Analysis of phenolic compounds in health care products by low‐pressure liquid‐chromatography with monolithic column and chemiluminescent detection

This paper presents a new application for monolithic columns with low‐pressure chromatographic separation using an flow injection analysis configuration with chemiluminescent detection for the determination of a mixture of phenolic compounds: phloroglucinol, 2,4‐dihydroxybenzoic acid, salicylic acid, methyl paraben and n‐propyl gallate. The procedure consists of the separation of these compounds on a reverse‐phase ultra‐short monolithic column with pH 3.0 acetate buffer and 5% acetonitrile as carrier phase. The detection is based on a chemiluminescence measurement coming from Ce(IV)–Rhodamine 6G chemistry with the incorporation of two different chemiluminescent chemical conditions in the chromatographic setup in order to enhance the sensitivity for the different phenolic compounds. All separation and detection variables were optimized to propose a determination method. The analysis is performed in 280?s, with the sampling frequency being some 13 h^?1. The calibration function is a double reciprocal function obtaining good results within two orders of magnitude. The limits of detection were 8.8 × 10 ^?8 m (phloroglucinol), 2.7 × 10 ^?8 m (2,4‐dihydroxybenzoic acid); 2.3 × 10 ^?8 m (salicylic acid); 5.2 × 10 ^?8 m (methyl paraben) and 4.1 × 10 ^?6 m (n‐propyl gallate), and the relative standard deviations at a medium level of the linear range were 4.4% (phloroglucinol), 2.8% (2,4‐dihydroxybenzoic acid), 5.2% (salicylic acid), 3.6% (methyl paraben) and 6.8% (n‐propyl gallate). The method was applied and validated satisfactorily for the determination of these compounds in healthcare products, comparing the results against an HPLC reference method. Copyright © 2009 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.     

Multiway analysis applied to time‐resolved chemiluminescence for simultaneous determination of paracetamol and codeine in pharmaceuticals

This method is based on the enhancing effect of codeine (COD) and paracetamol (PAR) on the chemiluminescence (CL) reaction of Ru(phen)₃²⁺ with Ce(IV). In the batch mode, COD gives a relatively sharp peak with the highest CL intensity at 4.0 s, whereas the maximum CL intensity of the PAR appears at ~60 s after injection of Ce(IV) solution. Whole CL time profiles allowed use of the time‐resolved CL data in combination with multiway calibration techniques, as multiway partial least squares (N‐PLS), for the quantitative determination of both COD and PAR in binary mixtures. In this work, we found that the impact of Ce(IV) concentration on the CL intensity was different for COD and PAR. Therefore, a Ce(IV) concentration mode was added to the time and sample modes to obtain 3D data. The percent relative standard deviation (%RSD) values for 10 determinations of 1.0 × 10^?5 mol/L of COD and 1.0 × 10^?4 mol/L of PAR were 6.1% and 8.7%, respectively. The limit of detection (LOD) values (S/N = 3) were 0.9 × 10^?8 mol/L and 1.0 × 10^?6 mol/L for COD and PAR, respectively. The proposed method was successfully applied to the determination of PAR and COD in commercial pharmaceutical formulations. Acceptable recoveries (90–110%) were obtained for the quantification of these drugs in the real samples. Copyright © 2016 John Wiley & Sons, Ltd.     

Production of phenolic compounds in callus cultures of tea plant under the effect of 2,4-D and NAA

The effect of hormone-like compounds at different concentrations: 2,4-D (2 × 10^?6; 2 × 10^?5; and 2 × 10^?4M) and 1-NAA (2 × 10^?7; 2 × 10^?6; 2 × 10^?5; 4 × 10^?5, and 6 × 10^?5 M) on the growth and production of phenolic compounds, including flavans and lignin, was investigated in callus culture of tea plant (Camellia sinensis L., a highly productive strain IFR ChS-2). The growth of the culture was vigorous, and production of phenolic compounds therein was efficient in the medium containing 2 × 10^?5 M 2,4-D. Substitution of 1-NAA for 2,4-D in all the cases decelerated the growth of the culture. These changes were more pronounced when 2 × 10^?7 and 2 × 10^?6 M 1-NAA was used; in this case, biomass accumulation decreased by 1.5–2.0 times as compared with control material growing on the medium with 2 × 10^?5 M 2,4-D. In the presence of 1-NAA, the content of total soluble phenolic compounds and flavans in the calli rose by 30% on the average as compared with control material. Accumulation of lignin remained essentially the same. Therefore, the replacement of 2,4-D with 1-NAA in the nutrient medium used for the growing of highly productive strain of tea plant callus did not induce considerable changes in its ability to produce phenolic compounds.     

