A validated silver‐nanoparticle‐enhanced chemiluminescence method for the determination of citalopram in pharmaceutical preparations and human plasma

A simple and sensitive chemiluminescence (CL) method was developed for the determination of citalopram in pharmaceutical preparations and human plasma. The method is based on the enhancement of the weak CL signal of the luminol–H₂O₂ system. It was found that the CL signal arising from the reaction between alkaline luminol and H₂O₂ was greatly increased by the addition of silver nanoparticles in the presence of citalopram. Prepared silver nanoparticles (AgNPs) were characterized by UV–visible spectroscopy and transmission electron microscopy (TEM). Various experimental parameters affecting CL intensity were studied and optimized for the determination of citalopram. Under optimized experimental conditions, CL intensity was found to be proportional to the concentration of citalopram in the range 40–2500 ng/mL, with a correlation coefficient of 0.9997. The limit of detection (LOD) and limit of quantification (LOQ) of the devised method were 3.78 and 12.62 ng/mL, respectively. Furthermore, the developed method was found to have excellent reproducibility with a relative standard deviation (RSD) of 3.65% (n = 7). Potential interference by common excipients was also studied. The method was validated statistically using recovery studies and was successfully applied to the determination of citalopram in the pure form, in pharmaceutical preparations and in spiked human plasma samples. Percentage recoveries were found to range from 97.71 to 101.99% for the pure form, from 97.84 to 102.78% for pharmaceutical preparations and from 95.65 to 100.35% for spiked human plasma. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and characterizations of iso‐luminol‐functionalized,tadpole‐shaped,gold nanomaterials

Iso‐luminol functionalized gold nanomaterials were synthesized in high yield by a simple seeding approach, using the chemiluminescent reagent iso‐luminol as reductant in the presence of HAuCl₄, AgNO₃ and cetyltrimethylammonium bromide (CTAB). The morphology of as‐prepared gold nanoparticles was characterized by transmission electron microscopy and UV–vis spectroscopy, showing that gold nanotadpoles (AuNTps) were obtained. Subsequent experiments revealed that the amounts of seed colloids and AgNO₃ and the concentrations of iso‐luminol and CTAB in the growth solution play critical roles in the formation of well‐shaped AuNTps. The surface state of AuNTps was characterized by UV–vis spectroscopy and fluorescence spectroscopy, indicating that iso‐luminol and its oxidation product, 4‐aminophthalate, coexisted on the surface of AuNTps. The CL behaviour was studied by static injection CL experiments, demonstrating that AuNTps were of CL activity. Finally, the growth mechanism of AuNTps was also discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

A novel green analytical procedure for monitoring of azoxystrobin in water samples by a flow injection chemiluminescence method with off‐line ultrasonic treatment

A simple and green flow injection chemiluminescence (FI‐CL) method for determination of the fungicide azoxystrobin was described for the first time. CL signal was generated when azoxystrobin was injected into a mixed stream of luminol and KMnO₄. The CL signal of azoxystrobin could be greatly improved when an off‐line ultrasonic treatment was adopted. Meanwhile, the signal intensity increases with the analyte concentration proportionally. Several variables, such as the ultrasonic parameters, flow rate of reagents, concentrations of sodium hydroxide solution and CL reagents (potassium permanganate, luminol) were investigated, and the optimal CL conditions were obtained. Under optimal conditions, the linear range of 1–100 ng/mL for azoxystrobin was obtained and the detection limit (3σ) was determined as 0.13 ng/mL. The relative standard deviation was 1.5% for 10 consecutive measurements of 20 ng/mL azoxystrobin. The method has been applied to the determination of azoxystrobin residues in water samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Determination of sulpiride in pharmaceutical preparations and biological fluids using a Cr (III) enhanced chemiluminescence method

