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1.
Four new complexes of 2,3,4-trimethoxybenzoic acid anion with manganese(II), cobalt(II), nickel(II) and copper(II) cations were synthesized, analysed and characterized by standard chemical and physical methods. 2,3,4-Trimethoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) are polycrystalline compounds with colours typical for M(II) ions. The carboxylate group in the anhydrous complexes of Mn(II), Co(II) and Ni(II) is monodentate and in that of Cu(II) monohydrate is bidentate bridging one. The anhydrous complexes of Mn(II), Co(II) and Ni(II) heated in air to 1273 K are stable up to 505–517 K. Next in the range of 505–1205 K they decompose to the following oxides: Mn3O4, CoO, NiO. The complex of Cu(II) is stable up to 390 K, and next in the range of 390–443 K it loses one molecule of water. The final product of its decomposition is CuO. The solubility in water at 293 K is of the order of 10–3 mol dm–3 for the Mn(II) complex and 10–4 mol dm–3 for Co(II), Ni(II) and Cu(II) complexes. The magnetic moment values of Mn2+, Co2+, Ni2+ and Cu2+ ions in 2,3,4-trimethoxybenzoates experimentally determined in the range of 77–300 K change from 5.64–6.57 μB (for Mn2+), 4.73–5.17 μB (for Co2+), 3.26–3.35 μB (for Ni2+) and 0.27–1.42 μB (for Cu2+). 2,3,4-Trimethoxybenzoates of Mn(II), Co(II) and Ni(II) follow the Curie–Weiss law, whereas that of Cu(II) forms a dimer.  相似文献   

2.

Complex formation equilibria involving pyridine-2-carboxaldehyde oxime (1), 1-(2-pyridinyl)ethanone oxime (2) and 6-methylpyridine-2-carboxaldehyde oxime (3), HL, with zinc(II) and cadmium(II) ions were studied in aqueous 0.1 M NaCl solution at 25° C by potentiometric titrations with a glass electrode. Experimental data were analysed with the least-squares computer program SUPERQUAD to determine the complexes formed and their stability constants. With Ligands 1 and 2 the sets of complexes for Zn(II) and Cd(II) are essentially the same, mono- and dinuclear oxime complexes and their deprotonated/hydrolysed products HpMq(HL)2q+p r. Owing to the steric requirements of the 6-methyl group, sets of complexes formed with 3 are distinctly different. For zinc(II), only dinuclear oximato species HpZn2(HL)4q+p 2 ( p = ? 2, ? 3, ? 4) are found, while for the larger cadmium(II) ion mononuclear oximato species CdL+ and CdL2 are detected in addition to the dinuclear complex HpCd2(HL)4q+p 2 ( p = ? 3).  相似文献   

3.
Summary.  Sparingly water soluble complexes of lead(II), cadmium(II), and zinc(II) with N-phosphonomethylglycine (glyphosate, NPMG) of the general formulae C3H6O5NPPb, C3H6O5NPCdċ2H2O, and C3H6O5NPZn were synthesized. The complexes were also precipited from a dilute Roundup solution, and their solubility in water was determined. Thermal, diffractometric, and IR spectrophotometric analyses were carried out. It was found that the metal is bonded to glyphosate through the oxygen atoms of the carboxylic and phosphonate groups; metal-nitrogen binding is absent in the above compounds. Studying the complexing behaviour in solution by UV spectrophotometry pointed out that a complex of the composition Pb(II) : NPMG=1:1 with an absorption band at 232 nm is formed. Its stability constant as determined by Job’s method is logK=5.9±0.1. Using potentiometric techniques, the dissociation constant of N-phosphonomethylglycine and the stability constants of its complexes with cadmium (II) and zinc (II) were determined. Received June 30, 1999/Accepted July 21, 1999.  相似文献   

4.
The interaction of zinc(II), lead(II), and cadmium(II) with Glutathione (S‐L‐glutamyl‐Lcysteinylglycine) as primary ligand and zwitterionic buffers (N‐[2‐Hydroxyethyl]piperazine‐N′‐[2‐ethanesulfonic acid]) (HEPES) and (N‐Hydroxyethyl]piperazine‐N′‐[2‐hydroxy‐propanesulfonic acid]) (HEPPSO) as secondary ligands were studied by potentiometric‐pH titration in 1:1:1 ratio at 25.0 °C and I = 0.1 mol.dm?3 (KNO3). The formation constants of different normal and protonated binary and ternary complex species were calculated. Formation constants for the monohydroxy, and dihydroxy complexes for the binary systems M(II) + HEPES and M(II) + HEPPSO have been evaluated. The distribution curves for the various complex species as a function of pH were constructed.  相似文献   

