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The effects of coating 'Rocha' pear with alginate-based nanoemulsions enriched with lemongrass essential oil (LG) was evaluated and compared to the usual 1-MCP treatment. Fruit were treated with 1-MCP (312 nL L-1) or coated with nanoemulsions: sodium alginate 2 % (w/w) + lemongrass essential oil 1.25 % (w/w) (LG 1.25 %) or lemongrass essential oil 2.5 % (w/w) (LG 2.5 %). Then, fruit were stored at 0 degrees C and 90-95 % relative humidity (RH), for eight months. Fruit samples were collected at harvest and after two, four, six and eight months of cold storage, and then transferred to shelf-life at 22 degrees C. Upon removal and after 7 d shelf-life, fruit symptoms of superficial scald and internal browning, ethylene production, color CIE (L*, hue), firmness, soluble solids content (SSC), titratable acidity (TA), weight loss, electrolytic leakage (EL), antioxidant activity and fatty acids of pear peel, microbial growth and sensory analyses were evaluated. Coatings and 1-MCP reduced fruit color evolution and preserved better firmness than control. Coatings and 1-MCP did not affect SSC and TA. Treatments did not influence the sensory quality. Microbial growth was within the safety limits in all treatments. Treatments with 1-MCP and LG-nanoemulsions were similarly efficient to reduce superficial scald, nevertheless the LG-nanoemulsions showed higher internal disorders after 8 months of storage and LG 2.5 % had higher decay at the same period, similar to control. 1-MCP treated fruit had the lowest softening rate after shelf-life up to 4 months and LG 2.5 % showed higher weight loss. Also, ethylene production was higher in control and LG 1.25 % up to 6 months plus shelf-life, while after 8 months there was no difference among treatments. This study suggests that 1-MCP is the most efficient for preserving quality of 'Rocha' pear for 8 months, while up to 6 months the best effect is obtained with LG 1.25 % nanocoatings. info:eu-repo/semantics/publishedVersion

Die chemische Zusammensetzung der Rebtriebe ist durch onologische Verbindungen mit hohem Nutzen gekennzeichnet, die zum sensorischen Profil von Weinen beitragen konnten. In der hier vorgestellten Studie wurden gerostete Triebe zweier Sorten, in Form von Granulat oder als Holzschnitzel, dem Wein zu unterschiedlichen Zeitpunkten wahrend der Weinherstellung zugesetzt. Die Ergebnisse zeigten, dass onologische Zusatzstoffe, die von dem Rebholz stammten, die chemische Zusammensetzung von Weinen, und somit deren Qualitat, durch Holz- und sortentypische Aromen verbessern konnen. Diese Vorgehensweise entspricht einem neuen Konzept, welches Weinanbau und Weinherstellung verbindet: der zirkulare Weinbau.

Vine-shoots from two important Vitis vinifera, Airen and Cencibel, have been prepared in two different formats (chip and granule) and added (12 g/L) in their own wines in different winemaking steps. Results have shown significant differences depending in all conditions tested, and wine chemical composition was modulated while in contact with vine-shoots. Compounds such as trans-resveratrol, increased its concentration up to 4 mg/L in Airen white wines. In Cencibel red wines, vanillin was found in a concentration four times above its odor threshold and independently of the vine-shoot variety, format and moment of addition, compounds such as (−)-epicatechin and (+)-catechin increased the concentration with respect to the control wine. When vine-shoots were added after fermentation, β-ionol appeared for first time in all wines. In case of guaiacol, the higher increment was observed for Airen wines. Therefore, it is possible to elaborate distinctive wines using their own resources.

This work describes the development of a new selective photocontrollable molecularly imprinted-based sorbent for the selective enrichment/pre-concentration of dimethoate from spiked olive oil samples. To achieve this goal an improved molecularly imprinted strategy relying on the embedding of a functional monomer containing an azobenzene chromophore as light-responsive element, on the crosslinked tridimensional molecular imprinted network, has been assessed. To address the mechanisms underlying template recognition and uptake/release of the analyte from the functional imprinted material, computational studies using a quantum chemical approach, have been explored. This new functional sorbent provides a straightforward controllable uptake/release of the target template using light as the stimuli tool, which is highly advantageous due to light manipulation characteristics, such as superior clean, precision and remote controllable properties. In general, this work will contribute to the implementation of a photoswitchable analytical methodology that proves to be suitable for the selective isolation and further quantification of dimethoate from olive oil matrices at levels similar to the maximum residues limits imposed by the legislation. The limits of detection, calculated based on 3σ, was 1.6 mgL−1 and the limit of quantification, based on 10σ, was 5.2 mgL−1. The implemented sample preparation shows high reproducibility and recoveries (93.3 ± 0.4%).

International audience; The label authentication of monovarietal extra virgin olives is of great relevance from a socio-economical point of view. This work aims to gain insights into the prediction of the varietal origin of extra virgin olive oil (EVOO) samples obtained from single olive cultivars, French cultivars Oliviere, Salonenque, and Tanche and Portuguese cultivars Blanqueta, Carrasquenha, and Galega Vulgar, collected in 2016−2017 and 2017−2018 harvest seasons. To pursue this study, spectroscopic approaches based on one-dimensional nuclear magnetic resonance (1D NMR) spectroscopy, namely, 1 H and 13 C NMR distortionless enhancement by polarization transfer (DEPT) 45 pulse sequence, and Fourier transform mid-infrared spectroscopy (FT-MIR) are used in combination with partial least square discriminant analysis (PLS1-DA). The results obtained by PLS1-DA models using 1 H and 13 C NMR DEPT 45 data are compared to those of PLS1-DA models using MIR data. The application of a control chart method allows for the optimization of the interpretation of the PLS1-DA results, and an efficient two-step strategy is proposed to improve the discrimination of the six studied cultivars. Then, NMR and MIR data are combined by either a mid-or high-level data fusion approach to further improve the discrimination. The models are also tested on samples from other cultivars to check their ability to reject varieties that were not considered in the calibration process.

