Flow-injection chemiluminescent determination of metoclopramide hydrochloride in pharmaceutical formulations and biological fluids using the [Ru(dipy)(3)(2+)]-permanganate system

A flow-injection (FI) methodology using (2,2′-dipyridyl) ruthenium(II) [Ru(dipy)₃²⁺] chemiluminescence (CL) was developed for the rapid and sensitive determination of metoclopramide hydrochloride. The method is based on the CL reaction of metoclopramide with Ru(dipy)₃²⁺ and KMnO₄ in a sulfuric acid medium. Under the optimum conditions, a calibration graph was obtained over the concentration range 0.005-3.5 μg ml⁻¹ with a limit of detection (S/N=2) of 1 ng ml⁻¹. The correlation coefficient was 0.99993 (n=8) with a relative standard deviation of 0.48% for 10 determinations of 1 μg ml⁻¹ of drug. The method was successfully applied to the determination of metoclopramide in pharmaceutical preparations and biological fluids after IP administration of 25 mg kg⁻¹ dose to rats. The elimination half-life was 2.5±0.4 h.     

Fluorimetric determination of ascorbic acid with o-phenylenediamine

A simple and sensitive fluorimetric method for the determination of ascorbic acid (AA) is described. The method is based on the condensation reaction between AA and o-phenylenediamine (OPDA) in the absence of the oxidant. The fluorescence intensity is measured at excitation and emission wavelengths of 360 and 430 nm, respectively. Under optimum condition, a linear relationship is obtained between the fluorescence intensity and the concentration of AA in the range of 0.05-40 μg ml⁻¹. The detection limit is 0.006 μg ml⁻¹, which is obviously lower than that of other fluorimetric methods reported.     

Determination of trivalent europium using flow injection chemiluminescence method

A simple flow injection chemiluminescence (CL) analysis method for the determination of europium in mineral samples is reported. It is based on luminescence produced by NaIO₄-H₂O₂ CL system sensitized by [Eu(EDTA)]⁻. The relative chemiluminescence intensity of the Eu³⁺-EDTA-NaIO₄-H₂O₂ system is proportional to the amount of Eu³⁺. The optimized experimental conditions were investigated. The linear range and detection limit for Eu³⁺ are 2.0×10⁻⁷ to 1.0×10⁻⁵ and 6.2×10⁻⁸ M, respectively. The sample throughput of the method is 80 samples/h. This method was successfully applied to the determination of europium in rare earth oxides. And the mechanism of chemiluminescence is proposed.     

Determination of bisphenol A in water via inhibition of silver nanoparticles-enhanced chemiluminescence

Sensitive detection of trace bisphenol A (BPA) in water samples has been accomplished via inhibition of luminol chemiluminescence (CL) by BPA on the silver nanoparticles (AgNPs)-enhanced luminol–KMnO₄ CL system for the first time. Under the optimized experimental conditions, the CL intensity was found to be proportional to the concentration of BPA ranging from 1.0 × 10⁻⁸ to 5.0 × 10⁻⁵ g L⁻¹. The detection limit (3σ) was estimated to be 1 × 10⁻⁹ g L⁻¹. Such a concentration level is approximately 1–4 orders of magnitude lower than those reported by other methods. The feasibility of the method for determination of BPA in real water samples has been demonstrated. Via examining CL and UV–vis spectra of the CL system, possible mechanism inherent in the AgNPs-enhanced CL assay and the follow-up inhibition of BPA on the above system was proposed. The method described herein is simple, selective and obviates the need of extensive sample pretreatment.     

Kinetic spectrophotometric determination of trace manganese (II) with dahlia violet in nonionic microemulsion medium

A new catalytic kinetic spectrophotometric method has been developed for the determination of trace amount of manganese (II) in nonionic microemulsion medium. The method is based on the catalytic effect of manganese (II) on the oxidation of dahlia violet by potassium periodate with nitrilotriacetic acid as an activitor in the presence of nonionic microemulsion. Under the optimum conditions, the calibration graph is linear in the range of 0.0004-0.0056 μg ml⁻¹ of manganese (II) at 580 nm. The detection limit achieved is 3.75×10⁻⁵ μg ml⁻¹. Manganese (II) in foodstuff samples was determined with satisfactory results.     

