毛细管电泳安培检测扑热息痛及其水解物

研究了各种电化学预处理条件下碳纤维电极对扑热息痛及水解物的电化学行为。确定该体系最佳预处理条件为０．２Ｖ电位下阳极化１ｍｉｎ，再于－２．０Ｖ下阴极化１０ｓ。预处理后的碳纤维伏安响应得到明显提高。运用最佳条件并在支持电解中加入添加剂后，扑热息痛及其水解物在毛细管电泳上获得很好的分离和检测。其中扑热息痛的检测下限为２．７８ｐｇ；对氨基酚为１．８４ｐｇ。     

A new cloud-point preconcentration approach for the spectrophotometric determination of p-aminophenol in the presence of paracetamol with 2-(2-Hydroxyphenyl)-1H-benzimidazole as a coupling reagent

A preconcentration and determination method for trace p-aminophenol (PAP) in paracetamol was developed. Cloud-point extraction (CPE) was employed for the preconcentration of p-aminophenol prior to spectrophotometric determination using Triton X-100 (TX-100) as an extractant. The determination is based on the reaction of p-aminophenol with 2-(2-hydroxyphenyl)-1H-benzimidazole (HPBI) at room temperature in the presence of an oxidant to produce indophenol blue dye. The dye formed is subsequently entrapped in micelles of the surfactant TX-100. The surfactant-rich phase shows maximum absorbance at 650 nm and the proposed method is linear in the 0.1 to 5.0 mg mL⁻¹ concentration range. By preconcentrating 10 mL of the sample solution, a detection limit as low as 55 ng/mL was obtained after a single-step extraction and the experimental concentration factor achieved for this method was found to be 10. The stoichiometric composition of the dye is 1: 1 (PAP: HPBI). Some parameters such as HPBI, KIO₄, Na₂CO₃, and TX-100 concentration, extraction temperature, incubation, and centrifugation time, and the sample volume were investigated in detail. The established procedure was successfully adopted for the determination of p-aminophenol in the presence of paracetamol in various pharmaceutical preparations. The text was submitted by the authors in English.     

Colorimetric determination of p-aminophenol in the presence of paracetamol with 3-cyano-N-methoxypyridinium perchlorate

Two simple and sensitive calorimetric procedures for the determination of p-aminophenol with 3-cyano-N-methoxypyridinium perchlorate are presented. One is based on reaction in methoxyethanol in presence of sodium acetate, with direct measurement at 410 nm. The reaction product obtained by this procedure has been separated and identified. The other is based on reaction in methoxyethanol in presence of chloramine-T and direct measurement at 448 nm. The method has been applied to the determination of p-aminophenol in pure form and as an impurity in paracetamol and paracetamol- containing tablets, with a coefficient of variation less than 2%.     

Flow analysis-spectrophotometric determination of L-Dopa in pharmaceutical formulations by reaction with p-aminophenol

A new method has been developed for the spectrophotometric determination of L-Dopa in pharmaceutical formulations. The method is based on the reaction between the open-chain quinone of L-Dopa, obtained in NaOH, and the benzoquinoneimine form of p-aminophenol, in the presence of KIO(4). The reaction product is determined at 574 nm by using both alternately procedures, one based on the stopped-flow and another on a flow injection approach. Under the best experimental conditions L-Dopa can be determined with a limit of detection of 52 ng/ml and a relative standard deviation of 0.2% for three replicate measurements of a solution containing 4 microg/ml.     

Simultaneous high-performance liquid chromatographic stability-indicating analysis of acetaminophen and codeine phosphate in tablets and capsules

A high-performance liquid chromatographic method has been developed for the simultaneous determination of acetaminophen and codeine phosphate for product stability studies, and release and dissolution testing of tablets and capsules. The reversed-phase method utilizes UV detection at 214 nm, a C18 column and requires a maximum of 10 min per analysis. The method has been validated for use with products containing as much as 500 mg of acetaminophen and as little as 7.5 mg of codeine phosphate. The known potential degradation products, p-aminophenol, codeine N-oxide, and codeinone are separated for quantitation simultaneous with the parent compounds. The method has been shown to be linear, reproducible, specific, sensitive and rugged.     