5.
The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn2+, Co2+, Ni2+, Cu2+ and Zn2+ were obtained as polycrystalline solids with general formula M(C8H6ClO3)2·nH2O and colours typical for M(II) ions (Mn – slightly pink, Co – pink, Ni – slightly green, Cu – turquoise and Zn – white). The results of elemental, thermal and spectral analyses suggest that compounds of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate. The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) heated in air to 1273 K are dehydrated in one step in the range of 323–411 K and form anhydrous salts which next in the range of 433–1212 K are decomposed to the following oxides: Mn3O4, CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are CuO and Cu. The solubility value in water at 293 K for all complexes is in the order of 10–3 mol dm–3. The plots of χM vs. temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) follow the Curie–Weiss law. The magnetic moment values of Mn2+, Co2+, Ni2+ and Cu2+ ions in these complexes were determined in the range of 76−303 K and they change from: 5.88–6.04 μB for Mn(C8H6ClO3)2·4H2O, 3.96–4.75 μB for Co(C8H6ClO3)2·5H2O, 2.32–3.02 μB for Ni(C8H6ClO3)2·5H2O and 1.77–1.94 μB for Cu(C8H6ClO3)2·4H2O.  相似文献   

6.
Zinc(II), cadmium(II) and mercury(II) complexes of thiourea (TU) and selenourea (SeU) of general formula M(TU)2Cl2 or M(SeU)2Cl2 have been prepared. The complexes were characterized by elemental analysis and NMR (1H, 13C, 15N, 77Se and 113Cd) spectroscopy. A low-frequency shift of the C=S resonance of thiones in 13C NMR and high-frequency shifts of N–H resonances in 1H and 15N NMR are consistent with sulfur or selenium coordination to the metal ions. The Se nucleus in Cd(SeU)2Cl2 in 77Se NMR is deshielded by 87?ppm on coordination, relative to the free ligand. In comparison, the analogous Zn(II) and Hg(II) complexes show deshielding by 33 and 50?ppm, respectively, indicating that the orbital overlap of Se with Cd is better. Principal components of 77Se and 113Cd shielding tensors were determined from solid-state NMR data.  相似文献   

7.
A novel nanocomposite was obtained through the controlled surface modification of graphene nanosheets (nanographene) with Nafion by ultrasonic oscillation. The composite was used as an ultrasensitive platform for the detection of cadmium ions (Cd2+) by differential pulse anodic stripping voltammetry (DPASV) analysis. The performance of the nanographene-based sensor was systematically compared with that of a multiwall carbon nanotube (MWCNT)-modified sensor. The results indicate that the nanographene-based sensor exhibits significant advantages over the MWCNT-based sensor in terms of repeatability, sensitivity and limit of detection (LOD). The nanographene-based sensor displayed superior analytical performance over a linear range of Cd2+ concentrations from 0.25 μg L−1 to 5 μg L−1, with a LOD of 3.5 ng L−1. This sensor was also used to systematically screen for 6 types of chemicals, including sodium salts, magnesium salts and zinc salts. It was observed that the sensor could successfully differentiate cadmium ions from interferents (magnesium salts, zinc salts, etc.). The nanographene-based sensor was also demonstrated to be a promising and reliable tool for the rapid detection of cadmium existing in tap water and for the rapid on-site analysis of critical pollution levels of cadmium.  相似文献   

8.
在本文中,我们研制了一种基于T-T碱基错配特异性键合汞离子的荧光传感器用于汞离子的检测。该传感器由两条分别标记了荧光基团(F)和淬灭基团(Q)的DNA探针组成,并且含有两对用于结合汞离子的T-T错配碱基。当汞离子存在时,两条探针之间形成T-Hg2+-T结构,作用力增强,从而拉近了荧光基团与淬灭基团之间的距离,发生能量转移,使荧光信号在一定程度上被淬灭。在优化的条件下,我们使用该传感器对汞离子进行检测,动力学响应范围为50nM到1000nM,线性相关方程为y= 5281.13 - 1650.56 lg[Hg2+] ( R2 = 0.985),检测下限为79nM。此外,我们还考察了该传感器的选择性,当用其它干扰离子(浓度都为1.0µM)代替待测离子进行实验时,没有发生明显的荧光淬灭,说明该传感器具有较高的选择性。该传感器的构建为汞离子的检测提供了一条快速、简便的新途径。  相似文献   

