Colorimetric Estimation of Melatonin in Pharmaceutical Formulations

 Three simple and sensitive colorimetric methods (A–C) for the determination of melatonin in bulk samples and in pharmaceutical formulations are described. They are based on the formation of coloured species by reaction of ninhydrin with the drug (method A, λ_max 397 nm) by oxidation of the indol moiety in melatonin with potassium persulphate (method B, λ_max 450 nm) or by reduction of osmium (VIII) (method C, λ_max 516 nm). Regression analysis of Beer-Lambert plots showed good correlations in concentration ranges between 0.8–14.2, 70.0–140.0 and 2.0–40.0 μg/mL for methods A, B and C, respectively. The molar absorptivity, Sandell sensitivity and detection limit were calculated. For more accurate analysis, Ringbom optimum concentration ranges were calculated. The validity of the proposed methods was tested by analysing pharmaceutical formulations containing melatonin. The relative standard deviations were ≤ 0.95% with recoveries 99.0–101.33%. Received October 20, 1999. Revision February 10, 1999.     

Colorimetric Procedure for the Microdetermination of the Antibilharzial Drug Praziquantel and its Applications to Pharmaceutical Formulations

 A procedure for the colorimetric assay of praziquantel has been developed. The method is based on the formation of charge-transfer complexes with p-chloranil (I), dichloronitrophenol (II), 2,3-dichloro-5,6 dicyano-p-benzoquinone (III), 7,7,8,8-tetracyanoquinodimethane (IV) and tetracyanoethylene (V) as π-acceptors to give highly coloured species. The coloured products are measured spectrophotometrically at 550, 425, 460, 844 and 393 nm for I, II, III, IV and V, respectively. Optimization of the different reaction conditions is described. The colour system obeyed Beer’s law in non-aqueous media in the concentration range 2.0–48 μg ml⁻¹. It was stable for at least 4.0 h. The detection limit was found to be 0.6 μg ml⁻¹. Applications of the procedure to the analysis of various pharmaceutical samples gave reproducible and accurate results. Further, the validity of the procedure was confirmed by applying the standard addition technique. The total average recovery was 100.2%. Received June 10, 2000. Revision December 23, 2000.     

Titrimetric and Spectrophotometric Determination of Some Phenothiazine Psychotropics in Pure Form and in Pharmaceutical Formulations with Metavanadate

 Two simple, fast, accurate and precise methods for the determination of six phenothiazines and a number of their pharmaceutical formulations are described. The titrimetric method involves the oxidation of the drugs by metavanadate in sulphuric acid medium and titration of vanadium(IV) formed, with cerium(IV) using ferroin indicator and acetone as catalyst. In spectrophotometry, vanadium(IV) formed was reacted with ferriin and the resulting ferroin measured at 510 nm. Phenothiazines in the ranges 5–100 mg and 2.5–25.0 μg mL⁻¹ can be determined by titrimetry and spectrophotometry, respectively, with detection limits of 0.96–2.05 mg and 0.0359–0.0565 μg mL⁻¹, respectively. Both methods were applied successfully to the determination of the studied drugs in pharmaceutical preparations. The reliability of the assays was established by parallel determination by the official methods of British Pharmacopoeia and the results being statistically evaluated. Received September 26, 2000. Revision March 25, 2001.     

Spectrophotometric Estimation of Nimesulide and its Formulations

 Four simple and sensitive visible spectrophotometric methods (A–D) have been described for the assay of nimesulide (NMD) either in pure form or in pharmaceutical formulations. Methods A and B are based on the oxidative coupling between the reduced product of NMD (RNMD) and p-N,N-dimethyl phenylenediamine dihydrochloride (DMPD) in presence of chloramine – T (CAT) or 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) in presence of ferric chloride (Fe III) to form coloured products with λ_max at 540 nm and 600 nm respectively. Method C is based on the diazotization of RNMD with excess nitrous acid (HNO₂) and estimating the consumed HNO₂ with cresyl fast violet acetate (CFVA). Method D is based on the formation of the coloured charge-transfer complex, when RNMD is treated with metol (p-methyl aminophenol sulphate, PMAP) in presence of potassium dichromate. All variables have been optimized and the reaction sequence is presented. The concentration measurements are reproducible within a relative standard deviation of 1.0%. Recoveries are 98.6–100.2%. Received February 5, 1998. Revision February 20, 1999.     

