表面活性剂增敏催化光度法测定痕量亚硝酸根

基于稀磷酸介质中,溴化十六烷基吡啶对亚硝酸根催化溴酸钾氧化吡罗红B褪色反应的增敏作用,建立了测定亚硝酸根的表面活性剂增敏催化动力学光度法。加入溴化十六烷基吡啶,灵敏度增大2.2倍。测量亚硝酸根的线性范围为0.005-0.15 mg/L,检出限为0.004/L。用于水及蔬菜中痕量亚硝酸根的测定,结果满意。     

Extraction--spectrophotometric determination of oxalate in urine and blood serum

An extraction--spectrophotometric method is described for the determination of oxalate, based on the formation of a mixed ligand vanadium (V)--mandelohydroxamic acid--oxalate complex. The complex was extracted into a solution of trioctylmethylammonium chloride (Adogen 446) in toluene and the absorbance measured at 535 nm. The experimental variables and interferences in this determination were studied. The detection limit is 0.5 microgram ml-1 and the range of application is between 2 and 8 micrograms ml-1. The method was applied to the determination of oxalate in urine and blood serum.     

Kinetic determination of Hg(II) in different materials, based on its inhibitory effect on a catalysed process

A new kinetic method for the determination of Hg(II) based on its inhibitory effect on the Pd(II)-catalysed reaction between Co(III)-EDTA and hypophosphite is proposed. The reaction is followed spectrophotometrically at 540 nm by measuring the induction period. Both the influence of the reaction variables and the interference of many ions have been studied. A mechanism for the inhibition process is also proposed. Under the selected experimental conditions of 2.7 x 10(-1)M Co(III)-EDTA, pH-3.2 Britton-Robinson buffer, 0.3M H(2)PO(-)(2), 0.35 mug/ml Pd(II), and temperature 18 +/- 0.2 degrees , Hg(II) was determined in the range 13-120 ng/ml. The method was applied to the determination of Hg(II) in sphalerites and pharmaceuticals.     

Column preconcentration of trace manganese with the ion pair of 2-nitroso-1-naphthol-4-sulfonic acid tetradecyldimethylbenzyl-ammonium chloride supported on naphthalene and determination by derivative spectrophotometry

A column preconcentration method has been developed for the determination of trace amounts of manganese by preconcentration on 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S)-tetradecyldimethylbenzylammonium (TDBA) naphthalene as an adsorbent using a simple funnel tipped glass tube. Manganese reacts with nitroso-S to form a water soluble brown colored chelate anion. The chelate anion forms a water insoluble Mn-Nitroso-S-TDBA ion pair on naphthalene packed in a column in the pH range 9.6-10.5 at a flow rate of 1-2 ml/min. The solid mass consisting of manganese complex and naphthalene is dissolved in 5 ml of dimethylformamide (DMF) and the metal determined by second derivative spectrophotometry. The calibration curve is linear in the concentration range 0.25-35.0 micrograms of Mn in 5 ml of the final DMF solution. Eight replicate determinations of 25 micrograms of standard manganese solution give a mean peak height of 4.0 with a correlation coefficient of 0.9995 and relative standard deviation of +/- 1.1%. The sensitivity was calculated to be 0.502(d2 A/d lambda 2)/microgram ml-1 from the slope of the calibration curve. The detection limit was 0.020 microgram ml-1 for manganese at the minimum instrumental settings (signal to noise ratio = 2). Various parameters effecting the method such as the effect of pH, volume of aqueous phase and interference of a number of metal ions on the determination of manganese have been evaluated to optimize the conditions for its determination in standard alloys and biological samples.     

Determination of nickel in water by chemiluminescence

The acetone chemiluminescence determination of nickel in water was investigated. Optimization data for the determination of Ni2+ and interference data for over 20 species are provided. The limit of detection for Ni2+ by this method is 2.5 ng ml-1, and the linear dynamic range is from 10 ng ml-1 to 1 microgram ml-1. The application of the method to the determination of Ni2+ in river and waste waters is discussed.     

