Difference spectrophotometric determination of some pharmaceutically important thioxanthene derivatives in dosage forms

A Spectrophotometric method is described for the rapid determination of four thioxanthene derivatives, namely chlorprothixene, thiothixene, flupenthixol hydrochloride and clopenthixol hydrochloride. The method is based on measuring the first derivative spectrum (D ₁) of the oxidized drug relative to a solution of the underivatized drug. At the wavelength of maximum difference in first derivative (range 285–315 nm), only the oxidation products have an appreciable difference in first derivative and the oxidizing agent has no absorbance. The oxidation products (assumed to be the thioxanthone sulphoxides) are formed rapidly at room temperature by the addition of peroxyacetic acid, prepared by the slow reaction of hydrogen peroxide and glacial acetic acid. The first derivative of the absorbance is proportional to the concentration of the drugs in solution over the ranges 2–14 g ml^–1 for chloroprothixene, 2–20 g ml^–1 for clopenthixol hydrochloride, 2–24 g ml^–1 for thiothixene and 4–40 g ml^–1 for flupenthixol hydrochloride. The method is specific for the intact drug and can be adopted in the presence of oxidative and photochemical decomposition products and tablet excipients. The recoveries ranged from 99.7 ± 1.3 to 100.2 ± 1.5%. The validity of the method was tested by analysing synthetic samples of thioxanthenes and some dosage forms containing the drugs; the results were in accordance with those given by the official methods.     

Determination of 2-mercaptobenzothiazole in river water by HPLC

Summary A method is proposed for the determination of 2-mercaptobenzothiazole in river waters using multi-electrode electrochemical detection HPLC. 2-mercaptobenzothiazole determination is unsatisfactory by gas chromatography as it degrades readily on the column. Multielectrode electrochemical detection HPLC combines sensitivity and the ability to screen out other electrochemically active species. The development work leading up to the proposed method is discussed. The method has a limit of detection of 0.798gl^–1 2-mercaptobenzothiazole and a total standard deviation of 2.06gl^–1 2-mercaptobenzothiazole at a concentration of 7.97gl^–1 2-mercaptobenzothiazole in river water.     

Simultaneous Determination of Four Active Components in a Compound Formulation by Liquid Chromatography

Summary A rapid and accurate LC method is described for simultaneous determination of pseudoephedrine hydrochloride (PSE), acetaminophen (AMP), dextromethorphen hydrobromide (DEX), and diphenhydramine hydrochloride (DPH) in a compound formulation. Chromatographic separation of the four drugs was achieved on a Hypersil CN column (150 mm × 4.6 mm, 5 m particle) by use of a mobile phase comprising a mixture of 3 mM ion-pairing solution, 2% aqueous triethylamine solution, and 2 M phosphoric acid, 68:48:88 (v/v), pH 3.0, delivered at 1.0 mL min^–1. Compounds were detected at 215 nm and the run time was less than 10 min. The linearity, accuracy, and precision of the method were found to be acceptable over the concentration ranges 6.1–36.4 g mL^–1 for PSE, 65.0–390.0 g mL^–1 for AMP, 3.1–18.6 g mL^–1 for DEX, and 5.0–30.0 g mL^–1 for DPH.     

Simple Extraction and Rapid Quantitative Analysis of Isoflavones in Soybean Seeds

A simple extraction and rapid HPLC method, suitable to separate and quantify the isoflavonoids in soybean seeds, are proposed and discussed. The method has been applied to the separation and quantification of seed isoflavonoids in five naturally grown soy cultivars; the total amount of isoflavones ranged from 1.83 g kg^–1 to 11.88 g kg^–1 of fresh weight. The detection limits (200 g/kg^–1), evaluated for genistein and daidzein, are presented together with a list of the soy polyphenols analysed by HPLC-DAD and HPLC-MS.     

Determination of 6-amino-2,2-dimethyl-1,3-dioxepan-5-ol by postcolumn derivatization witho-phthalaldehyde/2-mercapto-ethanol after ion-pair chromatography

