Analysis of tetracycline antibiotics using HPLC with pulsed amperometric detection.

The analysis of tetracycline, oxytetracyline, chlortetracycline and doxycycline by high-performance liquid chromatography with pulsed amperometric detection using an anodized boron-doped diamond thin film (BDD) electrode is originally reported. The analyses were carried out using the mobile phase, phosphate buffer (0.01 M, pH 2.5)-acetonitrile (80:20; v/v), on a C18 column (250 x 4.6 mm i.d., 5 microm) at a flow rate of 1.0 mL/min. The optimal PAD waveform parameters at the anodized BDD were 1.5 V (versus Ag/AgCl) detection potential (E(det)) for 290 ms (200 ms delay time and 90 ms integration time), 2.0 V (versus Ag/AgCl) oxidation potential (E(oxd)) for 200 ms oxidation time (t(oxd)) and 0.4 V (versus Ag/AgCI) reduction potential (E(red)) for 200 ms reduction time (t(red)). The proposed method showed the simultaneous determination of tetracycline, oxytetracyline, chlortetracycline and doxycycline with a linear range of 0.1 - 100 microg/mL, detection limits of 0.05 - 0.1 microg/mL and recoveries of 70.8 - 96.0%. The application of this method to real samples was demonstrated and validated using a shrimp sample.     

Steady-state and flow-injection response of a metallic silver electrode for potentiometric detection of metal cyanide complex formartion

A metallic silver electrode provides a potentiometric response to Ag(I), Hg(II), Fe(III), Cu(II), Zn(II), Co(II) and Ni(II) ions, and large changes in the electrode potential of up to 400 mV are observed when these ions are injected into a 0.29 mM soulution of cyanide ion. Injection 10-μl aliquots into a reagent stream with a cyanide concentration of 0.1 mM is shown to give the expected sigmoidal-shaped response curve for peak height as a function of metal ion concentration. Sub-nanomole quantities of metal ions are detectable with a peak height of ca. 20 mV, depending on the cyanide concentration.     

Determination of s-triazines with copper and glassy carbon electrodes. Flow injection analysis of aziprotryne in water samples

The detection and determination of s-triazines, atrazine-desethyl and aziprotryne by cyclic voltammetry and an amperometric method using a metallic copper electrode and a glassy carbon electrode are described. The concentrations of atrazine-desethyl and aziprotryne in 0.1 M NaOH solutions were determined using the oxidation signal corresponding to the Cu(0)/Cu(I) redox process. The detection level calculated for these s-triazines were 0.3 and 0.5 microg/mL of analyte, respectively. The glassy carbon electrode was shown to give sensitive reduction response to aziprotryne in flow injection mode. No special activation was required for the glassy carbon electrode. A detection limit of 0.2 microg/mL (20 ng aziprotryne) was obtained for a sample loop of 0.1 mL at a fixed potential of -1.0 V (vs. Ag/AgCl) in 0.1 M HCl and a flow rate of 3.5 mL/min. Furthermore, the glassy carbon electrode showed stable response in such a system, and the relative standard deviation was only 2.7% using the same surface, and 6.3% using different surfaces. The method developed was applied to the determination of aziprotryne in environmental and tap water samples; using a prior solid-phase extraction step, aziprotryne concentrations lower than 1.0 ng/mL could be measured.     

The effect of potential on the gold dissolution in cyanide solutions in the presence of sulfide ions

The effect of potential on the rate of gold dissolution in the cyanide solutions in the presence of sulfide ions is studied. The dependences of current on the time after the electrode surface renewal were measured under the potentiostatic conditions. The majority of experiments were performed in the solution of the following composition, M: 0.1 KCN, 0.1 KOH, 0.01 KAu(CN)₂, (1.5–2) × 10^?5 Na₂S at 23°C. It is shown that, at the potentials more positive than ?0.1 V (NHE), the rate of gold dissolution starts to increase as soon as the surface is renewed, which is associated with high-rate chemisorption of catalytically active sulfide ions. At E < ?0.1 V, the chemisorption proceeds slowly, and a considerable increase in the current takes much time. Therefore, in the potentiodynamic measurements, at E < ?0.1 V, no catalytic effect of sulfide ions is observed. When the ratio between the concentrations of sulfide and cyanide ions is decreased, the potential, which, by convention, bounds the aforementioned ranges, shifts in the positive direction. Plausible explanations for these regularities are proposed.     

