Spectrofluorimetric flow injection method for the individual and successive determination of L-cysteine and L-cystine in pharmaceutical and urine samples.

A flow injection configuration is proposed for the determination of L-cysteine and L-cystine individually and for mixtures of both analytes. The procedure is based on the rapid oxidation of L-cysteine by thallium(III) with concomitant formation of fluorescent thallium(I). The inclusion of a selecting valve and of a copper-coated cadmium column in the configuration allows the successive determination of two analytes. Linear calibration graphs were obtained between 5 x 10(-6) and 5 x 10(-5) mol dm-3 of L-cysteine and between 2 x 10(-6) and 2 x 10(-5) mol dm-3 of L-cystine. The applicability of the method to the determination of L-cysteine and L-cystine in pharmaceutical preparations was demonstrated by investigating the effect of potential interferents and by the analysis of commercial preparations. The method was successfully applied to the determination of L-cysteine and L-cystine in urine samples.     

Determination of ethaverine and papaverine using ion-selective electrodes.

Ion-selective poly(vinyl chloride) membrane electrodes for the opium alkaloids papaverine and ethaverine are presented. The electrode membranes contain ion pairs of the alkaloids with the anionic counter ion tetraphenylborate. The detection limits for all electrodes were approximately 2 x 10(-6) mol dm-3 at pH 5.0 in 100 mmol dm-3 buffered solutions and the measured slopes were close to the values theoretically expected. The selectivity coefficient observed for the ethaverine-tetraphenylborate electrode is 10(-1.1) with respect to papaverine. The suitability of the membranes for single-use electrodes is discussed.     

Absorption spectra of the 4f electron transitions of the praseodymium complex with 1-cyclopropyl-6-fluoro-1,4-dihydro-7-(4-ethyl-1-piperazinyl) -4-oxo-3-quinoline carboxylic acid hydrochloride and its analytical application.

The absorption spectra of the praseodymium complex with 1-cyclopropyl-6-fluoro-1,4-dihydro-7-(4-ethyl-1-piperazinyl)-4-oxo-3- quinoline carboxylic acid hydrochloride (NNFX) has been studied by normal and derivative spectrophotometry. The complex showed maximum absorption at 350 nm at pH 6.0. The stoichiometry of the Pr-NNFX complex was calculated by the molar ratio and continuous variation methods. The ratio of Pr to NNFX was 1:3. The absorption bands of the 4f electron transitions of the praseodymium complex with NNFX are enhanced markedly, especially the wavelength at 481 nm. Using the third-derivative spectrum, the calibration graph is linear over the range 2.5 x 10(-5)-3.5 x 10(-4) mol dm-3 for praseodymium. The detection limits (signal-to-noise ratio of 2) is 1.4 x 10(-6) mol dm-3. The relative standard deviation is 1.2% for 7.0 x 10(-5) mol dm-3 of praseodymium. A method for the direct determination of praseodymium in rare earth mixtures with good accuracy and selectivity is described.     

Construction and performance characteristics of new fentanyl-selective plastic membrane electrode.

The construction and performance characteristics of an ion-selective electrode for fentanyl-drug cation, based on an ion-pair complex with tetrakis[3,5-bis-(trifluoromethyl)phenyl]borate anion in a PVC matrix were studied. A linear response for 1 x 10(-5) mol dm-3 to 1 x 10(-2) mol dm-3 drug with a slope of 57.9 +/- 0.5 mV/decade was established. The optimum pH range was 2 to 6. The lower detection limit was 6.29 x 10(-6) mol dm-3 fentanyl citrate (2.1165 micrograms cm-3 fentanyl). There were negligible interferences from a number of inorganic cations, structural analogues, and some common drug additives in injections. The electrode proposed has been successfully applied to determine fentanyl citrate in injections. The results correlated well with those obtained by the United States Pharmacopoeia standard procedure.     

Determination of 25-hydroxyvitamin D3 in human serum by fluorescence labelling and high-performance liquid chromatography.