9.
《Polyhedron》2011,30(6):1191-1200
In this paper we characterize new, mixed ligand complexes of zinc(II), cobalt(II) and cadmium(II) with tri-tert-butoxysilanethiolate and 2-(2′-hydroxyethyl)pyridine ligands. Due to the chelating versus non-chelating behavior of 2-(2′-hydroxyethyl)pyridine ligand we have obtained an interesting structural variety in the studied system. The presented coordination patterns together with the results of NMR studies have been used to illustrate a rapid chemical exchange undergoing in methanolic solutions of zinc(II) and cadmium(II) complexes. UV-Vis spectra of cobalt(II) species have also evidenced an exchange in the case of cobalt(II) complex. The relative strength of hydrogen bond formed by hydroxyl group bonded to Zn(II), Co(II) or Cd(II) was evaluated by analysis of structural parameters and position of the OH stretching vibrations in the FT-IR spectra of the complexes in solid state. The data were compared with the activity of zinc (native) alcohol dehydrogenase and alcohol dehydrogenase substituted with cobalt and cadmium ions. The enthalpies of proton abstraction in zinc and cobalt complexes were calculated and found to be very similar. The attempt to apply zinc tri-tert-butoxysilanethiolate as a catalyst in the biomimetic reaction of reduction of N-benzylnicotinamide chloride by ethanol was unsuccessful.  相似文献   

10.
A tetradentate N-donor ligand 1,4-bis[2-(2-pyridyl)benzimidazolato]butane (L) was prepared for construction of a coordination framework. Three one-dimensional coordination polymers {[M(II)L(NCS)2](DMF)2} n (M(II) = cadmium(II), 1, zinc(II), 2, manganese(II), 3) were obtained by reaction of metal ions and L in the presence of KSCN in DMF/water. The complexes are isostructural and consist of 1D zigzag [M(II)L(NCS)2] n chains and DMF molecules. Within the chains, the metal atoms are each octahedrally coordinated by four N atoms of L and two N atoms of the SCN? anions. Complexes 1 and 2 in the solid state at room temperature exhibit intense photoluminescence at 453 and 433 nm, respectively.  相似文献   

11.
New complexes of the general formula, [M(H2dap4NMetsc)(H2O)2](NO3)2·H2O (M = Zn2+, Cd2+; H2dap4NMetsc = 2,6-diacetylpyridinebis(4N-methylthiosemicarbazone) and [Sn((dap4NMetsc)X2] (X = Ph, Cl and I) (dap4NMetsc = the doubly deprotonated form of 2,6-diacetylpyridine bis(4N-methylthiosemicarbazone) have been synthesized and structurally characterized by a variety of physico-chemical techniques. X-ray crystallographic structure determination shows that in the zinc and cadmium complexes, the bis(thiosemicarbazone) ligand coordinates as a neutral N3S2 pentadentate chelating agent through the two azomethine nitrogen atoms, the pyridine nitrogen atom and the two thione sulfur atoms. The N3S2 donors of the ligand occupy the equatorial plane and the two aqua ligands occupy the sixth and seventh axial positions of the seven-coordinated cadmium(II) and zinc(II) ions. In the tin(IV) complexes, however, the thiosemicarbazone is coordinated to the tin(IV) ion as a dinegatively charged pentadentate chelating agent via the pyridine nitrogen atom, the two azomethine nitrogen atoms and the two thiolate sulfur atoms. The two apical positions of the seven-coordinate tin(IV) ion are occupied by either phenyl, chlorido or iodido ligands. In each of the complexes, the overall geometry adopted by the metal ion may be considered as a distorted pentagonal-bipyramid.  相似文献   

12.
Pb(II), Cd(II) and Cu(II) ions were separated and preconcentrated by solid-phase extraction on octadecyl-bonded silica membrane disks modified with a new S–N-containing Schiff base (bis-2-thiophenal propandiamine) (BTPD) followed by elution and atomic absorption spectrometric detection. The method was applied as a separation and detection method for lead(II), cadmium(II) and copper(II) in environmental and biological samples. Extraction efficiency and the influence of sample matrix, flow rate, pH, and type and minimum amount of stripping acid were investigated. The maximum capacity of the membrane disks modified by 4?mg of BTPD was found to be 668 ± 10, 480 ± 8 and 454 ± 7?µg of lead, cadmium and copper, respectively. The limit of detection of the proposed method is 0.25, 0.01 and 0.02?ng/mL for lead, cadmium and copper, respectively.  相似文献   

