Surface hydrophobization of bacterial and vegetable cellulose fibers using ionic liquids as solvent media and catalysts

The surface hydrophobization through heterogeneous chemical modification of bacterial (and vegetable) cellulose fibers with several anhydrides (acetic, butyric, hexanoic and alkenyl succinic anhydrides) and hexanoyl chloride suspended in an ionic liquid, tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl) imide, [TDTHP][NTf(2)], was studied. Furthermore, in the reaction with hexanoyl chloride, another ionic liquid, N-hexyl-4-(dimethylamino)pyridinium bis(trifluoromethylsulfonyl) imide, [C(6)N(CH(3))(2)py][NTf(2)], was used instead of common organic bases as catalyst and to trap the released HCl. The analysis of the ensuing modified fibers by FTIR, XRD and SEM clearly showed that the esterification reactions occurred essentially at the fibers' outmost layers, not affecting their ultrastructure. The degree of substitution (DS) of the ensuing esterified fibers ranged from less than 0.002 to 0.41; and in all instances, the fibers' surface acquired a high hydrophobicity. This novel approach constitutes an important strategy in the preparation of modified fibers under greener conditions relaying in the use of non-volatile solvents.FCT - SFRH/BD/72830/2010SFRH/BPD/41781/2007PTDC/QUI/68472/2006PTDC/QUI/72903/200

Structural reinforcements on AFO’s: a study using computer aided designing and finite element method

As state by the literature, is usual for thermoplastic AFO’s to open cracks as result of the undergoing stress forces of human gait. That mechanical stress forces trigger fractures areas on critical points, normally near the malleoli (see the picture below), as result as the range of movement of that specific region. David Showers and Lair David, claim that is possible to increase AFO’s resistence trough the inclusion of reinforcements (by waving the plastic) at the retromalleolar area. The purpose of this study is to verify the influence of the application of structural reinforcements has on the distribution of tension and deformation in an AFO in the stance phase of gait.info:eu-repo/semantics/publishedVersio

Simultaneous Separation of Antioxidants and Carbohydrates From Food Wastes Using Aqueous Biphasic Systems Formed by Cholinium-Derived Ionic Liquids

project CICECO-Aveiro Institute of Materials, UID/CTM/50011/2019. Associate Laboratory for Green Chemistry-LAQV, FCT Ref. UID/QUI/50006/2019. POCI-01-0145-FEDER-016403. Investigator FCT project IF/00621/2015. Programa Mais Centro under project CENTRO-07-ST24-FEDER-002008. COMPETE: PEst-C/SAU/UI0709/2011.The food industry produces significant amounts of waste, many of them rich in valuable compounds that could be recovered and reused in the framework of circular economy. The development of sustainable and cost-effective technologies to recover these value added compounds will contribute to a significant decrease of the environmental footprint and economic burden of this industry sector. Accordingly, in this work, aqueous biphasic systems (ABS) composed of cholinium-derived bistriflimide ionic liquids (ILs) and carbohydrates were investigated as an alternative process to simultaneously separate and recover antioxidants and carbohydrates from food waste. Aiming at improving the biocompatible character of the studied ILs and proposed process, cholinium-derived bistriflimide ILs were chosen, which were properly designed by playing with the cation alkyl side chain and the number of functional groups attached to the cation to be able to create ABS with carbohydrates. These ILs were characterized by cytotoxicity assays toward human intestinal epithelial cells (Caco-2 cell line), demonstrating to have a significantly lower toxicity than other well-known and commonly used fluorinated ILs. The capability of these ILs to form ABS with a series of carbohydrates, namely monosaccharides, disaccharides and polyols, was then appraised by the determination of the respective ternary liquid-liquid phase diagrams at 25 degrees C. The studied ABS were finally used to separate carbohydrates and antioxidants from real food waste samples, using an expired vanilla pudding as an example. With the studied systems, the separation of the two products occurs in one-step, where carbohydrates are enriched in the carbohydrate-rich phase and antioxidants are mainly present in the IL-rich phase. Extraction efficiencies of carbohydrates ranging between 89 and 92% to the carbohydrate-rich phase, and antioxidant relative activities ranging between 65 and 75% in the IL-rich phase were obtained. Furthermore, antioxidants from the IL-rich phase were recovered by solid-phase extraction, and the IL was recycled for two more times with no losses on the ABS separation performance. Overall, the obtained results show that the investigated ABS are promising platforms to simultaneously separate carbohydrates and antioxidants from real food waste samples, and could be used in further related applications foreseeing industrial food waste valorization.publishersversionpublishe