Oxidation of the cyanide ion at a platinum electrode studied by polarization modulation infrared reflection absorption spectroscopy

The anodic oxidation of the cyanide ion at a platinum electrode in aqueous solution was observed by polarization modulation infrared reflection absorption spectroscopy(PM IRRAS). The cyanide ion was adsorbed on the electrode surface in the potential region more negative than 0.4 V (versus Ag/AgCl). In the more positive region (> 0.4 V ), the adsorbed cyanide ion was oxidized to form the cyanate ion. Cyanogen was not detected during the oxidation reactions; this suggests direct electrochemical formation of the cyanate ion.     

Rayleigh relaxation of pyrazine,pyridine and piperidine molecules adsorbed on the roughened Ag electrode by light beating technique

The light beating technique (intensity correlation algorithm) was employed to analyze the Rayleigh scattering from the roughened Ag electrode in very dilute (10^?4 M) pyrazine, pyridine and piperidine aqueous solutions containing KC1 (0.1 M). The relaxation time is longer when the applied voltages are between ?0.4 V and ?0.8 V (vs. SCE) where the Raman effect also shows greater surface enhancement. Also observed was that for the piperidine case the relaxation time reaches its maximum at the more negative applied voltage. The origin of the relaxation is attributed mainly to the desorption process of the pyrazine, pyridine and piperidine molecules off the roughened Ag electrode. An electrostatic model was also proposed for the interpretation of these experimental observations.     

Electrochemical Investigation of Metal Oxide Conducting Electrodes for Direct Detection of Sulfide

This study examined the performance of four conducting metal oxide electrodes for the direct electrochemical analysis of sulfide; the electrode materials studied were indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO) and gallium doped zinc oxide (GZO). Cyclic voltammetry (CV) results obtained using the ITO, AZO, GZO and FTO electrodes showed direct electrooxidation peak potential of sulfide at 381, 507, 400, and 850 mV vs. Ag/AgCl, respectively; however, the less positive oxidation potential and high catalytic current response of the ITO electrode made it the electrode of choice for the direct oxidation of sulfide. The effects of different electrolytes and buffer solutions on the CV responses were also evaluated. A linear concentration range up to 350 µM and a detection limit of 8.0 µM were achieved. CV response was highly reproducible, remaining unaffected even after 50 measurements. The sensor was found to have good selectivity, with no interference from sulfite, sulfate or chloride ions. The present findings demonstrate that the bare ITO electrode can be used as the basis of an inexpensive, sensitive, selective and robust sulfide sensor.     

Highly selective and sensitive spectrophotometric determination of trace amounts of silver ion in surfactant media using 2-mercaptobenzoxazole

A simple and accurate spectrophotometric method for determination of trace amounts of silver ion in tap and wastewater solution and photographic solutions has been described. The spectrophotometric determination of silver ion using 2-mercaptobenzoxazole (MBO) in the presence of Triton X-100 as nonionic surfactant has been carried out. The Beer's law is obeyed over the concentration range of 0.1-9.0 microg mL(-1) of Ag+ ion with the detection limits of 1.6 ng mL(-1). The influence of type and amount of surfactant, pH, complexation time and amount of ligand on sensitivity of method were optimized. Finally the repeatability, accuracy and the effect of interfering ions on the determination of silver ion were evaluated. There is a good agreement between results of proposed method and atomic absorption spectrometry.     

Semi-quantitative "spot-test" of cyanide.

