Thermal Desorption of 2,4,6-Trichloroanisole from Cork.

While extensive efforts have been made over the past two decades to understand how cork becomes contaminated by 2,4,6-trichloroanisole (TCA), the nature of its bond to cork remains unclear. A deeper understanding of this interaction is crucial in designing processes to effectively remove TCA from cork stoppers. This study presents an investigation into the thermal desorption of TCA from cork under vacuum conditions. To facilitate detection by a quadrupole mass spectrometer, samples were artificially contaminated with sufficient TCA. A calibration system was developed to determine the absolute rate of TCA released from the cork. Desorption spectra revealed two peaks at 80 °C and 170 °C. Despite the known variability of cork, repeated measurements demonstrated reasonable repeatability. The low-temperature peak decreased with time and after preheating the sample to 50 °C. It is proposed that the high-temperature peak corresponds to TCA bonded to the cork material. Experiments with naturally contaminated cork stoppers revealed a significant reduction in the amount of releasable TCA following a vacuum-heating process. This study provides an insightful discussion on the adsorption of TCA on cork and proposes an estimate for the adsorption energy. Furthermore, it discloses a process capable of removing TCA from natural cork stoppers.

Prey species and abundance affect growth and photosynthetic performance of the polyphagous sea slug Elysia crispata.

Some sacoglossan sea slugs steal functional macroalgal chloroplasts (kleptoplasts). In this study, we investigated the effects of algal prey species and abundance on the growth and photosynthetic capacity of the tropical polyphagous sea slug Elysia crispata. Recently hatched sea slugs fed and acquired chloroplasts from the macroalga Bryopsis plumosa, but not from Acetabularia acetabulum. However, adult sea slugs were able to switch diet to A. acetabulum, rapidly replacing the great majority of the original kleptoplasts. When fed with B. plumosa, higher feeding frequency resulted in significantly higher growth and kleptoplast photosynthetic yield, as well as a slower relative decrease in these parameters upon starvation. Longevity of A. acetabulum-derived chloroplasts in E. crispata was over twofold that of B. plumosa. Furthermore, significantly lower relative weight loss under starvation was observed in sea slugs previously fed on A. acetabulum than on B. plumosa. This study shows that functionality and longevity of kleptoplasts in photosynthetic sea slugs depend on the origin of the plastids. Furthermore, we have identified A. acetabulum as a donor of photosynthetically efficient chloroplasts common to highly specialized monophagous and polyphagous sea slugs capable of long-term retention, which opens new experimental routes to unravel the unsolved mysteries of kleptoplasty.

Responsiveness to pulmonary rehabilitation in COPD is associated with changes in microbiota.

BACKGROUND: Pulmonary Rehabilitation (PR) is one of the most cost-effective therapies for chronic obstructive pulmonary disease (COPD) management. There are, however, people who do not respond to PR and reasons for non-response are mostly unknown. PR is likely to change the airway microbiota and this could play a role in its responsiveness. In this study we have explored the association between PR effectiveness and specific alterations in oral microbiota and inflammation. METHODS: A prospective longitudinal study was conducted. Data on exercise capacity, dyspnoea, impact of disease and 418 saliva samples were collected from 76 patients, half of whom participated in a 12-weeks PR programme. Responders and non-responders to PR (dyspnoea, exercise-capacity and impact of disease) were defined based on minimal clinically important differences. RESULTS: Changes in microbiota, including Prevotella melaninogenica and Streptococcus were observed upon PR. Prevotella, previously found to be depleted in severe COPD, increased during the first month of PR in responders. This increase was negatively correlated with Streptococcus and Lautropia, known to be enriched in severe cases of COPD. Simultaneously, an anti-inflammatory commensal of the respiratory tract, Rothia, correlated strongly and negatively with several pro-inflammatory markers, whose levels were generally boosted by PR. Conversely, in non-responders, the observed decline in Prevotella correlated negatively with Streptococcus and Lautropia whose fluctuations co-occurred with several pro-inflammatory markers. CONCLUSIONS: PR is associated with changes in oral microbiota. Specifically, PR increases salivary Prevotella melaninogenica and avoids the decline in Rothia and the increase in Streptococcus and Lautropia in responders, which may contribute to the benefits of PR.

