Integrated Approach to Extract and Purify Proteins from Honey by Ionic Liquid-Based Three-Phase Partitioning.

The purification of value-added compounds by three-phase partitioning (TPP) is a promising alternative to conventional processes since the target compound can be easily recovered from the liquid-liquid interphase. Although this technique has been successfully applied to the recovery of proteins, the minimization of the use of salts and solvents must be pursued to improve the overall process sustainability. Accordingly, we have here investigated the use of biobased glycine-betaine ionic liquids (IL) directly with honey, a carbohydrate-rich matrix, as phase-forming components of TPP systems. These ILTPP systems were applied in the purification of major royal jelly proteins (MRJPs) from honey. The results obtained show that MRJPs mostly precipitate in the ILTPP interphase, with a recovery yield ranging between 82.8% and 97.3%. In particular, MRJP1 can be obtained with a purity level up to 90.1%. Furthermore, these systems allow the simultaneous separation of antioxidants and carbohydrates to different liquid phases. The proposed approach allows the separation of proteins, antioxidants, and carbohydrates from honey in a single step, while using only ILs and a real carbohydrate-rich matrix, thus being sustainable TPP processes.

Ecotoxicity interspecies study of ionic liquids based on phosphonium and ammonium cations.

This work studies the effects of different bromide-based ionic liquids, with phosphonium and ammonium cations, towards several environmental biomodels: Daphnia magna, Allivibrio fischeri, Raphidocelis subcapitata. Results indicate that toxicity clearly depends on the biomodel, Allivibrio fischeri being the least sensitive one while Daphnia magna is more severely affected in the presence of the studied ionic liquids. In most of the cases, phosphonium moieties are less toxic than ammonium ionic liquids. Furthermore, a prediction about the oral toxicity and carcinogenicity of the studied ionic liquids has been also carried out, showing that these chemical structures may suggest significant toxicity but not present genotoxic or nongenotoxic carcinogenicity.

Glycine-betaine-derived ionic liquids: Synthesis, characterization and ecotoxicological evaluation.

Ionic Liquids (ILs) are generically regarded as environmentally "harmless" and thus, assumed as "non-toxic". However, due to the endless design possibilities, their ecotoxicological profile is still poorly known. An accurate knowledge on the toxicity of a substance is required, under the scope of environmental regulation worldwide, before their application and commercialization. Knowledge on the relationship between the chemical structure and toxic effects is essential for the future design of more biocompatible solvents. Focusing on the use of ILs as base lubricants, lubricant additives, or even as potential working fluids for absorption heat pumps, the knowledge on its environmental impact is of great importance, due to the possibility of spills. In this specific context, four analogues of glycine-betaine-based ILs (AGB-ILs) and four glycine-betaine based ILs (GB-ILs) were synthesized and characterized. Their ecotoxicity was assessed using representatives of two trophic levels in aquatic ecosystems, the bacteria Allivibrio fischeri (commonly used as a screening test organism) and the microalgae Raphidocelis subcapitata (as an alternative test organism that has been proven very sensitive to several IL families). The microalgae were more sensitive than the bacteria, hence, following a precautionary principle, we recommend considering the toxicity towards microalgae as an indicator in future studies regarding the focused ILs. Although four of the studied ILs were derived from a natural amino acid, all were considered hazardous for the aquatic environment, disproving the primary theory that all ILs derived from natural compounds are benign. Furthermore, the modification in the structure of anion and the cation can lead to the increase of toxicity.

Monitoring the Early Antiproliferative Effect of the Analgesic-Antitumor Peptide, BmK AGAP on Breast Cancer Using Intravoxel Incoherent Motion With a Reduced Distribution of Four b-Values.

