Simultaneous determination of calcium and magnesium by derivative spectrophotometry in pharmaceutical products

First- and second-derivative spectrophotometric methods for the simultaneous determination of calcium and magnesium in their mixtures are described. The methods are based on the colored complexes formed by calcium and magnesium with bromopyrogallol red in presence of Tween 80 as a surfactant. The zero-crossing method has been utilized to measure the first- and second-derivative value of the derivative spectrum. Calcium (0.8-4.8microgml(-1)) is determined in the presence of magnesium (0.5-3.5microgml(-1)) at the pH 10 and vice versa at zero-crossing wavelengths of 544.5 and 570nm in the first-derivative procedure and 574 and 531nm in the second-derivative procedure, respectively. The detection limits achieved were 0.0575microgml(-1) of calcium and 0.03microgml(-1) of magnesium. The relative standard deviations were in all instances less than 2%. The proposed method has been applied to the simultaneous determination of calcium and magnesium in different samples: commercial multivitamin, human serum and drinking water where excellent agreement between reported and obtained results was achieved.     

Artificial neural networks for simultaneous spectrophotometric differential kinetic determination of Co(II) and V(IV)

A method for simultaneous analysis of V(IV) and Co(II) has been developed by using artificial neural network (ANN). This method is based on the difference of the chemical reaction rate of V(IV) and Co(II) with Fe(III) in the presence of chromogenic reagent, 1,10-phenanthroline. The reduced product of the reaction, Fe(II), can form a colored complex with 1,10-phenanthroline and make a visible spectrophotometric signal for indirect monitoring of the V(IV) and Co(II) concentrations. Feed forward neural networks have been trained to quantify considered metal ions in mixtures under optimum conditions. The networks were shown to be capable of correlating reduced spectral kinetic data using principal component analysis (PCA) of mixtures with individual metal ion. In this way an ANN containing three layers of nodes was trained. Sigmoidal and linear transfer functions were used in the hidden and output layers, respectively, to facilitate nonlinear calibration. Both V(IV) and Co(II) were analyzed in the concentration range of 0.1-4.0 μg ml⁻¹. The proposed method was also applied satisfactorily to the determination of considered metal ions in several synthetic and water samples.     

Spectrophotometric determination of some drugs for osteoporosis

Three simple, accurate and sensitive spectrophotometric methods are developed for the determination of some new drugs for the treatment of osteoporosis: risedronate sodium (I), alendronate sodium (II) and etidronate disodium (III). The first method is based on the measurement of difference in absorbance (Delta A) of risedronate sodium in 0.01 mol l(-1) hydrochloric and 0.1 mol l(-1) sodium hydroxide at 262 nm. Beer's law is obeyed over a concentration range of 15-150 microg ml(-1) with mean recovery 99.75+/-1.22 and molar absorptivity (epsilon) 1.891 x 10(3). The second method is based on the reaction of the primary amino group of (II) with ninhydrin reagent in methanolic medium in the presence of 0.05 mol l(-1) sodium bicarbonate. The colored product is measured at 568 nm, and the linearity range is found to be 3.75-45 microg ml(-1) with mean recovery 99.77+/-0.73 and epsilon 9.425 x 10(3). The third method is based on oxidation of the three mentioned drugs with ceric (IV) sulphate in 0.5 mol l(-1) sulphuric acid at room temperature and subsequent measurement of the excess unreacted cerium (IV) sulphate at 320 nm. The method obeyed Beer's law over a concentration range of 2-24 microg ml(-1) for the three drugs with mean recovery 99.79+/-1.16, 99.73+/-1.38 and 99.86+/-1.13 and epsilon 14.427 x 10(3), 13.813 x 10(3) and 14.000 x 10(3) for drugs I, II, III respectively. The proposed methods were successfully applied for the determination of the studied drugs in bulk powder and in pharmaceutical formulations. The results were found to agree statistically with those obtained the reported methods. Furthermore, the methods were validated according to USP regulations and also assessed by applying the standard addition technique.     