Electrochemical Behaviour of Loprazolam and its Determination in Pharmaceutical Formulations

Abstract

The electrochemical behaviour of Loprrzoiam has been determined in aqueous solution at 37 > Cusing DC polarography, differential pulse polarography and voltammetry and linear sweep cyclic voltammetry. Loprazolam can be quantitavely determined up to 3.9 10^?6 M at pH 6.5 using DP polarography, the detection limit being established at 1.6 10^?7 M. The method developed was applied to the determination of the compound in its formulations, Somnovit 1 mg, obtaining errors lower than 4%.     

Voltammetric and Spectrophotometric Determination of Nizatidi ne in Pharmaceutical Formulations

 Two methods are described for quantitative determination of nizatidine. The first is a cathodic stripping voltammetric method which is based on the accumulation of the compound at the hanging mercury drop electrode. The adsorptive stripping response was evaluated with respect of accumulation time, potential, concentration, pH and other variables. A linear calibration graph was obtained over the range 3.0×10⁻⁸–1.0×10⁻⁶ M with a detection limit 3.0×10⁻⁸ M after a 20s accumulation time at −0.2 V accumulation potential. On the other hand, it was found that the detection limit could be lowered to 1.0×10⁻⁸ M after 180s accumulation time at −0.2 V accumulation potential. The relative standard deviation was in the range 1.2−2.0% for six measurements. The tolerance amounts of the common excipients have also been reported. The second is a spectrophotometric method which is based on the formation and extraction of the ion-pair complex formed between nizatidine and either bromocresol green or bromothymol blue. The extracted colored ion-pair complexes absorb at 416 nm. The effect of different factors such as: type of organic solvent, pH, reagent concentration, number of extraction times, shaking time, temperature and the tolerance amount of the common excipients have been reported. The calibration graph was linear in the range 6.0×10⁻⁷–1.8×10⁻⁵ M with a detection limit of 6.0×10⁻⁷ M and molar absorptivity of 2.1×10⁴ lċmol⁻¹ċcm⁻¹ when using bromocresol green, while the calibration graph was linear in the range 3.0×10⁻⁷–1.1×10⁻⁵ M with a detection limit of 3.0×10⁻⁷ M and molar absorptivity of 3.2×10⁴ lċmol⁻¹ċcm⁻¹ when using bromothymol blue. The spectrophotometric methods offer alternative methods with reasonable sensitivity, selectivity and accuracy with relative standard deviation in the range 2.1−6.0% and 1.2−4.7% (for six measurements) when using bromothymol blue and bromocresol green, respectively. The proposed two methods were applied for the determination of nizatidine in commercially available dosage forms. A comparison between the voltammetric and the extraction-spectrophotometric methods was also reported. Received April 19, 1999. Revision August 30, 1999.     

Ion-Pair Formation in Pharmaceutical Analysis. Conductimetric Determination of Promazine, Chlorpromazine, Promethazine, Imipramine and Ciprofloxacin Hydrochlorides in Pure Form, Drug Formulations and Urine

 Potassium ferricyanide and sodium tetraphenylborate were used as titrants for the conductimetric determination of promazine HCl, chlorpromazine HCl, promethazine HCl, imipramine HCl and ciprofloxacin HCl through ion-associate complex formation. The molar combining ratio, effects of dilution of titrant, temperature and solvent were studied. The accuracy of the method is indicated by excellent recovery (99.50–99.96%). The sensitivity of the proposed method is discussed and the results are compared with the pharmacopoeial or the official methods. The suggested method has been applied for the analysis of the mentioned compounds in their pharmaceutical formulations and urine. Received March 1, 1998. Revision May 31, 1999.     