Summary A high-performance liquid chromatographic method is discribed for the determination of 6-amino-2,2-dimethyl-1,3-dioxepan-5-ol using Spherisorb ODS II stationary phase and mobile phase 30:70 (v/v) methanol: aqueous 1-octane sulfonic acid. Detection was fluorimetric following postcolumn derivatization with o-phthaladehyde/2-mercaptoethanol. The procedure was applied to the analysis of aqueous solutions and microcrystalline suspensions in liquid paraffin, prepared for investigation of the toxicological profile. The method was validated for selectivity, linearity of detector response, repeatability, limit of detection and quantitation. The HPLC method was selective. The instrumental limit of detection was 0.5 ng per injection (0.05 g mL^–1). The method detection limits were 0.5 g mL^–1 aqueous solution and 5 g mL^–1 liquid paraffin suspension, the quantitation limit 0.05 mg mL^–1 aqueous solution and 1.0 mg mL^–1 liquid paraffin. Linearity was within 0.94–47.1 g mL^–1. Intra-assay accuracy accounted for 99–100% in the range 0.05–226 mg mL^–1 aqueous solution, intra-assay precision for 2% (C.V.). For microcrystalline liquid paraffin suspensions with 1 and 250 mg mL^–1 99 and 109% was found for intra-assay accuracy. Intra-assay precision was 5% (C.V.). Reliable results over a wide concentration range can be obtained. The procedure is considered valid for determination of the analyte in aqueous solution or microcrystalline paraffin oil suspensions.     

Short-term measurements of acrolein in ambient air

Summary A method has been developed for the determination of acrolein in air samples collected by a high-volume aqueous scrubber. The aldehyde is collected as the bisulfite adduct, which is decomposed before determination of acrolein by DNPH (2,4-dinitrophenylhydrazine) derivatization and HPLC. Approximately 95% of the acrolein reacts with DNPH within 3 h at DNPH:HSO₃ molar ratios of up to 10. The method appears promising for short-term air sampling at 8 L min^–1, enabling the achievement of a detection limit of 0.2 g m^–3 for acrolein.     

Development and validation of a novel HPLC/ELSD method for the direct determination of tobramycin in pharmaceuticals,plasma, and urine

A novel method for the direct determination of the aminoglycoside tobramycin was developed and validated based on reversed-phase high-performance liquid chromatography (RP-HPLC) with evaporative light scattering detector (ELSD). Using a Waters ODS-2 C18 Spherisorb column with an evaporation temperature of 45°C and nitrogen pressure of 3.5 bar, the selected mobile phase consisted of water/acetonitrile 55:45 containing 1.5 mL L^–1 HFBA (11.6 mM) in an isocratic mode at a rate of 1.0 mL min^–1. Tobramycins retention time was 4.3 min with an asymmetry factor of 1.7. A logarithmic calibration curve was obtained from 1 to 38 g mL^–1 (r > 0.9998). LOD was 0.3 g mL^–1; within-day %RSD was 1.0 (n = 3, 4.7 g mL^–1) and between-day %RSD was 1.1 (3 days within a week). The developed method was applied to the determination of tobramycin in a pharmaceutical crude substance and formulations (eye drops and ointments). Dilution experiments revealed the absence of interference from excipients (no constant and proportional errors); recovery from spiked samples was 99–103% with %RSD < 2.2 (n = 3×3). The developed HPLC/ELSD method was also found to be applicable in the determination of tobramycin in human plasma (0.6–12.5 g mL^–1) and urine (1.5–12.5 g mL^–1) after solid-phase extraction using carboxylate cartridges followed by solvent evaporation (×2 preconcentration). A mean recovery of 86% for plasma and 91% for urine was obtained.     

Ultraviolet Spectrophotometric Determination of Primary Amine-Containing Drugs via Their Charge-Transfer Complexes with Tetracyanoethylene

A spectrophotometric method is described for the quantitative determination of some drugs containing a primary amino-group, i.e. amantadine hydrochloride, tranylcypromine sulfate and tranexamic acid in their pure forms as well as in some pharmaceutical dosage forms. The procedure is based on the formation of a charge-transfer complex between tetracyanoethylene (TCNE) as -acceptor and the studied drugs as n-donors in the presence of acetonitrile as solvent. The spectra of the complexes show maxima at 330nm with high apparent molar absorptivities (from 2.1 × 10³ to 2.2 × 10⁴ L·mol^–1 cm^–1). Beers law is obeyed in the concentration ranges of 25–75 µg mL^–1, 2–30µgmL^–1 and 5–25µg mL^–1, and the mean percent recoveries are 99.68±0.92, 100.3±0.75 and 99.8±0.76 for amantadine hydrochloride, tranylcypromine sulfate and tranexamic acid, respectively. The proposed method is simple and can be applied to determine these drugs in their pharmaceutical dosage forms. The results compare favorably with those of reported methods.     

Spectrophotometric determination of some phenolic sympathomimetic drugs through reaction with 2,6-dihaloquinone chlorimides

A spectrophotometric procedure is described for the determination of three phenolic sympathomimetic drugs: etilefrine hydrochloride, prenalterol hydrochloride and ritodrine hydrochloride. The method involves the use of 2,6-dichloro- and 2,6-dibromoquinone chlorimides as chromogenic reagents. The phenolic drugs produce a blue color, peaking from 610 to 630 nm. The colors produced obey Beer's law and are suitable for the quantitative determination of the named compounds. The molar ratios of the reactions were established and a proposal for the reaction pathway is given. The procedures described were applied successfully to the determination of the compounds in their dosage forms. The results showed that the proposed procedures compared favourably with the reference methods and satisfactory sensitivity, accuracy and precision (SD < 0.1 g ml^–1) were noted. Detection limits are typically 0.2–0.4 g ml^–1. Other advantages of the procedures are their simplicity and speed.     

