Monitoring of Zn(II) and Cd(II) adsorption on activated carbon from aqueous multicomponent solutions by differential pulse polarography (DPP)

The adsorption process of Zn(II) and Cd(II) from aqueous solution has been investigated from both kinetic and equilibrium standpoints, using differential pulse polarography (DPP) on a mercury dropping electrode as the analytical technique. With such an aim, adsorption experiments were performed using not only a single metal ion–Zn(II) or Cd(II) solution but also a multi-component ion metal–Zn(II), Cd(II) and Hg(II) solution. The influence of the pH change in the multi-component ion metal solution on the adsorption of Zn(II) and Cd(II) was also studied. The adsorption processes is relatively fast for Zn(II) and Cd(II). The presence of two foreign ions in the solution slightly speeds up the adsorption process for Zn(II) and significantly slows it down for Cd(II). The adsorption isotherms are similarly shaped for Zn(II) and Cd(II). The addition of the foreign ions has a more unfavourable effect on the adsorption for Cd(II) than for Zn(II). At pH 2, neither Zn(II) nor Cd(II) is adsorbed practically on the carbon. The voltammetric approach has proved to be a fast and efficient method that, at the same time, enables one to monitor the adsorption of Zn(II) and Cd(II) with potential on-line application, which could be useful in waste-water treatment.     

Dual nanomolar and picomolar Zn(II) binding properties of metallothionein

Each of the seven Zn(II) ions in the Zn(3)S(9) and Zn(4)S(11) clusters of human metallothionein is in a tetrathiolate coordination environment. Yet analysis of Zn(II) association with thionein, the apoprotein, and analysis of Zn(II) dissociation from metallothionein using the fluorescent chelating agents FluoZin-3 and RhodZin-3 reveal at least three classes of sites with affinities that differ by 4 orders of magnitude. Four Zn(II) ions are bound with an apparent average log K of 11.8, and with the methods employed, their binding is indistinguishable. This binding property makes thionein a strong chelating agent. One Zn(II) ion is relatively weakly bound, with a log K of 7.7, making metallothionein a zinc donor in the absence of thionein. The binding data demonstrate that Zn(II) binds with at least four species: Zn(4)T, Zn(5)T, Zn(6)T, and Zn(7)T. Zn(5)T and Zn(6)T bind Zn(II) with a log K of approximately 10 and are the predominant species at micromolar concentrations of metallothionein in cells. Central to the function of the protein is the reactivity of its cysteine side chains in the absence and presence of Zn(II). Chelating agents, such as physiological ligands with moderate affinities for Zn(II), cause dissociation of Zn(II) ions from metallothionein at pH 7.4 (Zn(7)T <==> Zn(7-n)T + nZn(2+)), thereby affecting the reactivity of its thiols. Thus, the rate of thiol oxidation increases in the presence of Zn(II) acceptors but decreases if more free Zn(II) becomes available. Thionein is such an acceptor. It regulates the reactivity and availability of free Zn(II) from metallothionein. At thionein/metallothionein ratios > 0.75, free Zn(II) ions are below a pZn (-log[Zn(2+)](free)) of 11.8, and at ratios < 0.75, relatively large fluctuations of free Zn(II) ions are possible (pZn between 7 and 11). These chemical characteristics match cellular requirements for Zn(II) and suggest how the molecular structures and redox chemistries of metallothionein and thionein determine Zn(II) availability for biological processes.     

Zinspy sensors with enhanced dynamic range for imaging neuronal cell zinc uptake and mobilization

