfere with the progression of the peptide toward the formation of amyloid fibrils. On the other hand, conjugation of Zn(II) but not Cu(II) at the center of the PcTS macrocyclic ring modified substantially the binding profile of this phthalocyanine to Aβ 40 and became crucial to reverse the effects of metal-free PcTS on the fibril assembly of the peptide. Overall, our results provide a firm basis to understand the structural rules directing phthalocyanine-protein interactions and their implications on the amyloid fibril assembly of the target proteins; in particular, our results contradict the hypothesis that PcTS might have similar mechanisms of action in slowing the formation of a variety of pathological aggregates. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Construction of new biopolymer (chitosan)-based pincer-type Pd(II) complex and its catalytic application in Suzuki cross coupling reactions

NASA Astrophysics Data System (ADS)

Baran, Talat; Menteş, Ayfer

2017-04-01

In this paper we described the fabrication, characterization and application of a new biopolymer (chitosan)-based pincer-type Pd(II) catalyst in Suzuki cross coupling reactions using a non-toxic, cheap, eco-friendly and practical method. The catalytic activity tests showed remarkable product yields as well as TON (19800) and TOF (330000) values with a small catalyst loading. In addition, the catalyst indicated good recyclability in the Suzuki C-C reaction. This biopolymer supported catalyst can be used with various catalyst systems due to its unique properties, such as being inert, green in nature, low cost and chemically durable.

Dichlorido{[2-(diphenyl­phosphino)phenyl­imino­meth­yl]ferrocene-κ2 N,P}palladium(II) dichloro­methane hemi­solvate

PubMed Central

Liu, Huanyu; Shen, Dongsheng

2009-01-01

There are two independent PdII complex mol­ecules in the asymmetric unit of the title compound, [PdCl2{Fe(C5H5)(C24H19NP)}]·0.5CH2Cl2. One ferrocenyl ring of one complex mol­ecule is disordered over two sites with half-occupancy for each component. Both PdII cations adopt a distorted square-planar coordination geometry with a bidentate [2-(diphenyl­phosphino)phenyl­imino­meth­yl]ferrocene ligand and two chloride anions. PMID:21581545

Synthesis and characterization of new complexes of nickel (II), palladium (II) and platinum(II) with derived sulfonamide ligand: Structure, DFT study, antibacterial and cytotoxicity activities

NASA Astrophysics Data System (ADS)

Bouchoucha, Afaf; Zaater, Sihem; Bouacida, Sofiane; Merazig, Hocine; Djabbar, Safia

2018-06-01

The synthesis, characterization and biological study of new nickel (II), palladium (II), and platinum (II) complexes with sulfamethoxazole ligand used in pharmaceutical field, were reported. [MLCl2].nH2O is the general formula obtained for Pd(II) and Pt(II) complexes. These complexes have been prepared and characterized by elemental analysis, FTIR, 1HNMR spectral, magnetic measurements, UV-Visible spectra, and conductivity. The DFT calculation was applied to optimize the geometric structure of the Pd(II) and Pt(II) complexes. A new single-crystal X-ray structure of the Ni(II) complex has been determined. It crystallized in monoclinic system with P 21/c space group and Z = 8. The invitro antibacterial activity of ligand and complexes against Escherichia coli, P. aeruginosa, Klebsiella pneumoniae, S. aureus, Bacillus subtilis species has been carried out and compared using agar-diffusion method. The Pd(II) and Pt(II) complexes showed a remarkable inhibition against bacteria tested. The invitro cytotoxicity assay of the complexes against three cell lines chronic myelogenous leukaemia (K562), human colon adenocarcinoma (HT-29) and breast cancer (MCF-7) was also reported.

Removal of Cu(II) in water by polymer enhanced ultrafiltration: Influence of polymer nature and pH.

PubMed

Kochkodan, Olga D; Kochkodan, Viktor M; Sharma, Virender K

2018-01-02

This study presents an efficient removal of Cu(II) in water using the polymer enhanced ultrafiltration (PEUF) method. Polymer of different molecular weight (MW) (polyethyleneimine (PEI), sodium lignosulfonates (SLS) and dextrans) were investigated to evaluate efficiency in removal of Cu(II) in water by the PEUF method. The decomposition of Cu(II)-polymer complex was also evaluated in order to reuse polymers. Cu(II) complexation depends on the MW of chelating polymer and the pH of feed solution. It was found that the Cu(II) rejection increased with the polymer dosage with high removal of Cu(II) when using PEI and SLS at a 10:20 (mg/mg) ratio ([Cu(II)]:[polymer]). It was found that the maximum chelating capacity was 15 mg of Cu(II) per 20 mg of PEI. The Cu(II)-PEI complex could be decomposed by acid addition and the polymer could be efficiently reused with multiple complexation-decomplexation cycles. A conceptual flow chart of the integrated process of efficient removal of Cu(II) by PEUF method is suggested.

Effect of biofilm coatings at metal-oxide/water interfaces II: Competitive sorption between Pb(II) and Zn(II) at Shewanella oneidensis/metal-oxide/water interfaces

DOE PAGES

Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; ...

2016-05-07

Competitive sorption of Pb(II) and Zn(II) on Shewanella oneidensis MR-1 biofilm-coated single-crystal α-Al 2O 3 (1 –1 0 2) and α-Fe 2O 3 (0 0 0 1) surfaces was investigated using long-period X-ray standing wave-florescence yield (LP-XSW-FY) spectroscopy. In situ partitioning of aqueous Pb(II) and Zn(II) between the biofilms and underlying metal-oxide substrates was probed following exposure of these complex interfaces to equi-molar Pb and Zn solutions (0.01 M NaNO 3 as background electrolyte, pH = 6.0, and 3-h equilibration time). At higher Pb and Zn concentrations (≥10 –5 M), more than 99% of these ions partitioned into the biofilmsmore » at S. oneidensis/α-Al 2O 3 (1 –1 0 2)/water interfaces, which is consistent with the partitioning behavior of both Pb(II) or Zn(II) in single-metal-ion experiments. Furthermore, no apparent competitive effects were found in this system at these relatively high metal-ion concentrations. However, at lower equi-molar concentrations (≤10 –6 M), Pb(II) and Zn(II) partitioning in the same system changed significantly compared to the single-metal-ion systems. The presence of Zn(II) decreased Pb(II) partitioning onto α-Al 2O 3 (1 –1 0 2) substantially (~52% to ~13% at 10 –7 M, and ~23% to ~5% at 10–6 M), whereas the presence of Pb(II) caused more Zn(II) to partition onto α-Al 2O 3 (1 –1 0 2) surfaces (~15% to ~28% at 10 –7 M, and ~1% to ~7% at 10 –6 M) .The higher observed partitioning of Zn(II) (~28%) at the α-Al 2O 3 (1 –1 0 2) surfaces compared to Pb(II) (~13%) in the mixed-metal-ion systems at the lowest concentration (10 –7 M) suggests that Zn(II) is slightly favored over Pb(II) for sorption sites on α-Al 2O 3 (1 –1 0 2) surfaces under our experimental conditions.« less

Midrange affinity fluorescent Zn(II) sensors of the Zinpyr family: syntheses, characterization, and biological imaging applications.

PubMed

Nolan, Elizabeth M; Jaworski, Jacek; Racine, Maryann E; Sheng, Morgan; Lippard, Stephen J

2006-11-27

The syntheses and photophysical characterization of ZP9, 2-{2-chloro-6-hydroxy-3-oxo-5-[(2-{[pyridin-2-ylmethyl-(1H-pyrrol-2-ylmethyl)amino]methyl}phenylamino)methyl]-3H-xanthen-9-yl}benzoic acid, and ZP10, 2-{2-chloro-6-hydroxy-5-[(2-{[(1-methyl-1H-pyrrol-2-ylmethyl)pyridin-2-ylmethylamino]methyl}phenylamino)methyl]-3-oxo-3H-xanthen-9-yl}benzoic acid, two asymmetrically derivatized fluorescein-based dyes, are described. These sensors each contain an aniline-based ligand moiety functionalized with a pyridyl-amine-pyrrole group and have dissociation constants for Zn(II) in the sub-micromolar (ZP9) and low-micromolar (ZP10) range, which we define as "midrange". They give approximately 12- (ZP9) and approximately 7-fold (ZP10) fluorescence turn-on immediately following Zn(II) addition at neutral pH and exhibit improved selectivity for Zn(II) compared to the di-(2-picolyl)amine-based Zinpyr (ZP) sensors. Confocal microscopy studies indicate that such asymmetrical fluorescein-based probes are cell permeable and Zn(II) responsive in vivo.

Midrange Affinity Fluorescent Zn(II) Sensors of the Zinpyr Family: Syntheses, Characterization, and Biological Imaging Applications

PubMed Central

Nolan, Elizabeth M.; Jaworski, Jacek; Racine, Maryann E.; Sheng, Morgan; Lippard, Stephen J.

2006-01-01

The syntheses and photophysical characterization of ZP9, 2-{2-chloro-6-hydroxy-3-oxo-5-[(2-{[pyridin-2-ylmethyl-(1H-pyrrol-2-ylmethyl)amino]methyl}phenylamino)methyl]-3H-xanthen-9-yl}benzoic acid, and ZP10, 2-{2-chloro-6-hydroxy-5-[(2-{[(1-methyl-1H-pyrrol-2-ylmethyl)pyridin-2-ylmethylamino]methyl}phenylamino)methyl]-3-oxo-3H-xanthen-9-yl}benzoic acid, two asymmetrically derivatized fluorescein-based dyes, are described. These sensors each contain an aniline-based ligand moiety functionalized with a pyridyl-amine-pyrrole group and have dissociation constants for Zn(II) in the sub-micromolar (ZP9) and low-micromolar (ZP10) range, which we define as “midrange”. They give ~12- (ZP9) and ~7-fold (ZP10) fluorescence turn-on immediately following Zn(II) addition at neutral pH and exhibit improved selectivity for Zn(II) compared to the di-(2-picolyl)amine-based Zinpyr (ZP) sensors. Confocal microscopy studies indicate that such asymmetrical fluorescein-based probes are cell permeable and Zn(II) responsive in vivo. PMID:17112271

A novel polymer probe for Zn(II) detection with ratiometric fluorescence signal.

PubMed

Diao, Haipeng; Guo, Lixia; Liu, Wen; Feng, Liheng

2018-05-05

A conjugated polymer probe comprised of fluorene, quinolone and benzothiazole units was designed and synthesized by the Suzuki coupling reaction. Through the studies of photophysical and thermal properties, the polymer displays blue-emitting feature and good thermal stability. A ratiometric fluorescence signal of the probe for Zn(II) was observed in ethanol with a new emission peak at 555 nm. The probe possesses a high selectivity and sensitivity for Zn(II) during familiar metal ions in ethanol. The detection limit of the probe for Zn (II) is up to 10 -8  mol/L. The electron distributions of the polymer before and after bonding with Zn (II) were investigated by the Gaussian 09 software, which agreed with the experimental results. Noticeably, based on the color property of the probe with Zn(II), a series of color test paper were developed for visual detecting Zn(II) ions. This work helps to provide a platform or pattern for the development of polymer fluorescence probe in the chemosensor field. Copyright © 2018 Elsevier B.V. All rights reserved.

Removal of Zn(II) from electroplating effluent using yeast biofilm formed on gravels: batch and column studies

PubMed Central

2014-01-01

Background Present study deals with the removal of Zn(II) ions from effluent using yeast biofilm formed on gravels. Methods The biofilm forming ability of Candida rugosa and Cryptococcus laurentii was evaluated using XTT (2,3-bis[2-methoxy-4-nitro-5-sulfophenyl]-2H-tetrazolium-5-carboxanilide) reduction assay and monitored by scanning electron microscopy (SEM), and Confocal laser scanning microscopy (CLSM). Copious amount of extracellular polymeric substances (EPS) produced by yeast species was quantified and characterized by Fourier transform infrared spectroscopy (FT-IR). Results Yeast biofilm formed on gravels by C. rugosa and C. laurentii showed 88% and 74.2% removal of Zn(II) ions respectively in batch mode. In column mode, removal of Zn(II) ions from real effluent was found to be 95.29% by C. rugosa biofilm formed on gravels. Conclusion The results of the present study showed that there is a scope to develop a cost effective method for the efficient removal of Zn(II) from effluent using gravels coated with yeast biofilm. PMID:24397917

Novel crown-ether-methylenediphosphonotetrathioate hybrids as Zn(II) chelators.

PubMed

Meltzer, Diana; Gottlieb, Hugo E; Amir, Aviran; Shimon, Linda J W; Fischer, Bilha

2015-12-28

Hybrids of methylenediphosphonotetrathioate and crown-ether (MDPT-CE) were synthesized forming 7-,8-,9-,10- and 13-membered rings. Both 7- and 13-membered ring-containing compounds were found to be highly stable to air-oxidation for at least four weeks. These hybrids bind Zn(II) by both MDPT and CE moieties, forming a 2 : 1 L : Zn(II) complex. Interestingly, the 13-membered ring MDPT-CE showing a high affinity to Zn(II) (Ka 3 ± 0.5 × 10(6) mol(-2) L(2)) does not bind Li(I) or Na(I). The 13-Membered MDPT-CE hybrid is a promising water-soluble, air-stable, high-affinity Zn(II)-chelator, exhibiting selectivity to Zn(II) vs. Mg(II), Na(I), and Li(I).

Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions.

PubMed

Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

2015-09-16

In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = Ti(IV), Cu(II), Al(III), Sn(IV), Fe(III), Cr(III), Zr(IV) and Zn(II); for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with Ti(x)H(3-4x)PW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (Ti(x)H(3-4x)PW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse.

Novel chitosan derivative for the removal of cadmium in the presence of cyanide from electroplating wastewater.

PubMed

Sankararamakrishnan, Nalini; Sharma, Ajit Kumar; Sanghi, Rashmi

2007-09-05

Chitosan was chemically modified by introducing xanthate group onto its backbone using carbondisulfide under alkaline conditions. The chemically modified chitosan flakes (CMC) was used as an adsorbent for the removal of cadmium ions from electroplating waste effluent under laboratory conditions. CMC was found to be far more efficient than the conventionally used adsorbent activated carbon. The maximum uptake of cadmium by CMC in batch studies was found to be 357.14 mg/g at an optimum pH of 8.0 whereas for plain chitosan flakes it was 85.47 mg/g. Since electroplating wastewater contains cyanide in appreciable concentrations, interference of cyanide ions in cadmium adsorption was found to be very significant. This problem could be easily overcome by using higher doses of CMC, however, activated carbon was not found to be effective even at higher doses. Due to the high formation constant of cadmium with xanthate and adsorption was carried out at pH 8, cations like Pb(II), Cu(II), Ni(II) and Zn(II) did not interfere in the adsorption. Dynamics of the sorption process were studied and the values of rate constant of adsorption were calculated. Desorption of the bound cadmium from CMC was accomplished with 0.01 N H(2)SO(4). The data from regeneration efficiencies for 10 cycles evidenced the reusability of CMC in the treatment of cadmium-laden wastewater.

Synthesis, structure, DNA/BSA binding and antibacterial studies of NNO tridentate Schiff base metal complexes

NASA Astrophysics Data System (ADS)

Sakthi, Marimuthu; Ramu, Andy

2017-12-01

A new salicylaldehyde derived 2,4-diiodo-6-((2-phenylaminoethylimino)methyl)phenol Schiff base(L) and its transition metal complexes of the type MLCl where, M = Cu(II), Ni(II), Co(II), Mn(II) and Zn(II) have been synthesized. The coordination mode of Schiff base holding NNO donor atoms with metal ions was well investigated by elemental analysis, ESI-mass as well as IR, UV-vis, CV and NMR spectral studies. The binding efficiency and mode of these complexes with biological macromolecules viz., herring sperm DNA (HS- DNA) and bovine serum albumin (BSA) have been explored through various spectroscopic techniques. The characteristic changes in absorption, emission and, circular dichroism spectra of the complexes with DNA indicate the noticeable interaction between them. From the all spectral information complexes could interact with DNA via non-intercalation mode of binding. The hyperchromisim in absorption band and hypochromisim in emission intensity of BSA with different complex concentrations shown significant information, and the binding affinity value has been predicted from Stern-Volmer plots. Further, all the complexes could cleave the circular plasmid pUC19 DNA efficiently by using an activator H2O2. The ligand and all metal(II) complexes showed good antibacterial activities. The molecular docking studies of the complexes with DNA were performed in order to make a comparison and conclusion with spectral technic results.

Synthesis, spectral characterization and computed optical analysis of potent triazole based compounds

NASA Astrophysics Data System (ADS)

Sumrra, Sajjad H.; Mushtaq, Fazila; Khalid, Muhammad; Raza, Muhammad Asam; Nazar, Muhammad Faizan; Ali, Bakhat; Braga, Ataualpa A. C.

2018-02-01

Biologically active triazole Schiff base ligand (L) and metal complexes [Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)] are reported herein. The ligand acted as tridentate and coordinated towards metallic ions via azomethine-N, triazolic-N moiety and deprotonated-O of phenyl substituents in an octahedral manner. These compounds were characterized by physical, spectral and analytical analysis. The synthesized ligand and metal complexes were screened for antibacterial pathogens against Chromohalobacter salexigens, Chromohalobacter israelensi, Halomonas halofila and Halomonas salina, antifungal bioassay against Aspergillus niger and Aspergellus flavin, antioxidant (DPPH, phosphomolybdate) and also for enzyme inhibition [butyrylcholinesterase (BChE) and acetylcholinesterase (AChE)] studies. The results of these activities indicated the ligand to possess potential activity which significantly increased upon chelation. Moreover, vibrational bands, frontier molecular orbitals (FMOs) and natural bond analysis (NBO) of ligand (1) were carried out through density functional theory (DFT) with B3lYP/6-311 ++G (d,p) approach. While, UV-Vis analysis was performed by time dependent TD-DFT with B3lYP/6-311 ++G (d,p) method. NBO analysis revealed that investigated compound (L) contains enormous molecular stability owing to hyper conjugative interactions. Theoretical spectroscopic findings showed good agreement to experimental spectroscopic data. Global reactivity descriptors were calculated using the energies of FMOs which indicated compound (L) might be bioactive. These parameters confirmed the charge transfer phenomenon and reasonable correspondence with experimental bioactivity results.

Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd(ii) and Pb(ii) sorption by δ-MnO2 and ferrihydrite.

PubMed

van Genuchten, Case M; Peña, Jasquelin

2016-08-10

Birnessite minerals (layer-type MnO2), which bear both internal (cation vacancies) and external (particle edges) metal sorption sites, are important sinks of contaminants in soils and sediments. Although the particle edges of birnessite minerals often dominate the total reactive surface area, especially in the case of nanoscale crystallites, the metal sorption reactivity of birnessite particle edges remains elusive. In this study, we investigated the sorption selectivity of birnessite particle edges by combining Cd(ii) and Pb(ii) adsorption isotherms at pH 5.5 with surface structural characterization by differential pair distribution function (d-PDF) analysis. We compared the sorption reactivity of δ-MnO2 to that of the nanomineral, 2-line ferrihydrite, which exhibits only external surface sites. Our results show that, whereas Cd(ii) and Pb(ii) both bind to birnessite layer vacancies, only Pb(ii) binds extensively to birnessite particle edges. For ferrihydrite, significant Pb(ii) adsorption to external sites was observed (roughly 20 mol%), whereas Cd(ii) sorption was negligible. These results are supported by bond valence calculations that show comparable degrees of saturation of oxygen atoms on birnessite and ferrihydrite particle edges. Therefore, we propose that the sorption selectivity of birnessite edges follows the same order of that reported previously for ferrihydrite: Ca(ii) < Cd(ii) < Ni(ii) < Zn(ii) < Cu(ii) < Pb(ii).

A Method for Detection of Pseudobactin, the Siderophore Produced by a Plant-Growth-Promoting Pseudomonas Strain, in the Barley Rhizosphere

PubMed Central

Buyer, Jeffrey S.; Kratzke, Marian G.; Sikora, Lawrence J.

1993-01-01

Detection in the rhizosphere of the siderophore produced by an inoculated microorganism is critical to determining the role of microbial iron chelators on plant growth promotion. We previously reported the development of monoclonal antibodies (MAb) to ferric pseudobactin, the siderophore of plant-growth-promoting Pseudomonas strain B10. One of these MAb reacted less strongly to pseudobactin than to ferric pseudobactin. The MAb reacted to Al(III), Cr(III), Cu(II), and Mn(II) complexes of pseudobactin at a level similar to the level at which it reacted to ferric pseudobactin and reacted less to the Zn(II) complex, but these metals would make up only a small fraction of chelated pseudobactin in soil on the basis of relative abundance of metals and relative binding constants. Fourteen-day-old barley plants grown in limed and autoclaved soil were inoculated with 109 CFU of Pseudomonas strain Sm1-3, a strain of Pseudomonas B10 Rifr Nalr selected for enhanced colonization, and sampled 3 days later. Extraction and analysis of the roots and surrounding soil using the MAb in an immunoassay indicated a concentration of 3.5 × 10-10 mol of ferric pseudobacting g-1 (wet weight). This is the first direct measurement of a pseudobactin siderophore in soil or rhizosphere samples. PMID:16348884

Six complexes based on bis(imidazole/benzimidazole-1-yl)pyridazine ligands: Syntheses, structures and properties

NASA Astrophysics Data System (ADS)

Wang, Xin-Fang; Du, Ceng-Ceng; Zhou, Sheng-Bin; Wang, Duo-Zhi

2017-01-01

Herein we reported six new Ni(II)/Cu(II)/Zn(II) complexes, namely, [Ni(L1)4(OH)2] (1), [Cu(L1)4(OH)2] (2), [Cu(L1)2(SiF6)]n (3), {[Cu(L2)(HCOO)2]·H2O·CH3OH}n (4), [Ni(L2)2(NO3)2]n (5) and {[Zn(L2)Cl2]·DMF}n (6) (L1 = 3,6-bis(imidazole-1-yl)pyridazine, L2 = 3,6-bis(benzimidazole-1-yl)pyridazine), which were characterized by single-crystal X-ray diffraction, elemental analysis, IR, PXRD. These complexes have been successfully constructed under interface diffusion process, heating reflux or hydrothermal conditions. The structures of 1 and 2 are mononuclear complexes. Complex 3 exhibits a 6-connected 3D topology network with the Schläfli symbol of (412·63). In complex 4, two Cu(II) were connected through two HCOO- anions to form dinuclear structure unit, which is arranged into a 1D ladder-like structure by μ2-L2 ligands. Complexes 5 and 6 are 1D zigzag chains connected by L2 ligands, but the Ni(II) ion is six-coordinated in 5 and the Zn(II) ion is four-coordinated in 6. Moreover, the solid-state luminescence property and UV-vis diffuse reflection spectrum of complex 6 have been investigated and discussed.

ArsR arsenic-resistance regulatory protein from Cupriavidus metallidurans CH34

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Y.; van der Lelie, D.; Monchy, S.

The Cupriavidus metallidurans CH34 arsR gene, which is part of the arsRIC{sub 2}BC{sub 1}HP operon, and its putative arsenic-resistance regulatory protein were identified and characterized. The arsenic-induced transcriptome of C. metallidurans CH34 showed that the genes most upregulated in the presence of arsenate were all located within the ars operon, with none of the other numerous heavy metal resistance systems present in CH34 being induced. A transcriptional fusion between the luxCDABE operon and the arsR promoter/operator (P/O) region was used to confirm the in vivo induction of the ars operon by arsenite and arsenate. The arsR gene was cloned intomore » expression vectors allowing for the overexpression of the ArsR protein as either his-tagged or untagged protein. The ability of the purified ArsR proteins to bind to the ars P/O region was analyzed in vitro by gel mobility shift assays. ArsR showed an affinity almost exclusively to its own ars P/O region. Dissociation of ArsR and its P/O region was metal dependent, and based on decreasing degrees of dissociation three groups of heavy metals could be distinguished: As(III), Bi(III), Co(II), Cu(II), Ni(II); Cd(II); Pb(II) and Zn(II), while no dissociation was observed in the presence of As(V).« less

Multi-component sorption of Pb(II), Cu(II) and Zn(II) onto low-cost mineral adsorbent.

PubMed

Prasad, Murari; Xu, Huan-yan; Saxena, Sona

2008-06-15

Multi-component sorption studies were carried out for attenuation of divalent heavy metal cations (Pb2+, Cu2+ and Zn2+) by a low-cost mineral adsorbent from the aqueous solution. Kinetic and equilibrium batch-type sorption experiments were conducted under variable conditions for multi-component using low-grade (<12%P2O5) phosphate rock. Percentage of multiple heavy metal species removal increases with decreasing initial metals concentration and particle size. The equilibrium data were well described to a lesser extent by Freundlich model but Langmuir model seemed to be more appropriate with the fixation capacity obtained at room temperature for Pb2+, Cu2+ and Zn2+ was 227.2, 769.2 and 666.6 micromol g(-1), respectively. Two simple kinetic models were tested to investigate the adsorption mechanism. Rate constants have been found nearly constant at all metal concentrations for first order. The comparison of adsorption capacity of low-grade phosphate rock decreases in multi-component system as compared to single component due to ionic interactions. X-ray powder diffraction (XRPD) technique was used to ascertain the formation of new metal phases followed by surface complexation. Used adsorbents have been converted into a value added product by utilizing innovative Zero-waste concept to solve the used adsorbents disposal problem and thus protecting the environment.

Synthesis of metal complexes involving Schiff base ligand with methylenedioxy moiety: spectral, thermal, XRD and antimicrobial studies.

PubMed

Sundararajan, M L; Jeyakumar, T; Anandakumaran, J; Karpanai Selvan, B

2014-10-15

Metal complexes of Zn(II), Cd(II), Ni(II), Cu(II), Fe(III), Co(II), Mn(II) Hg(II), and Ag(I) have been synthesized from Schiff base ligand, prepared by the condensation of 3,4-(methylenedioxy)aniline and 5-bromo salicylaldehyde. All the compounds have been characterized by using elemental analysis, molar conductance, FT-IR, UV-Vis, (1)H NMR, (13)C NMR, mass spectra, powder XRD and thermal analysis (TG/DTA) technique. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). The FT-IR, (1)H NMR, (13)C NMR and UV-Vis spectral data suggest that the ligand coordinate to the metal atom by imino nitrogen and phenolic oxygen as bidentate manner. Mass spectral data further support the molecular mass of the compounds and their structure. Powder XRD indicates the crystalline state and morphology of the ligand and its metal complexes. The thermal behaviors of the complexes prove the presence of lattice as well as coordinated water molecules in the complexes. Melting point supports the thermal stability of all the compounds. The in vitro antimicrobial effects of the synthesized compounds were tested against five bacterial and three fungal species by well diffusion method. Antioxidant activities have also been performed for all the compounds. Metal complexes show more biological activity than the Schiff base. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of macroalgae enriched with microelements on egg quality parameters and mineral content of eggs, eggshell, blood, feathers and droppings.

PubMed

Michalak, I; Chojnacka, K; Dobrzański, Z; Górecki, H; Zielińska, A; Korczyński, M; Opaliński, S

2011-06-01

This study presents results obtained from feeding experiment on laying hens, which were fed with the diet supplemented with two marine macroalgae: Enteromorpha prolifera and Cladophora sp., enriched with microelements [Cu(II), Zn(II), Co(II), Mn(II), Cr(III)]. The applicability of the preparation was tested on five experimental groups of laying hens and one control group. In the control group, microelements were supplemented in the inorganic form, whereas in experimental groups, Cu, Zn, Co, Mn and Cr were replaced by macroalgae enriched with a given microelement ion. During feeding experiment, weight of laying hens, weight of eggs, eggshell thickness and mineral content of blood, feathers, droppings, eggs content (separately yolk and egg white) and eggshell were measured. Also egg number was counted and microclimate (temperature and relative humidity) was monitored. Supplementing bio-metallic feed additives to the diet of laying hens resulted in higher microelement transfer to eggs and enhanced the colour of yolk. It was also found that the presence of Enteromorpha prolifera and Cladophora sp. in laying hens diet influenced advantageously eggs weight, eggshell thickness as well as body weight of hens. On the basis of these results, it could be concluded that Enteromorpha prolifera and Cladophora sp. enriched with microelement ions could be potentially used as mineral feed additives in laying hens feeding. © 2010 Blackwell Verlag GmbH.

Screening the efficient biological prospects of triazole allied mixed ligand metal complexes

NASA Astrophysics Data System (ADS)

Utthra, Ponnukalai Ponya; Kumaravel, Ganesan; Raman, Natarajan

2017-12-01

Triazole appended mixed ligand complexes (1-8) of the general formula [ML (bpy/phen)2]Cl2, where M = Cu(II), Co(II), Ni(II) and Zn(II), L = triazole appended Schiff base (E)sbnd N-(4-nitrobenzylidene)-1H-1,2,4-triazol-3-amine and bpy/phen = 2,2‧-bipyridine/1,10-phenanthroline, have been synthesized. The design and synthesis of this elaborate ligand has been performed with the aim of increasing stability and conjugation of 1,2,4 triazole, whose Schiff base derivatives are known as biologically active compounds thereby exploring their DNA binding affinity and other biological applications. The compounds have been comprehensively characterized by elemental analysis, spectroscopic methods (IR, UV-Vis, EPR, 1H and 13C NMR spectroscopy), ESI mass spectrometry and magnetic susceptibility measurements. The complexes were found to exhibit octahedral geometry. The complexes 1-8 were subjected to DNA binding techniques evaluated using UV-Vis absorption, CV, CD, Fluorescence spectroscopy and hydrodynamic measurements. Complex 5 showed a Kb value of 3.9 × 105 M-1. The DNA damaging efficacy for the complexes was observed to be high compared to the ligand. The antimicrobial screening of the compounds against bacterial and fungal strains indicates that the complexes possess excellent antimicrobial activity than the ligand. The overall biological activity of the complexes with phen as a co-ligand possessed superior potential than the ligand.

Structural variation in transition-metal bispidine compounds.

PubMed

Comba, Peter; Kerscher, Marion; Merz, Michael; Müller, Vera; Pritzkow, Hans; Remenyi, Rainer; Schiek, Wolfgang; Xiong, Yun

2002-12-16

The experimentally determined molecular structures of 40 transition metal complexes with the tetradentate bispyridine-substituted bispidone ligand, 2,4-bis(2-pyridine)-3,7-diazabicyclo[3.3.1]nonane-9-one [M(bisp)XYZ]n+; M = CrIII, MnII, FeII, CoII, CuII, CuI, ZnII; X, Y, Z = mono- or bidentate co-ligands; penta-, hexa- or heptacoordinate complexes) are characterized in detail, supported by force-field and DFT calculations. While the bispidine ligand is very rigid (N3...N7 distance = 2.933 +/- 0.025 A), it tolerates a large range of metal-donor bond lengths (2.07 A < sigma(M-N)/4 < 2.35 A). Of particular interest is the ratio of the bond lengths between the metal center and the two tertiary amine donors (0.84 A < M-N3/M-N7 < 1.05 A) and the fact that, in terms of this ratio there seem to be two clusters with M-N3 < M-N7 and M-N3 > or = M-N7. Calculations indicate that the two structural types are close to degenerate, and the structural form therefore depends on the metal ion, the number and type of co-ligands, as well as structural variations of the bispidine ligand backbone. Tuning of the structures is of importance since the structurally differing complexes have very different stabilities and reactivities.

Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions

PubMed Central

Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

2015-01-01

In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = TiIV, CuII, AlIII, SnIV, FeIII, CrIII, ZrIV and ZnII; for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with TixH3−4xPW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (TixH3−4xPW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse. PMID:26374393

Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions

NASA Astrophysics Data System (ADS)

Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

2015-09-01

In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = TiIV, CuII, AlIII, SnIV, FeIII, CrIII, ZrIV and ZnII; for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with TixH3-4xPW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (TixH3-4xPW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse.

Hexavalent chromium adsorption from aqueous solution using carbon nano-onions (CNOs).

PubMed

Sakulthaew, Chainarong; Chokejaroenrat, Chanat; Poapolathep, Amnart; Satapanajaru, Tunlawit; Poapolathep, Saranya

2017-10-01

The capacity of carbon nano-onions (CNOs) to remove hexavalent chromium (Cr(VI)) from aqueous solution was investigated. Batch experiments were performed to quantify the effects of the dosage rate, pH, counter ions, and temperature. The adsorption of Cr(VI) onto CNOs was best described by a pseudo-second order rate expression. The adsorption efficiency increased with increasing adsorbent dosage and contact time and reached equilibrium in 24 h. The equilibrium data showed better compliance with a Langmuir isotherm than a Freundlich isotherm. Effective removal of Cr(VI) was demonstrated at pH values ranging from 2 to 10. The adsorption capacity of Cr(VI) was found to be highest (82%) at pH 3.4 and greatly depended on the solution pH. We found that Cr(VI) adsorption decreased with increasing pH over the pH range of 3.4-10. The adsorption capacity increased dramatically when the temperature increased from 10 °C to 50 °C regardless of the amount of CNOs used. Cr(VI) removal decreased by ∼13% when Zn(II), Cu(II), and Pb(II) were present, while there were no significant changes observed when NO 3 - or SO 4 2- was present. The overall results support that CNOs can be used as an alternative adsorbent material to remove Cr(VI) in the water treatment industry. Copyright © 2017 Elsevier Ltd. All rights reserved.

Removal of heavy metals from artificial metals contaminated water samples based on micelle-templated silica modified with pyoverdin I.

PubMed

Tansupo, Panadda; Worakarn, Chamonkolpradit; Saksit, Chanthai; Ruangviriyachai, Chalerm

2009-01-01

The micelle-templated silica (MTS) was firstly chemically modified with 3-glycidoxypropyl-trimethoxysilane (GPTMS) before immobilized with pyoverdin I. The characteristics of pyoverdin I-anchored onto the modified MTS were investigated using fluorescence, infrared spectra and scanning electron microscopy. The specific surface area of all materials was calculated by Brunauer, Emmett and Teller (BET) method using nitrogen isotherm adsorption data. As the results, the surface area of commercial silica gel decreased from 609.2 to 405.4 m2/g, it indicated that the pyoverdin I could be immobilized onto the surface of silica solid support. This adsorbent was used for extraction of Fe(III), Cu(II), Zn(II), and Pb(II) in artificial metals contaminated water. Experimental conditions for effective adsorption of trace levels of metal ions were optimized with respect to different experimental parameters using batch procedure. The optimum pH value for the removal of metal ions simultaneously on this adsorbent was 4.0. Complete desorption of the adsorbed metal ions from the adsorbent was carried out using 0.25 mol/L of EDTA. The effect of different cations and anions on the adsorption of these metals on adsorbent was studied and the results showed that the proposed adsorbent could be applied to the highly saline samples and the sample which contains some transition metals.

Synthesis, characterization and biocidal activities of heterobimetallic complexes having tin(IV) as a padlock

NASA Astrophysics Data System (ADS)

Husain, Ahmad; Nami, Shahab A. A.; Siddiqi, K. S.

2010-04-01

A mononuclear precursor complex, [(CH 3) 2Sn(tpdtc)] and several of its heterobimetallic derivatives of the type, [(CH 3) 2Sn(tpdtc)]MCl 2 have been synthesized by the simple addition reaction of transition metal chlorides, MCl 2· nH 2O where tpdtc = tetraethylenepentamine bis(dithiocarbamate) anion, M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II). The synthesized complexes have been systematically characterized by the physicochemical and spectroscopic techniques. A square-pyramidal geometry has been proposed for all the transition metal atoms with chloride ions occupying the axial while the three nitrogen atoms occupying the equatorial positions. A symmetrical bidentate coordination has been observed for the dithiocarbamato moiety leading to the formation of 18 member cavity. The thermal studies reveal that the mononuclear complex decomposes in three stages while its heterobimetallic analog exhibits a simple two-stage profile. The conductivity measurement data (1 mmol solution) implies a non-electrolytic behavior for all the complexes as evident by their low conductivity values obtained at room temperature. The heterobimetallic complexes have also been tested against the bacterial ( Escherichia coli and Pseudomonas aeruginosa) and antifungal strains ( Aspergillus niger and Fusarium oxysporum). All the complexes were found to be active against the test organisms and maximum activity was found for [(CH 3) 2Sn(tpdtc)]CuCl 2 complex.

A reagent-free tubular biofilm reactor for on-line determination of biochemical oxygen demand.

PubMed

Liu, Changyu; Zhao, Huijun; Gao, Shan; Jia, Jianbo; Zhao, Limin; Yong, Daming; Dong, Shaojun

2013-07-15

We reported a reagent-free tubular biofilm reactor (BFR) based analytical system for rapid online biochemical oxygen demand (BOD) determination. The BFR was cultivated using microbial seeds from activated sludge. It only needs tap water to operate and does not require any chemical reagent. The analytical performance of this reagent-free BFR system was found to be equal to or better than the BFR system operated using phosphate buffer saline (PBS) and high purity deionized water. The system can readily achieve a limit of detection of 0.25 mg O2 L(-1), possessing superior reproducibility, and long-term operational and storage stability. More importantly, we confirmed for the first time that the BFR system is capable of tolerating common toxicants found in wastewaters, such as 3,5-dichlorophenol and Zn(II), Cr(VI), Cd(II), Cu(II), Pb(II), Mn(II) and Ni(II), enabling the method to be applied to a wide range of wastewaters. The sloughing and clogging are the important attributes affecting the operational stability, hence, the reliability of most online wastewater monitoring systems, which can be effectively avoided, benefiting from the tubular geometry of the reactor and high flow rate conditions. These advantages, coupled with simplicity in device, convenience in operation and minimal maintenance, make such a reagent-free BFR analytical system promising for practical BOD online determination. Copyright © 2013 Elsevier B.V. All rights reserved.

Cement kiln dust (CKD)-filter sand permeable reactive barrier for the removal of Cu(II) and Zn(II) from simulated acidic groundwater.

PubMed

Sulaymon, Abbas H; Faisal, Ayad A H; Khaliefa, Qusey M

2015-10-30

The hydraulic conductivity and breakthrough curves of copper and zinc contaminants were measured in a set of continuous column experiments for 99 days using cement kiln dust (CKD)-filter sand as the permeable reactive barrier. The results of these experiments proved that the weight ratios of the cement kiln dust-filter sand (10:90 and 20:80) are adequate in preventing the loss of reactivity and hydraulic conductivity and, in turn, avoiding reduction in the groundwater flow. These results reveal a decrease in the hydraulic conductivity, which can be attributed to an accumulation of most of the quantity of the contaminant masses in the first sections of the column bed. Breakthrough curves for the description of the temporal contaminant transport within the barrier were found to be more representative by the Belter-Cussler-Hu and Yan models based on the coefficient of determination and Nash-Sutcliffe efficiency. The longevity of the barrier was simulated for the field scale, based on the laboratory column tests and the values verified that cement kiln dust can be effectively used in the future, as the reactive material in permeable reactive barrier technology. These results signify that the longevity of the barrier is directly proportional to its thickness and inversely to the percentage of the CKD used. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of inorganic electrolyte anions on enrichment of Cu(II) ions with aminated Fe3O4/graphene oxide: Cu(II) speciation prediction and surface charge measurement.

PubMed

Hu, Xin-jiang; Liu, Yun-guo; Zeng, Guang-ming; Wang, Hui; You, Shao-hong; Hu, Xi; Tan, Xiao-fei; Chen, An-wei; Guo, Fang-ying

2015-05-01

The present work evaluated the effects of six inorganic electrolyte anions on Cu(II) removal using aminated Fe3O4/graphene oxide (AMGO) in single- and multi-ion systems. A 2(6-2) fractional factorial design (FFD) was employed for assessing the effects of multiple anions on the adsorption process. The results indicated that the Cu(II) adsorption was strongly dependent on pH and could be significantly affected by inorganic electrolyte anions due to the changes in Cu(II) speciation and surface charge of AMGO. In the single-ion systems, the presence of monovalent anions (Cl(-), ClO4(-), and NO3(-)) slightly increased the Cu(II) adsorption onto AMGO at low pH, while the Cu(II) adsorption was largely enhanced by the presence of SO4(2-), CO3(2-), and HPO4(2-). Based on the estimates of major effects and interactions from FFD, the factorial effects of the six selected species on Cu(II) adsorption in multi-ion system were in the following sequence: HPO4(2-)>CO3(2-)>Cl(-)>SO4(2-)>NO3(-)=ClO4(-), and the combined factors of AD (Cl(-)×SO4(2-)) and EF (Cl(-)×SO4(2-)) had significant effects on Cu(II) removal. Copyright © 2015 Elsevier Ltd. All rights reserved.

Antineoplastic and cytogenetic effects of complexes of Pd (II) with 4N-substituted derivatives of 2-acetyl-pyridine-thiosemicarbazone.

PubMed

Papageorgiou, A; Iakovidou, Z; Mourelatos, D; Mioglou, E; Boutis, L; Kotsis, A; Kovala-Demertzi, D; Domopoulou, A; West, D X; Dermetzis, M A

1997-01-01

The effect of novel Pd(II) complexes with derivatives of 2-acetyl-pyridinethisemicarbazone, N4-ethyl (HAc4Et) and 3-hexamethyleneiminylthiosemicarbazone (HAchexim), on Sister Chromatid Exchange (SCE) rates and human lymphocyte proliferation kinetics was studied. Also, the effect of Pd(II) complexes on DNA synthesis of P388 and L1210 cell cultures and against Leukemia P388 was investigated. Among these compounds, the compound Bis(3-hexamethyleneiminyl-2-acetylpyridine-thisemicarbazonato++ +) palladium (II) was found to be distinctly effective against Leukemia P388, in inhibiting incorporation of 3H-thymidine into DNA and in inducing SCEs and cell division delays.

Antibacterial activity of Pd(II) complexes with salicylaldehyde-amino acids Schiff bases ligands.

PubMed

Rîmbu, Cristina; Danac, Ramona; Pui, Aurel

2014-01-01

Palladium(II) complexes with Schiff bases ligands derived from salicylaldehyde and amino acids (Ala, Gly, Met, Ser, Val) have been synthesized and characterized by Fourier transform (FT)-IR, UV-Vis and (1)H-NMR spectroscopy. The electrospray mass spectrometry (ES-MS) spectrometry confirms the formation of palladium(II) complexes in 1/2 (M/L) molar ratio. All the Pd(II) complexes 1, [Pd(SalAla)2]Cl2; 2, [Pd(SalGly)2]Cl2; 3, [Pd(SalMet)2]Cl2; 4, [Pd(SalSer)2]Cl2; 5, [Pd(SalVal)2]Cl2; have shown antibacterial activity against Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli.

Synthesis and spectral studies of platinum metal complexes of benzoin thiosemicarbazone

NASA Astrophysics Data System (ADS)

Offiong, Offiong E.

1994-11-01

The platinum metal chelates of benzoin thiosemicarbazone obtained with Ru(III), Rh(III), Ir(III), Pd(II) and Pt(II) were prepared from their corresponding halide salts. The complexes were characterized by elemental analysis, conductance measurement, IR, Raman, 1H-NMR, 13C-NMR and UV-visible spectra studies. Various ligand field parameters and nephelauxetic parameters were also calculated. The mode of bonding and the geometry of the ligand environment around the metal ion have been discussed in the light of the available data obtained. Complexes of Ru(III), Rh(III) and Ir(III) are six-coordinate octahedral, while Pd(II) and Pt(II) halide complexes are four-coordinated with halides bridging.

The Efficient Removal of Heavy Metal Ions from Industry Effluents Using Waste Biomass as Low-Cost Adsorbent: Thermodynamic and Kinetic Models

NASA Astrophysics Data System (ADS)

Indhumathi, Ponnuswamy; Sathiyaraj, Subbaiyan; Koelmel, Jeremy P.; Shoba, Srinivasan U.; Jayabalakrishnan, Chinnasamy; Saravanabhavan, Munusamy

2018-05-01

The ability of green micro algae Chlorella vulgaris for biosorption of Cu(II) ions from an aqueous solution was studied. The biosorption process was affected by the solution pH, contact time, temperature and initial Cu(II) concentration. Experimental data were analyzed in terms of pseudo-first order, pseudo-second order and intra particle diffusion models. Results showed that the sorption process of Cu(II) ions followed pseudo-second order kinetics. The sorption data of Cu(II) ions are fitted to Langmuir, Freundlich, and Redlich-Peterson isotherms, and the Temkin isotherm. The thermodynamic study shows the Cu(II) biosorption was exothermic in nature. The Cu(II) ions were recovered effectively from Chlorella vulgaris biomass using 0.1 M H2SO4 with up to 90.3% recovery, allowing for recycling of the Cu. Green algae from freshwater bodies showed significant potential for Cu(II) removal and recovery from industrial wastewater.

Efficacy and reusability of alginate-immobilized live and heat-inactivated Trichoderma asperellum cells for Cu (II) removal from aqueous solution.

PubMed

Tan, Wei Shang; Ting, Adeline Su Yien

2012-11-01

Cu(II) removal efficacies of alginate-immobilized Trichoderma asperellum using viable and non-viable forms were investigated with respect to time, pH, and initial Cu(II) concentrations. The reusability potential of the biomass was determined based on sorption/desorption tests. Cu(II) biosorption by immobilized heat-inactivated T. asperellum cells was the most efficient, with 134.22mg Cu(II) removed g(-1) adsorbent, compared to immobilized viable cells and plain alginate beads (control) with 105.96 and 94.04mg Cu(II) adsorbed g(-1) adsorbent, respectively. Immobilized non-viable cells achieved equilibrium more rapidly within 4h. For all biosorbents, optimum pH for Cu(II) removal was between pH 4 and 5. Reusability of all biosorbents were similar, with more than 90% Cu(II) desorbed with HCl. These alginate-immobilized cells can be applied to reduce clogging and post-separation process incurred from use of suspended biomass. Copyright © 2012 Elsevier Ltd. All rights reserved.

Copper Ion Detection in Drinking Water via a Fabric Nanocomposite Sensor

NASA Astrophysics Data System (ADS)

Yu, Guoqiang

Excessive Cu(II) ions in drinking water are always a big threat to people's health. In this work, we developed a flexible amperometric sensor by a simple dip-coating method, which was able to rapidly, sensitively, and selectively detect the Cu(II) ions in the range of 0.65 to 39 ppm in real time. The prepared Cu(II) sensor consisted of three layers that were electrospun nylon-6 nanofibers, multiwalled carbon nanotubes (MWCNTs), and 2,2':5',2''-terthiophene molecules, respectively. When a voltage was applied to the Cu(II) sensor, the current was obviously impeded in the presence of Cu(II) ions. Interfering metal ions, including Cd(II), Fe(II), Pb(II), Hg(II), and Ag(I) ions, had almost no influence on the responsiveness of the Cu(II) sensor.

Biogenic nanopalladium production by self-immobilized granular biomass: application for contaminant remediation.

PubMed

Suja, E; Nancharaiah, Y V; Venugopalan, V P

2014-11-15

Microbial granules cultivated in an aerobic bubble column sequencing batch reactor were used for reduction of Pd(II) and formation of biomass associated Pd(0) nanoparticles (Bio-Pd) for reductive transformation of organic and inorganic contaminants. Addition of Pd(II) to microbial granules incubated under fermentative conditions resulted in rapid formation of Bio-Pd. The reduction of soluble Pd(II) to biomass associated Pd(0) was predominantly mediated by H2 produced through fermentation. X-ray diffraction and scanning electron microscope analysis revealed that the produced Pd nanoparticles were associated with the microbial granules. The catalytic activity of Bio-Pd was determined using p-nitrophenol and Cr(VI) as model compounds. Reductive transformation of p-nitrophenol by Bio-Pd was ∼20 times higher in comparison to microbial granules without Pd. Complete reduction of up to 0.25 mM of Cr(VI) by Bio-Pd was achieved in 24 h. Bio-Pd synthesis using self-immobilized microbial granules is advantageous and obviates the need for nanoparticle encapsulation or use of barrier membranes for retaining Bio-Pd in practical applications. In short, microbial granules offer a dual purpose system for Bio-Pd production and retention, wherein in situ generated H2 serves as electron donor powering biotransformations. Copyright © 2014 Elsevier Ltd. All rights reserved.

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores.

PubMed

El-Safty, Sherif A; Shenashen, Mohamed A; Sakai, Masaru; Elshehy, Emad; Halada, Kohmei

2015-12-06

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in industrialized countries. Here, the development of optical mesosensors/adsorbents (MSAs) for efficient recognition and selective recovery of Pd(II), Au(III), and Co(II) from urban mine was achieved. A simple, general method for preparing MSAs based on using high-order mesoporous monolithic scaffolds was described. Hierarchical cubic Ia3d wagon-wheel-shaped MSAs were fabricated by anchoring chelating agents (colorants) into three-dimensional pores and micrometric particle surfaces of the mesoporous monolithic scaffolds. Findings show, for the first time, evidence of controlled optical recognition of Pd(II), Au(III), and Co(II) ions and a highly selective system for recovery of Pd(II) ions (up to ~95%) in ores and industrial wastes. Furthermore, the controlled assessment processes described herein involve evaluation of intrinsic properties (e.g., visual signal change, long-term stability, adsorption efficiency, extraordinary sensitivity, selectivity, and reusability); thus, expensive, sophisticated instruments are not required. Results show evidence that MSAs will attract worldwide attention as a promising technological means of recovering and recycling palladium, gold and cobalt metals.

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores

PubMed Central

El-Safty, Sherif A.; Shenashen, Mohamed A.; Sakai, Masaru; Elshehy, Emad; Halada, Kohmei

2015-01-01

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in industrialized countries. Here, the development of optical mesosensors/adsorbents (MSAs) for efficient recognition and selective recovery of Pd(II), Au(III), and Co(II) from urban mine was achieved. A simple, general method for preparing MSAs based on using high-order mesoporous monolithic scaffolds was described. Hierarchical cubic Ia3d wagon-wheel-shaped MSAs were fabricated by anchoring chelating agents (colorants) into three-dimensional pores and micrometric particle surfaces of the mesoporous monolithic scaffolds. Findings show, for the first time, evidence of controlled optical recognition of Pd(II), Au(III), and Co(II) ions and a highly selective system for recovery of Pd(II) ions (up to ~95%) in ores and industrial wastes. Furthermore, the controlled assessment processes described herein involve evaluation of intrinsic properties (e.g., visual signal change, long-term stability, adsorption efficiency, extraordinary sensitivity, selectivity, and reusability); thus, expensive, sophisticated instruments are not required. Results show evidence that MSAs will attract worldwide attention as a promising technological means of recovering and recycling palladium, gold and cobaltmetals. PMID:26709467

8-aminoquinoline functionalized silica nanoparticles: a fluorescent nanosensor for detection of divalent zinc in aqueous and in yeast cell suspension.

PubMed

Rastogi, Shiva K; Pal, Parul; Aston, D Eric; Bitterwolf, Thomas E; Branen, A Larry

2011-05-01

Zinc is one of the most important transition metal of physiological importance, existing primarily as a divalent cation. A number of sensors have been developed for Zn(II) detection. Here, we present a novel fluorescent nanosensor for Zn(II) detection using a derivative of 8-aminoquinoline (N-(quinolin-8-yl)-2-(3 (triethoxysilyl)propylamino)acetamide (QTEPA) grafted on silica nanoparticles (SiNPs). These functionalized SiNPs were used to demonstrate specific detection of Zn(II) in tris-HCl buffer (pH 7.22), in yeast cell (Saccharomyces cerevisiae) suspension, and in tap water. The silane QTEPA, SiNPs and final product were characterized using solution and solid state nuclear magnetic resonance, Fourier transform infrared, ultraviolet-visible absorption spectroscopy, transmission electron microscopy, elemental analysis, thermogravimetric techniques, and fluorescence spectroscopy. The nanosensor shows almost 2.8-fold fluorescence emission enhancement and about 55 nm red-shift upon excitation with 330 ± 5 nm wavelength in presence of 1 μM Zn(II) ions in tris-HCl (pH 7.22). The presence of other metal ions has no observable effect on the sensitivity and selectivity of nanosensor. This sensor selectively detects Zn(II) ions with submicromolar detection to a limit of 0.1 μM. The sensor shows good applicability in the determination of Zn(II) in tris-HCl buffer and yeast cell environment. Further, it shows enhancement in fluorescence intensity in tap water samples.

Interactive effects of sulfadiazine and Cu(II) on their sorption and desorption on two soils with different characteristics.

PubMed

Xu, Yonggang; Yu, Wantai; Ma, Qiang; Zhou, Hua

2015-11-01

Antibiotics and heavy metals often coexist in soils due to land application of animal wastes and other sources of inputs. The aim of this study is to evaluate the interaction of Cu(II) and sulfadiazine (SDZ) regarding to their sorption and desorption on Brown soil (BS, luvisols) and Red soil (RS, Udic Ferrosols) using batch experiments. The presence of Cu(II) significantly enhanced sorption of SDZ on BS at pH>5.0, and this trend increased with increasing pH, which was mainly ascribed to the formation of ternary complexes of Cu-SDZ-soil and/or SDZ-Cu-soil. In contrast, Cu(II) only slightly increased SDZ sorption on RS at pH<5.0 due to the decrease of equilibrium solution pH, whereas it hardly affected SDZ sorption at pH>5.0 because RS had high oxides contents and low affinity for Cu(II). In addition, Cu(II) inhibited SDZ desorption from BS but promoted SDZ desorption from RS, which was related to their different sorption mechanisms. The presence of SDZ exerted no significant effect on the sorption of Cu(II) on the two soils at pH<6.5 because of its low sorption coefficients (Kd), while slightly decreased Cu(II) sorption at pH>6.5 by forming water-soluble complexes. Furthermore, SDZ had little effect on Cu(II) desorption from the two soils at natural pH. These results indicate that soil characteristics strongly influence the interactions of Cu(II) and SDZ on their sorption and desorption on soils. Copyright © 2015 Elsevier Ltd. All rights reserved.

An efficient photochemical route to Pd nanoparticles; application to the one-step synthesis of Pd@polymer nanocomposite films

NASA Astrophysics Data System (ADS)

Wolak, Séverine; Vidal, Loïc; Becht, Jean-Michel; Michelin, Laure; Balan, Lavinia

2016-08-01

We have developed a facile, efficient, low cost and ‘green’ photochemical approach to preparing surfactant-free Pd nanoparticles and Pd-immobilized@acrylate photo-polymer films at room temperature, under air and without any additional treatment. The reaction system only includes a photo-initiator used as a generator of free radicals and a Pd(II) salt. In ethanol solution, the photochemical reduction of Pd(II) to Pd(0) generates very small metal particles with a narrow size distribution (2-4 nm). Furthermore, we have shown that the formation of Pd nanoparticles from a Pd(II) salt can be reversible thus allowing easy handling and safe storage with the possibility of generating the nanoparticles just before use. In the presence of an acrylate bifunctional monomer, Pd@polymer film was obtained through a ‘one-pot, one-step’ process resulting from a simultaneous photo-reduction of Pd(II) and photo-polymerization of acrylate units. The simultaneous generation of a 3D polymer network and of metal particles leads to a homogeneous distribution of Pd nanoparticles in the photo-polymer matrix with an average diameter of approximately 3.7 ± 1.1 nm. Such as-prepared Pd@polymer films were found to efficiently catalyze the Mizoroki-Heck reaction in the presence of only 0.9 mequiv. of supported palladium. The major interest of this arrangement is its recoverability and reusability, which makes it very attractive both from a practical and economical viewpoint. Finally, it is worth noting that this innovation offers a great advantage over concurrent methods in that it is simply generated within minutes, it is highly stable, and there is sharp monodispersity in the size of the Pd nanoparticles that can be stored for months without alteration of their physico-chemical properties and catalytic activity.

Adsorption of Cu(II) on Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated and Carboxylated Fullerenes

PubMed Central

Wang, Jing; Li, Zhan; Li, Shicheng; Qi, Wei; Liu, Peng; Liu, Fuqiang; Ye, Yuanlv; Wu, Liansheng; Wang, Lei; Wu, Wangsuo

2013-01-01

The adsorption of Cu(II) on oxidized multi-walled carbon nanotubes (oMWCNTs) as a function of contact time, pH, ionic strength, temperature, and hydroxylated fullerene (C60(OH)n) and carboxylated fullerene (C60(C(COOH)2)n) were studied under ambient conditions using batch techniques. The results showed that the adsorption of Cu(II) had rapidly reached equilibrium and the kinetic process was well described by a pseudo-second-order rate model. Cu(II) adsorption on oMWCNTs was dependent on pH but independent of ionic strength. Compared with the Freundlich model, the Langmuir model was more suitable for analyzing the adsorption isotherms. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Cu(II) adsorption on oMWCNTs was spontaneous and endothermic. The effect of C60(OH)n on Cu(II) adsorption of oMWCNTs was not significant at low C60(OH)n concentration, whereas a negative effect was observed at higher concentration. The adsorption of Cu(II) on oMWCNTs was enhanced with increasing pH values at pH < 5, but decreased at pH ≥ 5. The presence of C60(C(COOH)2)n inhibited the adsorption of Cu(II) onto oMWCNTs at pH 4–6. The double sorption site model was applied to simulate the adsorption isotherms of Cu(II) in the presence of C60(OH)n and fitted the experimental data well. PMID:24009683

Design, properties and application of a facile fluorescence switch for Cu(II).

PubMed

Diao, Haipeng; Niu, Weiping; Liu, Wen; Feng, Liheng; Xie, Jun

2017-01-05

A facile fluorescence switch based on Schiff base 2,2'-[1,3-phenylenbis- (methylidynenitrilo)]bis[benzenethiol] (PMBB) has been developed and used to sensing metal ions. UV-vis absorption and fluorescence emission spectra show that the PMBB receptor has high selectivity and sensitivity for Cu(II) ions. Based on the photoinduced electron transfer (PET) and chelation enhanced fluorescence (CHEF) mechanisms, the receptor exhibits an fluorescence "turn-on" switch signal for Cu(II). The 1:1 binding mode of PMBB and Cu (II) ions can be obtained by the Job-plot and ESI-Mass spectra data. Noticeably, the color changes (from colorless to yellow) of PMBB solutions for Cu(II) sensing can be observed by naked eyes in the sunlight. The detection limit of the receptor for Cu(II) may reach 10(-7)mol/L with a good linear relation in the lower concentrations of Cu(II). To develop the practical application, the Cu(II) ions in swimming pool water samples were detected. Results show that PMBB receptor as a fluorescent probe can use to detect the trace level of Cu(II) in the environmental samples. This work contributes to providing a facile strategy for designing efficient probes and developing their practical application value. Copyright © 2016 Elsevier B.V. All rights reserved.

X-ray crystal structure and theoretical study of a new dinuclear Cu(II) complex with two different geometry centers bridged with an oxo group

NASA Astrophysics Data System (ADS)

Golbedaghi, Reza; Azimi, Saeid; Molaei, Atefeh; Hatami, Masoud; Notash, Behrouz

2017-10-01

A new Schiff base ligand HL, 1,3-bis(2-((Z)-(2-aminoethylimino)methyl)phenoxy)ethylene di amine, has been synthesized from the reaction of a new aldehyde and ethylenediamine. After preparation the Schiff base, a new dinuclear Cu(II) complex with two different geometry for each metal ion was synthesized. Single crystal X-ray structure analysis of the complex Cu(II) showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. The crystal structure studying shows, a perchlorate ion has been coordinated to the two Cu(II) metal centers as bridged and another perchlorate coordinated to the one of Cu(II) ion as terminal. However, two interesting structures square pyramidal and distorted octahedral Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, we had a theoretical study to have a comparison of experimental and theoretical results we determined the HOMO and LUMO orbitals.

Responses of microalgae Coelastrella sp. to stress of cupric ions in treatment of anaerobically digested swine wastewater.

PubMed

Li, Xiang; Yang, William L; He, Huijun; Wu, Shaohua; Zhou, Qi; Yang, Chunping; Zeng, Guangming; Luo, Le; Lou, Wei

2018-03-01

Microalgae Coelastrella sp. could remove nutrients from anaerobically digested swine wastewater (ADSW) effectively, while its responses to the stress of Cu(II) were not well understood. In this paper, nutrients removal and growth of Coelastrella sp. were investigated at the presence of Cu(II) in ADSW. Results showed ammonium nitrogen concentration in ADSW decreased with culturing duration, while increased with an increased Cu(II) concentration. Total phosphorous concentration decreased with time, while did not drop in 4 days at Cu(II) concentration ≥1.0 mg/L. Microalgal growth was inhibited at all the Cu(II) concentrations, and ceased in about 6-8 days at Cu(II) concentration ≥1.0 mg/L. With an increased Cu(II) concentration, the contents of chlorophyll a and proteins decreased, those of malondialdehyde and superoxide dismutase, and ratios of octadecanoic acid (C18:0), hexadecanoic acid (C16:0) and octadecenoic acid (C18:1) to fatty acids in Coelastrella sp. increased, while octadecatrienoic acid (C18:3) gradually disappeared. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sensitive and selective detection of Cu(II) ion: A new effective 1,8-naphthalimide-based fluorescence 'turn off' sensor.

PubMed

Huang, Guozhen; Li, Chuang; Han, Xintong; Aderinto, Stephen Opeyemi; Shen, Kesheng; Mao, Shanshan; Wu, Huilu

2018-06-01

The present study reports the development of a new 1,8-naphthalimide-based fluorescent sensor V for monitoring Cu(II) ions. The sensor exhibited pH independence over a wide pH range 2.52-9.58, and indicated its possible use for monitoring Cu(II) ions in a competitive pH medium. The sensor also showed high selectivity and sensitivity towards the Cu(II) ions over other competitive metal ions in DMSO-HEPES buffer (v/v, 1:1; pH 7.4) with a fluorescence 'turn off' mode of 79.79% observed. A Job plot indicated the formation of a 1:1 binding mode of the sensor with Cu(II) ions. The association constant and detection limit were 1.14 × 10 6  M -1 and 4.67 × 10 -8 M, respectively. The fluorescence spectrum of the sensor was quenched due to the powerful paramagnetic nature of the Cu(II) ions. Potential application of this sensor was also demonstrated when determining Cu(II) ion levels in two different water samples. Copyright © 2018 John Wiley & Sons, Ltd.

Removal of Cu(II) from acidic electroplating effluent by biochars generated from crop straws.

