Flow-through Optosensor Research Articles

Determination of Chlorpyrifos by a Multicommutated Photochemically Induced Fluorescence Optosensor

We propose a multicommutated flow-through optosensor for the quantitation of the organophosphate pesticide chlorpyrifos in dried chili peppers. We used photochemically induced fluorescence detection to overcome the negligible native fluorescence of the target pesticide. Firstly, the photodegradation of chlorpyrifos was performed online with an ultraviolet lamp. Then, the fluorescent photoproduct was retained on a solid support (Sephadex QAE A-25) inside the flow-cell in order to record the analytical signal. The online photodegradation and preconcentration of the photoproduct on the solid support were critical for the automation, speed, and high sensitivity obtained. A QuEChERS procedure was selected for sample treatment, obtaining recovery yields close to 100%. The method proposed presents a quantitation limit of 18 mg kg−1 in real samples, hence fulfilling the maximum residue limit of Codex Alimentarius, 20 mg kg−1. Therefore, this approach offers a novel method for screening purposes in the agricultural and food industries.

Automated fluorimetric sensor for the determination of zearalenone mycotoxin in maize and cereals feedstuff

Zearalenone (ZEA), a mycotoxin produced by several Fusarium molds, can be found in many cereals and related products. The toxicity of ZEA has been reported for both humans and animals. Therefore, many countries have adopted regulations in foods and feed materials to limit the exposure to this contaminant. In this paper, we propose a multicommutated flow-through optosensor to quantify ZEA in different cereal samples. ZEA was retained and pre-concentrated on C18 silica gel, and the use of the multicommutated flow manifold allowed the automated retention/desorption of ZEA on the solid microbeads by the use of appropriate carrier/eluting solutions, hence increasing the selectivity and sensitivity of the system. The native fluorescence of ZEA was recorded on the solid phase at λexc/λem of 265/465 nm/nm. A QuEChERS procedure was used to carry out the extraction of ZEA from different cereal samples (feedstuff materials). Recovery studies were performed to assess the accuracy of the method, obtaining recovery yields between 93% and 107% in all the analyzed samples. LC-MS was employed as reference method. The quantitation limit of the proposed method was low enough to fulfill the maximum residue levels established by the Commission of the European Communities, thus demonstrating its potential use for the analysis of ZEA in feedstuffs.

A photochemically induced fluorescence based flow-through optosensor for screening of nitenpyram residues in cruciferous vegetables

ABSTRACTOne of the most used agrochemicals in agricultural production, nitenpyram (NTP), has been determined by using a flow-through optosensing device based on Photochemically Induced Fluorescence detection. The combination of both methodologies allows, on one hand, a quick on-line photodegradation of NTP and, on the other hand, the preconcentration, quantification and desorption of the fluorescent photoproduct generated when retained on Sephadex QAE-A25 as solid support, which was monitored at 295 and 362 nm for excitation and emission, respectively. The proposed analytical method presents a detection limit of 500 pg mL−1 by using Multicommutated Flow Injection Analysis. Recovery experiments were carried out in different kinds of cruciferous vegetables at or below the MRL established in Japan, demonstrating that this method combines advantages of simplicity, high sensibility and high selectivity, fulfilling the requirements for its application in quality control. Results obtained in the analysis of real samples were in good agreement with those provided by a reference HPLC method.

Multi-commutated fluorometric optosensor for the determination of citrinin in rice and red yeast rice supplements

Citrinin is a toxic secondary metabolite first isolated from Penicillium citrinum, although is also produced by other species of Penicillium and Aspergillus. It has highly toxic, mutagenic, teratogenic and carcinogenic properties and is often found in crops, vegetables and fruit. To our knowledge there is no specific legislation on maximum levels permitted for citrinin, so no official analytical method is currently available for its determination. Our laboratory developed a fluorometric flow-through optosensor using Sephadex SPC-25 as solid support. Multi-commutated flow injection analysis was used for the construction of the manifold and for handling solutions. In this way, we minimised waste generation and human intervention, which are critical aspects when dealing with highly toxic compounds such as citrinin. The optimum excitation/emission wavelengths were set at 330/494 nm; the calibration curve was linear in the concentration range 35–900 ng ml−1. A detection limit of 10.5 ng ml−1 and relative standard deviations (RSDs) lower than 3% were obtained. The developed optosensor was applied to the determination of citrinin in rice and dietary supplements containing red yeast rice.

