Spectrophotometric and spectrofluorimetric determinations of veterinary drug enrofloxacin in pharmaceutical formulation

Four simple, sensitive spectrophotometric and spectroflourimetric methods (A-D) for the determination of veterinary drug enrofloxacin (ENFX) in pharmaceutical formulation have been developed. Method (A) is based on formation of ternary complex of ENFX with Pd(II) in presence of methyl cellulose as surfactant and acetate-HCl buffer pH 4.0. Method (B) is based on the oxidation of ENFX with alkaline potassium permanganate to give a green colored reaction product. The reaction was monitored spectrophotometrically by measuring the absorbance of the reaction product at 604 nm. Method (C) is based on the oxidation of the ENFX by a known excess of potassium permanganate in acid medium and subsequent determination of unreacted oxidant by reacting it with safronine O (SFO). Method (D) is based on the chelation of ENFX with Zr(IV), to produce fluorescent chelate. At the optimum reaction conditions, the drug/metal chelate showed excitation maxima at 280 nm and emission maxima at 440 nm. The optimum experimental parameters for the reaction have been studied. The validity of the described procedures was assessed. Statistical analysis of the results has been carried out revealing high accuracy and good precision. The proposed methods were successfully applied for the determination of the selected drug in pharmaceutical preparations with good recoveries. The procedures were accurate, simple and suitable for quality control application.     

Flow Injection Kinetic Spectrophotometric Determination of Cerium Based on the Decolorization Reaction Between Arsenazo III and Cerium (IV)

ABSTRACT

Trace amounts of cerium were analyzed by flow injection kinetic spectrophotometry, based on the decolorization reaction between arsenazo III and Ce(IV) in sulfuric acid medium at room temperature. The absorbance difference (ΔA) of decolorization was linear with the concentration of Ce(IV). The flow injection technique was used to precisely control the timing. Under the optimum conditions, the determination of Ce(IV) in the range 0.0–8.0 µg mL^?1 with a correlation coefficient (r) of 0.9982, the regression equation was ΔA = 0.0014 + 0.0406c (µg mL^?1). The detection limit (3σ) of 0.2 µg mL^?1 was achieved at a sampling frequency of 60 h^?1. The proposed method was applied to the analyses of Ce in soil successfully.     

Application of potassium permanganate to spectrophotometric assay of metoclopramide hydrochloride in pharmaceuticals

Two simple, sensitive, and cost-effective spectrophotometric methods are described for the determination of metoclopramide hydrochloride (MCP) in pharmaceutical dosage forms. The methods are based on a redox reaction between MCP and KMnO₄ in alkaline and acid media. Direct spectrophotometry (method A) involves treating MCP with permanganate in an NaOH medium and measuring a bluish green product at 610 nm. In indirect spectrophotometry (method B), MCP is treated with a fixed concentration of KMnO₄ in an H₂SO₄ medium, and after a specified time, the unreacted KMnO4 is measured at 545 nm. Under optimum assay conditions, Beer’s law is obeyed over the ranges of 0.75–12.0 and 2.5–30.0 g/ml for methods A and B, respectively. Molar absorptivity values are calculated to be 2.33∙10⁴ and 2.66∙10⁴ l/mol cm for methods A and B, respectively, and corresponding Sandell’s sensitivity values are 0.015 and 0.013 g/cm². Limits of detection (LOD) and quantification (LOQ) are also reported. The applicability of the developed methods was demonstrated by the determination of MCP in tablet and injection forms. The accuracy and reliability of the proposed methods were further ascertained by recovery studies via standard addition technique.     

Application of 3-methylbenzothiazolin-2-one hydrazone for the quantitative spectrophotometric determination of oxcarbazepine in pharmaceuticals with cerium(IV) and periodate

Two simple, sensitive, selective, accurate, and cost-effective spectrophotometric methods are described for the assay of oxcarbazepine (OXC) in bulk drug and in tablets. The methods are based on an oxidative coupling reaction involving OXC, 3-methylbenzothiazolin-2-one hydrazone (MBTH), and cerium(IV) sulfate at pH 4.28 ± 0.07 (method A) or sodium periodate at pH > 4.0 (method B) to form an orange colored product with an absorption maximum at 450 nm. Under optimized experimental conditions, the calibration graphs are linear over the ranges of 4–80 and 2–32 μg/ml for methods A and B, respectively, with correlation coefficient (r) values of 0.9984 and 0.9976. The apparent molar absorptivity values are 3.13⋅10³ and 9.13⋅10³ l/mol⋅cm for methods A and B, respectively. The other optical characteristics such as Sandell’s sensitivity, limits of detection (LOD) and quantification (LOQ) values are also reported. The accuracy and precision of the methods were evaluated based on intra-day and inter-day variations. The proposed methods were successfully applied to the determination of OXC in tablets: the results were comparable with the published data obtained using the reference method. The reaction stoichiometry of OXC with MBTH (1:1 in method A and 1:2 in method B) was also evaluated using the limiting logarithmic method, and a possible reaction pathway is presented for the both methods.     

