Comparison of methods for the spectrophotometric determination of phenols in automobile exhaust fumes

Summary The piperonal chloride reaction has been used for the quantitative determination of phenols in raw automobile exhaust fumes. This method is compared with five other methods found suitable for this purpose, and accuracy, sensitivity, and simplicity of the procedures are evaluated. Recommendations are made for the selection of methods.

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Zusammenfassung Die quantitative Bestimmung von Phenolen in rohen Automobilauspuffgasen wurde unter Benutzung der Reaktion mit Piperonalchlorid ausgeführt. Diese Methode wurde mit fünf anderen für diesen Zweck geeignet erscheinenden Verfahren hinsichtlich Genauigkeit, Empfindlichkeit und Handlichkeit verglichen, woraus sich Vorschläge für die Wahl der jeweils geeignetsten Methode ergeben.

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Résumé On a utilisé la réaction au chlorure de pipéronal pour doser les phénols dans les fumées d'échappement brutes des automobiles. On compare cette méthode avec cinq autres que l'on estime satisfaisantes et l'on évalue la précision, la sensibilité et la simplicité des procédés. On donne des recommandations pour la sélection des méthodes.

     

分光光度法测定二氢乳清酸酶酶活的比较

分别采用紫外分光光度法测定二氢乳清酸(DHO)的减少量、PDAB显色法测定N-氨甲酰-天冬氨酸(CA-asp)的生成量来测定二氢乳清酸酶酶活,并对两种方法进行了比较。结果表明紫外分光光度法和PDAB显色法均有良好的回收率,分别为99.4%～101.2%、98.0%～101.3%。但由于PDAB显色法的检测范围为0.05～1.00g/L,较紫外法的检测范围0.05～0.30g/L更为宽泛,仪器要求低,便于实际操作。因此,采用PDAB显色法测定二氢乳清酸酶酶活较为方便。     

Sensitive spectrophotometric methods for the determination of pindolol

Two simple, sensitive and reproducible visible spectrophotometric methods for the determination of Pindolol in amounts as low as 1 g are described. The first method is based on the oxidation of Pindolol by sodium nitrite under acidic conditions and the coupling of the oxidised intermediate withN-1-(naphthyl)ethylenediamine dihydrochloride (NED) to the colored product. The spectrum of the colored solution is strongly dependent on the length of the incubation period at room temperature during oxidation (3 min, _max 620 nm; 10 min or above _max 540 nm). Other couplers [diphenylamine (DPA) or 1-naphthylamine (-NA)] or indole derivatives (indole, tryptophan or isatin) when used instead of NED or Pindolol, respectively, also react to give a colored product with same maximum in each case irrespective of the length of the incubation period during oxidation. The second method is based on the coupling reaction involving Pindolol and 1,2-naphthaquinone-4-sulphonic acid sodium salt to form a coloured product (_max 660 nm). Both the methods have been employed to determine Pindolol content in bulk forms and pharmaceutical preparations.     

Comparison of three colorimetric methods for the determination of manganese in freshwaters

Three calorimetric methods for the determination of manganese in freshwaters have been investigated and compared with the atomic-absorption spectrometry (AAS) method. Two of the methods, viz. the formaldoxime (FAD) and pyridylazonaphthol (PAN) methods were found to yield poor calibration curves upon standardization, and to have high average errors for the estimation of manganese concentrations in standard solutions. The FAD method, when applied to freshwater samples, was found to be subject to an interfering UV absorbance which could not be negated successfully by a reagent blank; the method thus tended to give high estimations at low concentrations of manganese, but the results obtained also appear to be very sensitive to the nature of the freshwater matrix. On the other hand the PAN method was found to give very high estimations for the concentration of manganese, in both standard solutions and in freshwater samples, owing to the nature of the absorbance of the ligand used for manganese determination. This method also appears to be affected by the freshwater matrix, leading to gross overestimation of manganese levels. A third method, based on a porphyrin ligand [T-(4-CP)P], was found to give results comparable with those of the AAS method in estimating the soluble manganese content in freshwaters.     

Comparison of HPLC and UV spectrophotometric methods for the determination of cefuroxime sodium in pharmaceutical products

This paper describes the development and evaluation of a HPLC and UV spectrophotometric methods to quantify cefuroxime sodium in injectables. HPLC analysis were carried out using a C18 Wat 054275 column and a mobile phase composed of methanol and water (70:30), with a flow rate of 0.8 mL/min and UV detection at 280 nm. For the spectrophotometric analysis, water was used as solvent and the wavelength of 280 nm was selected for the detection. Both methods were found to quantify cefuroxime sodium in injectables accurately. Therefore HPLC and UV methods presented the most reliable results for the analyses of injectables.     

