Synthesis and characterization of a novel molecularly imprinted polymer for simultaneous extraction and determination of water-soluble and fat-soluble synthetic colorants in chilli products by solid phase extraction and high performance liquid chromatography

A sorbent was synthesized and investigated for molecularly imprinted solid phase extraction (MISPE). Molecularly imprinted polymers (MIP) were synthesized via precipitation polymerization procedure, where 4-vinyl pyridine (4-VP) was used as functional monomer and ethylene glycol dimethacrylate (EDMA) as cross-linking agent. The imprinting effect of the MISPE was evaluated by elution experiments. The resulting MISPE showed high extraction selectivity to water-soluble and fat-soluble synthetic colorants. The determination of multi-residue for three kinds of water-soluble and six kinds of fat-soluble synthetic colorants in chilli products was also investigated by HPLC coupled with MISPE. The mean recoveries calculated by solvent calibration curve for water-soluble and fat-soluble synthetic colorants were from 72.1% to 95.6% for chilli spice and 72.1% to 92.3% for chilli powder. The decision limit (CCα) and the detection capability (CCβ) obtained for water-soluble and fat-soluble synthetic colorants were in the range of 1.2–1.6 and 1.9–2.4 μg kg⁻¹ in chilli spice and chilli powder. The resulting MISPE was successfully used off-line for the determination of nine kinds of synthetic colorants in chilli products.     

Simultaneous determination of eleven quinolones in animal feed by liquid chromatography with fluorescence and ultraviolet absorbance detection

A rapid and simple multi-residue procedure is described for assaying eleven quinolones (cinoxacin, ciprofloxacin, danofloxacin, difloxacin, enrofloxacin, flumequine, marbofloxacin, nalidixic acid, norfloxacin, oxolinic acid and sarafloxacin) in feeds at sub-additive levels (1–5 mg kg⁻¹). Five grams of sample were extracted by a metaphosphoric acid/acetonitrile mixture (70/30, v/v) and purified onto OASIS HLB cartridges. The determination was achieved by liquid chromatography (LC) using a GEMINI C18 analytical column both with fluorescence detection (FD) and photodiode-array (DAD). Limits of detection for each drug were in the range 0.04–0.8 mg kg⁻¹. Above the limit of quantification (LOQ), in poultry feed the recoveries were from 69 to 98% with relative standard deviations less than or equal 10%. Finally the measurement uncertainty was estimated using the bottom-up approach.     

Determination of multi-residue for malachite green,gentian violet and their metabolites in aquatic products by high-performance liquid chromatography coupled with molecularly imprinted solid-phase extraction

A sorbent was synthesized and investigated for molecularly imprinted solid-phase extraction (MISPE). Molecularly imprinted polymers (MIPs) were synthesized via precipitation polymerization procedure, where methacrylic acid (MAA) was used as functional monomer and ethylene glycol dimethacrylate (EDMA) as cross-linking agent. The imprinting effect and selectivity of the MISPE were evaluated by elution experiments. The resulting MISPE showed high extraction selectivity to malachite green, gentian violet and their metabolites, which may be caused by both the ion exchange and the hydrophobic interactions. The determination of multi-residue for malachite green, gentian violet and their metabolites in aquatic products by HPLC coupled with MISPE was also investigated. The mean recoveries calculated by solvent calibration curve for malachite green (MG), gentian violet (GV), leucomalachite green (LMG) and leucogentian violet (LGV) were from 89.8% to 99.1% for grass carp, 90.6% to 101.2% for shrimp and 91.3% to 96.3% for shellfish. The decision limit (CCα) and the detection capability (CCβ) obtained for MG, GV, LMG and LGV were in the range of 0.11–0.14 and 0.19–0.24 μg kg⁻¹ for grass carp, shrimp and shellfish. The MISPE was successfully used off-line for the determination of MG, GV and their metabolites in aquatic products.     