5-(4-Carboxylphenylazo)-8-aminoquinoline as an analytical reagent for the spectrophotometric determination of gold

The synthesis and analytical application of 5-(4-carboxylphenylazo)-8-aminoquinoline (CPAQ) are described. A simple, rapid, selective, and sensitive spectrophotometric method for the determination of microgram amounts of gold is developed, based on the colour reaction between the metal ion and CPAQ in the presence of cetyltrimethyl ammonium bromide. Gold (III) reacts with the reagent in the ratio 1 3 (metal to ligand) in alkaline solution to form a blue-green complex with an absorption maximum at 608 nm. Beer's law is obeyed over the concentration range 0–1.8 g · ml^–1 (ppm) of gold. The molar absorptivity and Sandell's sensitivity of the method are 9.11 × 10⁴ l · mole^–1 · cm^–1 and 0.00216 g · cm^–2, respectively. The interference of various ions has been studied and conditions were developed for the determination of gold in an ore and anode slimes.     

Inductively coupled plasma atomic emission spectrometric determination of arsenic in mussel products

Summary A precise, accurate procedure is proposed for the determination of arsenic in mussel products by inductively coupled plasma atomic emission spectrometry. Organic matter is destroyed by dry ashing. Experimental conditions for the determination of arsenic were selected and an interference study was carried out. The methodology developed has a detection limit of 0.1 g g^–1, a relative standard deviation of 3%, and a recovery percentage of 98±2%. The accuracy of the method was checked by analysis of a certified sample of NIST oyster tissue (certified 14.0±1.2 g g^–1; found 14.1±1.1 g g^–1). The proposed procedure was used to analyze real samples of mussel products.     

Use of quercetin in an improved method for molybdenum determination in waste water,silicate rocks and diverse alloys

A simple and highly sensitive spectrophotometric method for molybdenum (VI) determination has been developed. The method is based on solubilizing the binary molybdenum-quercetin complex and sensitizing the color reaction with cetyltrimethylammonium bromide (CTAB). The optimal conditions for the quantitative determination of molybdenum are studied. In KCl-HCl buffered medium of pH 2.3, the molar absorptivity of the 122 (Moquercetin-CTAB) ternary complex is 2.03 × 10⁵ 1 · mol^–1 · cm^–1 at 420 nm. The system obeys Beer's law up to 0.30 g/ml of molybdenum and the sensitivity index is 0.47 ng · cm^–2. The method is free of interference of most of the common metal ions and anions. The developed procedure has been successfully applied to molybdenum determination in waste water, silicate rocks and diverse alloys.     

Spectrophotometric determination of some pharmaceutically-important aminoquinoline antimalarials

A simple and rapid spectrophotometric method for the assay of amodiaquine hydrochloride, chloroquine phosphate and primequine phosphate is described. The method is based on the interaction of the drug with tetracyanoethylene to give a stable charge transfer complex. The spectra of the complex show maxima at 413, 415 and 415nm, respectively, with high apparent molar absorptivities. Beer's law is obeyed in the concentration ranges 2–12, 1–8 and 2–12 g ml^–1 of the three drugs studied. The proposed method is applied to the determination of these drugs in certain formulations and the results are favourably comparable to the official methods.     

Simultaneous Determination of Pioglitazone and Glimepiride by High-Performance Liquid Chromatography

A rapid and accurate HPLC method has been developed for simultaneous determination of pioglitazone and glimepiride. Chromatographic separation of the two pharmaceuticals was performed on a Cosmosil C₁₈ column (150 mm × 4.6 mm, 5 m) with a 45:35:20 (v/v) mixture of 0.01 m triammonium citrate (pH adjusted to 6.95 with orthophosphoric acid), acetonitrile, and methanol as mobile phase, at a flow rate of 1.0 mL min^–1, and detection at 228 nm. Separation was complete in less than 10 min. The method was validated for linearity, accuracy, precision, limit of quantitation, and robustness [1, 2]. Linearity, accuracy, and precision were found to be acceptable over the ranges 2.50–30.00 g mL^–1 for pioglitazone and 0.10–10.00 g mL^–1 for glimepiride.     