The Impact of Storage Conditions and Bottle Orientation on the Evolution of Phenolic and Volatile Compounds of Vintage Port Wine.

This work evaluates the influence of the cellar conditions and bottle orientation, on the phenolic and volatile composition of a Vintage Port wine, sealed with natural cork stoppers, for 44 months post-bottling. The storage was performed in two different cellars, namely a cellar A with controlled temperature and humidity, and a cellar B, representing a traditional cellar, with uncontrolled temperature and humidity. The impact of bottle orientation was studied in cellar A, where the bottles were stored in horizontal and vertical positions. The phenolic and volatile composition of the bottled Vintage Port wine were analyzed after 6, 15 and 44 months. The results unveiled that the cellar conditions and bottle orientation had an impact in Port wine composition which was higher at 44 months post-bottling. The samples stored in the traditional cellar unveiled significantly higher yellow tones, lower tannin specific activity, and higher levels of furfural and 5-methylfurfural. Furthermore, the samples stored in the horizontal position revealed significant higher levels of total proanthocyanidins and higher tannin specific activity than the samples stored in the vertical position. Interestingly, for the first time to our knowledge, an ellagitannin-derived compound (Corklin) was detected in Vintage Port wines stored in the horizontal position, which results from the reaction of cork constituents with phenolic compounds present in wines.

Cross Contamination of 2,4,6-Trichloroanisole in Cork Stoppers.

Cork stoppers are the preferred choice for sealing bottled wines around the world. However, the quality of cork stoppers is also defined by the presence of 2,4,6-trichloroanisole (TCA), which gives the wine an unpleasant moldy/musty taste. It is a matter of concern for both cork stopper manufacturers and wine producers whether TCA can be transported between stoppers. As little is known about cross contamination between stoppers, this work provides enough experimental data to discuss the extent of TCA transfer in naturally contaminated stoppers in the liquid and gas phase that can be useful to the cork industry and the wine industry. We found that when a clean stopper is soaked together with a contaminated one in hydro-alcoholic solution, 12% of the TCA can be transferred. In gas-phase contamination, only stoppers with 12 ng/L, or more, contaminate clean stoppers when enclosed together for several days. In a second experiment, where clean corks were exposed to a controlled contaminated environment, it was found that TCA contamination was not confined to the outermost layer of the stoppers. Based on these findings, some recommendations are given to prevent TCA cross contamination between stoppers during the cork stopper manufacturing, storage, wine making, and bottling.

The Impact of Different Closures on the Flavor Composition of Wines during Bottle Aging.

Wine flavor undergoes major changes during bottle aging and can be influenced by the type of closure. The interaction between wine, the type of closure and the external environment has the potential to significantly influence the overall quality of bottled wines, especially when the storage period is relatively long (more than five years). Therefore, the choice of closure (cork, synthetic or screw cap) deserves special attention in order to establish the ideal sealing conditions for optimizing wine flavor attributes. The contribution of different closures to the quality of bottled wine is through mass transfer phenomena, including permeation, sorption (scalping) or desorption of chemicals between closure materials and wines. Thus, this article aims to review the impact of different closures on the flavor composition of wines during post-bottling conditions. The implications of closures on wine sensory properties are also discussed.

[Gender Distribution in Medical Leadership Roles in Portugal: The Example of Candidacy to Bodies of the Portuguese Medical Association 2017-2019]. / Distribuição de Género em Cargos de Liderança na Área Médica em Portugal: O Exemplo das Candidaturas aos Órgãos da Ordem dos Médicos 2017-2019.