PubMed

Tong, Xuejiao; Xu, Renkou

2013-04-01

The removal efficiency of copper (Cu(II)) from an actual acidic electroplating effluent by biochars generated from canola, rice, soybean and peanut straws was investigated. The biochars simultaneously removed Cu(II) from the effluent, mainly through the mechanisms of adsorption and precipitation, and neutralized its acidity. The removal efficiency of Cu(II) by the biochars followed the order: peanut straw char > soybean straw char > canola straw char > rice straw char > a commercial activated carbonaceous material, which is consistent with the alkalinity of the biochars. The pH of the effluent was a key factor determining the removal efficiency of Cu(II) by biochars. Raising the initial pH of the effluent enhanced the removal of Cu(II) from it. The optimum pyrolysis temperature was 400 degrees C for producing biochar from crop straws for acidic wastewater treatment, and the optimum reaction time was 8 hr.

Copper(II) directs formation of toxic amorphous aggregates resulting in inhibition of hen egg white lysozyme fibrillation under alkaline salt-mediated conditions.

PubMed

Ghosh, Sudeshna; Pandey, Nitin K; Banerjee, Priyanka; Chaudhury, Koel; Nagy, Nóra Veronika; Dasgupta, Swagata

2015-01-01

Hen egg white lysozyme (HEWL) adopts a molten globule-like state at high pH (~12.75) and is found to form amyloid fibrils at alkaline pH. Here, we report that Cu(II) inhibits self-association of HEWL at pH 12.75 both at 37 and 65 °C. A significant reduction in Thioflavin T fluorescence intensity, attenuation in β-sheet content and reduction in hydrophobic exposure were observed with increasing Cu(II) stoichiometry. Electron paramagnetic resonance spectroscopy suggests a 4N type of coordination pattern around Cu(II) during fibrillation. Cu(II) is also capable of altering the cytotoxicity of the proteinaceous aggregates. Fibrillar species of diverse morphology were found in the absence of Cu(II) with the generation of amorphous aggregates in the presence of Cu(II), which are more toxic compared to the fibrils alone.

Platinum(II) and palladium(II) complexes with 2-acetylpyridine thiosemicarbazone: cytogenetic and antineoplastic effects.

PubMed

Lakovidou, Z; Papageorgiou, A; Demertzis, M A; Mioglou, E; Mourelatos, D; Kotsis, A; Yadav, P N; Kovala-Demertzi, D

2001-01-01

The effect of three novel complexes of Pt(II) and three complexes of Pd(II) with 2-acetylpyridine thiosemicarbazone (HAcTsc) on sister chromatid exchange (SCE) rates and human lymphocyte proliferation kinetics on a molar basis was studied. Also, the effect of Pt(II) and Pd(II) complexes against leukemia P388 was investigated. Among these compounds, the most effective in inducing antitumor and cytogenetic effects were the complexes [Pt(AcTsc)2] x H2O and [Pd(AcTsc)2] while the rest, i.e. (HAcTsc), [Pt(AcTsc)Cl], [Pt(HAcTsc)2]Cl2 x 2H2O, [Pd(AcTsc)Cl] and [Pd(HAcTsc)2]Cl2, displayed marginal cytogenetic and antitumor effects.

Analyzing the revolution of anaerobic ammonium oxidation (anammox) performance and sludge characteristics under zinc inhibition.

PubMed

Zhang, Qian-Qian; Zhang, Zheng-Zhe; Guo, Qiong; Wang, Jiao-Jiao; Wang, Hui-Zhong; Jin, Ren-Cun

2015-04-01

In the present study, the short- and long-term effects of Zn(II) on the anaerobic ammonium oxidation (anammox) performance and sludge characteristics were evaluated. The anammox activity decreased with increasing Zn(II) concentration and pre-exposure time in short-term tests. The half maximal inhibitory concentration (IC50) of Zn(II) was found to be 25.0 mg L(-1). The 24 and 48-h pre-exposure time was a restricted factor impacting the anammox activity, and washing the inhibited sludge with buffer solution only worked under 0 and 24-h pre-exposure time. The anammox sludge could tolerate 5 mg L(-1) Zn(II) but was suppressed at 8 mg L(-1). The inhibited performance could be remitted, as the combination strategies were applied, and after the short term of recovery period, the inhibited sludge characteristics were remitted to the normal.

Biosorption of copper ions from aqueous solution using rape straw powders: Optimization, equilibrium and kinetic studies.

PubMed

Liu, Xin; Chen, Zhao-Qiong; Han, Bin; Su, Chun-Li; Han, Qin; Chen, Wei-Zhong

2018-04-15

In this paper, the adsorption behaviors of Cu(II) from the aqueous solution using rape straw powders were studied. The effects of initial Cu(II) concentration, pH range and absorbent dosage on the adsorption efficiency of Cu(II) by rape straw powder were investigated by Box-Behnken Design based on response surface methodology. The values of coefficient constant of the nonlinear models were 0.9997, 0.9984 and 0.9944 for removal Cu(II) from aqueous solution using rape straw shell, seed pods and straw pith core, respectively, which could navigate the design space for various factors on effects of biosorption Cu(II) from aqueous solution. The various factors of pH and biosorbents dosage were the key factors that affecting the removal efficiency of Cu(II) from aqueous solution. The biosorption equilibrium data presented its favorable monolayer adsorption Cu(II) onto shell, seed pods and straw pith core, respectively. The pseudo-second order kinetic model was the proper approach to determine the adsorption kinetics. The biosorption of Cu(II) onto surfaces of rape straw powders were confirmed and ion-exchanged in the adsorption process by energy dispersive spectrometer. The critical groups, -OH, -CH, -NH 3 + , -CH 3 , -NH and -C-O, exhibited by the infrared spectra results, changed to suggest that these groups played critical roles, especially -CH 3 in the adsorption of copper ions onto rape straw powders. The study provided evidences that rape straw powders can be used for removing Cu(II) from aqueous water. Copyright © 2017 Elsevier Inc. All rights reserved.

Simultaneous Stripping Detection of Pb(II), Cd(II) and Zn(II) Using a Bimetallic Hg-Bi/Single-Walled Carbon Nanotubes Composite Electrode

PubMed Central

Ouyang, Ruizhuo; Zhu, Zhenqian; Tatum, Clarissa E.; Chambers, James Q.; Xue, Zi-Ling

2011-01-01

A new, sensitive platform for the simultaneous electrochemical assay of Zn(II), Cd(II) and Pb(II) in aqueous solution has been developed. The platform is based on a new bimetallic Hg-Bi/single-walled carbon nanotubes (SWNTs) composite modified glassy carbon electrode (GCE), demonstrating remarkably improved performance for the anodic stripping assay of Zn(II), Cd(II) and Pb(II). The synergistic effect of Hg and Bi as well as the enlarged, activated surface and good electrical conductivity of SWNTs on GCE contribute to the enhanced activity of the proposed electrode. The analytical curves for Zn(II), Cd(II) an Pb(II) cover two linear ranges varying from 0.5 to 11 μg L-1 and 10 to 130 μg L-1 with correlation coefficients higher than 0.992. The limits of detection for Zn(II), Cd(II) are lower than 2 μg L-1 (S/N = 3). For Pb(II), moreover, there is another lower, linear range from 5 to 1100 ng L-1 with a coefficient of 0.987 and a detection limit of 0.12 ng L-1. By using the standard addition method, Zn(II), Cd(II) and Pb(II) ions in river samples were successfully determined. These results suggest that the proposed method can be applied as a simple, efficient alternative for the simultaneous monitoring of heavy metals in water samples. In addition, this method demonstrates the powerful application of carbon nanotubes in electrochemical analysis of heavy metals. PMID:21660117

Optimizing Cu(II) removal from aqueous solution by magnetic nanoparticles immobilized on activated carbon using Taguchi method.

PubMed

Ebrahimi Zarandi, Mohammad Javad; Sohrabi, Mahmoud Reza; Khosravi, Morteza; Mansouriieh, Nafiseh; Davallo, Mehran; Khosravan, Azita

2016-01-01

This study synthesized magnetic nanoparticles (Fe(3)O(4)) immobilized on activated carbon (AC) and used them as an effective adsorbent for Cu(II) removal from aqueous solution. The effect of three parameters, including the concentration of Cu(II), dosage of Fe(3)O(4)/AC magnetic nanocomposite and pH on the removal of Cu(II) using Fe(3)O(4)/AC nanocomposite were studied. In order to examine and describe the optimum condition for each of the mentioned parameters, Taguchi's optimization method was used in a batch system and L9 orthogonal array was used for the experimental design. The removal percentage (R%) of Cu(II) and uptake capacity (q) were transformed into an accurate signal-to-noise ratio (S/N) for a 'larger-the-better' response. Taguchi results, which were analyzed based on choosing the best run by examining the S/N, were statistically tested using analysis of variance; the tests showed that all the parameters' main effects were significant within a 95% confidence level. The best conditions for removal of Cu(II) were determined at pH of 7, nanocomposite dosage of 0.1 gL(-1) and initial Cu(II) concentration of 20 mg L(-1) at constant temperature of 25 °C. Generally, the results showed that the simple Taguchi's method is suitable to optimize the Cu(II) removal experiments.

Enhanced performance of Zn(II)-doped lead-acid batteries with electrochemical active carbon in negative mass

NASA Astrophysics Data System (ADS)

Xiang, Jiayuan; Hu, Chen; Chen, Liying; Zhang, Dong; Ding, Ping; Chen, Dong; Liu, Hao; Chen, Jian; Wu, Xianzhang; Lai, Xiaokang

2016-10-01

The effect and mechanism of Zn(II) on improving the performances of lead-acid cell with electrochemical active carbon (EAC) in negative mass is investigated. The hydrogen evolution of the cell is significantly reduced due to the deposition of Zn on carbon surface and the increased porosity of negative mass. Zn(II) additives can also improve the low-temperature and high-rate capacities of the cell with EAC in negative mass, which ascribes to the formation of Zn on lead and carbon surface that constructs a conductive bridge among the active mass. Under the co-contribution of EAC and Zn(II), the partial-state-of-charge cycle life is greatly prolonged. EAC optimizes the NAM structure and porosity to enhance the charge acceptance and retard the lead sulfate accumulation. Zn(II) additive reduces the hydrogen evolution during charge process and improves the electric conductivity of the negative electrode. The cell with 0.6 wt% EAC and 0.006 wt% ZnO in negative mass exhibits 90% reversible capacity of the initial capacity after 2100 cycles. In contrast, the cell with 0.6 wt% EAC exhibits 84% reversible capacity after 2100 cycles and the control cell with no EAC and Zn(II) exhibits less than 80% reversible capacity after 1350 cycles.

Application of silica fume as a new SP-extractor for trace determination of Zn(II) and Cd(II) in pharmaceutical and environmental samples by square-wave anodic stripping voltammetry

NASA Astrophysics Data System (ADS)

Ahmed, Salwa A.; Gaber, Ahmed A. Abdel; Rahim, Asmaa M. Abdel

2017-05-01

In this work, silica fume (SF) is used as a solid-phase extractor for extraction of Zn(II) and Cd(II) from aqueous solutions. Characterization of SF is performed by Fourier transform infrared, X-ray diffraction, transmission and scanning electron microscopy. The optimum experimental conditions for the two metal ions are investigated using batch and column techniques. The maximum adsorption capacity values are found to be 54.13 and 121.28 mg g-1 at the optimum pH 6.0 and 8.0 for Zn(II) and Cd(II), respectively. The equilibrium data are analyzed using the Langmuir, Freundlich, and Temkin isotherms by nonlinear regression analysis. Also, the kinetics analysis revealed that the overall adsorption process is successfully fitted with the pseudo-second-order model. The method is applied for determination of the target metal ions in pharmaceutical and environmental samples using square-wave anodic stripping voltammetry. The limit of detection (LOD) values are 0.102 and 1.43 × 10-3 mg L-1 for Zn(II) and Cd(II), respectively. The percentage recovery values are 98.8-100.5 % which indicate the success of the proposed method for determination of Zn(II) and Cd(II) without interfering effects.

Experiment, modeling and optimization of liquid phase adsorption of Cu(II) using dried and carbonized biomass of Lyngbya majuscula

NASA Astrophysics Data System (ADS)

Kushwaha, Deepika; Dutta, Susmita

2017-05-01

The present work aims at evaluation of the potential of cyanobacterial biomass to remove Cu(II) from simulated wastewater. Both dried and carbonized forms of Lyngbya majuscula, a cyanobacterial strain, have been used for such purpose. The influences of different experimental parameters viz., initial Cu(II) concentration, solution pH and adsorbent dose have been examined on sorption of Cu(II). Kinetic and equilibrium studies on Cu(II) removal from simulated wastewater have been done using both dried and carbonized biomass individually. Pseudo-second-order model and Langmuir isotherm have been found to fit most satisfactorily to the kinetic and equilibrium data, respectively. Maximum 87.99 and 99.15 % of Cu(II) removal have been achieved with initial Cu(II) concentration of 10 and 25 mg/L for dried and carbonized algae, respectively, at an adsorbent dose of 10 g/L for 20 min of contact time and optimum pH 6. To optimize the removal process, Response Surface Methodology has been employed using both the dried and carbonized biomass. Removal with initial Cu(II) concentration of 20 mg/L, with 0.25 g adsorbent dose in 50 mL solution at pH 6 has been found to be optimum with both the adsorbents. This is the first ever attempt to make a comparative study on Cu(II) removal using both dried algal biomass and its activated carbon. Furthermore, regeneration of matrix was attempted and more than 70% and 80% of the adsorbent has been regenerated successfully in the case of dried and carbonized biomass respectively upto the 3rd cycle of regeneration study.

The second Cu(II)-binding site in a proton-rich environment interferes with the aggregation of amyloid-beta(1-40) into amyloid fibrils.

PubMed

Jun, Sangmi; Gillespie, Joel R; Shin, Byong-kyu; Saxena, Sunil

2009-11-17

The overall morphology and Cu(II) ion coordination for the aggregated amyloid-beta(1-40) [Abeta(1-40)] in N-ethylmorpholine (NEM) buffer are affected by Cu(II) ion concentration. This effect is investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and electron spin echo envelope modulation (ESEEM) spectroscopy. At lower than equimolar concentrations of Cu(II) ions, fibrillar aggregates of Abeta(1-40) are observed. At these concentrations of Cu(II), the monomeric and fibrillar Abeta(1-40) ESEEM data indicate that the Cu(II) ion is coordinated by histidine residues. For aggregated Abeta(1-40) at a Cu(II):Abeta molar ratio of 2:1, TEM and AFM images show both linear fibrils and granular amorphous aggregates. The ESEEM spectra show that the multi-histidine coordination for Cu(II) ion partially breaks up and becomes exposed to water or exchangeable protons of the peptide at a higher Cu(II) concentration. Since the continuous-wave electron spin resonance results also suggest two copper-binding sites in Abeta(1-40), the proton ESEEM peak may arise from the second copper-binding site, which may be significantly involved in the formation of granular amorphous aggregates. Thioflavin T fluorescence and circular dichroism experiments also show that Cu(II) inhibits the formation of fibrils and induces a nonfibrillar beta-sheet conformation. Therefore, we propose that Abeta(1-40) has a second copper-binding site in a proton-rich environment and the second binding Cu(II) ion interferes with a conformational transition into amyloid fibrils, inducing the formation of granular amorphous aggregates.

Ultrasensitive Detection of Cu2+ Using a Microcantilever Sensor Modified with L-Cysteine Self-Assembled Monolayer.

PubMed

Xu, Xiaohe; Zhang, Na; Brown, Gilbert M; Thundat, Thomas G; Ji, Hai-Feng

2017-10-01

A microcantilever was modified with a self-assembled monolayer (SAM) of L-cysteine for the sensitively and selectively response to Cu(II) ions in aqueous solution. The microcantilever undergoes bending due to sorption of Cu(II) ions. The interaction of Cu(II) ions with the L-cysteine on the cantilever is diffusion controlled and does not follow a simple Langmuir adsorption model. A concentration of 10 -10  M Cu(II) was detected in a fluid cell using this technology. Other cations, such as Ni 2+ , Zn 2+ , Pb 2+ , Cd 2+ , Ca 2+ , K + , and Na + , did not respond with a significant deflection, indicating that this L-cysteine-modified cantilever responded selectively and sensitively to Cu(II).

Structural diversity in multinuclear Pd(II) assemblies that show low-humidity proton conduction.

PubMed

Samanta, Dipak; Mukherjee, Partha Sarathi

2014-05-05

Systematic investigation on synergetic effects of geometry, length, denticity, and asymmetry of donors was performed through the formation of a series of uncommon Pd(II) aggregates by employing the donor in a multicomponent self-assembly of a cis-blocked 90° Pd(II) acceptor and a tetratopic donor. Some of these assemblies represent the first examples of these types of structures, and their formation is not anticipated by only taking the geometry of the donor and the acceptor building units into account. Analysis of the crystal packing of the X-ray structure revealed several H bonds between the counteranions (NO3 (-) ) and water molecules (OH⋅⋅⋅ON). Moreover, H-bonded 3D-networks of water are present in the molecular pockets, which show water-adsorption properties with some variation in water affinity. Interestingly, these complexes exhibit proton conductivity (1.87×10(-5) -6.52×10(-4)  Scm(-1) ) at 296 K and low relative humidity (ca. 46 %) with activation energies of 0.29-0.46 eV. Moreover, the conductivities further increase with the enhancement of humidity. The ability of these assemblies to exhibit proton-conducting properties under low-humidity conditions makes these materials highly appealing as electrolytes in batteries and in fuel-cell applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic, electrochemical and photovoltaic properties of Pt(ii) and Pd(ii) complexes of a chelating 1,10-phenanthroline appended perylene diimide.

PubMed

Işık Büyükekşi, Sebile; Şengül, Abdurrahman; Erdönmez, Seda; Altındal, Ahmet; Orman, Efe Baturhan; Özkaya, Ali Rıza

2018-02-20

In this study, a bis-chelating bridging perylene diimide ditopic ligand, namely N,N'-di(1,10-phenanthroline)-1,6,7,12-tetrakis-(4-methoxyphenoxy)perylene tetracarboxylic acid diimide (1), was synthesized and characterized. Further reactions of 1 with d 8 metal ions such as Pt(ii) and Pd(ii) having preferential square-planar geometry afforded the novel triads [(Cl 2 )M(ii)-(1)-M(ii)(Cl 2 )] where M(ii) = Pt(ii) (2), and Pd(ii) (3), respectively. The isolated triads and the key precursor were fully characterized by FT-IR, 1D-NMR ( 1 H NMR and 13 C DEPT NMR), 2D-NMR ( 1 H- 1 H COSY, 1 H- 13 C HSQC, 1 H- 13 C HMBC), MALDI-TOF mass and UV/Vis spectroscopy. The electrochemical properties of 1, 2 and 3 were investigated by cyclic voltammetry as well as in situ spectroelectrochemistry and also in situ electrocolorimetric measurements. These compounds were shown to exhibit net colour changes suitable for electrochromic applications. The compounds exhibited remarkably narrow HOMO-LUMO gaps, leading to their ease of reduction at low negative potentials. More importantly, dye-sensitized solar cells (DSSCs) were also fabricated using 1-3 to clarify the potential use of these complexes as a sensitizer. Analysis of the experimental data indicated that 2 has good potential as a sensitizer material for DSSCs.

Mono-component versus binary isotherm models for Cu(II) and Pb(II) sorption from binary metal solution by the green alga Pithophora oedogonia.

PubMed

Kumar, Dhananjay; Singh, Alpana; Gaur, J P

2008-11-01

The sorption of Cu(II) and Pb(II) by Pithophora markedly decreased as the concentration of the secondary metal ion, Cu(II) or Pb(II), increased in the binary metal solution. However, the test alga showed a greater affinity to sorb Cu(II) than Pb(II) from the binary metal solution. Mono-component Freundlich, Langmuir, Redlich-Peterson and Sips isotherms successfully predicted the sorption of Cu(II) and Pb(II) from both single and binary metal solutions. None of the tested binary sorption isotherms could realistically predict Cu(II) and Pb(II) sorption capacity and affinity of the test alga for the binary metal solutions of varying composition, which mono-component isotherms could very well accomplish. Hence, mono-component isotherm modeling at different concentrations of the secondary metal ion seems to be a better option than binary isotherms for metal sorption from binary metal solution.

Rapid Photodegradation of Methyl Orange (MO) Assisted with Cu(II) and Tartaric Acid

PubMed Central

Guo, Jing; Chen, Xue; Shi, Ying; Lan, Yeqing; Qin, Chao

2015-01-01

Cu(II) and organic carboxylic acids, existing extensively in soil and aquatic environments, can form complexes that may play an important role in the photodegradation of organic contaminants. In this paper, the catalytic role of Cu(II) in the removal of methyl orange (MO) in the presence of tartaric acid with light was investigated through batch experiments. The results demonstrate that the introduction of Cu(II) could markedly enhance the photodegradation of MO. In addition, high initial concentrations of Cu(II) and tartaric acid benefited the decomposition of MO. The most rapid removal of MO assisted by Cu(II) was achieved at pH 3. The formation of Cu(II)-tartaric acid complexes was assumed to be the key factor, generating hydroxyl radicals (•OH) and other oxidizing free radicals under irradiation through a ligand-to-metal charge-transfer pathway that was responsible for the efficient degradation of MO. Some intermediates in the reaction system were also detected to support this reaction mechanism. PMID:26241043

A spectroscopic and voltammetric study of the pH-dependent Cu(II) coordination to the peptide GGGTH: relevance to the fifth Cu(II) site in the prion protein.

PubMed

Hureau, Christelle; Charlet, Laurent; Dorlet, Pierre; Gonnet, Florence; Spadini, Lorenzo; Anxolabéhère-Mallart, Elodie; Girerd, Jean-Jacques

2006-09-01

The GGGTH sequence has been proposed to be the minimal sequence involved in the binding of a fifth Cu(II) ion in addition to the octarepeat region of the prion protein (PrP) which binds four Cu(II) ions. Coordination of Cu(II) by the N- and C-protected Ac-GGGTH-NH(2) pentapeptide (P(5)) was investigated by using potentiometric titration, electrospray ionization mass spectrometry, UV-vis spectroscopy, electron paramagnetic resonance (EPR) spectroscopy and cyclic voltammetry experiments. Four different Cu(II) complexes were identified and characterized as a function of pH. The Cu(II) binding mode switches from NO(3) to N(4) for pH values ranging from 6.0 to 10.0. Quasi-reversible reduction of the [Cu(II)(P(5))H(-2)] complex formed at pH 6.7 occurs at E (1/2)=0.04 V versus Ag/AgCl, whereas reversible oxidation of the [Cu(II)(P(5))H(-3)](-) complex formed at pH 10.0 occurs at E (1/2)=0.66 V versus Ag/AgCl. Comparison of our EPR data with those of the rSHaPrP(90-231) (Burns et al. in Biochemistry 42:6794-6803, 2003) strongly suggests an N(3)O binding mode at physiological pH for the fifth Cu(II) site in the protein.

Nanoscale zero-valent iron (nZVI) for the treatment of concentrated Cu(II) wastewater: a field demonstration.

PubMed

Li, Shaolin; Wang, Wei; Yan, Weile; Zhang, Wei-xian

2014-03-01

A field demonstration was conducted to assess the feasibility of nanoscale zero-valent iron (nZVI) for the treatment of wastewater containing high levels of Cu(II). Pilot tests were performed at a printed-circuit-board manufacturing plant, treating 250,000 L of wastewater containing 70 mg L(-1) Cu(II) with a total of 55 kg of nZVI. A completely mixed reactor of 1,600 L was operated continuously with flow rates ranging from 1000 to 2500 L h(-1). The average Cu(II) removal efficiency was greater than 96% with 0.20 g L(-1) nZVI and a hydraulic retention time of 100 min. The nZVI reactor achieved a remarkably high volumetric loading rate of 1876 g Cu per m(3) per day for Cu(II) removal, surpassing the loading rates of conventional technologies by more than one order of magnitude. The average removal capacity of nZVI for Cu(II) was 0.343 g Cu per gram of Fe. The Cu(II) removal efficiency can be reliably regulated by the solution Eh, which in turn is a function of nZVI input and hydraulic retention time. The ease of separation and recycling of nZVI contribute to process up-scalability and cost effectiveness. Cu(II) was reduced to metallic copper and cuprite (Cu2O). The end product is a valuable composite of iron and copper (∼20-25%), which can partially offset the treatment costs.

Conformational heterogeneity in the C-terminal zinc fingers of human MTF-1: an NMR and zinc-binding study.

PubMed

Giedroc, D P; Chen, X; Pennella, M A; LiWang, A C

2001-11-09

The human metalloregulatory transcription factor, metal-response element (MRE)-binding transcription factor-1 (MTF-1), contains six TFIIIA-type Cys(2)-His(2) motifs, each of which was projected to form well-structured betabetaalpha domains upon Zn(II) binding. In this report, the structure and backbone dynamics of a fragment containing the unusual C-terminal fingers F4-F6 has been investigated. (15)N heteronuclear single quantum coherence (HSQC) spectra of uniformly (15)N-labeled hMTF-zf46 show that Zn(II) induces the folding of hMTF-zf46. Analysis of the secondary structure of Zn(3) hMTF-zf46 determined by (13)Calpha chemical shift indexing and the magnitude of (3)J(Halpha-HN) clearly reveal that zinc fingers F4 and F6 adopt typical betabetaalpha structures. An analysis of the heteronuclear backbone (15)N relaxation dynamics behavior is consistent with this picture and further reveals independent tumbling of the finger domains in solution. Titration of apo-MTF-zf46 with Zn(II) reveals that the F4 domain binds Zn(II) significantly more tightly than do the other two finger domains. In contrast to fingers F4 and F6, the betabetaalpha fold of finger F5 is unstable and only partially populated at substoichiometric Zn(II); a slight molar excess of zinc results in severe conformational exchange broadening of all F5 NH cross-peaks. Finally, although Cd(II) binds to apo-hMTF-zf46 as revealed by intense S(-)-->Cd(II) absorption, a non-native structure results; addition of stoichiometric Zn(II) to the Cd(II) complex results in quantitative refolding of the betabetaalpha structure in F4 and F6. The functional implications of these results are discussed.

Structural basis of Zn(II) induced metal detoxification and antibiotic resistance by histidine kinase CzcS in Pseudomonas aeruginosa

PubMed Central

Wang, Dan; Chen, Weizhong; Huang, Shanqing; He, Yafeng; Liu, Xichun; Hu, Qingyuan; Wei, Tianbiao; Sang, Hong; Gan, Jianhua

2017-01-01

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. PMID:28732057

Structural basis of Zn(II) induced metal detoxification and antibiotic resistance by histidine kinase CzcS in Pseudomonas aeruginosa.

PubMed

Wang, Dan; Chen, Weizhong; Huang, Shanqing; He, Yafeng; Liu, Xichun; Hu, Qingyuan; Wei, Tianbiao; Sang, Hong; Gan, Jianhua; Chen, Hao

2017-07-01

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.

The Hexahistidine Motif of Host-Defense Protein Human Calprotectin Contributes to Zinc Withholding and Its Functional Versatility.

PubMed

Nakashige, Toshiki G; Stephan, Jules R; Cunden, Lisa S; Brophy, Megan Brunjes; Wommack, Andrew J; Keegan, Brenna C; Shearer, Jason M; Nolan, Elizabeth M

2016-09-21

Human calprotectin (CP, S100A8/S100A9 oligomer, MRP-8/MRP-14 oligomer) is an abundant host-defense protein that is involved in the metal-withholding innate immune response. CP coordinates a variety of divalent first-row transition metal ions, which is implicated in its antimicrobial function, and its ability to sequester nutrient Zn(II) ions from microbial pathogens has been recognized for over two decades. CP has two distinct transition-metal-binding sites formed at the S100A8/S100A9 dimer interface, including a histidine-rich site composed of S100A8 residues His17 and His27 and S100A9 residues His91 and His95. In this study, we report that CP binds Zn(II) at this site using a hexahistidine motif, completed by His103 and His105 of the S100A9 C-terminal tail and previously identified as the high-affinity Mn(II) and Fe(II) coordination site. Zn(II) binding at this unique site shields the S100A9 C-terminal tail from proteolytic degradation by proteinase K. X-ray absorption spectroscopy and Zn(II) competition titrations support the formation of a Zn(II)-His6 motif. Microbial growth studies indicate that the hexahistidine motif is important for preventing microbial Zn(II) acquisition from CP by the probiotic Lactobacillus plantarum and the opportunistic human pathogen Candida albicans. The Zn(II)-His6 site of CP expands the known biological coordination chemistry of Zn(II) and provides new insight into how the human innate immune system starves microbes of essential metal nutrients.

Synthesis, characterization, crystal structure, DNA- and HSA-binding studies of a dinuclear Schiff base Zn(II) complex derived from 2-hydroxynaphtaldehyde and 2-picolylamine

NASA Astrophysics Data System (ADS)

Kazemi, Zahra; Rudbari, Hadi Amiri; Mirkhani, Valiollah; Sahihi, Mehdi; Moghadam, Majid; Tangestaninejad, Sharam; Mohammadpoor-Baltork, Iraj

2015-09-01

A tridentate Schiff base ligand NNO donor (HL: 1-((E)-((pyridin-2-yl)methylimino)methyl)naphthalen-2-ol was synthesized from condensation of 2-hydroxynaphtaldehyde and 2-picolylamine. Zinc complex, Zn2L2(NO3)2, was prepared from reaction of Zn(NO3)2 and HL at ambient temperature. The ligand and complex were characterized by FT-IR, 1H NMR, 13C NMR and elemental analysis (CHN). Furthermore, the structure of dinuclear Zn(II) complex was determined by single crystal X-ray analysis. The complex, Zn2L2(NO3)2, is centrosymmetric dimer in which deprotonated phenolates bridge the two Zn(II) atoms and link the two halves of the dimer. In the structure, Zinc(II) ions have a highly distorted six-coordinate structure bonded to two oxygen atoms from a bidentate nitrate group, the pyridine nitrogen, an amine nitrogen and phenolate oxygens. The interaction of dinuclear Zn(II) complex with fish sperm DNA (FS-DNA) and HSA was investigated under physiological conditions using fluorescence quenching, UV-Vis spectroscopy, molecular dynamics simulation and molecular docking methods. The estimated binding constants for the DNA-complex and HSA-complex were (3.60 ± 0.18) × 104 M-1 and (1.35 ± 0.24) × 104 M-1, respectively. The distance between dinuclear Zn(II) complex and HSA was obtained based on the Förster's theory of non-radiative energy transfer. Molecular docking studies revealed the binding of dinuclear Zn(II) complex to the major groove of FS-DNA and IIA site of protein by formation of hydrogen bond, π-cation and hydrophobic interactions.

Sorption kinetics of zinc and nickel on modified chitosan.

