Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

Anodic adsorptive stripping voltammetric determination of atrazine in spiked soil samples with a gold microelectrode

Microwave-assisted solvent extraction was combined with anodic adsorptive stripping voltammetry at a gold microelectrode to extract and quantify the herbicide atrazine in spiked soil samples. A systematic study of the experimental parameters affecting the stripping response was carried out by square-wave voltammetry. The voltammetric procedure is based on controlled adsorptive accumulation of atrazine at the potential of 0.35V (versus Ag/AgCl) in the presence of Britton–Robinson buffer pH (2.0). The limit of detection obtained for a 30 sec collection time was 4.3x10-7 mol L-1. Recovery experiments, at the 1µgg-1 level of spiking, gave good results for the global procedure, and the values found were comparable to those obtained by HPLC.

Influence of tobacco smoke on carcinogenic PAH composition in indoor PM10 and PM2.5

Because of the mutagenic and/or carcinogenic properties, Polycyclic Aromatic Hydrocarbons (PAH), have a direct impact on human population. Consequently, there is a widespread interest in analysing and evaluating the exposure to PAH in different indoor environments, influenced by different emission sources. The information on indoor PAH is still limited, mainly in terms of PAH distribution in indoor particles of different sizes; thus, this study evaluated the influence of tobacco smoke on PM10 and PM2.5 characteristics, namely on their PAH compositions, with further aim to understand the negative impact of tobacco smoke on human health. Samples were collected at one site influenced by tobacco smoke and at one reference (non-smoking) site using low-volume samplers; the analyses of 17 PAH were performed by Microwave Assisted Extraction combined with Liquid Chromatography (MAE–LC). At the site influenced by tobacco smoke PM concentrations were higher 650% for PM10, and 720% for PM2.5. When influenced by smoking, 4 ring PAH (fluoranthene, pyrene, and chrysene) were the most abundant PAH, with concentrations 4600–21 000% and 5100–20 800% higher than at the reference site for PM10 and PM2.5, respectively, accounting for 49% of total PAH (SPAH). Higher molecular weight PAH (5–6 rings) reached concentrations 300–1300% and 140–1700% higher for PM10 and PM2.5, respectively, at the site influenced by tobacco smoke. Considering 9 carcinogenic PAH this increase was 780% and 760% in PM10 and PM2.5, respectively, indicating the strong potential risk for human health. As different composition profiles of PAH in indoor PM were obtained for reference and smoking sites, those 9 carcinogens represented at the reference site 84% and 86% of SPAH in PM10 and PM2.5, respectively, and at the smoking site 56% and 55% of SPAH in PM10 and PM2.5, respectively. All PAH (including the carcinogenic ones) were mainly present in fine particles, which corresponds to a strong risk for cardiopulmonary disease and lung cancer; thus, these conclusions are relevant for the development of strategies to protect public health.

Voltammetric determination of dialifos in soils with a mercury film ultramicroelectrode

An extraction-adsorptive stripping voltammetric procedure for the determination of the pesticide dialifos in soil samples using microwave-assisted solvent extraction and a mercury film ultramicroelectrode was developed. The method is based on the use of hexane-acetone solvent (1:1, v/v) and on controlled adsorptive accumulation of the insecticide at the potential of -0.10V (versus Ag/AgCl) in the presence of Britton-Robinson buffer (pH 2.0). Soil sample extracts were analyzed directly after drying and redissolution with the supporting electrolyte, but without other pretreatment. The limit of detection obtained for a 10sec collection time was 2.0x10-8 mol L-1. Recovery experiments for the global procedure, at the 0.100µgg-1 level, gave satisfactory average and standard deviation results for the two different soils tested.