Simultaneous determination of carotenoids, tocopherols, and gamma-oryzanol in crude rice bran oil by liquid chromatography coupled to diode array and mass spectrometric detection employing silica C30 stationary phases

Crude rice bran oil contains tocopherols (vitamin E), carotenoids (vitamin A), and phytosterols, which possess antioxidant activities and show promising effects as preventive and therapeutic agents. The aim of this work was to establish methods and to compare C18 and C30 silica stationary phases in order to separate and detect tocopherols, carotenoids, and gamma-oryzanol in one single run. Comparing RP-LC on silica C18 and C30, higher resolution between all target compounds was obtained using the C30 stationary phase. Methanol was used as eluent and the elution strength was increased by the addition of tert-butyl methyl ether for highly hydrophobic analytes such as gamma-oryzanol. Detection was accomplished by diode array detection from 200 to 500 nm. Absorbance maxima were found at 295 nm for tocopherols, 324 nm for gammaoryzanol, and 450 nm for carotenoids. Furthermore, compounds were characterized and identified on the basis of their UV-spectra. Both RP systems were coupled to MS (LC-MS) by using an atmospheric pressure chemical ionization interface.     

Three simple spectrophotometric methods for the determination of sulphinpyrazone

Three simple and sensitive spectrophotometric methods for the determination of sulphinpyrazone (SP) in bulk samples and pharmaceutical formulations are described. They are based on the oxidation of sulphinpyrazone with excess N-bromosuccinimide (NBS) and determination of the unconsumed NBS with metol-isonicotinic acid hydrazide (method A, lambda(max): 620 nm); by the reduction of Folin-Ciocalteu reagent (method B, lambda(max) 770 nm); or by the formation of a chloroform-soluble, coloured ion-association complex between the drug and Methylene Violet (MV) at pH 7.0 (method C, lambda(max) 545 nm).     

Extractive spectrophotometric methods for determination of zolmitriptan in tablets

Two simple and sensitive extractive spectrophotometric methods have been developed for determination of zolmitriptan (ZTP) in tablets. These methods are based on the formation of yellow ion-pair complexes between ZTP and tropaeolin OO (TPOO) and bromothymol blue (BTB) in citrate-phosphate buffer of pH 4.0 and 6.0, respectively. The formed complexes were extracted with dichloromethane and measured at 411.5 and 410 nm for TPOO and BTB, respectively. The best conditions of the reactions were studied and optimized. Beer's law was obeyed in the concentration ranges of 2-20 and 1.5-17 microg/mL with molar absorptivities of 1.42 x 10(4) and 1.60 x 10(4) L/mol/cm for the TPOO and BTB methods, respectively. Correlation coefficients were 0.9998 and 0.9999 for TPOO and BTB methods, respectively. Limits of detection of the TPOO and BTB methods were 0.341 and 0.344 microg/mL, respectively, and the limits of quantitation were 1.034 and 1.051 microg/mL, respectively. Sandell's sensitivity and stability constant were also calculated. The proposed methods have been applied successfully for the analysis of the drug in its dosage forms. No interference was observed from excipients present in tablets. Statistical comparison of the results with those obtained by a high-performance liquid chromatography method showed excellent agreement and indicated no significant differences in accuracy and precision.     

Comparison of three analytical methods for the determination of trace elements in whole blood

Three different analytical techniques were compared in a study of the role of trace elements in multiple sclerosis. Data for eight elements (Cd, Co, Cr, Cu, Mg, Mn, Pb, Zn) from neutron activation, flame atomic absorption and electrothermal atomic absorption methods were compared and evaluated statistically. No difference (probability less than 0.001) was observed in the elemental values obtained. Comparison of data between suitably different analytical methods gives increased confidence in the results obtained and is of particular value when standard reference materials are not available.     

Kinetic and maximum-absorbance spectrophotometric methods for the determination of olanzapine

Two simple and sensitive spectrophotometric methods were developed for the determination of olanzapine (OLZ) based on its oxidation with potassium iodate in a sulfuric acid medium to produce an intense violet-colored species exhibiting a maximum absorbance at 537 nm. The initial rate of formation and the maximum absorbance of the violet-colored oxidized product were monitored, in the first and second methods. The various experimental parameters affecting the rate of development and stability of the oxidized product were carefully studied and optimized. Beer’s law was obeyed up to 4.0 and 7.0 μg cm⁻³ OLZ with correlation coefficients of 0.998 and 0.996 (n = 6) and detection limits of 0.1 and 0.15 μg cm⁻³, for the initial rate and maximum absorbance methods. The proposed methods were conveniently applied to the determination of OLZ in its dosage forms and in spiked serum samples.     