A selective, sensitive, rapid and simple-handling analytical method for the determination of cyanide at low detection limits in surface and underground water, soil and industrial waste samples was developed. The method is based on a reaction, proposed by Guilbault and Kramer, where free cyanide reacts with p-nitrobenzaldehyde to form an intermediate cyanohydrin, which reacts with o-dinitrobenzene to give a highly colored purple compound. The original procedure was modified for application in a small device containing a gas-permeable membrane. The cyanide is converted in the volatile hydrogen cyanide, which permeates through a PTFE membrane, reaching colorimetric reagents. In order to obtain semi-quantitative results, printed color scales were built. The method allows rapid, accurate, selective, low-cost and simple-handling determinations of free cyanide, even in complex samples. About 150 real samples were analyzed. Less than 10 ng of free cyanide per ml (10 microg l(-1)) can be easily detected. For more concentrated solutions, the results had been compared to those obtained using differential pulse polarography. The standard addition method was used for more diluted solutions.     

A study of Nafion-coated bismuth-film electrodes for the determination of trace metals by anodic stripping voltammetry

This work reports on the fabrication, characterization and applications of Nafion-coated bismuth-film electrodes (NCBFE's) for the determination of trace metals by anodic stripping voltammetry (ASV). A NCBFE was typically prepared by first applying a 5 microl drop of a 1% Nafion solution onto the surface of a glassy-carbon rotating-disk electrode. After evaporation of the solvent, the Bi film was plated on the electrode in situ(i.e. by spiking the sample with 1000 microg l(-1) of Bi(iii) and simultaneous electrolytic deposition of the metal ions and bismuth film on the electrode surface at -1.4 V) or ex-situ(i.e. by electrolytic deposition of the bismuth film in a separate solution containing 1000 microg l(-1) of Bi(iii), followed by the ASV measurement step in the sample solution). Various fabrication and operational parameters were thoroughly investigated and discussed in terms of their effect on the ASV signals. It was found that this voltammetric sensor was suitable for the determination of metals at trace levels by square-wave ASV (SWASV) due to its multi-element detection potential, improved analytical sensitivity, high resistance to surfactants, low cost, ease of fabrication, robustness, speed of analysis and low toxicity (as compared to traditional mercury electrodes). In the presence of 4 mg l(-1) of Triton X-100, the NCBFE afforded a 10-fold peak height enhancement for the Pb peak and a 14-fold enhancement for the Cd peak over a bare BFE while the determination of Zn was feasible only on the NCBFE. The limits of detection (at a signal-to-noise ratio of 3) were 0.1 microg l(-1) for Cd and Pb and 0.4 microg l(-1) for Zn for a deposition time of 10 min. Finally, the electrode was applied to different real samples (tap-water, urine and wine) for the analysis of trace metals with satisfactory results.     

High dispersion and electrocatalytic properties of platinum nanoparticles on graphitic carbon nanofibers (GCNFs)

Highly dispersed platinum nanoparticles were electrodeposited on graphitic carbon nanofibers (GCNFs) by cyclic voltammetry (CV) in 7.7 mM H2PtCl6+0.5 M HCl aqueous solutions. The graphitic carbon nanofibers (GCNFs) used in this paper were grown directly on a graphite disk by chemical vapor deposition (CVD). The micrographs and element composition of Pt/GCNFs/graphite electrode were characterized by scanning electron microscopy (SEM) and electron diffraction spectroscopy (EDS). The electrocatalytic properties of Pt/GCNFs/graphite electrode for methanol oxidation have been investigated by CV and excellent electrocatalytic activity can be observed even at very low platinum loading (md=8.79 microg cm(-2)). The highest mass activity (MA) for methanol oxidation reaches 323 Ag(-1) when Pt/GCNFs/graphite electrode was cycled at a sweep rate of 50 mVs(-1) by CV in 2 M CH3OH+1 M H2SO4 aqueous solutions. This may be attributed to the small particle size and high dispersion of platinum particles coated on GCNFs and shows good potential application in direct methanol fuel cell (DMFC). Additionally, the long-term cycling stability of platinum catalysts was also investigated.     

Potentiometric determination of silver(I) by selective membrane electrode based on derivative of porphyrin.