Kinetic fluorimetric determination of carbamazepine in serum by the stopped-flow technique

Summary A simple, fast method for the determination of carbamazepine in serum is reported for the first time. It is based on the fluorescent reaction of this drug with cerium(IV) in an acid medium. A stopped-flow mixing module coupled to a conventional spectrofluorimeter is used for this purpose. The linear range of the proposed method is 0.04–140 g ml^–1 of carbamazepine and the detection limit is 0.01 g ml^–1. The within- and between-assay precision data and selectivity results show the method to be adequate for the determination of carbamazepine in serum by including a preliminary extraction step with dichloromethane. Analytical recoveries from different serum samples are reported.     

Direct spectrophotometric method for the determination of cobalt with indane 1,2,3-trionetrioxime in aqueous medium

A simple, sensitive and selective Spectrophotometric method has been developed for the determination of cobalt using indane 1,2,3-trionetrioxime (ITT): The method is based on the colour reaction between ITT and cobalt(II) in sodium acetate-acetic acid buffer (pH 4.5–7.5) medium. The calibration graph for measurement at 320 nm is linear in the range 1.18–23.60g of cobalt per 25 ml, with molar absorptivity of 5.32×10⁴1mol^–1 cm^–1. The effect of interfering ions has been studied and the method was applied to the determination of cobalt in alloys, with good results.     

Extraction-spectrophotometric determination of amprolium hydrochloride using bromocresol green, bromophenol blue and bromothymol blue

A new procedure for the determination of amprolium hydrochloride by reaction with bromocresol green (BCG), bromophenol blue (BPB) and bromothymol blue (BTB) has been developed. The method consists of extracting the yellow ion-pair formed into chloroform from aqueous medium. The ion-pairs have absorption maxima at 420, 410 and 415 nm with molar absorptivities of 3.64 × 10⁴, 3.12 × 10⁴ and 2.31 × 10⁴1 mol^–1 cm^–1 for BCG, BPB and BTB, respectively. The method obeys Beer's law over the concentration ranges 0.6–12.0, 0.12–8.8 and 1.2–11.3 ag/ml amprolium hydrochloride for BCG, BPB and BTB, respectively. The method is simple, precise (relative standard deviation 0.665–2.210%), accurate (recovery 97.8–100.8%) and easily applied for pharmaceutical quality assurance for amprolium hydrochloride in raw materials and in formulated veterinary soluble powder.     

Flow injection method for the fluorimetric determination of Zn with 8-(benzenesulphonamido) quinoline

The development of a fluorimetric method for the determination of zinc, based on the fluorescence of the zinc-8-(benzenesulphonamido) quinoline chelate in a micellar medium of sodium dodecylsulfate, is reported. The detection limit is 0.2 g l^–1, the working range is 0.5–700 g l^–1, and the sample throughput is 145 h^–1. The method was evaluated for the determination of zinc in food samples.A batch procedure for the simultaneous determination of zinc and cadmium, based on the synchronous and derivative spectra, is also proposed.     

Simultaneous measurements of formaldehyde and ozone in air by annular denuder-HPLC techniques

Summary A denuder sampling method combined with HPLC analysis for the simultaneous determination of formaldehyde and ozone in ambient air is described. It is based on the reactions of CH₂O and O₃ with 2,4-dinitrophenylhydrazine (DNPH) and 4-allyl-2-methoxyphenol (eugenol)_respectively, both acting as coatings of two annular denuders connected in series. Formaldehyde released from the ozonolysis of eugenol is quantitatively collected on a third downstream DNPH-coated denuder. The two DNPH denuders are then extracted and analyzed as hydrazone derivative by HPLC with UV absorbance detection.The stoichiometric factor of the eugenol-ozone reaction was found to be 2.0±0.1 moles of O₃ per mole of CH₂O. The limits of detection are 0.8gm^–3 CH₂O and 3gm^–3 O₃ for 100l air sampled, corresponding to 1-h sampling at 1.7l min^–1.     

3-Hydroxy-2-(2-thienyl)-4H-chromen-4-one as a new reagent for the extraction and trace determination of molybdenum(VI)

A simple, sensitive and selective method for the extraction and trace determination of molybdenum(VI) has been developed; it is based on its reaction with 3-hydroxy-2-(2-thienyl)-4H-chromen-4-one (HTC) in sulphuric acid medium. The 1:2 Mo (VI)-HTC yellow complex is quantitatively extractable into chloroform (_max 420 nm) and is stable for more than 4 h. The procedure eliminates the interference of a large number of metal ions and complexing agents. Beer's law is obeyed in the range of 0–2.85 g Mo/mL with a molar absorptivity, Sandell's sensitivity and standard deviation of 5.28×10⁴ L mol^–1 cm^–1, 0.0018 g Mo/cm² and ±0.0054, respectively. The method has successfully been used for the spectrophotometric determination of molybdenum in steel samples.