Application of spectral beta-correction method and partial least squares for simultaneous determination of V(IV) and V(V) in surfactant media

Simultaneous determination of V(IV) and V(V) was performed by application of partial least squares when the calibration matrix was obtained using beta-correction spectra. Two reaction between V(IV) and V(V) and Pyrogallol Red as a ligand in presence of cethyltrimethylammoniumbromide (CTAB) media has been investigated and applied to the simultaneous spectrophotometric determination of these species. The parameters controlling behavior of the system were investigated and optimum conditions selected. Determinations were made over the concentration range 0.6-4.50 microg ml-1 of V(IV) and 0.3-5.50 microg ml-1 of V(V). Applying this method to simultaneous determination of these metal ions in several real samples with total relative standard error less than 5% validated the proposed method.     

Quantitative analysis of irbesartan in commercial dosage forms by kinetic spectrophotometry

The objective of this work is to develop a new kinetic spectrophotometric method for the determination of irbesartan in pharmaceutical formulations. The method is based on the reaction of carboxylic acid group of the oxidized irbesartan with a mixture of potassium iodate (KIO(3)) and iodide (KI) to form yellow colored triiodide ions in aqueous medium at 30+/-1 degrees C. The reaction is followed spectrophotometrically by measuring the rate of change of absorbance at 352 nm. The initial-rate and fixed-time (DeltaA) methods are adopted for constructing the calibration curves, which were found to be linear over the concentration ranges of 10.0-60.0 and 7.5-60.0 microg ml(-1) respectively. The regression analysis of calibration data yielded the linear equations: rate=-2.138 x 10(-6)+1.058 x 10(-4)C and DeltaA=-3.75 x 10(-3)+3.25 x 10(-3)C for initial rate and fixed time (DeltaA) methods, respectively. The limit of detection for initial rate and fixed time methods are 0.21 and 2.40 mug ml(-1), respectively. The various activation parameters such as E(a), DeltaH++, DeltaS++ and DeltaG++ are also calculated for the reaction and found to be 70.95+/-0.43 kJ mol(-1), 68.48+/-0.21 kJ mol(-1), 16.54+/-0.24 J K(-1) mol(-1) and -4.94+/-0.07 kJ mol(-1), respectively. The proposed methods are optimized and validated as per the guidelines of International Conference on Harmonisation (U.S.A.). The point and interval hypothesis tests have been performed which indicate that there is no significant difference between the proposed methods and the reference method. The methods have been successfully applied to the determination of irbesartan in commercial dosage forms.     

Spectrophotometric, spectrofluorometric and HPLC determination of desloratadine in dosage forms and human plasma

Four sensitive, simple and specific methods were developed for the determination of desloratadine (DSL), a new antihistaminic drug in pharmaceutical preparations and biological fluids. Methods I and II are based on coupling DSL with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) in borate buffer of pH 7.6 where a yellow colored reaction product was obtained and measured spectrophotometrically at 485 nm (Method I). The same product could be measured spectrofluorometrically at 538 nm after excitation at 480 nm (Method II). Methods III and IV, on the other hand, involved derivatization of DSL with 2,4-dinitrofluorobenzene (DNFB) in borate buffer of pH 9.0 producing a yellow colored product that absorbs maximally at 375 nm (Method III). The same derivative was determined after separation adopting HPLC (Method IV). The separation was performed on a column packed with cyanopropyl bonded stationary phase equilibrated with a mobile phase composed of acetonitrile-water (60 : 40, v/v) at a flow rate of 1.0 ml min(-1) with UV detection at 375 nm. The calibration curves were linear over the concentration ranges of 0.5-6, 0.02-0.4, 1-10 and 1-30 microg ml(-1) for Methods I, II, III and IV, respectively. The lower detection limits (LOD) were 0.112, 0.004, 0.172 and 0.290 microg ml(-1), respectively, for the four methods. The limits of quantification (LOQ) were 0.340, 0.012, 0.522 and 0.890 microg ml(-1) for Methods I, II, III and IV, respectively. The proposed methods were applied to the determination of desloratadine in its tablets and the results were in agreement with those obtained using a reference method. Furthermore, the spectrofluorometric method (Method II) was extended to the in-vitro determination of the drug in spiked human plasma, with a mean percentage recovery (n=4) of 99.7+/-3.54. Interference arising from endogenous amino acids has been overcome using solid phase extraction. The proposed methods are highly specific for determination of DSL in the presence of the parent drug loratadine. A proposal for the reaction pathways is postulated.     

