Cold vapour generation electrothermal atomic absorption spectrometry and solid phase extraction based on a new nanosorbent for sensitive HG determination in environmental samples (sea water and river water)

Mercury is not an essential element for plant or animal life and it is a potential environmental toxic because of its tendency to form covalent bonds with organic molecules and the high stability of the Hg-C bond. Reports estimate a total mercury concentration in natural waters ranging from 0.2 to 100 ng L-1. Due to this fact, highly sensitive methods are required for direct determination of such extremely low levels. In this work, a rapid and simple method was developed for separation and preconcentration of mercury by flow injection solid phase extraction coupled with on-line chemical vapour generation electrothermal atomic absorption spectrometry. The system is based on chelating retention of the analyte onto the mini column filled with a mesoporous silica functionalized with 1,5 bis (di-2-pyridyl) methylene thiocarbohydrazide. The main aim of this work was to develop a precise and accurate method for the determination of the Hg. Under the optima conditions and 120 s preconcentration time, the detection limit obtained was 0.009 μg L-1, with RSDs 3.7 % for 0.2 μg L-1, 4.8 % for 1 μg L-1 and enrichment factor 4, Furthermore, the method proposed has permitted the determination of Hg with a reduction in the analysis time, the sample throughput was about 18 h-1, low consumption of reagents and sample volume. The method was applied to the determination of Hg in sea water and river water. For the quality control of the analytical performance and the validation of the newly developed method, the analysis of two certified samples, TMDA 54.4 Fortified Lake, and LGC6187 River sediment was addressed. The results showed good agreement with the certified values.

Analyse des agents de chimiothérapie par extraction sur phase solide automatisée couplée à la chromatographie liquide et la spectrométrie de masse en tandem (SPE-LC-ESI-MS/MS)

Les dernières décennies ont été marquées par une augmentation du nombre des cas de cancers, ce qui a subséquemment conduit à une augmentation dans la consommation des agents de chimiothérapie. La toxicité et le caractère cancérogène de ces molécules justifient l’intérêt crucial porté à leur égard. Quelques études ont fait l’objet de détection et de quantification des agents de chimiothérapie dans des matrices environnementales. Dans ce projet, une méthode utilisant la chromatographie liquide couplée à la spectrométrie de masse en tandem (LC-MS/MS) précédée d’une extraction sur phase solide (SPE) automatisée ou en ligne a été développée pour la détection et la quantification d’un groupe de six agents de chimiothérapie. Parmi ceux-ci figurent les plus utilisés au Québec (gemcitabine, méthotrexate, cyclophosphamide, ifosfamide, irinotécan, épirubicine) et présentant des propriétés physico-chimiques et des structures chimiques différentes. La méthode développée a été validée dans une matrice réelle représentant l’affluent d’une station d’épuration dans la région de Montréal. Deux des six composés cytotoxiques étudiés en l’occurrence (cyclophosphamide et méthotrexate) ont été détectés dans huit échantillons sur les neuf qui ont été recensés, essentiellement au niveau de l’affluent et l’effluent de quelques stations d’épuration de la région de Montréal. Les résultats des analyses effectuées sur les échantillons réels ont montré qu’il n’y avait pas de différence significative dans la concentration entre l’affluent et l’effluent, et donc que les systèmes d’épuration semblent inefficaces pour la dégradation de ces molécules.

Dynamic Solid Phase DNA Extraction and PCR Amplification in Polyester-Toner Based Microchip

A variety of substrates have been used for fabrication of microchips for DNA extraction, PCR amplification, and DNA fragment separation, including the more conventional glass and silicon as well as alternative polymer-based materials. Polyester represents one such polymer, and the laser-printing of toner onto polyester films has been shown to be effective for generating polyester-toner (PeT) microfluidic devices with channel depths on the order of tens of micrometers. Here, we describe a novel and simple process that allows for the production of multilayer, high aspect-ratio PeT microdevices with substantially larger channel depths. This innovative process utilizes a CO(2) laser to create the microchannel in polyester sheets containing a uniform layer of printed toner, and multilayer devices can easily be constructed by sandwiching the channel layer between uncoated cover sheets of polyester containing precut access holes. The process allows the fabrication of deep channels, with similar to 270 mu m, and we demonstrate the effectiveness of multilayer PeT microchips for dynamic solid phase extraction (dSPE) and PCR amplification. With the former, we found that (i) more than 65% of DNA from 0.6 mu L of blood was recovered, (ii) the resultant DNA was concentrated to greater than 3 ng/mu L., (which was better than other chip-based extraction methods), and (iii) the DNA recovered was compatible with downstream microchip-based PCR amplification. Illustrative of the compatibility of PeT microchips with the PCR process, the successful amplification of a 520 bp fragment of lambda-phage DNA in a conventional thermocycler is shown. The ability to handle the diverse chemistries associated with DNA purification and extraction is a testimony to the potential utility of PeT microchips beyond separations and presents a promising new disposable platform for genetic analysis that is low cost and easy to fabricate.