PubMed

Tripathi, Nimisha; Choppala, Girish; Singh, Raj S; Srivastava, Prashant; Seshadri, Balaji

2016-09-01

This study was conducted to evaluate the effect of equilibration time on adsorption of zinc [Zn(II)] and nickel [Ni(II)] on pure and modified chitosan beads. The initial adsorption of Zn(II) was high on molybdenum (Mo)-impregnated chitosan beads (MoCB) during the initial 60 min. However, after 240 min, Zn(II) adsorption occurred more on single super phosphate chitosan beads (SSPCB), followed by monocalcium phosphate chitosan beads (MCPCB), untreated pure chitosan beads (UCB), and MoCB. Similarly, Ni(II) adsorption was greatest on MoCB during the initial 60 min. At the conclusion of the experiment (at 240 min), the greatest adsorption was occurred on MCPCB, followed by MoCB, UCB, and SSPCB. Chemical sorption and intra-particle diffusion were probably the dominant processes responsible for Zn(II) and Ni(II) sorption onto chitosan beads. The results demonstrated that modified chitosan beads were effective in adsorbing Zn and Ni and hence, could be used for the removal of these toxic metals from soil.

Copper(II) adsorption on the kaolinite(001) surface: Insights from first-principles calculations and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Kong, Xiang-Ping; Wang, Juan

2016-12-01

The adsorption behavior of Cu(II) on the basal hydroxylated kaolinite(001) surface in aqueous environment was investigated by first-principles calculations and molecular dynamics simulations. Structures of possible monodentate and bidentate inner-sphere adsorption complexes of Cu(II) were examined, and the charge transfer and bonding mechanism were analyzed. Combining the binding energy of complex, the radial distribution function of Cu(II) with oxygen and the extended X-ray absorption fine structure data, monodentate complex on site of surface oxygen with ;upright; hydrogen and bidentate complex on site of two oxygens (one with ;upright; hydrogen and one with ;lying; hydrogen) of single Al center have been found to be the major adsorption species of Cu(II). Both adsorption species are four-coordinated with a square planar geometry. The distribution of surface hydroxyls with ;lying; hydrogen around Cu(II) plays a key role in the structure and stability of adsorption complex. Upon the Mulliken population analysis and partial density of states, charge transfer occurs with Cu(II) accepting some electrons from both surface oxygens and aqua oxygens, and the bonding Cu 3d-O 2p state filling is primarily responsible for the strong covalent interaction of Cu(II) with surface oxygen.

Immobilization of heavy metals in electroplating sludge by biochar and iron sulfide.

PubMed

Lyu, Honghong; Gong, Yanyan; Tang, Jingcshun; Huang, Yao; Wang, Qilin

2016-07-01

Electroplating sludge (ES) containing large quantities of heavy metals is regarded as a hazardous waste in China. This paper introduced a simple method of treating ES using environmentally friendly fixatives biochar (BC) and iron sulfide (FeS), respectively. After 3 days of treatment with FeS at a FeS-to-ES mass ratio of 1:5, the toxicity characteristic leaching procedure (TCLP)-based leachability of total Cr (TCr), Cu(II), Ni(II), Pb(II), and Zn(II) was decreased by 59.6, 100, 63.8, 73.5, and 90.5 %, respectively. After 5 days of treatment with BC at a BC-to-ES mass ratio of 1:2, the TCLP-based leachability was declined by 35.1, 30.6, 22.3, 23.1, and 22.4 %, respectively. Pseudo first-order kinetic model adequately simulated the sorption kinetic data. Structure and morphology analysis showed that adsorption, electrostatic attraction, surface complexation, and chemical precipitation were dominant mechanisms for heavy metals immobilization by BC, and that chemical precipitation (formation of metal sulfide and hydroxide precipitates), iron exchange (formation of CuFeS2), and surface complexation were mainly responsible for heavy metals removal by FeS. Economic costs of BC and FeS were 500 and 768 CNY/t, lower than that of Na2S (940 CNY/t). The results suggest that BC and FeS are effective, economic, and environmentally friendly fixatives for immobilization of heavy metals in ES before landfill disposal.

The use of dialdehyde starch derivatives in the phytoremediation of soils contaminated with heavy metals.

PubMed

Antonkiewicz, Jacek; Para, Andrzej

2016-01-01

Products of the reaction between dialdehyde starch and Y-NH2 compounds (e.g. semicarbazide or hydrazine) are effective ligands for metal ions. The usefulness of these derivatives was tested in the experiment, both in terms of the immobilization of heavy metal ions in soil and the potential application in phytoextraction processes. The experimental model comprised maize and the ions of such metals as: Zn(II), Pb(II), Cu(II), Cd(II), and Ni(II). The amount of maize yield, as well as heavy metal content and uptake by the aboveground parts and roots of maize, were studied during a three-year pot experiment. The results of the study indicate the significant impact of heavy metals on reduced yield and increased heavy metal content in maize. Soil-applied dialdehyde starch derivatives resulted in lower yields, particularly disemicarbazone (DASS), but in heavy metal-contaminated soils they largely limited the negative impact of these metals both on yielding and heavy metal content in plants, particularly dihydrazone (DASH). It was demonstrated that the application of dihydrazone (DASH) to a soil polluted with heavy metals boosted the uptake of Zn, Pb, Cu, and Cd from the soil, hence there is a possibility to use this compound in the phytoextraction of these metals from the soil. Decreased Ni uptake was also determined, hence the possibility of using this compound in the immobilization of this metal. The study showed that dialdehyde starch disemicarbazone was ineffective in the discussed processes.

Sub-inhibitory concentrations of heavy metals facilitate the horizontal transfer of plasmid-mediated antibiotic resistance genes in water environment.

PubMed

Zhang, Ye; Gu, April Z; Cen, Tianyu; Li, Xiangyang; He, Miao; Li, Dan; Chen, Jianmin

2018-06-01

Although widespread antibiotic resistance has been mostly attributed to the selective pressure generated by overuse and misuse of antibiotics, recent growing evidence suggests that chemicals other than antibiotics, such as certain metals, can also select and stimulate antibiotic resistance via both co-resistance and cross-resistance mechanisms. For instance, tetL, merE, and oprD genes are resistant to both antibiotics and metals. However, the potential de novo resistance induced by heavy metals at environmentally-relevant low concentrations (much below theminimum inhibitory concentrations [MICs], also referred as sub-inhibitory) has hardly been explored. This study investigated and revealed that heavy metals, namely Cu(II), Ag(I), Cr(VI), and Zn(II), at environmentally-relevant and sub-inhibitory concentrations, promoted conjugative transfer of antibiotic resistance genes (ARGs) between E. coli strains. The mechanisms of this phenomenon were further explored, which involved intracellular reactive oxygen species (ROS) formation, SOS response, increased cell membrane permeability, and altered expression of conjugation-relevant genes. These findings suggest that sub-inhibitory levels of heavy metals that widely present in various environments contribute to the resistance phenomena via facilitating horizontal transfer of ARGs. This study provides evidence from multiple aspects implicating the ecological effect of low levels of heavy metals on antibiotic resistance dissemination and highlights the urgency of strengthening efficacious policy and technology to control metal pollutants in the environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Using ICP-OES and SEM-EDX in biosorption studies

PubMed Central

Chojnacka, Katarzyna; Marycz, Krzysztof

2010-01-01

We have compared the analytical results obtained by inductively coupled plasma optical emission spectroscopy (ICP-OES) and by scanning electron microscopy with an energy dispersive X-ray analytical system (SEM-EDX) in order to explore the mechanism of metal ions biosorption by biomass using two independent methods. The marine macroalga Enteromorpha sp. was enriched with Cu(II), Mn(II), Zn(II), and Co(II) ions via biosorption, and the biosorption capacity of alga determined from the solution and biomass composition before and after biosorption process was compared. The first technique was used to analyze the composition of the natural and metal-loaded biomass, and additionally the composition of the solution before and after biosorption. The second technique was used to obtain a picture of the surface of natural and metal ion-loaded macroalgae, to map the elements on the cell wall of dry biomass, and to determine their concentration before and after biosorption. ICP-OES showed a better precision and lower detection limit than EDX, but SEM-EDX gave more information regarding the sample composition of Enteromorpha sp. Both techniques confirmed that biosorption is a surface phenomenon, in which alkali and alkaline earth metal ions were exchanged by metal ions from aqueous solution. Figure The advantages and disadvantages of ICP-OES and SEM-EDX techniques Electronic supplementary material The online version of this article (doi:10.1007/s00604-010-0468-0) contains supplementary material, which is available to authorized users. PMID:21423317

Using ICP-OES and SEM-EDX in biosorption studies.

PubMed

Michalak, Izabela; Chojnacka, Katarzyna; Marycz, Krzysztof

2011-02-01

We have compared the analytical results obtained by inductively coupled plasma optical emission spectroscopy (ICP-OES) and by scanning electron microscopy with an energy dispersive X-ray analytical system (SEM-EDX) in order to explore the mechanism of metal ions biosorption by biomass using two independent methods. The marine macroalga Enteromorpha sp. was enriched with Cu(II), Mn(II), Zn(II), and Co(II) ions via biosorption, and the biosorption capacity of alga determined from the solution and biomass composition before and after biosorption process was compared. The first technique was used to analyze the composition of the natural and metal-loaded biomass, and additionally the composition of the solution before and after biosorption. The second technique was used to obtain a picture of the surface of natural and metal ion-loaded macroalgae, to map the elements on the cell wall of dry biomass, and to determine their concentration before and after biosorption. ICP-OES showed a better precision and lower detection limit than EDX, but SEM-EDX gave more information regarding the sample composition of Enteromorpha sp. Both techniques confirmed that biosorption is a surface phenomenon, in which alkali and alkaline earth metal ions were exchanged by metal ions from aqueous solution.FigureThe advantages and disadvantages of ICP-OES and SEM-EDX techniques ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00604-010-0468-0) contains supplementary material, which is available to authorized users.

Studies on DNA binding behaviour of biologically active transition metal complexes of new tetradentate N2O2 donor Schiff bases: inhibitory activity against bacteria.

PubMed

Sobha, S; Mahalakshmi, R; Raman, N

2012-06-15

A series of Cu(II), Ni(II) and Zn(II) complexes of the type ML have been synthesized with Schiff bases derived from o-acetoacetotoluidide, 2-hydroxybenzaldehyde and o-phenylenediamine/1,4-diaminobutane. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the six metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff bases are found to act as tetradentate ligands using N(2)O(2) donor set of atoms leading to a square-planar geometry for the complexes around all the metal ions. The binding properties of metal complexes with DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. Detailed analysis reveals that the metal complexes intercalate into the DNA base stack as intercalators. All the metal complexes cleave the pUC19 DNA in presence of H(2)O(2.) The Schiff bases and their complexes have been screened for their antibacterial activity against five bacterial strains (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae) by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligands. Copyright © 2012 Elsevier B.V. All rights reserved.

Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd( ii ) and Pb( ii ) sorption by δ-MnO 2 and ferrihydrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Genuchten, Case M.; Peña, Jasquelin

2016-01-01

Birnessite minerals (layer-type MnO2), which bear both internal (cation vacancies) and external (particle edges) metal sorption sites, are important sinks of contaminants in soils and sediments. Although the particle edges of birnessite minerals often dominate the total reactive surface area, especially in the case of nanoscale crystallites, the metal sorption reactivity of birnessite particle edges remains elusive. In this study, we investigated the sorption selectivity of birnessite particle edges by combining Cd(II) and Pb(II) adsorption isotherms at pH 5.5 with surface structural characterization by differential pair distribution function (d-PDF) analysis. We compared the sorption reactivity of δ-MnO2 to that ofmore » the nanomineral, 2-line ferrihydrite, which exhibits only external surface sites. Our results show that, whereas Cd(II) and Pb(II) both bind to birnessite layer vacancies, only Pb(II) binds extensively to birnessite particle edges. For ferrihydrite, significant Pb(II) adsorption to external sites was observed (roughly 20 mol%), whereas Cd(II) sorption was negligible. These results are supported by bond valence calculations that show comparable degrees of saturation of oxygen atoms on birnessite and ferrihydrite particle edges. Therefore, we propose that the sorption selectivity of birnessite edges follows the same order of that reported previously for ferrihydrite: Ca(II) < Cd(II) < Ni(II) < Zn(II) < Cu(II) < Pb(II).« less

Analysis of transition-metal acetylacetonate complexes by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Wyatt, Mark F; Havard, Stephen; Stein, Bridget K; Brenton, A Gareth

2008-01-01

Transition-metal acetylacetonate complexes of the form Metal(acac)(2), where Metal = Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), and Metal(acac)(3), where Metal = V(III), Cr(III), Mn(III), Fe(III), and Co(III), were investigated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). The data was acquired using the aprotic, electron transfer matrix, 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile (DCTB), and the observation of positive radical ions is shown clearly to depend on the metal element and the oxidation state it occupies. The ionization energy of DCTB was calculated to be 8.08 eV by density functional theory methods, which is notably lower than the experimental value, but within the range of other computational values. This value is very close to those of the analytes, so the existing electron transfer mechanism which is based on the ionization energies of the matrix and analyte, cannot be used predictively. Similarly, the data neither proves nor disproves the validity of the existing electron transfer ionization mechanism, with respect to metal coordination complexes without strong chromophores. In this case, periodic trends may be more useful in explaining the observed species and the prediction of species from sets of similar complexes. The addition of a sodium salt benefits the MALDI-TOFMS characterization of certain compounds studied, but the benefit of the addition of ammonium or silver salts is negligible.

Biosorption of Microelements by Spirulina: Towards Technology of Mineral Feed Supplements

PubMed Central

Chojnacka, Katarzyna

2014-01-01

Surface characterization and metal ion adsorption properties of Spirulina sp. and Spirulina maxima were verified by various instrumental techniques. FTIR spectroscopy and potentiometric titration were used for qualitative and quantitative determination of metal ion-binding groups. Comparative FTIR spectra of natural and Cu(II)-treated biomass proved involvement of both phosphoryl and sulfone groups in metal ions sorption. The potentiometric titration data analysis provided the best fit with the model assuming the presence of three types of surface functional groups and the carboxyl group as the major binding site. The mechanism of metal ions biosorption was investigated by comparing the results from multielemental analyses by ICP-OES and SEM-EDX. Biosorption of Cu(II), Mn(II), Zn(II), and Co(II) ions by lyophilized Spirulina sp. was performed to determine the metal affinity relationships for single- and multicomponent systems. Obtained results showed the replacement of naturally bound ions: Na(I), K(I), or Ca(II) with sorbed metal ions in a descending order of Mn(II) > Cu(II) > Zn(II) > Co(II) for single- and Cu(II) > Mn(II) > Co(II) > Zn(II) for multicomponent systems, respectively. Surface elemental composition of natural and metal-loaded material was determined both by ICP-OES and SEM-EDX analysis, showing relatively high value of correlation coefficient between the concentration of Na(I) ions in algal biomass. PMID:25386594

Functional and Expression Analysis of the Metal-Inducible dmeRF System from Rhizobium leguminosarum bv. viciae

PubMed Central

Rubio-Sanz, L.; Prieto, R. I.; Imperial, J.; Brito, B.

2013-01-01

A gene encoding a homolog to the cation diffusion facilitator protein DmeF from Cupriavidus metallidurans has been identified in the genome of Rhizobium leguminosarum UPM791. The R. leguminosarum dmeF gene is located downstream of an open reading frame (designated dmeR) encoding a protein homologous to the nickel- and cobalt-responsive transcriptional regulator RcnR from Escherichia coli. Analysis of gene expression showed that the R. leguminosarum dmeRF genes are organized as a transcriptional unit whose expression is strongly induced by nickel and cobalt ions, likely by alleviating the repressor activity of DmeR on dmeRF transcription. An R. leguminosarum dmeRF mutant strain displayed increased sensitivity to Co(II) and Ni(II), whereas no alterations of its resistance to Cd(II), Cu(II), or Zn(II) were observed. A decrease of symbiotic performance was observed when pea plants inoculated with an R. leguminosarum dmeRF deletion mutant strain were grown in the presence of high concentrations of nickel and cobalt. The same mutant induced significantly lower activity levels of NiFe hydrogenase in microaerobic cultures. These results indicate that the R. leguminosarum DmeRF system is a metal-responsive efflux mechanism acting as a key element for metal homeostasis in R. leguminosarum under free-living and symbiotic conditions. The presence of similar dmeRF gene clusters in other Rhizobiaceae suggests that the dmeRF system is a conserved mechanism for metal tolerance in legume endosymbiotic bacteria. PMID:23934501

Carbonic anhydrase inhibitors. A general approach for the preparation of water-soluble sulfonamides incorporating polyamino-polycarboxylate tails and of their metal complexes possessing long-lasting, topical intraocular pressure-lowering properties.

PubMed

Scozzafava, Andrea; Menabuoni, Luca; Mincione, Francesco; Supuran, Claudiu T

2002-03-28

Reaction of polyamino-polycarboxylic acids or their dianhydrides with aromatic/heterocyclic sulfonamides possessing a free amino/imino/hydrazino/hydroxy group afforded mono- and bis-sulfonamides containing polyamino-polycarboxylic acid moieties in their molecule. The acids/anhydrides used in synthesis included IDA, NTA, EDDA, EDTA and EDTA dianhydride, DTPA and DTPA dianhydride, EGTA and EGTA dianhydride, and EDDHA, among others. All the newly prepared derivatives showed strong affinity toward isozymes I, II, and IV of carbonic anhydrase (CA). Metal complexes of the new compounds have also been prepared. Metal ions used in such preparations included di- and trivalent main-group and transition cations, such as Zn(II), Cu(II), Al(III), etc. Some of the new sulfonamides/disulfonamides obtained in this way, as well as their metal complexes, behaved as nanomolar CA inhibitors against isozymes II and IV, being slightly less effective in inhibiting isozyme I. Some of these sulfonamides as well as their metal complexes strongly lowered intraocular pressure (IOP) when applied topically, directly into the normotensive/glaucomatous rabbit eye, as 1-2% water solutions/suspensions. The good water solubility of these sulfonamide CA inhibitors, correlated with the neutral pH of their water solutions used in the ophthalmologic applications and the long duration of action of the IOP-lowering effect, makes them interesting candidates for developing novel types of antiglaucoma drugs devoid of serious topical side effects.

Selective Adsorption of Pb(II) from Aqueous Solution by Triethylenetetramine-Grafted Polyacrylamide/Vermiculite

PubMed Central

Gu, Shiqing; Wang, Lan; Mao, Xinyou; Yang, Liping; Wang, Chuanyi

2018-01-01

Amine groups play significant roles in polymeric composites for heavy metals removal. However, generating a composite with a large number of functional and stable amine groups based on clay is still a challenge. In this work, a new amine-functionalized adsorbent based on acid-activated vermiculite (a-Verm) was prepared by organic modification of silane coupling agent as bridge, followed by in situ polymerization of acrylamide (AM) and further grafting of triethylene tetramine (TETA). The obtained polymeric composite g-PAM/OVerm was characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared (FTIR), thermal analysis (TG/DTG), X-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) analyses, confirming that amine groups were successfully grafted onto the surface of Verm. The efficacy g-PAM/OVerm for removing Pb(II) was tested. The adsorption equilibrium data on g-PAM/OVerm was in good accordance with the Langmuir adsorption isotherms, and the adsorption maximal value of Pb(II) was 219.4 mg·g−1. The adsorption kinetic data fit the pseudo-second-order kinetic model well. Additionally, g-PAM/OVerm has better selectivity for Pb(II) ion in comparison with Zn(II), Cd(II) and Cu(II) ions. The present work shows that g-PAM/OVerm holds great potential for removing Pb(II) from wastewater, and provides a new and efficient method for the removal of heavy metal ions from industrial wastewater. PMID:29597288

Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity

NASA Astrophysics Data System (ADS)

Devi, Jai; Batra, Nisha; Malhotra, Rajesh

2012-11-01

New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL1 and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL2 derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML(1-2)2 have been synthesized, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate ? coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mn < Zn < Cu < Co < Ni. The ligands and their complexes were tested for in vitro antibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu > Mn > Ni > Co > Zn.

Adsorption of As(III), As(V) and Cu(II) on zirconium oxide immobilized alginate beads in aqueous phase.

PubMed

Kwon, Oh-Hun; Kim, Jong-Oh; Cho, Dong-Wan; Kumar, Rahul; Baek, Seung Han; Kurade, Mayur B; Jeon, Byong-Hun

2016-10-01

A composite adsorbent to remove arsenite [As(III)], arsenate [As(V)], and copper [Cu(II)] from aqueous phase was synthesized by immobilizing zirconium oxide on alginate beads (ZOAB). The composition (wt%) of ZOAB (Zr-34.0; O-32.7; C-21.3; Ca-1.0) was confirmed by energy dispersive X-ray (EDX) analysis. Sorption studies were conducted on single and binary sorbate systems, and the effects of contact time, initial adsorbate concentration, and pH on the adsorption performance of ZOAB (pHPZC = 4.3) were monitored. The sorption process for As(III)/As(V) and Cu(II) reached an equilibrium state within 240 h and 24 h, respectively, with maximum sorption capacities of 32.3, 28.5, and 69.9 mg g(-1), respectively. The addition of Cu(II) was favorable for As(V) sorption in contrast to As(III). In the presence of 48.6 mg L(-1) Cu(II), the sorption capacity of As(V) increased from 1.5 to 3.8 mg g(-1) after 240 h. The sorption data for As(III)/As(V) and Cu(II) conformed the Freundlich and Langmuir isotherm models, respectively. The adsorption of As(III), As(V), and Cu(II) followed pseudo second order kinetics. The effect of arsenic species on Cu(II) sorption was insignificant. The results of present study demonstrated that the synthesized sorbent could be useful for the simultaneous removal of both anionic and cationic contaminants from wastewaters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparative absorption spectroscopy involving 4f-4f transitions to explore the kinetics of simultaneous coordination of uracil with Nd(III) and Zn(II) and its associated thermodynamics

NASA Astrophysics Data System (ADS)

Victory Devi, Ch.; Rajmuhon Singh, N.

2011-10-01

The interaction of uracil with Nd(III) has been explored in presence and absence of Zn(II) using the comparative absorption spectroscopy involving the 4f-4f transitions in different solvents. The complexation of uracil with Nd(III) is indicated by the change in intensity of 4f-4f bands expressing in terms of significant change in oscillator strength and Judd-Ofelt parameters. Intensification of this bands became more prominent in presence of Zn(II) suggesting the stimulative effect of Zn(II) towards the complexation of Nd(III) with uracil. Other spectral parameters namely Slator-Condon ( Fk's), nephelauxetic effect ( β), bonding ( b1/2) and percent covalency ( δ) parameters are computed to correlate their simultaneous binding of metal ions with uracil. The sensitivities of the observed 4f-4f transitions towards the minor coordination changes around Nd(III) has been used to monitor the simultaneous coordination of uracil with Nd(III) and Zn(II). The variation of intensities (oscillator strengths and Judd-Ofelt parameters) of 4f-4f bands during the complexation has helped in following the heterobimetallic complexation of uracil. Rate of complexation with respect to hypersensitive transition was evaluated. Energy of activation and thermodynamic parameters for the complexation reaction were also determined.

Ferrate(VI) oxidation of zinc-cyanide complex.

PubMed

Yngard, Ria; Damrongsiri, Seelawut; Osathaphan, Khemarath; Sharma, Virender K

2007-10-01

Zinc-cyanide complexes are found in gold mining effluents and in metal finishing rinse water. The effect of Zn(II) on the oxidation of cyanide by ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was thus investigated by studying the kinetics of the reaction of Fe(VI) with cyanide present in a potassium salt of a zinc cyanide complex (K(2)Zn(CN)(4)) and in a mixture of Zn(II) and cyanide solutions as a function of pH (9.0-11.0). The rate-law for the oxidation of Zn(CN)(4)(2-) by Fe(VI) was found to be -d[Fe(VI)]/dt=k[Fe(VI)][Zn(CN)(4)(2-)](0.5). The rate constant, k, decreased with an increase in pH. The effect of temperature (15-45 degrees C) on the oxidation was studied at pH 9.0, which gave an activation energy of 45.7+/-1.5kJmol(-1). The cyanide oxidation rate decreased in the presence of the Zn(II) ions. However, Zn(II) ions had no effect on the cyanide removal efficiency by Fe(VI) and the stoichiometry of Fe(VI) to cyanide was approximately 1:1; similar to the stoichiometry in absence of Zn(II) ions. The destruction of cyanide by Fe(VI) resulted in cyanate. The experiments on removal of cyanide from rinse water using Fe(VI) demonstrated complete conversion of cyanide to cyanate.

DNA as a Target for Anticancer Phen-Imidazole Pd(II) Complexes.

PubMed

Heydari, Maryam; Moghadam, Mahboube Eslami; Tarlani, AliAkbar; Farhangian, Hossein

2017-05-01

Imidazole ring is a known structure in many natural or synthetic drug molecules and its metal complexes can interact with DNA and do the cleavage. Hence, to study the influence of the structure and size of the ligand on biological behavior of metal complexes, two water-soluble Pd(II) complexes of phen and FIP ligands (where phen is 1,10-phenanthroline and FIP is 2-(Furan-2-yl)-1H-Imidazo[4,5-f][1, 10]phenanthroline) with the formula of [Pd(phen)(FIP)](NO 3 ) 2 and [Pd(FIP) 2 ]Cl 2 , that were activated against chronic myelogenous leukemia cell line, K562, were selected. Also, the interaction of these anticancer Pd(II) complexes with highly polymerized calf thymus DNA was extensively studied by means of electronic absorption, fluorescence, and circular dichroism in Tris-buffer. The results showed that the binding was positive cooperation and [Pd(phen)(FIP)](NO 3 ) 2 (K f  = 127 M -1 G = 1.2) exhibited higher binding constant and number of binding sites than [Pd(FIP) 2 ]Cl 2 (K f  = 13 M -1 G = 1.03) upon binding to DNA. The fluorescence data indicates that quenching effect for [Pd(phen)(FIP)](NO 3 ) 2 (K SV  = 58 mM -1 ) was higher than [Pd(FIP) 2 ]Cl 2 (K SV  = 12 mM -1 ). Also, [Pd(FIP) 2 ]Cl 2 interacts with ethidium bromide-DNA, as non-competitive inhibition, and can bind to DNA via groove binding and [Pd(phen)(FIP)](NO 3 ) 2 can intercalate in DNA. These results were confirmed by circular dichroism spectra. Docking data revealed that longer complexes have higher interaction energy and bind to DNA via groove binding. Graphical Abstract Two anticancer Pd(II) complexes of imidazole derivative have been synthesized and interacted with calf thymus DNA. Modes of binding have been studied by electronic absorption, fluorescence, and CD measurements. [Pd(FIP) 2 ]Cl 2 can bind to DNA via groove binding while intercalation mode of binding is observed for [Pd(phen)(FIP)](NO 3 ) 2 .

The facile synthesis of a chitosan Cu(II) complex by solution plasma process and evaluation of their antioxidant activities.

PubMed

Ma, Fengming; Li, Pu; Zhang, Baiqing; Wang, Zhenyu

2017-10-01

Synthesis of chitosan-Cu(II) complex by solution plasma process (SPP) irradiation was investigated. The effects of the distance between the electrodes, initial Cu(II) concentration, and initial pH on the Cu(II) adsorption capacity were evaluated. The results showed that narrower distance between the electrodes, higher initial Cu(II) concentration and higher initial pH (at pH<6) were favourable for the adsorption capacity of Cu(II). Characterization of the chitosan-Cu(II) complex by ultraviolet-visible (UV-vis), fourier transform infrared (FT-IR) and electron spin resonance (ESR) spectroscopy revealed that the main structure of chitosan was not changed after irradiation. Thermogravimetry (TG) analysis indicated that Cu(II) ions were well incorporated into the chitosan. The antioxidant activity of the chitosan-Cu(II) complex was evaluated by DPPH, ABTS, and reducing power assays. The chitosan-Cu(II) complex exhibited greater antioxidant activity than the original chitosan. Thus, SPP could be used for preparation of chitosan-Cu(II) complexes. Copyright © 2017. Published by Elsevier B.V.

Microcalorimetric and potentiometric titration studies on the adsorption of copper by extracellular polymeric substances (EPS), minerals and their composites.

PubMed

Fang, Linchuan; Huang, Qiaoyun; Wei, Xing; Liang, Wei; Rong, Xinming; Chen, Wenli; Cai, Peng

2010-08-01

Equilibrium adsorption experiments, isothermal titration calorimetry and potentiometric titration techniques were employed to investigate the adsorption of Cu(II) by extracellular polymeric substances (EPS) extracted from Pseudomonas putida X4, minerals (montmorillonite and goethite) and their composites. Compared with predicted values of Cu(II) adsorption on composites, the measured values of Cu(II) on EPS-montmorillonite composite increased, however, those on EPS-goethite composite decreased. Potentiometric titration results also showed that more surface sites were observed on EPS-montmorillonite composite and less reactive sites were found on EPS-goethite composite. The adsorption of Cu(II) on EPS molecules and their composites with minerals was an endothermic reaction, while that on minerals was exothermic. The positive values of enthalpy change (Delta H) and entropy change (DeltaS) for Cu(II) adsorption on EPS and mineral-EPS composites indicated that Cu(II) mainly interacts with carboxyl and phosphoryl groups as inner-sphere complexes on EPS molecules and their composites with minerals. (c) 2010 Elsevier Ltd. All rights reserved.

Cu(II) salen complex with propylene linkage: An efficient catalyst in the formation of Csbnd X bonds (X = N, O, S) and biological investigations

NASA Astrophysics Data System (ADS)

Azam, Mohammad; Dwivedi, Sourabh; Al-Resayes, Saud I.; Adil, S. F.; Islam, Mohammad Shahidul; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Lee, Dong-Ung

2017-02-01

The catalytic property of a mononuclear Cu(II) salen complex in Chan-Lam coupling reaction with phenyl boronic acid at room temperature is reported. The studied complex is found to be potential catalyst in the preparation of carbon-heteroatom bonds with excellent yields. The studied Cu(II) salen complex is monoclinic with cell parameters, a = 9.6807(5) (α 90°), (b = 17.2504(8) (β 112.429 (2), c = 11.1403 (6) (γ = 90°), and has distorted square planar environment around Cu(II) ion. Furthermore, there is no π⋯π interactions in the reported complex due to large distance between the centroid of aromatic rings. In addition, DNA binding study of Cu(II) salen complex by fluorescence and absorption spectroscopy is also reported. Moreover, the reported Cu(II) salen complex exhibits significant anticancer activity against MCF-7 cancer cell lines, and displays potential antimicrobial biofilm activity against P. aeruginosa, suggesting antimicrobial biofilm an important tool for suppression of resistant infections caused by P. aeruginosa.

Alginate-immobilized bentonite clay: adsorption efficacy and reusability for Cu(II) removal from aqueous solution.

PubMed

Tan, Wei Shang; Ting, Adeline Su Yien

2014-05-01

This study evaluated the use of alginate-immobilized bentonite to remove Cu(II) as an alternative to mitigate clogging problems. The adsorption efficacy (under the influence of time, pH and initial Cu(II) concentration) and reusability of immobilized-bentonite (1% w/v bentonite) was tested against plain alginate beads. Results revealed that immobilized bentonite demonstrated significantly higher sorption efficacy compared to plain alginate beads with 114.70 and 94.04 mg Cu(II) adsorbed g(-1) adsorbent, respectively. Both sorbents were comparable in other aspects where sorption equilibrium was achieved within 6 h, with optimum pH between pH 4 and 5 for adsorption, displayed maximum adsorption capacity at initial Cu(II) concentrations of 400 mg l(-1), and demonstrated excellent reusability potential with desorption greater than 90% throughout three consecutive adsorption-desorption cycles. Both sorbents also conformed to Langmuir isotherm and pseudo-second order kinetic model. Immobilized bentonite is therefore recommended for use in water treatments to remove Cu(II) without clogging the system. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effects of copper-oxide nanoparticles, dissolved copper and ultraviolet radiation on copper bioaccumulation, photosynthesis and oxidative stress in the aquatic macrophyte Elodea nuttallii.

