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The present study investigates the utilization of a supramolecular deep eutectic solvent (SUPRADES), consisting of sulfated-ß-cyclodextrin (S-ß-CD) and citric acid (CA), as a chiral selector (CS) in capillary electrophoresis for the enantiomeric separation of nefopam (NEF) and five cathinone derivatives (3-methylmethcathinone [3-MMC], 4-methylmethcathinone [4-MMC], 3,4-dimethylmethcathinone [3,4-DMMC], 4-methylethcathinone [4-MEC], and 3,4-methylendioxycathinone [MDMC]). A significant improvement in enantiomeric separation of the target analytes was observed upon the addition of S-ß-CD-CA to the background electrolyte (BGE), leading to a baseline separation of all analytes. In particular, the optimum percentage of S-ß-CD-CA, added to the BGE, was determined to be 0.075% v/v for NEF (Rs = 1.5) and 0.050% v/v for three out of five cathinone derivatives (Rs = 1.5, 1.6, and 2.4 for 3-MMC, 4-MEC, and 3,4-DMMC, respectively). In the case of 4-MMC and MDMC, a higher percentage of the CS, equal to 0.075% and 0.10% v/v, respectively, was required to achieve baseline separation (Rs = 1.5, 1.9 for MDMC and 4-MMC, respectively). The outcomes of the present study highlight the potential effectiveness of using SUPRADES as a CS in electrophoretic enantioseparations.

RESUMEN

In this study, an optimized environmentally friendly procedure was employed to enhance the sustainable utilization of phenolic antioxidants derived from aloe vera rind by-products. The procedure involved the application of ultrasound-assisted extraction (UAE) in combination with deep eutectic solvents (DESs). Eleven different DESs and three conventional solvents were employed as extraction media for polyphenolic compounds. Choline chloride-citric acid (ChCl-CA) was selected as the most suitable extractant, considering its extraction efficiency in relation to the total phenolic content. The operating conditions of UAE were optimized and modeled by the use of response surface methodology in order to maximize the yield of total phenolics and antioxidant capacity. The optimal operational parameters for the UAE procedure were determined to be 16.5 min, 74% (v/v) DES in water, and a solvent-to-solid ratio equal to 192. HPLC analysis, which was performed on the optimum extract, revealed significant levels of phenolics present in the aloe rind. Efficient recovery of the extracted antioxidants was obtained by the use of solid-phase extraction (SPE) and polyamide cartridges. The ChCl-CA DES exhibited excellent recycling capability with a yield of over 90% through SPE. Finally, the greenness of the method was evaluated using the green AGREE and AGREEprep metrics. The results highlighted the sustainability and the greenness of the proposed extraction procedure for the aloe by-product.

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In this study, a novel supramolecular deep eutectic solvent consisting of sulfated-ß-CD and citric acid (S-ß-CD-CA) is reported for the first time. This innovative system was evaluated as a sole chiral selector in capillary electrophoresis for the enantioseparation of six fluorine-substituted amphetamine analogs, yielding remarkable outcomes. Baseline separations of all amphetamine analogs under study were achieved in less than 21.00 min using the S-ß-CD-CA as the chiral selector. It was observed that the addition of 0.050 % v/v S-ß-CD-CA into the background electrolyte resulted in the baseline separation of five out of the six fluorine-substituted amphetamine analogs, while in the case of the para-substituted amphetamine analog, 4-fluoramphetamine (4-FA), a higher percentage (0.15 % v/v) was required to achieve baseline enantioseparation. These findings emphasized the potential of this new supramolecular system in providing a class of solvents with promising chiral recognition properties.

