Polarographic Determination of Lisinopril in Pharmaceuticals and Biological Fluids Through Treatment with Nitrous Acid

 A simple and highly sensitive polarographic method was developed for the determination of lisinopril in dosage forms and biological fluids. The method is based on treatment of the compound with nitrous acid followed by measuring the cathodic current produced by the resulting nitroso derivative. The polarographic behavior was studied adopting direct current (DC_t), differential pulse (DP) and alternating current (AC_t) polarography. A well-defined, diffusion-controlled cathodic wave over the pH range of 1.0–8.0 was obtained in Britton-Robinson buffers (BRb). At pH 3.0, the value of limiting diffusion-current constant (K) was 8.42 ± 0.23 (n = 7). The limiting diffusion current-concentration relationship was found to be rectilinear over the range of 2–24 μg/mL and 0.1–20 μg/mL using DC_t and DP polarographic modes, respectively. The minimum detectability was (S/N = 2) 0.02 μg/mL (4.54 × 10⁻⁸ M). The proposed method was successfully applied to the determination of lisinopril either per se or in dosage forms and the results obtained were in good agreement with those given using a reference method. The proposed method was further applied to the determination of lisinopril in spiked human urine and plasma. The percentage recoveries adopting the DP polarographic mode were 99.71 ± 1.87 and 97.16 ± 1.09, respectively. Received October 18, 2001; accepted July 31, 2002     

A New and Cost Effective Approach for Simultaneous Voltammetric Analysis of two Related Benzimidazole Drugs and their Determination in Biological Fluids

A polymerized film of eriochrome black T (EBT) was prepared on the surface of pencil graphite electrode in alkaline solution by cyclic voltammetry. The redox response of the poly (EBT) film at the electrode appeared in a couple of redox peak in 0.1 M sodium hydroxide. The poly (EBT) film‐coated electrode exhibited excellent electrocatalytic activity towards the oxidation of rabeprazole sodium (RAB sodium) and domperidone (DOM) in Britton‐Robinson buffer (pH 4.0). The polymer film modified electrode conspicuously enhanced the redox currents of the cited mixture and could sensitively and separately determine them. Both cyclic voltammetry (CV) and square wave adsorptive stripping voltammetric (SWAdSV) methods were utilized to determine this mixture. The linearity of CV ranged from 4.1‐120 μM and 5.2‐90 μM for RAB sodium and DOM, respectively while SWAdSV was 7.5‐80×10⁻⁷M and 5–70×10⁻⁷M for RAB sodium and DOM, respectively. With good selectivity and sensitivity, the present method provides a simple method for selective detection of RAB sodium and DOM binary mixture in synthetic mixtures and biological fluids.     

Determination of Flurbiprofen in Dosage form and in Biological Fluids by High Performance Liquid Chromatography

Abstract

A high performance liquid chromatograpy method is described for the determination of flurbiprofen in both dosage form and in biological fluids (urine and plasma) using fluorescence detection. The method for dosage forms involves grinding of a 100 mg tablet, suspension in methanol, filtration and adjusting to the appropriate concentration and 10 ul is injected onto the column. In the case of biological fluids a series of standard solutions were prepared in 0.IN sodium hydroxide and a known amount was added to 1 ml of serum or urine which was then acidified, extracted with ethylacetate, evaporated and the residue was then dissolved in a known volume of the mobile phase. Complete separation of the drug was achieved in about 6.5 minutes under the used conditions.     

Electrochemiluminescence Detection of Clarithromycin in Biological Fluids after Capillary Electrophoresis Separation

Abstract

A sensitive analytical method for the determination of clarithromycin in biological fluids with electrochemiluminescence detection after capillary electrophoresis separation was proposed in this paper, based on the enhancing effect of clarithromycin on electrochemiluminescence of tris(2,2-bipyridyl) ruthenium(II) (Ru(bpy)₃ ²⁺). Various factors influencing the separation and detection of clarithromycin were examined to establish the detection system. Under the optimized conditions, the electrochemiluminescence intensity is proportional with the concentration of the analyte over the range of 0.1–10 µM with a detection limit of 30 nM (S/N = 3). The proposed method has been successfully applied for clarithromycin content determination in spiked human plasma and urine samples.     