Separation of a binary mixture of pesticides in fruits using a flow-through optosensor

A flow-through optosensor is here proposed for the determination of mixtures of two widely used pesticides, carbendazim and o-phenylphenol, in fruits. The pesticides are separated on-line using an additional amount of solid support, C18 silica gel, in the flow-through cell. The resolution is performed due to the different retention/desorption kinetics of the analytes when interacting with the C18 microbeads. Therefore, both separation and determination are integrated in the same cell, considerably simplifying the system. In addition, the use of Sequential Injection Analysis provides a high degree of automation and minimum wastes generation. After the analytes are separated, their native fluorescence is measured, obtaining linearity in the 2.0–30 and 1.1–20mgkg−1 ranges for carbendazim and o-phenylphenol. The detection limits are 0.60 and 0.33mgkg−1 for carbendazim and o-phenylphenol respectively. The proposed method fulfills the maximum residue limits (MRLs) established in Europe and USA for these pesticides in cherries, pineapple, and mango: 5–10mgkg−1. In order to demonstrate the suitability of the method, several samples have been analyzed and the obtained results compared with a chromatographic method.

Determination of Carbendazim in Food Products Using a Sequential Injection Analysis Optosensor

Carbendazim (CBZ) is a widely used broad-spectrum benzimidazole fungicide used to control plant diseases in cereals, vegetables, and fruits. It has been recently found that it is useful for the control of aflatoxin contamination in chili peppers (Capsicum annuum). In addition, it is useful against other diseases in peppers and tomatoes (Solanum lycopersicum). A flow-through optosensor using C18 silica gel as solid support is here presented for the fluorimetric (λ exc/λ em = 276/306) determination of CBZ in Capsicum powder and dried tomatoes. The proposed system has been developed using sequential injection analysis, so improving the repeatability and automation of the system and minimizing wastes generation. The method presents a detection limit of 3 μg L−1, a sample throughput of 16 samples per hour and interday relative standard deviation lower than 6 %. Taking into account that the maximum residue limit specified in the Codex Alimentarius for dried peppers is 20 mg kg−1, recovery experiments have been carried out for CBZ concentrations in the 15–40 mg kg−1 range, obtaining satisfactory results. Therefore, the proposed method fulfills the current legislation and could be used as an alternative to other analytical methods, such as chromatographic ones.

Automated optosensor for the determination of carbaryl residues in vegetable edible oils and table olive extracts

Carbaryl, which belongs to the carbamate family, is a broad-spectrum insecticide used to control over 100 species of insects. In this paper, we propose a flow-through optosensor for the determination of this compound in edible vegetable oils (olive, sunflower and corn oils) and table olives. Two automated flow methodologies have been compared in order to develop the proposed system, Sequential Injection Analysis and Multicommutated Flow Injection Analysis, using C18 silica gel as solid support placed in the flow-cell. After proper extraction with a QuEChERS method, the proposed system presents a detection limit of 1mgkg−1, which is suitable taking into account the maximum residue limits (MRLs) established by Codex Alimentarius in olive oil (25mgkg−1) and table olives (30mgkg−1), obtaining relative standard deviations lower than 4% in all cases. Recovery experiments have been carried out in several samples of oils and table olives, at levels equal to and below those established by legislation, ranging between 85 and 115%, therefore demonstrating that the proposed analytical method fulfills the requirements for its applications in quality control analyses.