Thiophene moieties were incorporated into previously described Zinspy (ZS) fluorescent Zn(II) sensor motifs (Nolan, E. M.; Lippard, S. J. Inorg. Chem. 2004, 43, 8310-8317) to provide enhanced fluorescence properties, low-micromolar dissociation constants for Zn(II), and improved Zn(II) selectivity. Halogenation of the xanthenone and benzoate moieties of the fluorescein platform systematically modulates the excitation and emission profiles, pH-dependent fluorescence, Zn(II) affinity, and Zn(II) complexation rates, offering a general strategy for tuning multiple properties of xanthenone-based metal ion sensors. Extensive biological studies in cultured cells and primary neuronal cultures demonstrate 2-{6-hydroxy-3-oxo-4,5-bis[(pyridin-2-ylmethylthiophen-2-ylmethylamino)methyl]-3H-xanthen-9-yl}benzoic acid (ZS5) to be a versatile imaging tool for detecting Zn(II) in vivo. ZS5 localizes to the mitochondria of HeLa cells and allows visualization of glutamate-mediated Zn(II) uptake in dendrites and Zn(II) release resulting from nitrosative stress in neurons.     

QZ1 and QZ2: rapid, reversible quinoline-derivatized fluoresceins for sensing biological Zn(II)

QZ1, 2-[2-chloro-6-hydroxy-3-oxo-5-(quinolin-8-ylaminomethyl)-3H-xanthen-9-yl]benzoic acid, and QZ2, 2-[6-hydroxy-3-oxo-4,5-bis-(quinolin-8-ylaminomethyl)-3H-xanthen-9-yl]benzoic acid, two fluorescein-based dyes derivatized with 8-aminoquinoline, have been prepared and their photophysical, thermodynamic, and zinc-binding kinetic properties determined. Because of their low background fluorescence and highly emissive Zn(II) complexes, QZ1 and QZ2 have a large dynamic range, with approximately 42- and approximately 150-fold fluorescence enhancements upon Zn(II) coordination, respectively. These dyes have micromolar K(d) values for Zn(II) and are selective for Zn(II) over biologically relevant concentrations of the alkali and alkaline earth metals. The Zn(II) complexes also fluoresce brightly in the presence of excess Mn(II), Fe(II), Co(II), Cd(II), and Hg(II), offering improved specificity for Zn(II) over di(2-picolyl)amine-based Zn(II) sensors. Stopped-flow kinetic investigations indicate that QZ1 and QZ2 bind Zn(II) with k(on) values of (3-4) x 10(6) M(-1) s(-1), compared to (6-8) x 10(5) M(-1) s(-1) for select ZP (Zinpyr) dyes, at 4.3 degrees C. Dissociation of Zn(II) from QZ1 and QZ2 occurs with k(off) values of 150 and 160 s(-1), over 5 orders of magnitude larger than those for ZP probes, achieving reversibility on the biological (millisecond) time scale. Laser scanning confocal and two-photon microscopy studies reveal that QZ2 is cell-permeable and Zn(II)-responsive in vivo. Because of its weaker affinity for Zn(II), QZ2 responds to higher concentrations of intracellular Zn(II) than members of the ZP family, illustrating that binding affinity is an important parameter for Zn(II) detection in vivo.     

Zinc(II)-selective ratiometric fluorescent sensors based on inhibition of excited-state intramolecular proton transfer

To develop a zinc(II)-selective emission ratiometric probe suitable for biological applications, we explored the cation-induced inhibition of excited-state intramolecular proton transfer (ESIPT) with a series of 2-(2'-benzenesulfonamidophenyl)benzimidazole derivatives. In the absence of Zn(II) at neutral pH, the fluorophores undergo ESIPT to yield a highly Stokes' shifted emission from the proton-transfer tautomer. Coordination of Zn(II) inhibits the ESIPT process and yields a significant hypsochromic shift of the fluorescence emission maximum. Whereas the paramagnetic metal cations Cu(II), Fe(II), Ni(II), Co(II), and Mn(II) result in fluorescence quenching, the emission response is not altered by millimolar concentrations of Ca(II) or Mg(II), rendering the sensors selective for Zn(II) among all biologically important metal cations. Due to the modular architecture of the fluorophore, the Zn(II) binding affinity can be readily tuned by implementing simple structural modifications. The synthesized probes are suitable to gauge free Zn(II) concentrations in the micromolar to picomolar range under physiological conditions.     

