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1.
Interactions of nanofilms containing ethanolamino groups with cobalt(II), nickel(II), copper(II), and zinc(II) ammoniates at the surface of polyvinylchloride plates and with chromium(III) ammoniate in a solution of ammonium chloride were studied. It was found that the groups of the film, together with chloride ions, displace all ammonia molecules from the inner coordination sphere of the metal. The average number of the ethanolamino N atoms of the film participating in formation of the metal ion coordination sphere is 3.35, 3.47, 3.67, 3.42, and 3.37 for Co2+, Ni2+, Cu2+, Zn2+, and Cr3+ complexes, respectively. The average number of chloride ions is 2 for Co2+, Ni2+, Cu2+, and Zn2+ and 3 for Cr3+. The coordination number of the central atoms is 6. The Cr3+ ion forms a coordination sphere composed of three N atoms and three chloride ions and a coordination sphere (charged 1+) made up of four N atoms and two chloride ions, with the third chloride ion being in the outer sphere. The Co2+, Ni2+, and Cu2+ ions form uncharged coordination spheres of two types: (1) with four N atoms and two chloride ions and (2) with three N atoms, two chloride ions, and the O atom of the ethanol hydroxyl group.  相似文献   

2.
We demonstrate synthesis of water insoluble, novel copolymer PA1 from condensation of glyoxal dihydrazone and glyoxal dihydrazone bis(dithiocarbamate) monomers having high capacity to remove metal ions from aqueous solution. The presence of a high atomic percentage of nitrogen and sulfur atoms in PA1 leads to strong ligating ability with metal ions. The monomers and the polymer have been characterized by FTIR, UV–Visible spectroscopy, CHNS elemental analysis, NMR, MALDI-MS, and TG/DTA. As a proof of concept, the PA1 is tested for its ability to remove heavy metal ions Cu2+, Co2+, Fe2+, Ni2+, Mn2+, and CrO 7 2? from aqueous solutions. PA1 efficiently removed metals ions from the metal solutions. The highest absorption ability has been observed toward the iron salts where 0.969 g metal salt is absorbed by 1 g polymer. This study has implication for inexpensive and efficient polymer for purification of water.  相似文献   

3.
 本文报道了一种合成硫杂冠醚聚合物的新方法。以聚(2′-氯乙基-2,3-环硫丙基醚)为预聚物与二巯基化合物通过大分子反应直接环化,一步法合成了四种以聚硫醚为主链的新型硫杂冠醚聚合物(PD1-PD4)。并测定了它们对Ag+、Au3+)、Pd2+、Pt4+、Cu2+、Hg2+、Zn2+、Cd2+、Pb2+、Mg2+、K+、Ns+等金属离子的络合性能。结果表明:它们除不络合K+、Na+、Mg2+、Pb2+外,对其它八种离子有不同程度的络合,其中对Ag+、Au3+、Pd2+等贵金属离子的络合容量较高。  相似文献   

4.
A highly colored polystyrene derivative bearing side chain chromophores composed of dialkylanilino donor and cyano‐based acceptor groups, prepared by atom‐economic click postfunctionalization, displays the dual colorimetric detection behavior of several metal ions based on the specific interactions with different nitrogen atoms. Hard to borderline metal ions, such as Fe3+, Fe2+, and Sn2+, are always recognized by the dialkylanilino nitrogen atom, resulting in a decrease in the charge‐transfer (CT) band intensity of the donor–acceptor chromophores. On the other hand, the recognition site of a soft metal ion of Ag+ is the cyano nitrogen atom due to the readily formed multivalent coordination, which produces a bathochromic shift of the CT band.  相似文献   

5.
Investigation of the complexing of Na+, K+, Ca2+ and Ba2+ with some uncharged ligands by 13C-chemical shift and spin-lattice relaxation time measurements The influence of Na+, K+, Ca2+ and Ba2+ ions on 13C chemical shifts and on spin-lattice relaxation times of some electrically neutral ion carriers was investigated. In the solvents CD3CN and CD3OD and in presence of an excess of metal ions ligand 4 (see the Scheme) forms complexes of 1:1 stoichiometry. All four oxygen atoms of the ligand as well as solvent molecules take part in the coordination. In CDCl3 as solvent, for all ions investigated except sodium, only 1:2 complexes (metal/ligand) were observed with 4 . Sodium ions form both 1:1 and 1:2 complexes in this solvent. In the 1:2 complexes of the investigated monovalent ions only one, in those of the divalent ions both amide carbonyl groups of ligand 4 take part in the coordination.  相似文献   