INTRODUCTION: Gender equality is one of the sustainable development goals. Low participation of women in leadership roles is an example of gender inequality. In Portugal, there are few studies regarding gender inequality in medical leadership roles. Therefore, we aimed to analyse gender distribution of candidates to regional bodies of the Portuguese Medical Association. MATERIAL AND METHODS: We extracted data from the candidates to the regional bodies of the Portuguese Medical Association (2017 - 2019 mandate) from the Association's magazine (issue number 175). We calculated the percentage of women candidates, overall and stratified by list, region and roles. We obtained observed-vs-expected ratios overall and by region, and respective 95% confidence intervals, assuming a Poisson distribution. Finally, we conducted a sensitivity analysis, excluding substitute candidates. RESULTS: Women accounted for 37% of the candidates (regional variation: 29% - 51%). The national observed-vs-expected ratio was 0.74 (95% confidence interval: 0.58; 0.92), mainly driven by the ratio from the South Region: 0.58 (95% confidence interval: 0.41; 0.80). Women ran mainly for alternate candidates and secretary positions (56% and 54% respectively). DISCUSSION: Gender differences were identified, particularly in the South, regarding the frequency and type of candidacy. Previous works have identified maternity, the social role of women and perceptions regarding the leadership roles as possible reasons to explain such differences. Our analysis is limited to specific leadership roles and an election moment; further studies should be pursued. CONCLUSION: We identified a lower than expected participation of women in the elections for the Portuguese Medical Association. When they run, women are found mainly in less relevant positions or with less potential to be elected (secretary or alternate candidate). A deeper understanding and measures to fight gender inequality in leadership roles are required.

Introdução: A igualdade de género constitui um dos objetivos de desenvolvimento sustentável. Uma manifestação de desigualdade de género é a baixa participação de mulheres em cargos de liderança. Em Portugal, são escassos os estudos sobre a desigualdade de género na liderança na área médica. Assim, o presente trabalho pretendeu analisar a distribuição de género em candidaturas aos órgãos regionais da Ordem dos Médicos.Material e Métodos: Foram extraídos da Revista da Ordem dos Médicos (número 175) os dados dos candidatos aos órgãos regionais da Ordem dos Médicos (mandato de 2017 - 2019). Obtiveram-se as percentagens de mulheres candidatas, globalmente, por lista, regiões e cargos. Calcularam-se razões observado-versus-esperado por secção regional e intervalos de confiança a 95% assumindo uma distribuição de Poisson. Foi realizada análise de sensibilidade, excluindo os candidatos a suplentes.Resultados: Trinta e sete por cento dos candidatos eram médicas (variação por região: 29% - 51%). A nível nacional a razão observado-versus-esperado foi de 0,74 (intervalo confiança a 95%: 0,58; 0,92), principalmente influenciada pela razão da região Sul de 0,58 (intervalo confiança a 95%: 0,41; 0,80). Existiu uma predominância de mulheres nas candidaturas para suplentes e secretário (56% e 54% respetivamente).Discussão: A diferença entre géneros é particularmente acentuada na região Sul, na frequência e tipo de cargos a que se candidatam. As razões apontadas na literatura relacionam-se com a maternidade, o papel social da mulher e perceções sobre o desempenho dos cargos de lideraça. Este estudo é limitado à análise de um tipo de liderança e um momento eleitoral, sendo necessárias análises mais abrangentes.Conclusão: Houve menor participação do que o expectável por parte das médicas no processo eleitoral da Ordem dos Médicos. Quando participam, as mulheres tendem a fazê-lo em cargos de menor relevância ou com menos potencial para eleição (secretário ou suplente). É necessário aprofundar o estudo e introduzir medidas de combate à desigualdade de género em cargos de liderança.

Volatile profile of cork as a tool for classification of natural cork stoppers.

