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.

Tetranuclear COPPER(II) complexes with macrocyclic and open-chain disiloxane ligands as catalyst precursors for hydrocarboxylation and oxidation of alkanes and 1-phenylethanol

Two new tetranuclear complexes [Cu-4(mu-O)(L-1)-Cl-4] and [Cu-4(mu(4)-O)(L-2)(2)Cl-4] (2), where H2L1 is a macrocyclic ligand resulting from [2+2] condensation of 2,6-diformy1-4-methylphanol (DFF) and 1,3-bis(aminopropy1)tetramethyldisiloxane, and HL2 is a 1:2 condensation product: of DFF with trimethylsilyl p-aminobenzoate, have been prepared. The structures of the products were established by Xray diffraction. The complexes have been characterised by FTIR, UV/Vis spectroscopy, ES1 mass-spectrometry and magnetic susceptibility measurements. The latter revealed that the letrftriuclear complexes can be descr bed as two ferromagnetically coupled dinuclear units, in which the two copper(II) ions interact antiferromacinetically. The ccimpi.iunds act as homogeneous catalyst precursors for a number of single-pot reactions, including (I) hydrocarbaxylation, with CO, H2O and K2S2O8, of a variety of linear and cyclic (n = 5-8) alkanes into the corresponding Cn+1 carboxylic acids, (ii) peroxidative oxidation of cyclohexane, and (iii) solvent-free microwave-assisted oxidation of 1-phenyletha.nol.

Novel coordination polymers with (Pyrazolato)-based tectons: catalytic activity in the peroxidative oxidation of alcohols and cyclohexane

Coupling five rigid or flexible bis(pyrazolato)based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340-500 degrees C. As demonstrated by N-2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135-1758 m(2)/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (0 the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cydohexane to cydohexanol and cydohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 x 10(3)) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cydohexane, the latter value being higher than that granted by the current industrial process.

Catalytic oxidation of alcohols: recent advances

This review concerns metal-catalyzed reactions of oxidation of alcohols to the respective products, mainly ketones and aldehydes, mostly within the period of 2010–2014. Both conventional and unconventional systems, not only with usual reagents, but also with uncommon and prospective ones, are overviewed, with recently achieved developments.

VO2 thin films and nanoparticles for energy-saving applications in architectural elements

Vanadium dioxide (VO2) is a promising material with large interest in construction industry and architecture, due to its thermochromic properties. This material may be used to create "smart" coatings that result in improvements in the buildings energy efficiency, by reducing heat exchanges and, consequently, the need for acclimatization. In this work, VO2 thin films and coatings were produced and tested in laboratory, to apply in architectural elements, such as glass, rooftop tiles and exterior paints. Thin films were produced by RF magnetron sputtering and VO2 nanoparticles were obtained through hydrothermal synthesis, aiming to create "smart" windows and tiles, respectively. These coatings have demonstrated the capability to modulate the transmittance of infrared radiation by around 20%. The VO2 nanoparticle coatings were successfully applied on ceramic tiles. The critical temperature was reduced to around 40ºC by tungsten doping. Ultimately, two identical house models were built, in order to test the VO2 coatings, in real atmospheric conditions during one of the hottest months of the year, in Portugal – August.

Influence of digestion methods on the recovery of Iron, Zinc, Nickel, Chromium, Cadmium and Lead contents in 11 organic residues

There are currently many devices and techniques to quantify trace elements (TEs) in various matrices, but their efficacy is dependent on the digestion methods (DMs) employed in the opening of such matrices which, although "organic", present inorganic components which are difficult to solubilize. This study was carried out to evaluate the recovery of Fe, Zn, Cr, Ni, Cd and Pb contents in samples of composts and cattle, horse, chicken, quail, and swine manures, as well as in sewage sludges and peat. The DMs employed were acid digestion in microwaves with HNO3 (EPA 3051A); nitric-perchloric digestion with HNO3 + HClO4 in a digestion block (NP); dry ashing in a muffle furnace and solubilization of residual ash in nitric acid (MDA); digestion by using aqua regia solution (HCl:HNO3) in the digestion block (AR); and acid digestion with HCl and HNO3 + H2O2 (EPA 3050). The dry ashing method led to the greatest recovery of Cd in organic residues, but the EPA 3050 protocol can be an alternative method for the same purpose. The dry ashing should not be employed to determine the concentration of Cr, Fe, Ni, Pb and Zn in the residues. Higher Cr and Fe contents are recovered when NP and EPA 3050 are employed in the opening of organic matrices. For most of the residues analyzed, AR is the most effective method for recovering Ni. Microwave-assisted digestion methods (EPA3051 and 3050) led to the highest recovery of Pb. The choice of the DM that provides maximum recovery of Zn depends on the organic residue and trace element analyzed.