The knowledge of the isotopic composition of virgin olive oil (VOO) allows the evaluation of authenticity and geographical origin, being an important tool against fraud. This study aimed to assess if VOOs produced in three Mediterranean regions could be discriminated on the basis of multivariate statistical analysis of geoclimatic and isotopic data. A total of 138 geo-referenced VOO samples from Portugal, France and Turkey from two different cultivation years were collected. The isotopic composition (&delta, 13C, &delta, 2H and &delta, 18O) of VOOs was obtained using an elemental analyzer coupled to an isotope ratio mass spectrometer (EA-IRMS). One-way analysis of variance for &delta, 18O showed some significant differences either between crop years or geoclimatic conditions. Based on multiple regression analyses using meteorological and geographical parameters, a meteoric water line for olive oil from Portugal, France and Turkey, in two harvest years, were created to assess the impact of climate change on their &delta, 18O values. Principal component analysis and Linear Discriminant Analysis, used to sort samples according to geoclimatic origin, performed best for French and Portuguese olive oils. In light of the results, multivariate isotopic analysis of VOO samples may discriminate not only between geoclimatic regions but also among cultivation years.

A new generation of advanced materials developed by molecular imprinting technology showing a stimuli-responsive functionality are emerging. The switchable ability to control the uptake/release of the target analyte by action of external stimulus combined with a remarkable selectivity and specificity, makes these functional materials very attractive for sample preparation purposes. In this work, the usefulness of a sample preparation tool for the selective enrichment/pre-concentration of dimethoate from olive oil spiked samples based on &ldquo, tailor-made&rdquo, dual responsive magnetic and photonic molecularly imprinted polymers as sorbents is explored. To achieve this goal, a smart molecularly imprinted polymer (MIP) possessing magnetic and photonic responsiveness was successfully synthesized, and its physico-chemical and morphological characterization was assessed. Further, the trace analysis of dimethoate in spiked olive oil samples was validated and successfully implemented using smart-MIPs as sorbents in the sample preparation step, with high recoveries (83.5 &plusmn, 0.3%) and low detection limit (0.03&micro, g&middot, mL&minus, 1).

Amphora wines also known as Vinhos de Talha are typical of Alentejo, in the south of Portugal. Crushed berries are fermented in clay vessels, regardless being white, red or a mixture of both grapes, with a minimalist intervention, resulting in white, red or palhete wines. Due to the technological differences associated to the winemaking process of these wines, the present research aimed to evaluate the mineral characterization of amphora wines with the purpose of ensuring consumer food safety and exploring the possibility of using mineral composition to establish the geographic origin of the wines. Red, white and palhete amphora wines from Vidigueira, Vila Alva, Vila de Frades and Cuba (Alentejo region) were studied. Inductively coupled plasma mass spectrometry (ICPMS) was used and the concentration of 30 elements was determined. Data shows differences among red, white and palhete wines regarding the multi-element composition, and linear discriminant analysis allowed a classification according to the wine type and geographic origin. From all samples, only one red wine presented concentrations of Zn higher than the value published by International Organisation of Vine and Wine (OIV, 2015)., This work is funded by National Funds through FCT – Fundaçara para a Ciência e Tecnologiaão, under the Projects UID/AGR/00115/2013 to ICAAM and UID/Multi/04449/2013 to HERCULES. Raquel Garcia thanks the Fundação para a Ciência e a Tecnologia for a post-doctoral research fellowship (SFRH/BPD/109912/2015).

Vineyard soil management can modify the nitrogen soil availability and, therefore, grape amino acid content. These compounds are precursors of biogenic amines, which have negative effects on wine quality and human health. The objective was to study whether the effect of conventional tillage and two cover crops (barley and clover) on grapevine nitrogen status could be related to wine biogenic amines. Over 4 years, soil NO3- -N, nitrogen content in leaf and wine biogenic amine concentration were determined.; Results: Barley reduced soil NO3- -N availability and clover increased it. In 2011, at bloom, nitrogen content decreased with barley treatment in both blade and petiole. In 2012, nitrogen content in both leaf tissues at bloom was greater with clover than with tillage and barley treatments. Also, total biogenic amines decreased in barley with respect to tillage and clover treatments. There were correlations between some individual and total biogenic amine concentrations with respect to nitrogen content in leaf tissues.; Conclusion: Wine biogenic amine concentration can be affected by the grapevine nitrogen status, provoked by changes in the soil NO3- -N availability with both cover crop treatments. © 2017 Society of Chemical Industry.; © 2017 Society of Chemical Industry.