An untargeted approach, focused in the profile of volatile organic compounds (VOCs), was applied to differentiate natural cork stoppers with different levels of porosity, coded as Group 1 (low porosity), Group 2 (intermediate porosity) and Group 3 (high porosity). Statistically significant alterations were found in the levels of several VOCs between cork stoppers of low and intermediate porosity when compared with those of high porosity (Group 1 vs. 3 and Group 2 vs. 3). In addition, the levels of 2-pentylfuran, cyclene, camphene, camphor, limonene and eucalyptol enabled the discrimination of cork stoppers with low porosity (Group 1) into two subgroups, while furfural and 5-methyl-2-furfural enabled the discrimination of subgroups within the intermediate and high porosity stoppers (Group 2 and 3). A headspace solid-phase microextraction coupled to gas chromatography tandem mass spectrometry (HS-SPME-GC-MS/MS) method was developed to quantify the subgroup discriminant compounds, which may provide a proof-of-concept for the development of an efficient method to be applied in cork industry.

Variation in the Phenolic Composition of Cork Stoppers from Different Geographical Origins.

Cork stopper granulates from five geographical origins from Portugal and six from Spain were analyzed regarding polyphenol composition by HPLC-DAD/ESI-MS and geographical discrimination studied by near-infrared spectroscopy (NIRS). The phenolic composition of the eleven origins ranged from 30 to 52 mg/g cork granulates, with vescavaloninic acid, castalagin, sanguisorbic acid dilactone, vescalagin, castavaloninic acid, dehydrated tergallic-C-Glc, and ellagic acid being the major compounds. NIRS revealed to be a powerful tool to discriminate origins and predict the concentration of polyphenols. However, polyphenols do not fully explain the discrimination of geographical origins. Variability in the polyphenol composition of cork stoppers is not significantly influenced by geographical location but probably may be more related to the plant genetics, tree age, and phytosanitary and edaphoclimatic conditions.

Migration of Tannins and Pectic Polysaccharides from Natural Cork Stoppers to the Hydroalcoholic Solution.

Ellagitannins, condensed tannins, and pectic-derived polysaccharides were removed from natural cork stoppers using hydroalcoholic solution. Two main populations of migrated compounds were determined; the major one with molecular weight (MW) between 0.2 and 1 kDa and the second with 2.1 kDa and polydispersity of 1.3. Two residual populations mainly composed of condensed tannins were also observed between 2.5 and 4.5 kDa and higher than 15 kDa. Simple, C-glycosidic, complex, and oligomeric ellagitannins were identified by high-performance liquid chromatography-diode array detection/electrospray ionization-mass spectrometry (HPLC-DAD/ESI-MS). Ellagitannins linked to condensed tannins and some pectic-derived polysaccharides were also tentatively identified by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-ToF-MS). This preliminary work opens an opportunity for the cork stoppers industry due to the relevance of this type of compounds on the astringency and bitterness of wines.

Telehealth in Heart Failure Care during COVID-19 Pandemic Lockdown in Argentina.

Background and Objectives: During the coronavirus disease 2019 (COVID-19) pandemic, virtual visits (VVs) were recommended as an innovative and necessary alternative for patients with heart failure (HF). To assess the feasibility and acceptability of VVs in patients with HF, pulmonary hypertension (PH), and heart transplant (HT). Methods: We designed a single-centre cohort study. Consecutive VVs performed in our HF unit were analysed. The period comprehended between January 1st and March 19th (before COVID-19) and March 20th and June 30th (during COVID-19) was compared. We assessed acceptability, feasibility and the need for diagnostic studies, in-person medical evaluation, and hospitalization at 30 days. Results: HF unit medical doctors conducted 22 VVs in the pre-COVID period and 416 VVs during the COVID period. The VV was able to be performed in all patients scheduled for it and 44% answered the survey. Ninety percent of the patients who answered the survey strongly agreed that VVs were easy to be carried out. All the patients "strongly agreed" or "agreed" that their health problem could be resolved. Most patients (95%) rated the global experience as very good or excellent, with an overall average rate of 9.76±0.5 out of 10. We found no differences regarding the requirement of diagnostic studies, in-person medical evaluation and hospitalization during the first month after VVs between the 2 periods. Conclusions: VVs were feasible, presented high acceptability, and the overall experience was positive in patients with HF, PH, and HT, being this modality a valuable tool that complements in-person care.