13.
《中国化学会会志》2018,65(5):603-612
In this work, the electrochemical oxidation of methanol was investigated by different electrochemical methods at a carbon paste electrode (CPE) modified with (N‐5‐methoxysalicylaldehyde, N´‐2‐hydroxyacetophenon‐1, 2 phenylenediimino nickel(II) complex (Ni(II)–MHP) and reduced graphene oxide (RGO), which is named Ni(II)‐MHP/RGO/CPE, in an alkaline solution. This modified electrode was found to be efficient for the oxidation of methanol. It was found that methanol was oxidized by the NiOOH groups generated by further electrochemical oxidation of nickel(II) hydroxide on the surface of the modified electrode. Under optimum conditions, some parameters of the analyte (MeOH), such as the electron transfer coefficient (α), the electron transfer rate constant) ks), and the diffusion coefficient of species in a 0.1 M solution (pH = 13), were determined. The designed sensor showed a linear dynamic range of 2.0–100.0 and 100.0–1000.0 μM and a detection limit of 0.68 μM for MeOH determination. The Ni(II)‐MHP/RGO/CPE sensor was used in the determination of MeOH in a real sample.  相似文献   

14.
A multiwalled carbon nanotubes–sodium dodecyl benzene sulfonate (MWCNTs–NaDBS) modified stannum film electrode was employed for the determination of cadmium(II) and zinc(II). The Sn/MWCNTs‐NaDBS film electrode was prepared by applying MWCNTs–NaDBS suspension to the surface of the GCE, while the Sn film was plated in situ simultaneously with the target metal ions. Under optimal conditions, linear calibration curves were obtained in a range of 5.0 ?100.0 μg L?1 with detection limits of 0.9 μg L?1 for zinc(II) and 0.8 μg L?1 for cadmium(II), respectively. This film electrode was successfully applied to the determination of Zn(II) and Cd(II) in tap water sample.  相似文献   

15.
We report for the first time the synthesis of bismuth-modified (3-mercaptopropyl) trimethoxysilane (MPTMS) and its application for the determination of lead and cadmium by anodic stripping voltammetry. Xerogels made from bismuth-modified MPTMS and mixtures of it with tetraethoxysilane, under basic conditions (NH3·H2O), were characterized with scanning electron microscopy, energy dispersive spectroscopy, infrared spectroscopy and electrochemical methods. Bismuth-modified xerogels were mixed with 1.5% (v/v) Nafion in ethanol and applied on glassy carbon electrodes. During the electrolytic reductive deposition step, the bismuth compound on the electrode surface was reduced to metallic bismuth. The target metal cations were simultaneously reduced to the respective metals and were preconcentrated on the electrode surface by forming an alloy with bismuth. Then, an anodic voltammetric scan was applied in which the metals were oxidized and stripped back into the solution; the voltammogram was recorded and the stripping peak heights were related to the concentration of Cd(II) and Pb(II) ions in the sample. Various key parameters were investigated in detail and optimized. The effect of potential interferences was also examined. Under optimum conditions and for preconcentration period of 4 min, the 3σ limit of detection was 1.3 μg L−1 for Pb(II) and 0.37 μg L−1 for Cd(II), while the reproducibility of the method was 4.2% for lead (n = 5, 10.36 μg L−1 Pb(II)) and 3.9% for cadmium (n = 5, 5.62 μg L−1 Cd(II)). Finally, the sensors were applied to the determination of Cd(II) and Pb(II) ions in water samples.  相似文献   

16.
A new cadmium(II)-imprinted polymer based on cadmium(II) 2,2′-{ethane-1,2-diylbis[nitrilo(E)methylylidene]} diphenolate-4-vinylpyridine complex was obtained via suspension polymerization. The beads were used as a minicolumn packing for flow-injection-flame atomic absorption spectrometry (FI-FAAS) determination of cadmium(II) in water samples. Sorption effectiveness was optimal within pH range of 6.6-7.7. Nitric acid, 0.5% (v/v) was used as eluent. Fast cadmium(II) sorption by the proposed material enabled to apply sample flow rates up to 10 mL min−1 without loss in sorption effectiveness. Enrichment factor (EF), concentration efficiency (CE) and limit of detection (LOD, 3σ) found for 120-s sorption time were 117, 39.1 min−1 and 0.11 μg L−1, respectively. Sorbent stability was proved for at least 100 preconcentration cycles (RSD = 2.9%). When compared to non-imprinted polymer the new Cd(II)-imprinted polymer exhibited improved selectivity towards cadmium(II) against other heavy metal ions, especially Cu(II) and Pb(II), as well as light metal ions. Accuracy of the method was tested for ground water and waste water certified reference materials and fortified water. The method was applied to Cd(II) determination in natural water samples.  相似文献   

