Ana M. García-Campaña

Chemiluminescence in analytical chemistry

Historical evolution of chemiluminescence chemiluminescence-based analysis - an introduction to principles, instrumentation and applications the nature of chemiluminescence reactions recent evolution in chemiluminescence instrumentation application of chemiluminescence in organic analysis application of chemiluminescence in inorganic analysis mechanism and application of peroxyoxalate chemiluminescence kinetics in chemiluminescence analysis electrogenerated chemiluminescence applications of bioluminescence in analytical chemistry the role of organized media in chemiluminescence reactions chemiluminescence in flow injection analysis gas-phase chemiluminescence detection chemiluminescence detection in liquid chromatography chemiluminescence detection in capillary electrophoresis bioanalytical applications of chemiluminescence imaging photosensitized chemiluminescence and its application in medical routine and industrial analysis application of novel acridan esters as chemiluminogenic signal reagents in immunoassay chemiluminescence in DNA analysis recent developments in chemiluminescence sensors.

Recent developments in nanomaterial optical sensors

The application of nanomaterials in the field of optical sensors has become a new, growing area of interest in recent years. We review chemical sensors that apply the optical principles of nanomaterials to the determination of chemical and biochemical analytes. We mainly focus on the changes of spectral absorbance, photoluminescence (PL) and chemiluminescence (CL) phenomena induced by the interaction between nanomaterials and various analytes.

Multiclass mycotoxin analysis in Silybum marianum by ultra high performance liquid chromatography–tandem mass spectrometry using a procedure based on QuEChERS and dispersive liquid–liquid microextraction

Ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) has been proposed for the determination of 15 mycotoxins in milk thistle (Silybum marianum), including aflatoxins, fumonisins, trichothecenes, ochratoxin A, citrinin, sterigmatocystin and zearalenone. The mycotoxins were detected by electrospray ionization in positive ion mode and multiple reaction monitoring (MRM), achieving the separation in about 4min. Sample treatment consisted of a modified method based on a first step using a QuEChERS-based procedure which allowed the determination of fumonisin B1, fumonisin B2, nivalenol, deoxynivalenol and fusarenon-X, and a subsequent clean-up based on dispersive liquid-liquid microextraction (DLLME) for the determination of the rest of mycotoxins. The method has been validated in extract and seeds of milk thistle, obtaining limits of quantification lower than those usually permitted by legislation in food matrices, with precisions lower than 10%. Recoveries were between 62.3% and 98.9%, except for zearalenone in seeds samples and citrinin in extract. The method was also applied for studying the occurrence of these mycotoxins in market samples (six samples of seeds, three of them purchased in bulk in a street vendor, and one natural extract of milk thistle), and HT-2, T-2 and zearalenone have been found in some of the samples. To the best of our knowledge, this is the first time that this type of treatment has been used for these complex food matrices, allowing the analyses of the most important mycotoxins.

Applications of capillary electrophoresis to the determination of antibiotics in food and environmental samples.

In this paper we review applications of capillary electrophoresis (CE) to the determination of antibiotic residues in food derived from animals and in environmental samples. Although many CE methods have been used to determine antibiotics in the pharmaceutical field (drug quality control or therapeutic monitoring in biological samples), food and environmental applications have been increasing in recent years. Due to the maximum residue limits established by the EU, in Directive 2377/90/EEC, for foodstuffs of animal origin and considering the low levels that can be found in environmental or waste waters or soils, different strategies to increase sensitivity have been developed, including off-line preconcentration, on-line stacking modes to use higher sample volumes, or in-line solid-phase extraction. Also, several detection techniques, such as fluorescence, laser-induced fluorescence, electrochemical detection, or mass spectrometry have been used; the last of these also enables unequivocal identification of the residues, required by Commission Decision 2002/657/EC. All these aspects will be discussed in this paper, in relation to the main groups of antibiotics used in veterinary and human medicine, for which applications in food and environmental samples have been developed by using CE as an efficient alternative to liquid chromatography.

Laser induced fluorescence coupled to capillary electrophoresis for the determination of fluoroquinolones in foods of animal origin using molecularly imprinted polymers.

A method for the simultaneous determination of four fluoroquinolones of veterinary use (ciprofloxacin, danofloxacin, enrofloxacin and sarafloxacin) in two complex matrixes, such as bovine raw milk and pig kidney, has been established and validated. The method is based on the use of capillary electrophoresis (CE) coupled with a very sensitive detection mode, such as laser induced fluorescence (LIF) detection, due to the fact the all the compounds selected show native fluorescence. In order to achieve high selectivity in the sample treatment procedure, a commercially available molecularly imprinted polymer has been used for the solid phase extraction of the analytes. Once the retention and elution processes were optimized, the final extract was analyzed by CE-LIF using a 325 nm He-Cd laser. Optimum separation was obtained in a 70 cm x75 microm capillary using a 125 mM phosphoric acid solution at pH 2.8 with 36% methanol as background electrolyte. The method provided very low detection limits, ranging from 0.17 to 0.98 microg/kg for milk and 1.10 to 10.5 microg/kg for kidney, with acceptable precision and satisfactory recoveries.

Determination of sulfonamide residues in water samples by in-line solid-phase extraction-capillary electrophoresis.

