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1.
A quercetin monolayer has been prepared on top of the self‐assembled 3‐mercaptopropionic acid (MPA) layer for the copper ion determination. Cu2+ ions are readily accumulated on this modified electrode through the complex formation and electrochemically detected. With a quercetin layer, the redox process of Cu2+ became more reversible than at the MPA‐modified electrode. Complexation sites in MPA and quercetin were occupied within five min when the electrode was immersed in 10 μM Cu2+ solution. The MPA and quercetin layers were stable enough to allow repeated EDTA treatment to remove adsorbed Cu2+ for the surface regeneration. Only 7% decrease was found after ten times regeneration and use. Linear current response was found over the concentration range of 1 nM and 10 μM with detection limit of 0.1 nM. Common interfering ions such as Cd2+, Zn2+, and Fe2+/3+ did not show any electrochemical response in the potential range of Cu2+ determination.  相似文献   

2.
A new 3,5‐disubstituted pyridine with two porphyrin moieties was prepared through an efficient synthetic approach involving 2‐formyl‐5,10,15,20‐tetraphenylporphyrin ( 1 ), piperidine, and catalytic amounts of [La(OTf)3]. 3,5‐Bis(5,10,15,20‐tetraphenylporphyrin‐2‐ylmethyl)pyridine ( 2 ) was fully characterized and its sensing ability towards Zn2+, Cu2+, Hg2+, Cd2+, and Ag+ was evaluated in solution by absorption and fluorescence spectroscopy and in gas phase by using matrix‐assisted laser desorption/ionization (MALDI)‐TOF mass spectrometry. Strong changes in the ground and excited state were detected in the case of the soft metal ions Zn2+, Cd2+, Hg2+, and Cu2+. A three‐metal‐per‐ligand molar ratio was obtained in all cases and a significant ratiometric behavior was observed in the presence of Zn2+ with the appearance of a new band at 608 nm, which can be assigned to a metal‐to‐ligand charge transfer. The system was able to quantify 79 ppb of Zn2+ and the theoretical calculations are in accordance with the stoichiometry observed in solution. The gas‐phase sensorial ability of compound 2 towards all metal ions was confirmed by using MALDI‐TOF MS and in solid state by using polymeric films of polymethylmethacrylate (PMMA) doped with ligand 2 . The results showed that compound 2 can be analytically used to develop new colorimetric molecular devices that are able to discriminate between Hg2+ and Zn2+ in solid phase. The crystal structure of ZnII complex of 3,5‐bisporphyrinylpyridine was unequivocally elucidated by using single‐crystal X‐ray diffraction studies.  相似文献   

3.
The use of a reactive electrode (reactrode) consisting of graphite, a solid ion exchanger (HYPHAN) and paraffin for the batch analysis of Cd2+, Cu2+, Pb2+ and Hg2+ in aqueous samples and as a passive monitor for these metal ions is described. The metal ions are accumulated on the reactrode surface at an open-circuit potential in an ion-exchange reaction. After the accumulation, the ion exchanger-bonded metal ions are reduced to the metals which remain on the electrode surface. In a following step, the metals are anodically dissolved which is recorded by differential-pulse voltammetry. The 3s detection limits for the analysis of drinking water are: 1.1×10-7 mol/l for Pb2+, 5×10-8 mol/l for Hg2+ and 2.4×10-7 mol/l for Cu2+.The reactrode developed can be used for the passive monitoring of heavy metals in aqueous streams if the reactrode is mounted in a wall-jet cell which is part of a flow-through system. Using this arrangement, it has been possible to determine Hg2+, Cu2+ and Pb2+ in drinking water after 20 hours of accumulation.  相似文献   

4.
Copper is an indispensable trace element for human health. Too much or too little intake of copper ion (Cu2+) can lead to its own adverse health conditions. Therefore, detection of Cu2+ is always of vital importance. In this work, a simple sensor was developed for rapid detection of trace Cu2+ in water, in which L‐cysteine (Cys) as a molecular probe was self‐assembled on a gold interdigital electrode to form a monolayer for specific capture of Cu2+. The interfacial capacitance of interdigital electrode was detected to indicate the target adsorption level under an AC signal working as the excitation to induce directed movement and enrichment of Cu2+ to the electrode surface. This sensor reached a limit of detection of 4.14 fM and a satisfactory selectivity against eight other ions (Zn2+, Hg2+, Pb2+, Cd2+, Mg2+, Fe2+, As3+, and As5+). Testing of spiked tap water was also performed, demonstrating the sensor's usability. This sensor as well as the detection method shows a great application potential in fields such as environmental monitoring and medical diagnosis.  相似文献   