17.
Bismuth film modified and chemically activated carbon micro‐thread electrodes were investigated for the simultaneous determination of Cd(II) and Pb(II) using square wave anodic stripping voltammetry. The carbon thread electrode was characterised using both surface and electrochemical techniques. Electrochemical impedance spectroscopy (EIS) studies demonstrated that the H2SO4/IPA‐treated carbon thread electrode showed a much improved resistance response (Rct=23 Ω) compared to the IPA‐untreated carbon thread (Rct=8317 Ω). Furthermore, parameters such as the effect of deposition potential, deposition time and Bi(III) concentration were explored using square wave voltammetry. Detection limits (S/N=3) for Cd(II) and Pb(II) were found to be 1.08 µg L?1 and 0.87 µg L?1, respectively and response was found to be linear over the range 5–110 µg L?1. The proposed Bi/IPA‐treated carbon thread electrode exhibited a high selectivity towards Cd(II) and Pb(II) even in the presence of a range of heavy metals and is capable of repetitive and reproducible measurements, being attributed to the high surface area, geometry and electrode treatment characteristics. The proposed metal ion sensor was employed to determine cadmium and lead in river water samples and % RSD was found to be 5.46 % and 5.93 % for Cd(II) and Pb(II) respectively (n=3). Such facile sensing components favour the development of cost effective portable devices for environmental sample analysis and electrochemical applications.  相似文献   

18.
Reactions of the ligand 2-mercapto-1-cyclohexylimidazole (Hmimchexyl) with both zinc(II) and cadmium(II) bromides in ethanol solutions afforded 2:1 complexes of the type [M(Hmimchexyl)2(Br)2] (M = Zn 1, and Cd 2) with an MBr2S2 configurations. Spectroscopic evidence (FT-IR and 1H-13C NMR) confirms that the exocyclic thione sulfur atoms are the donors in both complexes. Complex 1 crystallizes in a monoclinic system, space group C2/c, a = 16.180(3), b = 10.817(5), c = 13.602(3); α = 90, β = 106.754(17), γ = 90; Z = 4; R1 = 0.0229, wR2 = 0.0554. The coordination geometry about the zinc(II) atom is distorted tetrahedral with average Zn-S and Zn-Br bond lengths of 3.3418(8) and 2.4017(6) Å, respectively. The bromide ions form intermolecular N–H…Br hydrogen bonding with the thione NH groups of the ligand molecule.  相似文献   

19.
A simple, low cost, and highly sensitive electrochemical sensor, based on a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode (N/IL/G/SPCE) was developed to determine zinc (Zn(II)), cadmium (Cd(II)), and lead (Pb(II)) simultaneously. This disposable electrode shows excellent conductivity and fast electron transfer kinetics. By in situ plating with a bismuth film (BiF), the developed electrode exhibited well-defined and separate peaks for Zn(II), Cd(II), and Pb(II) by square wave anodic stripping voltammetry (SWASV). Analytical characteristics of the BiF/N/IL/G/SPCE were explored with calibration curves which were found to be linear for Zn(II), Cd(II), and Pb(II) concentrations over the range from 0.1 to 100.0 ng L−1. With an accumulation period of 120 s detection limits of 0.09 ng mL−1, 0.06 ng L−1 and 0.08 ng L−1 were obtained for Zn(II), Cd(II) and Pb(II), respectively using the BiF/N/IL/G/SPCE sensor, calculated as 3σ value of the blank. In addition, the developed electrode displayed a good repeatability and reproducibility. The interference from other common ions associated with Zn(II), Cd(II) and Pb(II) detection could be effectively avoided. Finally, the proposed analytical procedure was applied to detect the trace metal ions in drinking water samples with satisfactory results which demonstrates the suitability of the BiF/N/IL/G/SPCE to detect heavy metals in water samples and the results agreed well with those obtained by inductively coupled plasma mass spectrometry.  相似文献   

20.
Two new zinc(II) and cadmium(II) complexes, [Zn(PDT)2(NCS)2] (1) and [Cd((PDT)2I1.6(H2O)0.4(OH)0.4] · 0.4H2O (2) (“PDT” is the abbreviation of 3-(2-pyridyl)-5, 6-diphenyl-1,2,4-triazine), have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, and studied by X-ray crystallography. Zinc(II) in 1 is six coordinate ZnN6. 2 is a co-crystal with cadmium(II) being 60% six-coordinated with a CdN4I2 environment and 40% seven-coordinated with a CdN4O2I environment. The supramolecular features in these complexes are guided/controlled by weak directional intermolecular S ··· π, C–H ··· π, C–H ··· I, and π ··· π interactions.  相似文献   

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