Stability-Indicating Method for the Determination of Meloxicam and Tetracaine Hydrochloride in the Presence of their Degradation Products

Abstract

Sensitive, spectrophotometric and densitometric methdos are described for the determination of meloxicam I and tetracaine hydrochloride II in the presence of their degradation products.

Meloxicam was determined in the presence of its degradation products (5-methyl-2-aminothiazole) III and benzothiazine carboxylic acid IV by two methods. These methods are the first derivative Spectrophotometry at 338 nm and TLC densitometric method at 365nm. The methods were applicable over the concentration range of 5–20μg.m^?1 and 2–10μg with mean accuracies of 99.66±0.91% and 99.99±0.70% respectively.     

Determination of Total Antioxidant Capacity by a New Spectrofluorometric Method Based on Ce(IV) Reduction: Ce(III) Fluorescence Probe for CERAC Assay

A Ce(IV)-based reducing capacity (CERAC) assay was developed to measure the total antioxidant capacity (TAC) of foods, in which Ce(IV) would selectively oxidize antioxidant compounds but not citric acid and reducing sugars which are not classified as antioxidants. The method is based on the electron-transfer (ET) reaction between Ce(IV) ion and antioxidants in optimized acidic sulphate medium (i.e., 0.3 M H₂SO₄ and 0.7 M Na₂SO₄) and subsequent determination of the produced Ce(III) ions by a fluorometric method. The fluorescent product, Ce(III), exhibited strong fluorescence at 360 nm with an excitation wavelength of 256 nm, the fluorescence intensity being correlated to antioxidant power of the original sample. The linear concentration range for most antioxidants was quite wide, e.g., 5.0 × 10⁻⁷–1.0 × 10⁻⁵ M for quercetin. The developed procedure was successfully applied to the TAC assay of antioxidant compounds such as trolox, quercetin, gallic acid, ascorbic acid, catechin, naringin, naringenin, caffeic acid, ferulic acid, glutathione, and cysteine. The proposed method was reproducible, additive in terms of TAC values of constituents of complex mixtures, and the trolox equivalent antioxidant capacities (TEAC coefficients) of the tested antioxidant compounds gave good correlations with those found by reference methods such as ABTS and CUPRAC.     

Colorimetric microdetermination of captopril in pure form and in pharmaceutical formulations

A simple, rapid, accurate, precise and sensitive colorimetric method for the determination of captopril (CAP) in bulk sample and in dosage forms is described. The method is based on oxidation of the drug by potassium permanganate in acidic medium and determination of the unreacted oxidant by measuring the decrease in absorbance for five different dyes; methylene blue (MB); acid blue 74 (AB), acid red 73 (AR), amaranth dye (AM) and acid orange 7 (AO) at a suitable λ_max (660, 610, 510, 520, and 485 nm), respectively. Regression analysis of Beer's plots showed good correlation in the concentration ranges (0.4-12.5, 0.3-10, 0.5-11, 0.4-8.3 and 0.5-9.3 μg ml⁻¹), respectively. The apparent molar absorbtivity, Sandell sensitivity, detection and quantitation limits were calculated. For more accurate results, Ringbom optimum concentration ranges were 0.5-12, 0.5-9.6, 0.6-10.5, 0.5-8.0 and 0.7-9.0 μg ml⁻¹, respectively. The validity of the proposed method was tested by analyzing in pure and dosage forms containing CAP whether alone or in combination with hydrochlorothiazide. Statistical analysis of the results reflects that the proposed procedures are precise, accurate and easily applicable for the determination of CAP in pure form and in pharmaceutical preparations. Also, the stability constant was determined and the free energy change was calculated potentiometrically.     

