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1.
《Electrophoresis》2018,39(8):1079-1085
Cyclodextrins (CD) form inclusion complexes with different “guests” owing to the fact that the shape of the CD molecule is a truncated cone with a hydrophobic cavity. The adducts of CD with metal complexes remain scantily explored. In this study, the stability constants of the adducts between succinate copper(II) complexes and β‐CD was determined using capillary electrophoresis. The β‐CD concentration in background electrolytes (BGE) was found to influence on the effective electrophoretic mobility of the copper(II) complexes in succinate BGEs. It was shown that succinic acid and its anions and copper(II) ions did not form a significant amount of the inclusion complexes with β‐CD and the mobility change was caused by the adduct formation between succinate copper(II) complexes and β‐CD. The stability constants of these adducts were determined at 25°С and ionic strength of 0.100 M: log β(CuL22−/β‐CD) = 1.76 ± 0.06, log β(CuL0/β‐CD) = 0.98 ± 0.09. The [CuHL]+ and [CuHL2] species were found to do not form adducts with β‐CD.  相似文献   

2.
The influence of 2‐hydroxy‐3‐[(2‐hydroxy‐1,1‐dimethylethyl)amino]propane‐1‐sulfonic acid (AMPSO=HL) on systems containing copper(II) was studied by glass‐electrode potentiometry (GEP) and direct‐current polarography (DCP), at fixed total‐ligand‐to‐total‐metal‐concentration ratios and various pH values (25°, 0.1M KNO3 medium). The predicted model ([CuL]+, [CuL(OH)], [CuL2], [CuL2(OH)]?, [CuL2(OH)2]2?, and [CuL3]?) and the overall stability constants for species found were obtained by combining results from both electrochemical techniques. The last five complexes are reported for the first time. For the species [CuL]+, [CuL2], [CuL3]?, and [CuL2(OH)2]2?, it was possible to determine stability constants with reasonable certainty and their values, as log β, were found to be 4.62±0.04, 9.5±0.1, 13.4±0.1, and 21.2±0.1, respectively. For the species [CuL(OH)] and [CuL2(OH)]?, stability constants 11.7±0.2 and 15.6±0.2, respectively, are presented as indicative values. It was demonstrated that AMPSO buffer may decrease the Cu2+ concentration by ten orders of magnitude by forming complexes with Cu2+. For the first time, the correction in DCP waves for the adsorption of the ligand and quasi‐reversibility of the metal allowed to determine stability‐constant values that are in good agreement with the values obtained by GEP. The importance of graphic analysis of data and significance of employing two analytical techniques was demonstrated; neither GEP nor DCP would be able to provide the correct M/L/OH? model and reliable stability constants when used independently.  相似文献   

3.
Two new unsymmetrical copper(II) Schiff base complexes, [CuLn(py)]ClO4 (n = 1, 2) in which Ln represents a tridentate N2O type Schiff base ligand, were synthesized. Lns were derived from monocondensation of meso-1,2-diphenyl-1,2-ethylenediamine with salicylaldehyde or 3-methoxysalicylaldehyde. The reaction between [CuLn(py)]ClO4 and other salicylaldehyde derivatives resulted in new N2O2 unsymmetrical tetradentate CuII complexes, CuL3–6. Crystal structures of [CuL1(py)]ClO4, CuL4, and CuL5 were obtained. These new complexes as well as a series of related symmetrical ones (i.e. CuL7–12) were tested for their in vitro anticancer activity against human liver cancer cell line (Hep-G2) by MTT and apoptosis assay. All of the complexes showed considerable cytotoxic activity against tumor cell lines (IC50 = 5.13–16.24 μg mL?1). The symmetrical CuL7 was the most potent anticancer derivative (IC50 = 5.13 μg mL?1) compared to the control drug 5-FU (IC50 = 5.4 μg mL-1, p < 0.05). Flow cytometry experiments showed that the copper derivatives especially [CuL2(py)]ClO4 and CuL7 induced more apoptosis on Hep-G2 tumor cell lines compared to 5-FU.  相似文献   