Simultaneous determination of quinoxaline‐1,4‐dioxides in feeds using molecularly imprinted solid‐phase extraction coupled with HPLC

A simple, selective, and reproducible molecularly imprinted SPE coupled with HPLC method was developed for monitoring quinoxaline‐1,4‐dioxides in feeds. Molecularly imprinted polymers were synthesized in methanol using mequindox (MEQ) as template molecule and acrylamide as functional monomer by bulk polymerization. Under the optimum SPE conditions, the novel polymer sorbents can selectively extract and enrich carbadox, MEQ, quinocetone, and cyadox from a variety of feeds. The molecularly imprinted SPE cartridge was better than nonimprinted, C₁₈, and HLB cartridges in terms of both recovery and precision. Mean recoveries of four quinoxaline‐1,4‐dioxides from six kinds of feeds spiked at 1.0, 10, and 100 mg/kg ranged between 75.2 and 94.7% with RSDs of less than 10%. The decision limits (CCαs) and the detection capabilities (CCβs) of four analytes were 0.15–0.20 mg/kg and 0.44–0.56 mg/kg, respectively. The class selectivity of the polymers was evaluated by checking three drugs with different molecular structures to that of MEQ.     

Forensic analysis of dyed textile fibers

A rapid, specific, and sensitive method has been developed using molecularly imprinted polymers (MIPs) as solid-phase extraction sorbents for extraction of trace tetracycline antibiotics (TCs) in foodstuffs. MIPs were prepared by precipitation polymerization using tetracycline as the template. Under the optimal condition, the imprinting factors for MIPs were 4.1 (oxytetracycline), 7.0 (tetracycline), 7.4 (chlortetracycline), 7.7 (doxycycline), respectively. Furthermore, the performance of MIPs as solid-phase extraction sorbents was evaluated and high extraction efficiency of molecularly imprinted solid-phase extraction (MISPE) procedure was demonstrated. Compared with commercial sorbents, MISPE gave a better cleanup efficiency than C18 cartridge and a higher recovery than Oasis HLB cartridge. Finally, the method of liquid chromatography–tandem mass spectrometry coupled with molecular-imprinted solid-phase extraction was validated in real samples including lobster, duck, honey, and egg. The spiked recoveries of TCs ranged from 94.51% to 103.0%. The limits of detection were in the range of 0.1–0.3 μg kg⁻¹. Chromatograms obtained by direct injection of the spiked egg extracts (5 × 10^-3 mmol L⁻¹) and purification with MISPE     

Simultaneous determination of tetracyclines in poultry muscle by capillary zone electrophoresis

A capillary zone electrophoresis method with UV detection was developed for the simultaneous detection and quantification of three tetracyclines in chicken meat samples: tetracycline (TC), oxytetracycline (OTC) and doxycycline (DOC). The separation conditions were: a running buffer containing 30 mM sodium phosphate, 2 mM EDTA disodium salt and 2.5% 2-propanol, pH 12.0, a 5 s hydrodynamic injection and a 14 kV separation voltage. Two different clean-up methodologies were employed: solid-phase extraction with C₁₈ cartridges and ion exchange with Amberlite XAD7 resin. Analytes were detected at 360 nm in less than 12 min. LODs ranged from 61 μg kg⁻¹ for OTC to 68 μg kg⁻¹ for DOC with C₁₈ cartridges, and 81 μg kg⁻¹ for DOC to 89 μg kg⁻¹ for TC with Amberlite XAD7 resin. The recoveries for TC, OTC and DOC obtained by both methods were between 85 and 95%, and the peak area repeatability for all of the samples was below 5% in all cases. Twenty-four samples of commercial chicken drumsticks were examined with both clean-up methodologies. In nine cases (37.5%) TC was detected, in a range from 197.8 to 2564.3 μg kg⁻¹, and in seven cases (29.2%) OTC was detected in a range from 83.0 to 2049.3 μg kg⁻¹. DOC was not detected in any of the tested samples. This method would be useful for the routine monitoring of TCs residues in poultry muscle.     

Application of probe sonication extraction for the determination of linear alkylbenzene sulfonates from sewage sludge. Comparison with other extraction methods

A new method based on probe sonication extraction (USP) prior to high performance liquid chromatography (HPLC) has been developed for the determination of linear alkylbenzene sulfonates (LAS) from sewage sludge. The optimized method was designed to be cost effective compared to existing extraction methods (ultrasonic assisted extraction, Soxhlet or pressurized liquid extraction) which may require large quantities of organic solvents, or costly instrumentation or equipment.The main factors affecting the extraction efficiency (extractant volume, ultrasounds power and extraction time) were optimized using compost sludge. The detection limit of total LAS in the sludge was 10 mg kg^− 1. The extraction of C₁₀-C₁₃ homologues is carried out using an extraction time of 7 min with 10 mL of methanol. Liquid chromatography with fluorescence (FL) detector is used for determination of LAS homologues. A mobile phase acetonitrile-water containing 0.1 M NaClO₄ (65:35) and isocratic elution was used. Compounds were eluted over 6 min at a flow rate of 1 mL/min. Polar interferences are eluted between 0 and 2 min and no purification of the samples is required prior to the final determination by high performance liquid chromatography (HPLC). The recoveries of LAS in spiked sewage sludge were between 84.0% and 97.0%, which reflect the efficiency of the method for extraction of these analytes from sewage sludge. Concentration levels found were between 11,858 mg kg^− 1 for digested sludge and 2379 mg kg^− 1 for compost sludge.     