A highly sensitive and simple method for identifying sulpiride in pharmaceutical formulations and biological fluids is presented. The method is based on increased chemiluminescence (CL) intensity of a luminol–H₂O₂ system in response to the addition of Cr (III) under alkaline conditions. The CL intensity of the luminol–H₂O₂–Cr (III) system was greatly enhanced by the addition of sulpiride and the CL intensity was proportional to the concentration of sulpiride in a sample solution. Various parameters affecting the CL intensity were systematically investigated and optimized for determination of the sulpiride in a sample. Under the optimum conditions, the CL intensity was proportional to the concentration of sulpiride in the range of 0.068–4.0 µg/mL, with a good correlation coefficient of 0.997. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 8.50 × 10^‐6 µg/mL and 2.83 × 10^‐5 µg/mL, respectively. The method presented here produced good reproducibility with a relative standard deviation (RSD) of 2.70% (n = 7). The effects of common excipients and metal ions were studied for their interference effect. The method was validated statistically through recovery studies and successfully applied for the determination of sulpiride in pure form, pharmaceutical preparations and spiked human plasma samples. The percentage recoveries were found to range from 99.10 to 100.05% for pure form, 98.12 to 100.18% for pharmaceutical preparations and 97.9 to 101.4% for spiked human plasma. Copyright © 2012 John Wiley & Sons, Ltd.     

Application of silver nanoparticles to the chemiluminescence determination of cefditoren pivoxil using the luminol–ferricyanide system

A new simple, accurate and sensitive sequential injection analysis chemiluminescence (CL) detection method for the determination of cefditoren pivoxil (CTP) has been developed. The developed method was based on the enhancement effect of silver nanoparticles on the CL signal arising from a luminol–potassium ferricyanide reaction in the presence of CTP. The optimum conditions relevant to the effect of luminol, potassium ferricyanide and silver nanoparticle concentrations were investigated. The proposed method showed linear relationships between relative CL intensity and the investigated drug concentration at the range 0.001–5000 ng/mL, (r = 0.9998, n = 12) with a detection limit of 0.5 pg/mL and quantification limit of 0.001 ng/mL. The relative standard deviation was 1.6%. The proposed method was employed for the determination of CTP in bulk drug, in its pharmaceutical dosage forms and biological fluids such as human serum and urine. The interference of some common additive compounds such as glucose, lactose, starch, talc and magnesium stearate was investigated. In addition, the interference of some related cephalosporins was tested. No interference was recorded. The obtained sequential injection analysis‐CL results were statistically compared with those from a reported method and did not show any significant differences. Copyright © 2014 John Wiley & Sons, Ltd.     

Flow‐injection chemiluminescence method to detect a β2 adrenergic agonist

A new method for the detection of β₂ adrenergic agonists was developed based on the chemiluminescence (CL) reaction of β₂ adrenergic agonist with potassium ferricyanide–luminol CL. The effect of β₂ adrenergic agonists including isoprenaline hydrochloride, salbutamol sulfate, terbutaline sulfate and ractopamine on the CL intensity of potassium ferricyanide–luminol was discovered. Detection of the β₂ adrenergic agonist was carried out in a flow system. Using uniform design experimentation, the influence factors of CL were optimized. The optimal experimental conditions were 1 mmol/L of potassium ferricyanide, 10 µmol/L of luminol, 1.2 mmol/L of sodium hydroxide, a flow speed of 2.6 mL/min and a distance of 1.2 cm from ‘Y₂’ to the flow cell. The linear ranges and limit of detection were 10–100 and 5 ng/mL for isoprenaline hydrochloride, 20–100 and 5 ng/mL for salbutamol sulfate, 8–200 and 1 ng/mL for terbutaline sulfate, 20–100 and 4 ng/mL for ractopamine, respectively. The proposed method allowed 200 injections/h with excellent repeatability and precision. It was successfully applied to the determination of three β₂ adrenergic agonists in commercial pharmaceutical formulations with recoveries in the range of 96.8–98.5%. The possible CL reaction mechanism of potassium ferricyanide–luminol–β₂ adrenergic agonist was discussed from the UV/vis spectra. Copyright © 2014 John Wiley & Sons, Ltd.     

