Chemiluminescence determination of chlorpheniramine using tris(1,10‐phenanthroline)–ruthenium(II) peroxydisulphate system and sequential injection analysis

A sequential injection (SI) method was developed for the determination of chlorpheniramine (CPA), based on the reaction of this drug with tris(1,10‐phenanthroline)–ruthenium(II) [Ru(phen)₃²⁺] and peroxydisulphate (S₂O₈^2–) in the presence of light. The instrumental set‐up utilized a syringe pump and a multiposition valve to aspirate the reagents [Ru(phen)₃²⁺ and S₂O₈^2–] and a peristaltic pump to propel the sample. The experimental conditions affecting the chemiluminescence reaction were systematically optimized, using the univariate approach. Under the optimum conditions linear calibration curves of 0.1–10 µg/ml were obtained. The detection limit was 0.04 µg/ml and the relative standard deviation (RSD) was always < 5%. The procedure was applied to the analysis of CPA in pharmaceutical products and was found to be free from interferences from concomitants usually present in these preparations. Copyright © 2008 John Wiley & Sons, Ltd.     

Analysis of fexofenadine in pharmaceutical formulations using tris(1,10‐phenanthroline)–ruthenium(II) peroxydisulphate chemiluminescence system in a multichip device

A simple, rapid and sensitive method has been developed for the analysis of fexofenadine (FEX) in pharmaceutical formulations, using a tris(1,10‐phenanthroline)–ruthenium(II) [Ru(phen)₃²⁺] peroxydisulphate chemiluminescence (CL) system in a multichip device. Various parameters that influence the CL signal intensity were optimized. These included pH, flow rates and concentration of reagents used. Under optimum conditions, a linear calibration curve in the range 0.05–5.0 µg/mL was obtained. The detection limit was found to be 0.001 µg/mL. The procedure was applied to the analysis of FEX in pharmaceutical products and was found to be free from interference from concomitants usually present in these preparations. Copyright © 2011 John Wiley & Sons, Ltd.     

Flow‐injection analysis for meloxicam based on tris(2,2′‐bipyridine) ruthenium(II)–Ce(IV) chemiluminescent system

It was found that meloxicam could enhance the chemiluminescence (CL) of the tris(2,2'‐bipyridine) ruthenium(II)–Ce(IV) system in the medium of sulfate acid. Based on this phenomenon a new flow‐injection system with chemiluminescent detection has been proposed for determination of meloxicam. Under optimum conditions, meloxicam had a good linear relationship with the CL intensity in the concentration range of 6.0  10^?4 to 1.0 µg/mL and the detection limit was 3.7 × 10^?4 µg/mL. The proposed method was applied to detect meloxicam in tablets and a satisfactory recovery was obtained. The possible mechanism for this CL system is also discussed in this paper. Copyright © 2009 John Wiley & Sons, Ltd.     

Flow injection chemiluminescent determination of tetracycline using a tris(2,2'-bipyridine)ruthenium(II)-cerium(IV) sulphate system.

A flow-injection chemiluminescence method for the determination of tetracycline was developed. The method is based on an enhancement by tetracycline of the chemiluminescence light emission of tris(2,2'-bipyridine)ruthenium(II). In sulphuric acid medium, the chemiluminescence is generated by the continuous oxidation of tris(2,2'-bipyridine)ruthenium(II) by cerium (IV) sulphate. The light-emission intensity is greatly enhanced in the presence of tetracycline. Under the optimum conditions, the calibration curve is linear over the range 3.75 x 10(-8) g/mL-1.5 x 10(-5) g/mL for tetracycline with the linear equation: deltaINT = 205.898 x C - 20.442 (R2 = 0.9974). The detection limit is 3.27 x 10(-8) g/mL. The proposed method was also successfully used to determine tetracycline in pharmaceutical formulation (mean recovery of tetracycline, 100.7%).     