4.
Characteristics of iron(III) complexes with malic acid in 0.55 mol L?1 NaCl were investigated by voltammetric techniques. Three iron(III)‐malate redox processes were detected in the pH range from 4.5 to 11: first one at ?0.11 V, second at ?0.35 V and third at ?0.60 V. First process was reversible, so stability constants of iron(III) and iron(II) complexes were calculated: log K1(FeIII(mal))=12.66±0.33, log β2(FeIII(mal)2)=15.21±0.25, log K1(FeII(mal))=2.25±0.36, and log β2(FeII(mal)2)=3.18±0.32. In the case of second and third reduction process, conditional cumulative stability constants of the involved complexes were determined using the competition method: log β(Fe(mal)2(OH)x)=15.28±0.10 and log β(Fe(mal)2(OH)y)=27.20±0.09.  相似文献   

5.
Schiff base mixed-ligand copper complexes [CuL1(phen)Cl2], [CuL1(bipy)Cl2], [Cu(L1)2Cl2], [Cu(L2)2Cl2], [CuL2(bipy)Cl2], and [CuL2(phen)Cl2] (where L1?=?4-[3,4-dimethoxy-benzylidene]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazole-3-one; L2?=?4-[3-hydroxy-4-nitro-benzylidene]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazole-3-one; phen?=?1,10-phenanthroline; and bipy?=?2,2′-bipyridine) have been synthesized and characterized. Their DNA-binding properties have been studied by electronic absorption spectra, viscosity, and electrochemical measurements. The absorption spectral and viscosity results suggest that the copper(II) complexes bind to DNA via partial intercalation. The addition of DNA resulting in the decrease of the peak current of the copper(II) complexes indicates their interaction. Interaction between the complexes and DNA has also been investigated by submarine gel electrophoresis. The copper complexes cleave supercoiled pUC19 DNA to nicked and linear forms through hydroxyl radical and singlet oxygen in the presence of 3-mercaptopropionic acid as the reducing agent. These copper complexes promote the photocleavage of pUC19 DNA under irradiation at 360?nm. Mechanistic study reveals that singlet oxygen is likely to be the reactive species responsible for the cleavage of plasmid DNA by the synthesized complexes. The in vitro antimicrobial study indicates that the metal chelates have higher activity against the bacterial and fungal strains than the free ligands.  相似文献   

6.
From extraction experiments and ??-activity measurements, the extraction constants corresponding to the general equilibrium Eu3+(aq) + 3A?(aq) + L(nb) ? EuL3+(nb) + 3A?(nb) taking part in the two-phase water?Cnitrobenzene system (A? = CF3SO3 ?; L = p-tert-butylcalix[6]arene, p-tert-butylcalix[8]arene; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Further, the stability constants of the EuL3+ complexes in nitrobenzene saturated with water were calculated for a temperature of 25 °C as log ?? nb(EuL3+) = 6.4 ± 0.1 (L = p-tert-butylcalix[6]arene) and log ?? nb(EuL3+) = 11.3 ± 0.1 (L = p-tert-butylcalix[8]arene).  相似文献   

7.
The composition and stability of coordination compounds of the anions of maleic (H2L) and succinic (H2Y) acids with copper(II) ions in water-ethanol solutions is studied by means of potentiometric titration at a sodium perchlorate ionic strength of 0.1 and a temperature of 298.15 K. The composition of the water-ethanol solvent was varied from 0 to 0.7 molar parts of ethanol for maleic acid and from 0 to 0.4 molar parts for succinic acid. The stability of monoligand complexes of copper ions with the anions of maleic and succinic acids grows with increase of ethanol concentration from 3.86 to 6.62 for logβCuL and from 2.98 to 6.01 for logβCuY. It is shown that a monotonic rise in stability upon an increase in the content of ethanol in solution is observed, while the values of logβCuL change more sharply. The succinic acid anion forms a stronger complex with copper ions than maleic acid anions do at an ethanol content of 0.4 molar parts. The possibility of the formation of a protonated CuHY+ particle is established.  相似文献   