Enhanced chemiluminescence of the luminol–AgNO3 system by Ag nanoparticles

The oxidation reaction of luminol with AgNO₃ can produce chemiluminescence (CL) in the presence of silver nanoparticles (NPs) in alkaline solution. Based on the studies of UV‐vis absorption spectra, photoluminescence (PL) spectra and CL spectra, a CL enhancement mechanism is proposed. The CL emission spectrum of the luminol–AgNO₃–Ag NPs system indicated that the luminophore was still 3‐aminophthalate. On injection of silver nanoparticles into the mixture of luminol and AgNO₃, they catalysed the reduction of AgNO₃ by luminol. The product luminol radicals reacted with the dissolved oxygen, to produce a strong CL emission. As a result, the CL intensity was substantially increased. Moreover, the influences of 18 amino acids, e.g. cystine, tyrosine and asparagine, and 25 organic compounds, including gallic acid, tannic acid and hydroquinone, on the luminol–AgNO₃–Ag NPs CL system were studied by a flow‐injection procedure, which led to an effective method for detecting these compounds. Copyright © 2011 John Wiley & Sons, Ltd.     

Turn‐off–on chemiluminescence determination of cyanide

A flow injection chemiluminescence (FI–CL) method was developed for the determination of cyanide (CN⁻) based on the recovered CL signal by Cu²⁺ inhibiting a glutathione (GSH)‐capped CdTe quantum dot (QD) and hydrogen peroxide system. In an alkaline medium, strong CL signals were observed from the reaction of CdTe QDs and H₂O₂, and addition of Cu²⁺ could cause significant CL inhibition of the CdTe QDs–H₂O₂ system. In the presence of CN⁻, Cu²⁺ can be removed from the surface of CdTe QDs via the formation of particularly stable [Cu(CN)_n]^(n‐1)– species, and the CL signal of the CdTe QDs–H₂O₂ system was efficiently recovered. Thus, the CL signals of CdTe QDs–H₂O₂ system were turned off and turned on by the addition of Cu²⁺ and CN⁻, respectively. Further, the results showed that among the tested ions, only CN⁻ could recover the CL signal, which suggested that the CdTe QDs–H₂O₂–Cu²⁺ CL system had highly selectivity for CN⁻. Under optimum conditions, the CL intensity and the concentration of CN⁻ show a good linear relationship in the range 0.0–650.0 ng/mL (R² = 0.9996). The limit of detection for CN⁻ was 6.0 ng/mL (3σ). This method has been applied to detect CN⁻ in river water and industrial wastewater with satisfactory results. Copyright © 2014 John Wiley & Sons, Ltd.     

A novel chemiluminescent flow‐injection analysis of transferrin by its reduction of the luminol—hydrogen peroxide reaction catalysed by meso‐tetra‐(3‐methoxyl‐4‐hydroxyl) phenyl manganese porphyrin

Based on the inhibition effect of transferrin (Tf) on the reaction of the luminol–hydrogen peroxide (H₂O₂) chemiluminescence (CL) system, catalysed by meso‐tetra‐(3‐methoxyl‐4‐hydroxyl) phenyl manganese porphyrin (MnP) as a mimetic enzyme of peroxides, a sensitive flow‐injection CL method has been developed for the determination of Tf in an alkaline medium. The CL reaction was carefully investigated by examining the variations of reaction conditions. Under optimum conditions, the linear range for the determination of transferrin was 0.04–20.0 μg/mL and the detection limit was 1.62 ng/mL. This proposed method was sensitive, convenient and simple, and has been successfully applied to the determination of transferrin in a serum sample. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of ferulic acid by flow injection chemiluminescence analysis based on enhancement of the N‐bromobutanimide–eosin–CrCl3 system in alkaline solution

A simple and sensitive flow injection chemiluminescence method has been developed for the determination of ferulic acid (FA) based on the significant enhancement effect of FA on the CL signal of the N‐bromobutanimide (NBS)–eosin–CrCl₃ system in alkaline solution. Under optimum conditions, the enhanced CL intensity is linearly related to the concentration of FA in its pharmaceutical preparations and human plasma samples. The corresponding linear regression equations were established over the 4.0 × 10^–10–1.0 × 10^–7 g/mL for FA tablets and 2.0 × 10^–10–1.0 × 10^–7 g/mL for plasma samples. The limit of detection for FA tablets and limit of quantification for plasma samples were 2.8 × 10^–10 g/mL (3 σ) and 3.04 × 10^–10 g/mL (10 σ), respectively. A complete analysis could be performed within 40 s, including washing and sampling, giving a throughput of ≈90/h. The proposed method was successfully applied to the determination of FA in pharmaceutical preparations and human plasma samples with satisfactory results. The recoveries of pharmaceutical preparations and human plasma samples at three different concentrations were 97.8–102.6% and 96.7–104.0%, respectively. Furthermore, the possible mechanism of CL reactions was also discussed briefly. Copyright © 2013 John Wiley & Sons, Ltd.     