Concentration levels of total and methylmercury in mussel samples collected along the coasts of Sardinia Island (Italy)

This paper reports the assessment of the total mercury (T-Hg) and methylmercury (MeHg) contamination of mussel samples collected by two sampling campaigns from along the coastline of Sardinia (Italy). T-Hg has been determined by a direct mercury analyser (DMA) whereas MeHg has been determined by gas chromatography-mass spectrometry (GC-MS) after acid extraction, and employs a novel NaBPh₄ derivatization method. The evaluation of the quality of measurements was carried out by analysing candidate certified reference material (CRM) BCR 710, for MeHg and T-Hg, and CRM IAEA-350 for T-Hg. In the analysed samples, the T-Hg concentrations range from 35 to 115 μg kg⁻¹ and from 40 to 830 μg kg⁻¹, for the two sampling campaigns, respectively, whereas the MeHg concentrations range from l5 to 51 μg kg⁻¹ and from 17 to 116 μg kg⁻¹. Consequently, the MeHg/T-Hg ratios range from 0.33 to 0.91 and from 0.14 to 0.98, respectively. Despite the increasing trend of Hg concentration from the first to the second sampling campaign, the T-Hg concentration of all the samples was much below the 0.5 μg g⁻¹ WHO limit, and the MeHg values ranged between 2.2 and 17.2 μg kg⁻¹, not exceeding the 43.5 μg kg⁻¹ tolerable daily residue level calculated for Italy.     

Determination of trace bisphenol A in complex samples using selective molecularly imprinted solid-phase extraction coupled with capillary electrophoresis

The highly selective, fast and effective sample pretreatment technique molecularly imprinted solid-phase extraction (MISPE) can overcome the low sensitivity of the highly efficient capillary electrophoresis-UV method (CE-UV). In this work, narrowly dispersible bisphenol A (BPA)-imprinted polymeric microspheres with a high capacity factor of k′ = 6.8 and an imprinted factor of I = 6.53 were investigated as selective solid-phase extraction (SPE) sorbents for use in extraction of BPA from different sample matrices (tap water, wastewater, Yangtze River water, soil from the Yangtze River, shrimp and human urine). Washing and eluting protocols of MISPE were optimized. Under optimal conditions, recoveries of MISPE were investigated. Recoveries were basically constant and the relative standard deviation (RSD) was lower than 5.8% when loading volumes changed from 1 to 50 mL. Recoveries ranged from 71.20% to 86.23% for different sample matrices. Compared with C18 SPE, MISPE had higher selectivity and recovery for BPA. BPA was determined with good accuracy and precision in different complex samples using CE-UV coupled with MISPE. Spiked recoveries ranged from 95.20% to 105.40%, and the RSD was less than 7.2%. Because a large loading volume was achieved, the enrichment efficiency of pretreatment and the sensitivity of this method were improved. The limits of detection of this MISPE-CE-UV method for BPA in tap water, wastewater, Yangtze River water, soil from the Yangtze River, shrimp and human urine were 3.0 μg L^− 1, 5.4 μg L^− 1, 6.9 μg L^− 1, 2.1 μg L^− 1, 1.8 μg L^− 1 and 84 μg L^− 1, respectively.     

Development of a multi-class method for the quantification of veterinary drug residues in feedingstuffs by liquid chromatography-tandem mass spectrometry