5.
The competitive removal of Pb2+, Cu2+, and Cd2+ ions from aqueous solutions by the copolymer of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and itaconic acid (IA), P(AMPS‐co‐IA), was investigated. Homopolymer of AMPS (PAMPS) was also used to remove these ions from their aqueous solution. In the preparation of AMPS–IA copolymer, the molar percentages of AMPS and IA were 80 and 20, respectively. In order to observe the changes in the structures of polymers due to metal adsorption, FTIR spectra by attenuated total reflectancetechnique and scanning electron microscopy (SEM) pictures of the polymers were taken both before and after adsorption experiments. Total metal ion removal capacities of PAMPS and P(AMPS‐co‐IA) were 1.685 and 1.722 mmol Me2+/gpolymer, respectively. Experimental data were evaluated to determine the kinetic characteristics of the adsorption process. Competitive adsorption of Pb2+, Cu2+, and Cd2+ ions onto both PAMPS and P(AMPS‐co‐IA) was found to fit pseudo‐second‐order type kinetics. In addition, the removal orders in the competitive adsorption of these metal ions onto PAMPS and P(AMPS‐co‐IA) were found to be Cd2+ > Pb2+ > Cu2+ and Pb2+ > Cd2+ > Cu2+, respectively. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

6.
Herein, we describe the self‐sorting of phosphate‐ and carboxylate‐containing molecules on the surface of monolayer‐protected gold nanoparticles. Self‐sorting is driven by selective interactions between the phosphate probe and Zn2+ complexes in one monolayer; these interactions force the carboxylate probe to move to a second type of nanoparticle. This process effectively separates the probes and causes their localization in well‐defined spaces surrounding the nanoparticles. The removal/addition of Zn2+ metal ions from the system is used to convert the system from an ordered to a disordered state and vice versa. The possibility to control the location and transport of populations of molecules in a complex mixture creates new perspectives for the development of innovative complex catalytic systems that mimic nature.  相似文献   

7.
To study the interaction between gatifloxacin (GT), metal ions (Cu2+, Cd2+, Co2+, Mg2+) and calf thymus DNA under condition of physiology pH, UV absorption and fluorescence methods were adopted. Result shows that metal ions and DNA are able to react with GT in ground state. In further research, by studying the influence of metal ions on binding of GT with DNA in metal ions–GT–DNA ternary system, we found that influential mechanism of Mg2+ on the binding of GT with DNA may be different from the other three. Mg2+ can act as a bridge in the binding of GT's carboxyl/carbonyl with DNA phosphate in certain concentration range; while Cu2+, Cd2+, Co2+ can combine directly with GT by reaction between GT carboxyl/carbonyl and DNA base, and enhance the binding ability of GT with DNA. The influence extent and type depend not only on the binding site of DNA with metal ions (phosphate or base), but also the binding ability of which. The stronger the binding ability of metal ions with DNA base is, the larger their promotion to binding of GT with DNA is. The order of metal ions’ influential ability on the binding of GT–DNA is identical to the binding ability order of metal ions with DNA base, that is: Cu2+ > Cd2+ > Co2+ > Mg2+.  相似文献   

8.
The catalytic effects of metal ions on the anodic oxidation of ascorbic acid on a Pt electrode in 1 M HClO4 were studied by linear sweep voltammetry. The anodic peak due to a two-electron oxidation of ascorbic acid shifts to the negative potential side on the addition of Bi3+. This indicates the accelerating effect of Bi3+ on the oxidation of ascorbic acid. The presence of other metal ions, such as Pb2+, Hg2+, Tl+, Ag+ and Sb3+, also exerts similar effects. These metal ions were adsorbed on a Pt electrode at underpotentials and the adsorbed metals (denoted as Mad) still remain on the electrode surface until the electrode potential goes up to and beyond the peak potential of the oxidation of ascorbic acid. On the other hand, metal ions forming no adsorbed layer on Pt, such as Co2+, Zn2+, Fe3+ and Ni2+, exhibit no catalytic effect. These facts suggest that the presence of a Mad on Pt is essential for the promotion of the anodic oxidation of ascorbic acid. However, there is a difference in the catalytic action among the Mad, for example, Cuad, Cdad, Inad, Snad and Moad display no catalytic action.The catalytic activity depends on the degree of surface coverage by the Mad. The maximal effect of the Mad is attained in the submonolayer region. The effects of metal ions were discussed on the basis that the Mad plays its major role in the removal of the adsorbed ascorbic acid occupying active sites on the electrode surface, and provides effective sites for the activation of adjacent water molecules. Furthermore, from the 13C NMR spectra for the oxidation products, the adsorbed water on the Mad appears to function by promoting the subsequent hydration steps, following the electron-transfer step of ascorbic acid.  相似文献   

