Screening of grapes and wine for azoxystrobin, kresoxim-methyl and trifloxystrobin fungicides by HPLC with diode array detection

The Quinone outside Inhibitors (QoI) are one of the most important and recent fungicide groups used in viticulture and also allowed by Integrated Pest Management. Azoxystrobin, kresoxim-methyl and trifloxystrobin are the main active ingredients for treating downy and powdery mildews that can be present in grapes and wines. In this paper, a method is reported for the analysis of these three QoI-fungicides in grapes and wine. After liquid-liquid extraction and a clean-up on commercial silica cartridges, analysis was by isocratic HPLC with diode array detection (DAD) with a run time of 13 min. Confirmation was by solid-phase micro-extraction (SPME), followed by GC/MS determination. The main validation parameters for the three compounds in grapes and wine were a limit of detection up to 0.073 mg kg^-1, a precision not exceeding 10.0% and an average recovery of 93% ± 38.     

Studies on genetic variants of α-lactalbumin and β-lactoglobulin from milk of native Portuguese ovine and caprine breeds

Summary α-Lactalbumin (α-La) and β-lactoglobulin (β-Lg) fractions were obtained from Portuguese native breeds of ewes and goats by preparative gel filtration and further purified by ion exchange; their genetic variants were characterized by isolectric focusing, and β-Lg isolated was further characterized by differential scanning calorimetry. Separation of β-Lg and α-La by molecular exclusion from native whey was relatively easy, whereas β-Lg from both breeds accounted for a single peak via ion exchange under various gradients of NaCl. Isoelectric focusing has indicated that α-La from ovine and caprine wheys appears as a single variant in each case, as well as β-Lg from caprine whey; however, β-Lg from ovine whey appears as two peaks, tentatively denoted as β-Lg A and B. Further comparison with bovine whey made it possible to rank whey proteins by increasing value of pI as follows: bovine β-Lg A, bovine α-La, bovine β-Lg B, ovine and caprine α-La, ovine β-Lg A, and finally ovine β-Lg B and caprine β-Lg. β-Lg from goat's whey showed the highest onset temperature of denaturation in the presence (78–97 °C) or absence (90–100 °C) of NaCl for every pH tested; when NaCl was present, a good correlation between pI and onset temperature of denaturation was obtained for pH values in the range 3.5–7.0.     

Comparative studies on Langmuir–Schaefer films of polyanilines

Langmuir isotherms of polyaniline (PANI), poly(o-toluidine) (POT), poly(o-anisidine) (POAS) and poly(o-ethoxy aniline) (PEOA) were investigated at aqueous subphase of pH 1, where doping during monolayer formation appeared as an essential step for high quality of the film. The effect of substituent groups in polyanilines plays a prominent role for the formation of Langmuir films. The area per unit repeat molecule was shown to increase by an increment of the substituent groups in polyanilines. Ultra-thin films of PANI, POT, POAS and PEOA were engineered by Langmuir–Schaefer (LS) technique. The uniformity of the deposited polyanilines LS films was verified by atomic force microscopy (AFM). The electrochemical properties of polyanilines LS films were investigated by cyclic voltammetry and current transient measurements, and the electrical characteristics were investigated by depositing the films on interdigitated electrodes. The electrochromic switching response time and diffusion coefficient of such LS films were also estimated by electrochemical surveyings.     

Optimization of modified atmosphere packaging with respect to physicochemical characteristics of Requeijão

The effects of modified atmosphere packaging on physicochemical and sensorial characteristics (contents of free fatty acids, lactose, lactic acid and moisture, as well as pH and rigidity) in Portuguese whey cheese (Requeijão) were studied following a response surface methodology using storage time, storage temperature and fraction of CO₂ in the flushing gas as manipulated variables. Inspection of the sensorial optima in terms of the different parameters indicated that it is convenient to set the storage temperature equal to 4°C because no significant lipolysis takes place, irrespective of overhead atmosphere. Plain CO₂ as flushing gas will in general ensure more constant composition until 15 days and will provide protection against extensive lipolysis. In terms of overall visual aspect, all packaged cheeses were preferred to their unpackaged counterparts; however, in terms of acidic smell, only whey cheeses stored at 4°C exhibited significant differences relative to those stored at higher temperatures.     