Social democracy based on welfare and the redistribution of social contributions is failing. The accumulation of wealth and the increase in inequalities are the two faces of Janus that social democracy has not been able to contain over the recent decades. In this context, it matters to discuss John Rawls’s influential difference principle. According to the maximin criterion put forth by Rawls, it does not suffice that no one becomes worse off; those who are worse off must also become better off than they are. Here, we note that the existence and growth of inequality find no opposition in the maximin rule. Despite appearances, strictly speaking it merely introduces a factor of social compensation, a sort of “assistencialism” to the victims of the greatest inequality. Even the most robust formulation of the principle of difference, according to which the greatest advantage to the less advantaged is indispensable, does not per se preclude an aggregate growth of inequalities. It seems clear that it was an egalitarian goal what Rawls had in mind in A Theory of Justice. Rawls’s critical comments on welfare capitalism must indeed not be forgotten—especially in his further explanations about the application of the principles of justice in a property-owning democracy. Here, as in liberal socialism, the dispersion of property, capital and resources prevents economic and political powers from being concentrated into the hands of a minority. However, the egalitarian aim does not strictly follow from the difference principle as stated, whether taken literally as an application of the maximin rule or inferring from its strongest formulation. A reformulation that does justice to the egalitarian aim of the principle of difference is, however, possible: namely, a degrowthist reformulation, truly requiring a degrowth in accumulation and inequalities, making explicit a brake clause that hinders the aggregate growth of inequalities. Such a degrowthist conception of the difference principle may justify some concrete rules that are able to enforce the egalitarian commitments of social democracy.

A new generation of advanced materials developed by molecular imprinting technology showing a stimuli-responsive functionality are emerging. The application of these imprinting materials as selective sorbents on the sample preparation field seems to be very promising, allowing at the same time their reutilization in several runs and promoting the sustainability of the extraction procedures with clear economic advantages. Moreover, those functional materials that merge an enhancement of selectivity with a controllable and switchable mode of action by means of specific stimulus constitutes a hot research topic on the sample preparation domain. The scope of this book chapter is to provide a general overview of the new trends in the advances of sample preparation using these smart materials, highlighting the most relevant applications, with special emphasis on its potential impact on the field of food sample preparation.

International audience; Nuclear magnetic resonance (NMR) spectroscopy has been extensively used to date for the analysis of olive oil samples and constitutes a valuable tool particularly for the study of the triacylglycerol fraction, which is the major fraction of olive oils. In this report, we demonstrate the usefulness of one-dimensional NMR spectroscopy (1 H and 13 C NMR) for the non-destructive analysis of the triacylglycerol fraction of olive oils. To achieve this goal, 13 C spectral editing technique known as distortionless enhancement by polarization transfer (DEPT), namely 13 C NMR DEPT 45, 13 C NMR DEPT 90, 13 C NMR DEPT 135 was used for the analysis of the triacylglycerol fraction of the olive oil sample owing to the simplification on peak assignments of 13 C spectra. The suitability and usefulness of those DEPT experiments using different angle values in only one pulse sequence will be explored on the interpretation of 13 C NMR spectra. In overall, DEPT tool improves the sensitivity of the analysis due to the enhancement in the signal-to-noise ratio, which is important for this type of analysis contributing to the characterization of olive oils.

The importance of yeasts in aroma production during wine fermentation is a significant concern for obtaining a wine that appraises a broad number of consumers. For wine producers, wine aroma modulation is an essential issue where the yeasts used during the winemaking process represents a feasible way to improve the complexity and enhance wines specific characteristics. During the fermentation process of wines, yeasts convert grapes sugars into alcohol, carbon dioxide and a large number of secondary metabolites, depending on yeast metabolism, affecting the wine composition, namely its aroma and amino acids (AAs) composition. So, the present work aims to study the effect of different Saccharomyces-type yeasts on the AAs composition and volatile profile of Arinto white wines. To pursue this goal, four white wines from Arinto grapes were fermented with three different commercial yeasts (Saccharomyces bayanus EC1118, Saccharomyces cerevisiae CY3079, Saccharomyces bayanus QA23) and one Native yeast. Arinto wines AAs composition was quantified by HPLC-DAD, after a derivatization step to obtain the aminoenone derivatives. The volatile content of Arinto wines was determined by GC/MS, after an HS-SPME extraction. Results showed significant differences among the AAs content and volatile profile in the Arinto wines. The higher AAs content was found in the Arinto wines fermented with the CY3079 yeast (470.74 mg•L-1), and the lowest content of AAs in the Arinto wines fermented with EC1118 yeast (343.06 mg•L-1). Native yeast results in wines with a volatile profile richer in esters compared to the other sample wines. Principal component analysis (PCA) obtained with combined data of AAs and volatile compounds, after normalization, for each Arinto wine samples, shows a clear separation of wines fermented with Native and CY3079 yeasts in relation to QA23 and EC1118 fermented wines . The first and second principal components are responsible for 44.40% and 32.20%, respectively, of the system's variance, which clearly showed a differentiation among wines.

The aged wine spirit is a beverage with great aromatic complexity. Their volatile compounds with odorant power coming from the distillate and from the wood used in its ageing, and the interactions that take place in the process, enhanced by oxygen, all contribute to this complexity. Due to time and cost inherent of ageing wine spirits in wooden barrels, research has sought to develop more sustainable alternatives to do it. In this context, the present study compares, the effect of traditional (wooden barrel) and alternative system (stainless steel tank with dipped staves and micro-oxygenation), on the odorant and sensory profile of a wine spirit, using Limousin oak and chestnut wood, after 12 months of ageing. The results suggest that the ageing process is accelerated by the alternative ageing technology and the chestnut wood, and the corresponding wine spirits presented characteristics of greater sensory evolution and strong wood compounds extraction.

