Sustainable hydrophobic terpene-based eutectic solvents for the extraction and separation of metals

Sustainable hydrophobic eutectic solvents, composed of low-priced and biodegradable terpenes and fatty acids, were used for the extraction and separation of Cu(ii) from other transition metals in mildly acidic solutions. Multiple parameters were evaluated for metal extraction and the hydrophobic eutectic solvent was successfully recovered and reused.This work was part of BATRE-ARES project (ERA-MIN/0001/2015) funded by ADEME and FCT and partly developed in the scope of the project CICECO – Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013). C. M. S. S. Neves acknowledges FCT for the postdoctoral grant (SFRH/BPD/109057/2015). M. A. R. Martins acknowledges financial support from NORTE 2020 (NORTE-01-0145-FEDER- 000006) and DeepBiorefinery (PTDC/AGRTEC/1191/2014) projects.info:eu-repo/semantics/publishedVersio

What a difference a methyl group makes-probing choline-urea molecular interactions through urea structure modification

There is a lack of fundamental knowledge on deep eutectic solvents, even for the most extensively studied mixtures, such as the mixture of cholinium chloride and urea, which prevents a judicious choice of components to prepare new solvents. The objective of this work is to study and understand the fundamental interactions between cholinium chloride and urea that lead to the experimentally observed melting temperature depression. To do so, the structure of urea was strategically and progressively modified, in order to block certain interaction centres, and the solid–liquid equilibrium data of each new binary system was experimentally measured. Using this approach, it was concluded that the most important interaction between cholinium chloride and urea occurs through hydrogen bonding between the chloride anion and the amine groups. Any blockage of these groups severely hampers the melting point depression effect. Raman spectroscopy and DFT calculations were utilized to study in more detail this hydrogen bonding and its nuances.This work was developed in the scope of the project CICECO – Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (Ref. FCT UID/CTM/50011/2019) and Associate Laboratory LSRELCM, POCI-01-0145-FEDER-006984 (Ref. FCT UID/EQU/50020/2019), and project MultiBiorefinery (POCI-01-0145-FEDER-016403), all financed by national funds through the FCT/ MCTES (PIDDAC) and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. M. A. R. M. acknowledges financial support from NORTE-01-0145-FEDER-000006 – funded by NORTE2020 through PT2020 and ERDF. L. P. S. acknowledges FCT for her PhD grant (SFRH/BD/135976/2018). C. F. A. acknowledges FCT for her PhD grant (SFRH/BD/129040/2017). M. M. N. and M. M. F. acknowledge FCT for their researcher contracts (IF/01468/2015 and IF/00894/2015 respectively) under the program IF 2015.info:eu-repo/semantics/publishedVersio

Measurement and PC-SAFT modeling of solid-liquid equilibrium of deep eutectic solvents of quaternary ammonium chlorides and carboxylic acids

In this study the solid-liquid equilibria (SLE) of 15 binary mixtures composed of one of three different symmetrical quaternary ammonium chlorides and one of five different fatty acids were measured. The experimental data obtained showed extreme negative deviations to ideality causing large melting-temperature depressions (up to 300 K) that are characteristic for deep eutectic systems. The experimental data revealed that cross-interactions between quaternary ammonium salt and fatty acid increase with increasing alkyl chain length of the quaternary ammonium chloride and with increasing chain length of the carboxylic acid. The pronounced decrease of melting temperatures in these deep eutectic systems is mainly caused by strong hydrogen-bonding interactions, and thermodynamic modeling required an approach that takes hydrogen bonding into account. Thus, the measured phase diagrams were modeled with perturbed-chain statistical associating fluid theory based on the classical molecular homonuclear approach. The model showed very good agreement with the experimental data using a semi-predictive modeling approach, in which binary interaction parameters between quaternary ammonium chloride and carboxylic acid correlated with chain length of the components. This supports the experimental findings on the phase behavior and interactions present in these systems and it allows estimating eutectic points of such highly non-ideal mixtures.This work was developed in the scope of the project CICECO e Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (Ref. FCT UID/CTM/50011/2013) and LSRE-LCM, POCI-01-0145- FEDER-006984jUID/EQU/50020/2013, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. M.A.R.M acknowledges FCT for her PhD grant (SFRH/BD/87084/2012). FCT is also acknowledged for funding the project DeepBiorefinery (PTDC/AGRTEC/ 1191/2014). P.V.A.P., G.J.M., M.D.H. and E.A.C.B thank the national funding agencies CNPq (National Council for Scientific and Technological Development) (305870/2014-9, 309780/2014, 406856/2013-3), FAPESP (Research Support Foundation of the State of S~ao Paulo) (2014/21252-0, 2016/08566-1), FAEPEX/UNICAMP (Fund for Research, Teaching, and Extension) (0125/16) and CAPES (Coordination of Improvement of Higher Level Personnel) for financial support and scholarships. E.A.C thanks Erasmusþ program of the European Union for co-funding.info:eu-repo/semantics/publishedVersio