Accelerated digestion for high-throughput proteomics analysis of whole bacterial proteomes.

In bottom-up proteomics, rapid and efficient protein digestion is crucial for data reliability. However, sample preparation remains one of the rate-limiting steps in proteomics workflows. In this study, we compared the conventional trypsin digestion procedure with two accelerated digestion protocols based on shorter reaction times and microwave-assisted digestion for the preparation of membrane-enriched protein fractions of the human pathogenic bacterium Staphylococcus aureus. Produced peptides were analyzed by Shotgun IPG-IEF, a methodology relying on separation of peptides by IPG-IEF before the conventional LC-MS/MS steps of shotgun proteomics. Data obtained on two LC-MS/MS platforms showed that accelerated digestion protocols, especially the one relying on microwave irradiation, enhanced the cleavage specificity of trypsin and thus improved the digestion efficiency especially for hydrophobic and membrane proteins. The combination of high-throughput proteomics with accelerated and efficient sample preparation should enhance the practicability of proteomics by reducing the time from sample collection to obtaining the results.

Microondas em síntese orgânica

The application of microwave heating to organic synthesis is presented in a concise manner. Issues such as the history of the microwave oven, dielectric heating, reactions techniques (dry reactions, MORE chemistry), domestic ovens, microwave reactors, microwave effect and control of selectivities are discussed. Selected examples from the literature showed faster reactions, improved yields, less thermal degradations and cleaner reactions.

Decomposição de argilas em forno de microondas e determinação simultânea dos seus constituintes principais por espectrometria de emissão óptica em plasma indutivamente acoplado

In this work a closed-vessel microwave-assisted acid decomposition procedure for clays was developed. Aluminum, Ca, Fe, K, Mg, Na, Si, and Ti were determined in clay digestates by inductively coupled plasma optical emission spectrometry. The most critical parameter for total decomposition of clays was the composition of the reagent mixture. The applied power and the heating time exerted a less critical influence. Best decomposition conditions were attained using a reagent mixture containing 4 mL aqua regia plus 3 mL HF and the heating program was implemented in 12 min. The accuracy of the results was demonstrated using two standard reference materials and a paired t-test showed a good agreement between determined and certified values at a 95% confidence level.

Atualizando a química orgânica experimental da licenciatura

The present contribution describes three different modern experiments for possible adoption in undergraduate organic chemistry laboratories. These are: 1. electrocatalytic hydrogenation of benzaldehyde to benzyl alcohol; 2. identification of three volatile components, obtained from pineapple fruit, by mass spectrometry and 3. microwave mediated fast synthesis of N-(p-chlorophenyl)phthalamic acid from phthalic anhydride and p-chloroaniline under solvent-free conditions. The experiments can be executed in a short period of time, putting the undergraduate student in contact with a variety of topics in organic chemistry and several techniques of analysis, showing multidisciplinarity in organic chemistry.

Planejamento fatorial aplicado à digestão de amostras de feijão assistida por radiação microondas

The use of factorial design was evaluated for optimization of focused-microwave-assisted digestion of bean samples. Calcium, Fe, Mg, Mn and Zn percentual recoveries were determined in digestates after focused-microwave-assisted digestion according to factorial design procedures. A cavity microwave digestion was carried out to certify the elemental compositions obtained. The accuracy was checked using a standard reference material, the NIST SRM 8433 - Corn Bran. Results are in agreement with certified values at the 95% confidence limit when the Student t-test was used. Volumes of nitric and sulfuric acid, temperature, and the interplay between HNO3 and H2SO4 initial volumes were significant variables according to P-values in the analysis of variance (ANOVA).

Digestão de óleo lubrificante encapsulado em forno de microondas com radiação focalizada por adição de amostra ao reagente pré-aquecido

The applicability of the recently proposed procedure based on gradual sample addition to microwave-assisted pre-heated concentrated acid is limited by the sample viscosity. In this work, lubricating oil samples with high viscosity were encapsulated and manually added to the microwave-assisted pre-heated concentrated digestion mixture. The procedure was applied for determination of Al, Ca, Cr, Cu, Fe, Mg, Ni, P, Pb, Si, Sn, Sr, V, W, and Zn in lubricating oil by inductively coupled plasma optical emission spectrometry (ICP OES). Determined and certified values for Ca, Mg, P, and Zn in lubricating oil were in agreement at a 95% confidence level.