To understand the impact of SO2 and ascorbic acid (AA) in must fermentation, Arinto and Siria musts were fermented under the same conditions, but in the presence of different doses of SO2 and with or without bentonite addition. Arinto was fermented with 0, 50, 100 mg/L of SO2 and 100 mg/L of AA. Siria was fermented with 0, 15, 30, 45 mg/L of SO2 and 100 mg/L of AA. The volatile organic compounds (VOCs) were analysed by HS-SPME-GC/MS. Based on PCA results obtained from VOCs profiles for both varieties, first and second principal components were responsible for more than 60% of the respective system's variance. In both wines, the presence or absence of bentonite was clearly discriminated. This work also shows that depending on the different doses of SO2 used, the resulting VOC profiles clearly discriminate these different fermentation conditions. The use of AA in both varieties resulted in a different VOC profile compared to the use of SO2. From this study it was also possible to verify from the VOCs profile, that Arinto wine is less resilient to fermentation changes then Siria wine, which may impact technological choices.

Aiming to introduce a multiresidue analysis for the trace detection of pesticide residues belonging to organophosphorus and triazine classes from olive oil samples, a new sample preparation methodology comprising the use of a dual layer of "tailor-made" molecularly imprinted polymers (MIPs) SPE for the simultaneous extraction of both pesticides in a single procedure has been attempted. This work has focused on the implementation of a dual MIP-layer SPE procedure (DL-MISPE) encompassing the use of two MIP layers as specific sorbents. In order to achieve higher recovery rates, the amount of MIP layers has been optimized as well as the influence of MIP packaging order. The optimized DL-MISPE approach has been used in the preconcentration of spiked organic olive oil samples with concentrations of dimethoate and terbuthylazine similar to the maximum residue limits and further quantification by HPLC. High recovery rates for dimethoate (95%) and terbuthylazine (94%) have been achieved with good accuracy and precision. Overall, this work constitutes the first attempt on the development of a dual pesticide residue methodology for the trace analysis of pesticide residues based on molecular imprinting technology. Thus, DL-MISPE constitutes a reliable, robust, and sensitive sample preparation methodology that enables preconcentration of the target pesticides in complex olive oil samples, even at levels similar to the maximum residue limits enforced by the legislation.

Aiming to address the claims of nutraceutical status described in the EU Regulation 432/2012 for Extra Virgin Olive Oils (EVOO), this work is focused on the assessment of total contents of tyrosol (Tyr) and hydroxytyrosol (HTyr) for Portuguese monovarietal olive oils. To achieve this main goal, a multi-technique-based approach was performed encompassing the use of a multiple suppression nuclear magnetic resonance (MS-NMR) experiment followed by chromatographic determinations using High Performance Liquid Chromatography (HPLC-DAD). NMR-based experiments enable to screening Tyr and HTyr and their derivatives using a non-destructive and straightforward methodology. Further quantification of their levels was performed by HPLC-DAD being preceded by a sample preparation pre-treatment. The results show that levels of those compounds in the EVOOs analyzed varies in the ranges 1.135–5.715 mg·20 g−1 (Tyr) and 0.651–5.259 mg·20 g−1 (HTyr). Thus, a nutraceutical status could be claim for the EVOO's from the varieties Picual, Cobrancosa, Verdeal Alentejana and Blanqueta.

Stable isotope contents of carbon, hydrogen and oxygen are known to reflect the geo-climatic conditions under which olives grown. This study aims to unravel the correlation between some of the main geographic variables and the isotopic composition of different Portuguese varietal extra virgin olive oil (EVOO) samples. Thus, the isotopic composition (δ13C, δ18O and δ2H) of 38 EVOO samples from 11 olive varieties from 2 Portuguese regions (Alentejo and Trás-os-Montes) was studied using an elemental analyzer coupled to an isotope ratio mass spectrometry. Multivariate analysis indicated that bulk δ13C, δ2H and δ18O values were enough to significantly (P < 0.05) predict altitude, latitude, longitude, temperature, rainfall, and sea distance. This work showed that the assessment of EVOO isotopic composition give information not only on the geographic origin, but also on the environmental conditions. To the best of our knowledge, this is the first report on bulk isotopic composition of Portuguese EVOOs. This work was funded by European Regional Development Fund (FEDER) and National Funds through Foundation for Science and Technology (FCT) under Project “Por3O - Portuguese Olive Oil Omics for traceability and authenticity - PTDC/AGRPRO/2003/2014, and by National Funds through FCT - Foundation for Science and Technology under the Projects UIDB/05183/2020 and UID/AGR/00690/2019. Pedro N. Jiménez-Morillo is acknowledged for statistical assistance. info:eu-repo/semantics/publishedVersion

O défice democrático - seja local, nacional, supranacional ou global - ilustra o hiato entre os representantes políticos e a vontade e visão dos indivíduos afectados por essas decisões, e mostra como a actual representatividade dos indivíduos nas instituições é inversamente proporcional à escala e escopo institucional. Este hiato é tanto mais preocupante quanto revela o desrespeito pelo direito humano à igualdade de oportunidades de participação política e suporta a crescente desigualdade económica e social entre os mais ricos e pobres do mundo. Neste artigo pretende-se mostrar como a via cosmopolita de combate ao défice democrático é mais adequada que a proposta de mera democratização faseada dos contextos doméstico e internacional, dado traduzir-se na criação de uma sobreposição de instituições transnacionais e regionais, no seio das quais os indivíduos participam directa ou indirectamente., The democratic deficit – whether local, national, supranational or global – illustrates the gap between the decision makers and the will and vision of individuals affected by these decisions; and reveals that the current representatively of individuals in institutions is inversely proportional to scope and scale institutional. This gap is all the more worrying as it reveals the disrespect for the human right to equal opportunity to political participation; and this carries with it the growing economic and social inequality between the richest and the poorest people of the world. This article aims to show how the cosmopolitan approach on democratic deficit fight is most appropriate that the proposal of mere democratization by steps on domestic and international contexts, since it translates into the creation of an overlapping of transnational and regional institutions, within which individuals participate direct or indirectly.