Flow injection kinetic spectrophotometric determination of trace amounts of Se(IV) in seawater

A simple, accurate, sensitive and selective flow injection catalytic kinetic spectrophotometric method for rapid determination of trace amounts of selenium is proposed in this paper. The proposed method is based on the accelerating effect of Se(IV) on the reaction of ethexlenediamine tetrecetic acid disodium salt (EDTA) and sodium nitrate with ammonium iron(II) sulfate hexahydrate in acidic media. The absorbance intensity was registered in this reaction solution at 440 nm. The calibration graph is linear in the range of 5 × 10⁻⁹-2 × 10⁻⁷ and 2 × 10⁻⁷-2 × 10⁻⁶ g ml⁻¹. The detection limit is 2 × 10⁻⁹ g ml⁻¹. The relative standard deviation was 3.4% for 5 × 10⁻⁸ g ml⁻¹ Se(IV) (n = 11), 2.7% for 5 × 10⁻⁷ g ml⁻¹ Se(IV) (n = 11). This method is very simple, rapid and suitable for automatic and continuous analysis. The presented system has been applied successfully to determination of Se(IV) of seawater samples.     

Determination of ketotifen by using calcein as chemiluminescence reagent

Chemiluminescence (CL) was observed when potassium hexacyanoferrate(III) reacted with the mixture of calcein and ketotifen. Interestingly, the CL intensity would be enhanced by trace amounts of Mg²⁺ and the CL intensity was strongly dependent on ketotifen concentration. Based on this phenomenon, a flow injection CL method was established for the determination of ketotifen. The possible CL mechanism is proposed based on the kinetic characteristic of the CL reaction, CL spectrum, ultraviolet (UV) spectra and fluorescent spectra. The CL intensity was correlated linearly with concentration of ketotifen over the range of 6.0 × 10⁻⁹ to 2.0 × 10⁻⁷ g mL⁻¹ and the detection limit was 3 × 10⁻⁹ g mL⁻¹. The relative standard deviation was 1.8% for 2.0 × 10⁻⁸ g mL⁻¹ ketotifen (n = 11). This method was applied to the determination of ketotifen in the tablets successfully.     

Simultaneous determination of zirconium and hafnium as ternary complexes with 5-Br-PADAP and fluoride using solid-phase extraction and reversed-phase liquid chromatography

Solid-phase extraction (SPE) along with reversed-phase liquid chromatography (RP-LC) was used for the simultaneous determination of Zr(IV) and Hf(IV) by means of their ternary chelates with fluoride and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP). The conditions of SPE sorption were examined in detail: type of SPE column, volume of the sample, volume of the eluent, concentrations of metal ions, fluoride salt, chromogenic reagent, organic phase, and pH. It was established that the sorption of Zr(IV) and Hf(IV), as their ternary chelates, on SPE Zorbax SPE C18 (EC) cartridge was the most efficient, when the sample containing metal ion (Zr(IV), Hf(IV), both, up to 2 μg), 5-Br-PADAP 1.5×10⁻⁴, NaF 7.5×10⁻⁵ mol l⁻¹, methanol 40%, pH 4.5±1 was applied for the SPE sorption. The chelates were discarded from SPE cartridge using acetonitrile/water (99.75+0.25, v/v) eluent containing 3.8×10⁻⁴ mol l⁻¹ sodium fluoride and subsequently separated by RP-LC method. The RP-LC separation of both chelates was optimized and Zorbax SB-C18 analytical LC column along with acetonitrile/water (65+35, v/v) eluent containing the 1.5×10⁻⁴ mol l⁻¹ sodium fluoride was used. The established SPE/LC conditions allow Zr(IV) 0.08-2.0 μg and Hf(IV) 0.04-2.0 μg determination in a sample volume up to 150 ml. The detection limits, 0.03 μg Hf(IV) and 0.05 μg Zr(IV), were obtained. Recoveries, (94±2)% for Hf(IV) chelate and (106±2)% for Zr(IV) chelate were obtained, when 1 μg of Zr(IV) and Hf(IV) ions were determined by the present SPE/LC method from the sample volume of 100 ml. The established, pre-concentration SPE conditions, along with the LC separation and determination allow the assay of Zr(IV) and Hf(IV) in complicated matrix materials. The present SPE/LC method was applied to the determination of Zr(IV) and Hf(IV) in tap water and reference geological material (rock, NCS DC 73303; certified content: Zr, 27.7×10⁻³% (w/w) and Hf, 6.5×10⁻⁴% (w/w)).     