A simple multi-residue method was developed for detecting and quantifying 33 analytes from 13 classes of antibiotics (tetracyclines (3), quinolones (7), penicillins (3), ionophore coccidiostats (7), macrolides (3), sulfonamides (1), quinoxalines (2), phenicols (2), lincosamides (1), diaminopyrimidines (1), polypeptides (1), streptogramins (1) and pleuromutilins (1)) in animal feeds. Extraction and clean-up procedures were optimized with spiked piglet feed. Samples were extracted by ultrasonic-assisted extraction with a mixture of methanol/acetonitrile/McIlvaine buffer at pH 4.6 (37.5/37.5/25, v/v/v) containing 0.3% of EDTA-Na₂, followed by a clean up using a dispersive solid-phase extraction (d-SPE) with PSA (primary secondary amine). Detection of antibiotics was achieved by liquid chromatography-electrospray tandem mass spectrometry (LC–ESI-MS/MS) within 28 min using both positive and negative ESI mode. Average recoveries ranged from 51% (oxytetracycline) to 116% (tilmicosin) with associated relative standard deviations of 7.3% and 9.0% and an overall mean of 87%. Limits of quantification ranged from 3.8 ng g⁻¹ (lincomycin) to 65.0 ng g⁻¹ (bacitracin). Following optimization, the method was further verified for bovine and lamb feedingstuffs; negative matrix effects were evaluated and overcome by a standard addition method.     

Validation of a high-performance liquid chromatographic method with fluorescence detection for the simultaneous determination of tetracyclines residues in bovine milk

A high-performance liquid chromatography-fluorescence detection method was optimized and validated to determine tetracyclines residues in bovine milk. Post-column derivatization using metal complexation in non-aqueous reagent increased the fluorescence of chelates by a factor up to 2.54 compared to water (signal-to-noise ratio enhancement). Overall recoveries ranged from 61 to 115%, with RSD_r from 5 to 15% (n = 54). Detection limits ranged from 5 to 35 μg kg⁻¹. Limits of quantification were established at 50 μg kg⁻¹. Decision limits (CCα) were 109, 108 and 124 μg kg⁻¹ and detection capabilities (CCβ) 119, 117 and 161 μg kg⁻¹ for oxytetracycline, tetracycline and chlortetracycline, respectively. The method was applied successfully in a national monitoring program.     

Optimisation of a liquid chromatography-tandem mass spectrometric method for the determination of acrylamide in foods

A robust and fitted routine method resulting from an analytical optimisation has been applied for the determination of acrylamide in several foods including mainly potato and cereal products. For the sample treatment, different materials were evaluated for filtration and purification of the extract. To increase the performances in terms of sensitivity, a preconcentration to small volume was introduced before liquid chromatography coupled to tandem mass spectrometry analysis on a μ-Bondapak C₁₈ column using d₃-acrylamide as internal standard. For identification, relative retention time and two diagnostic ions were monitored. A limit of detection of 10 μg kg⁻¹, a limit of quantitation of 20 μg kg⁻¹, mean recoveries ranging from 100 to 115%, coefficients of variation from 1.36 to 8.06% for repeatability and from 3.3 to 18.2% for reproducibility within the laboratory and a measurement uncertainty of 42% were obtained during an in-house validation procedure. Results of tests, validation data and Z-score obtained during participation to proficiency studies are presented.     

Trace determination of sulfonamides residues in meat with a combination of solid-phase microextraction and liquid chromatography-mass spectrometry

An integrated method of combining solid-phase microextraction (SPME) with liquid chromatography-mass spectrometry (LC-MS) was evaluated for determination trace amount of sulfonamides in meat products. Eight commonly used sulfonamides, sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMT), sulfamonomethoxine (SMMX), sulfamethoxazole (SMXZ), sulfaquinoxaline (SQX) and sulfadimethoxine (SDMX), were investigated in this study. Chromatography was performed on a C₁₈ reversed-phase column using an isocratic acetonitrile in water as the mobile phase. Fiber coated with a 65 μm thickness of polydimethylsiloxane/divinylbenzene (PDMS/DVB) was used to extract sulfonamides at optimum conditions. Analytes were desorbed with static desorption in an SPME-HPLC desorbed chamber for 15 min and then determined by LC-MS. The detection limits of these sulfonamides in pork were from 16 μg kg⁻¹ (SMT) to 39 μg kg⁻¹ (SMMX). According to the analysis, the linear range was from 50 to 2000 μg kg⁻¹ with relative standard deviation (R.S.D.s) value below 15% (intra-day) and 19% (inter-day). The proposed method was tested by analyzing meats from a local market for sulfonamides residues. Some sulfonamides in our study were detected in the meat samples. The concentration of these residual sulfonamides ranged from 66 μg kg⁻¹ (SDZ) to 157 μg kg⁻¹ (SQX) in a chicken sample. The results demonstrate that the SPME-LC-MS system is highly effective in analyzing trace sulfonamides in meat products.     