Amphora wines are known in Portugal as Vinhos de Talha. In this ancient technology, alcoholic fermentation takes place in clay vessels in the shape of amphoras. Traditionally, the clay vessels are pitched inside using pine pitch and red, white or a mixture of both grapes can be fermented giving raise to red, white or palhete wines, respectively. The traditional technology associated with these wines is quite different from the modern technology of winemaking. Thus, Vinhos de Talha have a unique sensorial profile, due to the ancestral technique of vinification that originates distinctive wines, full of character and identity. The present research aims to evaluate the volatile profile of amphora wines (red, white and palhete wines). The volatile fraction of the different types of amphora wines was analyzed using headspace solid-phase microextraction (HS-SPME) followed by gas chromatography mass spectrometry (GC/MS). A total of 117 volatile compounds in the different wines analyzed were tentatively identified and principal component analysis showed a clear separation among the different types of wine based on their volatile composition.

Aiming to implement an analytical methodology that is highly selective for the extraction and quantification of terbuthylazine from olive oil, we successfully achieved: (i) the development of a molecularly imprinted polymer by bulk polymerization using terbuthylazine as template molecule, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linker, and dichloromethane as porogen; (ii) characterization of the imprinting material using Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen adsorption at 77 K, and scanning electron microscopy; (iii) their molecular recognition for the template molecule using high-performance liquid chromatography, and (iv) optimization of a solid-phase extraction procedure using as sorbent the synthesized molecularly imprinted polymer for the selective extraction and clean-up of terbuthylazine from spiked organic olive oil and further quantification of the pesticide levels by high-performance liquid chromatography. The suitability of the implemented analytical methodology was demonstrated, as concentrations of terbuthylazine below the tolerated maximum residue limits in the spiked organic olive oil samples could be satisfactorily analyzed with good precision/accuracy with high recovery rates (96%). Overall, the implemented methodology has proven to be reliable and robust and is highly promising in the field of sample preparation, particularly for the isolation/preconcentration of terbuthylazine in complex food samples.

This study concerns the first attempt to prepare molecularly imprinted polymers for the selective recognition of dimethoate using an iniferter polymerization technique (Inif-MIP). The synthesized polymers were fully characterized. SEM micrographs show a large accessibility to the binding sites with a significant improvement in MIP morphology. Inif-MIPs displayed high adsorption capacity (Q = 5.3 mg g−1). The selectivity of this imprinting system was also assessed by means of cross-selectivity assays and the results obtained show that Inif-MIP displays a high selectivity for dimethoate, whereas some structural analogues (omethoate, malathion and methidathion) are poorly retained (6.3–28.7%) or not retained at all (fenthion). Inif-MISPE methodology was implemented by packing Inif-MIPs particles into a Solid Phase Extraction (SPE) cartridge and the loading, washing and eluting steps were optimized. The suitability of this sample preparation technique was demonstrated, as concentrations of dimethoate close to the tolerated maximum residue limits in the olive oil samples could be satisfactorily analyzed with good precision and accuracy. Some remarkable characteristics, like the sorbent reusability (at least 20 cycles without the lost of selectivity), low solvent consumption, reduced sample handling and, moreover higher recovery rates reaching 88% could be ascribed to the Inif-MISPE methodology.

Wines from different grape varieties, geographical zones, soil types, foliar N application, SO2 addition and oak ageing were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). For this purpose, ICP-MS methodology was optimized. The elements which allowed differentiate wines from studied grape varieties were Sr, Ca, Mg and Mn. Geographical zones were classified according to Sr, Ba, Ni, and Cu. Cs and Pb were the main elements to discriminate the wines from the 3 soil types. Wines from several N foliar doses application were classified by Pb, Ni, Mn and Zn. The content of Cs, Mg, Cu and Pb in wines characterized the SO2 addition. Finally, wines storage in barrels were differentiate by Na and Cs concentration. The discriminant functions classify 100% of the wines, with the exception of grape variety (97.0%) and oak ageing (95.8%). Consequently, ICP-MS can be applied to classified wines according to viticultural and oenological factors., This work has been supported by FEDER and National founds, through the Programa Operacional Regional do Alentejo (InAlentejo) Operation ALENT-07-0262-FEDER-001871/Laboratório de Biotecnologia Aplicada e Tecnologias Agro-Ambientais and FEDER Funds through the Operational Programme for Competitiveness Factors–COMPETE and National Funds through FCT–Foundation for Science and Technology under the Project UID/AGR/00115/2013. T. Garde-Cerdán thanks the Spanish MINECO for funding her Ramón y Cajal contract. E.P. Pérez-Álvarez thanks the Gobierno de La Rioja for her contract by the project R-03-16. Raquel Garcia thanks the Fundação para a Ciência e Tecnologia (FCT) for a post-doctoral research fellowship (SFRH/BPD/109912/2015)