可溶性锰(IV)化学发光反应的研究

发现了在甲醛存在的条件下, 可溶性锰(IV)与30余种有机物和无机物的化学发光反应. 以头孢菌素类药物(头孢曲松钠、头孢唑啉钠、头孢拉定和头孢哌酮钠)为分析对象优化了可溶性锰(IV)-甲醛-头孢菌素类药物化学发光反应的条件, 建立了测定四种头孢菌素类药物的流动注射化学发光新方法, 并将建立的方法用于药物制剂中头孢菌素类药物的含量测定．同时, 对化学发光反应的机理进行了初步探讨.     

The study and application of biomimic peroxidase ferric 2-hydroxy-1-naphthaldehyde thiosemicarbazone (Fe(III)-HNT)

Ferric 2-hydroxy-1-naphthaldehyde thiosemicarbazone (Fe(III)-HNT) has been synthesized and used to mimic the active group of horseradish peroxidase (HRP). The catalytic characteristics of this mimic-enzyme catalyst in the oxidation reaction of ascorbic acid with hydrogen peroxide has been studied. The experimental results showed that this peroxidase model compound has similar catalytic activity that of HRP. The catalytic activity of Fe(III)-HNT has been compared with those of HRP and common mimic-enzymes, metalloporphyrins (e.g. metal tetrakis(sulphophenyl)porphyrin (Me-TPPS(4))). Though the catalytic activity of Fe(III)-HNT is 75% of that of HRP, it can be used as a new kind of mimic-enzyme catalyst in determination of trace H(2)O(2). By coupling this mimetic catalytic reaction with the catalytic reaction of glucose oxidase, glucose can be determined indirectly. Under experimental conditions the linear relationship between DeltaA(265) and glucose concentration was in the range of 2.0-40.0 mug ml(-1), The correlation coefficient (r) was 0.9996. The R.S.D. (P=0.05, n=6) was 0.24%. The detection limit was determined to be 0.238 mug ml(-1). It was applied successfully to the determination of glucose in normal human and diabetic urine. The values of determination by the proposed method were compared with those of a routine method (enzymic glucose determination) applied in an hospital clinical laboratory. The agreement was very good.     

Spectrophotometric determination of certain CNS stimulants in dosage forms and spiked human urine via derivatization with 2,4-Dinitrofluorobenzene

A new spectrophotometric method is developed for the determination of phenylpropanolamine HCl (PPA), ephedrine HCl (EPH) and pseudoephedrine HCl (PSE) in pharmaceutical preparations and spiked human urine. The method involved heat-catalyzed derivatization of the three drugs with 2,4-dinitrofluorobenzene (DNFB) producing a yellow colored product peaking at 370 nm for PPA and 380 nm for EPH and PSE, respectively. The absorbance concentration plots were rectilinear over the range of 2-20 for PPA and 1-14 μg/mL for both of EPH and PSE, respectively. The limit of detection (LOD) values were 0.20, 0.13 and 0.20 μg/mL for PPA, EPH and PSE, respectively and limit of quantitation (LOQ) values of 0.60 and 0.40 and 0.59 μg/mL for PPA, EPH and PSE, respectively. The analytical performance of the method was fully validated and the results were satisfactory. The proposed method was successfully applied to the determination of the three studied drugs in their commercial dosage forms including tablets, capsules and ampoules with good percentage recoveries. The proposed method was further applied for the determination of PSE in spiked human urine with a mean percentage recovery of 108.17 ± 1.60 for (n = 3). Statistical comparison of the results obtained with those of the comparison methods showed good agreement and proved that there was no significant difference in the accuracy and precision between the two methods. The mechanism of the reaction pathway was postulated.     