Investigation on enhanced chemiluminescence reaction systems with bis(hydrogenperiodato) argentate(III) complex anion for fluoroquinolones synthetic antibiotics

A novel chemiluminescence (CL) reaction system with bis(hydrogenperiodato) argentate(III) complex anion (Ag(III) complex, [Ag(HIO₆)₂]⁵⁻), for the first time, is developed for the determination of lomefloxacin (LMFX), enrofloxacin (ENLX) and pefloxacin (PFLX). The possible CL emission mechanism was discussed by comparing the fluorescence emission with CL spectra. The CL conditions of [Ag(HIO₆)₂]⁵⁻-H₂SO₄-LMFX/ENLX/PFLX systems were investigated and optimized. Under the optimized experimental conditions, the CL intensity is proportional to the concentration of the drugs in the range 0.2994-36.80 × 10⁻⁷ g mL⁻¹ for LMFX, 4.00-30.0 × 10⁻⁷ g mL⁻¹ for ENLX and 1.54-27.64 × 10⁻⁷ g mL⁻¹ for PFLX. The limit of detection (s/n = 3) was 9.1 × 10⁻⁹ g mL⁻¹ for LMFX, 3.1 × 10⁻⁹ g mL⁻¹ for ENLX and 4.4 × 10⁻⁹ g mL⁻¹ for PFLX. The recovery of LMFX, ENLX and PELX from the spiked pharmaceutical preparations was in the range of 92.3-105% with the RSDs of 0.5-2.7%. For urine, serum and milk samples the recoveries of the three drugs were in the range of 85.1-107% for LMFX with the RSDs of 2.3-3.4%. 80.2-112% for ENLX with the RSDs of 1.4-2.8%, and 87.8-114% for PFLX with the RSDs of 1.6-2.7%. The proposed method was applied successfully to the determination of these compounds in real samples.     

Kinetic spectrophotometric determination of trace amounts of selenium based on the catalytic reduction of maxilon blue-SG by sulfide

A simple and sensitive catalytic spectrophotometric method was developed for the determination of trace amounts of selenium. The method is based on the catalytic effect of selenium in form Se(IV) on the reduction of Maxilon Blue-SG by sodium sulfide. Indicator reaction is followed spectrophotometrically by measuring the absorbance change at λ_max=654 nm and constant temperature (30.0±0.1 °C) by fixed time method. Selenium could quantitatively be determined in the range 0.004-0.200 μg ml⁻¹ Se(IV) with a detection limit of 0.205 ng ml⁻¹ Se(IV). All of the variables that affected the reaction rate were investigated and established optimum conditions to give maximum sensitivity. The R.S.D.s of the method (N=12) for the Se(IV) concentrations of 0.004, 0.016, 0.040 and 0.160 μg ml⁻¹ are between 2.27 and 0.32%, respectively, and depended on Se(IV) concentration. The interference effect of various anion and cations on the Se(IV) determination was also fully studied. The selectivity of catalytic reaction was greatly improved with the use of the strong cation exchange resin. The developed kinetic-catalytic reaction was applied to the determination of selenium in real samples as Antioxidant-S, Selsun (which is a healthcare product for the treatment of dandruff) and analytical grade sodium metabisulfite, and in spring water samples without any pre-concentration. The acceptable recoveries were obtained by the method for appropriate standard Se(IV) additions. The method is simple, practical and suitable for using in small laboratories owing to its precision, sensitivity and relative selectivity.     

