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1.
The equilibrium constants and thermodynamic parameters for complex formation of 18-Crown-6 (18C6) with Tl+, Pb2+, Hg2+, and Zn2+ metal cations have been determined by conductivity measurements in methanol (MeOH)-water (H2O) binary solutions. 18-Crown-6 forms 1:1 complexes with Hg2+ and Zn2+ cations, but in the case of Tl+ and Pb2+ cations, in addition to 1:1 stoichiometry, 1:2 (ML2) complexes are formed in some binary solvents. The thermodynamic parameters (ΔH c0 and ΔS c0), which were obtained from the temperature dependences of equilibrium constants, show that in most cases the complexes are enthalpy destabilized but entropy stabilized. Non-linear behavior is observed between the equilibrium constants (log K f ) of complexes and the composition of the mixed solvent. The selectivity of the ligand for these metal cations is sensitive to the solvent composition, and, in some cases, the selectivity order is reversed in certain compositions of the mixed solvent. The results also show that the mechanism of complexation reactions and the stoichiometry of complexes of some metal cations change with the nature and even with the composition of the mixed solvent. The article was submitted by the authors in English.  相似文献   

2.
Crystalline adducts of zinc and copper(II) dithiocarbamate complexes with dibutyl-and diisobutylamines of the general formula [M(NHR′2)(S2CNR2)2] (M = Zn, 63Cu, and 65Cu; R = CH3 and C2H5; R2 = (CH2)4O; R′ = C4H9 and i-C4H9) were synthesized. Their structures and spectroscopic properties were studied by EPR and solid-state natural abundance 13C and 15N CP/MAS NMR spectroscopy. Experimental EPR data and computer-assisted modeling confirmed the individual character of copper(II) adducts. The geometries of the copper coordination polyhedra were found to be intermediate between a tetragonal pyramid and a trigonal bipyramid (TBP). The contributions from TBP to the geometries of the adducts obtained were calculated from the EPR data. According to the X-ray diffraction data, the adduct of zinc diethyldithiocarbamate with diisobutylamine exists in two isomeric forms. The 13C and 15N CP/MAS NMR signals were assigned to the atomic positions in two crystallographically independent conformer molecules.  相似文献   

3.
The structures and spectroscopic properties of nickel(II), zinc(II), and copper(II) complexes with dibutyl- and diisobutyldithiocarbamate were studied by EPR and 13C and 15N CP/MAS NMR spectroscopy and X-ray diffraction analysis. According to the EPR data, copper(II) forms mononuclear [63/65Cu{S2CNR2}2] and heterobinuclear complexes [63/65CuZn{S2CNR2}4] under magnetic dilution conditions. The isomeric forms of nickel(II) and zinc(II) diisobutyldithiocarbamates were detected by 13C and 15N NMR spectroscopy. The crystalline zinc(II) diisobutyldithiocarbamate was found to have a unique structural organization with alternating mononuclear [Zn{S2CN(i-C4H9)2}2] and binuclear molecular forms [Zn2{ S2CN(i-C4H9)2}4] in the 1 : 1 ratio.  相似文献   

4.
A new insoluble solid functionalized ligand system bearing chelating ligand group of the general formula P-(CH2)3-N[CH2CONH(C6H4)NH2]2, where P represents [Si–O] n polysiloxane network, was prepared by the reaction of the immobilized diethyliminodiacetate polysiloxane ligand system, P-(CH2)3N(CH2CO2Et)2 with 1,2-diaminobenzene in toluene. 13C CP-MAS NMR, XPS and FTIR results showed that most ethylacetate groups (–COOEt) were converted into the amide groups (–N–C=O). The new functionalized ligand system exhibits high capacity for extraction and removal of the metal ions (Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) with efficiency of 95–97% after recovery from its primary metal complexes. This functionalized ligand system formed 1:1 metal to ligand complexes.  相似文献   