Resonance light‐scattering enhancement effect of the protein–Y3+–TTA–SLS system and its analytical application

In this paper, a sensitive resonance light scattering (RLS) method for the determination of protein is reported. In the Tris–HCl (pH 7.50) buffer, protein enhanced the RLS intensity of the Y³⁺–2‐thenoyltrifluoroacetone (TTA)–sodium dodecyl sulphate (SLS) system. The enhanced RLS intensities were in proportion to the concentrations of proteins in the range 8.0 × 10^?9–1.0 × 10^?5 g/mL for BSA, 1.0 × 10^–8–1.0 × 10^?5 g/mL for HSA and 1.0 × 10^–8–1.0 × 10^?6 g/mL for EA, and their detection limits were 5.0, 5.4 and 6.7 ng/mL, respectively. Actual samples were satisfactorily determined. The interaction mechanism was also studied. Copyright © 2008 John Wiley & Sons, Ltd.     

Chemiluminescence detection of trace iodide with flow injection analysis of KMnO4‐carbon dots system

Ultra‐weak chemiluminescence (CL) from the reaction of iodide and KMnO₄ was strongly enhanced by carbon nanodots (CNDs) in an acidic medium. The CL intensity was directly proportional to the concentration of iodide in the solution. Therefore, a flow‐injection CL system with high sensitivity, selectivity and reproducibility is proposed for the determination of iodide. The proposed method exhibited advantages over a linear range of 3.0 × 10^?6–1.0 × 10^?4 mol/L and had a detection limit of 3.5 × 10^?7 mol/L. The method was successfully applied to the evaluation of iodide in food samples with recoveries of between 96 and 103%. The relative standard deviations were 2.1 and 4.1% for intra‐ and inter‐assay precision, respectively.     

The behaviors of metal ions in the CdTe quantum dots–H2O2 chemiluminescence reaction and its sensing application

The behaviors of 15 kinds of metal ions in the thiol‐capped CdTe quantum dots (QDs)–H₂O₂ chemiluminescence (CL) reaction were investigated in detail. The results showed that Ag⁺, Cu²⁺ and Hg²⁺ could inhibit CdTe QDs and H₂O₂ CL reaction. A novel CL method for the selective determination of Ag⁺, Cu²⁺ and Hg²⁺ was developed, based on their inhibition of the reaction of CdTe QDs and H₂O₂. Under the optimal conditions, good linear relationships were realized between the CL intensity and the logarithm of concentrations of Ag⁺, Cu²⁺ and Hg²⁺. The linear ranges were from 2.0 × 10^?6 to 5.0 × 10^?8 mol L^?1 for Ag⁺, from 5.0 × 10^?6 to 7.0 × 10^?8 mol L^?1 for Cu²⁺ and from 2.0 × 10^?5 to 1.0 × 10^?7 mol L^?1 for Hg²⁺, respectively. The limits of detection (S/N = 3) were 3.0 × 10^?8, 4.0 × 10^?8 and 6.7 × 10^?8 mol L^?1 for Ag⁺, Cu²⁺ and Hg²⁺, respectively. A possible mechanism for the inhibition of CdTe QDs and H₂O₂ CL reaction was also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Catalytic resonance scattering spectral determination of ultratrace horseradish peroxidase using rhodamine S