Flow-injection chemiluminescence determination of aminomethylbenzoic acid and aminophylline based on N-bromosuccinimide-luminol reaction

A novel and sensitive chemiluminescence (CL) method for the determination of aminomethylbenzoic acid and aminophylline coupled with flow-injection analysis (FIA) technique is developed in this paper. It is based on the inhibition effect of the studied drugs on the chemiluminescence emission of N-bromosuccinimide-luminol (NBS-luminol) system. Under the optimum conditions, the decreased CL intensity is linear with the concentration of aminomethylbenzoic acid in the range of 2×10⁻⁸ to 1.0×10⁻⁶ g ml⁻¹ and with the concentration of aminophylline in the range of 1×10⁻⁷ to 7.0×10⁻⁶ g ml⁻¹, respectively. The detection limit is 7.0×10⁻⁹ g ml⁻¹ for aminomethylbenzoic acid (3σ) and 3.4×10⁻⁸ g ml⁻¹ for aminophylline (3σ). The relative standard deviations (R.S.D.) for 11 parallel measurements of 2.0×10⁻⁷ g ml⁻¹ aminomethylbenzoic acid and 1.0×10⁻⁶ g ml⁻¹ aminophylline are 2.6 and 3.0%, respectively. The proposed methods have been applied for the determination of the studied drugs in their pharmaceutical formulations with satisfactory results. The possible use of the proposed system for the determination of aminomethylbenzoic acid in plasma sample was also tested. The possible inhibition mechanism of aminomethylbenzoic acid and aminophylline on luminol-NBS system was discussed briefly.     

Flow-Injection Chemiluminescence Determination of Fluoroquinolones

ABSTRACT

A new flow-injection CL method was developed for the determination of fluoroquinolones including ofloxacin, norfloxacin, ciprofloxacin and lomefloxacin in pharmaceutical preparations, based on the chemiluminescence reaction of sulphite with cerium(IV) sensitized by these compounds. The linear ranges are 0.04 to 4.0 μg ml^?1 for ofloxacin and 0.4 to 40.0 μg ml^?1 for norfloxacin, ciprofloxacin and lomefloxacin, respectively. The detection limits are 0.016 μg ml^?1 for ofloxacin and 0.16 μg ml ^?1 for norfloxacin, ciprofloxacin and lomefloxacin, respectively. The relative standard deviations (RSD) are 2.1 to 2.6% (n=10) for these fluoroquinolones. The analytical procedure has been applied to the determination of the fluoroquinolones in pharmaceutical commercial formulations. The results are in agreement with those obtained by the official methods.     

Spectrophotometric determination of molybdenum with Alizarin Red S in the presence of poly(sulfonylpiperidinylmethylene hydroxide)

The present work describes a selective and rapid method for the determination of molybdenum with Alizarin Red S (ARS) in the presence of a water soluble polymer, poly(sulfonylpiperidinylmethylene hydroxide) (PSPMH). The ARS modified by PSPMH reacts with molybdenum(VI) in the solutions of pH 3.4-4.0 to produce a red complex. The composition of the complex is 1:4:1 mol ratio of Mo(VI): ARS:PSPMH. The complex obeys Beer's law from 0.05 to 5.50 μg ml⁻¹ with an optimum range. The molar absorptivity is 2.1×10⁴ l mol⁻¹ cm⁻¹ at 500 nm. The interference effects of the foreign cations have been examined and it has been determined that only Cu(II), Al(III) and Fe(III) have to be masked by EDTA and tungsten can be tolerated till 4-fold of molybdenum in case of masking by citrate. The method has been applied to the determination of geological samples without solvent extraction or separation steps.     