5.
Electron capture dissociation (ECD) and electron transfer dissociation (ETD) in metal-peptide complexes are dependent on the metal cation in the complex. The divalent transition metals Ni2+, Cu2+, and Zn2+ were used as charge carriers to produce metal-polyhistidine complexes in the absence of remote protons, since these metal cations strongly bind to neutral histidine residues in peptides. In the case of the ECD and ETD of Cu2+-polyhistidine complexes, the metal cation in the complex was reduced and the recombination energy was redistributed throughout the peptide to lead a zwitterionic peptide form having a protonated histidine residue and a deprotonated amide nitrogen. The zwitterion then underwent peptide bond cleavage, producing a and b fragment ions. In contrast, ECD and ETD induced different fragmentation processes in Zn2+-polyhistidine complexes. Although the N–Cα bond in the Zn2+-polyhistidine complex was cleaved by ETD, ECD of Zn2+-polyhistidine induced peptide bond cleavage accompanied with hydrogen atom release. The different fragmentation modes by ECD and ETD originated from the different electronic states of the charge-reduced complexes resulting from these processes. The details of the fragmentation processes were investigated by density functional theory.
Graphical Abstract ?
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6.
Isothermal titration calorimetry has been used to determine the stoichiometry, formation constants and thermodynamic parameters (ΔG o, ΔH, ΔS) for the formation of the citrate complexes with the Mn2+, Co2+, Ni2+ and Zn2+ ions. The measurements were run in Cacodylate, Pipes and Mes buffer solutions with a pH of 6, at 298.15 K. A constant ionic strength of 100 mM was maintained with NaClO4. The influence of a metal ion on its interaction energy with the citrate ions and the stability of the resulting complexes have been discussed.  相似文献   

7.
Paramagnetic shifts in the 1H n.m.r. spectra were observed for high-spin Co2+ complexes with 12--14-membered tetraazamacrocycles incorporating two amide groups and two pendant carboxymethyl groups. The pseudocontact term due to the dipolar interaction between the metal ion and the resonant protons was calculated on the basis of X-ray structures, and the Fermi contact term due to spin delocalization was determined. The ethylenediamine moiety of the ligand molecule is coordinated in an unsymmetric manner, even in solution, and internal motion (involving conformational change of the macrocyclic frame and exchange of coordinate bonds) is much slower than the n.m.r. observation frequency. In the 12-membered macrocyclic complex Co(L12), three of the eight CH2 groups fix their orientation in the n.m.r. time scale; in Co(L13) only one CH2 group fixes its orientation; in Co(L14) all CH2 groups undergo a rapid reorientation. The facility in internal motion increases with the ring size, and shows a correlation with the chemical stabilities of these Co2+ complexes against oxidation; to atmospheric oxygen, Co2+(L12) is the most resistant and Co2+(L14) is the most susceptible.  相似文献   

8.
The complexation reactions between La3+, Y3+ and Ce3+ cations with the macrocyclic ligand, kryptofix 21, were studied in methanol-acetonitrile (MeOH-AN) and methanol-methylacetate (MeOHMeOAc) binary mixed solvent solutions at different temperatures using the conductometric method. The conductance data show that in most solvent systems, the kryptofix 21 forms a 1: 1 [M: L] complex with La3+, Y3+ and Ce3+ metal cations, but in the case of Y3+ cation in pure methylacetate, in addition of formation of a 1: 1 [ML] complex, 1: 2 [ML2] and 1: 3 [ML3] complexes are formed in solution. In the case of Ce3+cation, a 1: 1 [ML] and also a 1: 2 [ML2] complexes are formed in this solvent system at all studied temperatures. The electrical conductance data in acetonitrile, show that a 1: 1 [ML] and also a 1: 2 [ML2] complexes are formed between the ligand and La3+ and Ce3+ metal cations at different temperatures. The stability constants of the 1: 1 [ML] complexes were determined using the conductometric data and a computer program, GENPLOT. A non-monotonic relationship was observed between logK f of the 1: 1 complexes with the composition of the binary solvent solutions which was discussed in term of solvent-solvent interactions and also preferential solvation of the metal cations and the ligand in solutions. The selectivity order of the ligand for the metal cations in MeOH–AN and MeOH–MeOAc binary solvent solutions, at 25°C was found to be: Y3+ > La3+ > Ce3+ and La3+ > Y3+ > Ce3+, respectively. The values of the standard thermodynamic quantities (ΔH c ° and ΔS c ° ) for formation of the 1: 1 complexes were obtained from temperature dependence of the stability constans of the complexes and the results show that the thermodynamics of the complexation reactions between kryptofix 21 and La3+, Y3+ and Ce3+ cations, is affected by the nature and composition of the mixed solvents systems.  相似文献   