Mechanisms of ZnII-activated magnetic resonance imaging agents

We report on the mechanism of a series of Zn (II)-activated magnetic resonance contrast agents that modulate the access of water to a paramagnetic Gd (III) ion to create an increase in relaxivity upon binding of Zn (II). In the absence and presence of Zn (II), the coordination at the Gd (III) center is modulated by appended Zn (II) binding groups. These groups were systematically varied to optimize the change in coordination upon Zn (II) binding. We observe that at least one appended aminoacetate must be present as a coordinating group to bind Gd (III) and effectively inhibit access of water. At least two binding groups are required to efficiently bind Zn (II), creating an unsaturated complex and allowing access of water. (13)C isotopic labeling of the acetate binding groups for NMR spectroscopy provides evidence of a change in the metal coordination of these groups upon the addition of Zn (II) supporting our proposed mechanism of activation as presented.     

微晶酚酞富集-分光光度法测定痕量Zn(II)

建立了一种利用修饰有结晶紫(CV^＋)的微晶酚酞作为固态吸附剂分离富集溶液中痕量Zn(II)的新方法, 富集后的Zn(II)含量可直接用光度法测定. 控制一定条件, Zn(II)能与常见阳离子Ni(II), Cd(II), Al(III), Ca(II), Mg(II), Co(II), Mn(II), Cu(II), Pb(II), Fe(III)等完全分离, 且富集时基本不受, , Br^－, Cl^－, I^－,等阴离子影响. 微晶酚酞对Zn(II)的吸附容量为25.8 mg/g; 富集因数可达200倍, 回收率在97.7%～102%之间, RSD小于2.7%. 该方法已成功应用于实际水样中Zn(II)的富集测定, 结果令人满意.     

Formation of 1 D and 3 D coordination polymers in the solid state induced by mechanochemical and annealing treatments: bis(3-cyano-pentane-2,4-dionato) metal complexes

Bis(3-cyano-pentane-2,4-dionato) (CNacac) metal complex, [M(CNacac)(2)], which acts as both a metal-ion-like and a ligand-like building unit, forms supramolecular structures by self-assembly. Co-grinding of the metal acetates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with CNacacH formed a CNacac complex in all cases: mononuclear complex was formed in the cases of Mn(II), Cu(II) and Zn(II), whereas polymeric ones were formed in the cases of Fe(II), Co(II) and Ni(II). Subsequent annealing converted the mononuclear complexes of Mn(II), Cu(II) and Zn(II) to their corresponding polymers as a result of dehydration of the mononuclear complexes. The resultant Mn(II), Fe(II), Co(II), Ni(II) and Zn(II) polymeric complexes had a common 3 D structure with high thermal stability. In the case of Cu(II), a 1 D polymer was obtained. The Mn(II), Cu(II) and Zn(II) polymeric complexes returned to their original mononuclear complexes on exposure to water vapour but they reverted to the polymeric complexes by re-annealing. Co-grinding of metal chlorides with CNacacH and annealing of the mononuclear CNacac complexes prepared from solution reactions were also examined for comparison. [Mn(CNacac)(2)(H(2)O)(2)], [M(CNacac)(2)(H(2)O)] (M=Cu(II) and Zn(II)) and [M(CNacac)(2)](infinity) (M=Mn(II), Fe(II) and Zn(II)) are new compounds, which clearly indicated the power of the combined mechanochemical/annealing method for the synthesis of varied metal coordination complexes.     

Simultaneous Spectrophotometric Determination of Zinc and Nickel in Water Samples by Mean Centering of Ratio Kinetic Profiles

The mean centering of ratio kinetic profiles method was used for the simultaneous determination of binary mixtures of Ni(II) and Zn(II) in water samples, without prior separation steps. The method is based on the difference in the rate of the reaction of Ni(II) and Zn(II) with xylenol orange at pH 5.3. The method allows rapid and accurate determination of Ni(II) and Zn(II). The analytical characteristics of the methods for the simultaneous determination of binary mixtures of Ni(II) and Zn(II) were calculated. The linear range was 0.025‐2.400 μg mL^?1 and 0.025‐2.20 μg mL^?1 for Zn(II) and Ni(II), respectively. Interference effects of common anions and cations were studied, and the method was successfully applied to the simultaneous determination of Zn(II) and Ni(II) in water samples.     