PubMed

Regier, Nicole; Cosio, Claudia; von Moos, Nadia; Slaveykova, Vera I

2015-06-01

In this study, the uptake and sub-toxic effects of CuO nanoparticles (CuO-NPs), dissolved Cu(II) alone or in combination with UV radiation on the aquatic macrophyte Elodea nuttallii were studied. Emphasis was on Cu accumulation, growth, photosynthesis and the oxidative stress related enzymes peroxidase (POD) and superoxide dismutase (SOD). The results showed stronger Cu accumulation in plants exposed to 10 mg L(-1) CuO-NPs, corresponding to 1.4-2 mg L(-1) dissolved Cu(II), than to 256 μg L(-1) Cu(II). However, the ratio between the accumulated Cu and dissolved Cu in CuO treatments was lower than in Cu(II) treatments. Additional UV exposure increased accumulation in both treatments, with the effect being stronger for Cu accumulation from CuO-NPs than for dissolved Cu(II). Photosynthetic capacity was strongly reduced by UV treatment, whereas remained unaffected by Cu(II) or CuO-NP treatments. Similarly, the increase of SOD activity was more pronounced in the UV treatments. On the other hand, POD activity enhancement was strongest in the plants exposed to CuO-NPs for 24 h. Expression of the copper transporter COPT1 as revealed by RT-qPCR was inhibited by Cu(II) and CuO-NP treatment, limiting the uptake of excess Cu into the cells. Overall, the combined exposure of E. nuttallii to UV radiation with CuO-NPs or Cu(II) has a higher impact than exposure to CuO-NPs or Cu(II) alone. The results imply that heavy pollution of natural water with CuO-NPs or dissolved Cu might have stronger effects in combination with natural UV irradiation on organisms in situ. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

DOE PAGES

Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; ...

2016-05-30

Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al 2O 3 and α-Fe 2O 3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-hmore » exposure time, Pb(II) binds preferentially to the alpha-Al 2O 3 (1-102) and α-Fe 2O 3 (0001) surfaces at low Pb concentration ([Pb] = 10 –7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10 –6 to 10 –4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10 –7 to 10 –4 M). In comparison, the α-Al 2O 3 (0001) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al 2O 3 (0001) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al 2O 3 (1-102) and α-Fe 2O 3 (0001). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al 2O 3 (1-102) and α-Fe 2O 3 (0001) at [Me(II)] of 10 –7 M; at 10 –5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10 –5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb L-III-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be complexed by carboxyl groups in S. oneidensis biofilms after 3-h exposure at pH 6.0 and [Me(II)] = 10 –5 M. In contrast with Burkholderia cepacia, which was used in our previous studies of monolayer biofilm-coated metal-oxide surfaces (Templeton et al., 2001), S. oneidensis MR-1 forms relatively thick biofilm coatings (6-20 μm) that are rich in reactive functional groups and are expected to dominate metal-ion adsorption. Lastly, our results show that even thick and highly reactive biofilms like S. oneidensis do not cause much change in the intrinsic chemical reactivities of the underlying metal-oxide surfaces with respect to aqueous Pb(II) and Zn(II) and don't block reactive sites on the metal-oxide surfaces; instead they reduce the rate of Pb(II) and Zn(II) sorption onto these surfaces.« less

Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

NASA Astrophysics Data System (ADS)

Wang, Yingge; Gélabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Gescher, Johannes; Ona-Nguema, Georges; Eng, Peter J.; Bargar, John R.; Farges, Francois; Spormann, Alfred M.; Brown, Gordon E.

2016-09-01

Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al2O3 and α-Fe2O3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-h exposure time, Pb(II) binds preferentially to the α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) surfaces at low Pb concentration ([Pb] = 10-7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10-6 to 10-4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10-7 to 10-4 M). In comparison, the α-Al2O3 (0 0 0 1) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al2O3 (0 0 0 1) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) at [Me(II)] of 10-7 M; at 10-5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10-5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb LIII-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be complexed by carboxyl groups in S. oneidensis biofilms after 3-h exposure at pH 6.0 and [Me(II)] = 10-5 M. In contrast with Burkholderia cepacia, which was used in our previous studies of monolayer biofilm-coated metal-oxide surfaces (Templeton et al., 2001), S. oneidensis MR-1 forms relatively thick biofilm coatings (6-20 μm) that are rich in reactive functional groups and are expected to dominate metal-ion adsorption. Our results show that even thick and highly reactive biofilms like S. oneidensis do not cause much change in the intrinsic chemical reactivities of the underlying metal-oxide surfaces with respect to aqueous Pb(II) and Zn(II) and don't block reactive sites on the metal-oxide surfaces; instead they reduce the rate of Pb(II) and Zn(II) sorption onto these surfaces.

Selective Iron(III) ion uptake using CuO-TiO2 nanostructure by inductively coupled plasma-optical emission spectrometry

PubMed Central

2012-01-01

Background CuO-TiO2 nanosheets (NSs), a kind of nanomaterials is one of the most attracting class of transition doped semiconductor materials due to its interesting and important optical, electrical, and structural properties and has many technical applications, such as in metal ions detection, photocatalysis, Chemi-sensors, bio-sensors, solar cells and so on. In this paper the synthesis of CuO-TiO2 nanosheets by the wet-chemically technique is reported. Methods CuO-TiO2 NSs were prepared by a wet-chemical process using reducing agents in alkaline medium and characterized by UV/vis., FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), and field-emission scanning electron microscopy (FE-SEM) etc. Results The structural and optical evaluation of synthesized NSs were measured by XRD pattern, Fourier transform infrared (FT-IR) and UV–vis spectroscopy, respectively which confirmed that the obtained NSs are well-crystalline CuO-TiO2 and possessing good optical properties. The morphological analysis of CuO-TiO2 NSs was executed by FE-SEM, which confirmed that the doped products were sheet-shaped and growth in large quantity. Here, the analytical efficiency of the NSs was applied for a selective adsorption of iron(III) ion prior to detection by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of NSs towards various metal ions, including Au(III), Cd(II), Co(II), Cr(III), Fe(III), Pd(II), and Zn(II) was analyzed. Conclusions Based on the selectivity study, it was confirmed that the selectivity of doped NSs phase was the most towards Fe(III) ion. The static adsorption capacity for Fe(III) was calculated to be 110.06 mgg−1. Results from adsorption isotherm also verified that the adsorption process was mainly monolayer-adsorption onto a surface containing a finite number of CuO-TiO2 NSs adsorption sites. PMID:23244218

Continuous flow operation with appropriately adjusting composites in influent for recovery of Cr(VI), Cu(II) and Cd(II) in self-driven MFC-MEC system.

PubMed

Li, Ming; Pan, Yuzhen; Huang, Liping; Zhang, Yong; Yang, Jinhui

2017-03-01

A self-driven microbial fuel cell (MFC) - microbial electrolysis cell (MEC) system, where electricity generated from MFCs is in situ utilized for powering MECs, has been previously reported for recovering Cr(VI), Cu(II) and Cd(II) with individual metals fed in different units of the system in batch operation. Here it was advanced with treating synthetic mixed metals' solution at appropriately adjusting composites in fed-batch and continuous flow operations for complete separation of Cr(VI), Cu(II) and Cd(II) from each other. Under an optimal condition of hydraulic residence time of 4 h, matching of two serially connected MFCs with one MEC, and fed with a composite of either 5 mg L -1 Cr(VI), 1 mg L -1 Cu(II) and 5 mg L -1 Cd(II), or 1 mg L -1 Cr(VI), 5 mg L -1 Cu(II) and 5 mg L -1 Cd(II), the self-driven MFC-MEC system can completely and sequentially recover Cu(II), Cr(VI) and Cd(II) from mixed metals. This study provides a true sustainable and zero-energy-consumed approach of using bioelectrochemical systems for completely recovering and separating Cr(VI), Cu(II) and Cd(II) from each other or from wastes or contaminated sites.

Mononuclear Copper Complex Catalyzed Four-Electron Reduction of Oxygen

PubMed Central

Fukuzumi, Shunichi; Kotani, Hiroaki; Lucas, Heather R.; Doi, Kaoru; Suenobu, Tomoyoshi; Peterson, Ryan L.; Karlin, Kenneth D.

2010-01-01

A mononuclear CuII complex acts as an efficient catalyst for four-electron reduction of O2 to H2O by a ferrocene derivative via formation of the dinuclear CuII peroxo complex that is further reduced in the presence of protons by a ferrocene derivative to regenerate the CuII complex. PMID:20443560

Sugar-Annulated Oxazoline Ligands: A Novel Pd(II) Complex and Its Application in Allylic Substitution.

PubMed

Kraft, Jochen; Mill, Katharina; Ziegler, Thomas

2016-12-10

Two novel carbohydrate-derived pyridyl (PYOX)- and cyclopropyl (CYBOX)-substituted oxazoline ligands were prepared from d-glucosamine hydrochloride and 1,3,4,6-tetra- O -acetyl-2-amino-2-deoxy-β-d-glucopyranose hydrochloride in two steps, respectively. The sugar-annulated PYOX ligand formed a stable metal complex with Pd(II), which was fully characterized by NMR spectroscopy and X-ray crystallography. NMR and X-ray analysis revealed a change of the conformation in the sugar moiety upon complexation with the palladium(II) species. Both glycosylated ligands resulted in high asymmetric induction (up to 98% ee ) upon application as chiral ligands in the Pd-catalyzed allylic alkylation of rac -1,3-diphenylallyl acetate with dimethyl malonate (Tsuji-Trost reaction). Both ligands provided mainly the ( R )-enantiomer of the alkylation product.

Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphyhaline

NASA Astrophysics Data System (ADS)

Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

2015-02-01

Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, 1H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ).

Synthesis, characterization, antimicrobial activity and carbonic anhydrase enzyme inhibitor effects of salicilaldehyde-N-methyl p-toluenesulfonylhydrazone and its Palladium(II), Cobalt(II) complexes

NASA Astrophysics Data System (ADS)

Alyar, Saliha; Adem, Şevki

2014-10-01

We report the synthesis of the ligand, salicilaldehyde-N-methyl p-toluenesulfonylhydrazone (salptsmh) derived from p-toluenesulfonicacid-1-methylhydrazide (ptsmh) and its Pd(II) and Co(II) metal complexes were synthesized for the first time. The structure of the ligand and their complexes were investigated using elemental analysis, magnetic susceptibility, molar conductance and spectral (IR, NMR and LC-MS) measurements. Salptsmh has also been characterized by single crystal X-ray diffraction. 1H and 13C shielding tensors for crystal structure were calculated with GIAO/DFT/B3LYP/6-311++G(d,p) methods in CDCl3. The complexes were found to have general composition [ML2]. The results of elemental analysis showed 1:2 (metal/ligand) stoichiometry for all the complex. Magnetic and spectral data indicate a square planar geometry for Pd(II) complex and a distorted tetrahedral geometry for Co(II) complexes. The ligand and its metal chelates have been screened for their antimicrobial activities using the disk diffusion method against the selected Gram positive bacteria: Bacillus subtilis, Bacillus cereus, Staphylococcus aureus, Enterococcus faecalis, Gram negative bacteria: Eschericha coli, Pseudomonas aeruginosa, Klebsiella pneumonia. The inhibition activities of these compounds on carbonic anhydrase II (CA II) and carbonic anhydrase I (CA I) have been investigated by comparing IC50 and Ki values and it has been found that Pd(II) complex have more enzyme inhibition efficiency than salptsmh and Co(II) complex.

Silica functionalized Cu(II) acetylacetonate Schiff base complex: An efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines

NASA Astrophysics Data System (ADS)

Anbarasu, G.; Malathy, M.; Karthikeyan, P.; Rajavel, R.

2017-09-01

Silica functionalized Cu(II) acetylacetonate Schiff base complex via the one pot reaction of silica functionalized 3-aminopropyltriethoxysilane with acetyl acetone and copper acetate has been reported. The synthesized material was well characterized by analytical techniques such as FT-IR, UV-DRS, XRD, SEM-EDX, HR-TEM, EPR, ICP-AES and BET analysis. The characterization results confirmed the grafting of Cu(II) Schiff base complex on the silica surface. The catalytic activity of synthesized silica functionalized Cu(II) acetylacetonate Schiff base complex was evaluated through the oxidative condensation reaction of benzyl alcohol to imine.

Hydrogen peroxide and dioxygen activation by dinuclear copper complexes in aqueous solution: hydroxyl radical production initiated by internal electron transfer.

PubMed

Zhu, Qing; Lian, Yuxiang; Thyagarajan, Sunita; Rokita, Steven E; Karlin, Kenneth D; Blough, Neil V

2008-05-21

Dinuclear Cu(II) complexes, CuII2Nn (n = 4 or 5), were recently found to specifically cleave DNA in the presence of a reducing thiol and O2 or in the presence of H2O2 alone. However, CuII2N3 and a closely related mononuclear Cu(II) complex exhibited no selective reaction under either condition. Spectroscopic studies indicate an intermediate is generated from CuII2Nn (n = 4 or 5) and mononuclear Cu(II) solutions in the presence of H2O2 or from CuI2Nn (n = 4 or 5) in the presence of O2. This intermediate decays to generate OH radicals and ligand degradation products at room temperature. The lack of reactivity of the intermediate with a series of added electron donors suggests the intermediate discharges through a rate-limiting intramolecular electron transfer from the ligand to the metal peroxo center to produce an OH radical and a ligand-based radical. These results imply that DNA cleavage does not result from direct reaction with a metal-peroxo intermediate but instead arises from reaction with either OH radicals or ligand-based radicals.

Salicylyl Fluorene Derivatives as Fluorescent Sensors for Cu(II) Ions.

PubMed

Khaokeaw, Chenwit; Sukwattanasinitt, Mongkol; Rashatasakhon, Paitoon

2016-03-01

Two derivatives of fluorene containing salicylic acid groups are successfully synthesized by palladium-catalyzed coupling reactions and subsequent hydrolysis of salicylate esters. The compounds are characterized by various spectroscopic methods. In phosphate buffer (pH 8.0) solutions, these compounds are well soluble. They show maximum absorption wavelengths in the range of 304-330 nm and exhibit maximum emission wavelength around 420 and 430 nm with the quantum yields of 2.7 and 4.4 %, respectively. The compound with alkynyl salicylate groups (2) exhibits a selective fluorescence quenching towards Cu(II) and Fe(II) with a relatively similar sensitivity. The selectivity favoring Cu(II) over Fe(II) and other metal ions can be achieved upon the addition of 30 μM Triton X-100. The Cu(II) detection limit in solution phase is 1.47 ppb. The fluorescence signal recovery upon the addition of EDTA indicate a reversible complexation between 2 and Cu(II) ion. Fabrication of 2 on filter paper using a 50 μM solution in THF affords a naked-eye detection for Cu(II) and Fe(II) in aqueous media at picomole level.

Novel Zn(II) complexes of 1,3-diphenyl-4-(arylazo)pyrazol-5-one derivatives: Synthesis, spectroscopic properties, DFT calculations and first order nonlinear optical properties

NASA Astrophysics Data System (ADS)

Abdel-Latif, Samir A.; Mohamed, Adel A.

2018-03-01

Eight novel Zn(II) complexes with substituted 1,3-diphenyl-4-(arylazo)pyrazol-5-one (L1-L4) derivatives have been synthesized and elucidated using various physicochemical techniques. Quantum mechanical calculations of energies, geometries were done by DFT using B3LYP/GEN functional combined with 6.311G (d,p) and LAN2DZ basis sets. The analyses of HOMO and LUMO have been used to explain the charge transfer within the ligands and complexes. The calculated small energy gap between HOMO and LUMO energies shows that the charge transfer occurs within Zn(II) complexes. Geometrical parameters, molecular electrostatic potential maps (MEP) and total electron densities analyses of the ligands and their Zn complexes have been carried out. Molecular stability, hyperconjugative interactions, intramolecular charge transfer (ICT) and bond strength has been investigated by the applying of natural bond orbital (NBO) analysis. Total static dipole moment (μ), the mean polarizability (<α>), the anisotropy of the polarizability (Δα), the mean first-order hyperpolarizability (<β>) have been also performed. The obtained values show that Zn(II) complexes is brilliant candidate to NLO materials. The analyses of the 1:1 complexes indicate that the Zn(II) ion is five-coordinated with water molecules at axial position in case of L1, L2 and L4 whereas, six-coordinated with L3 and non-electrolytic behaviour of complexes indicates the absence of counter ion.

Synthesis, spectroscopic, photoluminescence properties and biological evaluation of novel Zn(II) and Al(III) complexes of NOON tetradentate Schiff bases

NASA Astrophysics Data System (ADS)

Abdel Aziz, Ayman A.; Badr, Ibrahim H. A.; El-Sayed, Ibrahim S. A.

2012-11-01

Novel mononuclear Zn(II) and Al(III) complexes were synthesized from the reactions of Zn(OAc)2·2H2O and anhydrous AlCl3 with neutral N2O2 donor tetradentate Schiff bases; N,N'bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H2L1) and N,N'bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H2L2). The new complexes were fully characterized by using micro analyses (CHN), FT-IR, 1H NMR, UV-Vis spectra and thermal analysis. The analytical data have been showed that, the stoichiometry of the complexes is 1:1. Spectroscopic data suggested tetrahedral and square pyramidal geometries for Zn(II) and Al(III) complexes, respectively. The synthesized Zn(II), and Al(III) complexes exhibited intense fluorescence emission in the visible region upon UV-excitation in methylene chloride solution at ambient temperature. This high fluorescence emission was assigned to the strong coordination of the ligands to the small and the highly charged Zn(II) and Al(III) ions. Such strong coordination seems to extend the π-conjugation of the complexes. Thermal analysis measurements indicated that the complexes have good thermal stability. As a potential application the biological activity (e.g., antimicrobial action) of the prepared ligands and complexes was assessed by in-vitro testing of their effect on the growth of various strains of bacteria and fungi.

Synthesis, spectroscopic, photoluminescence properties and biological evaluation of novel Zn(II) and Al(III) complexes of NOON tetradentate Schiff bases.

PubMed

Abdel Aziz, Ayman A; Badr, Ibrahim H A; El-Sayed, Ibrahim S A

2012-11-01

Novel mononuclear Zn(II) and Al(III) complexes were synthesized from the reactions of Zn(OAc)(2).2H(2)O and anhydrous AlCl(3) with neutral N2O2 donor tetradentate Schiff bases; N,N'bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H(2)L(1)) and N,N'bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H(2)L(2)). The new complexes were fully characterized by using micro analyses (CHN), FT-IR, (1)H NMR, UV-Vis spectra and thermal analysis. The analytical data have been showed that, the stoichiometry of the complexes is 1:1. Spectroscopic data suggested tetrahedral and square pyramidal geometries for Zn(II) and Al(III) complexes, respectively. The synthesized Zn(II), and Al(III) complexes exhibited intense fluorescence emission in the visible region upon UV-excitation in methylene chloride solution at ambient temperature. This high fluorescence emission was assigned to the strong coordination of the ligands to the small and the highly charged Zn(II) and Al(III) ions. Such strong coordination seems to extend the π-conjugation of the complexes. Thermal analysis measurements indicated that the complexes have good thermal stability. As a potential application the biological activity (e.g., antimicrobial action) of the prepared ligands and complexes was assessed by in-vitro testing of their effect on the growth of various strains of bacteria and fungi. Copyright © 2012 Elsevier B.V. All rights reserved.

Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

PubMed

Ren, Xuemei; Yang, Shitong; Tan, Xiaoli; Chen, Changlun; Sheng, Guodong; Wang, Xiangke

2012-10-30

The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments. Copyright © 2012 Elsevier B.V. All rights reserved.

Adsorption of Cu(II) Ions in Aqueous Solutions by HCl Activated Carbon of Oil Palm

NASA Astrophysics Data System (ADS)

Muslim, A.; Syamsuddin, Y.; Salamun, A.; Abubakar; Ramadhan, D.; Peiono, D.

2017-06-01

Activated carbon was prepared from oil palm empty fruit bunch (OPEFB) by pyrolysis at 873.15 K in a furnace and chemical activation using 0.01 M HCl. Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy and BET (Brunauer, Emmett and Teller) surface area analyses were taken into account to investigate the chemical functional group, to characterise the surface morphology and to determine total surface area the OPEFB AC, respectively. Experiments in batch mode were conducted to investigate Cu(II) adsorption capacity by the OPEFB AC whereas the system consisted of 1 g the OPEFB AC in 100 mL Cu(II) aqueous solution with initial concentration in the range of 10-70 mg/L, magnetic stirring at 75 rpm, room temperature of 300.15 K (± 2 K), at 1 atm and neutral pH over contact time in the range of 0-150 min. As the result, Cu(II) adsorption capacity increased exponentially over contact time and initial concentration. The Cu(II) adsorption kinetics followed the pseudo second order kinetics with the correlation coefficients (R 2), kinetics rate constant and equilibrium adsorption capacity being 0.98, 4.81 mg/g and 0.15/min, respectively for initial Cu(II) concentration being 58.71 mg/L. In addition, Cu(II) adsorption isotherm followed the Langmuir equation with the R2 value, the mono-layer and over-all adsorption capacity being 0.99, 5.92 mg/g and 0.17 L/mg, respectively.

A saponification-triggered gelation of ester-based Zn(II) complex through conformational transformations.

PubMed

Kumar, Ashish; Dubey, Mrigendra; Kumar, Amit; Pandey, Daya Shankar

2014-09-11

Novel saponification-triggered gelation in an ester-based bis-salen Zn(II) complex (1) is described. Strategic structural modifications induced by NaOH in 1 tune the dipolar-/π-interactions leading to J-aggregation and the creation of an inorganic gel material (IGM), which has been established by photophysical, DFT and rheological studies.

Rational synthesis of an exceptionally stable Zn(II) metal-organic framework for the highly selective and sensitive detection of picric acid.

PubMed

Hu, Yingli; Ding, Meili; Liu, Xiao-Qin; Sun, Lin-Bing; Jiang, Hai-Long

2016-04-28

Based on an organic ligand involving both carboxylate and tetrazole groups, a chemically stable Zn(II) metal-organic framework has been rationally synthesized and behaves as a fluorescence chemosensor for the highly selective and sensitive detection of picric acid, an extremely hazardous and strong explosive.

Carbon–hydrogen (C–H) bond activation at PdIV: a Frontier in C–H functionalization catalysis

PubMed Central

Topczewski, Joseph J.

2015-01-01

The direct functionalization of carbon–hydrogen (C–H) bonds has emerged as a versatile strategy for the synthesis and derivatization of organic molecules. Among the methods for C–H bond activation, catalytic processes that utilize a PdII/PdIV redox cycle are increasingly common. The C–H activation step in most of these catalytic cycles is thought to occur at a PdII centre. However, a number of recent reports have suggested the feasibility of C–H cleavage occurring at PdIV complexes. Importantly, these latter processes often result in complementary reactivity and selectivity relative to analogous transformations at PdII. This mini review highlights proposed examples of C–H activation at PdIV centres. Applications of this transformation in catalysis as well as mechanistic details obtained from stoichiometric model studies are discussed. Furthermore, challenges and future perspectives for the field are reviewed. PMID:25544882

Magnetic Study of the Novel Polynuclear Compound [Cu(II)(6-Mercaptopurinolate 2-)] n

NASA Astrophysics Data System (ADS)

Acevedo-Chávez, Rodolfo; Costas, María. Eugenia; Escudero, Roberto

1997-08-01

Chemical reactions between Cu(II) and 6-mercaptopurine, both in aqueous and in methanolic media, yield the novel amorphous polynuclear compound [Cu(II)(6-mercaptopurinolate)2-]n, which is also obtained from diverse Cu(II)-heterocyclic ligand competitive reactions. The kinetic and thermodynamic stabilities associated with the formation of this compound are inferred as remarkable. The spectroscopic data let us suggest the involvement of the exocyclic S(6) donor site and the N atoms in the imidazolic moiety of the deprotonated heterocyclic ligand in the coordination to Cu(II) atoms, forming a distorted bidimensional metallic network. The magnetic studies show the existence of very weak antiferromagnetic coupling in the solid sample. This system represents the first example of a 1 : 1 metal : 6-mercaptopurinolate2-system with ad-type open shell metallic center. The magnetic study carried out also represents the first example of magnetic characterization for this type of polynuclear Cu(II) systems with the dianionic 6-mercaptopurine ligand.

Comparative study on kinetic adsorption of Cu(II), Cd(II) and Ni(II) ions from aqueous solutions using activated sludge and dried sludge

NASA Astrophysics Data System (ADS)

Ong, Soon-An; Toorisaka, Eiichi; Hirata, Makoto; Hano, Tadashi

2013-03-01

The adsorption of Cu(II), Cd(II) and Ni(II) ions from aqueous solutions by activated sludge and dried sludge was investigated under laboratory conditions to assess its potential in removing metal ions. The adsorption behavior of metal ions onto activated sludge and dried sludge was analyzed with Weber-Morris intra-particle diffusion model, Lagergren first-order model and pseudo second-order model. The rate constant of intra-particle diffusion on activated sludge and dried sludge increased in the sequence of Cu(II) > Ni(II) > Cd(II). According to the regression coefficients, it was observed that the kinetic adsorption data can fit better by the pseudo second-order model compared to the first-order Lagergren model with R 2 > 0.997. The adsorption capacities of metal ions onto activated sludge and dried sludge followed the sequence Ni(II) ≈ Cu(II) > Cd(II) and Cu(II) > Ni(II) > Cd(II).

A dye-binding assay for measurement of the binding of Cu(II) to proteins.

PubMed

Wilkinson-White, Lorna E; Easterbrook-Smith, Simon B

2008-10-01

We analysed the theory of the coupled equilibria between a metal ion, a metal ion-binding dye and a metal ion-binding protein in order to develop a procedure for estimating the apparent affinity constant of a metal ion:protein complex. This can be done by analysing from measurements of the change in the concentration of the metal ion:dye complex with variation in the concentration of either the metal ion or the protein. Using experimentally determined values for the affinity constant of Cu(II) for the dye, 2-(5-bromo-2-pyridylaxo)-5-(N-propyl-N-sulfopropylamino) aniline (5-Br-PSAA), this procedure was used to estimate the apparent affinity constants for formation of Cu(II):transthyretin, yielding values which were in agreement with literature values. An apparent affinity constant for Cu(II) binding to alpha-synuclein of approximately 1 x 10(9)M(-1) was obtained from measurements of tyrosine fluorescence quenching by Cu(II). This value was in good agreement with that obtained using 5-Br-PSAA. Our analysis and data therefore show that measurement of changes in the equilibria between Cu(II) and 5-Br-PSAA by Cu(II)-binding proteins provides a general procedure for estimating the affinities of proteins for Cu(II).

Constituting fully integrated visual analysis system for Cu(II) on TiO₂/cellulose paper.

PubMed

Li, Shun-Xing; Lin, Xiaofeng; Zheng, Feng-Ying; Liang, Wenjie; Zhong, Yanxue; Cai, Jiabai

2014-07-15

As a cheap and abundant porous material, cellulose filter paper was used to immobilize nano-TiO2 and denoted as TiO2/cellulose paper (TCP). With high adsorption capacity for Cu(II) (more than 1.65 mg), TCP was used as an adsorbent, photocatalyst, and colorimetric sensor at the same time. Under the optimum adsorption conditions, i.e., pH 6.5 and 25 °C, the adsorption ratio of Cu(II) was higher than 96.1%. Humic substances from the matrix could be enriched onto TCP but the interference of their colors on colorimetric detection could be eliminated by the photodegradation. In the presence of hydroxylamine, neocuproine, as a selective indicator, was added onto TCP, and a visual color change from white to orange was generated. The concentration of Cu(II) was quantified by the color intensity images using image processing software. This fully integrated visual analysis system was successfully applied for the detection of Cu(II) in 10.0 L of drinking water and seawater with a preconcentration factor of 10(4). The log-linear calibration curve for Cu(II) was in the range of 0.5-50.0 μg L(-1) with a determination coefficient (R(2)) of 0.985 and its detection limit was 0.073 μg L(-1).

Macroscopic and molecular approaches of enrofloxacin retention in soils in presence of Cu(II).

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2013-10-15

The co-adsorption of copper and the fluoroquinolone antibiotic enrofloxacin (ENR) at the water-soil interface was studied by means of batch adsorption experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The system was investigated over a pH range between 6 and 10, at different contact times, ionic strengths, and ENR concentrations. Adsorption coefficient - Kd - was determined at relevant environmental concentrations and the value obtained in water at a ionic strength imposed by the soil and at soil natural pH was equal to 0.66Lg(-1). ENR adsorption onto the soil showed strong pH dependence illustrating the influence of the electrostatic interactions in the sorption processes. The simultaneous co-adsorption of ENR and Cu(II) on the soil was also investigated. The presence of Cu(II) strongly influenced the retention of the antibiotic, leading to an increase up to 35% of adsorbed ENR amount. The combined quantitative and spectroscopic results showed that Cu(II) and ENR directly interacted at the water-soil interface to form ternary surface complexes. Cu K-edge EXAFS data indicated a molecular structure where the carboxylate and carbonyl groups of ENR coordinate to Cu(II) to form a 6-membered chelate ring and where Cu(II) bridges between ENR and the soil surface sites. Cu(II) bonds bidentately to the surface in an inner-sphere mode. Thus, the spectroscopic data allowed us to propose the formation of ternary surface complexes with the molecular architecture soil-Cu(II)-ENR. Copyright © 2013 Elsevier Inc. All rights reserved.

Preparation and characterization of chitosan-clay nanocomposites for the removal of Cu(II) from aqueous solution.