Parameters Affecting the Extraction of Polycyclic Aromatic Hydrocarbons with Pressurised Hot Water

Pressurised hot water extraction (PHWE) exploits the unique temperature-dependent solvent properties of water minimising the use of harmful organic solvents. Water is environmentally friendly, cheap and easily available extraction medium. The effects of temperature, pressure and extraction time in PHWE have often been studied, but here the emphasis was on other parameters important for the extraction, most notably the dimensions of the extraction vessel and the stability and solubility of the analytes to be extracted. Non-linear data analysis and self-organising maps were employed in the data analysis to obtain correlations between the parameters studied, recoveries and relative errors. First, pressurised hot water extraction (PHWE) was combined on-line with liquid chromatography-gas chromatography (LC-GC), and the system was applied to the extraction and analysis of polycyclic aromatic hydrocarbons (PAHs) in sediment. The method is of superior sensitivity compared with the traditional methods, and only a small 10 mg sample was required for analysis. The commercial extraction vessels were replaced by laboratory-made stainless steel vessels because of some problems that arose. The performance of the laboratory-made vessels was comparable to that of the commercial ones. In an investigation of the effect of thermal desorption in PHWE, it was found that at lower temperatures (200ºC and 250ºC) the effect of thermal desorption is smaller than the effect of the solvating property of hot water. At 300ºC, however, thermal desorption is the main mechanism. The effect of the geometry of the extraction vessel on recoveries was studied with five specially constructed extraction vessels. In addition to the extraction vessel geometry, the sediment packing style and the direction of water flow through the vessel were investigated. The geometry of the vessel was found to have only minor effect on the recoveries, and the same was true of the sediment packing style and the direction of water flow through the vessel. These are good results because these parameters do not have to be carefully optimised before the start of extractions. Liquid-liquid extraction (LLE) and solid-phase extraction (SPE) were compared as trapping techniques for PHWE. LLE was more robust than SPE and it provided better recoveries and repeatabilities than did SPE. Problems related to blocking of the Tenax trap and unrepeatable trapping of the analytes were encountered in SPE. Thus, although LLE is more labour intensive, it can be recommended over SPE. The stabilities of the PAHs in aqueous solutions were measured using a batch-type reaction vessel. Degradation was observed at 300ºC even with the shortest heating time. Ketones and quinones and other oxidation products were observed. Although the conditions of the stability studies differed considerably from the extraction conditions in PHWE, the results indicate that the risk of analyte degradation must be taken into account in PHWE. The aqueous solubilities of acenaphthene, anthracene and pyrene were measured, first below and then above the melting point of the analytes. Measurements below the melting point were made to check that the equipment was working, and the results were compared with those obtained earlier. Good agreement was found between the measured and literature values. A new saturation cell was constructed for the solubility measurements above the melting point of the analytes because the flow-through saturation cell could not be used above the melting point. An exponential relationship was found between the solubilities measured for pyrene and anthracene and temperature.

Performance of CMOS Devices in Silicon-on-Sapphire Films After Solid-Phase Epitaxial Growth With Rapid Electron-Beam Heating

The crystal quality of 0.3-μm-thick as-grown epitaxial silicon-on-sapphire (SOS) was improved using solid-phase epitaxy (SPE) by implantation with silicon to 1015 ions/cm2 at 175 keV and rapid annealing using electron-beam heating, n-channel and p-channel transistormobilities increased by 31 and 19 percent, respectively, and a reduction in ring-oscillator stage delay confirmed that crystal defects near the upper silicon surface had been removed. Leakage in n-channel transistors was not significantly affected by the regrowth process but for p-channel transistors back-channel leakage was considerably greater than for the control devices. This is attributed to aluminum released by damage to the sapphire during silicon implantation. © 1985 IEEE

Improvement of thin silicon on sapphire (SOS) film materials and device performances by solid phase epitaxy