The performance of silver metal complexes with meso-tetraphenylporphyrin ([H2T(4-CH3)]PP) as ionophores for ion-selective electrodes was studied. The electrode exhibited linear response with Nernstian slope of 59.2 +/- 1.0 mV per decade within the concentration range of 1.0 x 10(-7)-1.0 x 10(-1) M silver ions. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plot, was 1.0 x 10(-7) M. The response time of the electrode was < 10 s over the entire concentration range. The silver-selective electrode exhibited good selectivity for Ag(I) with respect to alkali, alkaline earth and heavy metal ions. The electrodes could be used at least three months without a considerable divergence in their potential. The electrodes are suitable for use in aqueous solutions in a wide pH range of 3.0-9.0. They were used as indicator electrodes in titration of Ag(I) with sodium iodide solution and were successfully applied to direct determination of silver in real samples.     

Cyanide ion selective solid contact electrode based on nickel complex of N,N′-bis-(4-phenylazosalicylidene)-o-phenylene diamine ionophore

A cyanide ion selective poly(aniline) solid contact electrode based on nickel complex of N,N′-bis-(4-phenylazosalicylidene)-o-phenylenediamine ionophore was successfully developed. The electrode exhibits a good linear response of 58.7 mV/decade (at 20 ± 0.2°C, r ² = 0.998) with in the concentration range of 1 × 10^?1.0-1 × 10^?6.0 M cyanide. The composition of this electrode was: ionophore 0.300, polyvinylchloride 0.300, 2-nitrophenyloctyl ether 0.670 (mass). This 2-nitrophenyloctyl ether plasticizer provides the best response characteristics. The electrode shows good selectivity for cyanide ion in comparison with any other anions and is suitable for use with aqueous solutions of pH 4.6–6.3. The standard deviations of the measured emf difference were ±1.92 and ±1.87 mV for cyanide sample solutions of 1.0 × 10^?2 M and 1.0 × 10^?3 M, respectively. The stabilization time was less than 183 s and response time was less than 38 s.     

Characterization of ceramic ion-selective membrane-electrodes-I The Ag(2)S electrode

The behaviour of a new type of electrode, made from ceramic Ag(2)S, has been investigated. The electrode response is Nernstian for Ag(+) over the range 10(-6)-2M and for Hg(2+) in the concentration range 10(-6)-10(-2)M, both at constant ionic strength (0.1M). The electrode is Ag(+)-selective, with maximum interference from Hg(2+). It can be used for acid-base potentiometric titration and for potentiometric Ag(+) and Hg(2+) precipitation titrations.     

无液接裸露式Ag/AgCl参比电极的研制及应用

提出了一种无液接裸露式Ag/AgC l参比电极制备方法,测试了该参比电极的稳定性、重现性、可逆性、响应时间、温度影响等因素。实验结果表明,该电极电位稳定在49 mV,响应时间在30 s以内时,具有重现性、可逆性好,使用寿命长,温度影响小等特点,可替代饱和甘汞和Ag/AgC l参比电极。     

Fabrication of a covalently attached multilayer film electrode containing cobalt phthalocyanine and its application as a potentiometric sensor of iodide ion

Construction of a highly stable covalently attached multilayer film electrode containing cobalt phthalocyanine was achieved by UV irradiation of ionic self-assembled multilayer films of diazo-resins (DAR) and cobalt phthalocyanine tetrasulfonic acid (CoTsPc) tetrasodium salt. The modified electrode had good potentiometric response to iodide ion. The potentiometric response was independent of the pH of the solution between pH 2.5 and 6.0, while it was dependent on the nature of the buffer media. The modified electrode had a linear dynamic range between 4.7×10⁻⁶ M and 0.1 M with a Nernstian slope of 58.8 mV per decade and a detection limit of 3.5×10⁻⁶ M in acetate buffer (0.1 M, pH 4.6). The modified electrode also exhibited a fast response, good stability and repeatability.     