Column chromatographic pre-concentration of iron(III) in alloys and biological samples with 1-nitroso-2-naphthol-3,6-disulphonate and benzyldimethyltetradecylammonium-perchlorate adsorbent supported on naphthalene using atomic absorption spectrometry

The solid ion-pair material produced from the reaction between benzyldimethyltetradecylammonium chloride (BDTA) and sodium perchlorate on naphthalene provides the basis for a simple, rapid and selective technique for pre-concentrating iron from up to 500 ml of aqueous solution. Iron reacts with disodium 1-nitroso-2-naphthol-3,6-disulphonate (Nitroso-R salt) to form a water-soluble coloured chelate anion. The iron chelate anion forms a water-insoluble, stable iron-Nitroso-R-BDTA complex on naphthalene packed in a column. Trace amounts of iron are quantitatively retained on naphthalene in the pH range 3.5-7.5 and at a flow-rate of 1-2 ml min-1. The solid mass is dissolved out from the column with 5 ml of N,N-dimethylformamide and iron is determined by means of an atomic absorption spectrometer at 248 nm. The calibration graph is linear for concentrations of iron over the range of 0.5-20 micrograms in 5 ml of final solution. The standard deviation and relative standard deviation were calculated. The detection limit of the method was 0.0196 micrograms ml-1 of iron. The sensitivity for 1% absorption was 0.072 microgram ml-1 (0.165 microgram ml-1 by direct atomic absorption spectrometry of aqueous solution). The proposed method was applied to the determination of iron in standard alloys and biological samples.     

Determination of thyreostatics in animal feed by micellar electrokinetic chromatography

The determination of the thyreostatics 2-thiouracil, its derivatives (4-methyl-2-thiouracil, 4-propyl-2-thiouracil and 4-phenyl-2-thiouracil) and methimazole in manufactured dried animal feed by micellar electrokinetic chromatography (MEKC) is described. A 99 +/- 5% extraction yield at the 20 micrograms g-1 level (n = 8) was achieved by shaking the milled fodder with methanol-1 M NaOH (80 + 20). Aliquots of the supernatant were injected in a 75 microns x 33.5 cm uncoated silica capillary using pressure; separation was performed at 23 degrees C with 15 kV (positive polarity) in a background electrolyte (BGE) containing 40 mM sodium dihydrogenphosphate, 50 mM sodium dodecyl sulfate and 15 mM Tween 20 at pH 9. When the surfactants were added to the BGE, all the thyreostatics were well resolved and the fodder extracts showed lower backgrounds. The peaks appeared within the 2.25-5.2 min range with efficiencies in the 2.5 x 10(4)-8 x 10(4) range; methimazole appeared in the vicinity of the electroosmotic migration time. Calibration curves were linear within the studied range (20-200 micrograms ml-1, r2 > 0.998). Limits of detection in the extracts of spiked fodder samples ranged from 0.25 to 0.4 microgram ml-1, which corresponded to 0.6-1.0 microgram of drug per gram of fodder. Peak area repeatabilities were about 4% at the 20 micrograms ml-1 level.     

Combined thin-layer chromatography-photography-densitometry for the quantitation of cyclophosphamide and its four principal urinary metabolites

A novel method for the quantitative determination of the anti-cancer drug cyclophosphamide and its principal urinary metabolites 4-oxocyclophosphamide, carboxyphosphamide, phosphoramide mustard and bis(2-chloroethyl)amine has been devised. The assay combines adsorption of drug-related material onto Amberlite XAD-2 and thin-layer chromatography with spot visualization using 4-(4-nitrobenzyl)pyridine, rapid photography and densitometry. The intra-assay coefficient of variation for each compound was less than 6%. The limit of detection of the assay was 1 microgram ml-1 for cyclophosphamide, phosphoramide mustard and bis(2-chloroethyl)amine and 0.5 microgram ml-1 for 4-oxocyclophosphamide and carboxyphosphamide. The method was validated for cyclophosphamide and 4-oxocyclophosphamide using gas chromatography. It is concluded that the method provides the first means of determining the full metabolic spectrum for cyclophosphamide in patients without recourse to the administration of radioisotopically labelled drug.     