A highly sensitive and selective resonance scattering spectral assay was proposed for the determination of horseradish peroxidase (HRP), based on its catalytic effect on the H₂O₂ oxidation of KI to form I₃^?. The I₃^? combined respectively with rhodamine (Rh) dye such as rhodamine S (RhS), rhodamine 6G (Rh6G), rhodamine B (RhB) and butyl‐rhodamine B (b‐RhB), to form association particles (Rh‐I₃)_n. The four Rh systems all exhibit a stronger resonance scattering (RS) peak at 424 nm. For the RhS, Rh6G, RhB and b‐RhB systems, HRP concentration in the range of 3.2 × 10^?12 to 4.8 × 10^?9, 2 × 10^?11 to 3.2 × 10^?9, 1.6 × 10^?11 to 3.2 × 10^?9 and 1.6 × 10^?11 to 4 × 10^?9 g/mL was linear to its RS intensity at 424 nm, with a detection limit of 2.2 × 10^?12, 2.5 × 10^?12, 4.4 × 10^?12 and 2.6 × 10^?12 g/mL, respectively. This RhS system was most sensitive and stable, and was applied for the determination of HRP in the hepatitis B surface antibody labeling HRP and water samples, with satisfactory results. Copyright © 2009 John Wiley & Sons, Ltd.     

Glutathione‐stabilized Cu nanocluster‐based fluorescent probe for sensitive and selective detection of Hg2+ in water

In this paper, an innovative and facile one‐pot method for synthesizing water‐soluble and stable fluorescent Cu nanoclusters (CuNCs), in which glutathione (GSH) served as protecting ligand and ascorbic acid (AA) as reducing agent was reported. The resultant CuNCs emitted blue‐green fluorescence at 440 nm, with a quantum yield (QD) of about 3.08%. In addition, the prepared CuNCs exhibited excellent properties such as good water solubility, photostability and high stability toward high ionic strength. On the basis of the selective quenching of Hg²⁺ on CuNCs fluorescence, which may be the result of Hg²⁺ ion‐induced aggregation of the CuNCs, the CuNCs was used for the selective and sensitive determination of Hg²⁺ in aqueous solution. The proposed analytical strategy permitted detection of Hg²⁺ in a linear range of 4 × 10^?8 to 6 × 10^?5 M, with a detection limit of 2.2 × 10^?8 M. Eventually, the practicability of this sensing approach was confirmed by its successful application to assay Hg²⁺ in tap water, Lotus lake water and river water samples with the quantitative spike recoveries ranging from 96.9% to 105.4%.     

Chemiluminescence determination of naproxen based on europium(III)‐sensitized KIO4–H2O2 reaction

A simple and sensitive chemiluminescence (CL) method combined with flow injection technique was developed for the determination of naproxen. It was based upon the weak CL signal arising from the reaction of KIO₄ with H₂O₂ being significantly increased by naproxen in the presence of europium(III) ion. The experimental conditions that affected the CL signal were carefully optimized and the CL reaction mechanism was briefly discussed. Under the optimum conditions, the increment of CL intensity was proportional to the concentration of naproxen ranging from 5.0 × 10^?8 to 5.0 × 10^?6 g/mL. The detection limit was 1 × 10^?8 g/mL naproxen and the relative standard deviation for 5.0 × 10^?7 g/mL naproxen solution was 2.1% (n = 11). The proposed method was applied to the determination of naproxen in tablets and in spiked human urine samples with satisfactory results. Copyright © 2009 John Wiley & Sons, Ltd.     

New luminol chemiluminescence reaction using diperiodatoargentate as oxidate for the determination of amikacin sulfate

A new chemiluminescence (CL) reaction between luminol and diperiodatoargentate {K₂ [Ag (H₂IO₆) (OH) ₂]} was observed in alkaline medium. The CL intensity could be greatly enhanced by amikacin sulfate. Therefore a new CL method for the determination of amikacin sulfate was built by combining with flow injection technology. A possible mechanism of the CL reaction was proposed via the investigation of the CL kinetic characteristics, the CL spectrum and the UV absorption spectra of some related substance. The concentration range of linear response was 5.1 × 10^?8 to 5.1 × 10^?6 mol L^?1 with a detection limit of 1.9 × 10^?8 mol L^?1 (3σ). The proposed method had good reproducibility with a relative standard deviation of 2.8% (n = 7) for 5.1 × 10^?7 mol L^?1 of amikacin sulfate. It was successfully applied to determine amikacin sulfate in serum. Copyright © 2009 John Wiley & Sons, Ltd.     