A method is described for the determination of 25-hydroxyvitamin D3 in human blood serum. The problems of sensitivity and selectivity encountered with previous techniques were avoided by the formation of a highly fluorescent Diels-Alder adduct following solid-phase extraction of the vitamin. After excess of reagent had been eliminated, quantification was achieved by high-performance liquid chromatography. The recovery of the vitamin from serum was 76.4 +/- 1.76%. The precision of the method was determined, and the relative standard deviations were 8.38% at a concentration of 47.0 x 10(-9) mol dm-3, 6.74% at a concentration of 99.8 x 10(-9) mol dm-3 and 3.79% at a concentration of 146.8 x 10(-9) mol dm-3. The detection limit for the adduct was 2.93 x 10(-14) mol injected, for a signal-to-noise ratio of 3:1, and serum concentrations of 0.25 x 10(-9) mol dm-3 could easily be quantified. No interference from endogenous or exogenous substances was observed.     

Determination of ascorbic acid in pharmaceuticals and urine by reverse flow injection.

Two reverse flow injection (FI) methods, using spectrophotometric detection, are proposed for the determination of ascorbic acid. Both methods are based on its reaction with the ethylenediaminetetraacetic acid-CoIII complex in a medium of 5% diethylamine. In the first method, using the peak-height FI technique, ascorbic acid is determined over the range from 2 x 10(-4) to 5 x 10(-3) mol dm-3 and in the second, using the peak-width FI method, the working range is extended (2 x 10(-3)-5 x 10(-2) mol dm-3). Both FI methods were applied to the determination of ascorbic acid in pharmaceuticals while the peak-height FI technique was also used to determine ascorbic acid in urine.     

Study of the electrochemical behavior of mitoxantrone and its determination at a Co-C modified ultramicroelectrode

In 0.005 mol dm-3 Tris-0.05 mol dm-3 NaCl buffer solution (pH 7.10), the electrochemical behavior of mitoxantrone was studied by linear-sweep voltammetry and cyclic voltammetry at a Co-carbon fiber ion implantation modified ultramicroelectrode. A sensitive reduction peak was obtained. The peak potential was -0.798 V (vs. SCE), the peak current was proportional to the concentration of mitoxantrone over the range of 2.0 x 10(-7)-6.0 x 10(6) mol dm-3 and the detection limit was 4.2 x 10(-8) mol dm-3. This method was applied to the direct determination of mitoxantrone in urine. Recoveries were in the range 95.4-105.8%. The reduction process was quasi-reversible with absorptive characteristics at a Co-C ultramicroelectrode. According to Laviron's theory, the electrode reaction rate constant ks and the electron transfer alpha of mitoxantrone were 4.4 s-1 and 0.48, respectively. The composition and depth distribution of elements on the surface of the Co-C ultramicroelectrode were determined by Auger electron spectroscopy. The experiments showed that Co was implanted into the surface of the carbon fiber, and the Co-C ultramicroelectrode had good stability and reproducibility.     

Homogeneous liquid-liquid extraction method for the selective spectrofluorimetric determination of trace amounts of tryptophan

Twenty-one amino acids were derivatized with fluorescamine (FLA) under basic conditions (pH 9) and the extraction of the amino acid-FLA derivatives was investigated using a homogeneous liquid-liquid extraction with perfluorooctanoic acid (HPFOA) based on phase separation under strongly acidic conditions. Under the optimum concentration conditions for the reagents ([PFOA]T = 3 x 10(-3) mol dm-3, [acetone]T = 3 vol.%, [HCl]T = 1.8 mol dm-3), the concentration factor was approximately 1000-fold (i.e., 30 microliters of the sedimented liquid phase was produced from 33 ml of the homogeneous aqueous solution). The percentage extraction (E) was determined for the 21 amino acid-FLA derivatives; the value for the tryptophan (Trp)-FLA derivative was 80.9%, whereas the other derivatives were not almost extracted (E < 0.4%). The Trp-FLA derivative was selective for the extraction using the homogeneous liquid-liquid extraction method with HPFOA. After the sedimented liquid phase containing Trp-FLA has been placed on a polytetrafluoroethylene filter-paper, the fluorescence intensity was determined using a spectrofluorimeter with filter-paper as the solid-sample holder. The calibration graph of Trp was linear over the range 1.0 x 10(-8)-1.5 x 10(-6) mol dm-3. The relative standard deviation for the central value of the calibration graph was 4.5% (five determinations) and the detection limit (S/N = 3) was 8.9 x 10(-9) mol dm-3. When the proposed method was applied to the highly sensitive spectrofluorimetric determination of Trp in animalin-L syrup, the results were satisfactory.     