Analysis of the isomerism effect on the mutual solubilities of bis(trifluoromethylsulfonyl)imide-based ionic liquids with water

The knowledge of the liquid-liquid equilibria (LLE) between ionic liquids (ILs) and water is of utmost importance for environmental monitoring, process design and optimization. Therefore, in this work, the mutual solubilities with water, for the ILs combining the 1-methylimidazolium, [C(1)im](+); 1-ethylimidazolium, [C(2)im](+); 1-ethyl-3-propylimidazolium, [C(2)C(3)im](+); and 1-butyl-2,3-dimethylimidazolium, [C(4)C(1)C(1)im](+) cations with the bis(trifluoromethylsulfonyl)imide anion, were determined and compared with the isomers of the symmetric 1,3-dialkylimidazolium bis(trifluoromethylsulfonyl)imide ([C(n)C(n)im][NTf2], with n=1-3) and of the asymmetric 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(n)C(1)im][NTf2], with n = 2-5) series of ILs. The results obtained provide a broad picture of the impact of the IL cation structural isomerism, including the number of alkyl side chains at the cation, on the water-IL mutual solubilities. Despite the hydrophobic behaviour associated to the [NTf2](-) anion, the results show a significant solubility of water in the IL-rich phase, while the solubility of ILs in the water-rich phase is much lower. The thermodynamic properties of solution indicate that the solubility of ILs in water is entropically driven and highly influenced by the cation size. Using the results obtained here in addition to literature data, a correlation between the solubility of [NTf2]-based ILs in water and their molar volume, for a large range of cations, is proposed. The COnductor like Screening MOdel for Real Solvents (COSMO-RS) was also used to estimate the LLE of the investigated systems and proved to be a useful predictive tool for the a priori screening of ILs aiming at finding suitable candidates before extensive experimental measurements.AcknowledgementsThe authors thank financial support from Fundacão para aCiência e a Tecnologia (FCT, Portugal), European Union, QREN,FEDER and COMPETE for funding the CICECO (project PEST-C/CTM/LA0011/2013), and LSRE/LCM (project PEST-C/EQB/LA0020/2013).Thanks are also due to FCT for financial support for the Ph.D. andpostdoctoral grants SFRH/BD/87084/2012, SFRH/BD/70641/2010,SFRH/BPD/88101/2012 for M.A.R.M., C.M.S.S.N., and K.A.K., respec-tively. S.P.P. also thanks FAPESB (APR0035/2014) for funding

The colors of paintings and viewers' preferences

One hypothesis to explain the aesthetics of paintings is that it depends on the extent to which they mimic natural image statistics. In fact, paintings and natural scenes share several statistical image regularities but the colors of paintings seem generally more biased towards red than natural scenes. Is the particular option for colors in each painting, even if less naturalistic, critical for perceived beauty? Here we show that it is. In the experiments, 50 naïve observers, unfamiliar with the 10 paintings tested, could rotate the color gamut of the paintings and select the one producing the best subjective impression. The distributions of angles obtained are described by normal distributions with maxima deviating, on average, only 7 degrees from the original gamut orientation and full width at half maximum just above the threshold to perceive a chromatic change in the paintings. Crucially, for data pooled across observers and abstract paintings the maximum of the distribution was at zero degrees, i.e., the same as the original. This demonstrates that artists know what chromatic compositions match viewers' preferences and that the option for less naturalistic colors does not constrain the aesthetic value of paintings.The authors thank two anonymous reviewers and the editor for useful suggestions. This study was funded by the Centro de Física of Minho University, by FEDER through the COMPETE Program and by the Portuguese Foundation for Science and Technology (FCT) in the framework of the project PTDC/MHC-PCN/4731/2012, and the COST-Action TD1201, Color and Space in Cultural Heritage (COSCH), Short Term Scientific Missions (STSM): “Hyperspectral imaging on historical manuscripts and natural scenes” (COST-STSM-TD1201- 010813-032699, 2013).The authors are grateful to Maria Helena de Freitas and all team members of CAM - Centro de Arte Moderna da Fundação Calouste Gulbenkian for their collaboration, in particular, to director Isabel Carlos and curator Ana Vasconcelos e Melo. We are also grateful to the Museu Nogueira da Silva in Braga, Portugal, for access to the paintings and facilities and to Maria H. Regalo for useful advice.info:eu-repo/semantics/publishedVersio