Determination of dipyridamole using TCPO–H2O2 chemiluminescence in the presence of silver nanoparticles

The method is based on the fact that dipyridamole can enhance the chemiluminescence (CL) emission from the redox reaction of bis (2,4,6‐tricholorophenyl) oxalate (TCPO) with H₂O₂ in the presence of silver nanoparticles (AgNPs). The CL reaction mechanism was discussed. The effect of concentrations of TCPO, H₂O₂, AgNPs and pH value on the CL reaction were investigated. Under the optimum conditions, the linear dynamic range was 1.0–1000 × 10^?9 g/mL and the detection limit (3σ) was 9 × 10^?10 g/mL. The relative standard deviation (RSD) was 4.8% for 1.0 × 10^?9 g/mL dipyridamole (n = 7). The proposed method has been successfully applied to the determination of dipyridamole tablets and the recovery was 99–103%. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of colloidal β-cyclodextrins-Fe(3) O(4) magnetic nanoparticles on the chemiluminescence enhancement of luminol-Ag(III) complex for rapid and sensitive determination of cysteine in human serum

Colloidals solution of Fe₃O₄ magnetic nanoparticles (MNPs), capped with β‐cyclodextrins (β‐CD) as inclusion complexes, were found to enhance the chemiluminescence (CL) intensity of the luminol–diperiodatoargentate(III) (DPA) system. On injection of cysteine into the luminol–DPA–β‐CD–Fe₃O₄ MNPs inclusion complexes system, the CL intensity is strongly enhanced. The enhanced CL signal is ascribed to the catalytic effect of Fe₃O₄ MNPs capped with β‐CD, which is assumed to stabilize the CL intermediate. Based on these findings, a rapid and sensitive assay was developed for the determination of cysteine in human serum. The effects of analytical variables on the CL signal were studied and optimized. Under the optimum conditions, the CL intensity was directly proportional to the concentration of cysteine in the range 8.0 × 10^–9–1.0 × 10^–6 mol/L. The detection limit was 2.8 × 10^–9 mol/L (3 S_b/m) and the relative standard deviation (RSD) for 10 replicate determinations of 1.0 × 10^–7 mol/L cysteine was 3.5%. The proposed method was applied to the sensitive determination of cysteine in human serum samples, and compared with the Ellman method with satisfactory results. Copyright © 2011 John Wiley & Sons, Ltd.     

Chemiluminescence determination of promazine in human serum and drug formulations using Ru(phen)32+–Ce(IV) system and a chemometrical optimization approach

A new chemiluminescence (CL) method using flow injection has been described for the rapid and sensitive determination of promazine hydrochloride (PMH). The method is based on the CL reaction of PMH with tris(1,10 phenanthroline)ruthenium(II), [Ru(phen)₃²⁺] and Ce(IV) in sulfuric acid medium. Effects of chemical variables were investigated employing central composite design and response surface methodology. Under the optimum conditions, the CL intensity was proportional to the concentration of the drug in solution over the ranges 0.020–0.32 and 0.32–32 µg/mL. The limit of detection (signal‐to‐noise ratio = 3) was 0.012 µg/mL. The method was applied successfully to the determination of PMH in drug formulations and human serum (recovery percentages between 96.7 and 105.0%). The relative standard deviation for 11 replicate determinations of 1.5 µg/mL of PMH was 1.7%. The minimum sampling rate was 100 samples per hour. Copyright © 2009 John Wiley & Sons, Ltd.     