Electrochemical determination of dopamine using a poly(2-picolinic acid) modified glassy carbon electrode

A poly(2-picolinic acid) chemically modified electrode (CME) for the determination of dopamine (DA) by cyclic voltammetry is described. Compared with a bare glassy carbon electrode, the CME exhibits a 200 mV shift of the oxidation potential of DA in the cathodic direction and a marked enhancement of the current response. In pH 7.0 buffer solution, a linear calibration graph is obtained over the range from 2.5 x 10(-7) to 1.0 x 10(-5) mol dm-3 with a correlation coefficient of 0.998. The detection limit is 3.0 x 10(-8) mol dm-3. The modified electrode eliminated efficiently the interference from ascorbic acid (AA) when present in a 150-fold concentration ratio. It also showed excellent stability and reproducibility.     

新型电流传感器-双拄碳纤维微电极

本文报道了双拄碳纤维微电极的研究及应用,分别用循环伏安法,计市电流法考察了该电极的性能,并用实验验证了双微电极的稳态电流理论公式,探讨了理论曲线与结果偏离的原因,采用发生一收集模式,提出间接测定维生素B~1的方法,并取得了满意的结果,维生素B~1的检测限为1.0×10^-^6mol.dm^-^3,线性范围为7.5 ×10^-^6-7.5×10^-^4mol.dm^-^3     

锗(IV)-茜素红-VOSO4-EDTA体系极谱吸附催化波研究

报导了在酸性缓冲液中锗(IV)-茜素红-VOSO4-EDTA体系的配合吸附平行催化波的研究.锗的最低检出量为1.0x10^-^9mol.dm^-^3.研究了催化波的机理.     

极谱法测定铑的铑(III)-5-Br-TAMB-CPC配合物新体系及其作用机理的探讨

本文建立了利用Rh(III)-5-Br-TAMB-CP配合物吸附波体系测定铑的电化学分析方法。研究了该体系吸附波的性质及阳离子表面活性剂CPC在体系中的作用机理。该方法灵敏度高, 选择性好, 可用于催化剂中铑的测定。     

Quantification of dibromodimethylhydantoin disinfectants in water by chemiluminescent method.

Quantification of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was studied by its chemiluminescence (CL) reaction with luminol in an alkaline medium. The stability of DBDMH, 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) and 1-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH) in water was initially assessed by its CL reaction capability. The results indicated that the hydrolysis process was critically dependent on the types of reagents and their pHs. Capillary electrophoresis (CE) separation with CL detection procedure was applied to the DBDMH solution. It was found that at least 3 species in the aqueous DBDMH solution could oxidize luminol to give luminescence: one of them was confirmed to be hypobromite and the others could be the unhydrolyzed or active oxygen produced in the hydrolysis reaction. Finally, a flow-injection chemiluminescent method was proposed for the determination of DBDMH. The concentration of the analyte showed a linear relationship with the CL intensity in the range of 1.2x10(-10) to 1.0x10(-6) mol dm-3 and the detection limit was as low as 6.2x10(-11) mol dm-3. The relative standard deviation (RSD) is 1.7% (n=9) for 2.8x10(-7) mol dm-3 DBDMH.     

Determination of epinephrine, norepinephrine, dopamine and L-dopa in pharmaceuticals by a photokinetic method.

A study of the photochemical reaction of the Rose Bengal (RB)-ethylenediaminetetraacetic acid system in the presence of epinephrine, norepinephrine, dopamine and L-dopa is presented. The rate of photoreduction of RB is dramatically retarded by small amounts of these catecholamines, which have an inhibitory effect on the excited state of RB, which is the activator of the process. Optimum conditions for the determination of catecholamines in the range of concentration between 5 x 10(-6) and 1 x 10(-4) mol dm-3 are described. The proposed method has been applied with excellent results to the determination of catecholamines in pharmaceuticals.     

Amperometric enzyme electrode for theophylline.

An amperometric biosensor for theophylline, based on the recently isolated enzyme theophylline oxidase, is described. The enzyme is entrapped, together with a ferricytochrome C cofactor, within a polymeric (Nafion) coating. The anodic detection (at +0.4 V versus Ag-AgCl) is facilitated by the addition of a redox-mediating hexacyanoferrate(III) ion. The influence of various experimental variables is described. The limit of detection is 2 x 10(-6) mol dm-3 theophylline, with linearity prevailing up to 3 x 10(-4) mol dm-3. The fast response and wash times permit rapid flow-injection measurements, with a frequency of 180 samples h-1 and a relative standard deviation of 3.0-4.0%. Prospects of using this electrode for clinical diagnostics are discussed.     