Backscattering light detection of nucleic acids with tetraphenylporphyrin-Al(III)-nucleic acids at liquid/liquid interface

A backscattering light (BSL) detection assembly is constructed and applied to the determination of nucleic acids with high sensitivity and selectivity based on the measurements of BSL signals at water/tetrachloromethane (H₂O/CCl₄) interface. In aqueous medium of pH 3, the binary complex of of Al(III)-DNAs could be formed by the interaction of Al(III) with the phosphate group of DNAs, which then could interact with tetraphenylporphyrin (TPP) in tetrachloromethane through liquid/liquid interaction, forming a ternary complex of TPP-Al(III)-DNAs at the interface. It was observed that greatly enhanced BSL signals occurred with maximum peak at 469 nm when the ternary complex of TPP-Al(III)-DNAs were absorbed to the liquid/liquid interface. The enhanced backscattering light intensity (I_BSL) is in proportion to the concentration of calf thymus DNA (ctDNA) and fish sperm DNA (fsDNA) in the range of 0.6-1200 ng ml⁻¹ and 1.1-1200 ng ml⁻¹, respectively. The limits of determination (3σ) are 60 pg ml⁻¹ and 110 pg ml⁻¹, correspondingly. Artificial samples with highly interference backgrounds were determined with the recovery ranging from 94.5 to 106.7%, and relative standard deviation (R.S.D.) less than 2.40%.     

Chemiluminescence determination of citrate and pyruvate and their mixtures by the stopped-flow mixing technique

A novel kinetic chemiluminescent method using the stopped-flow mixing technique has been investigated for the rapid and sensitive determination of citrate and pyruvate. The method is based on a tris(2,2′-bipyridiyl)ruthenium(III) (Ru(bpy)₃³⁺) chemiluminescence (CL) reaction. Ru(bpy)₃³⁺ was generated in the mixing chamber by oxidising tris(2,2′-bipyridyl)ruthenium(II) with cerium(IV). After selecting the best operating parameters, calibration graphs were obtained over the concentration ranges 0.38-38 μg ml⁻¹ and 8.7-1300 ng ml⁻¹ for citrate and pyruvate, respectively. The limits of detection were 0.1 μg ml⁻¹ for citrate and 0.3 ng ml⁻¹ for pyruvate. Based on the differential rate of the chemiluminescent reaction corresponding to citrate and pyruvate, a very simple kinetic procedure was developed for the simultaneous determination of both compounds. Mixtures of citrate and pyruvate in ratios between 15:1 and 1.5:1 were satisfactorily resolved. The proposed method was successfully applied to the determination of citrate in pharmaceutical formulations, pyruvate in animal blood serum and both compounds in human urine.     

Spectrophotometric study of Cd(II), Pb(II), Hg(II) and Zn(II) complexes with 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin

The reaction of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) with Cd(II), Pb(II), Hg(II) and Zn(II) was studied spectrophotometrically and kinetics, equilibrium constants as well as photodecomposition of complexes were determined. It was verified that these metal ions with large radius accelerate the incorporation reaction of zinc into TCPP. On the basis of the mechanism and kinetics of this reaction, a sensitive method for the spectrophotometric determination of trace amounts of Zn(II) has been developed. The molar absorptivity of examined Zn-TCPP complex and Sandell's sensitivity at 423 nm were 3.5×10⁵ M⁻¹ cm⁻¹ and 18.3 ng cm⁻². The detection limit for the recommended procedure was 1.4×10⁻⁹ M (0.9 ng ml⁻¹) and precision in range 20-100 ng ml⁻¹ not exceeds 2.7% RSD. The proposed method applied for zinc determination in natural waters and nutritional supplement was compared with AAS results and declared value.     

A simple and selective flow-injection spectrophotometric determination of copper(II) by using acetylsalicylhydroxamic acid

