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1.
Square-wave adsorptive stripping voltammetry technique was used to determine rosiglitazone (ROS) on the hanging mercury dropping electrode (HMDE) surface, in Britton Robinson buffer, pH = 5. The voltammetric cathodic peak was observed at ?1520 mV vs. Ag/AgCl reference electrode. The voltammetric peak response was characterized with respect to pH, supporting electrolyte, accumulation potential, preconcentration time, scan rate, frequency, pulse amplitude, surface area of the working electrode and the convection rate. Under optimal conditions, the voltammetric current is proportional to the concentration of ROS over the concentration range of 5 × 10?8–8 × 10?7 mol l?1 (r = 0.9899) with a detection limit of 3.2 × 10?11 mol l?1 using 120 s accumulation time. The developed SW-AdSV procedure showed a good reproducibility, the relative standard deviation RSD% (n = 10) at a concentration level of 5 × 10?7 mol l?1 was 0.33%, whereas the accuracy was 101% ± 1.0. The proposed method was successfully applied to assay the drug in the human urine and plasma samples with mean recoveries of 90 ± 0.71% and 86 ± 1.0%, respectively.  相似文献   

2.
Square-wave voltammetry was used to explore the adsorption property of ofloxacine complex with iron ion on the hanging mercury drop electrode (HMDE). By employing the adsorptive stripping voltammetric approach, a sensitive electroanalytical method for the quantitative analysis of ofloxacine antibiotic was achieved. A well-developed voltammetric peak was obtained in pH 7.5 Britton–Robinson buffer (B–R buffer) at ?1400 mV. The cyclic voltammetric studies indicated that the reduction process was irreversible and primarily controlled by adsorption. An investigations of the variation of adsorptive voltammetric peak current with supporting electrolyte, pH, accumulation time, accumulation potential, ion concentration, scan rate, pulse amplitude, SW frequency, working electrode area and convection rate has resulted in the recognition of optimal experimental conditions for ofloxacine analysis. The studied electroanalytical signal showed a linear response for ofloxacine in the concentration range 5 × 10?7 to 1.7 × 10?6 mol l?1 (r = 0.999). A limit of detection of 1.1 × 10?8 mol l?1 (3.98 ppb) with relative standard deviation of 1.21 RSD% and mean recovery of 99.6% were obtained. Possible interferences by several substances usually present in pharmaceutical formulation were also evaluated. The analytical quantification of ofloxacine in commercially available pharmaceutical formulation was performed and compared with data from HPLC technique.  相似文献   

3.
Two simple and highly sensitive spectrophotometric methods were developed for the quantitative determination of the drug sildenafil citrate (SC), Viagra, in pure form and in pharmaceutical formulations, through ion-associate formation reactions (method A) with mono-chromotropic acid azo dyes, chromotrope 2B (I) and chromotrope 2R (II) and ion-pair reactions (method B) with bi-chromotropic acid azo dyes, 3-phenylazo-6-o-carboxyphenylazo-chromotropic acid (III), bis-3,6-(o-hydroxyphenylazo)-chromotropic acid (IV), bis-3,6-(p-N,N-dimethylphenylazo)-chromotropic acid (V) and 3-phenylazo-6-o-hydroxyphenylazo-chromotorpic acid (VI). The reaction products, extractable in methylene chloride, were quantitatively measured at 540, 520, 540, 570, 600 and 575 nm using reagents, I–VI, respectively. The reaction conditions were studied and optimized. Beer's plots were linear in the concentration ranges 3.3–87.0, 3.3–96.0, 5.0–115.0, 2.5–125.0, 8.3–166.7 and 0.8–15.0 μg mL?1 with corresponding molar absorptivities 1.02 × 104, 8.34 × 103, 6.86 × 103, 5.42 × 103, 3.35 × 103 and 2.32 × 104 L mol?1 cm?1 using reagents I–VI, respectively. The limits of detection and Sandell's sensitivities were calculated. The methods were successfully applied to the analysis of commercial tablets (Vigoran) and the recovery study reveals that there is no interference from the common excipients that are present in tablets. Statistical comparison of the results was performed with regard to accuracy and precision using Student's t- and F-tests at 95% confidence level. There is no significant difference between the reported and proposed methods with regard to accuracy and precision.  相似文献   