Synergistic co-removal of zinc(II) and cefazolin by a Fe/amine-modified chitosan composite

A novel Fe/amine modified chitosan composite (Fe/N-CS) was facilely synthesized and showed higher affinity to both Zn(II) and cefazolin (CEF) than its precursors. Synergistic co-adsorption of them by Fe/N-CS was observed in varied conditions. The adsorption amount maximally increased by 100.1% for Zn and 68.2% for CEF in bi-solute systems. The initial adsorption rate of Zn(II) also improved with CEF. The increasing temperature facilitated coadsorption. The results of the preloading tests, FTIR/XPS characterizations and DFT calculations suggested that (1) both polyamines and Fe sites participated in the adsorption of Zn(II) and CEF, (2) Zn(II) could serve as a new efficient site for CEF, forming [amine-Zn-CEF]/[FeOH-Zn-CEF] ternary complexes, and (3) the co-presence of CEF shielded the electrostatic repulsion between protonated amines and Zn(II), contributing to the enhancement of Zn(II) adsorption. Further, the ion strength exerted positive and negative influences on the adsorption of Zn(II) and CEF, respectively. Additionally, CEF and Zn(II) were successively recovered by 0.1 mol/L NaOH followed by 2 mmol/L HCl. Fe/N-CS could be stably reused five times. The findings imply that Fe/N-CS is promising for the highly efficient co-removal of concurrent heavy metals and antibiotics.     

Spectrophotometric determination of traces of metallic ions and their mixtures with 3-methyl-1,2-cyclopentanodione dithiosemicarbazone: I. Zinc,cadmium, and mercury

The properties of zinc, cadmium, and mercury complexes of 3-methyl-1,2-cyclopentanodione dithiosemicarbazone and the optimal conditions for their formation are described. The complexes were used with success in the photometric determination of traces of zinc, cadmium, and mercury. Seven procedures are proposed for the accurate analysis of Zn(II)-Cd(II), Zn(II)-Hg(II), Zn(II)-Bi(III), Cd(II)-Hg(II), Cd(II)-Bi(III), Hg(II)-Bi(III), and Zn(II)-Cd(II)-Hg(II) mixtures. Satisfactory results were obtained.     

Application of chelate forming resin Amberlite XAD-2-o-vanillinthiosemicarbazone to the separation and preconcentration of copper(II), zinc(II) and lead(II)

A very stable chelating resin matrix was synthesized by covalently linking o-vanillinthiosemicarbazone (oVTSC) with the benzene ring of the polystyrene-divinylbenzene resin Amberlite XAD-2 through a -NN- group. The resin was used successfully for the separation and preconcentration of copper(II), zinc(II) and lead(II) prior to their determination by atomic absorption spectrophotometry. The total sorption capacity of the resin was 850, 1500 and 2000 mug g(-1) of the resin for Cu(II), Zn(II) and Pb(II), respectively. For the quantitative sorption and recovery of Cu(II), Zn(II) and Pb(II), the optimum pH and eluants were pH 2.5-4.0 and 4 M HCl or 2 M HNO(3) for Cu(II), pH 5.5-6.5 and 1.0-2.0 M HCl for Zn(II) and pH 6.0-7.5 and 3 M HCl or 1 M HNO(3) for Pb(II). Both, the uptake and stripping of these metal ions were fairly rapid, indicating a better accessibility of the chelating sites. The t (1 2 ) values for Cu(II), Zn(II) and Pb(II) were also determined. Limit of tolerance of some electrolytes like NaCl, NaF, NaNO(3), Na(2)SO(4) and Na(3)PO(4) have been reported. The preconcentration factor for Cu(II), Zn(II) and Pb(II) was 90, 140 and 100 respectively. The method was applied for the determination of Cu(II), Zn(II) and Pb(II) in the water samples collected from Sabarmati river, Ahmedabad, India.     