Batch and flow-injection methods for the spectrophotometric determination of olanzapine

An indirect batch spectrophotometric and direct flow-injection (FI) visible spectrophotometric methods have been developed for the determination of the novel anti-psychotic drug olanzapine (OLA). The batch method is based on the oxidation of olanzapine by a known excess of potassium hexacyanoferrate(III) in the presence of the mixture of sulphuric and phosphoric acids (1:1 (v/v)). The absorbance of unreacted oxidant is measured at 425 nm. The absorbance decreases linearly with increasing concentration of the assayed drug. The FI method with detection at 540 nm is based on the direct oxidation of olanzapine one of two oxidants, cerium(IV) sulphate or potassium hexacyanoferrate(III) in acidic medium. The calibration graph were linear over the range of 2.5-40 μg ml⁻¹ in the batch method and 0.05-300 and 0.5-250 μg ml⁻¹ in the FI methods, used cerium (IV) sulphate and potassium hexacyanoferrate (III) respectively. Both FI methods gave similar results in terms of precision and accuracy. The relative standard deviation (R.S.D.), was <1%. The accuracy, obtained from recovery experiments, was 97.9-99.4%. The batch method gave slightly higher R.S.D. values (up to 2.3%) and lower values of accuracy (the recovery was between 96.5 and 96.6%). The methods developed were applied to the determination of olanzapine in a pharmaceutical product.     

Kinetic and maximum-absorbance spectrophotometric methods for the determination of olanzapine

Two simple and sensitive spectrophotometric methods were developed for the determination of olanzapine (OLZ) based on its oxidation with potassium iodate in a sulfuric acid medium to produce an intense violet-colored species exhibiting a maximum absorbance at 537 nm. The initial rate of formation and the maximum absorbance of the violet-colored oxidized product were monitored, in the first and second methods. The various experimental parameters affecting the rate of development and stability of the oxidized product were carefully studied and optimized. Beer’s law was obeyed up to 4.0 and 7.0 μg cm⁻³ OLZ with correlation coefficients of 0.998 and 0.996 (n = 6) and detection limits of 0.1 and 0.15 μg cm⁻³, for the initial rate and maximum absorbance methods. The proposed methods were conveniently applied to the determination of OLZ in its dosage forms and in spiked serum samples. Correspondence: Ashraf A. Mohamed, Department of Chemistry, Faculty of Science, King Faisal University, P.O. Box 1759, Al-Hassa-31982, Saudi Arabia.     

Comparison of three methods for the determination of the electrical conductivity of ion-exchange polymers

The development of ion-exchange membranes techniques using an electrical potential gradient incite often to define the electrical conductivity of this category of functional polymers. The investigation methods of this conductivity did not stop to vary, to such a point that some results can be contradictory. So we have determined this dynamic characteristic in comparing three recent methods. This has been done with three ion-exchange membranes often used in industrial applications: CM1 and CM2, made from sulfonated and crosslinked polystyrene, and Nafion^® 117 made from sulfonated uncrosslinked polytetrafluoroethylene. Measurements were achieved in sodium chloride solutions, at concentrations from 0.1 to 2 mol l⁻¹. The results show, whatever the polymer microstructure, non-negligible disparities between the three methods.     

Comparison of spectrophotometric and HPLC methods for determination of lipid peroxidation products in rat brain tissues

Two methods for determination of lipid peroxidation (LPX) products in rat brain homogenates were compared. The thiobarbituric acid (TBA) test and HPLC assay for analysis of malondialdehyde (MDA) were applied. Rat brain homogenate dissolved in tris(hydroxymethyl)aminomethane hydrochloride (Tris-HCl) was mixed with TBA and H₃PO₄ and heated at 100°C to form colored complex that was extracted into butanol. No significant differences were found between the contents of TBA-reacting substances and their amount deduced from the MDA-TBA analysis. The presented results show that LPX products in brain homogenates can be determined without interferences also by the TBA test. Moreover, a survey of various methods used for the sample preparation before analysis of LPX products originating from different brain areas was made and compared with the obtained results.     

Four spectrophotometric methods for determination of nitrofurazone in pharmaceutical formulations

Four simple and sensitive visible spectrophotometric methods (A-D) for the determination of nitrofurazone in bulk samples and pharmaceutical formulations are described. They are based on the formation of colored species by treating either its reduction product with 3-methylbenzothiazolin-2-one hydrazone in the presence of ferric chloride (method A: _max 600 nm) or its hydrolysis product with thiobarbituric acid (method B: _max 520 nm, 440 nm) or barbituric acid (method C: _max 400 nm) or by oxidizing it with excess N-bromosuccinimide and determining the consumed NBS using metol-isonicotinic acid hydrazide (method D: _max 620 nm).     