Fluorimetric Determination of Cerium(IV) with Ascorbic Acid

A simple, sensitive, and selective method for the determination of cerium(IV), based on the oxidative reaction between cerium(IV) and ascorbic acid, has been described. The fluorescence comes from Ce(III) at λ_excitation 298 nm and λ_emission 358 nm, which, in turn, is obtained from the oxidation of ascorbic acid by Ce(IV) in the presence of sulfuric acid. The optimum conditions such as concentrations of ascorbic acid, sulfuric acid media and pH of the buffer solution were investigated. The fluorescent intensity of the system is linear over the range 0.0531 μg/ml to 0.3322 mg/ml Ce(IV) and detection limit and correlation coefficient are 0.0145 μg/ml and R=0.99987,respectively.     

Spectrophotometric determination of ofloxacin in pharmaceuticals by redox reaction

Two simple spectrophotometric methods have been developed to analyze ofloxacin (OFX) in pharmaceuticals. The methods are based on the oxidation of OFX by a measured excess of cerium(IV) sulfate in H₂SO₄ medium. This was followed by the determination of the unreacted oxidant by reacting it with either p-toluidine (p-TD) and measuring the absorbance at 525 nm (method A) or o-dianisidine (o-DA) and measuring the absorbance at 470 nm (method B). In both methods, the amount of cerium(IV) sulfate reacted corresponds to the amount of OFX. Calibration graphs were linear over the ranges of 0–120 and 0–4 g/ml OFX for methods A and B, respectively. The calculated molar absorptivity (2.34⋅10³ and 5.99⋅10⁴), Sandell sensitivity, and limit of quantification for the methods are reported. The intra-day precision (%RSD) and accuracy (%RE) were < 8.0 and ≤ 4.0%, respectively, and the inter-day RSD and RE values were within 5 and 4.0%, respectively. The applicability of the methods was demonstrated by determining OFX in tablets with an accuracy (%RE) of < 3% and precision (%RSD) of ≤2.65%. The accuracy of the methods was further ascertained by recovery experiments via a standard-addition procedure.     

Derivative Spectrophotometric and Colorbmetric Methods for the Determination of Guanoxan Sulphate in Tablets,Urine, and Serum.

Three simple and rapid methods for the determination of guanoxan sulphate in tablets, urine and serum are presented. The first method is based on the direct measurement of the first (¹D) and second (²D) (peak-trough) derivative values at 274–250 nm and 276–260 urn respectively. The other two methods depend on the formation of a charge- transfer chromogen with either tetracyanoethylene (TCNE) and 7,7,8,8- tetracyanoquinodimethane (TCNQ). The absorbance of the color developed at 416 and 840 nm respectively. The first and second derivative (¹D & ²D) values for the charge- transfer products were also measured. The methods were proved to be accurate and reproducible as indicated by relative standard deviation of less than 2%. The proposed methods have been applied to the determination of guanoxan sulphate in tablets, and spiked human urine and serum.     

Flow‐Injection Online Reduction Atomic Fluorescence Spectrometry Determination of Se(IV) and Se(VI) with Electrochemical Hydride Generation

Abstract

A new flow‐injection online reduction electrochemical hydride generation system for the determination of Se(IV) and Se(VI) by atomic fluorescence spectrometry (AFS) was developed. In the system, an electromagnetic induction oven was used as heating resource to reduce Se(VI) to Se(IV) and a homemade tubular electrolytic cell as hydride generator. All analytical procedures were automatically controlled by a computer. The conditions of online reduction, including temperature, HCl concentration, and reduction time, have been studied in detail. The detection limits (3σ) of Se(IV) and Se(VI) in aqueous solution were 0.26 µg L^?1 and 0.23 µg L^?1, respectively. The precision for 11 replicate measurements of 50 µg L^?1 Se(IV) and Se(VI) was 2.2% and 2.5%. This proposed method has been applied to the determination of Se(IV) and Se(VI) in springwater samples.     

Comparative Study of the Ratio Spectra Derivative Spectrophotometry,Derivative Spectrophotometry and Vierordt's Method Appued to the Analysis of Lisinopril and Hydrochlorothiazide in Tablets

Abstract

Three new spectrophotometric methods are described for the determination of lisinopril and hydrochlorothiazide in their binary mixturer: First derivative spectrophotometry ratio spectra derivative and Vierordt's method. The procedures do not require any prior separation. In the derivative spectrophotometry, the dA/dλ values in the first derivative spectra of the mixture were measured at 269.6 nm for lisinopril and at 279.8 nm for hydrochlorothiazide. The calibration graphs were linear in the range 25.56–129.50 μg.ml^?1 for lisinopril and 10.60–139.80 μg.ml^?1 for hydrochlorothiazide. In ratio spectra derivative spectrophotometry, the calibration graphs for 15.68–129.50 μg.ml^?1 lisinopril and for 5.98–139.80 μg.ml^?1 hydrochlorothiazide were obtained by measuring the signals at 253.7 nm and 243.6 nm for lisinopril and at 280.1 nm and 270.8 nm for hydrochlorothiazide. In Vierordt's method, A¹ ₁ (1 %, 1 cm) values of lisinopril and hydrochlorothiazide were determined at 259.8 nm and 272.7 nm in the zero-order spectra. The quantity of both compounds were calculated by using the A¹ ₁ (1 %, 1cm) values. The methods were successfully applied to a pharmaceutical formulation for determination of both active compounds.     