8.
The study of radionuclides speciation requires accurate evaluation of stability constants, which can be achieved by CE‐ICPMS. We have previously described a method for 1:1 metal complexes stability constants determination. In this paper, we present its extension to the case of successive complexations and its application to uranyl‐oxalate and lanthanum‐oxalate systems. Several significant steps are discussed: analytical conditions choice, mathematical treatment by non‐linear regression, ligand concentration and ionic strength corrections. The following values were obtained: at infinite dilution, log(β1°(UO2Oxa))=6.93±0.05, log(β2°(UO2(Oxa)22?))=11.92±0.43 and log(β3°(UO2(Oxa)34?))=15.11±0.12; log(β1°(LaOxa+))=5.90±0.07, log(β2°(La(Oxa)2?))=9.18±0.19 and log(β3°(La(Oxa)33?))=9.81±0.33. These values are in good agreement with the literature data, even though we suggest the existence of a new lanthanum‐oxalate complex: La(Oxa)33?. This study confirms the suitability of CE‐ICPMS for complexation studies.  相似文献   

9.
Stability constants for aqueous Ag+/Br?, Ag+/SCN?, and mixed Ag+/Br?/SCN? complexes are determined at 25° C by using data generated potentiometrically in solutions having ionic strengths of 0.4, 1.0, and 2.0 m. Monte Carlo numerical methods which yield apparent stability constants for these complexes as well as confidence limits are described in detail. Explicit consideration of speciation shows that under useful precipitation conditions (high bromide and low thiocyanate), a significant fraction of soluble silver is present as AgBrn (SCN)1?n?mm complexes. The most prevalent mixed complexes under these conditions are AgBr (SCN)? (log β11=8.0 ± 0.5) and AgBr2(SCN)2? (log β21=9.2 ± 0.3). The free energies of formation of the other tri- and tetra-coordinate mixed complexes are nearly indistinguishable (log β12=9.3 ± 0.5; log β31=9.0 ± 0.6; log β22=9.6 ± 0.9; log β13=10.3 ±0.5).  相似文献   

10.
The use of polarography to accurately determine stability constants of complexes formed under very acidic conditions (below pH 2) is demonstrated. The diffusion junction potentials, which must be accounted for below pH 2, were evaluated by applying protocols developed where Tl(I) is used as an internal reference. The Cu(II)‐picolinic acid (2‐pyridinecarboxylic acid) system studied was chosen since the CuL+ species only exists in solution below pH 2 under the conditions used and literature data exists to confirm the accuracy of procedure. Additionally, the reduction of Cu(II) was quasi‐reversible and procedures to determine the reversible half‐wave potentials were investigated. Average log β values of 7.75±0.09 for CuL+ and 14.8±0.1 for CuL2 were obtained, which compared well to literature data.  相似文献   

11.
The protonation constants of the anion of the cephalosporin antibiotic ceftazidime Ctzd and formation constants of its complexes with Ni2+ and Cu2+ have been determined by pH metric titration at 25°С and ionic strength 0.1 (KNO3): logβ(HCtzd) = 4.82 ± 0.04, logβ(H2Ctzd+) = 7.62 ± 0.06, logβ(H3Ctzd2+) = 9.23 ± 0.09, logβ(NiCtzd+) = 4.04 ± 0.03, logβ(Ni(Ctzd)2) = 6.41 ± 0.06, and logβ(CuCtzd+) = 5.03 ± 0.06. The potentiometric method has failed to reveal the complexation of Ctzd with Co2+, Zn2+, and Cd2+. The composition of the [Ni(Ctzd)2] and [CuCtzd]+ complexes has been confirmed by spectrophotometry. The computer models of the [NiCtzd]+ and [CuCtzd]+ complexes have been calculated by the DFT method with the use of the B3LYP hybrid functional and the LACV3P**++ basis set.  相似文献   