Background: The present study aimed to investigate the possibility of using intravoxel incoherent motion (IVIM) diffusion magnetic resonance imaging (MRI) to quantitatively assess the early therapeutic effect of the analgesic-antitumor peptide BmK AGAP on breast cancer and also evaluate the medical value of a reduced distribution of four b-values. Methods: IVIM diffusion MRI using 10 b-values and 4 b-values (0-1,000 s/mm2) was performed at five different time points on BALB/c mice bearing xenograft breast tumors treated with BmK AGAP. Variability in Dslow, Dfast, PF, and ADC derived from the set of 10 b-values and 4 b-values was assessed to evaluate the antitumor effect of BmK AGAP on breast tumor. Results: The data showed that PF values significantly decreased in rBmK AGAP-treated mice on day 12 (P = 0.044). PF displayed the greatest AUC but with a poor medical value (AUC = 0.65). The data showed no significant difference between IVIM measurements acquired from the two sets of b-values at different time points except in the PF on the day 3. The within-subject coefficients of variation were relatively higher in Dfast and PF. However, except for a case noticed on day 0 in PF measurements, the results indicated no statistically significant difference at various time points in the rBmK AGAP-treated or the untreated group (P < 0.05). Conclusion: IVIM showed poor medical value in the early evaluation of the antiproliferative effect of rBmK AGAP in breast cancer, suggesting sensitivity in PF. A reduced distribution of four b-values may provide remarkable measurements but with a potential loss of accuracy in the perfusion-related parameter PF.

Enhanced separation performance of aqueous biphasic systems formed by carbohydrates and tetraalkylphosphonium- or tetraalkylammonium-based ionic liquids.

Aiming at establishing more effective and sustainable separation processes, herein we propose the use of carbohydrates combined with tetralkylphosphonium- and tetralkylammonium-based ionic liquids (ILs) to form aqueous biphasic systems (ABS). The formation of ABS composed of non-aromatic and non-fluorinated ILs with carbohydrates is here shown for the first time. These novel systems are competive extraction platforms when compared against more conventional ABS formed by ILs and salts or fluorinated ILs and carbohydrates. Finally, it is shown that these systems can be efficiently recovered and reused.

Glycine-betaine ionic liquid analogues as novel phase-forming components of aqueous biphasic systems.

Given the biotechnology advances observed in recent years in terms of upstream, the development of effective downstream processes becomes mandatory to decrease the associated costs of biotechnological-based products. Although a large interest has been devoted to ionic-liquid-based aqueous biphasic systems (IL-based ABS) as tailored separation platforms, imidazolium-based ILs have been the preferred choice as phase-forming agents. To overcome some toxicity and biodegradability issues associated to imidazolium-based ILs, novel ABS composed of ILs analogues of glycine-betaine (AGB-ILs) are here proposed and investigated. Five AGB-ILs were synthesized, characterized in terms of ecotoxicity, and applied toward the development of novel ABS formed with Na2 SO4 . Three commercial ILs were also investigated for comparison purposes. The respective ABS ternary phase diagrams, as well as the tie-lines and tie-line lengths, were determined at 25°C. Finally, their performance as extraction strategies was evaluated with five amino acids (L-tryptophan, L-phenylalanine, D-phenylalanine, L-tyrosine and L-3,4-dihydroxyphenylalanine/L-dopa). In all studied systems amino acids preferentially migrate to the IL-rich phase, and with AGB-ILs, the amino acid extraction efficiencies to the IL-rich phase range between 65% and 100%, obtained in a single-step. Furthermore, the studied AGB-ILs display a higher ability to form ABS and to extract amino acids than ABS composed of more traditional and commercial ILs. In summary, novel ABS composed of AGB-ILs can be formed and used as separation routes of value-added compounds of biotechnological interest. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 2018 © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 34:1205-1212, 2018.

Thermodynamic and spectroscopic studies of copper (II) complexes with three bis(amide) ligands derived from L-tartaric acid.

The interactions of three bis(amide) ligands derived from tartaric acid with copper (II) were investigated in aqueous solution by a combination of potentiometry, UV-vis spectrophotometry, electron paramagnetic resonance (EPR), and mass spectrometry. The formation constants of the complexes were measured and their relative structures were reported. The sites of complexation of these ligands are investigated based mostly on their electronic and EPR spectra and on the comparison with the behaviour of some analog compounds.