Adsorption of Trivalent Cations on Silica

The temperature effect on the magnitude of adsorption was used to explain the mechanism of adsorption of gadolinium on silica at very low concentrations. Standard enthalpy of adsorption of gadolinium equals 36 kJ mol-1 for a total Gd concentration of 2 x 10(-8) mol dm-3 and 67 kJ mol-1 for 2 x 10(-5) mol dm-3. This result confirms the hypothesis that the Gd adsorption at low initial concentration is governed by formation of strong ternary surface complexes involving anionic impurities. Copyright 1999 Academic Press.     

电化学活化碳纤维微电极和脑神经递质及抗坏血酸在体测定

本文采用一种简单电化学方法,即恒电流法处理自制碳纤维电极,在脑神经递质测定中显示了很高的灵敏度和分辨能力.活化后的电极对多巴胺的检测限达5×10^-8mol.dm^-3,对多巴胺和抗坏血酸的伏安峰分离达170mV.作者使用该电极,采用半微分伏安法测定了活体大鼠脑内抗坏血酸,3,4-二羟苯乙酸和5-羟吲哚乙酸的浓度分别为1.7×10^-4,2.1×10^-5和 3.3×10^-6mol·dm^-3.本文对电极的制作,活化条件,伏安峰判别,在体药物实验和电极活化机理等进行了研究和探讨.     

Schiff碱型和仲胺型双冠醚II: 用双冠醚作载体的PVC膜钾离子选择性电极

用六个含二个苯并-15-冠-5单元的席夫碱型和仲胺型新型双冠醚作载体制备了钾离子选择性PVC膜电极,并研究了它们的电极行为,这些电极对所有的其它碱金属和碱土金属离子展现出显著的钾离子选择性,可期望有一定的应用价值.     

Determination of organic mercury species in soils by high-performance liquid chromatography with ultraviolet detection.

Reversed-phase high-performance liquid chromatography with ultraviolet detection was optimized for the simultaneous separation and quantification of nine organic mercury compounds: methyl-, ethyl-, phenyl-, methoxyethyl-, ethoxyethyl-, benzoic and tolylmercury, mersalylic acid and nitromersol. The nine compounds were successfully separated on octadecylsilane columns (200 x 3 mm i.d.) by gradient elution with a methanol-water mixture ranging from 30 to 50% v/v. The detection limits for the various compounds are in the range 7.0-95.1 micrograms dm-3. For the extraction of five organomercurials from spiked soils, eight different extraction solutions were tested to differentiate between the total content and the available/soluble fraction of the analytes. Ammonium acetate solutions (1 mol dm-3) and water proved to be suitable agents for the estimation of the available and soluble fractions of methyl-, ethyl-, benzoic, methoxyethyl- and ethoxyethylmercury. For the determination of the total content of methyl- and benzoic mercury in soils, solutions of potassium iodide (1 mol dm-3)-ascorbic acid (0.1 mol dm-3) and oxalic acid (1 mol dm-3) provided recoveries in the ranges 53-81%. None of the solutions tested is suitable for the extraction of ethyl-, methoxyethyl- and ethoxyethylmercury.     

Kinetically controlled separation of cadmium(II) from zinc(II) with dithizone in the presence of nitrilotriacetic acid.

The extraction rates of cadmium(II) and zinc(II) with dithizone (H2dz) in the presence of nitrilotriacetic acid (NTA) were measured, and the possible kinetic separation of cadmium(II) from zinc(II) was investigated. Upon the addition of NTA, the difference in the extraction rate between cadmium(II) and zinc(II) became large. Based on the observed rate constant under the condition [NTA] = 1 x 10(-2) mol dm-3, [H2dz]org = 1 x 10(-3) mol dm-3, and pH = 7.0, the shaking time required for the quantitative separation of cadmium(II) from zinc(II) was calculated to be between 326 and 995 s. The experimental results agreed with the prediction, and the quantitative separation of cadmium(II) from zinc(II) was performed within the above-mentioned range of shaking times.