9.
Crystalline adducts of zinc and copper(II) dithiocarbamate (Dtc) complexes with dialkylamines [M(NHR′2)(S2CNR2)2] (M = Zn, 63Cu, 65Cu; R = CH3, C2H5, or R2 = (CH2)4O; R′ = C2H5, C3H7) have been preparatively isolated. The structures and spectral properties of the adducts have been studied by EPR and 13C and 15N MAS NMR. Chemisorption of bases on powders of dinuclear dithiocarbamates leads to their dissociation into monomeric adducts. Computer simulation demonstrates that the experimental EPR spectra of isotope-substituted copper(II) adducts have an individual character. The geometry of the copper polyhedra is intermediate between a trigonal bipyramid (TBP) and a tetragonal pyramid (TP). The TBP and TP contributions have been quantified based on EPR data. 13C and 15N MAS NMR data show that the Dtc ligands incorporated into the zinc adduct molecule are structurally nonequivalent. The dependence of the isotropic 15N chemical shifts of the Dtc groups on the alkyl substituents at the nitrogen atom is interpreted based on the concept of joint manifestation of the (+)inductive effect of the alkyl substituents and the mesomeric effect of the Dtc groups.  相似文献   

10.
Synthesis of water-soluble potassium salts of carboxymethyl derivatives of calix[4]pyrogallols and dodeca(carboxylatomethyl)tetramethylcalix[4]pyrogallol (L) complexes with transition metal ions (Cu2+, Fe3+, La3+) is described. Their structures in the solid state and in solution were characterized by NMR spectroscopy, ESR, and IR spectroscopy. Calix[4]pyrogallol dodecacarboxylates exist in the rccc-configuration. Calix[4]pyrogallol with methyl substituents at the lower rim in a wide range concentrations exists in water predominantly in the dimeric form. The obtained polynuclear transition metal complexes possess less symmetric structure than potassium salt of calix[4]pyrogallol (K12L). All studied complexes contain water molecules bound by rather strong hydrogen bonds. At room temperature the Fe4L complex is characterized by the environment of the Fe3+ ions close to octahedral. The absence of signals in the ESR spectrum of the Cu6L complex indicates the strong antiferromagnetic interaction Cu2+-Cu2+.  相似文献   

11.
The complexation reactions between Ni2+, Cd2+ and Ag+ metal cations with the macrocyclic ligand Kryptofix22 (K22), in pure acetonitrile (AN), ethylacetate (EtOAc), methanol (MeOH) and their binary mixtures have been studied at different temperatures using conductometric method. The obtained results show that in most solvent systems, the stoichiometry of the complexes formed between the macrocyclic ligand and the metal cations is 1: 1 [ML], but in some of the solvent systems, a 1: 2 [ML2] complex and also [M2L], [M2L2] and [M2L3] complexes are formed in solutions. The stability constans of the 1: 1 complexes were obtained using a computer program GENPLOT. A non-liner behavior was observed for changes of logKf of the 1: 1 complexes versus the composition of AN–EtOAc binary solutions. The stability order of the 1: 1 complexes at 25°C in the binary solvent solution of AN–EtOAc (mol % AN = 50) was found to be: (K22.Ag)+ > (K22.Ni)2+ > (K22.Cd)2+. The obtained values of thermodynamic quantities (ΔHc0Sc0) show that in most of the AN–EtOAc binary solvent solutions, the 1:1 complexation reactions are enthropy stabilized, but from the enthalpy view point, depending on the nature and composition of mixed solvents they are exothermic or athermic.  相似文献   