6.
The electron‐donating unit 2,3,4,6‐tetrahydro‐1,6‐dithia‐3a‐azaphenalene (THDTAP) was introduced onto terpyridine (TPy) to give a donor‐acceptor (D‐A) type TPy‐ligand (compound 2 ). Upon selective oxidation of two sulfur atoms on the THDTAP moiety of 2 , the ligands 3 — 6 were created. The electronic structures of 2 — 6 were evaluated by theoretical, electrochemical, and spectroscopic investigations. The oxidation on the sulfur atoms brings significant influence on the electron‐donating ability of THDTAP moiety, subsequently, leads to fine modulations on intramolecular charge‐transfer (ICT) of 2 — 6 and the electronically excited states of the complexes of 2 — 6 with metal ions. Based on the optical response of 2 — 6 toward metal ions, the step‐by‐step recognition of Zn2+, Cd2+, and Ag+ ions is set up by employing 2 and 3 as combined fluorescence sensors.  相似文献   

7.
Red onion skin is highly effective for binding heavy metal ions from aqueous solutions. Color leaching can be prevented and the physical characteristics of the substrate can be improved by treatment with formaldehyde in an acidic medium. Batch and column experiments have been conducted with Cu2+, Cd2+, Zn2+, Ni2+, Hg2+, and Pb2+. Almost quantitative removal of the metal ions from solution can be achieved by using columns of the treated onion skin. Competition of the various metal ions for the substrate has been investigated. The capacity of the substrate in the majority of the metal ions studied is well above 1 meq/g. The use of polymerized onion skin to remove heavy metal ions from domestic and industrial wastewater to safe levels has been recommended as a cheap and effective alternative for commercial ion-exchange resins.  相似文献   

8.
In the present study, a novel p-phenylcarboxylic acid BODIPY ( L ) immobilized MCM-41 based solid chemosensor material L-propylsilyl@MCM-41 ( MS4 ) was developed to detect multiple metal ions in a pure aqueous medium. The synthesized solid chemosensor material MS4 shows high sensitivity and removal ability towards trivalent (Al3+, Cr3+) and divalent (Cu2+, Hg2+) metal ions. The emission intensity of MS4 enhanced multifold selectively in the presence of trivalent (Al3+, Cr3+) metal ions and shows quenching in the presence of divalent (Cu2+, Hg2+) metal ions. The limit of detection was calculated to be in the nanomolar range with Al3+, Cr3+, Cu2+, and Hg2+ metal ions in the aqueous medium. The spectroscopic and analytical results suggest that MS4 selectively binds with Al3+ and Cr3+ through −NH functionality and with Hg2+ and Cu2+ through −COOH functionality of p-phenylcarboxylic acid BODIPY ( L ). Further, MS4 selectively removes Al3+, Cr3+, Cu2+, and Hg2+ metal ions from the aqueous media with removal efficiency of 97.28 %, 96.34 %, 87.19 %, and 95.63 %, respectively. No noticeable change in the concentration was observed for other metal ions. The recycling potential of MS4 was evaluated using EDTA for up to seven cycles with no significant reduction in sensing capability.  相似文献   

9.
We measured quantitative spectra of firefly (Photinus pyralis) bioluminescence in the presence of Zn2+ and other bivalent metal ions to investigate the effects of these metal ions on luciferin‐luciferase reaction. We studied the dependence of the quantum yield and spectrum on quantity and kind of bivalent metal ions. Adding various amounts of Mg2+, Mn2+ and Ca2+ produced virtually no change in the quantum yields or the spectra of bioluminescence. In contrast, increasing amounts of ions such as Zn2+ and Cd2+ decreased quantum yields and changed the bioluminescence color from yellow‐green to red. Quantitative analysis showed that the sensitivities of the quantum yield and color to various metal ions were in the order of Hg2+>Zn2+, Cd2+>Ni2+, Co2+, Fe2+≫Mg2+, Mn2+, Ca2+. We propose that the changes in quantum yield and spectrum caused by the metal ions are due to their effect on luciferase that surrounds oxyluciferin during its radioactive decay. We also found that having more metal ions accelerated bioluminescence reactions. The sensitivity of the reaction rate had no correlation with those of the quantum yield and spectrum.  相似文献   

