Determination of Lead in Bee Products by Solid Surface Fluorescence Using Complexation and Coacervation at Room Temperature Processes. An Environmental Friendly Methodology.

An accurate, economic and green methodology for Pb(II) monitoring in bee products is proposed. Complexed metal traces were preconcentrated on Nylon membranes using the coacervation phenomenon based on room temperature reaction between the cationic surfactant hexadecyltrimethylammonium bromide and the bile salt sodium cholate. The increase in solid surface fluorescence signal of dyes 8-hydroxyquinoleine and o-phenanthroline due to Pb(II) presence was used for the metal quantification. Experimental variables that influence on preconcentration step and fluorimetric sensitivity were optimized using uni-varied assays. Pb(II) concentration was determined on membranes by solid surface fluorescence at λem = 470 nm (λexc = 445 nm), using a solid sample holder. The calibration at optimal experimental conditions showed a LOD of 4.2 × 10-4 mg Kg-1 with a linear range of 1.28 × 10-3 mg Kg-1 to 8.73 mg Kg-1 and was successfully applied to Pb(II) quantification in different bee products produced in central west region of Argentina. The proposed methodology was applied to all samples after appropriate dilution. Accuracy methodology was evaluated by comparison of the obtained results with those found by ICP-MS, with percentage relative error under 8%. The precision was better than 0.0344 CV for Pb(II) determination.

Sonochemical Synthesized Manganese Oxide Nanoparticles as Fluorescent Sensor for Selenium (IV) Quantification. Application to Food and Drink Samples.

Manganese oxide nanoparticles (MnO Nps), sonochemical synthesized and characterized in our laboratory, are proposed as fluorescent sensor for selenium (Se) determination. The new methodology has been developed based on the enhancing effect of the Se(IV) on fluorescent emission of MnO Nps. Experimental variables that influence on fluorimetric sensitivity were optimized. The calibration graph using zeroth order regression was linear from 0.189 ng L-1 to 8.00 × 103 µg L-1, with correlation coefficient better than 0.99. Under the optimal conditions, the limits of detection and quantification were of 0.062 ng L-1 and 0.189 ng L-1, respectively. The trueness of the methodology was assessed through standard addition method obtaining recovery near to 100%. This method showed good tolerance to foreign ions, particularly to Se(VI), and was applied to determination of Se(IV) trace in food and drink samples with satisfactory results. With the intention of preserving the environment from harmful effects, a degradation study of the used nanomaterials has been included for their subsequent disposal.

Copper Traces Quantification in Bee's Products by Solid Surface Fluorescence. A Green Analytical Proposal.

A new methodology based on the fluorescence of Cu(II) ternary system with o-phenanthroline (o-Phen) and eosin (Eo) dyes is proposed. The metal was selectively retained on Nylon membranes and the solid surface fluorescence (SSF) was used for anayte quantification. Experimental variables that influence the formation of Cu(II)-o-Phen-eo system and retention step were studied and optimized. At optimal experimental conditions, an adequate tolerance to foreign species was shown with a LOD of 1.18 ng L-1 and a LOQ of 3.57 ng L-1. The methodology was evaluated for their greenness profile and successfully applied to analyte determination in bee's products of West-Center Argentina. Recovery studies showed values near to 100% being satisfactorily validated by ICP-MS.

Tolfenamic acid on-line preconcentration strategy on carbon nanotubes minicolumn with fluorimetric detection.

Nonsteroidal anti-inflammatory agents (NSAIDs) are a group of pharmaceuticals considered one of the most popular drugs used in clinical practice applied to the treatment of acute and chronic conditions. Some pharmaceuticals products are excreted reaching the environment and altering the balance of ecosystems. This work proposes a new fluorimetric flow injection (FI) methodology for the NSAID tolfenamic acid quantification based on the quenching effect of the analyte on fluorescent signal of bovine serum albumin fluorophore. Results put in evidence a mechanism of static quenching, with a Stern Volmer constant value of 1.8 × 107 L mol-1. To achieve the selective on-line preconcentration of analyte, a carbon nanotubes mini column was introduced in the FI configuration producing a beneficial effect on high sampling frequency, minimum sample and reagents consumption. The experimental factors that influence batch fluorescent signal and FI analysis have been studied and optimized. At optimal experimental conditions, an adequate tolerance to foreign species was shown. With the flow configuration, a LOD of 0.019 µg L-1, a LOQ of 0.058 µg L-1 were obtained with a sampling rate of 30 samples h-1. The new methodology was successfully applied to analyte determination in tap water and pharmaceutical and factory waste samples with recuperation near to 100%.

