Microwave-assisted synthesis of water soluble thiol capped CdSe/ZnS quantum dots and its interaction with sulfonylurea herbicides.

A simple and fast procedure for water solubilization of CdSe/ZnS quantum dots (QDs) using microwave irradiation (MW) has been optimized. The CdSe/ZnS QDs were synthesized in organic media and water solubilization was achieved by replacing the initial hydrophobic ligands (TOPO and TOP) with hydrophilic heterobifunctional thiol ligands, such as L-cysteine (L-Cys), 3-mercaptopropionic acid (3-MPA) and cysteamine (CTAM). The use of MW irradiation allowed carrying out the modification of the surface thiol of QDs in a simple and fast way (only 40 s was required). Different optimization studies based on activation-time, irradiation-time, concentration of ligands, pH and lifetime fluorescent properties were carried out in order to obtain the best results for the solubilization of QDs. By the proposed method, the resulting water-soluble QDs exhibit a strong fluorescence emission at about 590 nm, with a high and reproducible photostability and acceptable yields. With the aim of contributing to exploiting the advantages of synthetized QDs from an analytical point of view, the different behavior with sulfonylurea herbicides (SUHs) were studied.

Determination of carbohydrates present in Saccharomyces cerevisiae using mid-infrared spectroscopy and partial least squares regression.

A fast and simple method to control variations in carbohydrate composition of Saccharomyces cerevisiae, baker's yeast, during fermentation was developed using mid-infrared (mid-IR) spectroscopy. The method allows for precise and accurate determinations with minimal or no sample preparation and reagent consumption based on mid-IR spectra and partial least squares (PLS) regression. The PLS models were developed employing the results from reference analysis of the yeast cells. The reference analyses quantify the amount of trehalose, glucose, glycogen, and mannan in S. cerevisiae. The selection and optimization of pretreatment steps of samples such as the disruption of the yeast cells and the hydrolysis of mannan and glycogen to obtain monosaccharides were carried out. Trehalose, glucose, and mannose were determined using high-performance liquid chromatography coupled with a refractive index detector and total carbohydrates were measured using the phenol-sulfuric method. Linear concentration range, accuracy, precision, LOD and LOQ were examined to check the reliability of the chromatographic method for each analyte.

Determination of neonicotinoid insecticides in environmental samples by micellar electrokinetic chromatography using solid-phase treatments.

A sensitive and reliable method based on MEKC has been developed and validated for trace determination of neonicotinoid insecticides (thiamethoxam, acetamiprid, and imidacloprid) and the metabolite 6-chloronicotinic acid in water and soil matrices. Optimum separation of the neonicotinoid insecticides was obtained on a 58 cm long capillary (75 µm id) using as the running electrolyte 40 mM SDS, 5 mM borate (pH 10.4), and 5% (v/v) methanol at a temperature of 25°C, a voltage of 25 kV and with hydrodynamic injection (10 s). The analysis time was less than 7 min. Prior to MEKC determination, the samples were purified and enriched by carrying out extraction-preconcentration steps. For aqueous samples, off-line SPE with a sorptive material such as Strata-X (polymeric hydrophobic sorbent) and octadecylsilane (C18) was carried out to clean up and preconcentrate the insecticides. However, for soil samples, matrix solid-phase dispersion (MSPD) was applied with C18 used as the dispersant. Good linearity, accuracy, and precision were obtained and the detection limits were in the range between 0.01 and 0.07 µg mL⁻¹ for river water and 0.17 and 0.37 µg g⁻¹ for soil samples. Recovery levels reached greater than 92% for all of the assayed neonicotinoids in river water samples with Strata-X. In soil matrices, the best recoveries (63-99%) were obtained with MSPD.

Analytical characterization of PEG polymers by MEKC.

Characterization of PEGs with average molecular masses of up to 2000 has been achieved using MEKC with UV detection. A rapid derivatization procedure with phenyl isocyanate using microwave radiation, in order to introduce chromophore groups in PEGs, has been developed involving a reaction time of 60 s. Different optimized conditions in accordance with the molecular weight have been studied to obtain the oligomer separation. The weight-average molecular mass the number-average molecular mass and the degree of polydispersity (molecular mass distribution) were calculated for the different PEGs obtaining similar results with those certified for standards. A good precision was obtained for characterizing the different oligomers. Ethylene glycol was used as the internal standard for the analysis of low-molecular-weight PEGs. The developed method was satisfactorily applied to the characterization of these polymers in several real samples, such as lubricant eye drops, toothpaste, tap water and eye make-up remover.

Development of a novel biotoxicity screening assay for analytical use.

A new biotoxicity assay has been developed and employed as an analytical screening tool. The proposed biotoxicity assay is simple and represents the first example of the use of Lactobacillus plantarum as a test micro-organism. The applicability of this method was demonstrated by evaluating the pollution of water due to the presence of several toxicants. Traditional parameters such as effective concentration (EC(50)) and lowest observed effect concentration (LOEC) provided by all the biotoxicity tests were employed in a screening method based on a binary toxic/non-toxic response. The threshold of the response was characterized by defining a mortality index (I(m)), which in this case was obtained by monitoring the consumption of glucose in the culture medium (Somogyi-Nelson method) or by turbidimetric measurements. Cut-off values established by the current legislation (or other preset values) were used as criteria to classify samples as positive or negative. Bacterial growth was inhibited by the presence of heavy metals such as mercury, cadmium, lead, copper and zinc. This methodology was applied to study the toxicity of heavy metals in different water samples.