KMnO4-甲醛化学发光体系测定对乙酰氨基酚

基于对乙酰氨基酚在酸性介质下对KMnO4-甲醛化学发光体系强烈的增敏作用,建立了对乙酰氨基酚的流动注射化学发光测定方法。在最佳测试条件下,方法对对乙酰氨基酚的检出限(S/N=3)为1.0×10-10mol/L,线性范围为1.0×10-9～1.0×10-5mol/L对乙酰氨基酚,相关系数R为0.9993;对1.0×10-6mol/L的对乙酰氨基酚溶液平行测定11次,其RSD为1.1%。该方法可应用于药物中对乙酰氨基酚含量的测定。     

偏最小二乘-速差动力学分光光度法同时测定杀虫剂残杀威和异丙威两组分

采用速差动力学分光光度法对氨基甲酸脂类杀虫剂残杀威和异丙威进行同时测定，这两种化 的能在碱性条件下水解生成酚盐，进而与对氨基苯酚及高碘酸钾的反应产物醌亚胺发生偶联反应，生成蓝色化合物。反应的速率适中，可用于动力学分析。实验采集了多个时间点下538－700nm间的动力学－吸光度数据，构成量测矩阵，并采用偏最小二乘（PLS）法对量测数据进行解析。本文还对合成样品和环境水样中的残杀威和异丙威含量进行测定，获较好的结果。     

Spectrofluorimetric determination of acetaminophen with N-bromosuccinimide

A simple, sensitive, and selective method for determination of acetaminophen based on its oxidation using N-bromosuccinimide (NBS) to produce a highly fluorescent product. Optimization of reaction variables was carried out concerning NBS concentration, pH, temperature, reaction time, and stability time. Under optimal analytical conditions, the fluorescent intensity was measured at lambda emission. 442 nm (excitation at lambda 330 nm). The linearity range is 120-800 ng/mL with lower detection limit of 33.6 ng/mL acetaminophen. The method was applied successfully to the determination of the compound in pharmaceutical preparations, with average recovery of 100.3 +/- 2%. The method was also applied successfully to the determination of the drug in spiked plasma samples, with an average recovery of 101.2 +/- 1%. Interference effects of some compounds, present in combination with acetaminophen, were studied and the tolerance limits of these compounds were determined.     

Spectrophotometric flow injection determination of formetanate and m-aminophenol in water after reaction with p-aminophenol

An automated procedure has been developed for the determination of formetanate and its metabolite m-aminophenol (MAP) in water samples. MAP can be selectively determined in the presence of formetanate by direct on-line reaction with p-aminophenol and spectrophotometric measurement of the absorbance at 576 nm in the presence of KIO(4), as oxidizing agent. The method has a limit of detection of 5 x 10(-7)M, it provides a recovery percentage from 95 to 104% and permits one to carry out 120 measurements/hr. The spectrophotometric determination of formetanate must be carried out after a previous hydrolysis to MAP. To determine formetanate in the presence of MAP, two steps are necessary. Firstly, the MAP content is selectively determined as has been mentioned above. After that, the sample is treated with 0.05M NaOH at 90' degrees C, to hydrolyze the formetanate to MAP, and then the sum of both is determined spectrophotometrically. The difference between the results obtained in each step gives the formetanate concentration. The developed procedure for the determination of formetanate provides a sensitivity of 1070 absorbance units mol(-1) l and a limit of detection of 1.9 x 10(-7)M, which corresponds to 50 mug/l of formetanate hydrochloride. The method has been applied to the analysis of natural water samples fortified with formetanate and MAP, and formetanate has also been quantitatively recovered in irrigation waters at a concentration level of 1.9 x 10(-6)M which corresponds to 500 mug/l. On the other hand, working in the stopped-flow mode, for a reaction time of 100 sec, the sensitivity of the formetanate determination can be increased to 4642 absorbance units mol(-1) l but the limit of detection remains of the order of 44 mug/l.     

Spectrophotometric determination of ethiofencarb in waters by reaction with p-aminophenol

Summary An automatized procedure has been developed for the spectrophotometric determination of ethiofencarb in water by reaction with p-aminophenol after alkaline hydrolysis to obtain the corresponding phenol sulphone. The hydrolyzed samples are continuously introduced into different manifolds at the same time as 300 mg/l p-aminophenol, 0.004 mol/l KIO₄ and 0.04 mol/l NaOH solutions. The absorbance is measured at 638 nm after a reaction time of 6 min in stop flow. This absorbance band corresponds to the indo dye obtained from the reaction between the phenol sulphone of ethiofencarb and the quinoneimine form of the p-aminophenol and it permits a matrix-free spectrophotometric determination of ethiofencarb with a limit of detection of 33 g/l. The recovery of ethiofencarb in different water matrices varies from 71 to 126%.     