Treatment of zinc-contaminated water using a multistage ferrihydrite sorption system

Previous studies demonstrated the environmental and economic benefits of treating lead(II)-contaminated water streams with ferrihydrite in multiple equilibrium sorption stages. In this work, multistage ferrihydrite sorption systems were evaluated for their effectiveness in reducing single-solute zinc(II) (Zn(II)) concentrations in contaminated water streams to very low levels. As for lead(II) (Pb(II)), experimental data and modeling results indicate that a multistage sorption system can significantly reduce Zn(II) effluent concentrations for the same total amount of sorbent or, alternatively, dramatically lower total sorbent consumption for the same effluent Zn(II) concentration. Compared to Pb(II), however, Zn(II) removal requires on the order of 10 times more sorbent to achieve the same target effluent concentration for the same pH and number of stages. Model predictions were made using a steady-state, multistage, equilibrium adsorber model that was previously developed for and integrated into OLI Systems' Environmental Simulation Program (ESP). The modified triple-layer model was used to simulate Zn(II) surface-liquid equilibria within the adsorber model. Engineering screening evaluations again indicate that a 2- to 3-stage sorption process can provide significant economic savings when compared to a 1-stage process operating with the same target effluent Zn(II) concentration. Additional equilibrium stages beyond 2 or 3 provide diminishing economic returns. The major economic driver for multiple contacting stages is reduced capital investment and operating costs for sludge handling, dewatering, and disposal.     

Readily Available Fluorescence Probes for Zinc Ion in Aqueous Solution of Neutral pH

Zinc ion in aqueous solution of neutral pH was detected by a probe that is readily obtained by simply mixing commercially available cyclen (a Zn(II) receptor) and lumazine or lumichrome (a heterocyclic fluorophore containing an imide moiety as partial structure) in an equal molar ratio. The initially generated cyclen-Zn(II) complex interacts with lumazine to form a cyclen-Zn(II)-lumazine complex whereby the intensity of fluorescence is enhanced. These Zn(II) probes showed excellent selectivity for Zn(II) over other divalent metal ions such as Pb(II), Cu(II), Co(II), Ni(II), and good selectivity over Cd(II). The X-ray crystal structure of the cyclen-Zn(II)-lumazine complex revealed that the cyclen-chelated Zn(II) binds deprotonated lumazine at the N-1.     

A highly selective and sensitive fluorescent PET (photoinduced electron transfer) chemosensor for Zn(II)

The naphthalimide derivative 1 was designed as a fluorescence PET sensor for Zn(II); 1 showed excellent selectivity for Zn(II) at pH 7.4, even in the presence of other competitive cations, the emission, being pH independent above pH 3.5, was switched on upon Zn(II) recognition.     

Synergistic co-removal of zinc(II) and cefazolin by a Fe/amine-modified chitosan composite

A novel Fe/amine modified chitosan composite (Fe/N-CS) was facilely synthesized and showed great potential in the efficient co-removal of heavy metal ions and antibiotics from wastewater.     

NMR spectroscopic characterization of copper(II) and zinc(II) complexes of indomethacin

Molecular diffusion constants were studied by NMR spectroscopy to provide information about the solution structures of a variety of Cu(II) and Zn(II) monomeric and dimeric complexes of indomethacin (IndoH). These studies showed that monomeric Zn(II)-Indo complexes substantially dimerize in DMF-d7 and DMSO-d6 solutions at room temperature, whereas the Cu(II) and Zn(II) dinuclear complexes remain largely intact in these solutions. There is evidence of an equilibrium between monomers and dimers for the Zn(II) complexes in solution, as shown by a reduced diffusion constant and lower average radius compared to the Cu(II) dimer. Such an equilibrium between monomers and dimers for the Zn(II) complexes is also consistent with previous results obtained from XAFS analysis of DMF solutions of such complexes. The greater lability and lower thermodynamic stability of the Zn(II) dimer complex compared to the Cu(II) analogue, as determined from the NMR experiments, is likely to result in the more ready release of free Indo in the GI tract. This is consistent with the previously observed higher GI toxicities of the Zn-Indo pharmaceutical preparations compared to the Cu(II)-Indo counterparts.     