9.
Rigid N‐(substituted)‐2‐aza‐[3]‐ferrocenophanes L1 and L2 were easily synthesized from 1,1 ‐dicarboxyaldehydeferrocene and the corresponding amines. Ligands L1 and L2 were characterized by 1H NMR, 13C NMR and single‐crystal X‐ray crystallography. The coordination abilities of L1 and L2 with metal ions such as Cu2+, Mg2+, Ni2+, Zn2+, Pb2+ and Cd2+ were evaluated by cyclic voltammetry. The electrochemical shift (ΔE1/2) of 125 mV was observed in the presence of Cu2+ ion, while no significant shift of the Fc/Fc + couple was observed when Mg2+, Ni2+, Zn2+, Pb2+, Cd2+ metal ions were added to the solution of L1 in the mixture of MeOH and H2O. Moreover, the extent of the anodic shift of redox potentials was approximately equal to that induced by Cu2+ alone when a mixture of Cu2+, Mg2+, Ni2+, Zn2+, Pb2+ and Cd2+ was added to a solution of L1. Ligand L1 was proved to selectively sense Cu2+ in the presence of large, excessive first‐row transition and late‐transition metal cations. The coordination model was proposed from the results of controlled experiments and quantum calculations. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

10.

The aim of this study is to prepare magnetic beads which can be used for the removal of heavy metal ions from synthetic solutions. Magnetic poly(ethylene glycol dimethacrylate‐vinyl imidazole) [m‐poly(EGDMA‐VIM)] beads were produced by suspension polymerization in the presence of magnetite Fe3O4 nano‐powder. The specific surface area of the m‐poly(EGDMA‐VIM) beads was found to be 63.1 m2/g with a size range of 150–200 µm in diameter and the swelling ratio was 85%. The average Fe3O4 content of the resulting m‐poly(EGDMA‐VIM) beads was 12.4%. The maximum binding capacities of the m‐poly(EGDMA‐VIM) beads were 32.4 mg/g for Cu2+, 45.8 mg/g for Zn2+, 84.2 mg/g for Cd2+and 134.5 mg/g for Pb2+. The affinity order on mass basis is Pb2+>Cd2+>Zn2+>Cu2+. Equilibrium data agreed well with the Langmuir model. pH significantly affected the binding capacity of the magnetic beads. Binding of heavy metal ions from synthetic wastewater was also studied. The binding capacities were 26.2 mg/g for Cu2+, 33.7 mg/g for Zn2+, 54.7 mg/g for Cd2+ and 108.4 mg/g for Pb2+. The magnetic beads could be regenerated up to about 97% by treating with 0.1 M HNO3. These features make m‐poly(EGDMA‐VIM) beads a potential candidate for support of heavy metal removal under magnetic field.  相似文献   

11.
The increased global concern on environmental protection has made researchers focus their attention on new and more efficient methods of pollutant removal. In this research, novel nanocomposite adsorbents,i.e., magnetic hydroxyapatite (Fe3O4@HA) and magnetic hydroxyapatite β‐cyclodextrin (Fe3O4@HA‐CD) were synthesized and used for heavy metal removal. The adsorbents were characterized by FTIR, XRD, TGA, VSM, and SEM. In order to investigate the effect of β‐cyclodextrin (β‐CD) removal efficiency, adsorption results of nine metal ions were compared for both adsorbents. β‐CD showed the most increasing effect for Cd2+ and Cu2+ removal, so these two ions were selected for further studies. The effect of diverse parameters including pH, contact time, initial metal ion concentration and adsorbent dosage on the adsorption process was discussed. The optimum pH was 6 and adsorption equilibrium was achieved after 1 hr. Adsorption kinetic data were well fitted by pseudo‐second‐order model proposing that metal ions were adsorbed via chemical reaction. Adsorption isotherm was best described by the Langmuir model, and maximum adsorption capacity for Cd2+ and Cu2+ was 100.00 and 66.66 (mg/g), respectively. Desorption experiment was also done, and the most efficient eluent used for desorption of metal ions was EDTA (0.001 M) with 91% and 88% of Cd2+ and Cu2+ release, respectively. Recyclability studies also showed a 19% decrease in the adsorption capacity of the adsorbent after five cycles of regeneration. Therefore, the synthesized adsorbents were recognized as potential candidates for heavy metal adsorption applications.  相似文献   