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RESUMEN

A comprehensive study was performed to determine an optimum enantioseparation method for fluorine-substituted amphetamine and cathinone derivatives (fluor-amphetamine and fluor-cathinone derivatives), using a binary system consisting of carboxymethyl-ß-CD (CM-ß-CD) and a deep eutectic solvent (DES), namely choline chloride-ethylene glycol (ChCl-EG). Under this framework, the optimization and modeling of the separation conditions in a binary system were performed with the objective of maximizing resolution and minimizing analysis time. This was achieved through the application of response surface methodology. In particular, the effect of chiral selector concentration and percentage of DES on resolution and analysis time were investigated and optimized using a complete experimental design. The optimum enantioseparation conditions were determined to be 13.84 mM CM-ß-CD and 0.15% v/v ChCl-EG for fluorine-substituted amphetamine derivatives and 14.36 mM and 0.75% v/v ChCl-EG for fluorine-substituted cathinone derivatives, respectively. This combination resulted in a baseline separation for eight out of the nine analytes studied. Overall, the results demonstrated the synergistic effect of the CM-ß-CD/DES dual system and highlighted the significance of DESs as additives in capillary electrophoresis.

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The effect of the combined use of amino acid-based ionic liquids (AAILs) and deep eutectic solvents (DESs) with either cyclodextrin- (CD) or cyclofructan- (CF) based chiral selectors for the chiral separation of amphetamine derivatives was investigated in the present study. A non-significant improvement in enantiomeric separation of target analytes was observed when AAILs were combined with either CF or CD. On the other side, a markedly improved chiral separation of enantiomers was obtained using the dual carboxymethyl-ß-cyclodextrin/DES system, highlighting the existence of a synergistic effect. After the addition of 0.5% v/v of choline chloride-ethylene glycol, the resolution of the enantiomers of amphetamine, methamphetamine and 3-fluorethamphetamine, increased from 1.4, 1.1, 1.0 to 1.8, 1.8, and 1.5 min, and the analysis times increased from 19.54, 20.48, 18.71 to 35.71, 35.78 and 32.90 min, respectively. This was not the case for the CF/DES dual system, in which the separation of amphetamines worsened, indicating an antagonistic effect. In conclusion, DESs are a very promising additive in capillary electrophoresis that can improve the separation of chiral molecules in combination with CDs but not CFs.

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During this study, a simple and easy-to-prepare electrophoretic method was developed for the enantioseparation of amphetamine and cathinone derivatives. Different types of ß-cyclodextrin and cyclofructan-based chiral selectors (CSs), both native and derivatized, were utilized, and the most effective ones, in terms of resolution and analysis time, were identified. In addition, several electrophoretic parameters, such as background electrolyte concentration and pH, and CS concentration, were examined to optimize the separation conditions. Under the optimal electrophoretic conditions, 10 psychoactive substances were enantiomerically separated using 1 mM sulfated cyclofructan-6 (SCF-6) for the amphetamine derivatives and 1 mM sulfated cyclofructan-7 (SCF-7) for the cathinone derivatives dissolved in an aqueous solution of 20-mM monobasic sodium phosphate at pH 2.5, a temperature of 25°C, and an applied voltage of 25 kV. In addition, the method was validated by estimating the intra- and interday precision.

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This study explores the potential for enhancing the production of ethyl lactate (EL), a green solvent, through enzymatic esterification. Different solvents were compared as organic media for conversion of lactate and ethanol into EL, catalyzed by Novozym 435. Chloroform and hexane were the most effective in low acid concentrations (0.01-0.1M) exhibiting maximum EL yields of 88% and 75% respectively. The yield of EL improved as the solvent's LogP increased up to a value of 2. Non-commercial immobilized biocatalysts consisting heterologous Rhizopous oryzae (rROL) and Candida rugosa (CRL) lipases immobilized on hydrophobic supports were compared to commercial biocatalysts clarifying that Novozym 435 and Lipozyme RM IM could be efficiently applied. Operational stability tests were conducted using Novozym 435, which retained higher activity in chloroform as compared to hexane. Although non-commercial biocatalysts were not competitive in esterification, they exhibited significant activity towards hydrolysis constituting a valuable alternative to higher-cost options.

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