Quantitative analysis of rabeprazole sodium in commercial dosage forms by spectrophotometry

The main aim of this work is to develop and validate two spectrophotometric methods for the quantitative analysis of rabeprazole sodium in commercial dosage forms. Method A is based on the reaction of drug with 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) in the presence of ammonium cerium(IV) nitrate in acetic acid medium at room temperature to form red-brown product which absorbs maximally at 470 nm. Method B utilizes the reaction of rabeprazole sodium with 1-chloro-2,4-dinitrobenzene (CDNB) in dimethyl sulfoxide (DMSO) at 45+/-1 degrees C to form yellow colored Meisenheimer complex. The colored complex has a characteristic band peaking at 420 nm. Under the optimized reaction conditions, proposed methods are validated as per ICH guidelines. Beer's law is obeyed in the concentration ranges of 14-140 and 7.5-165 microg ml(-1) with linear regression equations of A=6.041 x 10(-4)+1.07 x 10(-2)C and A=1.020 x 10(-3)+5.0 x 10(-3)C for methods A and B, respectively. The limits of detection for methods A and B are 1.38 and 0.75 microg ml(-1), respectively. Both methods have been applied successfully for the estimation of rabeprazole sodium in commercial dosage forms. The results are compared with the reference UV spectrophotometric method.     

A novel use of oxidative coupling reactions for determination of some statins (cholesterol-lowering drugs) in pharmaceutical formulations

New, accurate and reliable spectrophotometric methods for the assay of three statin drugs, atorvastatin calcium (AVS), fluvastatin sodium (FVS) and pravastatin sodium (PVS) in pure form and pharmaceutical formulations have been described. All methods involve the oxidative coupling reaction of AVS, FVS and PVS with 3-methyl-2-benzothiazolinone hydrazone hydrochloride monohydrate (MBTH) in the presence of Ce(IV) in an acidic medium to form colored products with λ(max) at 566, 615 and 664 nm, respectively. Beer's law was obeyed in the ranges of 2.0-20.0, 4.9-35.4 and 7.0-30.0 μg mL(-1) for AVS-MBTH, FVS-MBTH and PVS-MBTH, respectively. Molar absorptivities for the above three methods were found to be 3.24×10(4), 1.05×10(4) and 0.68×10(4) L mol(-1) cm(-1), respectively. Statistical treatment of the experimental results indicates that the methods are precise and accurate. The proposed methods have been applied to the determination of the components in commercial forms with no interference from the excipients. A comparative study between the suggested procedures and the official methods for these compounds in the commercial forms showed no significant difference between the two methods.     

Spectrophotometric, spectrofluorimetric, and densitometric methods for the determination of indapamide

Three sensitive spectrophotometric, spectrofluorimetric, and densitometric methods are described for the determination of indapamide. The first and second methods are based on the oxidative coupling reaction of indapamide with 3-methyl-2-benzothiazolinone hydrazone HCl (MBTH) in the presence of cerium(IV) ammonium sulfate in an acidic medium. The absorbance of the reaction product is measured at the lambdamax, 601 nm. With the same reaction, indapamide is determined by its quenching effect on the fluorescence of excess cerous ions at the emission lambdamax, 350 nm, and the excitation at lambdamax, 300 nm. The reaction conditions were optimized, and Beer's law was obeyed for indapamide at 1.2-9.6 microg/mL with mean recoveries of 99.92 +/- 0.83 and 99.97 +/- 1.11%, respectively. The third method, a stability-indicating densitometric assay, was developed for the determination of indapamide, using toluene-ethyl acetate-glacial acetic acid (69 + 30 + 1, v/v/v) as the developing system and scanning at the lambdamax, 242 nm, in the presence of the degradation product and related substance; for the indapamide concentration range of 0.6-6 microg/spot, the mean recovery was 99.73 +/- 0.71%. The proposed methods were successfully applied to the determination of indapamide in bulk powder and commercial tablets, and the results of the analysis agreed statistically with those obtained with the official method. Furthermore, the methods were validated according to the guidelines of the U.S. Pharmacopeia and also assessed by applying the standard additions technique.     