Polycyclic aromatic hydrocarbons in gas and particulate phases of indoor environments influenced by tobacco smoke: levels, phase distributions, and health risks

As polycyclic aromatic hydrocarbons (PAHs) have a negative impact on human health due to their mutagenic and/or carcinogenic properties, the objective of this work was to study the influence of tobacco smoke on levels and phase distribution of PAHs and to evaluate the associated health risks. The air samples were collected at two homes; 18 PAHs (the 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in gas phase and associated with thoracic (PM10) and respirable (PM2.5) particles. At home influenced by tobacco smoke the total concentrations of 18 PAHs in air ranged from 28.3 to 106 ngm 3 (mean of 66.7 25.4 ngm 3),∑PAHs being 95% higher than at the non-smoking one where the values ranged from 17.9 to 62.0 ngm 3 (mean of 34.5 16.5 ngm 3). On average 74% and 78% of ∑PAHs were present in gas phase at the smoking and non-smoking homes, respectively, demonstrating that adequate assessment of PAHs in air requires evaluation of PAHs in both gas and particulate phases. When influenced by tobacco smoke the health risks values were 3.5e3.6 times higher due to the exposure of PM10. The values of lifetime lung cancer risks were 4.1 10 3 and 1.7 10 3 for the smoking and nonsmoking homes, considerably exceeding the health-based guideline level at both homes also due to the contribution of outdoor traffic emissions. The results showed that evaluation of benzo[a]pyrene alone would probably underestimate the carcinogenic potential of the studied PAH mixtures; in total ten carcinogenic PAHs represented 36% and 32% of the gaseous ∑PAHs and in particulate phase they accounted for 75% and 71% of ∑PAHs at the smoking and non-smoking homes, respectively.

Determination of pesticides in fruit and fruit juices by chromatographic methods. An overview

In order to combat a variety of pests, pesticides are widely used in fruits. Several extraction procedures (liquid extraction, single drop microextraction, microwave-assisted extraction, pressurized liquid extraction, supercritical fluid extraction, solid-phase extraction, solid-phase microextraction, matrix solid-phase dispersion, and stir bar sorptive extraction) have been reported to determine pesticide residues in fruits and fruit juices. The significant change in recent years is the introduction of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods in these matrices analysis. A combination of techniques reported the use of new extraction methods and chromatography to provide better quantitative recoveries at low levels. The use of mass spectrometric detectors in combination with liquid and gas chromatography has played a vital role to solve many problems related to food safety. The main attention in this review is on the achievements that have been possible because of the progress in extraction methods and the latest advances and novelties in mass spectrometry, and how these progresses have influenced the best control of food, allowing for an increase in the food safety and quality standards.

Influence of traffic emissions on the carcinogenic polycyclic aromatic hydrocarbons in outdoor breathable particles

Because polycyclic aromatic hydrocarbons (PAHs) have been proven to be toxic, mutagenic, and/or carcinogenic, there is widespread interest in analyzing and evaluating exposure to PAHs in atmospheric environments influenced by different emission sources. Because traffic emissions are one of the biggest sources of fine particles, more information on carcinogenic PAHs associated with fine particles needs to be provided. Aiming to further understand the impact of traffic particulate matter (PM) on human health, this study evaluated the influence of traffic on PM10 (PM with aerodynamic diameter <10 µm) and PM2.5 (PM with aerodynamic diameter <2.5 µm), considering their concentrations and compositions in carcinogenic PAHs. Samples were collected at one site influenced by traffic emissions and at one reference site using lowvolume samplers. Analysis of PAHs was performed by microwave-assisted extraction combined with liquid chromatography (MAE-LC); 17 PAHs, including 9 carcinogenic ones, were quantified. At the site influenced by traffic emissions, PM10 and PM2.5 concentrations were, respectively, 380 and 390% higher than at the background site. When influenced by traffic emissions, the total concentration of nine carcinogenic compounds (naphthalene, chrysene, benzo(a)anthracene, benzo(b) fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene, and dibenzo(a,l)pyrene) was increased by 2400 and 3000% in PM10 and PM2.5, respectively; these nine carcinogenic compounds represented 68 and 74% of total PAHs (ƩPAHs) for PM10 and PM2.5, respectively. All PAHs, including the carcinogenic compounds, were mainly present in fine particles. Considering the strong influence of these fine particles on human health, these conclusions are relevant for the development of strategies to protect public health.