O-(ß-hydroxyethyl)rutosides determination by micellar flow injection (FI)-spectrofluorimetry.

A simple, eco-friendly, sensitive and economic flow injection spectrofluorimetric method was developed for the determination of O-(ß-hydroxyethyl)rutosides. The procedure was based on the use of an anionic surfactant such as sodium dodecyl sulfate to provide an appreciable O-(ß-hydroxyethyl)rutosides fluorescence enhancement, increasing considerably the sensitivity of detection. All the variables affecting the fluorescence intensity were studied and optimized. The flow rate was 5 mL/min with detection at 450 nm (after excitation at 346 nm). A linear correlation between drug amount and peak area was established for O-(ß-hydroxyethyl)rutosides in the range of 0.01-200 µg/mL with a detection limit of 0.001 µg/mL (s/n=3). Validation processes were performed by recovering studies with satisfactory results. The new methodology can be employed for the routine analysis of O-(ß-hydroxyethyl)rutosides in bulks as well as in commercial formulations.

Precision improvement for omeprazole determination through stability evaluation.

A new spectrofluorimetric method for the determination of omeprazole (OMP) based on its degradation reaction catalyzed by ultraviolet (UV) light is proposed. OMP in aqueous solution is very unstable, which renders a serious difficulty for controlling its quality. It does not show native fluorescence, but when exposed to UV radiation, it generates a highly fluorescent degradation product with adequate stability for indirect OMP quantification. Under the studied optimal experimental conditions (pH, temperature, exposure time to UV radiation), a specific rate constant of 2.851 min⁻¹--described by zero-order kinetic--was obtained for the degradation reaction. Using λ(exc) 293 nm and λ(em) 317 nm, a linear relationship was obtained (r² 0.9998) in the concentration range of 0.1 to 1.3 µg mL⁻¹, with a detection limit of 1.07 10⁻³ µg mL⁻¹ (S/N = 3). The methodology developed was successfully applied to OMP quality control in pure drugs and tablet dosage forms without previous treatment, with good tolerance to common excipient, and a high level of concordance between the nominal and experimental values. This work constitutes an important contribution to knowledge of the degradation mechanism of OMP. It has been shown to be appropriate for OMP quality control, to have an adequate sampling rate, low cost instrument, and to be a less polluting procedure.

Online naphazoline quality control by micellar-enhanced spectrofluorimetry.

The aim of this study was to develop a method for online spectrofluorimetric quality control of naphazoline (NPZ) in pharmaceuticals and raw drugs. A combination of a flow-injection analysis (FIA) system with micellar-enhanced fluorescence detection is presented as a powerful alternative for the rapid and sensitive analysis of naphazoline. Since NPZ shows low native fluorescence, the use of an anionic surfactant, such as sodium dodecyl sulphate (SDS), provides a considerable enhancement of fluorescence intensity and the nature of the technique allows a possible and easy adaptation to a FIA system. Using λ(exc) = 280 nm and λ(em) = 326 nm, a good linear relationship (LOL) was obtained in the range 0.003-10 µg mL(-1) with a detection limit (LOD) of 3 × 10(-4) µg mL(-1) (s/n = 3). Parameters related to the nature of the analytical signal and to the FIA manifold were optimized. Satisfactory recoveries were obtained in the analysis of commercial pharmaceutical formulations. The proposed method is simple, accurate and allows for high-speed sampling and considerably shorter analysis times. In addition, it requires inexpensive equipment and reagents and has easy operational conditions and no side effects, thus avoiding environmental pollution through toxic waste.