12.
Feather fibers were modified by treatment with 5% tannic acid (TA) solution. Kinetics of the modification was investigated as a function of the reaction time. The maximum loading of TA on feather reached 8.3% after being treated by TA for 9 h. The adsorption of metal cations (Cu2+, Zn2+) by unmodified and TA-modified feather fibers was investigated as a function of fiber weight gain, temperature, and pH of the metal solution. The adsorption was enhanced at alkaline pH and ambient temperature and increased with the weight gain of TA. The maximum uptake of metal cations (Cu2+, 0.77 mmol/g; Zn2+, 0.95 mmol/g) was obtained by TA-modified feather at weight gain: 8.3%, pH 11, while at the acidic pH, the adsorption of metal cations by either unmodified or TA-modified feather was negligible. The influence of anions on the adsorption of metal cations was also studied. The uptake of Cu2+ from chloride was higher and faster than that from nitrate. Desorption of the metals was performed at acidic pH 2.5 for 48 h. The feather–TA–metal complexes exhibited higher stability for metal cations than the feather–metal complexes. All these experiments reveal that TA-modified feather fibers have good adsorption to metal cations and can be used as metal adsorbent in wastewater treatment.  相似文献   

13.
The cadmium O,O′-dethyl (I) and O,O′-di-sec-butyl phosphorodithioate (II) complexes have been synthesized and characterized in detail by 13C, 31P, and 113Cd CP/MAS NMR. X-ray crystallography shows that complex II has a binuclear molecular structure [Cd2{S2P(O-s-C4H9)2}4]. For 31P and 113Cd NMR signals, the chemical shift anisotropy δaniso and the asymmetry parameter η have been calculated. The 31P NMR signals are assigned to the terminal and bridging ligands in the complexes.  相似文献   

14.
Coagulation factor VIII (FVIII) is a glycoprotein that plays a crucial role in the clotting cascade. Replacement therapies with recombinant and plasma-derived concentrates of FVIII are used for treatment of hemophilia A. We have previously purified the human plasma FVIII by immobilized metal affinity chromatography (IMAC) using Cu2+ as the metal ligand. In this work we report the purification of FVIII using Zn2+ and Co2+, two metal ions that bind proteins more weakly. Human plasma was directly applied to the anion-exchange ANX Sepharose FF column and the eluate was used as starting material for the studies in IMAC columns. Using imidazole as desorbing agent, FVIII was recovered with 65% activity in the IMAC-Zn2+ column and with 74% activity in the IMAC-Co2+ column. Purification factors were 4 and 9, respectively. Using a pH gradient, FVIII was eluted at pH 5.0 with 17% activity in the IMAC-Zn2+ and 77% activity in the IMAC-Co2+. Vitamin K-dependent proteins, a family of proteins that includes Prothrombin and coagulation factor IX, coeluted with FVIII in the ANX Sepharose FF column and were recovered with the unbound proteins on both IMAC columns. Therefore, Co2+ and Zn2+ columns were as effective as the Cu2+ column in separating FVIII from vitamin K-dependent proteins. Finally, we have shown that FVIII remained complexed with the von Willebrand factor.  相似文献   

15.
The structures and spectroscopic properties of mononuclear and binuclear mercury(II) and copper(II) complexes with four dithiocarbamate ligands R2NC(S)S? (R = CH3, C2H5, or iso-C3H7; R2 = (CH2)6) were studied by solid-state 13C and 15N CP/MAS NMR and EPR spectroscopy. Mercury(II) N,N-cyclohexamethylenedithiocarbamate [Hg2{S2CN(CH2)6}4] was obtained and characterized in detail by X-ray diffraction analysis at 299 K. The binuclear molecule of the complex is centrosymmetric; the central tricyclic fragment [Hg2S4C2] is in the chair conformation. In the 13C and 15N NMR spectra, the signals were assigned to the dithiocarbamate ligands with different structural functions: bidentate chelating and combined (both chelating and bridging) ones. The differences between the isotropic 15N chemical shifts for the dialkyldithiocarbamate ligands were interpreted in terms of combination of the mesomeric effect of the =NC(S)S-groups and the inductive effect of the alkyl substituents. According to the EPR data, copper(II) in magnetically diluted systems is mainly found in heterobinuclear molecules [CuHg(S2CNR2)4] and the geometry of the chromophores [CuS5] approximates to a tetragonal pyramid.  相似文献   