Determination of Trace Amounts of Lorazepam by Adsorptive Cathodic Differential Pulse Stripping Method in Pharmaceutical Formulations and Biological Fluids

Abstract

A new adsorptive cathodic differential pulse stripping voltammetry method for the direct determination of lorazepam at trace levels in pharmaceutical formulations and biological fluids is proposed. The procedure involves an adsorptive accumulation of lorazepam on a hanging mercury drop electrode (HMDE), followed by reduction of adsorbed lorazepam by voltammetric scan using differential pulse modulation. The optimum conditions for the analysis of lorazepam are pH=2 using Britton‐Robinson (B‐R) buffer, accumulation potential of ?0.2 V (vs. Ag/AgCl), and accumulation time of 40 sec. The peak current is proportional to the concentration of lorazepam, and a linear calibration graph is obtained at 0.05–1.15 µg mL^?1. A relative standard deviation of 2.41% (n=3) was obtained, and the limit of detection was 0.019 µg mL^?1. The capability of the method for the analysis of real samples was evaluated by determination of lorazepam in pharmaceutical preparations and biological (urine and plasma) fluids with satisfactory results.     

Construction and Validation of New Electrochemical Carbon Nanotubes Sensors for Determination of Acebutolol Hydrochloride in Pharmaceuticals and Biological Fluids

A simple, rapid and a highly selective method for direct electrochemical determination of acebutolol hydrochloride (AC) was developed. The developed method was based on the construction of three types of sensors conventional polymer (I), carbon paste (II) and modified carbon nanotubes (MCNTs) carbon paste (III). The fabricated sensors depend mainly on the incorporation of acebutolol hydrochloride with phosphotungstic acid (PTA) forming ion exchange acebutolol‐phosphotungstate (AC‐PT). The performance characteristics of the proposed sensors were studied. The sensors exhibited Nernstian responses (55.6 ± 0.5, 57.14 ± 0.2 and 58.6 ± 0.4 mV mol L^?1) at 25 °C over drug concentration ranges (1.0 × 10^?6‐1.0 × 10^?2, 1.0 × 10^?7‐1.0 × 10^?2 and 5.0 × 10^?8‐1.0 × 10^?2 mol L^?1 with lower detection limits of (5.0 × 10^?7, 5.0 × 10^?8 and 2.5 × 10^?8 mol L^?1 for sensors (I), (II) and (III), respectively. The influence of common and possible interfering species, pharmaceutical additives and some related pharmacological action drugs was investigated using separate solution method and no interference was found. The stability indicating using forced degradation of acebutolol hydrochloride was studied. The standard addition method was used for determination of the investigated drug in its pharmaceutical dosage forms and biological fluids. The results were validated and statistically analysed and compared with those from previously reported methods.     

Determination and Quantification of Pitavastatin Calcium in Tablet Dosage Formulation by HPTLC Method

Abstract

A simple, sensitive, reliable, and rapid HPTLC method has been developed for the determination of pitavastatin calcium in tablet dosage form. Identification and determination were performed on aluminum backed silica gel 60F₂₅₄ washed with methanol. The mobile phase of ethyl acetate‐methanol‐ammonia‐1 drop formic acid (7:2:0.8) calibration plots were established showing the dependence of response (peak area) on the amount chromatographed. The spot were scanned at 245 nm. The method has a linear range of 50–250 ng/spot. The method was validated for selectivity, repeatability, and accuracy. The method was used for determination of the compound in commercial pharmaceutical dosage forms. It is a more effective option than other chromatographic techniques in routine quality control.     