A simple and sensitive flow injection chemiluminescence immunoassay for chloramphenicol based on gold nanoparticle‐loaded enzyme

A simple and ultrasensitive flow injection chemiluminescence competitive immunoassay based on gold nanoparticle‐loaded enzyme for the detection of chloramphenicol (CAP) residues in shrimp and honey has been developed. Due to their good biocompatibility and large specific surface area, carboxylic resin beads can be used as solid phase carriers to immobilize more coating antigens (Ag). In addition, gold nanoparticles could provide an effective matrix for loading more CAP antibody and horseradish peroxidase, which would effectively catalyze the system of luminol–p‐iodophenol (PIP)–H₂O₂. A competitive immunoassay strategy was used for detection of CAP, in which CAP in the sample would compete with the coating Ag for the limited antibodies, leading to a chemiluminescence (CL) signal decrease with increase in CAP concentration. A wide linear range 0.001–10 ng ml^?1 (R² = 0.9961) was obtained under optimized conditions, and the detection limit (3σ) was calculated to be 0.33 pg ml^?1. This method was also been successfully applied to determine CAP in shrimp and honey samples. The immunosensor proposed in this study not only has the advantages of high sensitivity, wider linear range, and satisfactory stability, but also expands the application of flow injection CL immunoassay in antibiotic detection.     

[AuCl4]− and Fe3+/[Fe(CN)6]3− ions-derivated immunosensing interface for electrochemical immunoassay of carcinoembryonic antigen in human serum

[AuCl₄]⁻ was initially deposited by electrochemical reduction on a glassy carbon electrode (GCE) to form porous nanogold layer, then prussian blue (PB) was electrodeposited onto the as-prepared nanogold layer, and then secondary nanogold particles were fabricated again on the PB surface by electrochemical reduction for the immobilization of anti-CEA antibodies. The presence of double-layer porous gold nanoparticles enhanced the immobilized amount of biomolecules, and improved the sensitivity of the immunoassay. PB, as a good redox probe, was facile to electrochemical analysis and measurement. Under optimal conditions, the developed immunoassay exhibited dynamic range from 3.0 to 80.0 ng/mL with a detection limit of 0.9 ng/mL CEA (S/N = 3). Moreover, the selectivity, reproducibility and stability of the immunosensor were acceptable.     

Label-free and homogeneous DNA hybridization detection using gold nanoparticles-based chemiluiminescence system

We find that the catalytic activity of gold nanoparticles (GNPs) on luminol-H₂O₂ chemiluminescence (CL) system is greatly enhanced after it is aggregated by 0.5 M NaCl. We use this observation to design a CL detection of DNA hybridization. It is based on that the single- and double-stranded oligonucleotides have different propensities to adsorb on GNPs in colloidal solution, and the hybridization occurred between the probe DNA and target DNA can result in aggregation of the GNPs, producing strong CL emission. In the assay, no covalent functionalization of the GNPs, the probe, or the target DNA is required. The assay, including hybridization and detection, occurs in homogenous solution. The detection limit of target DNA (3σ) was estimated to be as low as 1.1 fM. The sensitivity was increased more than 6 orders of magnitude over that of GNPs-based colorimetric method. The present CL method for DNA hybridization detection offers the advantages of being simple, cheap, rapid and sensitive.     

Chemiluminescence flow biosensor for glucose based on gold nanoparticle-enhanced activities of glucose oxidase and horseradish peroxidase

In this work, a novel chemiluminescence (CL) flow biosensor for glucose was proposed. Glucose oxidase (GOD), horseradish peroxidase (HRP) and gold nanoparticles were immobilized with sol-gel method on the inside surface of the CL flow cell. The CL detection involved enzymatic oxidation of glucose to d-gluconic acid and H(2)O(2), and then the generated H(2)O(2) oxidizing luminol to produce CL emission in the presence of HRP. It was found that gold nanoparticles could remarkably enhance the CL respond of the glucose biosensor. The enhanced effect was closely related to the sizes of gold colloids, and the smaller the size of gold colloids had the higher CL respond. The immobilization condition and the CL condition were studied in detail. The CL emission intensity was linear with glucose concentration in the range of 1.0 x 10(-5)molL(-1) to 1.0 x 10(-3)molL(-1), and the detection limit was 5 x 10(-6)molL(-1) (3sigma). The apparent Michaelis-Menten constant of GOD in gold nanoparticles/sol-gel matrix was evaluated to be 0.3mmolL(-1), which was smaller than that of GOD immobilized in sol-gel matrix without gold nanoparticles. The proposed biosensor exhibited short response time, easy operation, low cost and simple assembly, and the proposed biosensor was successfully applied to the determination of glucose in human serum.     