Liquid Chromatography-Mass Spectrometry Determination of Six 5-Nitroimidazoles in Animal Feedstuff

A liquid chromatography-mass spectrometry method for the determination of the coccidiostats metronidazole, ronidazole, dimetridazole, secnidazole, tinidazole and ipronidazole in feedstuff was developed. The 5-nitroimidazoles were extracted from animal feed with a pH 2 phosphate buffer solution followed by a solid phase extraction procedure based on HLB cartridges. The liquid chromatographic separation of the extracts was performed on a C₁₈ bonded silica column applying a gradient of elution with pH 4.3 ammonium acetate buffer solution and acetonitrile. Quantification for each 5-nitroimidazole was carried out monitoring its molecular ion [M + H]⁺ obtained by positive electrospray ionisation mode. A pool of feedstuffs was used to optimise and validate the method. Linearity, quantification limit, intra-day and inter-day reproducibility and accuracy were estimated using this pool of feedstuffs spiked with the drugs. For the confirmatory assay, several fragment ions from each 5-nitroimidazole were obtained and monitored. The method was applied successfully to determine 5-nitroimidazoles in feedstuff at level of 0.05 mg kg⁻¹.     

Determination of arsenic compounds in marine mammals with high-performance liquid chromatography and an inductively coupled plasma mass spectrometer as element-specific detector

Total arsenic concentrations and the concentrations of individual arsenic compounds were determined in liver samples of pinnipeds [nine ringed seals (Phoca hispida), one bearded seal (Erginathus barbatus)] and cetaceans [two pilot whales (Globicephalus melas), one beluga whale (Deliphinapterus leucus)]. Total arsenic concentrations ranged from 0.167 to 2.40 mg As kg⁻¹ wet mass. The arsenic compounds extracted from the liver samples with a methanol/water mixture (9:1, v/v) were identified and quantified by anion- and cation-exchange chromatography. An ICP–MS equipped with a hydraulic high-pressure nebulizer served as the arsenic-specific detector. Arsenobetaine (0.052–1.67 mg As kg⁻¹ wet mass) was the predominant arsenic compound in all the liver samples. Arsenocholine was present in all livers (0.005–0.044 mg As kg⁻¹ wet mass). The tetramethylarsonium cation was detected in all pinnipeds ( < 0.009 to 0.043 mg As kg⁻¹) but not in any of the cetaceans. The concentration of dimethylarsinic acid ranged from < 0.001 to 0.109 mg As kg⁻¹ wet mass. Most of the concentrations for methylarsonic acid ( < 0.001 to 0.025 mg As kg⁻¹ wet mass) were below the detection limit. Arsenous acid and arsenic acid concentrations were below the detection limit of the method (0.001 mg As kg⁻¹). An unknown arsenic compound was present in all liver samples at concentrations from 0.002–0.027 mg As kg⁻¹. © 1998 John Wiley & Sons, Ltd.     

Alpha and gamma spectrometry for determination of natural and artificial radionuclides in tea, herbal tea and camomile marketed in Italy

Several kinds of tea, camomile and herbal tea were analysed to determine natural and artificial radioactivity. The radionuclides were determined by alpha (²¹⁰Po) and gamma (²²⁸Ac, ²¹⁴Pb, ²¹⁴Bi, ²¹⁰Pb, ⁴⁰K and ¹³⁷Cs) spectrometry. ²²⁸Ac ranged between 0.6 and 9.0 Bq kg⁻¹_dry; ²¹⁰Po between 1.90 and 36.1 Bq kg⁻¹_dry; ²¹⁴Pb and ²¹⁴Bi between 0.7 and 4.9 Bq kg⁻¹_dry; ²¹⁰Pb between < 10.0 and 58.9 Bq kg⁻¹_dry; ⁴⁰K between 463 and 936 Bq kg⁻¹_dry; ¹³⁷Cs between < 0.3 and 2.6 Bq kg⁻¹_dry. The percentage of ²¹⁰Po extraction in infusion was also determined; the arithmetical mean value of percentage of ²¹⁰Po extraction resulted 20.7 ± 7.50.     