Application of ruthenium catalyzed oxidation of [tris(2-aminoethyl)amine] in trace determination of ruthenium in environmental water samples

The ruthenium catalyzed oxidation of tris(2-aminoethyl)amine (TREN) by hexacyanoferrate(III) has been utilized for the development of a new and sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III). The reaction was followed spectrophotometrically by the decrease in absorbance at 420nm (lambda(max) of [Fe(CN)(6)](3-)). The CKM developed utilizes fixed time procedure under optimum reaction conditions where the change in absorbance (DeltaA(t)) versus ruthenium(III) concentrations is plotted. The calibration curve recommended for the method is linear in the concentration range 10.11-252.67ngml(-1) with very good accuracy and reproducibility and a maximum error 2.20%. The detection limits of the method for ruthenium(III) corresponding to 10, 15 and 20min are 8.02, 5.03 and 3.15ngml(-1), respectively. The ruthenium(III) has also been determined in the presence of several other interfering and non-interfering cations and anions and no foreign ions interfered in the determination of ruthenium(III) up to five-fold higher concentration of the foreign ions tested. The method is highly sensitive, selective and stable. It has successfully been applied for the determination of trace ruthenium(III) in some synthetic and environmental water samples. A review of most of the published catalytic kinetic and some other important methods for the determination of ruthenium has also been presented.     

Simultaneous determination of nifuroxazide and drotaverine hydrochloride in pharmaceutical preparations by bivariate and multivariate spectral analysis

The quantitative predictive abilities of the new and simple bivariate spectrophotometric method are compared with the results obtained by the use of multivariate calibration methods [the classical least squares (CLS), principle component regression (PCR) and partial least squares (PLS)], using the information contained in the absorption spectra of the appropriate solutions. Mixtures of the two drugs Nifuroxazide (NIF) and Drotaverine hydrochloride (DRO) were resolved by application of the bivariate method. The different chemometric approaches were applied also with previous optimization of the calibration matrix, as they are useful in simultaneous inclusion of many spectral wavelengths. The results found by application of the bivariate, CLS, PCR and PLS methods for the simultaneous determinations of mixtures of both components containing 2-12microgml(-1) of NIF and 2-8microgml(-1) of DRO are reported. Both approaches were satisfactorily applied to the simultaneous determination of NIF and DRO in pure form and in pharmaceutical formulation. The results were in accordance with those given by the EVA Pharma reference spectrophotometric method.     

Spectrophotometric determination of some antihistaminic drugs using 7,7,8,8-tetracyanoquinodimethane (TCNQ)

A simple and sensitive spectrophotometric method is suggested for analysis of 3 antihistaminic drugs, acrivastine (I), mequitazine (II), and dimethindene maleate (III). The method is based on reaction of the drugs with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in acetonitrile to form highly stable colored products that are measured at 750, 766, and 844 nm for I and II, and 480 and 618 nm for III. Beer's law is obeyed in the ranges of 5-60 microg/mL for 1, 5-50 microg/mL for II, and 10-70 microg/mL for III. The optimum assay conditions and their applicability to the determination of the cited drugs in pharmaceutical formulations are described. The method is statistically analyzed as compared with the European Pharmacopoeia (2001) method for the analysis of dimethindene maleate and reference methods for acrivastine and mequitazine drugs revealing good accuracy and precision.     

Catalytic Spectrophotometric Determination of Titanium(IV) Using Methylene Blue‐Ascorbic Acid Redox Reaction

A highly selective and sensitive catalytic method for the determination of trace amounts of titanium(IV) was developed. The method is based on the catalytic effect of titanium(IV) on the methylene blue‐ascorbic acid redox reaction. The reaction was followed spectrophotometrically by measuring the change in absorbance of methylene blue at 665 nm, 5 minutes after the initiation of the reaction. In this study experimental parameters were optimized and the effect of the presence of various cations and some anions on the determination of titanium(IV) was examined. The calibration graph was linear in the range of 3‐25 ng mL^?1 of titanium(IV). The relative standard deviation for the determination of 10 and 20 ng mL^?1 of titanium(IV) were 2.64% and 1.51%, respectively (n = 8). The detection limit calculated from three times of standard deviation of blank 3S_b was 0.6 ng mL^?1. The method was successfully applied to the determination of titanium(IV) in tap water and ore samples.     