The use of thermal lensing for the determination of pyrogens

Based on the optimized spectrophotometric determination of pyrogens (of various classes ( p-aminophenol and endotoxins), thermal lensing was applied to the determination of these substances at the submicrogram level. The limit of detection of p-aminophenol, a pyrogenic impurity in pharmaceutical formulations of paracetamol, by reaction with resorcinol in alkaline solutions is 100 ng mL(-1). Phloroglucinol was considered as an analog of resorcinol as a reagent in this reaction. The conditions of spectrophotometric determination of pyrogenic lipopolysaccharides (endotoxins) by ion-pair formation with methylene blue (the limit of detection is 100 ng mL(-1)), by ion-pair formation with Stains-All (1-ethyl-2-[3-(1-ethylnaphtho[1,2-d]thiazolin-2-ylidene)-2-methylpropenyl]naphtho[1,2-d]thiazolium bromide) (the limit of detection is 500 ng mL(-1)), and by reaction of 2-keto-3-deoxyoctonic acid with thiobarbituric acid (the limit of detection is 800 ng mL(-1)) were proposed. The optimized procedure for 2-keto-3-deoxyoctonic acid was applied for thermal lensing that provided a decrease in the limit of detection to 70 ng mL(-1) and was also used for lipopolysaccharide determination in the endotoxin standard from E. coli.     

鲁米诺-过氧化氢-纳米银化学发光体系测定药物中的对乙酰氨基酚

碱性条件下,对乙酰氨基酚对鲁米诺-过氧化氢-纳米银化学发光体系有较强的抑制作用,基于此,结合流动注射技术,建立了测定对乙酰氨基酚的新方法。 研究了影响化学发光强度的各种因素,并初步探讨了可能的发光机理。 在最佳实验条件下,对乙酰氨基酚浓度在2.0×10-8～1.0×10-4 mol/L范围内与相对发光强度呈线性关系,检出限(3σ)为4.0×10-9 mol/L。 对1.0×10-7 mol/L的对乙酰氨基酚平行测定9次,相对标准偏差为2.6%。 该法用于片剂中扑热息痛含量的测定,结果令人满意。     

Spectrophotometric determination of paracetamol with microwave assisted alkaline hydrolysis

A novel and rapid spectrophotometric method for the determination of paracetamol is proposed in this paper. The proposed method is based on the microwave assisted alkaline hydrolysis of paracetamol to p-aminophenol that reacts with S2- in the presence of Fe3+ as oxidant to produce a methylene blue-like dye having an absorptivity maximum at 540 nm. The experiment showed that paracetamol could be hydrolysed quantitatively to p-aminophenol in only 1.5 min under radiation power 640 W using a microwave in NaOH medium. The system obeys Beer's law in the range of 0-3.0 x 10(-4) mol l(-1) paracetamol. The molar absorptivity and Sandell's sensitivity were found to be 3.2 x 10(-3) l mol(-1) cm(-1) and 0.047 microg cm(-2), respectively. The relative standard deviation (n=11) was 1.7% for 8.0 x 10(-5) mol l(-1) paracetamol. The method has been applied successfully to analysis of paracetamol in pharmaceutical preparation.     

Simultaneous determination of acetaminophen and dextropropoxyphene napsylate in pharmaceutical preparations by reverse phase HPLC

The method reported provides a fast, sensitive, accurate and reproducible reverse-phase HPLC assay for acetaminophen and dextropropoxyphene simultaneously. The total elution time is < 5 min. The method is stability-indicating since it can also determine p-aminophenol, a degradation product of acetaminophen, in a concentration as low as 0.005% of the acetaminophen concentration.     

Simultaneous spectrophotometric determination of paracetamol and salicylamide in human serum and pharmaceutical formulations by a differential kinetic method

A rapid, simple, and sensitive differential kinetic method is presented for the determinations of acetaminophen (also known as paracetamol) and salicylamide. The method is based on their oxidation reaction by Fe3+ ion in the presence of 1, 10-phenanthroline as indicator. The reactions can be monitored spectrophotometrically by measuring the increase in the absorbance of the solution at 510 nm. Two times were selected one in which only paracetamol is oxidized by Fe3+ ion and the other in which both drugs are oxidized by Fe3+ ion. The data were evaluated by the proportional equations method. The method allowed the simultaneous determination of paracetamol and salicylamide at concentrations between 0.5-20 and 1-40 microg/mL with relative standard deviations of 3.47 and 2.58%, respectively. The method was applied to the simultaneous determination of paracetamol and salicylamide in human serum and pharmaceutical formulations.     