Chemiluminescence method for the determination of piroxicam by the enhancement of the tris‐(4,7‐diphenyl‐1,10‐phenanthrolinedisulphonic acid) ruthenium(II) (RuBPS)–cerium(IV) system and its application

A simple, rapid chemiluminescence (CL) method was described for the determination of piroxicam, a commonly used analgesic agent drug. A strong CL signal was detected when cerium(IV) sulphate was injected into tris‐(4,7‐diphenyl‐1,10‐phenanthrolinedisulphonic acid) ruthenium(II) (RuBPS)–piroxicam solution. The CL signal was proportional to the concentration of piroxicam in the range 2.8 × 10^–8–1.2 × 10^–5 mol/L. The detection limit was 2 × 10^–8 mol/L and the relative standard deviation (RSD) was 3.7% (c = 7.0 × 10^–7 mol/L piroxicam; n = 11). The proposed method was applied to the determination of piroxicam in pharmaceutical preparations in capsules, spiked serum and urine samples with satisfactory results. Copyright © 2008 John Wiley & Sons, Ltd.     

Flow‐injection chemiluminescence determination of olanzapine using N‐chlorosuccinimide–calcein reaction sensitized by zinc (II)

A novel, rapid and sensitive chemiluminescence (CL) method combined with flow‐injection (FI) has been established for the estimation of olanzapine. This method is based on the CL signal generated between N‐chlorosuccinimide and olanzapine in an alkaline medium in the presence of calcein and Zn(II). Under optimum conditions, the CL signal was proportional to the olanzapine concentration ranging from 1.0 × 10^‐10 to 3.0 × 10^‐7 g/mL. The detection limit is 8.9 × 10^‐11 g/mL olanzapine (3σ) and the relative standard deviation for 3.0 × 10^‐9 g/mL of olanzapine is 1.9% (n = 11). The current CL method was applied to determine olanzapine in pharmaceutical formulations and biological fluids with satisfactory results. The possible CL reaction mechanism is discussed briefly. Copyright © 2013 John Wiley & Sons, Ltd.     

Flow‐injection chemiluminescence and electrogenerated chemiluminescence determination of escitalopram oxalate in tablet form

Rapid, simple and highly sensitive flow‐injection (FI) chemiluminescence (CL) and flow‐injection electrogenerated chemiluminescence (ECL) methods were developed for the determination of escitalopram oxalate (ESC), a selective serotonin reuptake inhibitor used as an antidepressant drug. The CL method was based on the CL reaction of ESC with acidic cerium(IV) and tris(2,2'‐bipyridyl)ruthenium(II) (Ru). Various experimental parameters affecting CL intensity were carefully studied and optimised. The method enabled the determination of 0.001‐50 µg/mL of ESC in bulk form with a correlation coefficient r = 0.9999. The limit of detection (LOD) was 0.01 ng/mL (S/N = 3). The ECL method was based on the ECL reaction of Ru with the drug in an acidic medium, permitting the determination of ESC in the range of 0.00001‐70 µg/mL with r = 0.9999 and LOD of 1 x 10^‐4 ng/mL. The proposed methods were applied to the determination of ESC in commercial tablets. The results were compared statistically with those obtained from a published method using t‐ and F‐tests. Copyright © 2012 John Wiley & Sons, Ltd.     

Flow‐injection determination of vitamin A in pharmaceutical formulations using Tris(2,2′‐bipyridyl)Ru(II)–Ce(IV) chemiluminescence detection

A flow injection method with chemiluminescence detection is reported for the determination of vitamin A. The method is based on the enhancement effect of vitamin A on chemiluminescence of tris(2,2′‐bipyridyl)Ru(II)–Ce(IV) in acidic medium. The proposed procedure is used to quantitate vitamin A in the range 1.0–100 × 10^?6 mol/L with a correlation coefficient of 0.9991 (n = 9) and relative standard deviation in the range 1.2–2.3% (n = 4). The limit of detection (3 × blank) was 8.0 × 10^?8 mol/L with a sample throughput of 100/h. The effect of common excipients used in pharmaceutical formulations and some clinically important compounds was also studied. The method was applied to determine vitamin A in pharmaceutical formulations and the results obtained were in reasonable agreement with the amount quoted. The results were compared using spectrophotometric method and no significant difference was found between the results of the two methods at 95% confidence limit. Copyright © 2009 John Wiley & Sons, Ltd.     