12.
The synthesis and electronic and IR spectra of CuL2(NO3)2 and CuL4(NO3)2, where L stands for morpholine, are described. The thermal behaviour of the complexes is also discussed. The solids contain distorted octahedral Cu(II) bonded to morpholine through nitrogen only. In aqueous solutions only the species CuL3(aq)2+ is stable in the concentration range 0.5 < [L] < 2 mol dm?3, its stability constant being log K3 = 14.64 ± 0.15 at 25.00°C and ionic strength 1 mol dm?3; at very high morpholine concentrations, 3.4 < [L] < 6 mol dm?3, evidence is also found for CuL4(aq)2+, the value log K4 = 15.5 being estimated. The aggressiveness of morpholine-H2O2 towards metallic copper is compared with that of ammonia-H2O2, both on thermodynamics and kinetics grounds; experimental results seems to be dominated by kinetics factors. The relevance of these results to water treatment in secondary systems of nuclear power reactors is discussed.  相似文献   

13.
Carina M.M. Machado 《Talanta》2007,71(3):1352-1363
This work describes the application of polarography, a technique scarcely used for modelling and optimisation of stability constants, in the study of copper complexes with [(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)amino]-1-propanesulfonic acid (TAPS). Direct current polarography (DCP), using low total copper ion and large total ligand to total copper concentration, enabled the full characterization of Cu-(TAPS)x-(OH)y system, whose complexation occurs in the pH range of copper hydrolysis and Cu(OH)2 precipitation. Cu-(TAPS)x-(OH)y system was studied by DCP and glass electrode potentiometry (GEP) in aqueous solution at fixed total ligand to total metal concentrations ratios and varied pH values (25.0 °C; I = 0.1 M, KNO3). The predicted model, as well as the overall stability constants values, are (as log β): CuL+ = 4.2, CuL2 = 7.8, CuL2(OH) = 13.9 and CuL2(OH)22− = 18.94. GEP only allowed confirming the stability constants for CuL+ and CuL2 and was used to determine the pKa of TAPS, 8.342.Finally, a briefly comparative analysis between TAPS and other structural related buffers was done. Evaluation based on log βCuL versus pKa revealed that TES, TRIS, TAPS and AMPSO coordinated via amino and hydroxymethylgroups forming a five-membered chelate ring. For BIS-TRIS and TAPSO, and possibly DIPSO, one or more five-membered chelate rings involving additional hydroxyl groups are also likely formed.  相似文献   

14.
Two copper(II) complexes, [Cu2(μ-benzoato)(L1)2]NO3·2H2O (1) and [Cu2(μ-succinato)(L2)2(H2O)]ClO4 (2), have been synthesized, where L1 = N′-[(E)-phenyl(pyridin-2-yl)methylidene]benzoylhydrazone and L2 = N′-[(E)-pyridin-2-ylmethylidene]benzoylhydrazone. These complexes were characterized including by single-crystal X-ray diffraction studies. The copper is five-coordinate in 1 while in 2 one copper is five-coordinate and the other is six-coordinate. Electrochemical behavior of these complexes was measured by cyclic voltammetry. The conproportionation equilibrium constants (Kcon) for both complexes have been estimated. The superoxide dismutase (SOD) activities of 1 and 2 were measured by nitro blue tetrazolium assay. Complex 1 has better SOD activity than 2.  相似文献   