Characterization of chemical compounds susceptible to be extracted from cork by the wine using GC-MS and 1H NMR metabolomic approaches.

This work presents a metabolomics study of cork by gas chromatography-mass spectrometry (GC-MS) and 1H nuclear magnetic resonance (NMR) spectroscopy to characterize compounds susceptible to be extracted from cork by the wine in an attempt to find a relationship between the content of these compounds and the geographical origin of cork. Cork from eleven geographical regions was studied, five from Portugal and six from Spain. Unsupervised pattern recognition techniques unveiled three main clusters of regions according to their chemical similarity but not related with geographical proximity. Nineteen compounds were found to be responsible for the clusters, including terpenes (trans-squalene, friedelin, camphene, trans-3-pinanone, 1-terpinen-4-ol, two sesquiterpenes), polyphenols (vescalagin, castalagin), among others (pyrogallol, glucosan, sitost-4-en-3-one, o-cymene, quinic acid, five unknowns). These preliminary results unveiled the potential for a more efficient selection of cork planks for stoppers production based on the compounds susceptible to be extracted from cork by the wine.

Assessment of oxidation compounds in oaked Chardonnay wines: A GC-MS and 1H NMR metabolomics approach.

The oxidation of oaked Chardonnay wine during long-term storage was studied by headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry (HS-SPME-GC/MS) and proton (1H) nuclear magnetic resonance (NMR) spectroscopy. Three distinct groups of wine were defined based on the browning index: control, least oxidized (OX1) and most oxidized (OX2). HS-SPME-GC/MS and 1H NMR spectroscopy enabled the profiling of a total of 155 compounds in all wine samples including aldehydes, ketones, esters, polyphenols, among other classes. Acetaldehyde, 3-methylbutanal, 2-phenylacetaldehyde, methional, 3-penten-2-one, ß-damascenone and four unknown carbonyl compounds showed the highest percentage of variation with oxidation. Novel oxidation markers found in this work include pentanal, 3-methyl-2-butanone, 3-penten-2-one, 2-methyltetrahydrofuran-3-one, ß-damascenone, ethyl 2-methylbutanoate and vinyl decanoate. In addition, several correlations between polyphenols, aroma compounds and absorbance at 420 nm (A420) were observed, suggesting the occurrence of chemical reactions with a possible impact in wine browning.

Reactivity of Cork Extracts with (+)-Catechin and Malvidin-3-O-glucoside in Wine Model Solutions: Identification of a New Family of Ellagitannin-Derived Compounds (Corklins).

The aim of this study was to evaluate the reactivity of phenolic compounds extracted from cork stoppers to wine model solutions with two major wine components, namely, (+)-catechin and malvidin-3-O-glucoside. Besides the formation of some compounds already described in the literature, these reactions also yielded a new family of ellagitannin-derived compounds, named herein as corklins. This new family of compounds that were found to result from the interaction between ellagitannins in alcoholic solutions and (+)-catechin were structurally characterized by mass spectroscopy, nuclear magnetic resonance, and computational methods.

Antioxidant and biological properties of bioactive phenolic compounds from Quercus suber L.

Phenolic compounds, namely, hydrolyzable tannins and low molecular weight phenolic compounds, were isolated and purified from Portuguese cork from Quercus suber L. Some of these compounds were studied to evaluate their antioxidant activity, including free-radical scavenging capacity (DPPH method) and reducing capacity (FRAP method). All compounds tested showed significant antioxidant activity, namely, antiradical and reducing properties. The antiradical capacity seemed to increase with the presence of galloyl groups. Regarding the reducing capacity, this structure-activity relationship was not so clear. These compounds were also studied to evaluate the growth inhibitory effect on the estrogen responsive human breast cancer cell line (ER+) MCF-7 and two other colon cancer cell lines (Caco-2 and HT-29). Generally, all the compounds tested exhibited, after a continuous exposure during a 48 h period, a dose-dependent growth inhibitory effect. Relative inhibitory activity was primarily related to the number of phenolic hydroxyl groups (galloyl and HHDP moieties) found in the active structures, with more groups generally conferring increased effects, except for HHDP-di-galloyl-glucose. Mongolicain B showed a greater potential to inhibit the growth of the three cell lines tested, identical to the effect observed with castalagin. Since these compounds are structurally related with each other, this activity might be based within the C-glycosidic ellagitannin moiety.