10.
Azocrown ethers with sulphur atoms and pyrrole or imidazole residue as a part of macrocycle have been synthesised. Their metal complexation abilities in acetonitrile were studied using UV–vis spectrophotometry. The largest spectral changes were observed for both pyrrole- and imidazole-azothiacrown ethers on complexation with Pb2 + , Cu2 + , Zn2 + , Ni2 + , Co2 +  and Ag+ ions. In the case of alkali and alkaline earth metal ions no spectral changes were found. Preliminary studies of ion-selective membrane electrodes with synthesised ionophores are presented. In the measurement for transition/heavy metal cations, only copper and lead give high responses. X-ray structure of 18-membered pyrrole azothiacrown ether is described.  相似文献   

11.
Cellulose/chitosan composites were successfully prepared in a new and basic-based solvent system, ethylene diamine/potassium thiocyanate (EDA/KSCN), by dissolving cellulose and chitosan in 70/30 (w/w) EDA/KSCN at ?19 °C, and then coagulating in methanol. Wide angle X-ray diffraction studies revealed that the EDA/KSCN solvent system is capable of disrupting the hydrogen bonds in both cellulose and chitosan and increase the amorphous regions. Stability tests proved that the composites are stable in acidic aqueous solution due to the hydrogen bonds formed between cellulose and chitosan. This is the first time to dissolve chitosan in a basic-based solvent system and prepare cellulose/chitosan composites in a straightforward way. The adsorption of heavy metal ions (Cu2+, Cd2+, and Pb2+) onto the cellulose/chitosan composites was investigated. The adsorption capacity is highly dependent on pH and the maximum metal uptake was obtained at pH 5.0. Increasing initial metal concentration enhanced the diffusion of metal ions to the composite surface and therefore the metal removal efficiency. Higher percentage of chitosan in the composites also led to higher metal adsorption. The results indicated that the prepared cellulose/chitosan (1:1) composite can adsorb 0.53 mmol/g Cu2+, 0.28 mmol/g Cd2+ and 0.16 mmol/g Pb2+ ions at pH 5.0. The Freundlich model and the pseudo-second-order model were in good agreement with the adsorption isotherms and kinetics, respectively. X-ray photoelectron spectroscopy studies indicated that the binding of heavy metal ions is attributed to the nitrogen atoms of amino groups in chitosan. The composites can be reused for metal removal.  相似文献   

12.
Benzoaza-15-crown-5 ethers containing one or two nitrogen atoms in different positions of the macrocycle and bearing different substituents at these atoms were synthesized. The structures of azacrown ethers and their metal complexes were studied by X-ray diffraction. The stability constants of the complexes of azacrown ethers with Na+, Ca2+, Ba2+, Ag+, Pb2+, and EtNH3 + ions were determined by 1H NMR titration in MeCN-d3. In free benzoazacrown ethers containing secondary nitrogen atoms bound to the benzene ring, as well as in N-acetyl derivatives, the N atoms are sp2-hybridized and have a planar geometry. The nitrogen lone pairs on the p orbitals are efficiently conjugated to the benzene ring or the carbonyl fragment of the acetyl group, which is unfavorable for the complex formation. In addition, the formation of complexes with benzoazacrown ethers containing secondary nitrogen atoms is hindered because the hydrogen atoms of the NH groups are directed to the center of the macrocyclic cavity. In benzoazacrown ethers bearing N-alkyl substituents or secondary nitrogen atoms distant from the benzene ring, the N atoms show a substantial contribution of the sp3-hybridized state and have a pronounced pyramidal configuration, which promotes the complex formation. The lead and calcium cations form the most stable complexes due to the high affinity of Pb2+ ions for O,N-containing ligands, a high charge density on these ions, and the better correspondence of the cavity size of the 15-membered macrocycles to the diameter of the Ca2+ ion. An increase in the stability of the complexes is observed mainly in going from monoazacrown ethers to diazacrown ethers containing identical substituents at the N atoms and in the following series of substituents: C(O)Me < H < Me < CH2CO2Et. In the case of the CH2CO2Et substituents, the carbonyl oxygen atom is also involved in the coordination to the cation. The characteristic features of the complexing ability of N-alkylbenzomonoaza-15-crown-5 ethers bearing the nitrogen atom conjugated to the benzene ring show that macro-cyclic ligands having this structure are promising as selective and efficient complexing agents for metal cations.  相似文献   