The fluorescence enhancement of quercetin–nucleic acid system and the analytical application

Nucleic acid can greatly enhance the fluorescence intensity of quercetin in HMTA‐HCl (pH 5.5) buffer. The enhanced intensity is in proportion to the concentration of nucleic acids in the range 5.0 × 10^?9 to 1.0 × 10^?6 g/mL for fsDNA, 5.0 × 10^?9 to 7.0 × 10^?7 g/mL for ctDNA and 5.0 × 10^?9 to 1.0 × 10^?6 g/mL for yRNA, and their detection limits (S/N = 3) are 3.5 × 10^?9, 7.8 × 10^?10 and 2.6 × 10^?9 g/mL, respectively. In comparison with most reported fluorescent probes for the determination of nucleic acids, the proposed probe has higher sensitivity and lower toxicity. The interaction investigation indicates that quercetin binds with double‐strand DNA in groove binding mode, resulting in fluorescence enhancement of this system. Copyright © 2009 John Wiley & Sons, Ltd.     

Highly selective determination of phenolphthalein by flow injection chemiluminescence method based on a molecular imprinting polymer

The phenolphthalein‐imprinted polymer was prepared with methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross‐linker. Taking advantage of the quenching effect of phenolphthalein on the potassium permanganate–HCl–anhydrous alcohol chemiluminescence system, a new model was established to determine phenolphthalein by a highly selective flow injection chemiluminescence method. The traditional flow‐though cell was replaced with a novel flow path using a Y‐shaped polymethyl methacrylate column, through which the three reactants were injected simultaneously. The linear range of this assay was from 1.0 × 10^?8 to 1.0 × 10^?6 g/mL (r = 0.9978). The limit of detection was 8.9 × 10^?9 g/mL. The relative standard deviation for the determination of 1.0 × 10^?8 g/mL phenolphthalein solution was below 2.9% (n = 11). The proposed method was applied to the determination of phenolphthalein in real samples with satisfactory results. Copyright © 2009 John Wiley & Sons, Ltd.     

The determination of glutamine with flow‐injection chemiluminescence detection and mechanism study

The main purpose of this study was to develop an inexpensive, simple, rapid and sensitive chemiluminescence (CL) method for the determination of glutamine (Gln) using a flow‐injection (FI) system. Gln was found to strongly inhibit the CL signal of the luminol–H₂O₂–CuSO₄ system in Na₂B₄O₇ solution. A new FI‐CL method was developed for the determination of Gln. Parameters affecting the reproducibility and CL detection were optimized systematically. Under the optimized conditions, the corresponding linear regression equation was established over the range of 5.0 × 10^?7 to 2.5 × 10^?6 mol/L with the detection limit of 1.8 × 10^?8 mol/L. The relative standard deviation was found to be 1.8% for 11 replicate determinations of 1.5 × 10^?6 mol/L Gln. The proposed method has been satisfactorily applied for the determination of Gln in real samples (Marzulene‐s granules) with recoveries in the range of 98.7–108.6%. The minimum sampling rate was about 100 samples/h. The possible mechanism of this inhibitory CL was studied by fluorescence spectrophotometer and UV–vis spectrophotometer. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of subnanomolar concentrations of vanadium in environmental water samples using flow injection with luminol chemiluminescence detection

A flow injection chemiluminescence method is described for the determination of subnanomolar concentrations of vanadium in environmental water samples. The procedure is based on the oxidation of luminol in the presence of dissolved oxygen catalyzed by vanadium(IV). Vanadium(V) reduction and preconcentration of vanadium(IV) was carried out using in‐line silver reductor and 8‐hydroxyquinoline chelating columns at pH 3.15, respectively. The calibration graph for vanadium(IV) was linear in the concentration range of 0.025–10 µg/L with relative standard deviation in the range of 0.4–5.58%. The detection limit (3s blank) was 3.8 × 10^?3 µg/L without preconcentration; when the vanadium(IV) was preconcentrated with an 8‐HQ column for 1 min (2.0 mL of sample loaded), the detection limit of 5.1 × 10^?4 µg/L was achieved. One analytical cycle can be completed in 2.0 min. The analysis of certified reference materials (CASS‐4, NASS‐5 and SLRS‐4) by the proposed method showed good agreement with the certified values. The method was successfully applied to the determination of total dissolved vanadium in environmental water samples. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of pholcodine in syrups and human plasma using the chemiluminescence system of tris(1,10 phenanthroline)ruthenium(II) and acidic Ce(IV)