Sample preparation still remains a great challenge in the analytical workflow representing the most time-consuming and laborious step in analytical procedures. Ideally, sample pre-treatment procedures must be more selective, cheap, quick and environmental friendly. Molecular imprinting technology is a powerful tool in the development of highly selective sample preparation methodologies enabling to preconcentrate the analytes from a complex food matrix. Actually, the design and development of molecularly imprinted polymers-based functional materials that merge an enhancement of selectivity with a controllable and switchable mode of action by means of specific stimulus constitutes a hot research topic in the field of food analysis. Thus, combining the stimuli responsive mechanism and imprinting technology a new generation of materials are emerging. The application of these smart materials in sample preparation is in early stage of development, nevertheless new improvements will promote a new driven in the demanding field of food sample preparation. The new trends in the advancement of food sample preparation using these smart materials will be presented in this review and highlighted the most relevant applications in this particular area of knowledge.

Meat industry needs to reduce salt in their products due to health issues. The present study evaluated the effect of salt reduction from 6% to 3% in two Portuguese traditional blood dry-cured sausages. Physicochemical and microbiological parameters, biogenic amines, fatty acids and texture profiles and sensory panel evaluations were considered. Differences due to salt reduction were perceptible in a faint decline of water activity, which slightly favoured microbial growth. Total biogenic amines content ranged from 88.86 to 796.68mgkg-1 fresh matter, with higher amounts, particularly of cadaverine, histamine and tyramine, in low-salt products. Still, histamine and other vasoactive amines remained at low levels, thus not affecting consumers' health. Regarding fatty acids, no significant differences were observed due to salt. However, texture profile analysis revealed lower resilience and cohesiveness in low-salt products, although no textural changes were observed by the sensory panel. Nevertheless, low-salt sausages were clearly preferred by panellists.

Authentication is becoming an issue of increasing relevance in olive oil and is generally motivated by economic benefits. Blending of extra virgin olive oil (EVOO) with refined olive oil (ROO) constitutes one of the most common types of adulteration of this top grade product. Concerning this particular topic, the most recent attempts of several research groups on the finding of some target compounds as markers of adulteration of EVOO with ROO will be reviewed. All efforts developed until now to find markers of adulteration in blends of EVOO with ROO have contributed to increase the knowledge about this topic although it is mandatory to exploit new compounds that could be assigned as reliable adulteration markers able to detect with high selectivity, sensitivity and accuracy this fraudulent practice.

Several studies have suggested that differences in the natural rooting ability of plant cuttings could be attributed to differences in endogenous auxin levels. Hence, during rooting experiments, it is important to be able to routinely monitor the evolution of endogenous levels of plant hormones. This work reports the development of a new method for the quantification of free auxins in auxin-treated Olea europaea (L.) explants, using dispersive liquid–liquid microextraction (DLLME) and microwave assisted derivatization (MAD) followed by gas chromatography/mass spectrometry (GC/MS) analysis. Linear ranges of 0.5–500 ng mL−1 and 1–500 μg mL−1 were used for the quantification of indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA), respectively. Determined by serial dilutions, the limits of detection (LOD) and quantification (LOQ) were 0.05 ng mL−1 and 0.25 ng mL−1, respectively for both compounds. When using the calibration curve for determination, the LOQ corresponded to 0.5 ng mL−1 (IAA) and 0.5 μg mL−1 (IBA). The proposed method proved to be substantially faster than other alternatives, and allowed free auxin quantification in real samples of semi-hardwood cuttings and microshoots of two olive cultivars. The concentrations found in the analyzed samples are in the range of 0.131–0.342 μg g−1 (IAA) and 20–264 μg g−1 (IBA).

Plant hormones, and especially auxins, are low molecular weight compounds highly involved in the control of plant growth and development. Auxins are also broadly used in horticulture, as part of vegetative plant propagation protocols, allowing the cloning of genotypes of interest. Over the years, large efforts have been put in the development of more sensitive and precise methods of analysis and quantification of plant hormone levels in plant tissues. Although analytical techniques have evolved, and new methods have been implemented, sample preparation is still the limiting step of auxin analysis. In this review, the current methods of auxin analysis are discussed. Sample preparation procedures, including extraction, purification and derivatization, are reviewed and compared. The different analytical techniques, ranging from chromatographic and mass spectrometry methods to immunoassays and electrokinetic methods, as well as other types of detection are also discussed. Considering that auxin analysis mirrors the evolution in analytical chemistry, the number of publications describing new and/or improved methods is always increasing and we considered appropriate to update the available information. For that reason, this article aims to review the current advances in auxin analysis, and thus only reports from the past 15 years will be covered.

Olive (Olea europaea) is one of the most important fruit species in the Mediterranean basin, where 95% of the world’s olive orchards are planted, and it has become an economically valuable crop worldwide, due to an increasing interest in olive oil for human consumption. New olive orchards are being planted outside the Mediterranean, calling for an effort to identify the genotypes best adapted to the new conditions. However, some olive cultivars remain difficult to propagate, which significantly reduces the capacity to use the full genetic diversity of the species. Improving rooting ability in cuttings from recalcitrant olive cultivars has become a critical topic, which implies fundamental research on the anatomy, physiology, biochemistry and genetics of the adventitious root formation process. Besides, the existence of different rooting behaviors among olive cultivars also makes the species a candidate model plant for these studies. Olive propagation techniques evolved through time from field- or nursery-planted hardwood cuttings, to semi-hardwood cuttings in greenhouses under mist, and, more recently, to in vitro culture techniques. Nevertheless, research about adventitious root formation carried on each propagation method was mostly based on trial and error approaches. Researchers have mainly investigated different factors involved in the process of adventitious rooting by testing their effect in the rooting capacity of different cultivars, leading to a high dispersion and fragmentation of the available information. The goal of this review is to present the most relevant results achieved on adventitious root formation in olive cuttings, aiming to provide an integrated perspective of the current knowledge.

