Quantification,confirmation and screening capability of UHPLC coupled to triple quadrupole and hybrid quadrupole time‐of‐flight mass spectrometry in pesticide residue analysis

The potential of three mass spectrometry (MS) analyzers (triple quadrupole, QqQ; time of flight, TOF; and quadrupole time of flight, QTOF) has been investigated and compared for quantification, confirmation and screening purposes in pesticide residue analysis of fruit and vegetable samples. For this purpose, analytical methodology for multiresidue determination of 11 pesticides, taken as a model, has been developed and validated in nine food matrices for the three mass analyzers coupled to ultra high pressure liquid chromatography. In all cases, limits of quantification around 0.01 mg/kg were reached, fulfilling the most restrictive case of baby‐food analysis. Regarding absolute sensitivity, the lower limits of detection were obtained, as expected, for QqQ (100 fg), whereas slightly higher limits (300 fg) were obtained for both TOF and QTOF. Confirmative capacity of each analyzer was studied for each analyte based on the identification points (IPs) criterion, useful for a comprehensive comparison. QTOF mass analyzer showed the highest confirmatory capacity, although QqQ normally led to sufficient number of IPs, even at lower concentration levels. The potential of TOF MS was also investigated for screening purposes. To this aim, around 50 commercial fruits and vegetables samples were analyzed, searching for more than 400 pesticides. TOF MS proved to be an attractive analytical tool for rapid detection and reliable identification of a large number of pesticides thanks to the full spectrum acquisition at accurate mass with satisfactory sensitivity. This process is readily boosted when combined with specialized software packages, together with theoretical exact mass databases. Several pesticides (e.g. carbendazim in citrus and indoxacarb in grape) were detected in the samples. Further unequivocal confirmation of the identity was performed using reference standards and/or QTOF MS/MS experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

Optimization of a heart-cutting multidimensional gas chromatography-based method for the assessment of enantiomeric fractions of o,p′-DDT in environmental samples

The enantiomeric fractions present in soil samples may provide information useful in distinguishing recent inputs of DDT from past DDT pollution. In this study, a chromatographic procedure for the determination of the enantiomeric fractions of o,p′-DDT based on heart-cutting multidimensional gas chromatography was developed. The optimization carried out achieved low ratios of DDT degradation (<15%) in the chromatographic system. High selectivity and sensitivity in the detection of the target compounds, with a limit of detection as low as 2.1 pg μL⁻¹, was reached. In addition, high degrees of repeatability (RSD < 2.0%) and reproducibility (RSD < 3.2%) were obtained for the enantiomeric fractions measured in analytical standards and soil samples.     

可见光响应碳掺杂的光催化剂涂覆于塞流反应器上分解气态芳香化合物(英文)

A plug‐flow reactor coated with carbon‐doped TiO2 (C‐TiO2 ) powder was investigated for the control of vaporous aromatics (benzene, toluene, ethylbenzene, and o‐xylene (BTEX)) under a range of experimental conditions. The characteristics of the as‐prepared C‐TiO2 and a reference Degussa P25 TiO2 powder were examined using X‐ray diffraction, scanning electron microscopy, diffuse‐reflectance ultraviolet‐visible‐near infrared spectroscopy, and Fourier transform infrared spectroscopy. The experimental conditions for the photocatalytic performance of the as‐prepared C‐TiO2 photocatalyst were controlled using three operational parameters, relative humidity, flow rate, and input concentration. Unlike other target compounds, very little benzene was removed by the C‐TiO2 photocatalyst under visible‐light irradiation. In contrast, the C‐TiO2 exhibited higher removal efficiencies for the other three target compounds (toluene, ethylbenzene, and xylene) compared with those achieved using unmodified TiO2 under visible‐light irradiation. The highest removal efficiency was obtained at a relative humidity value of 45%. Specifically, the toluene removal efficiency determined at a relative humidity of 45% was 78%, whereas it was close to 0%, 7.2%, and 5.5% for relative humidity values of 20%, 70%, and 95%, respectively. In addition, the removal efficiencies for the three target compounds decreased as the flow rate or input concentration increased. These findings indicate that the as‐prepared C‐TiO2 photocatalyst could be used for the removal of toxic vaporous aromatics under optimized operating conditions.     

Optical Fiber Sensor Technology in Portugal

Abstract

A general overview of the R&D activity in fiber optic sensing developed over the last fifteen years in Portugal is given. Different topics are addressed, including interferometric, intensity and Bragg grating based fiber optic sensors, signal processing and multiplexing techniques, optical current sensors, together with some references to field trials and applications. Possible guidelines for present and future national R&D activity on this subject are outlined.     

Modelling the metabolic action of human and rat CYP1A2 and its relationship with the carcinogenicity of heterocyclic amines

Cytochrome P450 (CYP) is a family of enzymes responsible for organism detoxification. However, some of the members of the CYP1A subfamily also catalyse the activation of heterocyclic amines (HAs), present in cooked meat, to carcinogenic compounds which have been shown to increase the risk of breast, colorectal and lung cancer. In humans, CYP1A2 is the enzyme with the most significant action in HA metabolism but in rodents CYP1A1 is also important in this biotransformation. Understanding the metabolic action of these enzymes is essential to predict the factors that enable the formation of the carcinogenic products. We have built two models of CYP1A2, one for the human enzyme and one for the rat homologue. The templates chosen include the only X-ray structure published to date for a mammal CYP, a quimeric C2A5 from rabbit, as well as CYPs belonging to Bacillus megaterium (CYPBm-3), Pseudomonas putida (CYPcam), Pseudomonas sp. (CYPterp), and Saccharopolyspora erythraea (CYPeryf). Two HAs, MeIQ (2-amino-3,4-dimethylimidazo[4,5-?]quinoline) and MeIQx (2-amino-3,8-dimethylimidazo[4,5-?]quinoxaline), known substrates of human and rat CYPIA2, were docked in the active site of the models, providing information regarding the different catalytic rates associated with the metabolisms in both enzymes. This is important for analysing the behaviour of animal models concerning the testing of anticancer drugs.     

Antibacterial Activity of Biosynthesized Selenium Nanoparticles Using Extracts of Calendula officinalis against Potentially Clinical Bacterial Strains

The use of selenium nanoparticles (SeNPs) in the biomedical area has been increasing as an alternative to the growing bacterial resistance to antibiotics. In this research, SeNPs were synthesized by green synthesis using ascorbic acid (AsAc) as a reducing agent and methanolic extract of Calendula officinalis L. flowers as a stabilizer. Characterization of SeNPs was performed by UV-vis spectrophotometry, infrared spectrophotometry (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) techniques. SeNPs of 40–60 nm and spherical morphologies were obtained. The antibacterial activity of marigold extracts and fractions was evaluated by disk diffusion methodology. The evaluation of SeNPs at different incubation times was performed through the colony-forming unit (CFU) count, in both cases against Serratia marcescens, Enterobacter cloacae, and Alcaligenes faecalis bacteria. Partial antibacterial activity was observed with methanolic extracts of marigold leaves and flowers and total inhibition with SeNPs from 2 h for S. marcescens, 1 h for E. cloacae, and 30 min for A. faecalis. In addition, SeNPs were found to exhibit antioxidant activity. The results indicate that SeNPs present a potentiated effect of both antimicrobial and antioxidant activity compared to the individual use of marigold extracts or sodium selenite (Na₂SeO₃). Their application emerges as an alternative for the control of clinical pathogens.