Fluorimetric determination of thiabendazole residues in mushrooms using sequential injection analysis

Thiabendazole is a benzimidazole fungicide of general use that is specifically used to control mushroom diseases, mainly cobweb diseases, which is caused by members of the genus Cladobotryum. Although this compound is legislated and its maximum residue limit established at 60mgkg−1 by Codex Alimentarius, there is almost a complete absence of analytical methods available for its determination in mushrooms. Here, we propose an automated method, using Sequential Injection Analysis with fluorescence detection (λexc/λem=305/345nm) for the determination of thiabendazole in mushrooms. We have developed a flow-through optosensor using C18 silica gel as solid support placed in the flow-cell where the determination is performed. This method presents a detection limit of 0.5mgkg−1, and recovery experiments have been carried out in different kinds of mushrooms at levels below the legislated maximum residue limit, demonstrating that the proposed analytical method fulfils the requirements for its applications in quality control of mushrooms.

An automatic optosensing device for the simultaneous determination of resveratrol and piceid in wines

For the first time, a spectrofluorimetric method is reported for the simultaneous determination of resveratrol (RVT) and piceid (PCD), two stilbenes showing diverse interesting physiological and biochemical attributes, as well as a wide range of health benefits ranging from cardioprotection to chemoprevention. The method makes use of a multicommutated flow-through optosensor in which the resolution of RVT and PCD is accomplished by means the sequential arrival of their photoproducts, on-line generated by UV-irradiation, to the detection area. This is possible due to the different kinetic behaviour of these latter on a solid support (C 18 silica gel) filling a minicolumn placed before the detector. The measurement in solid-phase of the photochemically induced fluorescence of the photoproducts ( λ ex: 257 nm/ λ em: 382 nm) is used as analytical signal for monitoring both compounds. The method has been applied to the analysis of RVT and PCD in wines and requires a previous solid-phase extraction (SPE) using Bakerbond C 18 cartridges. This pretreatment and the use of a solid-support in both the minicolumn and the flow-cell of the detector allow the determination of RVT and PCD by external calibration. Detection limits (DLs) are 9.3 and 12.6 ng mL −1 for RVT and PCD, respectively. Commercial red and white wine samples have been analysed and the results obtained have been satisfactorily validated by high-performance liquid chromatography (HPLC).

Chemometrics−Assisted Fluorimetry for the Rapid and Selective Determination of Heavy Polycyclic Aromatic Hydrocarbons in Contaminated River Waters and Activated Sludges

The most concerned polycyclic aromatic hydrocarbons (PAHs) benzo[a]pyrene, dibenz[a,h]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene and benz[a]anthracene were simultaneously determined in the presence of other 10 interfering PAHs, applying second-order multivariate calibration to the data obtained with a flow-through optosensor interfaced to a fast-scanning spectrofluorimeter. Using a sample volume of 2.5 mL, detection limits in the range 5-115 ng L(-1) were obtained in interfering samples, with a sample frequency of ca. 15 samples per hour, and with a minimum use of organic solvents, competing very favorably with chromatographic methods. The significance of this study lies in the solution of the quantitative analysis problem of six PAHs in real matrices of unknown composition. The unfolded partial least-squares/residual bilinearization (U-PLS/RBL) algorithm showed the best performance in resolving the complex studied system.