Brewer's spent grain from different types of malt: Evaluation of the antioxidant activity and identification of the major phenolic compounds

The antioxidant activity and phenolic composition of brewer's spent grain (BSG) extracts obtained by microwave-assisted extraction from twomalt types (light and darkmalts) were investigated. The total phenolic content (TPC) and antioxidant activity among the light BSG extracts (pilsen, melano, melano 80 and carared)were significantly different (p b 0.05) compared to dark extracts (chocolate and black types), with the pilsen BSG showing higher TPC (20 ± 1 mgGAE/g dry BSG). In addition, the antioxidant activity assessed by 2,2-diphenyl- 1-picrylhydrazyl, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) and deoxyribose assays decreased as a result of increasing kilning temperatures in the following order: pilsen N melano N melano 80 N carared N chocolate N black. HPLC-DAD/ESI-MS/MS analysis indicated the presence of phenolic acids, such as ferulic, p-coumaric and syringic acids, as well as several isomeric ferulate dehydrodimers and one dehydrotrimer. Chocolate and black extracts, obtained frommalts submitted to the highest kilning temperatures, showed the lowest levels of ferulic and p-coumaric acids. These results suggested that BSG extracts from pilsen malt might be used as an inexpensive and good natural source of antioxidants with potential interest for the food, pharmaceutical and/or cosmetic industries after purification.

Evaluation of atmospheric deposition and patterns of polycyclic aromatic hydrocarbons in façades of historic monuments of Oporto (Portugal)

Atmospheric pollution by motor vehicles is considered a relevant source of damage to architectural heritage. Thus the aim of this work was to assess the atmospheric depositions and patterns of polycyclic aromatic hydrocarbons (PAHs) in façades of historical monuments. Eighteen PAHs (16 PAHs considered by US EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in thin black layers collected from façades of two historical monuments: Hospital Santo António and Lapa Church (Oporto, Portugal). Scanning electron microscopy (SEM) was used for morphological and elemental characterisation of thin black layers; PAHs were quantified by microwave-assisted extraction combined with liquid chromatography (MAE-LC). The thickness of thin black layers were 80–110 μm and they contained significant levels of iron, sulfur, calcium and phosphorus. Total concentrations of 18 PAHs ranged from 7.74 to 147.92 ng/g (mean of 45.52 ng/g) in thin black layers of Hospital Santo António, giving a range three times lower than at Lapa Church (5.44– 429.26 ng/g; mean of 110.25 ng/g); four to six rings compounds accounted at both monuments approximately for 80–85% of ΣPAHs. The diagnostic ratios showed that traffic emissions were significant source of PAHs in thin black layers. Composition profiles of PAHs in thin black layers of both monuments were similar to those of ambient air, thus showing that air pollution has a significant impact on the conditions and stone decay of historical building façades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere.

Automated design of microwave discrete tuning differential capacitance circuits in Si-integrated technologies

A genetic algorithm used to design radio-frequency binary-weighted differential switched capacitor arrays (RFDSCAs) is presented in this article. The algorithm provides a set of circuits all having the same maximum performance. This article also describes the design, implementation, and measurements results of a 0.25 lm BiCMOS 3-bit RFDSCA. The experimental results show that the circuit presents the expected performance up to 40 GHz. The similarity between the evolutionary solutions, circuit simulations, and measured results indicates that the genetic synthesis method is a very useful tool for designing optimum performance RFDSCAs.

Automated synthesis procedure of RF discrete tuning differential capacitance circuits

The paper presents a RFDSCA automated synthesis procedure. This algorithm determines several RFDSCA circuits from the top-level system specifications all with the same maximum performance. The genetic synthesis tool optimizes a fitness function proportional to the RFDSCA quality factor and uses the epsiv-concept and maximin sorting scheme to achieve a set of solutions well distributed along a non-dominated front. To confirm the results of the algorithm, three RFDSCAs were simulated in SpectreRF and one of them was implemented and tested. The design used a 0.25 mum BiCMOS process. All the results (synthesized, simulated and measured) are very close, which indicate that the genetic synthesis method is a very useful tool to design optimum performance RFDSCAs.