13.
Electron capture dissociation (ECD) of model peptides adducted with first row divalent transition metal ions, including Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+, were investigated. Model peptides with general sequence of ZGGGXGGGZ were used as probes to unveil the ECD mechanism of metalated peptides, where X is either V or W; and Z is either R or N. Peptides metalated with different divalent transition metal ions were found to generate different ECD tandem mass spectra. ECD spectra of peptides metalated by Mn2+ and Zn2+ were similar to those generated by ECD of peptides adducted with alkaline earth metal ions. Series of c-/z-type fragment ions with and without metal ions were observed. ECD of Fe2+, Co2+, and Ni2+ adducted peptides yielded abundant metalated a-/y-type fragment ions; whereas ECD of Cu2+ adducted peptides generated predominantly metalated b-/y-type fragment ions. From the present experimental results, it was postulated that electronic configuration of metal ions is an important factor in determining the ECD behavior of the metalated peptides. Due presumably to the stability of the electronic configuration, metal ions with fully-filled (i.e., Zn2+) and half filled (i.e., Mn2+) d-orbitals might not capture the incoming electron. Dissociation of the metal ions adducted peptides would proceed through the usual ECD channel(s) via “hot-hydrogen” or “superbase” intermediates, to form series of c-/z - fragments. For other transition metal ions studied, reduction of the metal ions might occur preferentially. The energy liberated by the metal ion reduction would provide enough internal energy to generate the “slow-heating” type of fragment ions, i.e., metalated a-/y- fragments and metalated b-/y- fragments.  相似文献   

14.
The interactions of various types of cations with the tungsten trioxide lattice have been investigated to evaluate possible intercalation of these cations and the occurrence of lattice polarization leading to the near-surface structural lattice damage. The interactions of cations, such as the large monovalent cations (K+, Et4N+, CtMe3N+ cations), transition metal dications (Ni2+), heavy metal ions (Cd2+), and representative lanthanides (La3+) and actinides (Th4+), in competition with intercalation of H+ ions have been investigated using pulse-nanogravimetric technique. The effects of these cations in electrochromic processes of WO3 proceeding during cathodic reduction have been assessed. For all of the metal ions studied, a large increase in the apparent mass uptake (up to eightfold) in comparison to pure H+ ion ingress was observed upon the film coloration induced by a cathodic potential pulse. The experiments indicate that the apparent mass gains, although large, are insufficient to confirm predominant contribution of metal ions in the ion transport along the channels in WO3 lattice. The lower decoloration rate in the case of Ni2+ ions, in comparison to H+ and other transition metal cations (Cd2+), has been attributed to a slow dissociation of Ni2+ ions from lattice-bound oxygen atoms. For et4N+ cation, which is too large to enter channels in WO3, a dissociative reduction of the WO3 and severe lattice damage was observed. Among the metal ions investigated, only K+ ions have been found to cause a dissociative reduction of WO3 and near-surface lattice damage. Strong lattice polarization effects and irreversible binding have been found for La3+ and Th4+ cations.  相似文献   

15.
Formation constants of mixed ligand complexes of Cu2+, Zn2+, Ni2+, Co2+, and Mn2+,with cyadine-5′-monophosphoric acid (CMP) and various primary ligands such as 1,10-phenanthroline(phen), glycylglycine(glygly) and salicylic acid (sal) have been determined in aqueous solution at 35°C and 0.1 M (KNO3) by potentiomeric measurements. The acid dissociation constants of all the above mentioned ligands together with their 1 : 1 binary metal complex formation constants were also measured at 35°C. In general all the 1 : 1 binary complexes follow the Irving-Williams order of stability. Further the binary metal complexes of primary ligands are more stable than their ternary complexes with CMP. For ternary complexes, Δ(log K) values seem to change from positive to highly negative as the coordinating atoms of the primary ligands were varied from N,N to N,O? to O?O?. The higher stability of ternary complexes involving phen is due to its Π-bonding interaction with the above metal ions and the relative decrease in the stability of other ternary systems is due to the coulombic repulsion of donor oxygen atoms of primary and secondary ligands. Thus for ternary complexes the stabilities follow a decreasing order of M-phen-CMP > M-glygly-CMP > M-sal-CMP.  相似文献   