A thionine-based reversible redox sensor in a sequential injection system

According to the current demands of Green Analytical Chemistry and regarding the need for lower reagent consumption with improved analytical performance, an automatic methodology with a flow-through optosensor incorporating solid-phase spectrophotometric detection was developed. The sensor used in this work was based on the redox state of thionine whose oxidized form is blue and reduced form is colorless with monitoring carried out at 621 nm. This redox indicator was immobilized on gel beads and subsequently packed into a flow-through cell. It was then assembled into a sequential injection system and was shown to be an excellent alternative to monitor enzymatic redox reactions automatically as the redox catalysis is performed by glucose dehydrogenase. This enzyme is a representative dehydrogenase enzyme and uses NAD + as cofactor, promoting the oxidation of glucose to glucono-lactone and reduction of NAD + to NADH. The produced NADH promotes color depletion on the surface of the sensor. The calibration graph for glucose was linear between 5.74 × 10 −4 and 2.00 × 10 −3 mol L −1 and detection limit was 1.72 × 10 −4 mol L −1. Glucose concentration in different samples including sera, salines, perfusion solutions, powder for preparing oral solutions and solutions for hemodialysis was determined. The method proved to be reproducible with a RSD < 5% for glucose determinations.

Flow injection analysis with on-line nylon powder extraction for room-temperature phosphorescence determination of thiabendazole

A fast and very selective flow-through phosphorescence optosensor was designed and characterized for the determination of the fungicide thiabendazole in water samples. For the first time, thiabendazole was determined using a flow-through optosensor based on the phosphorescence signals obtained when it is retained in a solid support. While thiabendazole does not phosphoresce in packing materials commonly used to fill the flow-cell, significant emission signals are observed when it is retained on nylon powder in the presence of iodide and sulfite. The experimental set-up was based on a flow-injection manifold coupled to an on-line phosphorescence detector containing nylon powder packed in a conventional flow-cell. Potassium iodide and sodium sulfite were added to sample aliquots to improve the thiabendazole phosphorescence and injected in the flow manifold using water as carrier. After the phosphorescence emission was registered, the analyte was eluted from the packed nylon with a 65% (v/v) methanol–water mixture. Optimal instrumentation, experimental and flow conditions were evaluated. Using a sample volume of 2000 μL, the analytical signal showed a very good linearity in the range 12.9–110 ng mL −1, with a detection limit of 4.5 ng mL −1, and a sample throughput of about 14 samples per hour. The effects of the presence of concomitant species in the thiabendazole phosphorescence signal were studied, and a comparison with the fluorescence nylon-powder optosensor was carried out and discussed. Finally, the applicability of the proposed optosensor was tested in water samples, and satisfactory recoveries ranging between 97% and 105% were obtained.

Simultaneous Flow-Injection Solid-Phase Fluorometric Determination of Thiabendazole and Metsulfuron Methyl Using Photochemical Derivatization

A flow-through optosensor implemented with photochemically induced fluorescence (PIF) is reported for the simultaneous determination of thiabendazole (TBZ) and metsulfuron methyl (MET). TBZ is determined by measuring its native fluorescence once retained on the solid support filling the flow-cell of a FI-system. On the other hand, a strongly fluorescent photoproduct from MET is generated on-line in micellar medium by UV irradiation and monitored in a similar way to TBZ. MET photoproduct and TBZ are separated by placing in the flow-system a minicolumn, filled with C(18) silica gel, which allows their sequential arrival to the detection area. The sorption of the species on the solid support in the detection area provides a noticeable improvement in sensitivity and selectivity when comparing with their determination in homogeneous solution. The detection limits and RSDs for TBZ and MET are 2.5 and 3.3 ng ml(-1) and 1.1 and 2.4%, respectively. The method is successfully applied to environmental water samples.

Flow-through Fluorescence-based Optosensor for the Screening of Zinc in Drinking Water

A single and rapid solid surface fluorescence-based flow-through optosensor has been developed for the screening of trace amounts of Zn(II) in drinking water samples. The proposed method is based on the transient immobilization of the target species: the complex formed between Zn(II) and the fluorogenic reagent p-(tosylamino)quinoline (p-TAQ) on an appropriate solid support (C(18) silica gel). The fluorescence of the complex was continuously monitored at an emission wavelength of 495 nm upon excitation at 377 nm. The instrumental, chemical and flow-injection variables were carefully investigated and optimized. The sensor was calibrated over the range of 5 - 125 ng mL(-1), obtaining a limit of detection of 0.9 ng mL(-1), a RSD of 1.8%, with a sampling frequency of 20 h(-1). The proposed method was successfully applied to different drinking water samples with recoveries between 98 and 104%.