Spectrophotometric Determination of Prochlorperazine Maleate in Pure and Pharmaceutical Preparations

 Prochlorperazine maleate reacts with 1-naphthylamine and sodium nitrite, after heating for 110 s at 80 °C to give an orange red colour having maximum absorbance at 460 nm. The reaction is selective for prochlorperazine maleate with 0.01 mg/mL as visual limit of quantitation and provides a basis for a new spectrophotometric determination. The colour reaction obeys Beer’s law from 0.01 mg/10 mL to 0.33 mg/10 mL of prochlorperazine maleate and the relative standard deviation is 0.68%. The quantitative assessment of tolerable amounts of other drugs is also studied. Received September 22, 2000. Revision June 19, 2001     

Fluorimetric Determination of Gatifloxacin in Aqueous,Pure and Pharmaceutical Formulations

Abstract

A spectrofluorimetric method was developed for the determination of gatifloxacin. The emission peak for gatifloxacin was recorded at 495 nm upon excitation at 291 nm. The fluorescence process was pH dependent. The dynamic range for the method was 16–80 ng ml^?1with detection limit of 3.97 ng ml^?1. A linear relationship between the fluorescence intensity and the concentration of gatifloxacin solution was obtained with r ² of 0.9968. The method has successfully applied to the determination of gatifloxacin in pure, authentic and aqueous samples.     

Spectrofluorimetric Determination of Methyl Paraben in Pharmaceutical Preparations by Means of its Dansyl Chloride Derivative

 A spectrofluorimetric method for the determination of methyl paraben based on derivatization with the labelling reagent dansyl chloride (DNS-Cl), is presented. The effect of the reaction variables (pH, DNS-Cl concentration, temperature, reaction time) and instrumental parameters, has been examined. A linear calibration graph in the ng/ml range has been established. The limit of detection is 18 ng/ml with relative standard deviation less than 3%. The proposed method has been satisfactorily applied to determination of the paraben in two pharmaceutical preparations. Received May 25, 1999. Revision October 20, 1999.     

New and Sensitive Method for the Spectrophotometric Determination of Certain Tricyclic Antidepressants

 A new, simple, and sensitive spectrophotometric method for the determination of certain tricyclic antidepressants, belonging to the dibenzazepine class of drugs, has been developed. The proposed method is based on the reaction of imipramine hydrochloride (IPH), desipramine hydrochloride (DPH), clomipramine hydrochloride (CPH), trimipramine maleate (TPM) or opipramol (OPP) with iron(III), and subsequent reaction with ferricyanide in an acetic acid medium, to yield a blue product, with maximum absorption at 720–730 nm. Received January 24, 2000     

Electroreduction and Quantification of Furazolidone and Furaltadone in Different Media

 Adsorptive cathodic stripping voltammetry was used for the determination of furazolidone (FZ) and furaltadone (FD) in borax and phosphate buffers, respectively, using HMDE as working electrode. The influence of different factors upon the peak current response such as accumulation potential, scan rate, preconcentration time, pH and other variables was studied. Furazolidone and furaltadone showed an adsorption character on HMDE in presence of borax and phosphate buffers, respectively. A single cathodic peak at −0.36 V in borax (pH = 9.5) was observed for FZ, while FD gave a cathodic peak at −0.32 V in phosphate buffer (pH = 8.5). The calibration graph showed a linear behavior over the range 3×10⁻⁹–9×10⁻⁸ mol dm⁻³ for furazolidone. In the case of FD, concentrations from 3×10⁻⁹ to 2×10⁻⁷ mol dm⁻³ gave a linear relationship with the peak current. A detection limit of 2×10⁻⁹ mol dm⁻³ and 1×10⁻⁹ mol dm⁻³ was obtained for furazolidone and furaltadone, respectively. This method was applied to determine these drugs in pharmaceutical formulations, urine and serum samples. Received December 15, 1998. Revision February 4, 2000.     