An in-line solid-phase extraction-capillary electrophoresis method with UV-vis detection was developed for the monitoring of residues of five sulfonamides (sulfadoxin, sulfadimethoxine, sulfamerazine, sulfachloropyridazine and sulfamethoxazole) in tap, bottled mineral and river waters. For this purpose an analyte concentrator was constructed, based on the introduction of a small portion of a solid-phase extraction sorbent into the electrophoretic capillary to carry out an in-line concentration step, improving sensitivity. A detailed study was carried out to optimize parameters affecting the in-line solid-phase extraction process, such as the design of the concentrator device, type of sorbent and conditions of elution and injection. The proposed method is simple for the environmental monitoring of these antibiotic residues in waters, allowing the direct injection of the samples without any off-line pretreatment and achieving limits of detection between 0.3 and 0.6 microg/L. Recoveries ranging 52.2-109.2% and relative standard deviations below 13.4% were obtained.

Determination of ochratoxin A in wines by capillary liquid chromatography with laser induced fluorescence detection using dispersive liquid-liquid microextraction

A method based on reverse phase capillary high performance liquid chromatography (capillary HPLC) coupled to laser-induced fluorescence detection (LIF) has been proposed for the determination of ochratoxin A (OTA) in wine samples. An anionic micellar medium was added to the mobile phase for increasing the fluorescence intensity and peak efficiency. Dispersive liquid-liquid microextraction (DLLME) has been used as a simple and efficient sample pretreatment method for the analysis of OTA in wines, being optimised by means of experimental design. The limit of detection was 5.5 ng L(-1) (3 × S/N) and recoveries for different wines ranged from 91.7 to 98.1%. The proposed methodology could be classified as a green analytical chemistry alternative, combining the low organic solvent volumes required in the DLLME with the reduced consumption of mobile phase in capillary HPLC. The use of LIF as detector provided an extremely sensitive method for the determination of OTA in wines.

Comparison of different sample treatments for the analysis of quinolones in milk by capillary-liquid chromatography with laser induced fluorescence detection.

A simple and very sensitive capillary-liquid chromatography method coupled with laser induced fluorescence detection has been developed for the simultaneous determination of seven quinolones of veterinary use in milk. Moreover, a comparison between two different sample treatments (QuEChERS and molecularly imprinted polymer, MIP) has been carried out in terms of efficiency of the extraction (number of analytes to be analysed and absence of interferences), throughput, linear dynamic range in matrix-matches calibrations, detection and quantification limits and accuracy (trueness and precision, by means of recovery assays). The results showed that the QuEChERS procedure was more efficient and faster, showing good recoveries, sensitivity and precision for all the studied compounds. Employing this proposed method, very low detection limits, between 0.4 μg/kg for danofloxacin, and 6 μg/kg for sarafloxacin, have been obtained.

Trace determination of β-lactam antibiotics in environmental aqueous samples using off-line and on-line preconcentration in capillary electrophoresis☆

A sensitive and reliable method using capillary zone electrophoresis with UV-diode array detection (CZE-DAD) has been developed and validated for trace determination of beta-lactam antibiotics in waste, well and river water matrices. Due to the lack of sensitivity of the UV-vis detection, a solvent extraction/solid-phase extraction (SPE) method applied for off-line preconcentration and cleanup of water samples, in combination with an on-line preconcentration methodology named large volume sample stacking (LVSS) have been applied. The analytes included nafcillin, dicloxacillin, cloxacillin, oxacillin, ampicillin, penicillin G and amoxicillin. Average recoveries for water samples fortified with the studied beta-lactams at different concentration levels (1.0, 2.0 and 4.0 microg/L) were ranging between 94 and 99%, with relative standard deviations (RSDs) lower than 10%. The precision, calculated as intra-day and inter-day standard deviations fell within acceptable ranges (3.3-7.2%). The limits of detection were estimated to range between 0.08 and 0.80 microgL(-1) for the studied compounds. All the samples analyzed were negative for all the analytes at these levels of concentration and the method showed its usefulness for the detection of these widely applied beta-lactam antibiotics in different kinds of waters.

Determination of N-methylcarbamate pesticides in water and vegetable samples by HPLC with post-column chemiluminescence detection using the luminol reaction

In this paper we proposed a reverse high performance liquid chromatography method for the simultaneous determination of three N-methylcarbamates (NMCs) named carbofuran, carbaryl and methiocarb, using the post-column chemiluminescence (CL) detection with the luminol reaction. This method is based on the enhancing effect of these analytes on the CL emission generated by the oxidation of luminol with potassium permanganate in alkaline medium. The separation was reached in less than 14 min using a C18 column and an isocratic binary mobile phase consisting of acetonitrile:water (50:50, v/v) pumped at a flow rate of 1 mL min(-1). CL reagents (luminol and KMnO(4)) were incorporated by means of a peristaltic pump and were firstly mixed using a three-way connector. Then this stream was mixed with the eluate using another three-way connector just before reaching the detection cell. The optimization of variables affecting the CL reaction (reaction medium, concentration, flow rate of reagents and distance between both connectors) were optimized by means of experimental designs. Ethiofencarb, a NMC which has nowadays fallen into disuse was used as internal standard. For the analysis of theses pesticides in real water samples a pre-treatment step consisting of solid phase extraction (SPE) was conducted in order to reach sensitivity levels below the legal maximum concentration permitted. In the case of vegetable sample, SPE was used for matrix cleaning purpose.