Development of a flow-through optosensor for determination of Co(II)

A flow-through optical fibre chemical sensor for the determination of Co(II) at trace level using immobilised 2-(4-pyridylazo)resorcinol (PAR) as the reagent phase is proposed. PAR is physically adsorbed onto XAD-7. This method provided a great sensitivity and simplicity with wide linear response range from 1 × 10 −2 to 1 × 10 3 ppm and detection limit of 20 ppb. This method also showed a reproducible result with relative standard deviation (R.S.D.) of 1.78% and response time of ∼5 min. The response towards Co(II) was also reversible using acidified KCl as the regenerating solution. Interference studies showed that Cr(III) significantly interfered during the determination. Excellent agreement with reference to inductively coupled plasma optical emission spectroscopy (ICPOES) method was achieved when the developed sensor was applied for determination of Co(II) in aqueous samples.

Multicommuted Fluorometric Multiparameter Sensor for Simultaneous Determination of Naproxen and Salicylic Acid in Biological Fluids

A combined approach based on solid-phase optosensing and multicommutation principles has been applied to develop a method for the simultaneous analysis of two pharmaceuticals (naproxen and salicylic acid) in biological fluids. The multicommuted flow-through optosensor was based on direct native fluorescence measurements of both analgesics using a non-polar sorbent (C18 silica gel) as a solid sensing zone. The flow system was controlled by Java-written home-made software and designed using three-way solenoid valves for an independent automated manipulation of sample and carrier solutions. Using an optimized sampling time, the method was calibrated in the range of 1 - 25 and 5 - 200 ng mL(-1). The obtained detection limits were 0.3 and 1.3 ng mL(-1) for naproxen and salicylic acid, respectively, with RSD (%) values of better than 2% for both analytes. The proposed methodology was successfully applied to urine, serum and pharmaceutical preparations. Recovery percentages ranging from 96.1 to 104% were obtained for both analytes.

Environmental Water Samples Analysis of Pesticides by Means of Chemometrics Combined with Fluorimetric Multioptosensing

A single flow-through optosensor spectrofluorimetric system is proposed for the resolution of mixtures of three pesticides, alpha-naphthol, o-phenylphenol and thiabendazole, at microg l(-1) levels using a partial least-squares (PLS) calibration approach. The sensor was developed in conjunction with a monochannel flow-injection analysis system with fluorimetric detection using C18 silicagel as an active sorbent substrate in the flow cell. By using 20% methanol-water (v:v) solution as carrier solution, the multisensor responds linearly in the measuring range without requiring additional reagents or derivatization. First derivative emission spectra of the corresponding analytes recorded during the process of retention-elution were used to provide multivariate data. The different kinetic on the retention process of the analytes on the sensing zone allows the selection of a time matrix for each analyte providing best results in the PLS approach. Accurate prediction results were obtained for the three analytes with RMSEP values of 1.86%, 3.34% and 0.50% were obtained for alpha-naphthol, o-phenylphenol and thiabendazole respectively. In the analysis of environmental waters samples, a mean recovery of 103% was obtained.