4.
This paper reports an electroanalytical method developed for determining the antioxidant tert-butylhydroquinone (TBHQ) in biodiesel, based on the enhancement effect of cetyltrimethylammonium bromide (CTAB). In pH 6.5 Britton–Robinson buffer, a poorly defined oxidation peak was observed for TBHQ at a carbon paste electrode (CPE). In the presence of low concentrations of CTAB, however, the oxidation peak current was markedly increased. Several parameters were studied and optimized for the development of this methodology, and under optimal conditions the oxidation peak current was proportional to TBHQ concentration in the range of (1.05–10.15) × 10−6 mol L−1, with limits of detection and quantification of 7.11 × 10−8 mol L−1 and 2.37 × 10−7 mol L−1, respectively, by linear sweep voltammetry (LSV). The method was applied to TBHQ determination in soybean biodiesel samples. The results were satisfactory in comparison with those obtained using high-performance liquid chromatography (HPLC).  相似文献   

5.
Binding of copper to three peptide fragments of prion (Cu2+ binding sites: 60–91, 92–96 and 180–193 amino acid residues) was investigated by anodic stripping voltammetry to determine the stoichiometries of Cu2+-prion peptide interactions. The method relies on the synthesis of N-terminally acetylated/C-terminally amidated peptide fragments of prion by solid-phase synthesis and direct monitoring of the oxidation current of copper in the absence and presence of each prion fragment. Titration curves of Cu2+ with Ac-PHGGGWGQ-NH2, Ac-GGGTH-NH2 and Ac-VNITKQHTVTTTT-NH2 were obtained in concentrations ranging from 8.52 × 10?7 to 5.08 × 10?6, 3.95 × 10?7 to 1.94 × 10?6 and 7.82 × 10?8 to 4.51 × 10?7 M, respectively. The acquired data were used to calculate the stoichiometries (one peptide per Cu2+ ion for all the three studied systems) and apparent dissociation constants (Kd = 4.37 × 10?8–3.50 × 10?10 M) for the three complexes.  相似文献   

6.
A highly sensitive visible spectrophotometric method has been developed to determine ethamsylate in this paper, which is based on using Cu(II) as spectroscopic probe reagent. The study indicates that in the presence of SCN? and KNO3, Cu(II) is reduced to Cu(I) by ethamsylate at pH 5.0, and the in situ formed Cu(I) reacts with SCN? to form into the white emulsion CuSCN that could be stayed upon the surface of water. According to the amount of residual Cu(II), the amount of ethamsylate can be indirectly determined. Under the optimal conditions, Beer's law is applicable in the range of 0.2–9.0 μg/mL (7.60 × 10?7–3.42 × 10?5 mol/L) for aqueous standard solution of ethamsylate with linear correlation coefficient of 0.9998. The detection limit and relative standard deviation are 0.12 μg/mL and 1.5%, respectively. And the molar absorption coefficient of the indirect determination of ethamsylate is 1.0 × 105 L/mol cm. The method is successfully applied to determine ethamsylate in pharmaceutical preparations and biological samples.  相似文献   

7.
Electron paramagnetic resonance (EPR) study of Cu2+ doped bis (glycinato) Mg (II) monohydrate single crystals is carried out at room temperature. Copper enters the lattice substitutionally and is trapped at two magnetically inequivalent sites. The observed spectra are fitted to a spin-Hamiltonian of rhombic symmetry with the following values of the parameters: Cu2+ (I), gx = 2.1577 ± 0.0002, gy = 2.2018 ± 0.0002, gz = 2.3259 ± 0.0002, Ax = (87 ± 2) × 10?4 cm?1, Ay = (107 ± 2) × 10?4 cm?1, Az = (141 ± 2) × 10?4 cm?1; Cu 2+ (II), gx = 2.1108 ± 0.0002, gy = 2.1622 ± 0.0002, gz = 2.2971 ± 0.0002, Ax = (69 ± 2) × 10?4 cm?1, Ay = (117 ± 2) × 10?4 cm?1and Az = (134 ± 2) × 10?4 cm?1. The ground state wave function of the Cu2+ ion in this lattice is evaluated to be predominantly |x2 ? y2. The g-factor anisotropy is also calculated and compared with the experimental value. With the help of the optical absorption study, the nature of bonding in the complex is discussed.  相似文献   