15.
Bis-tris propane or 1,3-bis(tris(hydroxymethyl)methylamino)propane (BTP) and N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES) are pH buffers which have been used in biological experiments. To characterize BTP and BES complexation properties with Cu(II), glass electrode potentiometry and direct current polarography were conducted using total ligand to total copper concentration ratios of different orders of magnitude and pH values at 25 °C and 0.1 M KNO3 ionic strength. The graphic analysis is a very powerful tool in the prediction and refinement operations of both systems. For the Cu-BTP system, six species were found to describe totally the system, CuL, CuL(OH), CuL(OH)2, CuL2, CuL2(OH), and CuL2(OH)2, with respective stability constants determined as 10.7 ± 0.1, 19.4 ± 0.4, 24.3 ± 0.2, 18.8 ± 0.1, 24.7 ± 0.2, and 29.8 ± 0.2. CuL2, CuL2(OH), and CuL2(OH)2 were described for the first time. In the case of the Cu-BES system, complexation behavior was described by the model constituted by CuL, CuL(OH), and CuL(OH)2, the latter two described for the first time, with respective stability constants determined as 3.24 ± 0.08, 10.9 ± 0.2, and 16.0 ± 0.3, respectively. UV–vis results allowed us to establish coordination modes for the Cu-BTP and Cu-BES complexes.  相似文献   

16.
The speciation of curium(III) with L-threonine and O-phospho-L-threonine was determined by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at trace Cm(III) concentrations (3?×?10?7?M). Curium species of the type MpHqLr were identified in the L-threonine- and O-phospho-L-threonine system. These complexes are characterized by their individual luminescence spectra and luminescence lifetimes. The following formation constants were determined (a) for L-threonine: log?β101?=?6.72?±?0.07, log?β102?=?10.22?±?0.09, and log?β1–22?=?(7.22?±?0.19) at ionic strength I?=?0.5?M and (b) for O-phospho-L-threonine: log?β121?=?18.03?±?0.13 and log?β111?=?14.17?±?0.09 at ionic strength I?=?0.154?M. Possible structures of the identified curium species are discussed on the basis of the luminescence lifetime measurements and the magnitude of the formation constants.  相似文献   

17.
The complexation of 1-methyl-2-hydroxymethyl-imidazole (L) with Cu(I) and Cu(II) has been studied in aqueous acetonitrile (AN). Cu(I) forms three complexes, Cu(AN)L+, CuL2+, and Cu(AN)H?1L, with stability constants logK(Cu(AN)+ + L ? Cu(AN)L+) = 4.60 ± 0.02, logβ2 = 11.31 ± 0.04, and logK(Cu(AN)H?1L+H+ ? Cu(AN)L+) = 10.43 ± 0.08 in 0.15M AN. The main species for Cu(II) are CuL2+, CuH?1L+, CuH?1L2+, and CuH?2L2. The autoxidation of CuL2+ was followed with an oxygen sensor and spectrophotometrically. Competition between the formation of superoxide in a one-electron reduction of O2 and a path leading to H2O2 via binuclear (CuL2)2O was inferred from the rate law with ka = (2.31 ± 0.12) · 104M ?2S ?1, kb = (1.0 ± 0.2) · 103M ?1, kc = (2.85 ± 0.07) · 102M ?2S ?1, kd = 3.89 ± 0.14M ?1S ?1, ke = 0.112 ± 0.004, kf = (2.06 ± 0.24) · 10?10M S ?1, kg = (1.35 ± 0.07) · 10?7 S ?1, and kh = (6.8 ± 1.4) · 10?7M ?1 S ?1.  相似文献   