16.
The influence of Ca2+-, Cu2+- and Fe3+-exchanged montmorillonite (MMT) on the type of interaction with aniline in the interlayer space of MMT has been studied by means of X-ray powder diffraction and infrared spectra. Results of X-ray diffraction showed that aniline was successfully intercalated into the interlayer space of MMT. Based on IR spectra evaluation, aniline was indirectly coordinated through a water-bridge in Ca2+- and Fe3+-MMT and it was indirectly coordinated through a water-bridge as well as protonated in Cu2+-MMT (the spectrum of protonated aniline showed deformation and changes in the NH 3 + absorption at approximately 1521 cm?1). It is important to point out that Cu2+-MMT indirect coordination and protonation occur simultaneously.  相似文献   

17.
The standard real and chemical thermodynamic characteristics of transfer of the K+, Ca2+, Cd2+, and Br? ions from water into water-acetone solvents of various compositions were analyzed to study the rules governing the solvation of these ions in mixed solvents and its special features. All calculations were performed within the framework of the vertical jet method at 298.15 K. The energy of resolvation as a function of ion charges and crystallographic radii was found to increase in the series K+ < Ca2+ < Cd2+ < Al3+  相似文献   

18.
The complex formation of the Ni2+ and Cu2+ ions in aqueous solutions of 16 organic solvents of different nature (hydrophilic, hydrophobic, and neutral according to the dielectric data) was studied by the electronic spectroscopy. It was shown that in the case of nickel, the solvents under study behaved similarly (except for acetonitrile), i.e., were coordinated to the metal ion through oxygen, and turned weaker than water as regards the spectrochemical series. In the case of copper, the organic solvents exhibited their pronounced hydrophilic and hydrophobic nature. This is explained by nonequivalence of the equatorial and axial positions in the coordination polyhedron of copper due to the Jahn-Teller effect.  相似文献   

19.
The imidazol side group of histidine has two nitrogen atoms capable of being protonated or participating in metal binding. Hence, histidine can take on various metal-bound and protonated forms in proteins. Because of its variable structural state, histidine often functions as a key amino acid residue in enzymatic reactions. Ab initio (HF and MP2) calculations were done in modeling the cation (H+, Li+, Na+, K+, Mg2+, Ca2+) interaction with side chain of histidine. The region selectivity of metal ion complexation is controlled by the affinity of the side of attack. In the imidazol unite of histidine the ring nitrogen has much higher metal ion (as well as proton) affinity. The complexation energies with the model systems decrease in the following order: Mg2+ > Ca2+ > Li+ > Na+ > K+. The variation of the bond lengths and the extent of charge transfer upon complexation correlate well with the computed interaction energies.  相似文献   

20.
Two novel coordination polymers, namely {[Co(Ttac)0.5(1,4-Bib)(H2O)] · H2O}n (I) and {[La(HTtac)2(2H2O)] · H2O}n (II) (H4Ttac = 4,5-di(3'-carboxylphenyl)-phthalic acid, 1,4-Bib = 1,4-bis(1-imidazoly) benzene), have been designed and successfully prepared via hydrothermal process, and characterized by elemental analyses, IR spectroscopy, and single crystal X-ray diffraction (CIF files CCDC nos. 1039298 (I), 1039300 (II)). Structural analysis reveals that the H4Ttac ligands adopt different coordination modes in the as-synthesized I and II, and thus give rise to the targeted coordination polymers with different configurations. It is worth mentioning that, coordination polymer I is assembled from low-dimensional structures into three-dimensional (3D) via π···π stacking interactions, while three-dimensional coordination polymer II is formed by covalent bonds. Luminescent properties of coordination polymer II have been studied at ambient temperature. Significantly, luminescent measurement indicates that coordination polymer II may be acted as potential luminescent recognition sensors towards Cu2+ and Mn2+ ions.  相似文献   

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