12.
A new sensor has been developed for the simultaneous detection of cadmium, lead, copper and mercury, using differential pulse and square wave anodic stripping voltammetry (DPASV and SWASV) at a graphite–polyurethane composite electrode with SBA‐15 silica organofunctionalized with 2‐benzothiazolethiol as bulk modifier. The heavy metal ions were preconcentrated on the surface of the modified electrode at ?1.1 V vs. SCE where they complex with 2‐benzothiazolethiol and are reduced to the metals, and are then reoxidized. Optimum SWASV conditions lead to nanomolar detection limits and simultaneous determination of Cd2+, Pb2+, Cu2+ and Hg2+ in natural waters was achieved.  相似文献   

13.
《Analytical letters》2012,45(15):3373-3395
ABSTRACT

Porous solid siloxane polymer carrying glycinate functional group of formula –(CH2)3NHCH2COOH has been prepared by the sol-gel process. Treatment of aqueous solutions of divalent metal ions with the polysiloxane glycinate ligand system demonstrates that this material exhibits high potential for preconcentration of metal ions (Cu2+, Zn2+ and Cd2+). The ligand system chemisorbs these divalent metal ions, at optimum conditions, in the order: Cd2+ < Zn2+ < Cu2+. The uptake of copper ions is concentration dependent but it is independent on the presence of other competing ions. Treatment of the glycinate ligand system with acidic solution results in leaching of bound ligands. The highest leaching occurs in presence of copper ions at low pH  相似文献   

14.
The first photoactivated doped quantum dot vector for metal‐ion release has been developed. A facile method for doping copper(I) cations within ZnS quantum dot shells was achieved through the use of metal‐dithiocarbamates, with Cu+ ions elucidated by X‐ray photoelectron spectroscopy. Photoexcitation of the quantum dots has been shown to release Cu+ ions, which was employed as an effective catalyst for the Huisgen [3+2] cycloaddition reaction. The relationship between the extent of doping, catalytic activity, and the fluorescence quenching was also explored.  相似文献   

15.
ALI Moghimi 《中国化学》2007,25(5):640-644
A fast and simple method for preconcentration of Ni^2+, Cd^2+, Pb^2+, Zn^2+, Cu^2+ and Co^2+ from natural water samples was developed. The metal ions were complexed with sodium diethyldithiocarbamate (Na-DDTC), then adsorbed onto octadecyl silica membrane disk, recovered and determined by FAAS. Extraction efficiency, influence of sample volume and eluent flow rates, effects of pH, amount of Na-DDTC, nature and amount of eluent for elution of metal ions from membrane disk, break through volume and limit of detection have been evaluated. The effect of foreign ions on the percent recovery of heavy metal ions has also been studied. The limit of detection of the proposed method for Ni^2+, Cd^2+, Pb^2+, Zn^2+, Cu^2+ and Co^2+was found to be 2.03, 0.47, 3.13, 0.44, 1.24 and 2.05 ng·mL^-1, respectively. The proposed (DDTC) method has been successfully applied to the recovery and determination of heavy metal ions in different water samples.  相似文献   

16.
《Analytical letters》2012,45(14):2327-2343
Abstract

A novel approach for the voltammetric determination of Pb2+, Cu2+, and Hg2+ in the presence of macromolecule contaminants was developed. An Au nanoparticles array was directly electrodeposited onto the gold electrode surface followed by a further modification of a mercaptoethanesulfonate (MES) monolayer. Square wave stripping voltammetry (SWSV) of Pb2+, Cu2+, and Hg2+ was performed on the doubly modified electrode. The electrodeposited gold nanoparticles provided a significantly improved sensitivity. Simultaneously, the MES monolayer efficiently prevented the macromolecules accessing the electrode surface. Compared with the bare gold electrode, the doubly modified electrode has the ability to detect metal ions in the presence of macromolecule contaminants, even when their concentration reach 100 ppm. Under the optimal conditions, the detection limits of 0.16, 0.15, and 0.14 ppb for Pb2+, Cu2+, and Hg2+ were obtained, respectively. The calibration graphs were linear in the concentration range of 1–100 ppb. The results of the analysis of a real metallurgy wastewater sample were reported. The electrode system has a great potential for the direct determination of trace metals in the complex environment and biological samples.  相似文献   