Simple chemiluminescence determination of ketotifen using tris(1,10 phenanthroline)ruthenium(II)‐ Ce(IV) system

A new method using chemiluminescence (CL) detection has been developed for the simple determination of ketotifen fumarate (KF). The method is based on the catalytic effect of KF in the CL reaction of tris(1,10 phenanthroline)ruthenium(II), Ru(phen)₃²⁺, with Ce(IV) in sulfuric acid medium. The CL response was detected using a lab‐made chemiluminometer. Effects of chemical variables were investigated and under optimum conditions, the CL intensity was proportional to the concentration of the drug over the range 0.34‐34.00 µg mL^?1 KF. The limit of detection (S/N=3) was 0.09 µg mL^?1. Effects of common ingredients were investigated and the method was applied successfully for determining KF in pharmaceutical formulations and human plasma. The percent of relative standard deviation (n=11) at level of 3.4 µg mL^?1 of KF was 4.6% and the minimum sampling rate was 70 samples per hour. The possible CL mechanism is proposed based on the kinetic characteristic of the CL reaction, CL spectrum, UV‐Vis and phosphorescence spectra. Copyright © 2015 John Wiley & Sons, Ltd.     

1,10‐Phenanthroline–H2O2–KSCN–CuSO4–NaOH oscillating chemiluminescence system

In this paper, oscillating chemiluminescence (CL), 1,10‐phenanthroline H₂O₂–KSCN–CuSO₄–NaOH system, was studied in a batch reactor. The system described is a novel, slowly damped oscillating CL system, generated by coupling the well‐known Epstein–Orban, H₂O₂–KSCN–CuSO₄–NaOH chemical oscillator reaction with the CL reaction involving the oxidation of 1,10‐phenanthroline by hydrogen peroxide, catalyzed by copper(II) in alkaline medium. In this system, the CL reaction acts as a detector or indicator system of the far‐from‐equilibrium dynamic system. Narrow and slightly asymmetric light pulses of 1.2 s half‐width are emitted at 440 nm with an emitted light time of 200–1000 s, induction period of 3.5–357 s and oscillation period of 28–304 s depending on the reagent concentrations. In this report the effect of the concentration variation of components involved in the oscillating CL system on the induction period, the oscillation period and amplitude was investigated and the parameters were plotted with respect to reagent concentrations. Copper concentration showed a significant effect on the oscillation period. The possible mechanism for the oscillating CL reaction was also discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Photoinduced oxidation of a tris(2,2'‐bipyridyl)ruthenium(II)–peroxodisulfate chemiluminescence system for the analysis of mebeverine HCl pharmaceutical formulations and biological fluids using a two‐chip device

A new method for the analysis of mebeverine hydrochloride (MEB) has been developed using a two‐chip device. The method is highly selective, sensitive, rapid and consumes minute amount of reagents. The developed method is free of interference from the degradation products of MEB and from common ingredients present in pharmaceutical formulations. The limit of detection was 0.043 µg/mL, and the limit of quantification was 0.138 µg/mL. The short analysis time per sample (20 s) allowed a large number of analyses to be performed within a very short time. Various samples were analyzed, including two different pharmaceutical formulations and a uniformity of content analysis for 20 tablets from a known batch and two biological samples at different concentrations. In addition, the method was compared with a validated high‐performance liquid chromatography (HPLC) method and the results clearly indicated the suitability of the developed method for routine analyses. A new mechanism for the tris(2,2'‐bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺)‐peroxodisulfate (S₂O₈^2?) chemiluminescence (CL) system has also been proposed. The mechanism is based on photoinduced oxidation of Ru(bpy)₃²⁺ to Ru(bpy)₃³⁺ via the formation of Ru(bpy)₃²⁺* upon irradiation with visible light. S₂O₈^2? then oxidizes Ru(bpy)₃²⁺* to Ru(bpy)₃³⁺ and the analyte subsequently reduces the resultant Ru(bpy)₃³⁺ to Ru(bpy)₃²⁺*, which then produces the CL signal. Copyright © 2013 John Wiley & Sons, Ltd.     