Stability-Indicating LC Determination of Nitazoxanide in Bulk Drug and in Pharmaceutical Dosage Form

A novel stability-indicating high-performance liquid chromatographic assay method was developed and validated for quantitative determination of nitazoxanide in bulk drugs and in pharmaceutical dosage form in the presence of degradation products generated from forced decomposition studies. An isocratic, reversed phase LC method was developed to separate the drug from the degradation products, using an Ace5- C18 (250 mm × 4.6 mm, 5 μm) column, and 50 mM ammonium acetate (pH 5.5 by acetic acid) and acetonitrile (55:45 v/v) as a mobile phase. The detection was carried out at a wavelength of 240 nm. The nitazoxanide was subjected to stress conditions of hydrolysis (acid, base), oxidation, photolysis and thermal degradation. Degradation was observed for nitazoxanide in base, acid and in 30% H₂O₂ conditions. The drug was found to be stable in the other stress conditions attempted. The degradation products were well resolved from the main peak. The percentage recovery of nitazoxanide was from (100.55 to 101.25%) in the pharmaceutical dosage form. The developed method was validated with respect to linearity, accuracy (recovery), precision, system suitability, specificity and robustness. The forced degradation studies prove the stability indicating power of the method.     

Validated Voltammetric Method for the Simultaneous Determination of Anti‐diabetic Drugs,Linagliptin and Empagliflozin in Bulk,Pharmaceutical Dosage Forms and Biological Fluids

A cobalt oxide nanoparticles (Co₃O₄NPs) and multi walled carbon nanotubes (MWCNTs) modified carbon paste electrodes were used to study the electrochemical behavior of linagliptin and empagliflozin in Britton Robinson buffer solution of pH 8.0 using cyclic and square wave voltammetry. The above mentioned modified electrodes showed highly sensitive sensing and gave an excellent anodic response for both drugs. The peak current varied linearly over the concentration ranges: 3.98×10^?5–1.53×10^?3 mol L^?1 (18.82–723.00 μg/mL) and 7.94×10^?6–1.07×10^?4 mol L^?1 (3.65–48.25 μg/mL) with determination coefficients of 0.9999 and 0.9998 for linagliptin and empagliflozin, respectively. The recoveries and relative standard deviations were found in the following ranges: 98.80 %–102.00 % and 0.23 %–1.90 % for linagliptin and 98.30 %–101.80 % and 0.11 %–1.86 % for empagliflozin. The detection and quantification limits were 1.13×10^?5 and 3.76×10^?5 mol L^?1 (5.34and17.77 μg/mL) for linagliptin, 1.71×10^?6and 5.68×10^?6 mol L^?1 (0.77 and 2.56 μg/mL) for empagliflozin. The proposed sensors have been successfully applied for the determination of the drugs in bulk, pharmaceutical formulations and biological fluids.     

Simultaneous Anodic Adsorptive Stripping Voltammetric Determination of Luteolin and 3‐Hydroxyflavone in Biological Fluids Using Renewable Pencil Graphite Electrodes

Simultaneous anodic adsorptive stripping voltammetry was applied for selective and sensitive electrochemical determination of the flavones luteolin (LU) and the basic flavone core 3‐hydroxyflavone (3HF) using a renewable pencil graphite electrode (PGE). The increased separation of the anodic peak potential of LU and 3HF on a PGE surface together with the increased sensitivity renders their simultaneous determination feasible by square wave anodic adsorptive stripping voltammetry (SWAASV). The electrochemical parameters such as surface concentration (Γ), electron transfer coefficient (α), and the standard rate constant (k_s) of both LU and 3HF at a PGE were calculated. For simultaneous detection of both compounds by synchronous change of the concentration of LU and 3HF, the detection limits were 1.34 nM and 5.15 nM, respectively. The proposed procedure was successfully applied for the simultaneous detection of LU and 3HF in human serum and urine samples with satisfactory results.     

N'-(4,6-二取代嘧啶-2-基)氧化烟酰硫脲的合成与生物活性测定

合成并表征了9种未见文献报道的N'-(4,6-二取代嘧啶-2-基)氧化烟酰硫脲衍生物3,结构经IR,1HNMR,元素分析得到确证.初步的生物活性测试表明化合物3a具有较好的除草活性,化合物3b具有一定的杀虫活性.     