Spectrophotometric Determination of Dithionite in Household Commercial Formulations Using Naphthol Yellow S

 A rapid and quantitative procedure for the determination of dithionite based on the reduction of naphthol yellow S in ammonia containing solution and measurement of the absorbance of the product formed at 502 nm is described. The mechanism of the reaction is discussed and its analytical application is shown to be possible in a concentration range of dithionite between 16.7 and 133.1 mg l⁻¹ (1.3 × 10⁻⁴ and 1.04 × 10⁻³ mol l⁻¹). The procedure was applied to the determination of dithionite in commercial formulations used in the household. In a 0.5 g sample of decolorant, dithionite was found to be present at concentrations between 25 and 35% (w/w), which can be determined without interference of its decomposition products. The results are shown to be in good agreement with those of polarographic determinations. Received April 26, 2001. Revision August 2, 2001.     

New Spectrophotometric Methods for Microdetermination of Fluoxacillin and Cloxacillin in Pure and Dosage Forms

 Two simple, rapid and sensitive methods for the microdetermination of penicillin derivatives are described. The studied compounds are fluoxacillin and cloxacillin. The methods are based on the reaction of these drugs as n-electron donors with either 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) or 7,7, 8,8-tetracyanoquinodimethane (TCNQ) as π-acceptors, to give a highly coloured radical anion. The coloured products were quantified spectrophotometrically at 460 and 840 nm for DDQ and TCNQ, respectively. The proposed methods were applied successfully to the determination of the two penicillins investigated, either in pure or dosage forms, with good accuracy and precision. The results were compared with those given by the official method. Received December 15, 2000. Revision July 10, 2001.     

Disposable Pencil Graphite Electrode for Ciprofloxacin Determination in Pharmaceutical Formulations by Square Wave Voltammetry

In this work, a new electrochemical sensor based on pencil graphite with interesting features, such as low cost (US$ 0.01 per electrode), ease manufacture, and portability was developed. The sensor showed an adequate manufacturing reproducibility with RSD <5.3 %. Under this electrochemical platform, ciprofloxacin underwent an irreversible oxidation process at 1.03 V, characterized by the diffusion of electroactive species. A simple method by square wave voltammetry (SWV) has been optimized for the determination of ciprofloxacin in pharmaceutical formulations using a pencil graphite electrode (PGE). The method showed satisfactory analytical performance, with a wide linear range (12 to 55 μmol L⁻¹), low detection limit (5.6 μmol L⁻¹), adequate precision (RSD <3.2 %), and accuracy with an average recovery of (102±15)%. Samples of pharmaceutical formulations were evaluated, obtaining levels of ciprofloxacin close to those established by the manufacturers. In addition, the samples were analyzed by liquid chromatography and there was no significant difference between the methods at the 95 % confidence level. In this sense, the method developed proved to be reliable and promising for the quality control of pharmaceutical formulations.     

Spectrophotometric Determination of Phenytoin Sodium in Pure and Pharmaceutical Preparations

 Phenytoin sodium reacts with o-nitrobenzoic acid in alkaline media after heating for 10 minutes at 70 °C, to give a red coloured complex having maximum absorbance at 510 nm. The reaction is selective for phenytoin sodium with 0.01 mg/10 mL as visual limit of quantitation and provides a basis for a new spectrophotometric determination. The colour reaction obeys Beer’s law from 0.01 mg to 3 mg/10 mL of phenytoin sodium and the relative standard deviation is 0.29%. The quantitative assessment of tolerable amounts of other drugs is also studied. Received May 2, 2000. Revision May 11, 2001.     