PubMed

Azzam, Eid M S; Eshaq, Gh; Rabie, A M; Bakr, A A; Abd-Elaal, Ali A; El Metwally, A E; Tawfik, Salah M

2016-08-01

In the present study, chitosan assembled on gold and silver nanoparticles were prepared and characterized by UV-vis, TEM, EDX and DLS techniques. The nanocomposites chitosan (Ch)/clay, chitosan (Ch)/AgNPs/clay and chitosan (Ch)/AuNPs/clay were prepared by solution mixing method and characterized by FTIR, XRD, and SEM techniques. The adsorption of copper(II) ions onto the prepared hybrid composites from an aqueous solution using batch adsorption was examined. The results showed that benefiting from the surface property of clay, the abundant amino and hydroxyl functional groups of chitosan, the adsorbent provides adequate and versatile adsorption for the Cu(II) ions under investigation. The batch adsorption experiments showed that the adsorption of the Cu(II) is considerably dependent on pH of milieu, the amount of adsorbent, and contact time. Batch adsorption studies revealed that the adsorption capacity of Cu(II) increased with increase in initial concentration and contact time with optimum pH in the range around neutral. The maximum uptake of Cu(II) ions by (Ch)/AgNPs/clay composite was found to be 181.5mg/g. The adsorption efficiency of Cu(II) ions by prepared (Ch)/AgNPs/clay and (Ch)/AuNPs/clay is bigger than that the individual chitosan (Ch)/clay composite which clarifies the role of metal nanoparticles in enhancement the adsorption characters. The study suggests that the (Ch)/AgNPs/clay hybrid composite is a promising nano-adsorbent for the removal of Cu(II) ions from aqueous solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, molecular docking and DNA binding studies of phthalimide-based copper(II) complex: In vitro antibacterial, hemolytic and antioxidant assessment

NASA Astrophysics Data System (ADS)

Arif, Rizwan; Nayab, Pattan Sirajuddin; Ansari, Istikhar A.; Shahid, M.; Irfan, Mohammad; Alam, Shadab; Abid, Mohammad; Rahisuddin

2018-05-01

In the present research work, we prepared N-substituted phthalimide, 2-(-(2-(2-(2-(1,3-dioxoisoindoline-2-yl-ethylamino)ethylamino)ethyl)isoindoline-1,3-dione (DEEI) and its copper(II) complex. The ligand (DEEI) and its Cu(II) complex were structurally identified using absorption, FTIR, NMR, electron spin resonance, X-ray diffraction spectral studies, thermogravimetric and elemental analyses. The electronic spectrum and magnetic moment value proposed that Cu(II) complex has square planar geometry. The DNA interaction ability of the ligand (DEEI) and Cu(II) complex was studied by means of absorption and fluorescence spectrophotometer, viscosity measurements, cyclic voltammetery, and circular dichroism methods. The extent of DNA binding (Kb) with Calf thymus (Ct-DNA) follows the order of Cu(II) complex (1.11 × 106 M-1) > DEEI (1.0 × 105 M-1), indicating that Cu(II) complex interact with Ct-DNA through groove binding mode and more sturdily than ligand (DEEI). Interestingly, in silico predictions were corroborated with in vitro DNA binding studies. The antibacterial evaluation of these compounds was screened against a panel of bacterial strains Pseudomonas aeruginosa (MTCC 2453), Salmonella enterica (MTCC 3224), Streptococcus pneumoniae (MTCC 655), Enterococcus faecalis (MTCC 439), Klebsiella pneumonia and Escherichia coli (ATCC 25922). The results showed that the copper(II) complex has significant antibacterial potential (IC50 = 0.0019 μg/mL) against Salmonella enteric comparable with ligand (DEEI) and standard drug ciprofloxacin. Growth curve study of Cu(II) complex against only three bacterial strains S. enterica, E. faecalis and S. pneumoniae showed its bactericidal nature. Cu(II) complex showed less than 2% hemolysis on human RBCs indicating its non toxic nature. The results of antioxidant assay demonstrated that scavenging activity of Cu(II) complex is higher as compared to ligand and ascorbic acid as standard.

Factors that control catalytic two- versus four-electron reduction of dioxygen by copper complexes.

PubMed

Fukuzumi, Shunichi; Tahsini, Laleh; Lee, Yong-Min; Ohkubo, Kei; Nam, Wonwoo; Karlin, Kenneth D

2012-04-25

The selective two-electron reduction of O(2) by one-electron reductants such as decamethylferrocene (Fc*) and octamethylferrocene (Me(8)Fc) is efficiently catalyzed by a binuclear Cu(II) complex [Cu(II)(2)(LO)(OH)](2+) (D1) {LO is a binucleating ligand with copper-bridging phenolate moiety} in the presence of trifluoroacetic acid (HOTF) in acetone. The protonation of the hydroxide group of [Cu(II)(2)(LO)(OH)](2+) with HOTF to produce [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF) makes it possible for this to be reduced by 2 equiv of Fc* via a two-step electron-transfer sequence. Reactions of the fully reduced complex [Cu(I)(2)(LO)](+) (D3) with O(2) in the presence of HOTF led to the low-temperature detection of the absorption spectra due to the peroxo complex [Cu(II)(2)(LO)(OO)] (D) and the protonated hydroperoxo complex [Cu(II)(2)(LO)(OOH)](2+) (D4). No further Fc* reduction of D4 occurs, and it is instead further protonated by HOTF to yield H(2)O(2) accompanied by regeneration of [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF), thus completing the catalytic cycle for the two-electron reduction of O(2) by Fc*. Kinetic studies on the formation of Fc*(+) under catalytic conditions as well as for separate examination of the electron transfer from Fc* to D1-OTF reveal there are two important reaction pathways operating. One is a rate-determining second reduction of D1-OTF, thus electron transfer from Fc* to a mixed-valent intermediate [Cu(II)Cu(I)(LO)](2+) (D2), which leads to [Cu(I)(2)(LO)](+) that is coupled with O(2) binding to produce [Cu(II)(2)(LO)(OO)](+) (D). The other involves direct reaction of O(2) with the mixed-valent compound D2 followed by rapid Fc* reduction of a putative superoxo-dicopper(II) species thus formed, producing D.

Chemotherapeutic response to cisplatin-like drugs in human breast cancer cells probed by vibrational microspectroscopy.

PubMed

Batista de Carvalho, A L M; Pilling, M; Gardner, P; Doherty, J; Cinque, G; Wehbe, K; Kelley, C; Batista de Carvalho, L A E; Marques, M P M

2016-06-23

Studies of drug-cell interactions in cancer model systems are essential in the preclinical stage of rational drug design, which relies on a thorough understanding of the mechanisms underlying cytotoxic activity and biological effects, at a molecular level. This study aimed at applying complementary vibrational spectroscopy methods to evaluate the cellular impact of two Pt(ii) and Pd(ii) dinuclear chelates with spermine (Pt2Spm and Pd2Spm), using cisplatin (cis-Pt(NH3)2Cl2) as a reference compound. Their effects on cellular metabolism were monitored in a human triple-negative metastatic breast cancer cell line (MDA-MB-231) by Raman and synchrotron-radiation infrared microspectroscopies, for different drug concentrations (2-8 μM) at 48 h exposure. Multivariate data analysis was applied (unsupervised PCA), unveiling drug- and concentration-dependent effects: apart from discrimination between control and drug-treated cells, a clear separation was obtained for the different agents studied - mononuclear vs. polynuclear, and Pt(ii) vs. Pd(ii). Spectral biomarkers of drug action were identified, as well as the cellular response to the chemotherapeutic insult. The main effect of the tested compounds was found to be on DNA, lipids and proteins, the Pd(ii) agent having a more significant impact on proteins while its Pt(ii) homologue affected the cellular lipid content at lower concentrations, which suggests the occurrence of distinct and unconventional pathways of cytotoxicity for these dinuclear polyamine complexes. Raman and FTIR microspectroscopies were confirmed as powerful non-invasive techniques to obtain unique spectral signatures of the biochemical impact and physiological reaction of cells to anticancer agents.

Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline.

PubMed

Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

2015-02-25

Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, (1)H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ). Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, crystal structures and properties of new homoleptic Ni(II)/Pd(II) β-oxodithioester chelates

NASA Astrophysics Data System (ADS)

Yadav, Chote L.; Manar, Krishna K.; Yadav, Manoj K.; Tiwari, Neeraj; Singh, Rakesh K.; Drew, Michael G. B.; Singh, Nanhai

2018-05-01

Six new cis-chelate complexes, [M(L)2] (L = methyl-3-hydroxy-3-(furyl)-2-propenedithioate L1, M = Ni(II) 1, Pd(II) 4; methyl-3-hydroxy-3-(thiophenyl)-2-propenedithioate L2, M = Ni(II) 2, Pd(II) 5 and methyl-3-hydroxy-3-(phenyl)-2-propenedithioate L3, M = Ni(II) 3, Pd(II) 6 have been prepared and characterized by elemental analyses, spectroscopy (IR, UV-Vis., 1H and 13C{1H} NMR). The structures of 2-6 have been revealed by X-ray crystallography. In all the crystal structures, the metal has four-coordinate slightly distorted square planar geometry with a cis-configuration of the ligands. Anti-leishmanial properties of the complexes have been studied; 2, 3 and 6 showed potential anti-promastigote and anti-amastigote activities with IC50 values of 1.70 ± 0.50, 1.62 ± 0.19, 9.20 ± 2.16 μg/mL and IC50 2.50 ± 0.10, 2.05 ± 0.40, 12.84 ± 3.46 μg/mL respectively. Cytotoxicity assays on these complexes showed toxicity on the promastigotes but less toxicity against RAW 264.7 cell lines at different concentrations. Palladium complexes 4, 5 and 6 show luminescent characteristics in CH2Cl2 solution at room temperature. Complexes 1-6 are weakly conducting (σrt = 10-4-10-6 S cm-1, Ea = 0.19-1.13 eV) but show semiconducting behavior in the solid phase.

Induction of G-quadruplex DNA structure by Zn(II) 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin.

PubMed

Bhattacharjee, Amlan J; Ahluwalia, Karan; Taylor, Scott; Jin, Ou; Nicoludis, John M; Buscaglia, Robert; Brad Chaires, J; Kornfilt, David J P; Marquardt, David G S; Yatsunyk, Liliya A

2011-08-01

G-quadruplexes (GQ) are formed by the association of guanine-rich stretches of DNA. Certain small molecules can influence kinetics and thermodynamics of this association. Understanding the mechanism of ligand-assisted GQ folding is necessary for the design of more efficient cancer therapeutics. The oligonucleotide d(TAGGG)(2) forms parallel bimolecular GQ in the presence of ≥66 mM K(+); GQs are not formed under Na(+), Li(+) or low K(+) conditions. The thermodynamic parameters for GQ folding at 60 μM oligonucleotide and 100 mM KCl are ΔH = -35 ± 2 kcal mol(-1) and ΔG(310) = -1.4 kcal mol(-1). Quadruplex [d(TAGGG)(2)](2) binds 2-3 K(+) ions with K(d) of 0.5 ± 0.2 mM. Our work addresses the question of whether metal free 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP4) and its Zn(II), Cu(II), and Pt(II) derivatives are capable of facilitating GQ folding of d(TAGGG)(2) from single stranded, or binding to preformed GQ, using UV-vis and circular dichroism (CD) spectroscopies. ZnTMPyP4 is unique among other porphyrins in its ability to induce GQ structure of d(TAGGG)(2), which also requires at least a low amount of potassium. ZnTMPyP4 binds with 2:1 stoichiometry possibly in an end-stacking mode with a ~10(6) M(-1) binding constant, determined through UV-vis and ITC titrations. This process is entropically driven and has ΔG(298) of -8.0 kcal mol(-1). TMPyP4 binds with 3:1 stoichiometry and K(a) of ~10(6) M(-1). ZnTMPyP4 and TMPyP4 are efficient stabilizers of [d(TAGGG)(2)](2) displaying ΔT(1/2) of 13.5 and 13.8 °C, respectively, at 1:2 GQ to porphyrin ratio; CuTMPyP4 shows a much weaker effect (ΔT(1/2) = 4.7 °C) and PtTMPyP4 is weakly destabilizing (ΔT(1/2) = -2.9 °C). The selectivity of ZnTMPyP4 for GQ versus dsDNA is comparable to that of TMPyP4. The ability of ZnTMPyP4 to bind and stabilize GQ, to induce GQ formation, and speed up its folding may suggest an important biological activity for this molecule. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Investigation of sorption/desorption equilibria of heavy metal ions on/from quartz using rhamnolipid biosurfactant.

PubMed

Aşçi, Yeliz; Nurbaş, Macid; Sağ Açikel, Yeşim

2010-01-01

In the present study, the sorption characteristics of Cd(II) and Zn(II) ions on quartz, a representative soil-component, and the desorption of these metal ions from quartz using rhamnolipid biosurfactant were investigated. In the first part of the studies, the effects of initial metal ion concentration and pH on sorption of Cd(II) and Zn(II) ions by a fixed amount of quartz (1.5g) were studied in laboratory batch mode. The equilibrium sorption capacity for Cd(II) and Zn(II) ions was measured and the best correlation between experimental and model predicted equilibrium uptake was obtained using the Freundlich model. Although investigations on the desorption of heavy metal ions from the main soil-components are crucial to better understand the mobility and bioavailability of metals in the environment, studies on the description of desorption equilibrium were performed rarely. In the second part, the desorption of Cd(II) and Zn(II) from quartz using rhamnolipid biosurfactant was investigated as a function of pH, rhamnolipid concentration, and the amounts of sorbed Cd(II) and Zn(II) ions by quartz. The Freundlich model was also well fitted to the obtained desorption isotherms. Several indexes were calculated based on the differences of the quantity of Cd-Zn sorbed and desorbed. A desorption hysteresis (irreversibility) index based on the Freundlich exponent, concentration-dependent metal distribution coefficients, and the irreversibility index based on the metal distribution coefficient were used to quantify hysteretic behavior observed in the systems. 2009 Elsevier Ltd. All rights reserved.

Two luminescent Zn(II) metal-organic frameworks for exceptionally selective detection of picric acid explosives.

PubMed

Shi, Zhi-Qiang; Guo, Zi-Jian; Zheng, He-Gen

2015-05-14

Two luminescent Zn(II) metal-organic frameworks were prepared from a π-conjugated thiophene-containing carboxylic acid ligand. These two MOFs show strong luminescene and their luminescence could be quenched by a series of nitroaromatic explosives. Importantly, they exhibit very highly sensitive and selective detection of picric acid compared to other nitroaromatic explosives.

DNA-dependent RNA polymerase II from Candida species is a multiple zinc-containing metalloenzyme.

PubMed

Patturajan, M; Sevugan, M; Chatterji, D

1999-08-01

We have purified DNA-dependent RNA polymerase II from Candida albicans, a human pathogenic yeast. The enzyme consists of 9 polypeptides that are unique to C. albicans, their mobility on SDS-PAGE being different from the mobility of the corresponding subunits of RNA polymerase II from Saccharomyces cerevisiae or C. utilis. In the present study we also demonstrate that RNA pol II from C. albican and C. utilis are metalloproteins containing approximately 5 mol of zinc per mole of enzyme. Although prolonged dialysis in 10 or 20 mM EDTA failed to remove Zn(II) from the C. albicans enzyme, in the C. utilis enzyme 3 Zn(II) ions could be removed and then reconstituted in the presence of excess Zn(II). o-Phenanthroline (5 mM) removed Zn(II) from C. albicans enzyme irreversibly in a time-dependent fashion with concomitant loss of enzyme activity. Circular dichroism studies revealed structural changes on removal of zinc, thus suggesting a role for Zn in maintenance of structural stability. Further, we demonstrate that the largest subunit of the C. utilis enzyme and the 3 large subunits of the C. albicans enzyme can bind radioactive zinc.

Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2] (Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato).

PubMed

Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Tsuchimoto, Masanobu; Re, Nazzareno

2013-11-04

Carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn(II)L(n)(H2O)2]·xH2O, Ln(III)(NO3)3·6H2O, and triethylamine, where Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato. Each Zn(II)2Ln(III)2 structure possessing an inversion center can be described as two di-μ-phenoxo-bridged {Zn(II)L(n)Ln(III)(NO3)} binuclear units bridged by two carbonato CO3(2-) ions. The Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of L(n) and one oxygen atom of a bridging carbonato ion at the axial site. Ln(III) ion is coordinated by nine oxygen atoms consisting of four from the deprotonated Schiff-base L(n), two from a chelating nitrate, and three from two carbonate groups. The temperature-dependent magnetic susceptibilities in the range 1.9-300 K, field-dependent magnetization from 0 to 5 T at 1.9 K, and alternating current magnetic susceptibilities under the direct current bias fields of 0 and 1000 Oe were measured. The magnetic properties of the Zn(II)2Ln(III)2 complexes are analyzed on the basis of the dicarbonato-bridged binuclear Ln(III)-Ln(III) structure, as the Zn(II) ion with d(10) electronic configuration is diamagnetic. ZnGd1 (L(1)) and ZnGd2 (L(2)) show a ferromagnetic Gd(III)-Gd(III) interaction with J(Gd-Gd) = +0.042 and +0.028 cm(-1), respectively, on the basis of the Hamiltonian H = -2J(Gd-Gd)ŜGd1·ŜGd2. The magnetic data of the Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) were analyzed by a spin Hamiltonian including the crystal field effect on the Ln(III) ions and the Ln(III)-Ln(III) magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn(II)2Tb(III)2 complexes were observed, while those of Zn(II)2Dy(III)2 were not detected. The fine structure assignable to the (5)D4 → (7)F6 transition of ZnTb1 and ZnTb2 is in good accord with the energy pattern from the magnetic analysis. The Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) showed an out-of-phase signal with frequency-dependence in alternating current susceptibility, indicative of single molecule magnet. Under a dc bias field of 1000 Oe, the signals become significantly more intense and the energy barrier, Δ/kB, for the magnetic relaxation was estimated from the Arrhenius plot to be 39(1) and 42(8) K for ZnTb1 and ZnTb2, and 52(2) and 67(2) K for ZnDy1 and ZnDy2, respectively.

The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands

DOE PAGES

Alexandratos, Spiro D.; Zhu, Xiaoping

2017-08-18

Environmental remediation requires ion-selective polymers that operate under a wide range of solution conditions. In one example, removal of trivalent and divalent metal ions from waste streams resulting from mining operations before they enter the environment requires treatment at acidic pH. The monoethyl ester phosphate ligands developed in this report operate from acidic solutions. They have been prepared on polystyrene-bound ethylene glycol, glycerol, and pentaerythritol, and it is found that intra-ligand hydrogen bonding affects their metal ion affinities. The affinity for a set of trivalent (Fe(III), Al(III), La(III), and Lu(III)) and divalent (Pb(II), Cd(II), Cu(II), and Zn(II)) ions is greatermore » than that of corresponding neutral diethyl esters and phosphonic acid. In an earlier study, hydrogen bonding was found important in determining the metal ion affinities of immobilized phosphorylated polyol diethyl ester coordinating ligands; their Fourier transform infrared (FTIR) band shifts indicated that the basicity of the phosphoryl oxygen increased by hydrogen bonding to auxiliary –OH groups on the neighboring polyol. The same mechanism is operative with the monoprotic resins along with hydrogen bonding to the P–OH acid site. This is reflected in the FTIR spectra: the neutral phosphate diethyl ester resins have the P=O band at 1265 cm -1 while the monoethyl ester resins have the band shifted to 1230 cm -1; hydrogen bonding is further indicated by the broadness of this region down to 900 cm -1. Of the polymers studied, monoprotic pentaerythritol has the highest metal ion affinities.« less

Synthesis, spectral, thermal and biological studies of mixed ligand complexes with newly prepared Schiff base and 1,10-phenanthroline ligands

NASA Astrophysics Data System (ADS)

Abd El-Halim, Hanan F.; Mohamed, Gehad G.; Khalil, Eman A. M.

2017-10-01

A series of mixed ligand complexes were prepared from the Schiff base (L1) as a primary ligand, prepared by condensation of oxamide and furan-2-carbaldehyde, and 1,10-phenanthroline (1,10-phen) as a secondary ligand. The Schiff base ligand and its mixed ligand chelates were characterized based on elemental analysis, IR, 1H NMR, thermal analysis, UV-Visible, mass, molar conductance, magnetic moment. X-ray diffraction, solid reflectance and ESR also have been studied. The mixed ligand complexes were found to have the formulae of [M(L1) (1,10-phen)]Clm.nH2O (M = Cr(III) and Fe(III) (m = 3) (n = 0); M = Mn(II), Cu(II) and Cd(II) (m = 2) (n = 0); and M = Co(II) (m = 2) (n = 1), Ni(II) (m = 2) (n = 2) and Zn(II) (m = 2) (n = 3)) and that the geometrical structure of the complexes were octahedral. The parameters of thermodynamic using Coats-Redfern and Horowitz-Metzger equations were calculated. The synthesized Schiff base ligand, 1,10-phenanthroline ligand and Their mixed ligand complexes were also investigated for their antibacterial and antifungal activity against bacterial species (Gram-Ve bacteria: Pseudomonas aeruginosa and Escherichia coli) and (Gram + Ve bacteria: Bacillus subtilis and Streptococcus pneumonia) and fungi (Aspergillus fumigates and Candida albicans). The anticancer activity of the new compounds had been tested against breast (MFC7) and colon (HCT-116) cell lines. The results showed high activity for the synthesized compounds.

Novel mixed ligand complexes of bioactive Schiff base (E)-4-(phenyl (phenylimino) methyl) benzene-1,3-diol and 2-aminophenol/2-aminobenzoic acid: Synthesis, spectral characterization, antimicrobial and nuclease studies

NASA Astrophysics Data System (ADS)

Subbaraj, P.; Ramu, A.; Raman, N.; Dharmaraja, J.

2014-01-01

A novel bidentate Schiff base ligand has been synthesized using 2,4-dihydroxybenzophenone and aniline. Its mixed ligand complexes of MAB type [M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); HA = Schiff base and B = 2-aminophenol/2-aminobenzoic acid] have been synthesized and characterized on the basis of spectral data UV-Vis, IR, 1H NMR, FAB-Mass, EPR, SEM and magnetic studies. All the complexes were soluble in DMF and DMSO. Elemental analysis and molar conductance values indicate that the complexes are non-electrolytes. HA binds with M(II) ions through azomethine and deprotonated phenolic group and B binds through the primary amine group and deprotonated phenolic/carboxylic groups. Using FAB-Mass the cleavage pattern of the ligand (HA) has been established. All the complexes adopt octahedral geometry around the metal ions. It has been confirmed with the help of UV-Vis, IR, 1H NMR and FAB-Mass spectral data. DNA binding activities of the complexes 1d and 2d are studied by UV-Vis spectroscopy and cleavage studies of Schiff base ligand and its complexes 1d and 2d have been by agarose gel electrophoresis method. In vitro biological activities of the free ligand (HA) and their metal complexes (1a-1e and 2a-2e) were screened against few bacteria, Escherichia coli, Staphylococcus saphyphiticus, Staphylococcus aureus, Pseudomonas aeruginosa and fungi Aspergillus niger, Enterobacter species, Candida albicans by well diffusion technique.

Photosensitizers derived from 132-oxo-methyl pyropheophorbide-a: enhanced effect of indium(III) as a central metal in in vitro and in vivo photosensitizing efficacy.

PubMed

Rosenfeld, Andrew; Morgan, Janet; Goswami, Lalit N; Ohulchanskyy, Tymish; Zheng, Xiang; Prasad, Paras N; Oseroff, Allan; Pandey, Ravindra K

2006-01-01

The effects of an additional keto group on absorption wavelength and the corresponding metal complexes Zn(II), Cu(II) In(III) on singlet oxygen production and photodynamic efficacy were examined among the alkyl ether analogs of pyropheophorbide-a. For the preparation of the desired photosensitizers, the methyl 13(2)-oxo-pyropheophorbide-a obtained by reacting methyl pyropheophorbide-a with aqueous LiOH-THF was converted into a series of alkyl ether analogs. These compounds were evaluated for photophysical properties and in vitro (by means of the MTT assay and intracellular localization in RIF cells) and in vivo (in C3H mice implanted with RIF tumors) photosensitizing efficacy. Among the alkyl ether derivatives, the methyl 3-decyloxyethyl-3-devinyl-13(2)-oxo-pyropheophorbide-a was found to be most effective and the insertion of In(III) into this analog further enhanced its in vitro and in vivo photosensitizing efficacy. Fluorescence microscopy showed that, in contrast to the hexyl and dodecyl ether derivatives of HPPH (which localize in mitochondria and lysosomes, respectively), the diketo-analogs and their In(III) complexes localized in Golgi bodies. The preliminary in vitro and in vivo results suggest that, in both free-base and metalated analogs, the introduction of an additional keto group at the five-member exocyclic ring in pyropheophorbide-a diminishes its photosensitizing efficacy. This may be due to a shift in subcellular localization from mitochondria to the Golgi bodies. The further introduction of In(III) enhances photoactivity, but not by shifting the localization of the photosensitizer.

The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexandratos, Spiro D.; Zhu, Xiaoping

Environmental remediation requires ion-selective polymers that operate under a wide range of solution conditions. In one example, removal of trivalent and divalent metal ions from waste streams resulting from mining operations before they enter the environment requires treatment at acidic pH. The monoethyl ester phosphate ligands developed in this report operate from acidic solutions. They have been prepared on polystyrene-bound ethylene glycol, glycerol, and pentaerythritol, and it is found that intra-ligand hydrogen bonding affects their metal ion affinities. The affinity for a set of trivalent (Fe(III), Al(III), La(III), and Lu(III)) and divalent (Pb(II), Cd(II), Cu(II), and Zn(II)) ions is greatermore » than that of corresponding neutral diethyl esters and phosphonic acid. In an earlier study, hydrogen bonding was found important in determining the metal ion affinities of immobilized phosphorylated polyol diethyl ester coordinating ligands; their Fourier transform infrared (FTIR) band shifts indicated that the basicity of the phosphoryl oxygen increased by hydrogen bonding to auxiliary –OH groups on the neighboring polyol. The same mechanism is operative with the monoprotic resins along with hydrogen bonding to the P–OH acid site. This is reflected in the FTIR spectra: the neutral phosphate diethyl ester resins have the P=O band at 1265 cm -1 while the monoethyl ester resins have the band shifted to 1230 cm -1; hydrogen bonding is further indicated by the broadness of this region down to 900 cm -1. Of the polymers studied, monoprotic pentaerythritol has the highest metal ion affinities.« less

Coordination behavior of new bis Schiff base ligand derived from 2-furan carboxaldehyde and propane-1,3-diamine. Spectroscopic, thermal, anticancer and antibacterial activity studies

NASA Astrophysics Data System (ADS)

Mohamed, Gehad G.; Zayed, Ehab M.; Hindy, Ahmed M. M.

2015-06-01

Novel bis Schiff base ligand, [N1,N3-bis(furan-2-ylmethylene)propane-1,3-diamine], was prepared by the condensation of furan-2-carboxaldehyde with propane-1,3-diamine. Its conformational changes on complexation with transition metal ions [Co(II), Ni(II), Cu(II), Mn(II), Cd(II), Zn(II) and Fe(III)] have been studied on the basis of elemental analysis, conductivity measurements, spectral (infrared, 1H NMR, electronic), magnetic and thermogravimetric studies. The conductance data of the complexes revealed their electrolytic nature suggesting them as 1:2 (for bivalent metal ions) and 1:3 (for Fe(III) ion) electrolytes. The complexes were found to have octahedral geometry based on magnetic moment and solid reflectance measurements. Thermal analysis data revealed the decomposition of the complexes in successive steps with the removal of anions, coordinated water and bis Schiff base ligand. The thermodynamic parameters were calculated using Coats-Redfern equation. The Anticancer screening studies were performed on human colorectal cancer (HCT), hepatic cancer (HepG2) and breast cancer (MCF-7) cell lines. The antimicrobial activity of all the compounds was studied against Gram negative (Escherichia coli and Proteus vulgaris) and Gram positive (Bacillus vulgaris and Staphylococcus pyogones) bacteria. It was observed that the coordination of metal ion has a pronounced effect on the microbial activities of the bis Schiff base ligand. All the metal complexes have shown higher antimicrobial effect than the free bis Schiff base ligand.

Selective divalent cobalt ions detection using Ag2O3-ZnO nanocones by ICP-OES method for environmental remediation.

PubMed

Rahman, Mohammed M; Khan, Sher Bahadar; Marwani, Hadi M; Asiri, Abdullah M

2014-01-01

Here, we have synthesized Ag2O3-ZnO nanocones (NCs) by a wet-chemical route using reducing agents at low temperature. The structural, optical and morphological properties of Ag2O3-ZnO NCs were investigated by several conventional techniques such as powder XRD, XPS, FESEM, XEDS, FTIR and UV/vis. spectroscopy. The analytical parameters of prepared NCs were also calculated for a selective detection of divalent cobalt [Co(II)] prior to its determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of NCs toward various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II), and Zn(II) was studied. Results of the selectivity study demonstrated that Ag2O3-ZnO NC phase was the most selective towards Co(II) ion. The uptake capacity for Co(II) ion was experimentally calculated to be ∼76.69 mgg-1. Moreover, adsorption isotherm data provided that the adsorption process was mainly monolayer on homogeneous adsorbent surfaces of Ag2O3-ZnO NCs. Kinetic study revealed that the adsorption of Co(II) on Ag2O3-ZnO NCs phase followed the pseudo-second-order kinetic model. In addition, thermodynamic results provided that the adsorption mechanism of Co(II) ions on Ag2O3-ZnO NCs was a spontaneous process and thermodynamically favorable. Finally, the proposed method was validated by applying it to real environmental water samples with reasonable results.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 ofmore » 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.« less

Ion-imprinted polymethacrylic microbeads as new sorbent for preconcentration and speciation of mercury.

PubMed

Dakova, Ivanka; Karadjova, Irina; Georgieva, Ventsislava; Georgiev, George

2009-04-30

Metal ion-imprinted polymer particles have been prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as cross-linking agent and 2,2'-azobisisobutyronitrile as initiator, in the presence of Hg(II)-1-(2-thiazolylazo)-2-naphthol complex. The separation and preconcentration characteristics of the Hg-ion-imprinted microbeads for inorganic mercury have been investigated by batch procedure. The optimal pH value for the quantitative sorption is 7. The adsorbed inorganic mercury is easily eluted by 2 mL 4M HNO(3). The adsorption capacity of the newly synthesized Hg ion-imprinted microbeads is 32.0 micromol g(-1) for dry copolymer. The selectivity of the copolymer toward inorganic mercury (Hg(II)) ion is confirmed through the comparison of the competitive adsorptions of Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II)) and high values of the selectivity and distribution coefficients have been calculated. Experiments performed for selective determination of inorganic mercury in mineral and sea waters showed that the interfering matrix does not influence the extraction efficiency of Hg ion-imprinted microbeads. The detection limit for inorganic mercury is 0.006 microg L(-1) (3 sigma), determined by cold vapor atomic adsorption spectrometry. The relative standard deviation varied in the range 5-9 % at 0.02-1 microg L(-1) Hg levels. The new Hg-ion-imprinted microbeads have been tested and applied for the speciation of Hg in river and mineral waters: inorganic mercury has been determined selectively in nondigested sample, while total mercury e.g. sum of inorganic and methylmercury, has been determined in digested sample.

Novel bis-(−)-nor-meptazinol derivatives act as dual binding site AChE inhibitors with metal-complexing property

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Wei; NPFPC Key Laboratory of Contraceptives and Devices, Shanghai Institute of Planned Parenthood Research, 2140 Xietu Road, Shanghai 200032; Li, Juan

The strategy of dual binding site acetylcholinesterase (AChE) inhibition along with metal chelation may represent a promising direction for multi-targeted interventions in the pathophysiological processes of Alzheimer's disease (AD). In the present study, two derivatives (ZLA and ZLB) of a potent dual binding site AChE inhibitor bis-(−)-nor-meptazinol (bis-MEP) were designed and synthesized by introducing metal chelating pharmacophores into the middle chain of bis-MEP. They could inhibit human AChE activity with IC{sub 50} values of 9.63 μM (for ZLA) and 8.64 μM (for ZLB), and prevent AChE-induced amyloid-β (Aβ) aggregation with IC{sub 50} values of 49.1 μM (for ZLA) and 55.3more » μM (for ZLB). In parallel, molecular docking analysis showed that they are capable of interacting with both the catalytic and peripheral anionic sites of AChE. Furthermore, they exhibited abilities to complex metal ions such as Cu(II) and Zn(II), and inhibit Aβ aggregation triggered by these metals. Collectively, these results suggest that ZLA and ZLB may act as dual binding site AChEIs with metal-chelating potency, and may be potential leads of value for further study on disease-modifying treatment of AD. -- Highlights: ► Two novel bis-(−)-nor-meptazinol derivatives are designed and synthesized. ► ZLA and ZLB may act as dual binding site AChEIs with metal-chelating potency. ► They are potential leads for disease-modifying treatment of Alzheimer's disease.« less

Selective Divalent Cobalt Ions Detection Using Ag2O3-ZnO Nanocones by ICP-OES Method for Environmental Remediation

PubMed Central

Rahman, Mohammed M.; Khan, Sher Bahadar; Marwani, Hadi M.; Asiri, Abdullah M.