17.
A new chemically modified carbon paste electrode was constructed and used for rapid, simple, accurate, selective and highly sensitive simultaneous determination of cadmium, copper and mercury using square wave anodic stripping voltammetry (SWASV). The carbon paste electrode was modified by N,N′-bis(3-(2-thenylidenimino)propyl)piperazine coated silica nanoparticles. Compared with carbon paste electrode, the stripping peak currents had a significant increase at the modified electrode. Under the optimized conditions (deposition potential, −1.100 V vs. Ag/AgCl; deposition time, 60 s; resting time, 10 s; SW frequency, 25 Hz; pulse amplitude, 0.15 V; dc voltage step height, 4.4 mV), the detection limit was 0.3, 0.1 and 0.05 ng mL−1 for the determination of Cd2+, Cu2+ and Hg2+, respectively. The complexation reaction of the ligand with several metal cations in methanol was studied and the stability constants of the complexes were obtained. The effects of different cations and anions on the simultaneous determination of metal ions were studied and it was found that the electrode is highly selective for the simultaneous determination of Cd2+, Cu2+ and Hg2+. Furthermore, the present method was applied to the determination of Cd2+, Cu2+ and Hg2+ in water and some foodstuff samples.  相似文献   

18.
Carboxylated peptide‐functionalized gold nanoparticles (peptide‐GNPs) self‐assemble into two‐ and three‐dimensional nanostructures in the presence of various heavy metal ions (i.e. Pb2+, Cd2+, Cu2+, and Zn2+) in aqueous solution. The assembly process is monitored by following the changes in the surface plasmon resonance (SPR) band of gold nanoparticles in a UV/Vis spectrophotometer, which shows the development of a new SPR band in the higher‐wavelength region. The extent of assembly is dependent on the amount of metal ions present in the medium and also the time of assembly. TEM analysis clearly shows formation of two‐ and three‐dimensional nanostructures. The assembly process is completely reversible by addition of alkaline ethylenediaminetetraacetic acid (EDTA) solution. The driving force for the assembly of peptide‐GNPs is mainly metal ion/carboxylate coordination. The color and spectral changes due to this assembly can be used for detection of these heavy‐metal ions in solution.  相似文献   

19.
The efficiencies and performances of silver nanoparticle loaded activated carbon modified with 2-(4-isopropylbenzylideneamino)thiophenol (IPBATP-Ag-NP-AC) and activated carbon modified with IPBATP (IPBATP-AC), as new sorbents, were evaluated for separation and preconcentration of Cu2+, Zn2+, Co2+, Cd2+ and Pb2+ ions from real environmental samples. The retained metals content was reversibly eluted using 5?mL of CH3COOH (6.0?mol?L?1) and/or 10?mL of 4.0?mol?L?1 HNO3 for IPBATP-Ag-NP-AC and IPBATP-AC, respectively. The experimental parameters influence the recoveries of metal ions including pH, amounts of ligand and supports, condition of eluents, sample and eluent flow rates of has been investigated. The preconcentration factors were found to be 100 for Zn2+, Cd2+, Co2+, Cu2+ and 50 for Pb2+ ions using IPBATP-Ag-NP-AC, and 50 for Zn2+, Cd2+, Co2+, Cu2+ and 25 for Pb2+ ions using IPBATP-AC. The detection limit of both SPE-based sorbents was between 1.6–2.5?ng?mL?1 for IPBATP-AC and 1.3–2.5?ng?mL?1 for IPBATP-Ag-NP-AC. The proposed methods have been successfully applied for the extraction and determination of the understudy metal ions content in some real samples with extraction efficiencies higher than 90% and relative standard deviations (RSD) lower than 2.4%.  相似文献   

20.
Li M  Li DW  Li YT  Xu DK  Long YT 《Analytica chimica acta》2011,701(2):157-163
A novel and facile hybrid analytical method coupling electrochemical “adsorption–desorption” and colorimetric analyses was developed to detect heavy metal ions in turbid water samples. The target metal ions were deposited onto an electrode inserted into the original sample, which was referred to as the “adsorption” process. After changing the medium, the concentrated target metal ions were dissolved in a new, clean buffer (blank buffer), which was referred to as the “desorption” process. The concentrations of the target metal ions were measured by colorimetric analyses after the addition of specific indicator amounts. We demonstrated the applicability of this method by detecting Cd2+, Pb2+ and Cu2+ with co-depositing Bi3+ on portable screen-printed electrodes (SPEs). A good correlation (correlation coefficient of R = 0.997) was observed between concentrations ranging from 1 to 200 μM and absorbance values. After the multiple “desorption” process, the even better detection limits as low as 10, 10 and 100 nM were achieved for Cd2+, Pb2+ and Cu2+, respectively. The practicality of this hybrid method was confirmed by the detection of Cd2+, Pb2+ and Cu2+ in wastewater samples, and these results were in agreement with inductively coupled plasma atomic emission spectroscopy (ICP-AES). Overall, this hybrid method provides a simple, selective and effective technique for environmental pollutant analyses.  相似文献   

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