Search

The separation of structurally similar compounds, such as cholic acid (CA) and deoxycholic acid (DCA), is challenging due to their nearly identical physicochemical properties. This study demonstrates a synergistic 'push and pull' strategy with an ionic liquid (IL) biphasic system for significantly enhanced CA/DCA separation efficiency. Ethyl acetate was selected as the feed solvent to 'push' CA into the IL-rich extractant phase, while the IL 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl) was chosen to 'pull' CA due to their strong hydrogen bonding interaction. This 'push and pull' system yielded a remarkable CA/DCA selectivity up to 47.8, much higher than the case using n-butanol which pulls both CA and DCA. The underlying separation mechanism was elucidated through computational screening with COSMO-RS, NMR analysis, and solvatochromic measurements. Results revealed the critical roles of specific hydrogen bonding between the chloride anion of [EMIM]Cl and the hydroxyl/carboxyl groups of CA/DCA, along with nonspecific interactions between the feed solvent and CA/DCA. Thermodynamic analysis of the phase transfer process confirmed the 'push and pull' synergy is energetically favorable for preferentially transferring CA from the ethyl acetate feed solution into the IL-rich extractant phase. Multi-stage simulation indicated that 99% purity and recovery of both CA and DCA can be obtained through this biphasic system under optimized conditions. Overall, strategically tuning both the feed solvent and IL extractant could significantly enhance the separation efficiency of structurally similar compounds while minimizing solvent and energy consumption. This 'push and pull' approach may shed light on improving separation processes for other structural analogues. [ABSTRACT FROM AUTHOR]

A series of mechanoresponsive fluorescence composite films were prepared by doping pyrene (Py) and its derivatives including 1-hydroxypyrene (HPY), 1-pyrenemethanol (PYM) and 1-pyrenylboronic acid (PBA) into thermoplastic polyurethane (PU) via physical blending, respectively. The fluorescence property of the composite films was found to be influenced by the polar group of pyrene derivatives and the content of hard segment of PU. The doped PYM showed a stronger trend to aggregate in PU matrixes, relative to other dyes. Contrary to PU/Py and most of previously reported mechanoresponsive materials, the emission intensity of aggregated PYM molecules in both PU25/PYM and PU50/PYM films exhibited a stretching-enhanced-emission feature. When PU25/PYM was stretched up to 500%, the intensity ratio of its dual emission peaks at 490 and 400 nm increased from 2.3 to 5.3. This interesting mechanoresponsive behavior was related to the formation of strong hydrogen bonding between PYM and hard segment of PU matrixes proved by FT-IR spectrograph. Enhancing instead of reducing the emission intensity of dyes through stretching would be remarkable in the field of mechanoresponsive materials. In the fluorescent polyurethane composite systems, the polar units of fluorescent dyes played an important role in the mechanoresponsive behavior of polyurethane. The doped 1-pyrenemethanol film exhibited a stretching-enhanced emission feature when polyurethane with hard segments of over 20 wt% used as the matrix, which is contrary to that in the doped pyrene film and most of polymer composite systems in the literature. [Display omitted] • Polar units of Py dyes have a significant influence on fluorescent property of PU. • PU/PYM (1-pyrenemethanol) doped film exhibited stretching-enhanced emission behavior. • The fluorescent intensity of PU/PYM doped film is sensitive to large deformation. [ABSTRACT FROM AUTHOR]