8.
The adsorptive collection of zinc(II) complex with alizarin ligand, coupled with the square-wave voltammetric technique at the hanging mercury drop electrode, yields a very sensitive electroanalytical procedure for the determination of zinc. The optimized experimental conditions include: supporting electrolyte (carbonate buffer), pH (11), alizarin concentration (1 × 10?6 mol l?1), accumulation time (60 s), accumulation potential (?0.1 V), scan rate (700 mV s?1), pulse amplitude (0.06 V) and SW frequency (80 Hz). The monitored stripping voltammetric current was linear over the range of 5 × 10?8 – 4 × 10?7 mol l?1 and the detection limit was 1 × 10?8 mol l?1. The relative standard deviation was calculated as 1.3% (n = 10) for 1 × 10?8 mol l?1 Zn(II) and the obtained electrochemical signal was stabile for up to 60 min. Possible interferences by either co-existing metal ions or other chelating agents were also investigated. The applicability of the proposed SW-AdSV method to the analysis of foodstuff was assessed by the determination of zinc content in instant coffee samples. The accuracy of the obtained voltammetric analytical results was validated by comparing with that obtained by atomic absorption spectrometric method and conducting the necessary statistical evaluation.  相似文献   

9.
The behavior of a modified carbon platinum electrode (Pt) for lead(II) determination by square wave voltammetry (SWV) was studied. The modified electrode is obtained by electrodeposition of hydroxyapatite (HAP) on the surface of a bare platinum electrode. The new electrode (HAP/Pt) revealed interesting electroanalytical detection of lead(II) based on the adsorption of this metal onto hydroxyapatite under open circuit conditions. After optimization of the experimental and voltammetric conditions, the best voltammetric responses-current intensity and voltammetric profile were obtained in 0.2 mol L?1 KNO3 with: 30 min accumulation time, 5 mV pulse amplitude and 1 mV s?1 scan rate. The observed detection (DL, 3σ) and quantification (DL, 10σ) limits in pure water were 2.01 × 10?8 and 6.7 × 10?7 mol L?1, respectively. The reproducibility of the proposed method was determined from five different measurements in a solution containing 2.2 × 10?6 mol L?1 lead(II) with a coefficients of variation of 2.08%.The electrochemical of hydroxyapatite at platinum surfaces was characterized, after calcinations 900 °C, by X-ray diffraction, infrared spectroscopy, chemical and electrochemical analysis.  相似文献   

10.
A polycrystalline rare earth double perovskite oxide, strontium cerium antimonate, Sr2CeSbO6 (SCS), is synthesized by solid-state reaction technique. The X-ray diffraction pattern at room temperature of SCS shows orthorhombic phase with the lattice parameters, a = 8.84 Å, b = 6.22 Å, and c = 5.83 Å. Fourier transform infrared spectrum shows two phonon modes of the sample at around 550 cm?1 and 670 cm?1 due to the antisymmetric SbO6 stretching vibration. The compound shows significant frequency dispersion in its dielectric properties. The complex impedance plane plots show that the relaxation (conduction) mechanism in SCS is purely a bulk effect arising from the semiconductive grains having the grain resistance = 3.8 × 106 Ω and the grain capacitance = 1.03 × 10?10 F at 603 K. The frequency-dependent conductivity spectra follow the universal power law. The conductivity at 100 Hz varies from 2 × 10?7 Sm?1 to 1.97 × 10?5 Sm?1 with the increase of temperature from 303 K to 703 K, respectively. The relaxation mechanism of the sample in the framework of electric modulus formalism is modelled by Davidson–Cole equation. The activation energy of the sample, calculated from both conductivity and modulus spectra is found to be ~0.15 eV. Such a value of activation energy indicates that the conduction mechanism for SCS is due to electron hopping. The scaling behaviour of imaginary electric modulus suggests that the relaxation describes the same mechanism at various temperatures.  相似文献   