A new simple, and rapid flow-injection spectrophotometric method is developed for the determination of trace amounts of Cu(II) by using a new chromogenic reagent acetylsalicylhydroxamic acid (AcSHA). The method is based on the formation of colored Cu(II)-(AcSHA)₂ complex. The optimum conditions for the chromogenic reaction of Cu(II) with AcSHA is studied and the colored (green) complex is selectively monitored at λ_max 700 nm. With the reagent carrier solvent (dimethylsulfoxide (DMSO) and acetate buffer, pH 4.2) flow-rate of 1 ml min⁻¹, a detection limit (2S) of 1 μg l⁻¹ Cu(II) was obtained at a sampling rate of 80 sample h⁻¹. The calibration graph was linear in the Cu(II) concentration range 5-120 μg l⁻¹. The relative standard deviation (n=10) was 0.64% for a sample containing 60 μg l⁻¹ Cu(II). The detailed study of various interferences confirmed the high selectivity of the developed method. The method was successfully applied to determine trace amounts of copper(II) in river and seawater samples. The accuracy of the method was demonstrated by the analysis of standard reference materials C12X3500 and C14XHS 50.     

A novel tetrachlorothallate (III)-PVC membrane sensor for the potentiometric determination of thallium (III)

A novel tetrachlorothallate (III) (TCT)-selective membrane sensor consisting of tetrachlorothallate (III)-2,3,5-triphenyl-2-H-tetrazolium ion pair dispersed in a PVC matrix plasticized with dioctylphthalate is described. The electrode shows a stable, near-Nernstian response for 1×10⁻³-4×10⁻⁶ M thallium (III) at 25 °C with an anionic slope of 56.5±0.5 over the pH range 3-6. The lower detection limit and the response time are 2×10⁻⁶ M and 30-60 s, respectively. Selectivity coefficients for Tl(III) relative to a number of interfering substances were investigated. There is negligible interference from many cations and anions; however, iodide and bromide are significantly interfere. The determination of 0.5-200 μg ml⁻¹ of Tl(III) in aqueous solutions shows an average recovery of 99.0% and a mean relative standard deviation of 1.4% at 50.0 μg ml⁻¹. The direct determination of Tl(III) in spiked wastewater gave results that compare favorably with those obtained by the atomic absorption spectrometric method. The electrode was successfully applied for the determination of thallium in zinc concentrate. Also the tetrachlorothallate electrode has been utilized as an end point indicator electrode for the determination of thallium using potentiometric titration.     

Chemiluminescence determination of carbofuran at trace levels in lettuce and waters by flow-injection analysis

A simple, fast chemiluminescence (CL) flow-injection (FI) method based on the reaction of luminol with KMnO₄ in alkaline medium has been described for the direct determination of carbofuran. The method is based on the enhancing effect in the emission light from the oxidation of luminol produced in presence of carbofuran. The optimisation of instrumental and chemical variables influencing the CL response of the method has been carried out by applying experimental design, using the proposed flow-injection manifold. Under the optimal conditions, the CL intensity was linear for a carbofuran concentration over the range of 0.06-0.5 μg ml⁻¹, with a detection limit of 0.02 μg ml⁻¹. The method has been successfully applied to the determination of carbofuran residues in spiked water and lettuce samples.     

Flow-injection chemiluminescence assay for ultra-trace determination of DNA using rhodamine B-Ce(IV)-DNA ternary system in sulfuric acid media

A novel flow-injection chemiluminescence method for the determination of DNA at ultra-trace level has been established. In 0.8 M sulfuric acid media, the chemiluminescence of the rhodamine B-cerium (IV) or Ce(IV) system is enhanced by DNA, activated previously by imidazole-HCl buffer solution (pH 7.0). The enhanced intensity of chemiluminescence is in proportion to log DNA concentration 1.0×10⁻⁸ to 0.1 μg ml⁻¹ for herring sperm DNA and 2.0×10⁻⁶ to 0.2 μg ml⁻¹ for calf thymus DNA with 3σ detection limits of 8.3×10⁻⁹ μg ml⁻¹ for herring sperm DNA and 3.5×10⁻⁷ μg ml⁻¹ for calf thymus DNA, respectively. The relative standard deviation for 1.0×10⁻⁴ μg ml⁻¹ herring sperm DNA was 0.99% and 2.0×10⁻³ μg ml⁻¹ for calf thymus DNA was 1.1% (n=11). Using the optimized system, DNA contents in six synthetic samples has been determined with recoveries of 99.5-109.0%. The possible mechanism has also been studied in this paper.