18.
《Electroanalysis》2005,17(23):2129-2136
The investigation of the dissolved iron(III)–nitrilotriacetate–hydroxide system in the water solution (I=0.1 mol L?1 in NaClO4; pH 8.0±0.1) using differential pulse cathodic voltammetry, cyclic voltammetry, and sampled direct current (DC) polarography, was carried out on a static mercury drop electrode (SMDE). The dissolved iron(III) ion concentrations varied from 2.68×10?6 to 6×10?4 mol L?1 and nitrilotriacetate concentrations were 1×10?4 and 5×10?4 mol L?1. By deconvoluting of the overlapped reduction voltammetric peaks using Fourier transformation, four relatively stable, dissolved iron(III) complex species were characterized, as follows: [Fe(NTA)2]3?, mixed ligand complexes [FeOHNTA]? and [Fe(OH)2NTA]2?, showing a one‐electron quasireversible reduction, and binuclear diiron(III) complex [NTAFeOFeNTA]2?, detected above 4×10?4 mol L?1 of the added iron(III) ions, showing a one‐electron irreversible reduction character. The calculations with the constants from the literature were done and compared with the potential shifts of the voltammetric peaks. Fitting was obtained by changing the following literature constants: log β2([Fe(NTA)2]3?) from 24 to 27.2, log β1([FeNTA]?) from 8.9 to 9.2, log β2([Fe(NTA)2]4?) from 11.89 to 15.7 and log β2([Fe(OH)2NTA]3?) from 15.63 to 19. The determination of the electrochemical parameters of the mixed ligand complex [FeOHNTA]?, such as: transfer coefficient (α), rate constant (ks) and formal potential (E°') was done using a sampled DC polarography, and found to be 0.46±0.05, 1.0±0.3×10?3 cm s?1, and ?0.154±0.010 V, respectively. Although known previously in the literature, these four species have now for the first time been recorded simultaneously, i.e. proved to exist simultaneously under the given conditions.  相似文献   

19.
Two tetranuclear manganese complexes, [Mn4(L1)6](ClO4)2?2.75H2O (1) [HL1 = 4-methyl-2-((pyridin-2-ylmethylene)amino)phenol] and [Mn4(L2)4(NO3)3(OH)]?pz?3H2O (2) [HL2 = (1H-pyrazol-1-yl)(pyridin-2-yl)methanol, pz = pyrazole], have been synthesized and characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, and magnetic measurements. The structural analysis revealed that the central manganese ion is linked with three apical manganese ions through six phenoxo-bridges creating a Mn4O6 core for 1; 2 has a cubane-like topology with the Mn(II) ions and the deprotonated oxygens from L2 alternatively occupying vertices. The magnetic studies indicated a weak ferromagnetic coupling interaction (J = 0.48 ± 0.087 cm?1, g = 2.00, θ = ?0.78 K) for 1 and a weak antiferromagnetic spin-exchange interaction (J1 = ?0.50 ± 0.075 cm?1, J2 = ?0.13 ± 0.082 cm?1, g = 1.98) between Mn(II) ions for 2. The magnetostructural correlations of the two Mn4 clusters have been discussed tentatively.  相似文献   

20.
A variety of novel copper complexes were synthesized and characterized of the formulae [Cu(L1)(OAc)], [CuL2(H2O)], [CuL3(H2O)], [CuL4(OAc)], [CuL5(H2O)] [CuL6], [CuL7], [CuL8](OAc) and [CuL9], where L1 L9 represents Schiff base ligands [derived by the condensation of 5‐hydroxyflavone with 4‐aminoantipyrine (L1), o‐aminophenol (L2), o‐aminobenzoic acid (L3), o‐aminothiazole (L4), thiosemicarbazide (L5), 4‐aminoantipyrine‐o‐aminophenol (L6), 4‐aminoantipyrine‐o‐aminobenzoic acid (L7), 4‐aminoantipyrine‐o‐aminothiazole(L8) and 4‐aminoantipyrine‐thiosemicarbazide (L9)]. The spectral and magnetic results of the Cu(II) complexes exhibit square planar geometry. The DNA binding properties of copper complexes were studied by using electronic absorption spectra, viscosity and thermal denaturation experiments. The results show that the complexes were interacting with calf thymus (CT DNA). The in vitro antimicrobial activities of the investigated compounds were tested against the bacterial species and fungal species. Superoxide dismutase and antioxidant activities of the copper complexes have also been studied. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

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