11.
The development of UV and fluorescence spectrophotometric methods for the quantitative determination of alprazolam in dosage forms using As(III)?SDS system. The two simple and sensitive, spectrophotometric and spectrofluorimetric methods were developed for the determination of alprazolam (ALP) in tablets. These methods are based on formation of ALP?As(III) complex in the presence of SDS. The UV-spectrum of 30% methanolic solution of ALP (5 × 10?5 M) at pH 6.5 (Mclivaine buffer) was run between 200 and 380 nm. The absorption spectrum of ALP exhibits two peaks with a λmax. at 255 nm and a weak band at 325 nm. When the spectra of the drug were run at varying pH in the region 200–380 nm, one isosbestic point at 290 nm was observed, which indicated the presence of two ionic conditions in solution. The complex exhibited an absorption maximum at 265 nm and emission peak at 520 nm with respect to the excitation wavelength of 325 nm. The spectrophotometric method was found to be linear in 8.0–17.0 μg ml?1 range with detection limit of 13.520 μg ml?1, while 0.05–9.5 μg ml?1 range was with detection limit of 1.048 × 10?2 μg ml?1 by spectrofluorimetric method. The mean percentage recovery of the added quantity was found to be 99.54 (spectrophotometric method) and 100.22 (spectrofluorimetric method) and the %RSD are lower than 0.478 and 0.296 determined spectrophotomerically and spectrofluorimtrically, respectively. This indicates that the proposed method is accurate. The apparent ionization constant of ALP was found to be 9.29. The spectra, experimental conditions were set followed by determination stoichiometry, stability constant and thermodynamic parameters of the As(III), Co(II), Ni(II), and Zn(II) complexes with ALP at pH 6.5. The proposed methods have been successfully applied to the assay of ALP in tablets and the results were statistically evaluated.  相似文献   

12.
A kinetic spectrophotometric method for the determination of thiocyanate, based on its inhibitory effect on silver(I) catalyzed substitution of cyanide ion, by phenylhydrazine in hexacyanoferrate(II) is described. Thiocyanate ions form strong complexes with silver(I) catalyst which is used as the basis for its determination at trace level. The progress of reaction was monitored, spectrophotometrically, at 488 nm (λmax of [Fe(CN)5PhNHNH2]3?, complex) under the optimum reaction conditions at: 2.5 × 10?3 M [Fe(CN)6]4?, 1.0 × 10?3 M [PhNHNH2], 8.0 × 10?7 M [Ag+], pH 2.8 ± 0.02, ionic strength (μ) 0.02 M (KNO3) and temperature 30 ± 0.1 °C. A linear relationship obtained between absorbance (measured at 488 nm at different times) and inhibitor concentration, under specified conditions, has been used for the determination of [thiocyanate] in the range of 0.8–8.0 × 10?8 M with a detection limit of 2 × 10?9 M. The standard deviation and percentage error have been calculated and reported with each datum. A most plausible mechanistic scheme has been proposed for the reaction. The values of equilibrium constants for complex formation between catalyst–inhibitor (KCI), catalyst–substrate (Ks) and Michaelis–Menten constant (Km) have been computed from the kinetic data. The influence of possible interference by major cations and anions on the determination of thiocyanate and their limits has been investigated.  相似文献   