The increased emphasis on sub-micron CMOS/SOS devices has placed a demand for high quality thin silicon on sapphire (SOS) films with thickness of the order 100-200 nm. It is demonstrated that the crystalline quality of as-grown thin SOS films by the CVD method can be greatly improved by solid phase epitaxy (SPE) process: implantation of self-silicon ions and subsequent thermal annealing. Subsequent regrowth of this amorphous layer leads to a greater improvement in silicon layer crystallinity and channel carrier mobility, evidenced, respectively, by double crystal X-ray diffraction and electrical measurements. We concluded that the thin SPE SOS films are suitable for application to high-performance CMOS circuitry. (C) 2000 Elsevier Science S.A. All rights reserved.

Improvement of thin silicon on sapphire (SOS) film materials and device performances by solid phase epitaxy

The increased emphasis on sub-micron CMOS/SOS devices has placed a demand for high quality thin silicon on sapphire (SOS) films with thickness of the order 100-200 nm. It is demonstrated that the crystalline quality of as-grown thin SOS films by the CVD method can be greatly improved by solid phase epitaxy (SPE) process: implantation of self-silicon ions and subsequent thermal annealing. Subsequent regrowth of this amorphous layer leads to a greater improvement in silicon layer crystallinity and channel carrier mobility, evidenced, respectively, by double crystal X-ray diffraction and electrical measurements. We concluded that the thin SPE SOS films are suitable for application to high-performance CMOS circuitry. (C) 2000 Elsevier Science S.A. All rights reserved.

Synthesis of caffeic acid and p-hydroxybenzoic acid molecularly imprinted polymers and their application for the selective extraction of polyphenols from olive mill waste waters

Using caffeic acid and p-hydroxybenzoic acid as templates, two molecularly imprinted polymers (MIPs) were prepared that were used for isolation of polyphenols from olive mill waste water samples (OMWWs) without previous pre-treatment. For the preparation of the caffeic acid MIPs 4-vinylpyridine, allylurea, allylaniline and methacrylic acid were tested as functional monomers, ethylene glycol dimethylacrylate (EDMA), pentaerythritol trimethylacrylate (PETRA) and divinylbenzene 80 (DVB80) as cross-linkers and tetrahydrofuran as porogen. For p-hydroxybenzoic acid 4-vinylpyridine, allylurea and allylaniline were tested as functional monomers, EDMA and PETRA as cross-linkers and acetonitrile as porogen. The performance of the synthesized polymers was evaluated against seven structurally related compounds by means of polymer-based HPLC. The two polymers that presented the most interesting properties were further evaluated by batch rebinding and from the derived isotherms their capacity and binding strength were determined. Using solid-phase extraction (SPE), their ability to recognize and bind the template molecule from an aqueous solution as well as the pH dependence of the binding strength were explored. After establishing the best SPE protocol, an aqueous model mixture of compounds and a raw OMWWs sample were loaded on the two best polymers. The result of the consecutive use of the two polymers on the same sample was explored. It was concluded that acidic conditions favour the recognition abilities of both polymers and that they can be used for a quick and efficient isolation of the polyphenol fraction directly from raw OMWW.

Molecularly imprinted polymers for the extraction of imiquimod from biological samples using a template analogue strategy

Molecularly Imprinted Polymers (MIPs) against imiquimod, a highly potent immune response modifier used in the treatment of skin cancer, were synthesised using a template analogue strategy and were compared with imprints of the drug itself. An investigation of the complexation between the functional monomer and the template analogue revealed an association constant of 1,376 ± 122 M-1, significantly higher than previously reported values for similar systems. The binding characteristics of the synthesised imprinted polymers were evaluated and extremely strong binding for imiquimod was observed while imprinting factors as high as 17 were calculated. When applied as sorbents in solid-phase extraction of imiquimod from aqueous, urine and blood serum samples, clean extracts and recoveries up to 95% were achieved, and it is concluded that while imiquimod imprints exhibited higher capacity for the drug, template analogue imprints are more selective. The results obtained suggest potential applications of imiquimod imprints as sorbents in rapid extraction and monitoring of undesirable systemic release of the drug.