Vanadophosphoric Acid as a Modified Reagent for the Spectrophotometric Determination of Certain Cephalosporins and their Dosage Forms

Summary.  Vanadophosphoric acid in acidic medium is proposed as a modified reagent for the spectrophotometric determination of cephalexin, cephaprine sodium, cefazolin sodium, and cefotaxime in pure samples and in pharmaceutical preparations. The method is based on acid hydrolysis of cephalosporins and subsequent oxidation with vanadophosphoric acid. The resulting solution exhibits maximum absorption at about 516 nm. The effects of reaction conditions were investigated. Lambert-Beer’s law was obeyed over a concentration range of about 0.4–45 μg · cm⁻³. For more accurate results, Ringbom optimum concentration ranges were obtained, and the molar absorptivities and Sandell sensitivities were derived. The proposed method was applied to the determination of the drugs in pharmaceutical formulations; the results demonstrated that the proposed method is as accurate, pecise, and reproducible as the official methods. Received August 13, 1999. Accepted (revised) December 7, 1999     

A Novel Catalytic Procedure for the Determination of Ultratrace Zirconium

 A novel catalytic procedure for zirconium was proposed based on Zr(IV) catalyzed oxidation of gallocyanine by hydrogen peroxide in hexamethylene tetramine-hydrochloric acid buffer medium. The calibration graph is linear for 0–110 ngċml⁻¹, and the detection limit is 0.4 ngċml⁻¹ Zr(IV). Most foreign ions do not interfere with the determination, except for Cu²⁺, Fe³⁺ and Cr(VI). The interferences of Cu²⁺ and Fe³⁺ could be eliminated by masking with EDTA and mannitol, and that of Cr(VI) by reducing to Cr(III) with ascorbic acid. The typical features of this procedure are that it is sensitive for zirconium, and the determination could be carried out at room temperature. It had been used to the determination of zirconium in zirconium bronze, simulated samples and a certified reference material. The recoveries were 98.6 ∼ 102%, and relative standard deviations (R.S.D.) were 0.9 ∼ 1.5%, respectively. Received September 12, 1999. Revision April 10, 2000.     

Determination of Thiosemicarbazones by Means of the Induced Iodine-Azide Reaction

 The iodine-azide reaction induced by eight thiosemicarbazones was investigated. Inducing properties of thiosemicarbazones are different and depend on the parent carbonyl compound used for synthesis. The inductor coefficients of the examined thiosemicarbazones vary from 61 to 176. Optimum conditions for the determination of microamounts of thiosemicarbazones are given. The detection limit for the determination by the back-titration method depends on the inducing activity and is 0.9 μg for phenyl-thiosemicarbazones and 2 μg for diethyl-thiosemicarbazone in a 5-mL sample, and this corresponds to a concentration of 0.9 × 10⁻⁶ mol/L and , respectively. The automatic titration with the diluted iodine solution decreases the detection limit to about 50 ng in a 10-mL sample. Received October 28, 1998. Revision April 9, 1999.     

Spectrophotometric Determination of Some Phenolic Antibiotics in Dosage Forms

 A simple and sensitive spectrophotometric method is described for the determination of some phenolic antibiotics namely: cefadroxil, amoxicillin and vancomycin. The method is based on the measurement of the orange yellow species produced when the drugs are coupled with diazotized benzocaine in triethylamine medium. The method is applicable over the range of 0.8–12 μg/ml for cefadroxil, 2–16 μg/ml for amoxicillin and 2–18 μg/ml for vancomycin. The formed compounds absorb at 455 nm for both cefadroxil and amoxicillin and at 442 nm for vancomycin. The proposed method has detection limits of 0.018 μg for cefadroxil, 0.0034 μg for amoxicillin and 0.0156 μg for vancomycin. The stoichiometric ratio for the studied compounds was found to be 1:1 and a proposal of the reaction pathway was made. The proposed method was applied for the analysis of the cited drugs in their pharmaceutical preparations. The results are in good agreement with those obtained by the official methods. Received February 7, 2000. Revision June 14, 2000.