Comparison of three gas chromatography methods for the determination of slip agents in polyethylene films

Polymers require the use of some slip agents, such as oleamide and erucamide, in order to reduce their friction coefficient and to make films easier to handle. In this communication, three analytical methods consisting in pressurized liquid extraction (PLE) and gas chromatography (GC) are used to determine oleamide and erucamide in polyethylene films. The sample was extracted with pure isopropanol (two times) at 105 degrees C for 16 min. Then, the liquid extract containing oleamide and erucamide was analyzed by GC and three different detection systems: flame ionization detector (FID), thermoionic selective detector (TSD) and ion-trap mass spectrometry detector (MSD). Oleamide and erucamide were separated using a 30 m x 0.25 mm (I.D.) 5% phenyl-95% dimethyl-polysiloxane capillary column in 12 min. The chromatographic methods were characterized and compared in terms of repeatability, linearity and sensitivity. The GC-FID and GC-TSD methods were linear up to about 60 microg ml(-1), whereas the linear range for the GC-MSD method was shorter, from 20.5 to 42 microg ml(-1). LODs identified with GC-MSD were two times higher than those identified with the other two methods. Repeatability values (expressed as relative standard deviation) of less than 2.5% were found for FID and TSD but they were above 10% for MSD. Finally, each method was applied to determine the content of erucamide and oleamide in several polyethylene films and the results obtained were compared with those obtained from the nitrogen content measured by pyrolysis and gas-phase chemiluminescence. No significant differences were observed between the results of the methods.     

Comparison of atomic absorption spectrometric,spectrophotometric, and fluorimetric methods for determination of aluminum in water

Three methods for quantifying aluminum in water samples are compared. An electrothermal atomic absorption method is assumed to be free of interferences and has an applicable range of 10 to above 1000 μg Al l^-1. The colorimetric ferron method has multiple interferences and is useful in the 50–1500 μg Al l^-1 range. The fluorimetric method based on lumogallion has few important interferences and is useful to below 1 μg Al l^-1.     

Studies on spectrophotometric methods of thallium determination

Eight sensitive methods of spectrophotometric determination of thallium have been studied and compared experimentally. The comparative criteria were: molar absorptivity, colour contrast of the basic reaction, working concentration interval and practical determination limit for thallium, precision of the method (the standard deviation), and selectivity. According to these criteria the best methods of extraction-spectrophotometric determination of thallium are those using Brilliant Green, Crystal Violet, Methyl Violet and Rhodamine B. The sensitivity depends very much on the oxidant used for conversion of Tl(I) into Tl(III). The oxidants suitable for each of the recommended methods are discussed.     

Modifications of spectrophotometric methods for total phosphorus determination in meat samples

Spectrophotometric determination of total phosphorus in meat samples was modified using the molybdenum blue reaction with the following reducing agents: ascorbic acid (AA), hydrazine sulphate (HS), and mixture of hydroquinone and hydrazine sulphate (HHS). Proposed methods were validated by evaluation of statistical parameters such as: linearity, sensitivity, limits of detection (DL) and quantification (QL), precision, and accuracy, against the standard and malachite green (MG) modified procedures and by applying food certified materials. The values of within-day and between-days precision in meat samples for all tested reducing agents were better than 3.4 % and 4.2 %, respectively. The recoveries for CRMs analyses were between 92 % and 102.3 %. Obtained results suggest usefulness of the hydroquinone and hydrazine sulphate mixture in the determination of phosphorus ions.     

Coupled liquid chromatography-gas chromatography for the rapid analysis of gamma-oryzanol in rice lipids

An approach based on on-line coupled liquid chromatography-gas chromatography (LC-GC) was developed for the rapid analysis of gamma-oryzanol in rice. Total lipids were extracted from rice and subjected to LC-GC without any prior purification. gamma-Oryzanol was pre-separated by HPLC from rice lipids and transferred on-line to GC analysis in order to separate its major constituents. 24-methylenecycloartanyl ferulate, cycloartenyl ferulate, campesteryl ferulate, beta-sitosteryl ferulate and campestanyl ferulate. The identities of the compounds were confirmed by off-line GC-MS analysis. Total gamma-oryzanol content could be quantified by HPLC-UV detection and the distribution of gamma-oryzanol constituents could be determined by on-line coupled GC analysis. The proposed methodology paves the way for high-throughput investigations providing information on natural variations in gamma-oryzanol content and its composition in different rice varieties.