Artificial receptors for the extraction of nucleoside metabolite 7-methylguanosine from aqueous media made by molecular imprinting

A series of imprinted polymers targeting nucleoside metabolites, prepared using a template analogue approach, are presented. These were prepared following selection of the optimum functional monomer by solution association studies using 1H-NMR titrations whereby methacrylic acid was shown to be the strongest receptor with and affinity constant of 621 ± 51 L mol-1 vs. 110 ± 16 L mol-1 for acrylamide. The best performing polymers were prepared using methanol as porogenic co-solvent and although average binding site affinities were marginally reduced, 2.3×104 L mol-1 vs. 2.7×104 L mol-1 measured for a polymer prepared in acetonitrile, these polymers contained the highest number of binding sites, 5.27 μmol g-1¬¬ vs. 1.64 μmol g-1, while they also exhibited enhanced selectivity for methylated guanosine derivatives. When applied as sorbents in the extraction of nucleoside derivative cancer biomarkers from synthetic urine samples, significant sample clean-up and recoveries of up to 90% for 7-methylguanosine were achieved.

Multiresidue determination of herbicides in environmental waters from Primavera do Leste region (Middle West of Brazil) by SPE-GC-NPD

A study on the presence of herbicides, namely simazine, metribuzin, metolachlor, trifluralin, atrazine and two metabolites, deisopropylatrazine (DIA) and deethylatrazine (DEA), was performed in ground and surface waters from Primavera do Leste region, Mato Grosso state (Middle West of Brazil). The analytical procedure was based on solid-phase extraction (SPE) with Sep-Pak C18 disposable cartridges and ethyl acetate for elution solvent. Residue levels were determined by gas chromatography with nitrogen-phosphorus detection. For most of the pesticides average recoveries at different fortification levels were >with relative standard deviation < The recoveries of DIA and trifluralin in water were 25% and 56%, respectively, which were attributed to the incomplete retention of DIA and strong retention on the sorbing material and high volatility of trifluralin. Detection limits ranged from 0.023 to 0.088 μg L-1. This method was applied for the analysis of 5 superficial water samples and 28 groundwater samples, in places used for human consumption without previous treatment, collected in Primavera do Leste, Mato Grosso, Brazil. Results indicated that the highest level of contamination in a water sample was 1.732 μg L-1 for metolachlor, while metribuzin was the most frequently detected herbicide with maximum concentration of 0.351 μg L-1. ©2006 Sociedade Brasileira de Química.

UV filters in water samples: Experimental design on the SPE optimization followed by GC-MS/MS analysis

Esse estudo descreve o desenvolvimento e otimização de um método de extração em fase solida (SPE) para análise dos filtros ultravioletas (UV): benzofenona-3 (BP-3), etilhexil salicilato (ES), etilhexil metoxinamato (EHMC) e octocrileno (OC) em matrizes ambientais. Um planejamento fatorial fracionário (PFF) 25-1 foi empregado na avaliação das variáveis significativas do método de extração. As condições experimentais otimizadas da avaliação estatística foram: capacidade do cartucho de 500 mL, eluente acetato de etila, metanol como solvente de lavagem (10% em água, v/v) and volume do eluente de 3 × 2 mL e pH 3. Os parâmetros analíticos avaliados foram satisfatõrios, apresentando linearidade de 100 a 4000 ng L -1, recuperaç ões para os quatro níveis de fortificação (Limite de Quantificação do Método, 200, 1000 e 2000 ng L-1) entre 62 e 107% com desvio padrão relativo menor que 14%. Os limites de quantificação foram encontrados na faixa de ng L-1, variando entre 10 e 100 ng L-1. O método proposto foi aplicado para a determinação dos quatro filtros UV em amostras de águas naturais. This study describes the development and optimization of a solid-phase extraction (SPE) method for analysis of ultraviolet (UV) filters, benzophenone-3 (BP-3), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate (ES) and octocrylene (OC), in environmental matrices. A 25-1 fractional factorial design (FFD) was used to evaluate the significant variables for the extraction method. The optimized experimental conditions determined from the statistical evaluation were: breakthrough volume of 500 mL, eluent of ethyl acetate, wash solvent of methanol (10% in water, v/v), eluent volume of 3 × 2 mL and pH 3. The evaluated analytical parameters were satisfactory for the analytes and showed linearity between 100 and 4000 ng L-1, recoveries for four fortification levels (Method Quantification Limit, 200, 1000 and 2000 ng L-1) were between 62 and 107% with relative standard deviations less than 14%. Limits of quantification were in the ng L-1 range and were between 10 and 100 ng L-1. The proposed method was used to analyze four UV filters in natural water samples. ©2013 Sociedade Brasileira de Química.