Analytical utility of coupled transport across a supported liquid membrane Selective preconcentration of zinc

A liquid membrane comprising 5-10% bis(2,4,4-trimethylpentyl)phosphinic acid in dodecane that is supported between an aqueous sample at pH 4.7-6.0 and a 0.1M HCl receiver results in uphill transport of Zn(II) from the sample into the receiver. With 2 ml of receiver, a 5 cm(2) membrane and 60 min dialysis time, Zn(II) is preconcentrated by a factor of ca. 13 when the initial concentration in the sample is in the range 1.5 x 10(-7)-1.5 x 10(-4)M. The enrichment factor is directly proportional to time up to 30 min since the transport rate of Zn(II) across the membrane is constant over this period. At longer times the flux is slowed as the system begins to approach equilibrium. The presence of other metals such as Cu(II), Co(II), Ni(II), Cd(II), Pb(II) and Fe(II) does not change the enrichment factor for Zn(II), even when the interferent is at a concentration high enough for the rate of transport (nmole/min) of the interferent and Zn(II) to be about the same. The flux of Zn(II) was about 40 times that of Cu(II) and 100 times that of Co(II) when their concentrations in the sample were equal. The other metal ions examined are not significantly transported.     

Solvent induced cooperativity of Zn(II) complexes cleaving a phosphate diester RNA analog in methanol

The kinetics of cyclization of 2-hydroxypropyl p-nitrophenyl phosphate (1) promoted by two mononuclear Zn(II) catalytic complexes of bis(2-pyridylmethyl)benzylamine (4) and bis(2-methyl 6-pyridylmethyl)benzylamine (5) in methanol were studied under (s)(s)pH-controlled conditions (where (s)(s)pH refers to [H(+)] activity in methanol). Potentiometric titrations of the ligands in the absence and presence of Zn(2+) and a non-reactive model for 1 (2-hydroxylpropyl isopropyl phosphate (HPIPP, 6)) indicate that the phosphate is bound tightly to the 4:Zn(II) and 5:Zn(II) complexes as L:Zn(II):6(-), and that each of these undergoes an additional ionization to produce L:Zn(II):6(-):((-)OCH(3)) or a bound deprotonated form of the phosphate, L:Zn(II):6(2-). Kinetic studies as a function of [L:Zn(II)] indicate that the rate is linear in [L:Zn(II)] at concentrations well above those required for complete binding of the substrate. Plots of the second order rate constants (defined as the gradient of the rate constant vs. [complex] plot) vs. (s)(s)pH in methanol are bell-shaped with rate maxima of 23 dm mol(-1) s(-1) and 146 dm mol(-1) s(-1) for 4:Zn(II) and 5:Zn(II), respectively, at their (s)(s)pH maxima of 10.5 and 10. A mechanism is proposed that involves binding of one molecule of complex to the phosphate to yield a poorly reactive 1 : 1 complex, which associates with a second molecule of complex to produce a transient cooperative 2 : 1 complex within which the cyclization of 1 is rapid. The observations support an effect of the reduced polarity solvent that encourages the cooperative association of phosphate and two independent mononuclear complexes to give a reactive entity.     

A sensitive probe for the detection of Zn(II) by time-resolved fluorescence

A new, highly sensitive fluorescent sensor for Zn(II) ion (a tris(2-pyridylmethyl)amine derivative) shows very strong binding and Zn(II) concentration-dependent biexponential time-resolved fluorescence (TRF) decay profiles that can be used for ratiometric estimates of Zn(II) concentrations. The ligand-metal complexes were characterized in solution by spectroscopic techniques and in the solid state by X-ray crystallography. The TRF studies revealed that the sensor aggregates in the absence of Zn(II) in a ligand concentration-dependent manner, a complication that is discerned by TRF but not by steady-state fluorescence ratiometric sensing techniques. It is shown that the same TRF methods are highly useful for monitoring Zn(II) concentrations in A549 epithelial lung cells in vitro and that the results were consistent with those in solution.