Spectrofluorimetric kinetic determination of selenium (IV) by flow injection analysis in cationic micellar medium

A sensitive catalytic kinetic spectrofluorimetric method for determining ng ml(-1) of selenium by flow injection analysis has been developed. The method, based on the catalytic effect of Se (IV) on the reduction of resorufin by sulphide, in the presence of cetylpyridinium chloride, is monitored spectrofluorimetrically (lambda(ex)=480 nm; lambda(em)=583 nm). The linearity range of the calibration graph is dependent on the concentration of sulphide. The variables affecting the rate of the reaction were investigated. The method is simple, rapid, precise, sensitive, and widely applicable. The limit of detection is 1 ng ml(-1) Se (IV), and the calibration range is 5-1000 ng ml(-1). Sampling rate is 60 samples h(-1), and the relative standard deviation of 12 determinations of 100 ng ml(-1) Se was 0.76%. The determination of Se (IV) in the presence of Se (VI) and total selenium is described. The method was applied to the determination of Se in selenium tablets, and several synthetic samples.     

Test determination of titanium(IV) and germanium(IV) in waste and natural waters in the presence of each other

It was demonstrated that trihydroxyfluorones immobilized on cellulose matrices can be used as the reagents for the rapid determination of titanium(IV) and germanium(IV). A high retention of trihydroxyfluorones on cellulose paper (78–98%) and strong chemically stable mixed fabric (74–97%) makes it possible to use these materials for the immobilization of the reagents. Mixed fabric (viscose with cotton) with immobilized phenylfluorone was used for the test determination of 0.05–5 mg/L titanium(IV) and 0.01–5 mg/L germanium( IV) by the color intensity of the reaction zone of the indicator matrix after passing 20 mL of the analyzed solution through it. A test procedure was developed for the determination of 1–200 mg/L titanium(IV) and 0.5–1000 mg/L germanium(IV) by the length of the colored zones of the test strips sealed in a polymer film. The time of the analysis is 10–15 min. The relative standard deviation of the results of the determination of germanium( IV) and titanium(IV) is no higher than 30%.     

Development and validation of a spectrophotometric method for the determination of macrolide antibiotics by using 2,4-dinitrophenylhydrazine

A simple, novel, sensitive, and specific spectrophotometric method was developed and validated for the determination of azithromycin (AZ), clarithromycin (CLA), and roxithromycin (ROX) in bulk powders and their dosage forms. The proposed method was based on the interaction of any of the cited drugs with 2,4-dinitrophenylhydrazine in the presence of an acid catalyst, followed by treatment with a methanolic solution of potassium hydroxide; an intensely colored chromogen was formed that was measured in dimethylformamide, as the diluting solvent, at 542-545, 523-526, and 539-542 nm for AZ, CLA, and ROX, respectively. All variables affecting the development of the measured chromogens were studied and optimized. Beer's law was obeyed in the concentration ranges of 5-40, 5-35, and 5-35 microg/mL for AZ, CLA, and ROX, respectively, with good correlation coefficients (0.9991-0.9999). The limits of detection for this method ranged from 0.77 to 1.47 microg/mL, and the relative standard deviations were 1.24-1.8%. The proposed method was applied successfully to the determination of the 3 drugs in pure bulk form, tablets, and suspensions without interference from commonly encountered additives. The results compared favorably with those of a previously reported method. The mechanism of the reaction was also studied.     

Kinetic determination of traces of Th(IV) on the basis of its catalytic effect in environmental water samples

A new analytic kinetic-catalytic method based on catalytic effect of traces of Th(IV) on the reaction oxidation of 4-hydroxycoumarin by KMnO₄ were developed and validated in this study. The linearity of the method was obtained in the range of concentrations of Th(IV) from 0.2 to 2 ??g mL^?1. The probable relative error is in the interval from 7.88 to 3.50% for the range of concentration of Th(IV) from 0.5 to 2 ??g mL^?1. Kinetic equations of investigated reactions were established. The proposed kinetic method was directly applied on determination of Th(IV) in environmental water samples. It was found that the results of Th(IV) determination in water samples obtained by proposed kinetic method and comparative atomic absorption spectrometry method were statistically agreeable.