Determination of Candesartan Cilexetil in Tablet Dosage Forms and Dissolution Testing Samples by First Derivative UV Spectrophotometric Method

Abstract

This article describes the development and validation of a first derivative UV quantitative analytical method for determination of candesartan cilexetil in tablet dosage forms. A signal at 270.1 nm of the first derivative spectrum (ID_270.1) was found adequate for quantification. The limit of quantification was 3.06 µg/ml. The linearity between ID_270.1 nm and concentration of candesartan cilexetil in the range of 6.00–32.00 µg/ml presented a correlation coefficient of (r²) = 0.9990. The mean recovery percentage was 100.97 and 99.23% for candesartan cilexetil standard solution and candesartan standard cilexetil solution with excipients, respectively. The intraday and interday accuracy of the assay was 98.60% and 99.10% respectively. The intraday and interday variability was below 2.0%.

The proposed method is accurate, precise, sensitive, and selective and can be used in quality control laboratories for its intended purpose.     

Electrochemical Behavior of Carvedilol and Its Adsorptive Stripping Determination in Dosage Forms and Biological Fluids

Carvedilol is used in the management of hypertension and angina pectoris and as an adjunct to standard therapy in symptomatic heart failure. The electrochemical oxidation of carvedilol was investigated using cyclic, linear sweep voltammetry at a glassy carbon electrode. In cyclic voltammetry, in all values of pH, the compound shows two irreversible oxidation peaks. These two peaks are related to the different electroactive part of the molecule. First and second peak currents were found as diffusion and adsorption controlled, respectively. Using second oxidation step, two voltammetric methods were described for the determination of carvedilol by differential pulse adsorptive stripping voltammetry (AdSDPV) and square‐wave adsorptive stripping voltammetry (AdSSWV) at a glassy carbon electrode. Accumulation of carvedilol was found to be optimized in 0.2 M H₂SO₄ solution following 275 second accumulation time at open circuit condition. Under optimized conditions, the current showed a linear dependence with concentration in the range between 2×10^?7 M and 2×10^?5 M in supporting electrolyte and in the range between 2×10^?7 M and 1×10^?5 M in spiked human serum samples for both methods. These methods were successfully applied for the analysis of carvedilol pharmaceutical dosage forms and spiked human serum samples. The repeatability and reproducibility of the methods for all media were determined. Precision and accuracy were also found. No electroactive interferences from the tablet excipients and endogenous substances from biological material were found.     

Development and Validation of Spectrophotometric Methods for the Determination of Cefetamet in Pharmaceutical Dosage Forms

Two simple and sensitive spectrophotometric methods for the determination of cefetamet in either pure form or in its pharmaceutical formulations were described. The method Ⅰ is based on the interaction of 3-methylbenzo[d]- thiazolin-2-one hydrazone （MBTH） with cefetamet in the presence of freshly prepared ferric chloride in a neutral medium. The resulting blue colored product has λmax at 628 nm. The method Ⅱ describes the reduction of ferric ion by the drug to ferrous ion followed by a complex formation reaction with 1,10-phenanthroline （1,10-phen） to form an orange red colored chromogen exhibiting 2max at 510 nm. The products are stable for more than 5 and 8 h respectively. Common excipients used as additives in pharmaceutical preparations do not interfere in the proposed methods. Both methods are highly reproducible and have been applied to a wide variety of pharmaceutical preparations and the results are comparable with those of official methods.     

Simultaneous Determination of Diclofenac Sodium and Rabeprazole Sodium in Bulk and Pharmaceutical Dosage Form by LC

A simple, selective, rapid, precise and accurate reverse phase high pressure liquid chromatographic method has been developed for the simultaneous estimation of diclofenac sodium and rabeprazole sodium from pharmaceutical formulations. The method was developed using a HiQ SiL C18 (250 mm × 4.6 mm i.d.) column with a mobile phase consisting of methanol:water, (80:20 v/v), at a flow rate of 1.25 mL min^?1. Detection was carried out at 284 nm. Indapamide was used as an internal standard. The developed method was validated for linearity, accuracy, precision, limit of detection and limit of quantitation. The proposed method can be used for the estimation of these drugs in combined dosage forms.     