Direct screening of tetracyclines in water and bovine milk using room temperature phosphorescence detection

A fast and simple flow-through optosensor was designed and characterized for the direct screening of four tetracycline (TCC) antibiotics (tetracycline, oxytetracycline, chlortetracycline and doxycycline) in water and bovine milk samples. The proposed optosensor provides rapid binary yes/no overall responses, being appropriate for the screening of this family of antibiotics above or below a pre-set concentration threshold. The experimental set-up is based on a flow-injection manifold coupled on-line to a phosphorescence detector. Aliquots of the samples are pretreated with Eu(III) to form room temperature phosphorescent metal chelates and injected in the flow manifold. Those chelates are then on-line retained on a conventional flow-cell (packed with polymeric Amberlite XAD-4 particles) which is placed inside the cell holder of the phosphorimeter. After the emission is registered, the antibiotic–metal complexes are eluted from the packed resin with 1 M HCl (for milk samples a second regeneration step, using methanol, should be performed). A sample throughput of about 20 samples per hour was obtained. Optimum experimental conditions include a pH 9, a Eu(III) concentration of 2 × 10 −4 M and 8 mM sodium sulphite as chemical deoxygenant. The phosphorescence emitted by the europium–TCC complexes was measured at 394 and 617 nm for excitation and emission wavelengths, respectively. The unreliability region, given by the probability of false positives and false negatives, respectively (set at 5% in both cases) was in the range between 0.2 and 11.6 nМ for detection of tetracyclines in water samples (at a cut-off level of 4 nM) and in the range between 165 and 238 nM for detection of tetracyclines in milk (cut-off level fixed at the normative EU level of 200 nM). Finally, the applicability of the proposed screening optosensor was tested for the reliable control of tetracyclines in contaminated and uncontaminated water and milk samples.

Flow-through optosensor combined with photochemically induced fluorescence for simultaneous determination of binary mixtures of sulfonamides in pharmaceuticals, milk and urine

A sensitive and selective flow-through optosensor implemented with photochemically induced fluorescence (PIF) is proposed for the simultaneous determination of mixtures sulfamethoxazole/sulfanilamide and sulfathiazole/sulfanilamide. The resolution was accomplished by placing in the flow system a minicolumn filled with an appropriate solid support. Whereas one of the sulfonamides is not retained in the minicolumn and is determined by measuring its native fluorescence on the solid surface of the sensing microbeads in the detection area, the other one is retained and, after its elution, it is photochemically converted into a strongly fluorescent photoproduct which is transitorily retained on the sensing support in the flow cell and monitored. Linear calibration graphs were obtained over a concentration range of 2–3 orders of magnitude. The detection limits for the determination of sulfamethoxazole, sulfanilamide and sulfathiazole are 8.1, 2.9 and 5.7 ng mL −1, respectively. The method was applied to pharmaceuticals, milk and human urine. The recovery of sulfamethoxazole from pharmaceuticals was 102.5% indicating no interference from trimethoprim which is not photochemically active. The recoveries for urine and milk samples fortified with sulfonamides at levels between 0.1 and 0.7 μg mL −1 agreed within 95.0–107.5% of spiked levels.

Flow-through solid-phase reflectometric method for simultaneous multiresidue determination of nitrophenol derivatives

In this paper, a flow-through optosensor based on diffuse reflectance spectroscopy and multivariate regression modelling is proposed for simultaneous multiresidue determination of trace level concentrations of nitro-substituted phenols. The optrode integrates on-line anion-exchange sorptive preconcentration and matrix removal with direct detection of sorbed species onto the sensing layer and chemometric deconvolution of overlapped spectra. After recording of the reflectometric spectrum, fast chemosensor regeneration is accomplished with an acidic methanolic eluent followed by a metered volume of alkaline solution. The full automation of the analytical procedure is ensured by flow-programming as executed via a software-controlled multisyringe pump and a set of multiposition and solenoid valves. Under the optimized chemical and physical variables, the 3 σ blank detection limits for 2-, and 4-nitrophenol and 2,4-dinitrophenol were 0.69, 0.42 and 0.37 μg L −1, respectively, for a sample loading volume of 4.0 mL with enrichment factors of 73, 74 and 81, respectively , and repeatability better than 3.0%. The analytical applicability of the optosensing system was asserted by the satisfactory results attained in its application to monitoring of nitrophenol derivatives in spiked environmental waters including highly saline matrices via the standard additions method.