Effect of phosphate buffer on photodegradation reactions of riboflavin in aqueous solution

The effect of phosphate buffer on aerobic photodegradation reactions of riboflavin (RF) at pH 7.0 has been studied. The photoproducts of the two major reactions, viz., intramolecular photoreduction and intramolecular photoaddition, have been determined by a specific multicomponent spectrophotometric method. The overall photodegradation of riboflavin in the presence of phosphate buffer involves the participation of both H2PO4-and HPO4(2-) species. The second-order rate constants for the H2PO4(-)-catalysed photodegradation of riboflavin (normal photolysis) to lumichrome (LC) and HPO4(2-)-catalysed photodegradation of riboflavin (photoaddition) to cyclodehydroriboflavin (CDRF) are 0.93 x 10(-4) and 4.0 x 10(-4) M(-1) s(-1), respectively. The addition of 0.25-2.00 M phosphate to RF solutions at pH 7.0 gives rise to RF-HPO4(2-) complex and hence the quenching of 4-36% fluorescence, respectively. This results in the suppression of normal photolysis leading to the formation of LC in favour of photoaddition to yield CDRF. The present study shows the involvement of H2PO4- anions in the base-catalysed degradation of riboflavin by normal photolysis vis-a-vis the involvement of HPO42- anions in photoaddition reactions of riboflavin suggested earlier [M. Schuman Jorns, G. Schollnhammer, P. Hemmerich, Intramolecular addition of the riboflavin side chain. Anion-catalysed neutral photochemistry, Eur. J. Biochem. 57 (1975) 35-48].     

A highly sensitive spectrophotometric method for the determination of some phenothiazine antipsychotics using chloramine-T and indigocarmine.

A new simple, accurate and precise spectrophotometric method for the determination of six phenothiazine drugs in pure form and in dosage forms is described. The method is based on the oxidation of the studied drugs by a known excess of Chloramine-T in hydrochloric acid medium and subsequent determination of the unreacted oxidant by reacting it with indigocarmine in the same acid medium. The reacted oxidant corresponds to the drug content. The colored species exhibits maximum absorption at 610 nm. The apparent molar absorptivity values and Sandell sensitivity values are in the range 1.53 x 10(4)-2.96 x 10(4) l mol-1 cm-1 and 13.75-37.15 ng cm-2, respectively. The method is highly sensitive and suitable for 1-15 micrograms ml-1 concentrations with the detection limits being in the range, 0.0651-0.1724 microgram ml-1. The method was successfully applied to the studied drugs in their dosage forms. The results are reproducible within +/- 1% and compare favorably with those obtained by the procedures of the British Pharmacopeia.     

High-performance liquid chromatographic method for the comparison of the photostability of five sunscreen agents

Sunscreen agents are commonly used in cosmetic products to filter out noxious radiation in sunlight. A convenient high-performance liquid chromatographic (HPLC) method for the quantification of five sunscreens after irradiation has been selected. We used this analytical method to compare the photostability of benzophenone-3, PEG-25 PABA, octyl dimethyl PABA, 4-methylbenzylidene camphor and butyl methoxydibenzoylmethane, at levels in the range of 25-60 microM. The assay was carried out, using a C8 column with a methanol--water mobile phase. The detector was set at a wavelength of 300 nm. The assay was linear with the following limits: 0.2 microgram ml-1 for benzophenone-3, 1 microgram ml-1 for PEG-25 PABA, 0.15 microgram ml-1 for octyl dimethyl PABA, 0.1 microgram ml-1 for methylbenzylidene camphor and 0.05 microgram ml-1 for butyl methoxydibenzoylmethane. The half-lives calculated indicate a very good photostability of the sunscreens studied and permit to classify amongst themselves.     

Simultaneous determination of twelve tea catechins by high-performance liquid chromatography with electrochemical detection.