生物样品中短链脂肪酸的提取与测定

综述了生物样品(主要为粪便、尿液、血液和培养液)中短链脂肪酸的提取与测定方法,讨论了各种样品提取方法的优缺点,并比较了气相色谱、高效液相色谱和毛细管电泳分离检测的优点和局限性。引用文献63篇。     

Trace Determination of Copper in Foodstuffs and Biological Samples

Abstract

A new heterocyclic bis-azo dye, 2,6-bis(4-sulfo-1-hydroxy-2-naphthylazo)pyridine, sodium salt (PBS), has been prepared and developed as a sensitive and highly selective chromogenic reagent for spectrophotometric determination of copper. The reagent is found to give a 1:2 (M/L) complex at pH 6.0. Beer's law is followed up to 1.8 ppm with an optimal concentration range between 0.2 and 1.4 ppm. Sandell's sensitivity of the color reaction was calculated to be 0.0013 µg cm^?2 with molar absorptivity of 4.9 × 10⁴ l·mol^?1 cm^?1 at 572 nm. The interfering effects of various cations and anions were also studied. The proposed method was successfully applied to the determination of copper(II) in milk, tea samples, cereals, and legume grains consumed by the Indian vegetarians and in some biological samples. Comparison of the results with those obtained using an atomic absorption spectrophotometer tested the validity of the method.     

New Validated Potentiometric Determination of Vasodilator Pentoxifylline in its Pharmaceutical Formulations and Biological Fluids

The construction and performance characteristics of pentoxifylline selective electrodes were developed. Two types of electrodes: plastic membrane I and coated wire II were constructed based on the incorporation of pentoxifylline with phosphotungstic acid (PTA). The influence of membrane composition, kind of plasticizer, pH of the test solution, soaking time, and foreign ions on the electrodes was investigated. The electrodes showed a Nernstain response with a mean calibration graph slope of 56.77 ± 0.19 and 55.76 ± 0.71 mV decade^‐1 at 25 °C for electrode I and II respectively, over pentoxifylline concentration range from 1.0 × 10^‐5‐1.0 × 10^‐2 and 9.0 × 10^‐6‐1.0 × 10^‐2 mol L^‐1, with detection limits 4.89 × 10^‐6 and 3.90 × 10^‐6 mol L^‐1 for electrode I and II, respectively. The pH range of the constructed electrodes was 4‐6. Interferences from common cations, alkaloids, sugars, amino acids and drug excipients were reported. The results obtained by the proposed electrodes were also applied successfully to the determination of the drug in its pharmaceutical preparations and biological fluids.     

Renewable Pencil Electrodes for Highly Sensitive Anodic Stripping Voltammetric Determination of 3‐Hydroxyflavone and Morin in Bulk Form and in Biological Fluids

An electrochemical anodic adsorptive stripping procedure for ultra‐trace assay of 3‐hydroxyflavone (3HF) and Morin at a renewable pencil electrode (PGE) in bulk form and in biological fluids is described. The nature of the oxidation process of 3HF and Morin taking place at the PGE was characterized by cyclic voltammetry. The results show that the determination of the oxidation peak current is the basis of a simple, accurate and rapid method for quantification of 3HF by square‐wave anodic stripping voltammetry. Determination of Morin was achieved by square‐wave anodic adsorptive stripping voltammetry of the formed Morin? Cu(II) complex at a PGE. Factors influencing the trace measurements of 3HF and the Morin? Cu (II) complex at a PGE are assessed. The limits of detection and quantitation for the determination of 3HF and Morin in bulk form and in biological fluids were determined. The statistical analysis and the calibration curve data for trace determination of 3HF and Morin are reported.     

Direct and Second Order Analogue Derivative Extraction-Spectrophotometric Determination of Iron with 2 (4, 5-Dimethyl-2-Thiazolylazo)-4, 6-Dimethylphenol

Abstract

An extraction-spectrophotometric method for the determination of trace amounts of iron based on its extraction into chloroform with 2-(4, 5-dimethyl-2-thiazolylazo)-4, 6-dimethylphenol has been developed, which allows the determination of 5–28 μg Fe (?₇₇₃ = 1.38×10⁴ 1. mol^?1. cm^?1). The use of second order analogue derivative spectrophotometry allows the determination of down to 0.2–5 μg, Fe. The methods are quite selective and have been applied to the determination of iron in mineral waters.