one-step extraction and separation of betalains and chlorophylls using thermoreversible aqueous biphasic systems

This work was partly developed within the scope of the projects CICECO-Aveiro Institute of Materials, LA/P/0006/2020 and the Associate Laboratory for Green Chemistry-LA/P/0008/2020, financed by national funds through the FCT/MCTES (PIDDAC). Publisher Copyright: © 2023 The Royal Society of Chemistry.Globally, up to 50% of root crops, fruits and vegetables produced is wasted. Beetroot stems and leaves fit into this scenario, with only a small fraction being used in cattle food. One way of approaching this problem is through their valorisation, by extracting and recovering valuable compounds present in this type of waste that could be used in other applications, while contributing towards a circular economy. In this work, a new integrated process using thermoreversible aqueous biphasic systems (ABS) composed of quaternary ammonium-based ionic liquids (ILs) and polypropyleneglycol 400 g mol−1 (PPG) is shown to allow the one-step extraction and separation of two pigment classes—betalains and chlorophylls—from red beet stems and leaves. The pigment extraction was carried out with a monophasic aqueous solution of the IL and PPG, whose phase separation was then achieved by a temperature switch, resulting in the simultaneous separation of chlorophylls and betalains into opposite phases. A central composite design was used to optimise the extraction parameters (time, temperature, and solid : liquid (S/L) ratio) of both pigment extraction yields, reaching at 20 °C, 70 min and a S/L ratio of 0.12 a maximum extraction yield of 6.67 wt% for betalains and 1.82 wt% for chlorophylls (per weight of biomass). Moreover, it is shown that aqueous solutions of ILs better stabilise betalains than the gold standard solvent used for the extraction method. Among the studied systems, the ABS comprising the IL N-ethyl-N-methyl-N,N-bis(2-hydroxyethyl) bromide ([N21(2OH)(2OH)]Br) presented the best separation performance, with an extraction efficiency of 92% and 95% for chlorophylls and betalains, respectively, for opposite phases. The pigments were removed from the respective phases using affinity resins, with high recoveries: 96% for betalains and 98% for chlorophylls, further allowing the IL reuse. Finally, the cyto- and ecotoxicities of the quaternary ammonium-based ILs were determined. The obtained results disclosed low to negligible toxicity in the thousands of mg L−1 range, with [N21(2OH)(2OH)]Br being harmless from an ecotoxicological point of view. Overall, it is shown here that the developed process is an innovative approach for the one-step extraction and selective separation of pigments contributing to the valorisation of waste biomass.publishersversionpublishe

Comparative complete scheme and booster effectiveness of COVID‐19 vaccines in preventing SARS‐CoV‐2 infections with SARS‐CoV‐2 Omicron (BA.1) and Delta (B.1.617.2) variants: A case–case study based on electronic health records