A high-performance liquid chromatographic method with electrochemical detection was developed for the determination of twelve tea catechins including four major catechins: epicatechin (EC), epigallocatechin (EGC), epicatechin gallate (ECG) and epigallocatechin gallate (EGCG); four of their epimers at the C-2 position, C, GC, CG and GCG; and four methylated catechin derivatives, epigallocatechin-3-O-(3-O-methyl)gallate, gallocatechin-3-O-(3-O-methyl)gallate, epigallocatechin-3-O-(4-O-methyl)gallate and epicatechin-3-O-(3-O-methyl)gallate. These catechins were separated on an ODS C18 reversed-phase column by isocratic elution with 0.1 M NaH2PO4 buffer (pH 2.5)-acetonitrile (87:13) containing 0.1 mM EDTA.2Na. The detection limits (S/N = 3) of these catechins were approximately 10-40 pmol ml-1 at an applied voltage of 600 mV. Extracting these catechins from tea leaf powder with H2O-acetonitrile (1:1) at 30 degrees C for 40 min inhibited the epimerization at C-2 significantly from these epicatechins compared to extraction with hot water at 90 degrees C. This analytical method is sensitive to and appropriate for the simultaneous determination of various biologically active catechins in green tea.     

Complexation study of diclofenac with beta-cyclodextrin and spectrofluorimetric determination

The inclusional complexation between the anti-inflammatory pharmaceutical diclofenac and beta-cyclodextrin (beta-CD) was studied by potentiometry, spectrophotometry and spectrofluorimetry, in both acid and neutral pH. Guest-host 1:1 stoichiometries for the complexes in both media were determined, and their equilibrium constants were calculated. The values obtained from the different methods used are in very good agreement and are in the order of 10(3). From the analysis of the pKa value for diclofenac in both the absence and presence of beta-CD (4.84 and 4.90 respectively), it was inferred that in the inclusion complex the carboxylic group is located outside the cavity. Further structural characterization of the inclusate was carried out by means of 1H NMR spectra and AM1 semiempirical calculations. Based on the obtained results, a spectrofluorimetric method for the determination of diclofenac in the presence of beta-CD was developed in the range of 0-5 micrograms ml-1. Better limits of detection (0.03 microgram ml-1) and quantification (0.1 microgram ml-1) were obtained in this latter case with respect to those obtained in the absence of beta-CD. The method was satisfactorily applied to the quantification of diclofenac in pharmaceutical preparations.     

Kinetic determination of iodide in pharmaceutical and food samples

A kinetic method for the determination of iodide based on its inhibitory effect on the Pd(III) catalysed reaction between ethylenediaminetetraacetic acid (EDTA)-Co(III) and the hypophosphite ion is described. The reaction was followed spectrophotometrically by measuring the decrease in the absorbance at 540 nm. Under the optimum experimental conditions of 2.6 x 10(-3) mol dm(-3)Co(III)-EDTA, 0.4 mol dm(-3)H2PO2-, pH 3.2 (adjusted with Britton-Robinson buffer), 0.57 micrograms ml(-1) Pd(III) and 20 +/- 0.2 degrees C, iodide was determined in the range 2-28 ng ml(-1). The method was applied to the determination of iodide in pharmaceutical products, iodinated salts, cow's milk and infants' powdered milk.     

溴酸钾氧化吡口罗红G催化动力学光度法测定痕量NO-2

研究了在磷酸介质中亚硝酸根催化溴酸钾氧化吡口罗红Ｇ而使其褪色，建立了催化动力学光度法测定痕量亚硝酸根的新方法，测定范围为０．２～２０μｇ／ｍＬ，检出限为０．２ｎｇ／ｍＬ，用于食品和水样中的亚硝酸根测定获得满意结果     

Determination of proteins in serum by fluorescence quenching of rose bengal using the stopped-flow mixing technique

The stopped-flow mixing technique was used to develop a very fast, sensitive and accurate method for determining total proteins. The method is based on the lower fluorescence of Rose Bengal caused by binding of the dye to the proteins. The decrease in the fluorescence intensity, measured at 572 nm with excitation 555 nm, was linearly related to protein concentration from 1.3 to 24.5 micrograms ml-1. The detection limit was 0.3 microgram ml-1. The method was satisfactorily applied to the determination of total proteins in different serum samples.     