Tissue is alive: New technologies are needed to address the problems of protein biomarker pre-analytical variability

Instability of tissue protein biomarkers is a critical issue for molecular profiling. Pre-analytical variables during tissue procurement, such as time delays during which the tissue remains stored at room temperature, can cause significant variability and bias in downstream molecular analysis. Living tissue, ex vivo, goes through a defined stage of reactive changes that begin with oxidative, hypoxic and metabolic stress, and culminate in apoptosis. Depending on the delay time ex vivo, and reactive stage, protein biomarkers, such as signal pathway phosphoproteins will be elevated or suppressed in a manner which does not represent the biomarker levels at the time of excision. Proteomic data documenting reactive tissue protein changes post collection indicate the need to recognize and address tissue stability, preservation of post-translational modifications, and preservation of morphologic features for molecular analysis. Based on the analysis of phosphoproteins, one of the most labile tissue protein biomarkers, we set forth tissue procurement guidelines for clinical research. We propose technical solutions for (i) assessing the state of protein analyte preservation and specimen quality via identification of a panel of natural proteins (surrogate stability markers), and (ii) using multi-purpose fixative solution designed to stabilize, preserve and maintain proteins, nucleic acids, and tissue architecture.     

Novel photochromic 2,2′-bithiophene azo dyes

The photochromic properties and colour constancy of two series of 2,2′-bithiophene azo dyes in THF solution were strongly dependent on the substitution pattern of the dyes. Under visible irradiation (>420 nm) while some dyes exhibited a significant change in colour intensity others exhibited an almost stable absorption. The photokinetic parameters of the systems are also described.     

Synthesis,characterization and spectroscopic studies of two new schiff-base bithienyl pendant-armed 15-crown-5 molecular probes

Two new ligands provided with a 15-crown-5 as a receptor unit and bithiophen unit as an emissive probe have been synthesized and characterized in order to evaluate the coordination capabilities and their sensor effect. Ligand L1 presents an aromatic crown ether moiety that is directly linked to the imine-2,2′-bithiophene π–conjugated system, and ligand L2 is constituted by an aliphatic crown ether moiety that is linked to the same imine-2,2′-bithiophene system through a methylene unit. Solid metal complexes of Ni(II), Pd(II), Hg(II) and Na(I) have been synthesized using both macrocyclic compounds, and have been studied in solution in the presence of the same metal ions. All solid compounds have been characterized by common analytical and spectroscopic techniques. The sensorial effect has been studied using absorption, emission and MALDI-TOF-MS spectroscopies.     

Analysis of companies’ environmental strategies for a green society

The present research is based on a survey sent to large, medium and small size companies, located in Portugal and within what are considered the most pollutant industrial sectors. The analyses of the results, processed with the Statistical Package for Social Sciences (SPSS) 11.0, show that generally companies are concerned with the implementation of clean processes, green products and eco-equipment to have a cleaner environment, i.e. a more sustainable society. Statistically, the results show that the 98 potential polluting companies are moderately contributing for a green society (x_m=3.1) regarding the ten environmental strategies under research. It can also be concluded that, globally, environmental strategies are directly linked to the companies’ size.     

Evaluation of the non-enzymatic browning in thermally processed apple juice by front-face fluorescence spectroscopy

Fresh apple juice was heated at 95 °C for 30 and 60 min, and then stored for 6 days for obtaining different extent of non-enzymatic browning. Front-face fluorescence excitation–emission-matrix (EEM) with excitation at 355 and 400 nm and emission ranges of 385–600, and 430–600 nm was used to measure the juice samples. The sign test pointed out an enhanced sensitivity of EEM compared to commonly used browning indicators, such as non-enzymatic browning index (NEBI), color readings in L^∗a^∗b^∗ space, and the concentration of 5-hydroxymethylfurfural (HMF). Using the fluorescence data, the correctness of classifications of fresh juice, heated juice, and stored juice were >85%. Multivariate analyses were applied to study the relations of fluorescence emission spectra and common indicators. For predicting NEBI, b^∗, and HMF, the correlation coefficients were >0.80. Resulting, the spectroscopic analyses of fluorescent neoformed products such as HMF provide a feasible approach to monitor non-enzymatic browning of juice.     

Effect of particle size upon the extent of extraction of antioxidant power from the plants Agrimonia eupatoria, Salvia sp. and Satureja montana

The dependence of the extent of aqueous extraction of antioxidant compounds on particle size and contact time was studied for three important medicinal plants, that are commonly used in infusions: agrimony, sage and savoury. The effect of extraction time was dependent on the plant considered; however, ca. 5 min can be taken as the minimum period required to assure an acceptable degree of extraction of those compounds. As expected, a smaller particle size led to a higher extraction extents; a typical value of 0.2 mm is accordingly recommended. Chlorogenic acid was the dominant phenolic compound extracted from agrimony, whereas caffeic acid dominated in the case of sage or savoury. A mathematical model based on Fick’s law was developed from first principles, and its two parameters were suitably fitted to the experimental data generated – in attempts to predict the evolution of antioxidant capacity extracted during contact time, for each plant and each particle size.