Sensitive and selective determination of fluvoxamine maleate using a sensitive chemiluminescence system based on the alkaline permanganate–Rhodamine B–gold nanoparticles reaction

A high‐yield chemiluminescence (CL) system based on the alkaline permanganate–Rhodamine B reaction was developed for the sensitive determination of fluvoxamine maleate (Flu). Rhodamine B is oxidized by alkaline KMnO₄ and a weak CL emission is produced. It was demonstrated that gold nanoparticles greatly enhance this CL emission due to their interaction with Rhodamine B molecules. It is also observed that sodium dodecyl sulfate, an anionic surfactant, can strongly increase this enhancement. In addition, it was demonstrated that a notable decrease in the CL intensity is observed in the presence of Flu. This may be related to Flu oxidation with KMnO₄. There is a linear relationship between the decrease in CL intensity and the Flu concentration over a range of 2–300 µg/L. A new simple, rapid and sensitive CL method was developed for the determination of Flu with a detection limit (3s) of 1.35 µg/L. The proposed method was used for the determination of Flu in pharmaceutical and urine samples. Copyright © 2014 John Wiley & Sons, Ltd.     

Flow injection analysis of riboflavin with chemiluminescence detection using a N-halo compounds-luminol system.

A chemiluminescent method for the determination of riboflavin is described. The method is based on the chemiluminescence (CL) generated during the oxidation of luminol by N-bromosuccinimide (NBS) and N-chlorosuccinimide (NCS) in alkaline medium. It was found that riboflavin could greatly enhance this CL intensity when present in the luminol solution. Based on this observation, a new flow-injection CL method for the determination of riboflavin is proposed in this paper. The detection limits were 7.5 ng/mL and 3.5 ng/mL of riboflavin for the NBS- and NCS-luminol CL systems, respectively. The relative CL intensity was linear, with riboflavin concentration in the range 19-600 ng/mL and 600-2000 ng/mL for the NBS-luminol CL system, and 12-200 ng/mL and 200-2000 ng/mL for the NCS-luminol CL system. The results obtained for the assay of pharmaceutical preparations compared well with those obtained by the official method and demonstrated good accuracy and precision.     

Chemiluminescence determination of moxifloxacin in pharmaceutical and biological samples based on its enhancing effect of the luminol–ferricyanide system using a microfluidic chip

A sensitive determination of a synthetic fluoroquinolone antibacterial agent, moxifloxacin (MOX), by an enhanced chemiluminescence (CL) method using a microfluidic chip is described. The microfluidic chip was fabricated by a soft‐lithographic procedure using polydimethyl siloxane (PDMS). The fabricated PDMS microfluidic chip had three‐inlet microchannels for introducing the sample, chemiluminescent reagent and oxidant, and a 500 µm wide, 250 µm deep and 82 mm long microchannel. An enhanced CL system, luminol–ferricyanide, was adopted to analyze the MOX concentration in a sample solution. CL light was emitted continuously after mixing luminol and ferricyanide in the presence of MOX on the PDMS microfluidic chip. The amount of MOX in the luminol–ferricyanide system influenced the intensity of the CL light. The linear range of MOX concentration was 0.14–55.0 ng/mL with a correlation coefficient of 0.9992. The limit of detection (LOD) and limit of quantification (LOQ) were 0.06 and 0.2 ng/mL respectively. The presented method afforded good reproducibility, with a relative standard deviation (RSD) of 1.05% for 10 ng/mL of MOX, and has been successfully applied for the determination of MOX in pharmaceutical and biological samples. Copyright © 2013 John Wiley & Sons, Ltd.