Band 91, Heft 8

A novel class of aqueous biphasic systems (ABS) formed by zwitterions (ZI) has been investigated in the present work. A series of water soluble ZIs have been synthesized using triethylamine, N -Methylimidazole, N -Vinylimidazole, pyridine, N -Methylpyrrolidine, N -Ethylpiperidine and 1,4 butane sultone. The synthesized ZIs were explored for their ability to form biphasic systems in combination with aqueous inorganic salt solutions of K 3 PO 4 , K 2 HPO 4 and K 2 CO 3 . The phase diagrams for all systems have been constructed through cloud point titration method at 298.15 K and atmospheric pressure. The phase behavior of ZI based ABS have been analyzed to understand the structural effects of ZIs as well as the effect of nature of salt used on the overall phase formation. Further the temperature dependence of the ZI based ABS was also explored by studying the phase behavior at variable temperatures of 298.15, 308.15 and 318.15 K. In order to estimate the applicability of proposed ZI based ABS, extraction experiments have been performed for an alkaloid i.e. caffeine for all synthesized ZIs with K 3 PO 4 and at 298.15 K. ZI based ABS have been found to be capable of single step extraction of caffeine similar to IL based ABS thus providing the possibilities to explore these ZI based ABS as efficient extraction and separation systems.

Solvation Gibbs energies are basically defined as a chemical potential change when transferring a fixed molecule from a perfect gas to a real liquid mixture. This quantity is of special interest for many practical applications as it quantifies the degree of affinity of a solute for its solvent. Few methods are currently available in the literature for the prediction of solvation Gibbs energies. In this article, a new approach is proposed: the use of a predictive cubic equation of state (EoS). The UMR-PRU (Universal Mixing Rule Peng-Robinson UNIFAC) EoS has been selected for its known capacity to semi-predict behaviors of complex systems including polar and associating compounds (by semi-prediction, it is meant that the EoS predicts binary interaction parameters but requires pure-component properties as input parameters). UMR-PRU predictions have been compared to experimental data extracted from the extensive CompSol database (containing around 22 000 pure component data and 70 000 binary data). Accurate predictions were obtained (a mean absolute deviation of 0.36 kcal/mol was obtained for all the binary data). Finally, when using a fully-predictive approach (i.e. pure-component EoS parameters are predicted from group-contribution methods), the prediction accuracy is roughly preserved.

Heat transfer fluids materials are manufactured for the purpose of transfer, distribution and storage of heat. Several of their important properties can be listed (for example flash point, thermal expansivity or technical safety). However, to assess the thermal exchange performance of these fluids, a prior knowledge of their heat capacity, density, viscosity and thermal conductivity is obligatory. The most popular heat transfer fluids are based on organic liquids, such as ethylene glycol. However, new technologies and development require more efficient materials. Ionanofluids, mixtures of ionic liquids and nanoparticles, were proposed as a viable replacement for those commonly used fluids due to the properties of ionic liquids (wide liquid range or low vapour pressure and flammability) combined with enhanced thermophysical properties of nanofluids caused by the dispersion of nanoparticles (mainly thermal conductivity and heat capacity). Very few authors reported the extensive analysis of those systems thermophysical properties and impact on the heat exchange efficiency. Moreover, the availability of published data is very limited. The aim of this work is to investigate ionanofluids based on the trihexyl(tetradecyl)phosphonium cation paired with the acetate, butanoate, hexanoate, octanoate or decanoate anion, mixed with carbon nanotubes, boron nitride, graphite or mesoporous carbon as nanoparticles with concentration up to 3 wt %. The density, heat capacity, thermal stability, thermal conductivity and viscosity of selected ionanofluids were determined experimentally as functions of the temperature (up to 363.15 K) and compared with theoretical tools to evaluate the predictive capability. Based on the experimental results, lubrication, heat storage potential and economic analysis were also discussed and compared to commercial heat transfer fluids.

Compared to conventional solvents used in the chemical industry, deep eutectic solvents (DESs) are considered as promising potentially sustainable solvents. DESs are binary mixtures and the resulting liquid mixture is characterized by a large melting point depression with respect to the melting temperatures of its constituents. The relative melting point depression becomes larger as the two components have stronger attractive interactions, resulting in non-ideal behavior. The compositional range over which such binary mixtures are liquids is set by the location of the solid–liquid phase boundary. Here we present experimental phase diagrams of various recent and new DESs that vary in the degree of non-ideality. We investigate whether thermodynamic models are able to describe the solid–liquid equilibria and focus on relating the parameters of these models to the non-ideal behavior, including asymmetric behavior of the activity coefficients. It is shown that the orthogonal Redlich–Kister-like polynomial (OP) expansion, including an additional first order term, provides an accurate description. This theory can be considered as an extension of regular solution theory and enables physical interpretation of the fit parameters.

The manuscript reports on a new class of aqueous biphasic systems (ABSs) formed in mixtures of inorganic salts (ISs) and zwitterionic salts (ZWSs). Aqueous ternary phase diagrams characterized by a binodal curve were determined for systems consisting of four ISs, K 3 PO 4 , K 2 HPO 4 , K 2 HPO 4 /KH 2 PO 4 , and K 2 CO 3 , and three structurally similar ZWSs differing in hydrophobicity. Comparison of phase behaviour of ABSs composed of ZWSs, ionic liquids (ILs) and zwitterions was provided. Potential of ZWSs based systems for extraction of aromatic molecules and amino acids, such as glycine, L-tryptophan, DL-phenylalanine, eugenol, and phenol was examined. Feasibility and limitations of isolation of products after partition and recovery of ZWS were discussed.