Development of a group selective molecularly imprinted polymers based solid phase extraction of malachite green from fish water and fish feed samples

A group selective molecularly imprinted solid phase extraction (MISPE) for malachite green (MG) from fish water and fish feed samples was developed. Using MG as template molecule, methacrylic acid as functional monomer, ethylene glycoldimethacrylate as linking agent and bulk polymerization as synthetic method, the molecularly imprinted polymers (MIPs) were synthesized and characterized with rebinding experiment. The Scatchard polt's analysis revealed that the template-polymer system showed the two-site binding behavior with dissociation constants of 0.3194 μmol L⁻¹ and 15.70 μmol L⁻¹, respectively. MG and two structurally related compounds, leucomalachite green (LMG) and crystal violet (CV) were employed for selectivity test. The MIPs exhibited the highest selective rebinding to MG, but also displayed 83.0% and 87.5% of cross-reactivity with LMG and CV, demonstrating that MIPs could be used as group recognition sorbents in solid phase extraction. The extraction conditions of MISPE column for MG were optimized. Tap water samples spiked with MG at concentration of 0.5-10 ng mL⁻¹ were extracted by MISPE column and analyzed by high performance liquid chromatography. The recoveries of MISPE column for MG extraction were found to be 76.8-93.7% with the relative standard deviations of 2.12-10.09%, indicating the feasibility of the prepared MIPs for MG extraction. No detectable MG was observed in one fish farming water sample and two fish feed samples; while the MG concentrations in two pet fishpond water samples were found at 1.50 ng mL⁻¹ and 0.67 ng mL⁻¹, respectively.     

Determination of cobalamins (hydroxo-, cyano-, adenosyl- and methyl-cobalamins) in seawater using reversed-phase liquid chromatography with diode-array detection

A high-performance liquid chromatography method was developed for the separation and determination of four cobalamins in seawater. Chromatographic separation was performed on a reversed-phase discovery RP-amide C₁₆ column with buffer potassium dihydrogenphosphate and acetonitrile as the mobile phases in linear gradients elution mode. Cobalamins were previously preconcentrated in C₁₈ resins cartridges. Detection was performed using UV-diode array detector in a range of λ of 200–400 nm. The method showed to be linear over a range of 1–300 ng mL⁻¹ with acceptable precision and accuracy. The detection limits ranged between 0.07 pg mL⁻¹ for 5′-deoxyadenosylcobalamin and 0.5 pg mL⁻¹ for hydroxocobalamin. The mean cobalamins recoveries for direct determination ranged between 76 and 93% for hydroxo-, cyano- and methylcobalamin, while the recovery for 5′-deoxyadenosylcobalamin was only 31% suggesting that the preconcentration method was not valid for this cobalamin. The method was successfully applied to coastal seawater where the concentrations ranged from 4.2 to 7.3 ng L⁻¹ for hydroxo-, 1.4–3.9 ng L⁻¹ for cyano-, 2.1–4.6 ng L⁻¹ for 5′-deoxyadenosyl- and 33–83.5 ng L⁻¹ for methylcobalamin.     

Acid-base equilibria of phthalic acid in saline media: ion association from Pitzer equations

The protonation constants of 1,2-benzenedicarboxylic acid (phthalic acid) at 25 °C in NaCl and CaCl₂ (ionic strengths ranging from 0.1 to 2 mol kg⁻¹) were determined potentiometrically, and the results were analyzed by means of Pitzer equations. The values of the logarithm of the first and second dissociation constants ranged from 2.730 and 4.948 (in 0.101 mol kg⁻¹ NaCl) to 2.449 and 3.984 (in 0.624 mol kg⁻¹ CaCl₂), respectively. Tabulated interaction parameters for the inorganic species involved along with salting coefficients estimated from literature allowed the calculation of new interaction parameters for the phthalate-Na⁺/Ca²⁺ systems. The specific ion interaction model considered seems to account for the influence of the formation of weak complexes of phthalate with calcium ions on the equilibrium constants.     

Development of a photochemically induced fluorescence-based optosensor for the determination of imidacloprid in peppers and environmental waters

A novel flow-through solid phase spectroscopic assembly implemented with photochemically induced fluorescence (PIF) has been developed for the rapid, sensitive and selective determination of imidacloprid. The pesticide is derivatized on-line by irradiation with ultraviolet light providing an intensively fluorescent compound. The determination is carried out by measuring the fluorescence intensity of the photoproduct once retained on C₁₈ silica gel filling the flow-cell. The method proposed has been applied to the determination of imidacloprid in natural waters and peppers. The quantification limit (QL) (0.015 mg kg⁻¹) in peppers was lower than the maximum residue limit (MRL) established by Spanish Legislation (0.5 mg kg⁻¹). The method also seems to be suitable for environmental water analysis providing satisfactory recoveries (94.0-108.6%). The results obtained in the analysis of real samples are in good agreement with those provided by a reference liquid chromatography (HPLC) method.