The aim of this work was to study the influence of foliar applications of different wood aqueous extracts on the amino acid content of musts and wines from Airén variety; and to study their relationship with the volatile compounds formed during alcoholic fermentation. For this purpose, the foliar treatments proposed were a vine-shoot aqueous extract applied in one and two times, and an oak extract which was only applied once. Results obtained show the potential of Airén vine-shoot waste aqueous extracts to be used as foliar fertilizer, enhancing the wine amino acid content especially when they were applied once. Similar results were observed with the aqueous oak extract. Regarding wine fermentative volatile compounds, there is a close relationship between musts and their wines amino acid content allowing us to discuss about the role of proline during the alcoholic fermentation and the generation of certain volatiles., Many thanks for the financial support given by the Ministerio de Economía y Competitividad of the Spanish Government to the Project AGL2012-33132. T. G.-C. also wishes to thank the Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria (INIA)-Gobierno de La Rioja and FEDER of the European Community for her doctoral contract and R. S.-G. wishes to thank the Universidad de Castilla-La Mancha for the predoctoral contract.

Botanical species used on aging process must be wisely and judiciously chosen, and for this selection, a basic knowledge of the chemical composition of woods is warranted. Aiming to contribute to extend the knowledge of the chemical composition of several wood species useful for enological purposes, we have focused our studies on Portuguese chestnut and French, American and Portuguese oak chips. The profile of low molecular weight phenolic composition of these chips was achieved, using an optimized extraction method based on pressurized liquid extraction, followed by the quantification of phenolic acids, phenolic aldehydes and furanic derivatives by high-performance liquid chromatography (HPLC-DAD). The identification of those compounds was also confirmed by LC-DAD/ESI-MS. This study allowed the determination of the low molecular phenolic composition of Portuguese chestnut and French, American and Portuguese oak wood. According to our results, the influence of the botanical species seems to be more relevant than the geographic origin of the wood species.

Background and Aims: Phenolic compounds influence colour, flavour and astringency of wines. Technology and grape variety are the main factor affecting the phenolic content of wines. Different multivariate statistical approaches were used to investigate the relationships between the profile of phenolic compounds and grape variety and also the impact of malolactic fermentation (MLF). Methods and Results: A reversed phase liquid chromatography/diode array detection method was used for the analysis of major non-flavonoid phenolic compounds in wines from Trincadeira, Aragonez, Cabernet Sauvignon, Alfrocheiro, Casteao and Touriga Nacional varieties before and after MLF. The impact of MLF and grape variety on phenolic profile was evaluated by principal component analysis (PCA), variation partitioning analysis (VPA) and artificial neural network (ANN). PCA explained 86.5% of the total variance among samples. ANN showed a significant clustering of samples according to grape variety and confirmed that MLF has a minor effect on wine phenolic profile. VPA enabled more information to be extracted from the data by identifying explanatory variables responsible for variability among samples. Conclusions: Compared with PCA and ANN, VPA provides more information concerning the variability on the sample system. Also, grape varieties have a more effective impact on wine low molecular weight phenolic compounds than MLF. Significance of the Study: Each one of the three multivariate statistical approaches showed ways of analysing large chemistry experimental datasets. VPA is a step forward in data analysis, providing more solid and complete assessment of sample system variability, not possible by PCA and ANN.

A transformacao do acido p-cumarico, acido ferulico e acido cafeico em 4-etilfenol, 4-etilguaiacol e 4-etilcatecol foi estudada na presenca de Dekkera bruxelensis ISA 1791, sob condicoes controladas, em meio sintetico e em vinho tinto. Os compostos fenolicos foram doseados por cromatografia em fase liquida (HPLC-DAD) e os fenois volateis foram doseados por cromatografia em fase gasosa (GC) com detector de ionizacao de chama (FID), recorrendo a uma metodologia que nao requer previa derivatizacao da amostra. A identificacao dos compostos foi comprovada por espectrometria de massa (GC-MS). Os resultados demonstram que os teores em acidos fenolicos diminuem enquanto se observa um aumento dos teores em fenois volateis. O acido cafeico e dos tres acidos em estudo, o menos utilizado pela levedura, dai os teores em 4-etilcatecol serem os mais baixos observados. Esta sintese de 4-etilcatecol por Dekkeras bruxelensis em vinhos nunca tinha sido demonstrada. Os resultados obtidos contribuem, decisivamente, para um melhor conhecimento sobre a origem precisa dos fenois volateis nos vinhos. A acumulacao destes compostos no vinho e,hoje em dia, considerada como um dos fatores-chave do controle de qualidade.