In this work, the physical, transport and electrochemical properties of various electrolytic solutions containing the 1-propyl-1-methylpyrrolidinium bis[fluorosulfonyl]imide ([C 3 C 1 pyr][FSI]) mixed with the lithium bis[(trifluoromethyl)sulfonyl]imide (Li[TFSI]) over a wide range of compositions are reported as a function of temperature at atmospheric pressure. First, the ionicity, lithium transference number, and transport properties (viscosity and conductivity) as well as the volumetric properties (density and molar volume) were determined as a function of lithium salt concentration from 293 to 343 K. Second, the self-diffusion coefficient of each ion in solution was measured by nuclear magnetic resonance (NMR) spectroscopy with pulsed field gradients (PFG). Moreover, an analysis of the collected nuclear Overhauser effect (NOE) data along with ab initio and COSMO-RS calculations was conducted to depict intra and intermolecular neighbouring within the electrolytic mixtures. Based on this analysis, and as expected, all activation energies increase with the Li[TFSI] concentration in solution, and all activation energies were determined from the self-diffusion data for all ions. Interestingly, regardless of the composition in solution, these activation energies were similar, except for those determined for the [FSI] − anion. The activation energy of [FSI] − self-diffusion relatively decreases compared to the other ions as the lithium salt concentration increases. Furthermore, the lithium transference was strongly affected by the lithium salt concentration, reaching an optimal value and an ionicity of approximately 50 % at a molality close to 0.75 mol · kg −1 . Finally, these electrolytes were used in lithium-ion batteries (i.e. Li/NMC and LTO/NMC), demonstrating a clear relationship between the electrolyte formulation, its transport parameters and battery performance.

Leishmaniasis is a group of zoonotic diseases caused by a trypanosomatid parasite mostly in impoverished populations of low-income countries. In their different forms, leishmaniasis is prevalent in more than 98 countries all over the world and approximately 360-million people are at risk. Since no vaccine is currently available to prevent any form of the disease, the control strategy of leishmaniasis mainly relies on early case detection followed by adequate pharmacological treatment that may improve the prognosis and can reduce transmission. A handful of compounds and formulations are available for the treatment of leishmaniasis in humans, but only few of them are currently in use since most of these agents are associated with toxicity problems such as nephrotoxicity and cardiotoxicity in addition to resistance problems. In recent decades, very few novel drugs, new formulations of standard drugs or combinations of them have been approved against leishmaniasis. This review highlights the current drugs and combinations that are used medical practice and recent advances in new treatments against leishmaniasis that were pointed out in the recent 2 nd Conference, Global Challenges in Neglected Tropical Diseases, held in San Juan, Puerto Rico in June 2018, emphasizing the plethora of new families of molecules that are bridging the gap between preclinical and first-in-man trials in next future.

Many marine derived fatty acids, mainly from sponges, possess vinylic halogenated moieties (bromine or iodine) but their assessment as antileishmanial candidates remains elusive. In this work, we undertook the first total synthesis of a novel series of 2-allyl-3-halo-2-nonadecenoic acids, which preferentially inhibit the Leishmania DNA topoisomerase IB enzyme ( L TopIB) over the human topoisomerase IB enzyme (hTopIB). The synthesis of 2-allyl-3-bromo-2 E -nonadecenoic acid ( 1a ) and 2-allyl-3-chloro-2 E -nonadecenoic acid ( 2a ) was achieved through a palladium catalyzed haloallylation of 2-nonadecynoic acid (2-NDA) using either allyl bromide or allyl chloride in the presence of PdCl 2 (PhCN) 2 in 57–83 % overall yields. Among the new halogenated synthetic compounds, 1a was the most inhibitory of L TopIB with an EC 50  = 7 μM, while the shorter chain analogs 2-allyl-3-bromo-2 E -dodecenoic acid ( 1b ) and 2-allyl-3-chloro-2 E -dodecenoic acid ( 2b ), synthesized from 2-dodecynoic acid, were not inhibitory of L TopIB (EC 50  > 100 μM) resulting in the overall order of inhibition 1a  > 2-NDA >  2a  > >  1b  ≅  2b . The acids 1a and 2a inhibit L TopIB by a Gimatecan-independent mechanism. The enhanced L TopIB inhibition of 1a was computationally rationalized in terms of a halogen bond between the bromine in 1a and a DNA phosphate (binding energy = − 4.85 kcal/mol). Acid 1a also displayed preferential cytotoxicity towards Leishmania infantum amastigotes (EC 50  = 2.5 μM) over L. infantum promastigotes (EC 50  > 25 μM).

Isolation of endogenous constituents of foods is generally performed in order to elucidate the biological activity of individual compounds and their role with respect to factors such as organoleptic qualities, health and nutritional benefits, plant protection against herbivores, pathogens and competition, and presence of toxic constituents. However, unless such compounds are unequivocally defined with respect to structure and purity, any biological activity data will be compromised. Procedures are therefore proposed for comprehensive elucidation of food-based organic structures using modern spectroscopic and spectrometric techniques. Also included are guidelines for the experimental details and types of data that should be reported in order for subsequent investigators to repeat and validate the work. Because food chemistry usually involves interdisciplinary collaboration, the purpose is to inform chemists and scientists from different fields, such as biological sciences, of common standards for the type and quality of data to be presented in elucidating and reporting structures of biologically active food constituents. The guidelines are designed to be understandable to chemists and non-chemists alike. This will enable unambiguous identification of compounds and ensure that the biological activity is based on a secure structural chemistry foundation.