Flow‐injection determination of manganese (II) using surfactant enhanced diperiodatonickelate (IV)‐rhodamine 6G chemiluminescence

Chemiluminescence (CL) of the rhodamine 6‐G‐diperiodatonickelate (IV) (Rh6‐G‐Ni(IV) complex) in the presence of Brij‐35 was examined in an alkaline medium and implemented using flow‐injection analysis to analyze Mn(II) in natural waters. Brij‐35 was identified as the surfactant of choice that enhanced CL intensity by about 62% of the reaction. The calibration curves were linear in the range 1.7 × 10^?3 – 0.2 (0.9990, n = 7) and 8.0 × 10^?4 – 0.1 μg ml^?1 (0.9990, n = 7) with limits of detection (LODs) (S:N = 3) of 5.0 × 10^?4 and 2.4 × 10^?4 μg ml^?1 without and with using an in‐line 8‐hydroxyquinoline (8‐HQ) resin mini‐column, respectively. The sample throughput and relative standard deviation were 200 h^?1 and 1.7–2.2% in the range studied respectively. Mn(II) concentrations in certified reference materials and natural water samples was successfully determined. A brief discussion about the possible CL reaction mechanism is also given. In addition, analysis of V(III), Cr(III) and Fe(II) was also performed without and with using an in‐line 8–HQ column and selective elution of each metal ion was achieved by adjusting the pH of the sample carrier stream with aqueous HCl solution.     

Liquid chromatographic determination of acetylcholine based on pre‐column alkaline cleavage reaction and post‐column tris(2,2′‐bipyridyl)ruthenium(III) chemiluminescence detection

A method for the determination of acetylcholine (ACh) has been developed using liquid chromatography with chemiluminescence detection. This method is based on the pre‐column alkaline cleavage of ACh to form trimethylamine (TMA) and the post‐column tris(2,2′‐bipyridyl)ruthenium(III) chemiluminescence detection of TMA. ACh was converted to TMA with high yield at 180°C in the presence of lithium hydroxide, and the produced TMA was separated on a cation‐exchange/reversed‐phase dual‐functional column using a mixture of 0.2 m potassium phosphate buffer (pH 5.9) and acetonitrile (20:1, v/v) as the mobile phase. The eluate was online mixed with acidic tris(2,2′‐bipyridyl)ruthenium(III) solution, and the generated chemiluminescence was detected. The detection limit (signal‐to‐noise ratio = 3) for ACh was 0.80 nmol/mL, which corresponded to 1.1 pmol TMA per injection volume of 5 µL. This is simple and robust method that does not need an expensive device and unstable enzymes, and was applied to the determination of ACh in pharmaceutical formulations. Copyright © 2009 John Wiley & Sons, Ltd.     

High‐throughput method for the analysis of venlafaxine in pharmaceutical formulations and biological fluids,using a tris(2,2′‐bipyridyl) ruthenium(II)–peroxydisulphate chemiluminescence system in a two‐chip device

A simple, rapid and sensitive chemiluminescent (CL) method for the assay of venlafaxine (VEN) in pharmaceutical formulations and serum samples by a two‐chip device is proposed. The method is based on the reaction of this drug with a tris(2,2′‐bipyridyl) ruthenium(II)–peroxydisulphate CL system. The optimum chemical conditions for CL emission were investigated. The calibration graph was linear for the concentration range 0.02–8.0 µg/mL. The detection and quantification limits were found to be 0.006 and 0.018 µg/mL, respectively, while the relative standard deviation (RSD) was <2.0%. The present CL procedure was applied to the determination of VEN in pharmaceutical formulations and serum samples; the recovery levels were in the range 96.5–101.2%. The results suggest that the method is unaffected by the presence of common formulation excipients found in these samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Electrochemiluminescence of tris(2,2′‐bipyridyl)ruthenium and its applications in bioanalysis: a review

Electrochemiluminescence (ECL) of tris(2,2’‐bipyridyl)ruthenium(II) [Ru(bpy)₃²⁺] is an active research area and includes the synthesis of ECL‐active materials, mechanistic studies and broad applications. Extensive research has been focused on this area, due to its scientific and practical importance. In this mini‐review we focus on the bio‐related applications of ECL. After a brief introduction to Ru(bpy)₃²⁺ ECL and its mechanisms, its application in constructing an effective bioassay is discussed in detail. Three types of ECL assay are covered: DNA, immunoassay and functional nucleic acid sensors. Finally, future directions for these assays are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Flow injection determination of benzhexol based on its sensitizing effect on the chemiluminescent reaction of Ce(IV)–sulfite