Preparation and properties of nanocrystalline powders in (Y1−xCex)3Al5O12 system

Nano-sized cerium-doped yttrium aluminum garnet (YAG:Ce) phosphors were synthesized via a simple sol-gel process using metal nitrate precursors. The prepared phosphors were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy, respectively. Pure cubic garnet phase was formed at temperatures ∼900 ^οC. The particle sizes of as-prepared powders were mostly in the range of 17-27 nm. The crystalline YAG:Ce showed broad emission peaks in the range of 400-700 nm and maximum intensities at 500 and 520 nm. It is found also that the emission intensity decreased with increasing Ce doping concentration from 0.1 to 1.5 at%. With increasing Ce doping concentration, the PL intensity was shifted towards shorter wavelengths.     

Fluorometric Determination of Bopindolol and Celiprolol in Pharmaceutical Preparations and Biological Fluids

Two sensitive fluorometric methods were developed for the determination of both bopindolol malonate (BOP) and celiprolol HCl (CLP) based on measuring their native fluorescence in methanol and acetonitrile, respectively. For BOP, the fluorescence was measured at 316?nm after excitation at 278?nm. The proposed method was successfully applied to the assay of commercial tablets as well as content uniformity testing. For CLP, the fluorescence was enhanced by the addition of carboxymethylcellulose solution and measured at 455?nm after excitation at 339?nm. The method was successfully applied to the analysis of CLP in tablets and biological fluids. In both methods, interference likely to be introduced from co-formulated, co-administered, or chemically related drugs was studied. The results were statistically compared with those obtained by reference methods and were found to be in good agreement.     

Fluorimetric Determination of Ketorolac in Urine by Stopped-Flow Sequential Injection Analysis

ABSTRACT

An automatic fluorescence method was developed for the determination of ketorolac tromethamine. The method is based on the direct oxidation of the analyte by an acidic solution of permanganate, being the resulting fluorescence measured at 227 nm/320 nm (λ_ex/λ_em). The reaction is carried out online due to the use of the Sequential Injection Analysis methodology. A detection limit of 0.12 µ g mL^?1 and a R.S.D. lower than 3% (n = 10) were obtained under optimum conditions. The analyte was satisfactorily determined in pharmaceuticals and urine samples. Recovery experiments were carried out on human urine, with recoveries in the range 92–108%.     

Green & Sensitive pH-dependent Spectrofluorimetric Assay of Tamsulosin Hydrochloride and Tadalafil in their New Combined Formulation for Benign Prostatic Hyperplasia: Application to Spiked Human Plasma

Sensitive and green spectrofluorimetric methods were utilized for Tamsulosin Hydrochloride (TAM) and Tadalafil (TDL) assessment in bulk and their newly available combined mixture for benign prostatic hyperplasia and erectile dysfunction. The technique relies on measuring native fluorescence of TAM in 0.1 N HCl at 324 nm and TDL in 0.1 N NaOH at 348 nm due to their different fluorimetric behavior in acidic and basic media where TAM has no fluorescence in basic medium and vice versa. To achieve better regression, the spectra were derivatized allowing determination of TAM at 314 nm and TDL at 320 and 380 nm (peak to peak) by applying third and first derivative, respectively. In addition, pH-dependent “constant-wavelength synchronous” spectrofluorimetry was applied where TAM and TDL were determined at 218 nm in acidic medium and at 268 nm in basic medium, respectively. Finally, derivatizing the latter emission spectra allowed determination of TAM and TDL at 232 nm and at 262 and 278 nm (peak to peak), respectively. Acidic and basic emission spectra where scanned at λ_exc?=?225 nm (for TAM assay) and at λ_exc?=?247 nm (for TDL assay), respectively. Fluorescence–concentration plots were linear and the proposed methods were used for analysis of TAM and TDL combined laboratory prepared formulation. These procedures are green, sensitive and of low cost which make them suitable for quality control analysis of the two drugs. In addition, the high selectivity of the proposed methods was tested by successfully applying them for TAM and TDL assay in plasma samples.