13.
Picolyl, pyridine, and methyl functionalized N-heterocyclic carbene iridium complexes [Cp1Ir(C^N)Cl]Cl (4, C^N = 3-Methyl-1-picolyimidazol-2-ylidene), [Cp1Ir(C^N)Cl][Cp1IrCl3] (5), [Cp1Ir(C-N)Cl]Cl (6, C-N = 3-Methyl-1-pyridylimidazol-2-ylidene) and [Cp1Ir(L)Cl2] (7, L = 1,3-dimethylimidazol-2-ylidene) have been synthesized by transmetallation from Ag(I) carbene species, and characterized by 1H NMR, 13C NMR spectra and elemental analyses. The molecular structures of 5–7 have been confirmed by X-ray single-crystal analyses. The iridium carbene complexes 4 and 6 show moderate catalytic activities (3.03 × 105 g PNB (mol Ir)?1 h?1 and 1.70 × 106 g PNB (mol Ir)?1 h?1) for the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) as co-catalyst. The produced polynorbornene have been characterized by IR, 1H NMR and 13C NMR spectra, showing it follows the vinyl-addition-type of polymerization.  相似文献   

14.
The electrochemistry of a single-component redox flow battery employing vanadium(III) acetylacetonate in acetonitrile and tetraethylammonium tetrafluoroborate has been investigated. The electrode kinetics of the anodic and cathodic reactions were studied using cyclic voltammetry. The V(II)/V(III) and V(III)/V(IV) couples were quasi-reversible and together yielded a cell potential of 2.2 V. The diffusion coefficient for vanadium acetylacetonate was estimated to be in the range of 1.8–2.9 × 10?6 cm2 s?1 at room temperature. The charge–discharge characteristics of this system were evaluated in an H-type glass cell, and coulombic efficiencies near 50% were achieved.  相似文献   

15.
A new β-cyclodextrin (β-CD) inclusion compound Zn(2H1NA)2·2β-CD (2H1NA = 2-hydroxy-1-naphthoic acid) was prepared. The structure was characterized by 1H NMR, IR, the fluorescence spectra, thermogravimetric analysis (TG–DTA) and elementary analysis. Meanwhile, the mechanism of the formation of the supramolecular system (2H1NA:Zn(II):β-CD) was studied and discussed by spectrofluorimetry. The results showed that the naphthalene rings of the Zn(II) aromatic complex Zn(2H1NA)2 were encapsulated within the β-CD's cavity to form a 2:1 stoichiometry host–guest compound. The inclusion constant calculated was 1.27 × 104 (L/mol)2. A spectrofluorimetric method for the determination of 2H1NA in bulk aqueous solution in the presence of β-CD was developed based on the great enhancement of the fluorescence intensity of 2H1NA. The linear relationship was obtained in the range of 9.00 × 10?7 to 2.50 × 10?5 mol/L and the detection limit was 8.00 × 10?7 mol/L. The proposed method was successfully applied to determine 2H1NA in waste water with recoveries of 97–104%.  相似文献   

16.
Three simple, accurate and sensitive methods (A–C) for the spectrophotometric assay of captopril (CPL) in bulk drug, in dosage forms and in the presence of its oxidative degradates have been described. The methods are based on the bromination of captopril with a solution of excess brominating mixture in hydrochloric acid medium. After bromination, the excess brominating mixture is followed by the estimation of surplus bromine by three different reaction schemes. In the first method (A), the determination of the residual bromine is based on its ability to bleach the indigo carmine dye and measuring the absorbance at 610 nm. Method B, involves treating the unreacted bromine with a measured excess of iron(II) and the remaining iron(II) is complexed with 1,10-phenanthroline and the increase in absorbance is measured at 510 nm. In method (C), the surplus bromine is treated with excess of iron(II) and the resulting iron(III) is complexed with thiocyanate and the absorbance is measured at 478 nm. In all the methods, the amount of bromine reacted corresponds to the drug content. The different experimental parameters affecting the development and stability of the color are carefully studied and optimized. Beer's law is valid within a concentration range of 0.4–6.0, 0.4–2.8 and 1.2–4.8 μg mL?1 for methods A, B and C, respectively. The calculated apparent molar absorptivity was found to be 5.16 × 104, 9.95 × 104 and 1.74 × 105 L mol?1 cm?1, for methods A, B and C, respectively. Sandell's sensitivity, correlation coefficients, detection and quantification limits are also reported. No interference was observed from common additives found in pharmaceutical preparations. The proposed methods are successfully applied to the determination of CPL in the tablet formulations with mean recoveries of 99.94–100.11% and the results were statistically compared with those of a reference method by applying Student's t- and F-test.  相似文献   