Pholcodine is an opiate derivative drug which is widely used in pediatric medicine. In this study, a chemiluminescence (CL) method is described that determines pholcodine in human plasma and syrup samples. This method is based on the fact that pholcodine can greatly enhance the weak CL emission of reaction between tris(1,10 phenanthroline)ruthenium(II), Ru(phen)₃²⁺, and acidic Ce(IV). The CL mechanism is described in detail using UV–vis light, fluorescence and CL spectra. Effects of chemical variables were investigated and under optimum conditions, CL intensity was proportional to the pholcodine concentration over the range 4.0 × 10^?8 to 8.0 × 10^?6 mol  L^?1. The limit of detection (LOD) (S/N = 3) was 2.5 × 10^?8 mol  L^?1. Percent of relative standard deviations (%RSD) for 3.0 × 10^?7 and 3.0 × 10^?6 mol  L^?1 of pholcodine was 2.9 and 4.0%, respectively. Effects of common ingredients were investigated and the method was applied successfully to the determination of pholcodine in syrup samples and human plasma.     

Synchronous fluorescence determination of ferulic acid with Ce(IV) and sodium tripolyphosphate

In this study, a synchronous fluorescence detection method for ferulic acid (FA) is proposed based on a redox reaction between FA and Ce(IV) sulfate in dilute sulfuric acid medium at room temperature. It was found that FA could reduce Ce(IV) to Ce(III) in acidic medium, and sodium tripolyphosphate could further enhance the intrinsic fluorescence of the Ce(III) produced. The enhanced extent of synchronous fluorescence intensity was in proportion to the concentration of FA over the range 3.0 × 10^‐8 to 1.0 × 10^‐5 mol/L. The corresponding limit of determination (S/N = 3) was 1.3 × 10^‐8 mol/L. The proposed method was applied to the determination of sodium ferulate for injection sample with satisfactory results. Copyright © 2013 John Wiley & Sons, Ltd.     

Exploring the electrochemiluminescent behavior of procaterol hydrochloride in the presence of Ru(bpy)32+ and its analytical application in pharmaceutical preparation

Based on the strong enhancement effect of procaterol hydrochloride on the electrochemiluminescence (ECL) of Ru(bpy)₃²⁺ (bpy = 2,2′‐bipyridine) in an alkaline H₃PO₄–NaOH buffer solution on a bare Pt electrode, a simple, rapid and sensitive method was developed for the determination of procaterol hydrochloride. The optimum conditions for the enhanced ECL have been developed in detail in this work. Under optimum conditions, the logarithmic ECL enhancement vs. the logarithmic concentration of procaterol hydrochloride is linear over a wide concentration range of 2.0 × 10^?7 to 2.0 × 10^?4 M (r =  0.9976), with a limit of detection of 1.1 × 10^?8 M (S/N =  3), and a relative standard deviation of 2.1% (n =  7, c =  5.0 × 10^?6 M). The proposed method was applied to the determination of this drug in tablets with recoveries of 89.7%–98.5%. In addition, a possible mechanism for the enhanced ECL of Ru(bpy)₃²⁺, which is caused by ProH, has also been proposed.     

A novel chemiluminescent flow injection analysis of trace amounts of rutin by its inhibition of the luminol–hydrogen peroxide reaction catalyzed by tetrasulfonated colbalt phthalocyanine

Based on the inhibition effect of rutin on the luminol–hydrogen peroxide chemiluminescence (CL) system catalyzed by tetrasulfonated colbalt phthalocyanine (CoTSPc), a sensitive flow‐injection CL method has been developed for the determination of rutin. The CL reaction mechanism was carefully investigated by examining CL emission spectra, UV–visible spectra and variation of reaction conditions. It was found that there existed a linear relationship between CL intensity and the concentration of rutin in the range of 8.0 × 10^?9 to 1.0 × 10^?6 mol L^?1, and the detection limit is 3.8 × 10^?9 mol L^?1. This proposed method is sensitive, convenient and simple, and has been applied to the determination of rutin in commercial rutin tablets with satisfactory results. Copyright © 2009 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.