Background: Information on vaccine effectiveness in a context of novel variants of concern (VOC) emergence is of key importance to inform public health policies. This study aimed to estimate a measure of comparative vaccine effectiveness between Omicron (BA.1) and Delta (B.1.617.2 and sub-lineages) VOC according to vaccination exposure (primary or booster). Methods: We developed a case–case study using data on RT-PCR SARS-CoV2-positive cases notified in Portugal during Weeks 49–51, 2021. To obtain measure of comparative vaccine effectiveness, we compared the odds of vaccination in Omicron cases versus Delta using logistic regression adjusted for age group, sex, region, week of diagnosis, and laboratory of origin. Results: Higher odds of vaccination were observed in cases infected by Omicron VOC compared with Delta VOC cases for both complete primary vaccination (odds ratio [OR] = 2.1; 95% confidence interval [CI]: 1.8 to 2.4) and booster dose (OR = 5.2; 95% CI: 3.1 to 8.8), equivalent to reduction of vaccine effectiveness from 44.7% and 92.8%, observed against infection with Delta, to 6.0% (95% CI: 29.2% to 12.7%) and 62.7% (95% CI: 35.7% to 77.9%), observed against infection with Omicron, for complete primary vaccination and booster dose, respectively. Conclusion: Consistent reduction in vaccine-induced protection against infection with Omicron was observed. Complete primary vaccination may not be protective against SARS-CoV-2 infection in regions where Omicron variant is dominant.Grant no. 2021/PHF/23776; POCI-01-0145-FEDER-022184; Project ALG-D2-2021-06info:eu-repo/semantics/publishedVersio

The fate of Holoregmia, a monospecific genus endemic to the Brazilian Caatinga, under different future climate scenarios

Background and aims – Climatic fluctuations during the Pleistocene altered the distribution of many species and even entire biomes, allowing some species to increase their range while others underwent reductions. Recent and ongoing anthropogenic climate change is altering climatic patterns very rapidly and is likely to impact species’ distributions over shorter timescales than previous natural fluctuations. Therefore, we aimed to understand how Pleistocene and Holocene climatic fluctuations might have shaped the current distribution of Holoregmia and explore its expected distribution under future climate scenarios. Material and methods – We modelled the potential distribution of Holoregmia viscida (Martyniaceae), a monospecific plant genus endemic to the semi-arid Caatinga Domain in Brazil. We used an ensemble approach to model suitable areas for Holoregmia under present conditions, Paleoclimatic scenarios, and global warming scenarios in 2050 and 2090. Key results – Holocene climates in most Caatinga were too humid for Holoregmia, which restricted its suitable areas to the southern Caatinga, similar to its current distribution. However, under global warming scenarios, the Caatinga is expected to become too dry for this lineage, resulting in a steady decline in the area suitable for Holoregmia and even its possible extinction under the most pessimistic scenario modelled. Conclusion – The predicted extinction of the ancient and highly specialized Holoregmia viscida highlights the possible consequences of climate change for some species of endemic Caatinga flora. Invaluable phylogenetic diversity may be lost in the coming decades, representing millions of years of unique evolutionary history and consequent loss of evolutionary potential to adapt to future environmental changes in semi-arid environments

Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure

[EN] A series of alkyltributylphosphonium chloride ionic liquids, prepared from tributylphosphine and the respective 1-chloroalkane, CnH2n+1Cl (where n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 or 14), is reported. This work is a continuation of an extended series of tetraalkylphosphonium ionic liquids, where the focus is on the variability of n and its impact on the physical properties, such as melting points/glass transitions, thermal stability, density and viscosity. Experimental density and viscosity data were interpreted using QPSR and group contribution methods and the crystal structure of propyl(tributyl) phosphonium chloride is detailed.This work was funded by Cytec Canada, Inc. G.A. would like to thank Dr Douglas Harris (Cytec) for fruitful comments and advice at the beginning of this work; Prof. Chris Strauss, Dr Markus Fanselow and Dr Giulia Fiorani for microwave assistance and helpful guidance, and Prof. P.R. Raithby for the X-ray diffraction data collection. L.P.N.R. thanks Fundacao para a Ciencia e Tecnologia, Portugal, for support under grants PTDC/QUI-QUI/101794/2008 and PTDC/QUI/71331/2006.Adamova, G.; Gardas, RL.; Nieuwenhuyzen, M.; Vaca Puga, A.; Rebelo, LPN.; Robertson, AJ.; Seddon, KR. (2012). Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure. Dalton Transactions. 41(27):8316-8332. doi:10.1039/c1dt10466gS83168332412