17.
Novel Schiff base Cu(II), Ni(II), Co(II) and Zn(II) complexes have been designed and synthesized using the macrocyclic ligand derived from the condensation of diethylphthalate with Schiff base, obtained from benzene-1,2-diamine and 3-benzylidene-pentane-2,4-dione. The ligand and its complexes have been characterized by analytical and spectral techniques. DNA binding properties of these complexes have been investigated by UV–vis, viscosity measurements, cyclic voltammetric and differential pulse voltammogram studies. The intrinsic binding constants for Co(II), Ni(II), Cu(II) and Zn(II) complexes are 1.6 × 106, 1.8 × 106, 2.0 × 106 and 1.5 × 106 M?1 respectively which are obtained from electronic absorption experiment. Control DNA cleavage experiments using pUC19 supercoiled (SC) DNA and minor groove binder (distamycin) suggest the major groove binding tendency for the synthesized complexes. In the presence of a reducing agent like 3-mercaptopropionic acid (MPA), the synthesized complexes show chemical nuclease activity under dark reaction condition. The complexes also show efficient photo-induced DNA cleavage activity on irradiation with a monochromatic UV light of 360 nm in the presence of inhibitors. Control experiments show inhibition of cleavage in the presence of singlet oxygen quencher like sodium azide and enhancement of cleavage in D2O, suggesting the formation of singlet oxygen as a reactive species in a type-II process.  相似文献   

18.
In this work, the reactions involving l-phenylalanine and d,l-tryptophan in the presence of Cu(II) ion were studied. Optimum conditions for the reactions were established as pH 7 and λ = 641 nm. When the reaction was kinetic, it was observed that the following rate formula was found as dA/An = k dt and k = 3.2 × 10?4 s?1, according to absorbance measurements. Using a perpetual change curve, the ratio of [Cu]/[Cu] + l-phenylalanine + [d,l-tryptophan] was found 1:1:1. According to this result, one molecule of l-phenylalanine and one molecule of d,l-tryptophan react with one molecule Cu(II) ion.  相似文献   

19.
The temperature dependence of the rate constant of the inversion substitution reactions CH3X + O2 → CH3O2? + X? (X = SH, NO2), can be expressed as k = 6.8 × 10–12(T/1000)1.49exp(–62816 cal mol–1/RT) cm3 s–1 (X = SH) and k = 6.8 × 10–12(T/1000)1.26 × × exp(–61319 cal mol–1/RT) cm3 s–1 (X = NO2), as found with the use of high-level quantum chemical methods and the transition state theory.  相似文献   

20.
This paper describes a novel strategy for actinide separation by extraction chromatography with Np(III) valence adjustment. Neptunium(IV) was reduced to Np(III) using Cr(II) and then selectively separated from uranium (IV) on a TEVA resin. After elution, Np(III) was retained on a DGA resin in order to remove any detrimental chromium impurities. Neptunium(III) formation was demonstrated by the complete and selective elution of Np from TEVA resin (99 ± 7%) in less than 12 mL of 9 M HCl from U(IV) (0.7 ± 0.7%). It was determined by UV–visible and kinetic studies that Cr(II) was the only species responsible for the elution of Np(IV) as Np(III) and that the Cr(II) solution could be prepared from 2 to 30 min before its use without the need of complex degassing systems to prevent the oxidation of Np(III) by oxygen. The methodology proposed here with TEVA/DGA resins provides removal of Cr(III) impurities produced at high decontamination factors (2.8 × 103 and 7.3 × 104 respectively).  相似文献   

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