Selection of hydrotropes for enhancing the solubility of artemisinin in aqueous solutions

Artemisinin is an antimalarial substance very sparingly soluble in water. In the attempt to identify environmental-friendly and non-toxic aqueous-based solvents to extract it from Artemisia annua L., the solubility of artemisinin in aqueous solutions of different hydrotropes was measured at 303.2 K, for hydrotrope concentrations up to 5 M. The ability of the studied hydrotropes for enhancing the artemisinin solubility increases in the following order: Na[N(CN)2] < Na[SCN] < [Chol][Van] < [Chol][Gal] < [N4,4,4,4]Cl < [Chol][Sal] < [P4,4,4,4]Cl < Na[Sal], with Na[Sal] allowing an increase in the solubility of 750 fold compared to pure water. The COSMO-RS model and experimental Kamlet-Taft solvatochromic parameters were applied to connect the solubility enhancement with solvent properties. At low hydrotrope concentration, the solubility increases with the decreasing of the difference between the Apolar Factors of the hydrotrope and artemisinin, while for higher hydrotrope concentration, the hydrogen-bond acceptor character of the hydrotrope seems to have an impact on the solubility enhancement. Even if some mechanistic understanding is still to unfold, quantitatively the empirical correlations of solubility enhancement with the hydrotrope concentration and the solvatochromic parameters show very high accuracy. In particular, 93% of the change on the artemisinin solubility enhancement could be explained using the hydrotrope concentration and two combined solvatochromic parameters (αβ and π∗2) as explaining variables.This work was developed within the scope of the projects CICECOAveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, CIMO-Mountain Research Center, UIDB/00690/2020, and Green Health (Norte-01-0145-FEDER-000042) all financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 and NORTE 2020 Partnership Agreement. Isabela Sales and Silvana Mattedi thanks the finantial support from CAPES and CNPq/ Brazil (CAPES: Proc. 88881.189075/2018-01 and 88887.494428/2020- 00. CNPq: Grant 303089/2019-9 and Proc.438036/2018-2).info:eu-repo/semantics/publishedVersio

Enhancing artemisinin solubility in aqueous solutions: searching for hydrotropes based on ionic liquids

Artemisinin is a sesquiterpenoid lactone peroxide, known for its potent antimalarial activity that can be extracted from Artemisia annua L. This compound is only sparingly soluble in water, making its extraction using environmental-friendly and non-toxic aqueous solvents difficult. In the attempt to overcome this limitation, hydrotropes, which are a class of compounds that can assist in increasing the solubility of hydrophobic solutes in water, were investigated in this work. In particular, the hydrotropic capability of ionic liquids (ILs) on the aqueous solubility of artemisinin was studied. The effects of IL concentration and anion nature of 1-butyl-3-methylimidazolium-based ILs on the solubility of artemisinin at 303.2 K in water were evaluated. It is here shown the excellent capacity of ILs containing thiocyanate or dicyanamide anions to enhance the solubility of artemisinin in aqueous media, with a magnitude comparable to that obtained with the best organic solvents. Furthermore, solvatochromic parameters of the ILs aqueous solutions were also measured and combined with COSMO-RS and the cooperative hydrotropy model to establish relations between the artemisinin solubility enhancement and the solvent characteristics. The solubility enhancement of artemisinin is favored by the apolarity of the medium and the lower hydrogen-bond acceptor character of the hydrotrope.This work was developed within the scope of the projects CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, CIMO-Mountain Research Center, UIDB/00690/2020, all financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. Isabela Sales and Silvana Mattedi thanks the finantial support from CAPES and CNPq/Brazil (CAPES: Proc. 88881.189075/2018-01 and 88887.494428/2020-00. CNPq: Grant 303089/2019-9 and Proc.438036/2018-2).info:eu-repo/semantics/publishedVersio

Accounting for risk of non linear portfolios: a novel Fourier approach

The presence of non linear instruments is responsible for the emergence of non Gaussian features in the price changes distribution of realistic portfolios, even for Normally distributed risk factors. This is especially true for the benchmark Delta Gamma Normal model, which in general exhibits exponentially damped power law tails. We show how the knowledge of the model characteristic function leads to Fourier representations for two standard risk measures, the Value at Risk and the Expected Shortfall, and for their sensitivities with respect to the model parameters. We detail the numerical implementation of our formulae and we emphasizes the reliability and efficiency of our results in comparison with Monte Carlo simulation.Comment: 10 pages, 12 figures. Final version accepted for publication on Eur. Phys. J.

High pressure separation of greenhouse gases from air with 1-ethyl-3-methylimidazolium methyl-phosphonate

Increasing pollutants emissions, along with the limitations present on the existing control methods and stricter legislation to come, demand the development of new methods to reduce them. Ionic liquids (ILs) have been attracting an outstanding attention during the last decade and rose as a promising class of viable solvents to capture pollutants and for gas separation processes. As part of a continuing effort to develop an ionic liquid based process for high pressure capture of greenhouse gases, the phase equilibria of carbon dioxide (CO2), nitrous oxide (N2O), methane (CH4) and nitrogen (N-2) in 1-ethyl-3-methylimidazolium methyl-phosphonate ([C(2)mim][CH3OHPO2]) were studied in this work. Experimental measurements for the CO2, N2O, CH4 and N-2 solubilities in [C(2)mim][CH3OHPO2] were carried out for gases mole fractions ranging from (0.018 to 0.504), in the temperature range (293.23 to 363.34) K and for pressures from (1.16 to 87.61) MPa. The particular behavior of the selected highly polar ionic liquid is here shown for the first time through the reported experimental data. The low N-2, CH4 and CO2 solubilities, with the later system presenting positive deviations to ideality, show the ionic liquid unfavorable interactions with the studied gases and the necessity to find a proper compromise between the solvent polarity and its molar volume in order to achieve high CO2/N-2 or CO2/CH4 separation selectivities. The good soft-SAFT EoS performance in describing the thermophysical properties of ionic liquids and the phase equilibria of their mixtures with gases was extended in this work for the description of the experimental data reported. New and reliable molecular schemes for N2O and [C(2)mim][CH3OHPO2], not yet studied within the soft-SAFT framework, were proposed. Using no more than one binary interaction parameter, the soft-SAFT EoS is able to take into account the particular pressure and temperature behavior of the different gases solubilities in the selected ionic liquid. This empowers the equation to be reliably used for other similar systems, as tool to optimize the given process, searching for the best conditions for capture. (C) 2013 Elsevier Ltd. All rights reserved