Synthesis, characterization and antiproliferative activity on cancer cell lines of new ionic liquids from ampicillin

Ionic Liquids (ILs) are ionic compounds that possess melting temperature below 100ºC and they have been a topic of great interest since the mid-1990s due to their unique properties. The range of IL uses has been broadened, due to a significant increase in the variety of physical, chemical and biological ILs properties. They are now used as Active Pharmaceutical Ingredients (APIs) and recent interests are focused on their application as innovative solutions in new medical treatment and delivery options.1 In this work, our principal objective was the synthesis and investigation of physicochemical and medical properties of ionic liquids (ILs) and organic salts from ampicillin. This approach is of huge interest in pharmaceutical industry as cation and anion composition of ILs and organic salts can greatly alter their desired properties, namely the melting temperature and even synergistic effects can be obtained.2,3 For the synthesis of these compounds we used a recently developed method proposed by Ohno et al.4 for the preparation of quaternary ammonium and phosphonium hydroxides, that were neutralized by ampicillin. After purification we obtained pure ILs and salts in good yields. These ILs shows good antimicrobial and antifungal activities. As it is well known that some ionic liquids containing phosphonium and ammonium cation also shows anti-cancer activity1,5 we also decided to study these compounds against some cancer cell lines.

Fungidal and bacterial activity of N,N-dimethyl-4-(2,2,2-trichloro-1-(phenylamino)ethyl)aniline

N,N-dimethyl-4-((phenylamino)methyl)aniline (1) was prepared by condensation of aniline and 4-(dimethylamino)benzaldehyde [1] N,N-dimethyl-4-(2,2,2-trichloro-1-(phenylamino)ethyl)aniline (2) was synthesized by trichloromethylation of the imine (N,N-dimethyl-4-((phenylimino)methyl)aniline (1)) with trichloroacetic anhydride under microwave irradiation [2] (Sheme 1). The present work reports the study of bacterial and yeast activity for the compound 2. The bacteria used in this study are Staphylococcus aureus, Escherichia coli and the yeast are Saccharomyces Cerevisiae Candida albican.The results that we will present are the determination of minimal inhibitory concentration (MIC), by means of microdilution by plate method and the specific growth constants for this microorganism. Further studies are being performed to determine viability and cellular injury with this drug.

Steroselective synthesis of imidazolidin-4-ones from α-amino amides of the antimalarial primaquine and substituted benzaldehydes

Imidazolidin-4-ones are commonly employed as skeletal modifications in bioactive oligopeptides, either as proline surrogates or for protection of the N-terminal amino acid against aminopeptidase-catalysed hydrolysis . We have been working on the synthesis of imidazolidin-4-ones of the antimalarial primaquine , through acylation of primaquine with an α-amino acid and subsequent reaction of the resulting α-aminoamide with a ketone or aldehyde. Thus, when using racemic primaquine, an optically pure chiral α-amino acid and an aldehyde as starting materials, four imidazolidin-4-one diastereomers are to be expected (Scheme 1). However, we have recently observed that imidazolidin-4-one synthesis was stereoselective when 2-carboxybenzaldehyde (2CBA)* was used, as only two diastereomers were produced2. Computational studies have shown that the imine formed prior to ring closure had, for structures derived from 2CBA, a quasi-cyclic rigid structure2. This rigid conformation is stabilized by an intramolecular hydrogen bond involving the C=O oxygen atom of the 2-carboxyl substituent in 2CBA and the N-H group of the α-amino amide moiety2. These findings led us to postulate that the 2-carbonyl substituent in the benzaldehyde moiety was the key for the stereoselective synthesis of the imidazolidin-4-ones2.

Structural, physical, and chemical modifications induced by microwave heating on native agar-like galactans

Native agars from Gracilaria vermiculophylla produced in sustainable aquaculture systems (IMTA) were extracted under conventional (TWE) and microwave (MAE) heating. The optimal extracts from both processes were compared in terms of their properties. The agars’ structure was further investigated through Fourier transform infrared and NMR spectroscopy. Both samples showed a regular structure with an identical backbone, β-D-galactose (G) and 3,6-anhydro-α-L-galactose (LA) units; a considerable degree of methylation was found at C6 of the G units and, to a lesser extent, at C2 of the LA residues. The methylation degree in the G units was lower for MAEopt agar; the sulfate content was also reduced. MAE led to higher agar recoveries with drastic extraction time and solvent volume reductions. Two times lower values of [η] and Mv obtained for the MAEopt sample indicate substantial depolymerization of the polysaccharide backbone; this was reflected in its gelling properties; yet it was clearly appropriate for commercial application in soft-texture food products.