2014-01-01

Here, we have synthesized Ag2O3-ZnO nanocones (NCs) by a wet-chemical route using reducing agents at low temperature. The structural, optical and morphological properties of Ag2O3-ZnO NCs were investigated by several conventional techniques such as powder XRD, XPS, FESEM, XEDS, FTIR and UV/vis. spectroscopy. The analytical parameters of prepared NCs were also calculated for a selective detection of divalent cobalt [Co(II)] prior to its determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of NCs toward various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II), and Zn(II) was studied. Results of the selectivity study demonstrated that Ag2O3-ZnO NC phase was the most selective towards Co(II) ion. The uptake capacity for Co(II) ion was experimentally calculated to be ∼76.69 mgg−1. Moreover, adsorption isotherm data provided that the adsorption process was mainly monolayer on homogeneous adsorbent surfaces of Ag2O3-ZnO NCs. Kinetic study revealed that the adsorption of Co(II) on Ag2O3-ZnO NCs phase followed the pseudo-second-order kinetic model. In addition, thermodynamic results provided that the adsorption mechanism of Co(II) ions on Ag2O3-ZnO NCs was a spontaneous process and thermodynamically favorable. Finally, the proposed method was validated by applying it to real environmental water samples with reasonable results. PMID:25464507

Predicting heavy metals' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics.

PubMed

Hu, Qinghai; Xiao, Zhongjin; Xiong, Xinmei; Zhou, Gongming; Guan, Xiaohong

2015-01-01

Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics, edge, and isotherm data with one pH-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, KS-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, KS-Langmuir. The modified Langmuir kinetic model (MLK model) and modified Langmuir isotherm model (MLI model) incorporating pH factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on MnO2 at pH3.2 or 3.3 to get the values of KS-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model), and the values of KS-Langmuir were obtained. The values of KS-kinetic and KS-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with KS-kinetic constants could predict the adsorption edges of heavy metals on MnO2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on MnO2 at various pH levels could be predicted reasonably well by the MLI model with the KS-kinetic constants. Copyright © 2014. Published by Elsevier B.V.

Ternary complexes of Zn(II) and Cu(II) with 1-((2-hydroxynaphthalen-1-yl)methylene)-4-phenylthiosemicarbazide in the presence of heterocyclic bases as auxiliary ligands: Synthesis, spectroscopic and structural characterization and antibacterial activity

NASA Astrophysics Data System (ADS)

Azarkish, Mohammad; Akbari, Alireza; Sedaghat, Tahereh; Simpson, Jim

2018-03-01

The new ternary complexes, ZnLL‧ [L = 1-((2-hydroxynaphthalen-1-yl)methylene)-4-phenylthiosemicarbazide and L‧ = imidazole (1), 2, 2‧-bipyridine (2) and 2-methyimidazole (3)], Zn2L2L‧ [L‧ = 4, 4‧-bipy (4)] and CuLL‧ [L‧ = 2, 2‧-bipy (5)] have been synthesized by the reaction of a metal(II) acetate salt with the thiosemicarbazone and in presence of heterocyclic bases as auxiliary ligands. The synthesized compounds were investigated by elemental analysis and IR, 1H NMR, and 13C NMR spectroscopy and complex 5 was structurally characterized by X-ray crystallography. The results indicate the thiosemicarbazone doubly deprotonated and coordinates to metal through the thiolate sulfur, imine nitrogen and phenolic oxygen atoms. The nitrogen atom(s) of the auxiliary ligand complete the coordination sphere. Complex 4 is binuclear with 4, 4‧-bipy acting as a bridging ligand. The structure of 5 is a distorted square pyramid with one of the bipyridine nitrogen atoms in the apical position. This compound creates an inversion dimer in solid state by intermolecular hydrogen bonds of Nsbnd H⋯S type. The in vitro antibacterial activity of the synthesized compounds were evaluated against Gram-positive (B. subtilis and S. aureus) and Gram-negative (P. aeruginosa) bacteria and is compared to that of standard antibacterial drugs. All complexes exhibit good inhibitory effects and are significantly more effective than the parent ligand.

Simultaneous removal of Cu(II) and Cr(VI) by Mg-Al-Cl layered double hydroxide and mechanism insight.

PubMed

Yue, Xianyang; Liu, Weizhen; Chen, Zuliang; Lin, Zhang

2017-03-01

Mg-Al-Cl layered double hydroxide (Cl-LDH) was prepared to simultaneously remove Cu(II) and Cr(VI) from aqueous solution. The coexisting Cu(II) (20mg/L) and Cr(VI) (40mg/L) were completely removed within 30min by Cl-LDH in a dosage of 2.0g/L; the removal rate of Cu(II) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(II) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(II) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(II) (200mg/L) and Cr(VI) (400mg/L). The affecting factors (such as solution initial pH, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg 2+ and Al 3+ in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl - in Cl-LDH interlayer, isomorphic substitution of Mg 2+ with Cu 2+ , formation of Cu 2 Cl(OH) 3 precipitation, and the adsorption of Cr(VI) by Cu 2 Cl(OH) 3 . This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH. Copyright © 2016. Published by Elsevier B.V.

Characterization and copper binding properties of human COMMD1 (MURR1).

PubMed

Narindrasorasak, Suree; Kulkarni, Prasad; Deschamps, Patrick; She, Yi-Min; Sarkar, Bibudhendra

2007-03-20

COMMD1 (copper metabolism gene MURR1 (mouse U2af1-rs1 region1) domain) belongs to a family of multifunctional proteins that inhibit nuclear factor NF-kappaB. COMMD1 was implicated as a regulator of copper metabolism by the discovery that a deletion of exon 2 of COMMD1 causes copper toxicosis in Bedlington terriers. Here, we report the detailed characterization and specific copper binding properties of purified recombinant human COMMD1 as well as that of the exon 2 product, COMMD(61-154). By using various techniques including native-PAGE, EPR, UV-visible electronic absorption, intrinsic fluorescence spectroscopies as well as DEPC modification of histidines, we demonstrate that COMMD1 specifically binds copper as Cu(II) in 1:1 stoichiometry and does not bind other divalent metals. Moreover, the exon 2 product, COMMD(61-154), alone was able to bind Cu(II) as well as the wild type protein, with a stoichiometry of 1 mol of Cu(II) per protein monomer. The protection of DEPC modification of COMMD1 by Cu(II) implied that Cu(II) binding involves His residues. Further investigation by DEPC modification of COMMD(61-154) and subsequent MALDI MS mapping and MS/MS sequencing identified the protection of His101 and His134 residues in the presence of Cu(II). Fluorescence studies of single point mutants of the full-length protein revealed the involvement of M110 in addition to H134 in direct Cu(II) binding. Taken together, the data provide insight into the function of COMMD1 and especially COMMD(61-154), a product of exon 2 that is deleted in terriers affected by copper toxicosis, as a regulator of copper homeostasis.

Sorption Mechanisms of Cesium on Cu II2Fe II(CN) 6and Cu II3[Fe III(CN) 6] 2Hexacyanoferrates and Their Relation to the Crystalline Structure

NASA Astrophysics Data System (ADS)

Ayrault, S.; Jimenez, B.; Garnier, E.; Fedoroff, M.; Jones, D. J.; Loos-Neskovic, C.

1998-12-01

CuII2FeII(CN)6·xH2O and CuII3[FeIII(CN)6]2·xH2O can be prepared with reproducible chemical compositions and structures after careful washing. They have cubicFmoverline3mstructures with iron vacancies. In CuII2FeII(CN)6, copper occupies two different sites: Cu1 in position 4blinked to Fe through the CN groups, and Cu2 not linked to the CN groups and partially occupying the interstitial 24epositions. The second type of site is not present in CuII3[FeIII(CN)6]2. Sorption kinetics and isotherms were determined for cesium on both hexacyanoferrates by batch experiments. On CuII3[FeIII(CN)6]2, the maximum uptake is only 0.073 Cs/Fe (at./at.). On CuII2FeII(CN)6, the uptake reaches 1.5 Cs/Fe. The sorption kinetics include at least two steps: at1/2variation until approximately 72 h and then a slow evolution studied up to 6 months. The sorption mechanism is complex. The main process seems to be diffusion of ion pairs, followed by a reorganization of the solid, resulting in one or more new solid phases. The presence of the Cu2 site seems to play a favorable role in the sorption. Owing to its good midterm stability and the first rapid step of exchange, CuII2FeII(CN)6·xH2O seems to be one of the most promising compounds for the recovery of cesium from nuclear liquid wastes.

Removal of heavy metal Cu(II) in simulated aquaculture wastewater by modified palygorskite.

PubMed

Cao, Jia-Shun; Wang, Cheng; Fang, Fang; Lin, Jun-Xiong

2016-12-01

Palygorskite (PAL) is a good heavy metal adsorbent due to its high surface area, low cost, and environmentally compatibility. But the natural PAL has limited its adsorption capacity and selectivity. In this study, a cost-effective and readily-generated absorbent, l-threonine-modified palygorskite (L-PAL), was used and its performance for Cu(II) removal in simulated aquaculture wastewater was evaluated. After preparation, L-PAL was characterized by using Fourier transform infrared spectroscopy, scanning electron microscope, energy dispersive X-ray spectroscopy, X-ray diffractometer, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis. The impacts of pH, adsorbent dosage, contact time, and initial Cu(II) concentration on the adsorption capacity of L-PAL were examined. The Cu(II) adsorption capacity on L-PAL was enhanced almost 10 times than that of raw PAL. The adsorption isotherms of Cu(II) fit the Langmuir isotherms, and the adsorption kinetics was dominated by the pseudo-second-order model. The thermodynamic parameters at four temperatures were calculated, which indicated that the adsorption was spontaneous and endothermic. The adsorption mechanism involves complexation, chelation, electrostatic attraction, and micro-precipitation. Furthermore, L-PAL is shown to have a high regeneration capacity. These results indicate that L-PAL is a cheap and promising absorbent for Cu(II) removal and hold potential to be used for aquaculture wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Microcalorimetric and potentiometric titration studies on the adsorption of copper by P. putida and B. thuringiensis and their composites with minerals.

PubMed

Fang, Linchuan; Cai, Peng; Li, Pengxiang; Wu, Huayong; Liang, Wei; Rong, Xingmin; Chen, Wenli; Huang, Qiaoyun

2010-09-15

In order to have a better understanding of the interactions of heavy metals with bacteria and minerals in soil and associated environments, isothermal titration calorimetry (ITC), potentiometric titration and equilibrium sorption experiments were conducted to investigate the adsorption behavior of Cu(II) by Bacillus thuringiensis, Pseudomonas putida and their composites with minerals. The interaction of montmorillonite with bacteria increased the reactive sites and resulted in greater adsorption for Cu(II) on their composites, while decreased adsorption sites and capacities for Cu(II) were observed on goethite-bacteria composites. A gram-positive bacterium B. thuringiensis played a more important role than a gram-negative bacterium P. putida in determining the properties of the bacteria-minerals interfaces. The enthalpy changes (DeltaH(ads)) from endothermic (6.14 kJ mol(-1)) to slightly exothermic (-0.78 kJ mol(-1)) suggested that Cu(II) is complexed with the anionic oxygen ligands on the surface of bacteria-mineral composites. Large entropies (32.96-58.89 J mol(-1) K(-1)) of Cu(II) adsorption onto bacteria-mineral composites demonstrated the formation of inner-sphere complexes in the presence of bacteria. The thermodynamic data implied that Cu(II) mainly bound to the carboxyl and phosphoryl groups as inner-sphere complexes on bacteria and mineral-bacteria composites. Copyright 2010 Elsevier B.V. All rights reserved.

Internal electron transfer between hemes and Cu(II) bound at cysteine beta93 promotes methemoglobin reduction by carbon monoxide.

PubMed

Bonaventura, C; Godette, G; Tesh, S; Holm, D E; Bonaventura, J; Crumbliss, A L; Pearce, L L; Peterson, J

1999-02-26

Previous studies showed that CO/H2O oxidation provides electrons to drive the reduction of oxidized hemoglobin (metHb). We report here that Cu(II) addition accelerates the rate of metHb beta chain reduction by CO by a factor of about 1000. A mechanism whereby electron transfer occurs via an internal pathway coupling CO/H2O oxidation to Fe(III) and Cu(II) reduction is suggested by the observation that the copper-induced rate enhancement is inhibited by blocking Cys-beta93 with N-ethylmaleimide. Furthermore, this internal electron-transfer pathway is more readily established at low Cu(II) concentrations in Hb Deer Lodge (beta2His --> Arg) and other species lacking His-beta2 than in Hb A0. This difference is consistent with preferential binding of Cu(II) in Hb A0 to a high affinity site involving His-beta2, which is ineffective in promoting electron exchange between Cu(II) and the beta heme iron. Effective electron transfer is thus affected by Hb type but is not governed by the R left arrow over right arrow T conformational equilibrium. The beta hemes in Cu(II)-metHb are reduced under CO at rates close to those observed for cytochrome c oxidase, where heme and copper are present together in the oxygen-binding site and where internal electron transfer also occurs.

Catalytic role of Cu(II) in the reduction of Cr(VI) by citric acid under an irradiation of simulated solar light.

PubMed

Li, Ying; Chen, Cheng; Zhang, Jing; Lan, Yeqing

2015-05-01

The catalytic role of Cu(II) in the reduction of Cr(VI) by citric acid with simulated solar light was investigated. The results demonstrated that Cu(II) could significantly accelerate Cr(VI) reduction and the reaction obeyed to pseudo zero-order kinetics with respect to Cr(VI). The removal of Cr(VI) was related to the initial concentrations of Cu(II), citric acid, and the types of organic acids. The optimal removal of Cr(VI) was achieved at pH 4, and the rates of Cu(II) photocatalytic reduction of Cr(VI) by organic acids were in the order: tartaric acid (two α-OH groups, two -COOH groups)>citric acid (one α-OH group, three -COOH groups)>malic acid (one α-OH group, two -COOH groups)>lactic acid (one α-OH group, one -COOH group)≫succinic acid (two -COOH groups), suggesting that the number of α-OH was the key factor for the reaction, followed by the number of -COOH. The formation of Cu(II)-citric acid complex could generate Cu(I) and radicals through a pathway of metal-ligand-electron transfer, promoting the reduction of Cr(VI). This study is helpful to fully understanding the conversion of Cr(VI) in the existence of both organic acids and Cu(II) with solar light in aquatic environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Statistical Analysis of Main and Interaction Effects on Cu(II) and Cr(VI) Decontamination by Nitrogen-Doped Magnetic Graphene Oxide

NASA Astrophysics Data System (ADS)

Hu, Xinjiang; Wang, Hui; Liu, Yunguo

2016-10-01

A nitrogen-doped magnetic graphene oxide (NMGO) was synthesized and applied as an adsorbent to remove Cu(II) and Cr(VI) ions from aqueous solutions. The individual and combined effects of various factors (A: pH, B: temperature, C: initial concentration of metal ions, D: CaCl2, and E: humic acid [HA]) on the adsorption were analyzed by a 25-1 fractional factorial design (FFD). The results from this study indicated that the NMGO had higher adsorption capacities for Cu(II) ions than for Cr(VI) ions under most conditions, and the five selected variables affected the two adsorption processes to different extents. A, AC, and C were the very important factors and interactions for Cu(II) adsorption. For Cr(VI) adsorption, A, B, C, AB, and BC were found to be very important influencing variables. The solution pH (A) was the most important influencing factor for removal of both the ions. The main effects of A-E on the removal of Cu(II) were positive. For Cr(VI) adsorption, the main effects of A and D were negative, while B, C, and E were observed to have positive effects. The maximum adsorption capacities for Cu(II) and Cr(VI) ions over NMGO were 146.365 and 72.978 mg/g, respectively, under optimal process conditions.

Cu(II) binding by a pH-fractionated fulvic acid

USGS Publications Warehouse

Brown, G.K.; Cabaniss, S.E.; MacCarthy, P.; Leenheer, J.A.

1999-01-01

The relationship between acidity, Cu(II) binding and sorption to XAD resin was examined using Suwannee River fulvic acid (SRFA). The work was based on the hypothesis that fractions of SRFA eluted from an XAD column at various pH's from 1.0 to 12.0 would show systematic variations in acidity and possibly aromaticity which in turn would lead to different Cu(II) binding properties. We measured equilibrium Cu(II) binding to these fractions using Cu2+ ion-selective electrode (ISE) potentiometry at pH 6.0. Several model ligands were also examined, including cyclopentane-1,2,3,4-tetracarboxylic acid (CP-TCA) and tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THF-TCA), the latter binding Cu(II) much more strongly as a consequence of the ether linkage. The SRFA Cu(II) binding properties agreed with previous work at high ionic strength, and binding was enhanced substantially at lower ionic strength, in agreement with Poisson-Boltzmann predictions for small spheres. Determining Cu binding constants (K(i)) by non-linear regression with total ligand concentrations (L(Ti)) taken from previous work, the fractions eluted at varying pH had K(i) similar to the unfractionated SRFA, with a maximum enhancement of 0.50 log units. We conclude that variable-pH elution from XAD does not isolate significantly strong (or weak) Cu(II)-binding components from the SRFA mixture. Copyright (C) 1999 Elsevier Science B.V.

Evaluation of different isotherm models, kinetic, thermodynamic, and copper biosorption efficiency of Lobaria pulmonaria (L.) Hoffm.

PubMed

Kiliç, Zeynep; Atakol, Orhan; Aras, Sümer; Cansaran-Duman, Demet; Celikkol, Pelin; Emregul, Emel

2014-01-01

The biosorption characteristics of Cu(II) ions from aqueous solution using Lobaria pulmonaria (L.) Hoffm. biomass were investigated. The biosorption efficiency of Cu(II) onto biomass was significantly influenced by the operating parameters. The maximum biosorption efficiency of L. pulmonaria was 65.3% at 10 mg/L initial metal concentration for 5 g/L lichen biomass dosage. The biosorption of Cu(II) ions onto biomass fits the Langmuir isotherm model and the pseudo-second-order kinetic model well. The thermodynamic parameters indicate the feasibility and exothermic and spontaneous nature of the biosorption. The effective desorption achieved with HCl was 96%. Information on the nature of possible interactions between the functional groups of the L. pulmonaria biomass and Cu(II) ions was obtained via Fourier transform infrared (FTIR) spectroscopy. The results indicated that the carboxyl (-COOH) and hydroxyl (-OH) groups of the biomass were mainly involved in the biosorption of Cu(II) onto L. pulmonaria biomass. The L. pulmonaria is a promising biosorbent for Cu(lI) ions because of its availability, low cost, and high metal biosorption and desorption capacities. Lobaria pulmonaria is a promising biosorbent for Cu(II) ions because of its availability, low cost, and high metal biosorption and desorption capacities. To the best of our knowledge, this is the first paper on the biosorption Cu by L. pulmonaria.

Design, synthesis, characterization and cation sensing behavior of amino-naphthoquinone receptor: Selective colorimetric sensing of Cu(II) ion in nearly aqueous solution with mimicking logic gate operation

NASA Astrophysics Data System (ADS)

Parthiban, C.; Elango, Kuppanagounder P.

2017-03-01

An amino-naphthoquione receptor (R1) has been rationally designed, synthesized and characterized using 1H and 13C NMR, LCMS and single crystal X-ray diffraction studies. The receptor exhibits an instantaneous colour change from yellow to blue selectively with Cu(II) ions in water-DMF (98:2% v/v) medium. The results of UV-Vis and fluorescence spectral studies indicates that the mechanism of sensing involves formation of a 1:1 complex between R1 and Cu(II) ion. The proposed mechanism has been confirmed through product analysis using FT-IR, UV-Vis, EPR and HRMS studies in addition to magnetic moment and elemental analysis measurements. The formed [Cu(R1)Cl2] possess a square planar geometry. The binding constant for the interaction of Cu(II) ion with the present unsubstituted quinone is found to be relatively higher than that with quinones containing electron withdrawing chlorine atom and electron releasing methyl group reported in literature. The detection limit of Cu(II) ion in aqueous solution by R1 is observed to be 8.7 nM. The detection of Cu(II) ion by R1 in aqueous solution produces remarkable changes in the electronic and fluorescence spectra, which is applied to construct logic gate at molecular level.

Cu(II) promotes amyloid pore formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hangyu, E-mail: hangyuz@uw.edu; Rochet, Jean-Christophe; Stanciu, Lia A.

2015-08-14

The aggregation of α-synuclein is associated with dopamine neuron death in Parkinson's disease. There is controversy in the field over the question of which species of the aggregates, fibrils or protofibrils, are toxic. Moreover, compelling evidence suggested the exposure to heavy metals to be a risk of PD. Nevertheless, the mechanism of metal ions in promoting PD remains unclear. In this research, we investigated the structural basis of Cu(II) induced aggregation of α-synuclein. Using transmission electron microscopy experiments, Cu(II) was found to promote in vitro aggregation of α-synuclein by facilitating annular protofibril formation rather than fibril formation. Furthermore, neuroprotective baicalein disaggregatedmore » annular protofibrils accompanied by considerable decrease of β-sheet content. These results strongly support the hypothesis that annular protofibrils are the toxic species, rather than fibrils, thereby inspiring us to search novel therapeutic strategies for the suppression of the toxic annular protofibril formation. - Highlights: • Cu(II) promoted the annular protofibril formation of α-synuclein in vitro. • Cu(II) postponed the in vitro fibrillization of α-synuclein. • Neuroprotective baicalein disaggregated annular protofibrils.« less

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A.

2014-10-27

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI uponmore » reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.« less

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A.

2014-09-12

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI uponmore » reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.« less

Redox cycling of Cu(II) by 6-mercaptopurine leads to ROS generation and DNA breakage: possible mechanism of anticancer activity.

PubMed

Rehman, Sayeed Ur; Zubair, Haseeb; Sarwar, Tarique; Husain, Mohammed Amir; Ishqi, Hassan Mubarak; Nehar, Shamshun; Tabish, Mohammad

2015-02-01

6-Mercaptopurine (6MP) is a well-known purine antimetabolite used to treat childhood acute lymphoblastic leukemia and other diseases. Cancer cells as compared to normal cells are under increased oxidative stress and show high copper level. These differences between cancer cells and normal cells can be targeted to develop effective cancer therapy. Pro-oxidant property of 6MP in the presence of metal ions is not well documented. Redox cycling of Cu(II) to Cu(I) was found to be efficiently mediated by 6MP. We have performed a series of in vitro experiments to demonstrate the pro-oxidant property of 6MP in the presence of Cu(II). Studies on human lymphocytes confirmed the DNA damaging ability of 6MP in the presence of Cu(II). Since 6MP possesses DNA damaging ability by producing reactive oxygen species (ROS) in the presence of Cu(II), it may also possess apoptosis-inducing activity by involving endogenous copper ions. Essentially, this would be an alternative and copper-dependent pathway for anticancer activity of 6MP.

Synthesis, characterization, X-ray crystal structure and conductometry studying of a number of new Schiff base complexes; a new example of binuclear square pyramidal geometry of Cu(II) complex bridged with an oxo group

NASA Astrophysics Data System (ADS)

Golbedaghi, Reza; Alavipour, Ehsan

2015-11-01

Three new binuclear Cu(II), Mn(II), Co(II) complexes [Cu2(L) (ClO4)](ClO4)2 (1), [Mn2(L) (ClO4)](ClO4)2 (2), and [Co2(L) (ClO4)](ClO4)2 (3), {L = 1,3-bis(2-((Z)-(2-aminopropylimino)methyl)phenoxy)propan-2-ol} have been synthesized. Single crystal X-ray structure analysis of complex 1 showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. In addition, the crystal structure studying shows, a perchlorate ion has been bridged to the Cu(II) metal centers. However, two distorted square pyramidal Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, the conductometry behaviors of all complexes were studied in acetonitrile solution.

Structural characterization and antioxidant properties of Cu(II) and Ni(II) complexes derived from dicyandiamide

NASA Astrophysics Data System (ADS)

Kertmen, Seda Nur; Gonul, Ilyas; Kose, Muhammet

2018-01-01

New Cu(II) and Ni(II) complexes derived from dicyandiamide were synthesized and characterised by spectroscopic and analytical methods. Molecular structures of the complexes were determined by single crystal X-ray diffraction studies. In the complexes, the Cu(II) or Ni(II) ions are four-coordinate with a slight distorted square planar geometry. The ligands (L-nPen and L-iPen) derived from dicyandiamide formed via nucleophilic addition of alcohol solvent molecule in the presence Cu(II) or Ni(II) ions. Complexes were stabilised by intricate array of hydrogen bonding interactions. Antioxidant activity of the complexes was evaluated by DPPH radical scavenging and CUPRAC methods. The complexes exhibit antioxidant activity, however, their activities were much lower than standard antioxidants (Vitamin C and trolox).

Adsorption of enrofloxacin in presence of Zn(II) on a calcareous soil.

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2015-12-01

As a result of their consumption, excretion, disposal and persistence, antibiotics enter the soil environment and may be transported to surface and ground waters. During their transfer through soils, retention processes play a key role in their mobility. Antibiotics often coexist with heavy metals in soils due to agricultural practices and other sources of inputs. In this context, this study deals with the co-adsorption of Zn(II) and enrofloxacin (ENR), a widely-used veterinary antibiotic, on a calcareous soil using batch retention experiments and X-ray Absorption Near Edge Structure (XANES) spectroscopy. To improve our understanding of the interaction of this emerging organic contaminant with metal cations at the water-soil interface, the ternary system containing ENR, Zn(II) and a selected calcareous soil was investigated over a pH range between 7 and 10, at different solid-solution contact times and ENR concentrations. The presence of Zn(II) slightly influenced the retention of the antibiotic, leading to an increase of the adsorbed ENR amounts. The distribution coefficient Kd value increased from 0.66 Lg(-1) for single ENR adsorption to 1.04 Lg(-1) in presence of Zn(II) at a 1/2 ENR/Zn(II) ratio. The combination of adsorption isotherm data, solution speciation diagrams and XANES spectra evidenced a small proportion of Zn(II)-ENR complexes at soil pH leading to the slight increase of ENR adsorption in presence of zinc. These results suggest that it is necessary to consider the interaction between ENR and metal cations when assessing the mobility of ENR in soils. Copyright © 2015 Elsevier Inc. All rights reserved.

Identification of the function of extracellular polymeric substances (EPS) in denitrifying phosphorus removal sludge in the presence of copper ion.

PubMed

Wang, Yayi; Qin, Jian; Zhou, Shuai; Lin, Ximao; Ye, Liu; Song, Chengkang; Yan, Yuan

2015-04-15

Industrial wastewater containing heavy metals that enters municipal wastewater treatment plants inevitably has a toxic impact on biological treatment processes. In this study, the impact of Cu(II) (0, 1.5, 2, 2.5, 3 mg/L) on the performance of denitrifying phosphorus removal (DPR) and microbial community structures was investigated. Particularly, the dynamic change in the amount and composition of extracellular polymeric substances (EPS), and the role of EPS in P removal, were assessed using three-dimensional excitation-emission matrix fluorescence spectroscopy combined with parallel factor (PARAFAC) analysis. The results showed that, after long-term adjustment, the P removal efficiency was maintained at 95 ± 2.7% at Cu(II) addition up to 2.5 mg/L, but deteriorated when the Cu(II) addition was 3 mg/L. The EPS content, including proteins and humic substances, increased with increasing Cu(II) additions at concentrations ≤2.5 mg/L. This property of EPS was beneficial for protecting phosphate-accumulating organisms (PAOs) against heavy metals, as both proteins and humic substances are strong ligands for Cu(II). Therefore, the PAOs abundance was still relatively high (67 ± 3%) when Cu(II) accumulation in sludge was up to 10 mg/g SS. PARAFAC confirmed that aromatic proteins could be transformed into soluble microbial byproduct-like material when microorganisms were subjected to Cu(II) stress, owing to their strong metal ion complexing capacity. The increase in the percentage of humic-like substances enhanced the detoxification function of the sludge EPS. EPS accounted for approximately 26-47% of P removed by adsorption when Cu(II) additions were between 0 and 2.5 mg/L. The EPS function, including binding toxic heavy metals and P storage, enhanced the operating stability of DPR systems. This study provides us with a better understanding of (1) the tolerance of DPR sludge to copper toxicity and (2) the function of sludge EPS in the presence of heavy metals in biological P removal systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

Genome-wide analysis of the Zn(II)2Cys6 zinc cluster-encoding gene family in Aspergillus flavus

USDA-ARS?s Scientific Manuscript database

Proteins with a Zn(II)2Cys6 domain, Cys-X2-Cys-X6-Cys-X5-12-Cys-X2-Cys-X6-9-Cys (hereafter, referred to as the C6 domain), form a subclass of zinc finger proteins found exclusively in fungi and yeast. Genome sequence databases of Saccharomyces cerevisiae and Candida albicans have provided an overvie...

Highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste with amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent.

PubMed

Bao, Shuangyou; Tang, Lihong; Li, Kai; Ning, Ping; Peng, Jinhui; Guo, Huibin; Zhu, Tingting; Liu, Ye

2016-01-15

Amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent was used as a novel sorbent to highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste in the presence of Fe(II). These hot-dip galvanizing pickling waste mainly contain ZnCl2 and FeCl2 in aqueous HCl media. The properties of this magnetic adsorbent were examined by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), infrared spectrometer (FT-IR) and BET surface area measurements. Various factors influencing the adsorption of Zn(II) ion such as initial concentration of metal ions, the amount of adsorbent, pH value of the solutions, the concentration of coexisting iron ion were investigated by batch experiments. The results indicated that the adsorption equilibrium data obeyed the Freundlich model with maximum adsorption capacities for Zn(II) to 169.5mg/g. The maximum adsorption occurred at pH 5±0.1 and Fe(II) interferences had no obvious influence. This work provides a potential and unique technique for zinc ion removal from hot-dip galvanizing pickling waste. Copyright © 2015 Elsevier Inc. All rights reserved.

Hypothesis testing for the validation of the kinetic spectrophotometric methods for the determination of lansoprazole in bulk and drug formulations via Fe(III) and Zn(II) chelates.