Rapid separation of DNA constituents, bases, nucleosides and nucleotides, under the same chromatographic conditions using high-performance liquid chromatography with a reversed-phase column

Four components of three sets of DNA constituents, bases, deoxyribonucleosides and deoxyribonucleoside 5'-monophosphate, were sufficiently resolved under one set of chromatographic conditions using high-performance liquid chromatography with a reversed-phase column (Zorbax ODS) and the solvent 0.4 M NH4H2PO4 (pH 3.5). The effect of pH and salt concentration in the solvent on the retention of these compounds in the column was thoroughly investigated. Proportionality of peak height to the content, and reproducibility and recovery of the four bases were satisfactory under appropriate conditions and as little as 1 microgram of DNA could be analysed for its base composition by this method.     

Dapsone a new diazotizing reagent for the spectrophotometric determination of nitrite in waste and natural water samples

A new diazotizing reagent for the spectrophotometric determination of nitrite is described. The method is based on diazotization-coupling reaction between dapsone and phloroglucinol in hydrochloric acid medium. The reactions were conducted at room temperature, the molor absorptivity at 425 nm is 4.28 x 10(4) l mol-1cm-1 and was stable for 50 h. Beer's law was obeyed in the nitrite range of 0.008-1.0 microgram ml-1. Tolerance limits were tested for 33 species. The method has been found to be applicable for the determination of nitrite in natural and wastewater.     

Sensitive detection of tetracyclines using europium-sensitized fluorescence with EDTA as co-ligand and cetyltrimethylammonium chloride as surfactant

The determination of tetracyclines (TC) in aqueous solutions, based on europium-sensitized fluorescence, has been improved using EDTA as co-ligand and cetyltrimethylammonium chloride as surfactant. The method involves working in slightly alkaline solutions with the formation of a new chelate where the lanthanide ion is bound to the beta-diketone group. The method is about 6 times more sensitive than that with the Eu-TC-Triton system and LODs are 2.5 x 10(-10), 5 x 10(-10), 1.5 x 10(-9) and 2 x 10(-9) mol l-1 for TC, oxytetracycline, chlortetracycline and doxycycline, respectively. The method has been applied to the determination of TC in calf serum without sample pretreatment. The mean recovery was close to 102% and the lowest concentration attainable in serum samples was better than 0.1 microgram ml-1.     

Atomic absorption spectrometric determination of trace zinc in alloys and biological samples after preconcentration with [1-(2-pyridylazo)-2-naphthol] on microcrystalline naphthalene

An atomic absorption spectrometric method for the determination of trace amounts of zinc after adsorption of its [1-(2-pyridylazo)-2-naphthol] complex on microcrystalline naphthalene has been developed. This complex is adsorbed on microcrystalline naphthalene in the pH range 3.5-7.5 from large volumes of aqueous solutions of various alloys and biological samples with a preconcentration factor of 40. After filtration, the solid mass consisting of the zinc complex and naphthalene was dissolved with 5 ml of dimethylformamide and the metal was determined by flame atomic absorption spectrometry. Zinc can alternatively be quantitatively adsorbed on [1-(2-pyridylazo)-2-naphthol]-naphthalene adsorbent packed in a column and determined similarly. About 0.5 ng of zinc can be concentrated in a column from 200 ml of aqueous sample, where its concentration is as low as 2.5 pg ml-1. The calibration curve is linear in the range 0.1-6.5 ng ml-1 in dimethylformamide solution. Eight replicate determinations of 2 ng ml-1 of zinc gave a mean absorbance of 0.145 with a relative standard deviation of 1.5%. The sensitivity for 1% absorption was 0.061 ng ml-1. Various parameters, such as the effect of pH and the interference of a number of metal ions on the determination of zinc, have been studied in detail to optimize the conditions for the determination of zinc in various standard complex materials.