The cyclic renewable mercury film silver based electrode for determination of molybdenum(VI) traces using adsorptive stripping voltammetry

The new cyclic renewable mercury film silver based electrode (Hg(Ag)FE), applied for the determination of molybdenum(VI) traces using differential pulse adsorptive cathodic stripping voltammetry (DP AdSV) is presented. The Hg(Ag)FE electrode is characterized by very good surface reproducibility (相似文献   

Comparison of different fibers for the solid-phase microextraction of phthalate esters from water

Solid-phase microextraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS) has been applied to determine six phthalate esters and one adipate ester in water. The SPME parameters were optimized for several commercially available fibers. A 65-microm polydimethylsiloxane-divinylbenzene (PDMS-DVB) was the fiber selected and was applied to analysis of water from the Ebro river and the industrial port of Tarragona. The studied compounds were found at concentrations ranging from 0.4 microg l(-1) for di-n-butyl phthalate ester (DnBP) to 3.2 microg l(-1) for bis(2-ethylhexyl) phthalate ester (DEHP). The linear range for real samples was from 0.1 to 10 microg l(-1) for most phthalates, and the limits of detection of the method were between 3 and 30 ng l(-1). Repeatability and reproducibility between days (n = 5) for 1 microg l(-1) samples were below 13 and 18%, respectively.     

Flow injection analysis of doxycycline or chlortetracycline in pharmaceutical formulations with pulsed amperometric detection

A flow injection with pulsed amperometric detection for determination of doxycycline or chlortetracycline in pharmaceutical formulations is described. Doxycycline or chlortetracycline were studied at a gold rotating disk electrode with cyclic voltammetry as a function of pH of supporting electrolyte solution. The optimized PAD waveform parameters were obtained with a flow injection system. The optimized pulsed conditions of doxycycline were 1150 mV (versus Ag/AgCl reference electrode) detection potential (E_det) for 220 ms (150 ms delay time and 70 ms integration time), 1500 mV (versus Ag/AgCl reference electrode) oxidation potential (E_oxd) for 70 ms oxidation time (t_oxd) and 250 mV (versus Ag/AgCl reference electrode) reduction potentail (E_red) for 400 ms reactivation time (t_red). The optimized pulsed conditions of chlortetracycline were 1050 mV (versus Ag/AgCl reference electrode) detection potential (E_det) for 300 ms (200 ms delay time and 100 ms integration time), 1300 mV (versus Ag/AgCl reference electrode) oxidation potential (E_oxd) for 70 ms oxidation time (t_oxd) and 250 mV (versus Ag/AgCl reference electrode) reduction potentail (E_red) for 400 ms reactivation time (t_red). The optimized PAD waveform was applied to the determination of doxycycline hydrochloride and chlortetracycline hydrochloride standard solution and in pharmaceutical formulations. The linear dynamic ranges of doxycycline hydrochloride and chlortetracycline hydrochloride were 1 μM–0.1 mM. The sensitivity of this method was found to be 23 μA/mM for doxycycline hydrochloride and 33.76 μA/mM for chlortetracycline hydrochloride. The detection limit for both compounds is 1 μM. The doxycycline hydrochloride and chlortetracycline hydrochloride content in commercially available tablet dosage forms by the proposed method was comparable to those specified by the manufacturer.     

Potentiometric determination of chlorides with an "Air-Gap" cyanide sensor

A new electroanalytical method for determining chloride ions with an Air-Gap cyanide sensor system is described. The method is based on the reaction of chloride with mercury(II) cyanide in dilute sulphuric acid. This reaction leads to hydrogen cyanide which can be determined with an Air-Gap cyanide sensor. Optimum concentrations of mercury(II) cyanide and sulphuric acid were established and an analytical curve was prepared for 1 x 10(-1)-1 x 10(-5)M Cl(-). The slope of the calibration curve was equal to 62.8 mV/log C. The correlation coefficient (R) was equal to 0.9992. The method can determine chloride with good results in high saline solutions and in the presence of surfactants, which is in contrast to direct potentiometry with a chloride electrode. The method was applied for chloride determination in fuses used for initiating explosions. The chlorides were determined both in the raw materials used to prepare the fuse braids and in the other fuse components. Chloride was also determined in drinking water and river water. In dependence of source, chloride amount analyzed in drinking water was in the range 2.18-182.6 mg/l. and 25.8 mg/l. in river water. A comparative analysis was carried out. In the first case, chloride was determined by a turbidimetric method, whereas in the second one by potentiometric titration against a chloride-ISE.