PubMed

Rahman, Nafisur; Kashif, Mohammad

2010-03-01

Point and interval hypothesis tests performed to validate two simple and economical, kinetic spectrophotometric methods for the assay of lansoprazole are described. The methods are based on the formation of chelate complex of the drug with Fe(III) and Zn(II). The reaction is followed spectrophotometrically by measuring the rate of change of absorbance of coloured chelates of the drug with Fe(III) and Zn(II) at 445 and 510 nm, respectively. The stoichiometric ratio of lansoprazole to Fe(III) and Zn(II) complexes were found to be 1:1 and 2:1, respectively. The initial-rate and fixed-time methods are adopted for determination of drug concentrations. The calibration graphs are linear in the range 50-200 µg ml⁻¹ (initial-rate method), 20-180 µg ml⁻¹ (fixed-time method) for lansoprazole-Fe(III) complex and 120-300 (initial-rate method), and 90-210 µg ml⁻¹ (fixed-time method) for lansoprazole-Zn(II) complex. The inter-day and intra-day precision data showed good accuracy and precision of the proposed procedure for analysis of lansoprazole. The point and interval hypothesis tests indicate that the proposed procedures are not biased. Copyright © 2010 John Wiley & Sons, Ltd.

Time-dependent Translational Response of E. coli to Excess Zn(II)

PubMed Central

Easton, J. Allen; Thompson, Peter; Crowder, Michael W.

2006-01-01

Zinc homeostasis is not well understood beyond methods of import and export. In order to better understand zinc homeostasis in Escherichia coli by identifying Zn(ii)-responsive proteins, a proteomic approach was taken. Through the use of two-dimensional gel electrophoresis, we were able to show that the levels of OmpF, AspC, YcdO, Eno, and CysE increased after 30 min of Zn(ii) stress, while the levels of Tig, TufA, SelA, and LeuC decreased relative to non-stressed controls. After 4 h of Zn(ii) stress, the levels of three proteins (DnaK, YeaU, and Mdh) were found to be up-regulated, while the levels of seven amino acid importers (HisJ, ArgT, LivJ, DppA, OppA, RbsB, and GinH) were found to be decreased. None of these proteins had been reported to be up- or down-regulated in any previously published cDNA microarray experiments. This result raises questions about the validity of cDNA arrays when they are used to make assumptions concerning protein levels within bacterial cells. These data also suggest that time is a factor when characterizing how the E. coli proteome responds to Zn(ii) stress. PMID:17122063

Synthesis of novel palladium(0) nanocatalysts by microorganisms from heavy-metal-influenced high-alpine sites for dehalogenation of polychlorinated dioxins.

PubMed

Schlüter, Michael; Hentzel, Thomas; Suarez, Christian; Koch, Mandy; Lorenz, Wilhelm G; Böhm, Leonard; Düring, Rolf-Alexander; Koinig, Karin A; Bunge, Michael

2014-12-01

In a search for new aqueous-phase systems for catalyzing reactions of environmental and industrial importance, we prepared novel biogenerated palladium (Pd) nanocatalysts using a "green" approach based on microorganisms isolated from high-alpine sites naturally impacted by heavy metals. Bacteria and fungi were enriched and isolated from serpentinite-influenced ponds (Totalp region, Parsenn, near Davos, Graubünden, Switzerland). Effects on growth dynamics were monitored using an automated assay in 96-well microtiter plates, which allowed for simultaneous cultivation and on-line analysis of Pd(II)- and Ni(II)-mediated growth inhibition. Microorganisms from Totalp ponds tolerated up to 3mM Pd(II) and bacterial isolates were selected for cultivation and reductive synthesis of Pd(0) nanocatalysts at microbial interfaces. During reduction of Pd(II) with formate as the electron donor, Pd(0) nanoparticles were formed and deposited in the cell envelope. The Pd(0) catalysts produced in the presence of Pd(II)-tolerant Alpine Pseudomonas species were catalytically active in the reductive dehalogenation of model polychlorinated dioxin congeners. This is the first report which shows that Pd(0) synthesized in the presence of microorganisms catalyzes the reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs). Because the "bioPd(0)" catalyzed the dechlorination reactions preferably via non-lateral chlorinated intermediates, such a pathway could potentially detoxify PCDDs via a "safe route". It remains to be determined whether the microbial formation of catalytically active metal catalysts (e.g., Zn, Ni, Fe) occurs in situ and whether processes involving such catalysts can alter the fate and transport of persistent organic pollutants (POPs) in Alpine habitats. Copyright © 2014 Elsevier Ltd. All rights reserved.

Formation of palladium(0) nanoparticles at microbial surfaces.

PubMed

Bunge, Michael; Søbjerg, Lina S; Rotaru, Amelia-Elena; Gauthier, Delphine; Lindhardt, Anders T; Hause, Gerd; Finster, Kai; Kingshott, Peter; Skrydstrup, Troels; Meyer, Rikke L

2010-10-01

The increasing demand and limited natural resources for industrially important platinum-group metal (PGM) catalysts render the recovery from secondary sources such as industrial waste economically interesting. In the process of palladium (Pd) recovery, microorganisms have revealed a strong potential. Hitherto, bacteria with the property of dissimilatory metal reduction have been in focus, although the biochemical reactions linking enzymatic Pd(II) reduction and Pd(0) deposition have not yet been identified. In this study we investigated Pd(II) reduction with formate as the electron donor in the presence of Gram-negative bacteria with no documented capacity for reducing metals for energy production: Cupriavidus necator, Pseudomonas putida, and Paracoccus denitrificans. Only large and close-packed Pd(0) aggregates were formed in cell-free buffer solutions. Pd(II) reduction in the presence of bacteria resulted in smaller, well-suspended Pd(0) particles that were associated with the cells (called "bioPd(0)" in the following). Nanosize Pd(0) particles (3-30 nm) were only observed in the presence of bacteria, and particles in this size range were located in the periplasmic space. Pd(0) nanoparticles were still deposited on autoclaved cells of C. necator that had no hydrogenase activity, suggesting a hydrogenase-independent formation mechanism. The catalytic properties of Pd(0) and bioPd(0) were determined by the amount of hydrogen released in a reaction with hypophosphite. Generally, bioPd(0) demonstrated a lower level of activity than the Pd(0) control, possibly due to the inaccessibility of the Pd(0) fraction embedded in the cell envelope. Our results demonstrate the suitability of bacterial cells for the recovery of Pd(0), and formation and immobilization of Pd(0) nanoparticles inside the cell envelope. However, procedures to make periplasmic Pd(0) catalytically accessible need to be developed for future nanobiotechnological applications.

Neutral Ni(II), Pd(II) and Pt(II) ONS-pincer complexes of 5-acetylbarbituric-4N-dimethylthiosemicarbazone: synthesis, characterization and properties.

PubMed

Castiñeiras, Alfonso; Fernández-Hermida, Nuria; García-Santos, Isabel; Gómez-Rodríguez, Lourdes

2012-11-21

Octahedral 1:1 Ni(II) and square-planar 1:1 Pd(II) and Pt(II) complexes of formulae [Ni(HAcb4DM)(AcO)(H2O)2]·H2O (1), [Pd(HAcb4DM)Cl]·5H2O (2) and [Pt(HAcb4DM)Cl]·3H2O (3), where H2Acb4DM = 5-acetylbarbituric-4N-dimethylthiosemicarbazone (H2 denoting its two dissociable protons, one enolic and one thiolic), have been synthesized and characterized by elemental analysis and by 1H and 13C NMR, UV-vis, and IR spectroscopy. Crystallisation of compounds 1–3 from DMSO afforded complexes of formulae [Ni(HAcb4DM)2]·2H2O (1a), [Pd(Acb4DM)(DMSO)]·DMSO (2a) and [Pt(Acb4DM)(DMSO)]·DMSO (3a), the molecular and crystal structures of which were determined by X-ray diffractometry. The thiosemicarbazone in 1a coordinates to the metal ions in an ONS-tridentate manner in the O-enolate/S-thione form, but in complexes 2a and 3a the thiosemicarbazone binds Pd(II) or Pt(II) as an ONS-pincer ligand in the O-enolate/S-thiolate form. The 195Pt NMR spectrum of 3 shows a signal at −2950 ppm along with two new signals at −3348 and −2731 ppm, indicating the presence of solvolysis products. The catalytic activity of complex 2a has been explored in aryl–aryl Suzuki cross-coupling reactions. H2Acb4DM and complexes 2 and 3 were screened for in vitro cytotoxicity against a human tumour cell line (HeLa-229), with the clinically employed drug cisplatin as a reference.

Pilot Study of 64Cu(I) for PET Imaging of Melanoma

DOE PAGES

Jiang, Lei; Tu, Yingfeng; Hu, Xiang; ...

2017-05-31

Currently, 64Cu(II) labeled tracers including 64CuCl 2 have been widely applied in the research of molecular imaging and therapy. Human copper transporter 1 (hCTR1) is the major high affinity copper influx transporter in mammalian cells, and specially responsible for the transportation of Cu(I) not Cu(II). Thus, we investigated the feasible application of 64Cu(I) for PET imaging. 64Cu(II) was reduced to 64Cu(I) with the existence of sodium L-ascorbate, DL-Dithiothreitol or cysteine. Cell uptake and efflux assay was investigated using B16F10 and A375 cell lines, respectively. Small animal PET and biodistribution studies were performed in both B16F10 and A375 tumor-bearing mice. Comparedmore » with 64Cu(II), 64Cu(I) exhibited higher cellular uptake by melanoma, which testified CTR1 specially influx of Cu(I). But, due to oxidation reaction in vivo, no significant difference between 64Cu(I) and 64Cu(II) was observed through PET images and biodistribution. In addition, radiation absorbed doses for major tissues of human were calculated based on the mouse biodistribution. Radiodosimetry calculations for 64/67Cu(I) and 64/67Cu(II) were similar, which suggested that although melanoma were with high radiation absorbed doses, high radioactivity accumulation by liver and kidney should be noticed for the further application. Thus, 64Cu(I) should be further studied to evaluate it as a PET imaging radiotracer.« less

New copper(II) complexes with dopamine hydrochloride and vanillymandelic acid: Spectroscopic and thermal characterization

NASA Astrophysics Data System (ADS)

Mohamed, Gehad G.; Nour El-Dien, F. A.; El-Nahas, R. G.

2011-10-01

The dopamine derivatives participate in the regulation of wide variety of physiological functions in the human body and in medication life. Increase and/or decrease in the concentration of dopamine in human body reflect an indication for diseases such as Schizophrenia and/or Parkinson diseases. The Cu(II) chelates with coupled products of dopamine hydrochloride (DO.HCl) and vanillymandelic acid (VMA) with 4-aminoantipyrine (4-AAP) are prepared and characterized. Different physico-chemical techniques namely IR, magnetic and UV-vis spectra are used to investigate the structure of these chelates. Cu(II) forms 1:1 (Cu:DO) and 1:2 (Cu:VMA) chelates. DO behave as a uninegative tridentate ligand in binding to the Cu(II) ion while VMA behaves as a uninegative bidentate ligand. IR spectra show that the DO is coordinated to the Cu(II) ion in a tridentate manner with ONO donor sites of the phenolic- OH, -NH and carbonyl- O, while VMA is coordinated with OO donor sites of the phenolic- OH and -NH. Magnetic moment measurements reveal the presence of Cu(II) chelates in octahedral and square planar geometries with DO and VMA, respectively. The thermal decomposition of Cu(II) complexes is studied using thermogravimetric (TG) and differential thermal analysis (DTA) techniques. The activation thermodynamic parameters, such as, energy of activation, enthalpy, entropy and free energy change of the complexes are evaluated and the relative thermal stability of the complexes are discussed.

Pilot Study of 64Cu(I) for PET Imaging of Melanoma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Lei; Tu, Yingfeng; Hu, Xiang

Currently, 64Cu(II) labeled tracers including 64CuCl 2 have been widely applied in the research of molecular imaging and therapy. Human copper transporter 1 (hCTR1) is the major high affinity copper influx transporter in mammalian cells, and specially responsible for the transportation of Cu(I) not Cu(II). Thus, we investigated the feasible application of 64Cu(I) for PET imaging. 64Cu(II) was reduced to 64Cu(I) with the existence of sodium L-ascorbate, DL-Dithiothreitol or cysteine. Cell uptake and efflux assay was investigated using B16F10 and A375 cell lines, respectively. Small animal PET and biodistribution studies were performed in both B16F10 and A375 tumor-bearing mice. Comparedmore » with 64Cu(II), 64Cu(I) exhibited higher cellular uptake by melanoma, which testified CTR1 specially influx of Cu(I). But, due to oxidation reaction in vivo, no significant difference between 64Cu(I) and 64Cu(II) was observed through PET images and biodistribution. In addition, radiation absorbed doses for major tissues of human were calculated based on the mouse biodistribution. Radiodosimetry calculations for 64/67Cu(I) and 64/67Cu(II) were similar, which suggested that although melanoma were with high radiation absorbed doses, high radioactivity accumulation by liver and kidney should be noticed for the further application. Thus, 64Cu(I) should be further studied to evaluate it as a PET imaging radiotracer.« less

An optimized procedure for preconcentration, determination and on-line recovery of palladium using highly selective diphenyldiketone-monothiosemicarbazone modified silica gel.

PubMed

Sharma, R K; Pandey, Amit; Gulati, Shikha; Adholeya, Alok

2012-03-30

A novel, highly selective, efficient and reusable chelating resin, diphenyldiketone-monothiosemicarbazone modified silica gel, was prepared and applied for the on-line separation and preconcentration of Pd(II) ions in catalytic converter and spiked tap water samples. Several parameters like effect of pH, sample volume, flow rate, type of eluent, and influence of various ionic interferences, etc. were evaluated for effective adsorption of palladium at trace levels. The resin was found to be highly selective for Pd(II) ions in the pH range 4-5 with a very high sorption capacity of 0.73 mmol/g and preconcentration factor of 335. The present environment friendly procedure has also been applied for large-scale extraction by employing the use of newly designed reactor in which on-line separation and preconcentration of Pd can be carried out easily and efficiently in short duration of time. Copyright © 2012 Elsevier B.V. All rights reserved.

Reactions of Pd(II) and Pt(II) Complexes With Tetraethylthiouram Disulfide

PubMed Central

Cervantes, G.; Molins, E.; Miravitlles, C.

1997-01-01

The reactions of tetraethylthiouram disulfide (DTS), an inhibitor of the nephrotoxicity of Pt(II) drugs, an efficient agent in the treatment of chronic alcoholism, in the treatment of HIV infections, AIDS and heavy metal toxicity, and a fungicide and herbicide, with K2[PtCl4], in ratio 1:1 and 1:2, gave the compounds [PtCl2DTS] and [Pt(S2CNEt2)2] respectively. The reaction of the complexes K2[PdCl4], Pd(AcO)2 and [PdCl2(PhCN)2], where PhCN = Benzonitrile, with tetraethylthiouram disulfide in ratio 1:1 or 1:2, yielded orange crystals identified as [Pd(S2CNEt2)2]. The crystals were suitable for study by X-ray diffraction. The -S-S- bridge in the tetraethylthiouram disulfude molecule was broken and the two molecules of the thiocarbamate derivative were bound to the Pd(II) by the equivalents sulfur atoms. All the compounds were characterized by IR, 1H and 13C NMR spectroscopies. PMID:18475812

Synthesis, structural characterization, fluorescence, antimicrobial, antioxidant and DNA cleavage studies of Cu(II) complexes of formyl chromone Schiff bases.

PubMed

Kavitha, P; Saritha, M; Laxma Reddy, K

2013-02-01

Cu(II) complexes have been synthesized from different Schiff bases, such as 3-((2-hydroxy phenylimino)methyl)-4H-chromen-4-one (HL(1)), 2-((4-oxo-4H-chromen-3-yl)methylneamino) benzoicacid (HL(2)), 3-((3-hydroxypyridin-2-ylimino)methyl)-4H-chromen-4-one (HL(3)) and 3-((2-mercaptophenylimino)methyl)-4H-chromen-4-one (HL(4)). The complexes were characterized by analytical, molar conductance, IR, electronic, magnetic, ESR, thermal, powder XRD and SEM studies. The analytical data reveal that metal to ligand molar ratio is 1:2 in all the complexes. Molar conductivity data indicates that all the Cu(II) complexes are neutral. On the basis of magnetic and electronic spectral data, distorted octahedral geometry is proposed for all the Cu(II) complexes. Thermal behaviour of the synthesized complexes illustrates the presence of lattice water molecules in the complexes. X-ray diffraction studies reveal that all the ligands and their Cu(II) complexes have triclinic system with different unit cell parameters. Antimicrobial, antioxidant and DNA cleavage activities indicate that metal complexes exhibited greater activity as compared with ligands. Copyright © 2012 Elsevier B.V. All rights reserved.

Zinc(II) binds to the neuroprotective peptide humanin.

PubMed

Armas, Ambar; Sonois, Vanessa; Mothes, Emmanuelle; Mazarguil, Honoré; Faller, Peter

2006-10-01

The abnormal accumulation of the peptide amyloid-beta in the form of senile (or amyloid) plaques is one of the hallmarks of Alzheimer's disease (AD). Zinc ions have been implicated in AD and plaques formation. Recently, the peptide humanin has been discovered. Humanin showed neuroprotective activity against amyloid-beta insults. Here the question investigated is if humanin could interact directly with Zn(II). It is shown that Zn(II) and its substitutes Cd(II)/Co(II) bind to humanin via a thiolate bond from the side chain of the single cysteine at position 8. The low intensity of the d-d bands of Co(II)-humanin indicated an octahedral coordination geometry. Titration experiments suggest that Zn(II) binds to humanin with an apparent affinity in the low muM range. This apparent Zn-binding affinity is in the same order as for amyloid-beta and glutathione and could thus be of physiological relevance.

Cu(II) Binding to the Peptide Ala-His-His, a Chimera of the Canonical Cu(II)-Binding Motifs Xxx-His and Xxx-Zzz-His.

PubMed

Gonzalez, Paulina; Vileno, Bertrand; Bossak, Karolina; El Khoury, Youssef; Hellwig, Petra; Bal, Wojciech; Hureau, Christelle; Faller, Peter

2017-12-18

Peptides and proteins with the N-terminal motifs NH 2 -Xxx-His and NH 2 -Xxx-Zzz-His form well-established Cu(II) complexes. The canonical peptides are Gly-His-Lys and Asp-Ala-His-Lys (from the wound healing factor and human serum albumin, respectively). Cu(II) is bound to NH 2 -Xxx-His via three nitrogens from the peptide and an external ligand in the equatorial plane (called 3N form here). In contrast, Cu(II) is bound to NH 2 -Xxx-Zzz-His via four nitrogens from the peptide in the equatorial plane (called 4N form here). These two motifs are not mutually exclusive, as the peptides with the sequence NH 2 -Xxx-His-His contain both of them. However, this chimera has never been fully explored. In this work, we use a multispectroscopic approach to analyze the Cu(II) binding to the chimeric peptide Ala-His-His (AHH). AHH is capable of forming the 3N- and 4N-type complexes in a pH dependent manner. The 3N form predominates at pH ∼ 4-6.5 and the 4N form at ∼ pH 6.5-10. NMR experiments showed that at pH 8.5, where Cu(II) is almost exclusively bound in the 4N form, the Cu(II)-exchange between AHH or the amidated AHH-NH 2 is fast, in comparison to the nonchimeric 4N form (AAH). Together, the results show that the chimeric AHH can access both Cu(II) coordination types, that minor changes in the second (or further) coordination sphere can impact considerably the equilibrium between the forms, and that Cu kinetic exchange is fast even when Cu-AHH is mainly in the 4N form.

A novel copper(II) coordination at His186 in full-length murine prion protein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watanabe, Yasuko; Hiraoka, Wakako; Igarashi, Manabu

2010-04-09

To explore Cu(II) ion coordination by His{sup 186} in the C-terminal domain of full-length prion protein (moPrP), we utilized the magnetic dipolar interaction between a paramagnetic metal, Cu(II) ion, and a spin probe introduced in the neighborhood of the postulated binding site by the spin labeling technique (SDSL technique). Six moPrP mutants, moPrP(D143C), moPrP(Y148C), moPrP(E151C), moPrP(Y156C), moPrP(T189C), and moPrP(Y156C,H186A), were reacted with a methane thiosulfonate spin probe and a nitroxide residue (R1) was created in the binding site of each one. Line broadening of the ESR spectra was induced in the presence of Cu(II) ions in moPrP(Y148R1), moPrP(Y151R1), moPrP(Y156R1), andmore » moPrP(T189R1) but not moPrP(D143R1). This line broadening indicated the presence of electron-electron dipolar interaction between Cu(II) and the nitroxide spin probe, suggesting that each interspin distance was within 20 A. The interspin distance ranges between Cu(II) and the spin probes of moPrP(Y148R1), moPrP(Y151R1), moPrP(Y156R1), and moPrP(T189R1) were estimated to be 12.1 A, 18.1 A, 10.7 A, and 8.4 A, respectively. In moPrP(Y156R1,H186A), line broadening between Cu(II) and the spin probe was not observed. These results suggest that a novel Cu(II) binding site is involved in His186 in the Helix2 region of the C-terminal domain of moPrP{sup C}.« less

Spectroscopic and mycological studies of Co(II), Ni(II) and Cu(II) complexes with 4-aminoantipyrine derivative

NASA Astrophysics Data System (ADS)

Sharma, Amit Kumar; Chandra, Sulekh

2011-10-01

Complexes of the type [M(L)X 2], where M = Co(II), Ni(II) and Cu(II), have been synthesized with novel NO-donor Schiff's base ligand, 1,4-diformylpiperazine bis(4-imino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) which is obtained by the acid catalyzed condensation of 1,4-diformylpiperazine with 4-aminoantipyrine. The elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV, NMR, mass and EPR studies of the compounds led to the conclusion that the ligand acts as tetradentate chelate. The Schiff's base ligand forms hexacoordinated complexes having octahedral geometry for Ni(II) and tetragonal geometry for Co(II) and Cu(II) complexes. The mycological studies of the compounds were examined against the several opportunistic pathogens, i.e., Alternaria brassicae, Aspergillus niger and Fusarium oxysporum. The Cu(II) complexes were found to have most fungicidal behavior.

The Evolution of Pd0/PdII-Catalyzed Aromatic Fluorination

PubMed Central

2016-01-01

Conspectus Aromatic fluorides are prevalent in both agrochemical and pharmaceutical agents. However, methods for their rapid and general preparation from widely available starting materials are limited. Traditional approaches such as the Balz–Schiemann and Halex reactions require harsh conditions that limit functional group tolerance and substrate scope. The use of transition metals to affect C–F bond formation has provided some useful alternatives, but a broadly applicable method remains elusive. In contrast to the widespread use of Pd0/PdII catalysis for aryl–Z bond formation (Z = C, N, O), the analogous C–F cross-coupling process was unknown until fairly recently. In large part, this is due to the challenging Ar–F reductive elimination from Pd(II) intermediates. We have discovered that certain biaryl monophosphine ligands are uniquely capable of promoting this transformation. In this Account, we describe the discovery and development of a Pd-catalyzed C–F cross-coupling process and the systematic developments that made this once hypothetical reaction possible. Key to these developments was the discovery of an unusual in situ ligand modification process in which a molecule of substrate is incorporated into the ligand scaffold and the identity of the modifying group is crucial to the outcome of the reaction. This prompted the synthesis of a variety of “premodified” ligands and the identification of one that led to an expanded substrate scope, including (hetero)aryl triflates and bromides. Contemporaneously, a new Pd(0) precatalyst was also discovered that avoids the need to reduce Pd(II) in situ, a process that was often inefficient and led to the formation of byproducts. The use of inexpensive but hygroscopic sources of fluoride necessitates a reaction setup inside of a N2-filled glovebox, limiting the practicality of the method. Thus, a preformed wax capsule was designed to isolate the catalyst and reagents from the atmosphere and permit benchtop storage and setup. This new technology thus removes the requirement to employ a glovebox for the aromatic fluorination process and other air-sensitive protocols. In every catalyst system that we have studied to date, we observed the formation of regioisomeric fluoride side products. Through deuterium labeling studies it was found that they likely arise from a deprotonation event resulting in the formation of HF and a Pd–benzyne intermediate. Through an investigation of the mechanism of this undesired pathway, a new ligand was designed that substantially reduces the formation of the aryl fluoride regioisomer and even allows room-temperature Ar–F reductive elimination from a Pd(II) intermediate. PMID:27656765

Zinc(II) complexes with potent cyclin-dependent kinase inhibitors derived from 6-benzylaminopurine: synthesis, characterization, X-ray structures and biological activity.

PubMed

Trávnícek, Zdenek; Krystof, Vladimír; Sipl, Michal

2006-02-01

The synthesis, characterization and biological activity of the first zinc(II) complexes with potent inhibitors of cyclin-dependent kinases (CDKs) derived from 6-benzylaminopurine are described. Based on the results following from elemental analyses, infrared, NMR and ES+MS (electrospray mass spectra in the positive ion mode) spectroscopies, conductivity data, thermal analysis and X-ray structures, the tetrahedral Zn(II) complexes of the compositions [Zn(Olo)Cl(2)](n) (1), [Zn(iprOlo)Cl(2)](n) (2), [Zn(BohH(+))Cl(3)] x H(2)O (3) and [Zn(iprOloH(+))Cl(3)] x H(2)O (4) have been prepared, where Olo=2-(2-hydroxyethylamino)-6-benzylamino-9-methylpurine (Olomoucine), iprOlo=2-(2-hydroxyethylamino)-6-benzylamino-9-isopropylpurine (i-propyl-Olomoucine), Boh=2-(3-hydroxypropylamino)-6-benzylamino-9-isopropylpurine (Bohemine). The 1D-polymeric chain structure for [Zn(Olo)Cl(2)](n) (1) as well as the monomeric one for [Zn(BohH(+))Cl(3)] x H(2)O (3) and [Zn(iprOloH(+))Cl(3)] x H(2)O (4) have been revealed unambiguously by single crystal X-ray analyses. The 1D-polymeric chain of 1 consists of Zn(Olo)Cl(2) monomeric units in which the Zn(II) ion is coordinated by two chlorine atoms and one oxygen atom of the 2-hydroxyethylamino group of Olomoucine. The next monomeric unit is bonded to Zn(II) through the N7 atom of a purine ring. Thus, each of Zn(II) ions is tetrahedrally coordinated and a ZnCl(2)NO chromophore occurs in the complex 1. The complexes 3 and 4 are mononuclear species with a distorted tetrahedral arrangement of donor atoms around the Zn(II) ion with a ZnCl(3)N chromophore. The corresponding CDK inhibitor, i.e., both Boh and iprOlo, is coordinated to Zn(II) via the N7 atom of the purine ring in 3 and 4. The cytotoxicity of the zinc(II) complexes against human melanoma, sarcoma, leukaemia and carcinoma cell lines has been determined as well as the inhibition of the CDK2/cyclin E kinase. A relationship between the structure and biological activity of the complexes is also discussed.

Characterization and mechanism of copper biosorption by a highly copper-resistant fungal strain isolated from copper-polluted acidic orchard soil.

PubMed

Tu, Chen; Liu, Ying; Wei, Jing; Li, Lianzhen; Scheckel, Kirk G; Luo, Yongming

2018-06-22

In this paper, a highly copper-resistant fungal strain NT-1 was characterized by morphological, physiological, biochemical, and molecular biological techniques. Physiological response to Cu(II) stress, effects of environmental factors on Cu(II) biosorption, as well as mechanisms of Cu(II) biosorption by strain NT-1 were also investigated in this study. The results showed that NT-1 belonged to the genus Gibberella, which exhibited high tolerance to both acidic conditions and Cu(II) contamination in the environment. High concentrations of copper stress inhibited the growth of NT-1 to various degrees, leading to the decreases in mycelial biomass and colony diameter, as well as changes in morphology. Under optimal conditions (initial copper concentration: 200 mg L -1 , temperature 28 °C, pH 5.0, and inoculum dose 10%), the maximum copper removal percentage from solution through culture of strain NT-1 within 5 days reached up to 45.5%. The biosorption of Cu(II) by NT-1 conformed to quasi-second-order kinetics and Langmuir isothermal adsorption model and was confirmed to be a monolayer adsorption process dominated by surface adsorption. The binding of NT-1 to Cu(II) was mainly achieved by forming polydentate complexes with carboxylate and amide group through covalent interactions and forming Cu-nitrogen-containing heterocyclic complexes via Cu(II)-π interaction. The results of this study provide a new fungal resource and key parameters influencing growth and copper removal capacity of the strain for developing an effective bioremediation strategy for copper-contaminated acidic orchard soils.

Cell death induced by flavonoid glycosides with and without copper.

PubMed

Hsu, Hsue-Yin; Tsang, Shih-Fang; Lin, Kai-Wei; Yang, Shyh-Chyun; Lin, Chun-Nan

2008-07-01

The ability of flavonoid glycosides isolated from several plants to induce DNA breakage was examined using supercoiled plasmid pBR322 DNA by agarose gel electrophoresis in the presence of Cu(II). Among all the compounds, 1, 4, and 6 could cause significant breakages of supercoiled plasmid pBR322 DNA in the presence of Cu(II). Cu(I) was not shown to be an essential intermediate in the process of pBR322 DNA breakage by using the Cu(I)-specific sequestering reagent neocuproine. A decreased cell viability was enhanced in gastric carcinoma SCM-1 cells treating with lower concentrations of 1 and 6 when cotreated with increased concentrations of Cu(II), respectively. Treatments of SCM-1 cells with 500 microM of 1 in the presence of 300 or 500 microM of Cu(II) inhibited the Cu(II)-induced apoptosis. Compound 1 (500 microM) could prevent cell death by inhibiting the 500 microM Cu(II)-induced apoptosis and necrosis, but did not have any effect on the mitochondrial membrane potential changed by 500 microM Cu(II). Both compounds 1 and 6 could inhibit the DNA breakages caused by O2- while 1 also revealed inhibitory effect on xanthine oxidase with an IC50 value of 22.7+/-6.9 microM. These results indicated that compound 1 with a higher concentration may probably mediate through the suppression of xanthine oxidase activity and reduce reactive oxygen species (ROS) induced by high concentration of Cu(II) (500 microM) and prevent the following cell death.

Synthesis, structure, and characterization of two Zn(II) complex containing two-dimensional bilayer structure

NASA Astrophysics Data System (ADS)

Zhang, Meili; Ren, Yixia; Chen, Xiaoli

2014-10-01

Two new Zn(II) complexes, [Zn2(L)(H2O)3]ṡH2O (1) and [Zn3(HL)2(bpp)2(Hbpp)2]ṡ10H2Oṡ2ClO4 (2) (H4L = cis,cis,cis,cis-1,2,3,4-cyclopentanetracarboxylic acid, bpp = 1,3-bis(4-pyridyl)propane), have been synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction techniques. The structure indicates that the complex 1 crystallizes in triclinic, space group Pī, in which, the four carboxylate groups of L ligand adopt μ2-η1:η0, μ2-η1:η1, μ1-η1:η1 coordination modes, respectively, bridging Zn(II) atoms to generate a (4,6)-connected 2D bilayer network. The structure indicates that the complex 2 crystallizes in monoclinic, space group C2/c, in which, three deprotonated carboxylate groups of L ligand adopt uniform μ1-η1:η0 coordination mode linking Zn(II) atoms to form a 1D polymeric ribbon, the bpp ligands further extend such ribbon giving rised to a (3,4)-connected 2D bilayer network. The most striking feature of 1 and 2 is that both of bilayer networks contain 1D solvent channel, where water molecules are located. In additional, luminescent properties of two complexes have also been studied.