     

Artificial neural networks versus partial least squares and multivariate resolution-alternating least squares approaches for the assay of ascorbic acid,rutin, and hesperidin in an antioxidant formulation

Abstract

This study was concerned with the assay of ascorbic acid (ASC), rutin, and hesperidin (HES) in their combined formulation using a multivariate approach. Three chemometric-assisted spectrophotometric models namely: partial least squares, multivariate curve resolution-alternating least squares, and artificial neural networks were developed and validated. The quantitative analyses of all the proposed models were assessed by percentage recoveries, root mean square error of prediction, and standard error of prediction. The proposed models were used in the range of 10.0–70.0, 2.0–10.0, and 2.0–10.0?µg mL^?1 for ASC, rutin, and HES, respectively. In addition, correlation coefficients between the pure and estimated spectral profiles were used for the qualitative analysis of a multivariate curve resolution-alternating least squares model. Artificial neural networks showed higher speed and methodological simplicity over the other two models. These models presented powerful multivariate statistical tools that were applied to the analysis of the combined dosage form in the Australian market. They have the ability to overcome difficulties such as colinearity and spectral overlaps. Statistical comparison between the proposed and reported methods showed no significant difference. The proposed methods can be used for the routine analysis of the studied drugs in quality control laboratories.     

Luminescent properties of RE-activated CaAl2B2O7 (RE=Tb, Ce) in VUV-visible region

RE³⁺-activated α- and β-CaAl₂B₂O₇ (RE=Tb, Ce) were synthesized with the method of high-temperature solid-state reaction. Their VUV excitation and VUV-excited emission spectra are measured and discussed in the present article. The charge transfer band of Tb³⁺ and Ce³⁺ is respectively calculated to be at 151±2 and 159±3 nm. All the samples show an activator-independent excitation peak at about 175 nm and an emission peak at 350-360 nm ascribed to the host absorption and emission band, respectively.     

Colorimetric and Spectrofluorimetric Methods for the Determination of Melatonin in Tablets and Serum

Abstract

Two sensitive and accurate colorimetric and spectrofluonmetric methods, are presented for the determination of melatonin in tablets and serum. The first method utilizes the reactions of p-dimethylaminobenzaldehyde in hydrochloric acid (van Urk reagent)-ferric chloride in sulphuric acid (Salkowski reagent) mixture. The blue color of the resulting reaction product is measured at 630 nm. The second method is based on the reaction of melatonin with o-phthalaldehyde in acid medium which yields highly fluorescent condensation product that is measured at 465 nm as emission wavelength, using excitation wavelength at 355 nm. No interference was observed from tableting additives, and the applicability of the methods was examined by analysing tablets containing melatonin (single and combined with pyridoxine). Mean percentage recoveries from tablets were found to be 99.9+0.31 for single and 100.5+0.15 for combined tablets using colorimetric method, while by applying spectrofluorimetric method the recoveries were found to be 100.610.41 for single and 100.2+0.39 for combined tablets. Furthermore, the proposed methods were extended to the in-vitro determination of melatonin in serum. The detection limits are 0.27 ug ml^?1 for colorimetric method and 0.00035 ug ml^?1 for spectrofluorimetric method.     

Determination of Selenium (IV) in Natural Waters by HG‐AAS Using an Integrated Reaction Chamber Gas–Liquid Separator

Abstract

A simple online sequential insertion manifold coupled to a hydride generation atomic absorption spectrometer (HG‐AAS) has been developed for selective inorganic Se(IV) determination. The online method is based on the sequential insertion of sample and reagents in the integrated reaction chamber gas–liquid separator (RC‐GLS), which operates initially as reaction chamber for various sample volumes (up to 20 mL) and subsequently as gas–liquid separator with limited dead volume. The generated hydride from a large sample volume is trapped in the RC‐GLS for a short time and then it is flashed in the atomic absorption cell. The HCl and the NaBH₄ concentration was optimized for selective inorganic Se(IV) determination. For 8‐mL and 16‐mL sample consumption, the sampling frequency is 40 h^?1 and 24 h^?1, while the detection limit is 0.04 µg L^?1 and 0.03 µg L^?1, respectively. The precision (relative standard deviation) for 2.0 µg L^?1 Se(IV) (n=10) is 2.6% and 2.8% for 8 mL and 16 mL sample volumes, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1643d, and also by analyzing spiked natural water.