In this paper, a novel chemiluminescent (CL) method for the determination of benzhexol has been developed by combining the flow injection technique and its sensitizing effect on the weak CL reaction between sulfite and acidic cerium(IV). A mechanism for the CL reaction has been proposed on the basis of CL spectra. Under the optimized conditions, the proposed method allows the measurement of benzhexol hydrochloride over the range 0.1–10 μg/mL with a correlation coefficient of 0.9992 (n = 8), a detection limit of 0.02 μg/mL (3σ), and a relative standard deviation for 2.0 μg/mL benzhexol (n = 11) of 1.65%. The utility of this method was demonstrated by determining benzhexol hydrochloride in tablets. Copyright © 2009 John Wiley & Sons, Ltd.     

Flow injection–chemiluminescence determination of amoxycillin using potassium permanganate and formaldehyde system

It was found that amoxycillin can react with potassium permanganate in an acidic medium to produce chemiluminescence, which is greatly enhanced by formaldehyde. The optimum conditions for this chemiluminescent reaction were studied in detail using a flow‐injection system. The experimental results indicate that, under optimum conditions, the chemiluminescence intensity is linearly related to the concentration of amoxycillin in the range 5.48 × 10^?8–2.74 × 10^?6 mol[sol ]L, with a detection limit (3σ) of 4.1 × 10^?8 mol[sol ]L. The relative standard deviation was 1.0% at 1.1 × 10^?6 mol[sol ]L amoxycillin (n = 11 measurements). This method has the advantages of high sensitivity, fast response and ease of operation. The method was successfully applied to the determination of amoxycillin in raw medicines and capsules. Copyright © 2005 John Wiley & Sons, Ltd.     

Flow‐injection chemiluminescence determination of ofloxacin using the Ru(bpy)2(CIP)2+−Ce(IV) system and its application

This paper reports a flow‐injection chemiluminescence method for the determination of ofloxacin (OFLX) using the Ru(bpy)₂(CIP)²⁺–Ce(IV) system. Under the optimum conditions, the relative CL intensity was proportional to the concentration of OFLX in the range 3.0 × 10^–8–1.0 × 10^–5 mol/L and the detection limit was 4.2 × 10^–9 mol/L. The proposed method has been successfully applied to the determination of ofloxacin in pharmaceuticals and human urine. The chemiluminescence mechanism of the system is also discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Flow‐injection method for the determination of iodide/iodine using Ru(bpy)33+–NADH chemiluminescence detection

A two‐channel flow‐injection (FI) method is reported for the determination of iodide and iodine by its enhancement effect on the Ru(bpy)₃³⁺–NADH chemiluminescence (CL) system. The limit of detection (3 s of blank) was 1.0 × 10^–9 mol/L iodide/iodine, with a sample throughput of 60/h. The calibration graphs over the range 1.0–50 × 10^–8 mol/L gave correlation coefficients of 0.9994 and 0.999 (n = 5) with relative standard deviations (RSD; n = 4) of 1.0–2.5%, respectively. The effects of interfering cations, anions and some organic compounds were also studied. The method was applied to iodized salts and pharmaceutical samples and the results obtained were in good agreement with the value quoted. The CL method developed was compared with spectrophotometric method. Copyright © 2008 John Wiley & Sons, Ltd.     

Flow‐injection chemiluminescence determination of haemoglobin in the blood

In this study, a sensitive and simple flow‐injection chemiluminescence (CL) method was developed for the quantitative analysis of haemoglobin. The method is based on the ability of haemoglobin to enhance the CL signal generated by a H₂O₂–K₄Fe(CN)₆–fluorescein alkaline system enhanced by CdTe quantum dots. Under the optimized conditions, haemoglobin can be detected in concentration range 7.35 × 10^–9–2.5 × 10^–6 mol/L, with a detection limit (3σ) of 1.8 × 10^–9 mol/L and a relative standard deviation (RSD; for 5 × 10^–7 mol/L haemoglobin) of 2.06% (n = 11). The present CL method was successfully applied for the determination of haemoglobin in three kinds of blood samples taken from an infant, an adult man, an adult woman and two reference samples. Compared with previous reports, the CL method described in this work is simple and rapid, with high sensitivity. Copyright © 2012 John Wiley & Sons, Ltd.