Spectrofluorimetric Determination of Fenoterol in Pharmaceuticals

A highly sensitive spectrofluorimetric method was developed for the determination of fenoterol HBr in pharmaceutical preparations. The method is based on the nitrosation of fenoterol followed by reaction with 2‐cyanoacetamide in the presence of ammonia and measuring the produced fluorescence at 380 nm after excitation at 338 nm. All the variables affecting the reaction conditions were carefully studied and optimized. Linear calibration graph was obtained in the range of 0.064–0.64 μg.mL^?1 with a correlation coefficient of 0.9999 and a relative standard deviation of 0.83%. The method was applied to dosage forms and the results obtained agreed well with those obtained by the official method. A proposal of the reaction pathway was suggested.     

Unbiased spectrophotometric method for estimating phenol or o-cresol in unknown water samples

The generalised H-point standard addition method (GHPSAM) was applied to quantify phenol and o-cresol in waters and compared with other analytical approaches. The method is based on spectroscopic and kinetic measurement of the formation of derivatives with p-aminophenol and KIO(4) in presence of NaOH. First, pseudo-first order kinetic behaviour of the reaction products was demonstrated. The unbiased formation rate constants of phenol and o-cresol derivatives were calculated. The analytical figures of merit were determined using the GHPSAM as calibration method. Detection limits achieved were 0.2 microg L(-1) of phenol and 0.2 microg L(-1) of o-cresol using a preconcentration factor of 10. Styrene-divinyl benzene cartridges were used in the preconcentration step. Repeatability values were 3.7% for phenol and 2.0% for o-cresol; reproducibility values were 6.9% and 3.5%, respectively. Accurate and precise results were obtained when the method was applied to real samples of natural water.     

Chemiluminescence Behavior and Application of Ce (IV)-Tween20-Tryptophan System

It was observed that the chemiluminescence intensity from the reaction of Ce (IV) with Tween20 was greatly enhanced in the presence of tryptophan, and the possible reaction mechanism was explored. Based on the reaction, a sequential injection procedure with chemiluminescence detection was developed for the determination of tryptophan. Under the optimum conditions, a linear dynamic range of 0.2–8.0 μM, a 3σ detection limit of 0.15 μM and a coefficient of variation of 0.7% at 3.0 μM level were obtained. The method was applied to the determination of tryptophan in beer and amino acid injections.     

Kinetic spectrophotometric determination of ethamsylate in dosage forms

A simple and sensitive kinetic method has been developed for the determination of ethamsylate (ESL) in its pharmaceutical preparations. The method is based upon oxidation of ESL with 3-methyl-2-benzothiazolinone hydrazone hydrochloride in presence of cerium (IV) ammonium sulfate at room temperature for 20 min. The absorbance of the reaction product is measured at 514 nm. The absorbance-concentration plot was rectilinear over the range of 4-30 microg/mL (r = 0.9999). The lower detection limit was 0.267 microl/mL (9.110 x 10(-6) M) and the lower quantitation limit was 0.808 microg/mL. The different experimental parameters affecting the development and stability of the reaction product were studied and optimized. The proposed method was applied to the determination of ESL in formulations, and the results obtained were in good agreement with those obtained using a reference method. The proposed method was also used for the in vitro detection of ESL in spiked human plasma at its therapeutic concentration level.     

Spectrofluorometric determination of fluvoxamine in dosage forms, spiked plasma, and real human plasma by derivatization with fluorescamine

A sensitive, simple, and selective spectrofluorometric method was developed for the determination of fluvoxamine (FXM) in pharmaceutical formulations and biological fluids. The method is based upon the reaction between the drug and fluorescamine in borate buffer of pH 8.0 to yield a highly fluorescent derivative that is measured at 481 nm after excitation at 383 nm. The different experimental parameters affecting the development and stability of the reaction product were carefully studied and optimized. The method was applied for the determination of the drug over the concentration range of 0.1-1.1 microg/mL with a detection limit of 0.01 microg/mL (2 x 10(-8) M). The proposed method was successfully applied to the analysis of commercial tablets. The results obtained were in good agreement with those obtained using a reported spectrophotometric method. The method was applied for the determination of FXM in spiked human plasma with recovery (n=4) of 97.32 +/- 1.23%, while that in real human plasma (n=3) was 90.79 +/- 2.73%. A proposal for the reaction pathway is presented.