Fungi naturally present in olive trees were identified and tested for their antagonistic potential against Colletotrichum acutatum. A total of 14 isolates were identified, 12 belonged to genera Alternaria, Epicoccum, Fusarium, Aspergillus, Anthrinium, Chaetomium, Diaporthe, Nigrospora, one to family Xylariaceae and one was unclassified. All fungal isolates showed some inhibitory action over the growth of C. acutatum during dual culture growth, however, when agar-diffusible tests were performed only five fungal isolates caused C. acutatum growth inhibition: Alternaria sp. isolate 2 (26.8%), the fungus from Xylariaceae family (14.3%), Alternaria sp. isolate 1 (10.7%); Diaporthe sp. (10.7%), Nigrospora oryzae (3.5%). Volatile substances produced by these isolates were identified through gas-chromatography techniques, as phenylethyl alcohol, 4-methylquinazoline, benzothiazole, benzyl alcohol, lilial, galaxolide, among others. These inhibitory volatiles could play a significant role in reduction of C. acutatum expansion in olive and their study as potential biocontrol agents should be further explored. Inalentejo ALENT-07-0324- FEDER-001747, OPERAC¸ ÃO: Gestão Integrada da Protec¸ ão do Olival Alentejano. Contributos para o seu desenvolvimento e implementac¸ ão. Carla Marisa R. Varanda is recipient of a PhD fellowship from Fundac¸ ão para a Ciência e a Tecnologia (FCT), SFRH/BPD/76194/2011, financed by QREN – POPH – Typology 4.1—co-financed by MES national funding and the European Social Fund. This work has been supported by FEDER and National funds, through the Programa Operacional Regional do Alentejo (InAlentejo) Operation ALENT-07-0262-FEDER-001871/Laboratório de Biotecnologia Aplicada e Tecnologias Agro-Ambientais.

Use of commercial starters for malolactic fermentation (MLF) is a common practice, and outcomes of this procedure are very relevant for wine producers because aroma attributes might change according to the strain used. MLF was carried out in the Trincadeira wine variety in three batches: spontaneously and with inoculation of two different commercial starters. Wine extracts before and after MLF were obtained through liquid–liquid extraction. Gas chromatography/ion trap mass spectrometry analysis allowed the detection of 21 compounds, some of them tentatively identified through electron impact spectra comparison with a database, through interpretation of multistage mass spectrometry and chemical ionization mass spectrometry spectra and confirmation by comprehensive multidimensional gas chromatography/time of flight-mass spectrometry (GC × GC/ToF-MS). After MLF, an increase in ethyl lactate, γ-butyrolactone and diethyl succinate and a drop in isoamyl acetate, ethyl octanoate, ethyl decanoate, 2,3-dimethyl-hexan-3-ol, propanol, isobutanol and 2,3-butanediol was observed. The concentrations of the 10 compounds are statistically different in wines before and after MLF, and wines after MLF show significant differences for the nine compounds. PRACTICAL APPLICATIONS The Trincadeira variety is broadly used in the production of red wine in the south region of Portugal. Nevertheless, little was published concerning this red wine variety in international literature, where most frequently, the analysis of the volatile constituents of Trincadeira is not the goal. Moreover, the evaluation of the malolactic fermentation (MLF) impact produced by indigenous or selected starter bacteria on the aroma composition of the wines produced with their grapes was never studied before. The interesting behavior of this variety during MLF described in this work might possibly explain the unique characteristics of the overall bouquet produced with it. The main volatile compounds obtained after all three MLF processes were identified and quantified using gas chromatography/ion trap mass spectrometry, gas chromatography/chemical ionization mass spectrometry (GC/CI/MS) and gas chromatography/multistage mass spectrometry (GC/MS/MS) and standard coinjection. Comprehensive multidimensional gas chromatography (GC × GC) was used for confirmation purposes in all cases where standards were not available in order to also validate the results obtained by GC/CI/MS and GC/MS/MS.

The increasing application of pesticides for agricultural purposes involves serious risk to the environment and human health due to either exposure or through residues in food and drinking water. Since food safety is of mandatory importance there is a growing interest on the development of selective, simple, rapid, cost-effective and reliable analytical methodologies in order to ensure that pesticides residues should not be found at levels above the established maximum pesticide residue limits (MRLs). In recent years, a new methodology based on the development of molecularly imprinting polymers (MIPs) allows not only pre-concentration and cleaning of the sample but also selective extraction of the target analyte, which is crucial, particularly when the sample is complex and impurities can interfere with quantification. The scope of this review is to provide a general overview on MIPs field, with emphasis on MIP preparation and its use as sorbents for solid-phase extraction. This paper will be focused on the review of the current state of the art in the use of MIPs as selective materials in molecularly imprinted solid-phase extraction (MISPE) for the analysis of pesticide residues from food matrices. A review of preparation and application of MIPs in food matrices, will also be discussed.

Ao longo da historia, a relacao entre a filosofia e a politica tem-se revelado espinhosa, denunciando a dificuldade em se conceptualizar sobre o que e por natureza antagonico a cristalizacao, porque particular e pluralista. Na esfera da opiniao, o filosofo deve restringir-se a analisar, criticar, rever e aperfeicoar os valores politicos coevos, a explicar aos seus conterrâneos o universo de acepcoes sociais partilhadas, consciente de que a sua concepcao fundamenta uma via entre as muitas poss...

Publicada no ano de 1896, num contexto politico adverso a propaganda anarquista – considerada como um crime pela Lei de 13 de Fevereiro desse mesmo ano –, esta obra revela os contornos doutrinarios e historicos do anarquismo, sobretudo da feicao dominante na militância anarquista em Portugal, o “anarquismo social”. Como assinala Joao Freire em “Revistas anarquistas portuguesas: entre a politica e a cultura” (in Revistas, Ideias e Doutrinas, 2003), “o anarquismo social era certamente um social...