Utilidad de un protocolo informatizado para el control estricto de la glucemia en pacientes de cirugía cardíaca / Usefulness of a Computer-Assisted Protocol for Strict Glycemic Control in Patients Submitted to Cardiac Surgery

El control estricto de la glucemia durante el posoperatorio de cirugía cardíaca mejora la evolución de los pacientes, pero es de difícil implementación a pesar del uso de protocolos de manejo impresos. Objetivo Determinar si la utilización de un protocolo informatizado para el control estricto de la glucemia incrementa la adherencia del equipo de salud a las conductas sugeridas y mejora el control de la glucemia en pacientes sometidos a cirugía cardíaca. Material y métodos Se incluyeron 118 pacientes consecutivos intervenidos quirúrgicamente durante el último trimestre de 2005, en los cuales el control estricto de la glucemia se realizó mediante un protocolo de manejo impreso (grupo control), y 117 pacientes consecutivos del último trimestre de 2006, en los que se utilizó el mismo protocolo pero informatizado (grupo tratamiento). Resultados En concordancia con lo sugerido por los protocolos de manejo para un control estricto adecuado de la glucemia, los pacientes del grupo tratamiento tuvieron un tiempo menor a la primera medición de glucemia (60 RIC 40-65 versus 150 RIC 60-270 min; p < 0,001) y un número mayor de mediciones de glucemia (18 ± 6,6 versus 11 ± 6,4; p < 0,0001). Los pacientes del grupo tratamiento presentaron un porcentaje mayor de mediciones normoglucémicas (67% ± 18% versus 50% ± 25%; p < 0,0001) y un tiempo menor hasta el logro de la normoglucemia (165 RIC 105-280 versus 420 RIC 295-720 min; p < 0,001). Conclusión El empleo de un protocolo informatizado permite incrementar la adherencia del equipo de salud a las conductas sugeridas y mejorar el control de la glucemia en pacientes sometidos a cirugía cardíaca.

The outcomes of patients improve with a strict glycemic control during the postoperative period of cardiovascular surgery; however, written protocols may fail to achieve a tight control of glycemia. Objective To determine the usefulness of a computer-assisted protocol for strict glycemic control in order to increase the adherence of health care providers to current recommendations and to improve the glycemic control in patients submitted to cardiovascular surgery. Material and Methods Patients were divided into two groups. Control group included 118 consecutive patients who underwent coronary artery bypass graft surgery during the last quarter of 2005; strict glycemic control was managed with a written protocol. Treatment group consisted of 117 consecutive patients operated on during the last quarter of 2006; in this group of patients glycemic control was managed with a computerassisted protocol. Both protocols were identical. Results As protocols for strict glycemic control recommend, the first glycemia was determined earlier in the treatment group versus the control group (60 IQR 40-65 versus 150 IQR 60- 270 min; p<0,001) and blood glucose levels were measured more times (18±6.6 versus 11±6.4; p<0,0001). The percentage of determinations with normoglycemia was greater among patients in the treatment group (67%±18% versus 50%±25%; p<0.0001) and the time interval to normoglycemia was lower (165 IQR 105-280 versus 420 IQR 295-720 min; p<0,001). Conclusion A computer-assisted protocol is useful to increase the adherence of health care providers to current recommendations and to improve the glycemic control in patients submitted to cardiovascular surgery.