16.
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   

17.
The two hexamines (H2N? CH2? CH2? )2N? (CH2)n? N(? CH2? CH2? NH2)2, «penten» (n = 2) and «ptetraen» (n=3) have been investigated as chelating agents for COIII (preparative Study) and some of the divalent metal ions (potentiometric and calorimetric studies). Both amines function as sexadentate ligands for CoIII, CoII and NiII, but one of the terminal aminogroups is much easier detached from the metal in case of M (penten)v+ than in case of M(ptetraen)v+, thus revealing more strain in the fivemembered chelate rings of the girdle plane of the «penten» complexes. On the other hand, the sixmembered chelate ring in M(ptetraen)v+ is more strained than the five-membered ring comprising the tertiary nitrogen atoms of M(penten)v+ CuII and ZnII coordinate with both ligands only 5 of the 6 basic nitrogen atoms present. Both hexaamines function as sexadentates again with MnII, but the metal is coordinated with a molecule of water in addition to the 6 nitrogen atoms in the «penten» complex in contrast to the «ptetraen» complex. The thermodynamic functions for the protonation of the hexamines and for the addition of metal ions in aqueous solution are understood in almost every detail. The dielectric shielding of the charges of the reactants exerted by the solvent has to be taken into account; it is reduced by electrostriction as well as by an increase in temperature. It is shown that the approach of charges of equal sign often is an exothermic process.  相似文献   

18.
Transition metal ions (Pb2+, Zn2+, Cd2+, Co2+, Mn2+, Cu2+, Ni2+, Hg2+, Ag+, Fe3+) in water are used to quench emission of 2-(6-oxido-6H-dibenz 〈c,e〉 〈1,2〉 oxaphosphorin-6-yl)-1,4-phenylene-bis(p-pentyloxylbenzoate)s (MD5) with aggregation-induced emission enhancement (AIEE) in water-acetonitrile (AN) mixture (80:20 by volume). Among all metal ions, Fe3+ exhibits the highest quenching efficiency on AIEE of MD5 even when the concentration of Fe3+ is lower than 1×10−6 mol/L. The quenching efficiency of Hg2+ is lower than that of Fe3+ at the same concentration, though MD5 is used to detect Hg2+ efficiently, too. To other metal ions, low quenching efficiency has few relations with a wider concentration range. The UV absorbance spectra show only red shift of absorbance wavelength in the presence of Hg2+ and Fe3+, which indicates a salt-induced Jaggregation. SEM photos reveal larger aggregation and morphological change of nanoparticles of MD5 in water containing Hg2+ and Fe3+, which reduce the surface area of MD5 emission for further aggregation. The selective quenching effect of transition metal ions to emission of MD5 has a potential application in chemical sensors of some metal ions.  相似文献   

19.
A new dioxime ligand, N,N-bis(2-{[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]amino} ethyl)N′,N′-dihydroxyethanediimidamide (H2L), and its mononuclear complexes with Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ are synthesized. H2L forms transition metal complexes [Co(LH)2(H2O)2] and [M(LH)2] (M = Ni2+, Cu2+) with a metal : ligand ratio of 1 : 2. Complexes [M(H2L)(Cl)2] (Zn2+, Cd2+) have a metal : ligand ratio of 1 : 1. The mononuclear Co2+, Ni2+, and Cu2+ complexes indicate that the metal ions coordinate ligand through its two N atoms, as the most of dioximes. In the Co2+ complex, two water molecules and in the Zn2+ and Cd2+ complexes two chloride ions are also coordinated to the metal ion. The structures of these compounds are identified by elemental analyses, IR, 1H and 13C NMR, electronic spectra, magnetic susceptibility measurements, conductivity, and thermogravimetric analysis.__________From Koordinatsionnaya Khimiya, Vol. 31, No. 7, 2005, pp. 540–544.Original English Text Copyright © 2005 by Canpolat, Kaya.The text was submitted by the authors in English.  相似文献   

20.
A series of novel tripodal ligands 3a-d, based on a mesitylene anchor, containing aza-thioethers as donor atoms and coupled with 4-(4/3/2-nitrophenyl)azophenol or 4-(2-chlorophenyl)azophenol have been synthesized as chromogenic receptors, which are highly selective for silver(I). The complexation behavior of 3a-d with various metal ions has been evaluated by UV-vis spectrometry in dioxane/water (1:9/v:v) solution at 25 °C. The UV-vis spectra show that the complexation of 3a-c with Ag+ have pronounced bathochromic shifts accompanied by a unique color change in the solution from yellow to red, which is visible with the naked eye. The ligands do not show any significant change on addition of other metal ions like Li+, Na+, K+, Sr2+, Ca2+, Cd2+, Zn2+, Hg2+, Pb2+, Ni2+, and Cu2+ and thus are highly specific and selective for Ag+ in the aqueous medium.  相似文献   

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