Mechanisms of phase separation in temperature-responsive acidic aqueous biphasic systems
文献信息
Nicolas Schaeffer, German Pérez-Sánchez, Helena Passos, José R. B. Gomes, Nicolas Papaiconomou, João A. P. Coutinho
The temperature responsive solubility of ionic liquids with ‘bulky’ polar regions, such as tributyltetradecyl phosphonium chloride ([P44414]Cl), in acidic aqueous solutions is elucidated through a combined experimental and computational approach. The temperature effect in the acidic aqueous biphasic system HCl/[P44414]Cl/H2O was characterised in the range 273 K to 373 K and was found to significantly deviate from the corresponding aqueous biphasic system with NaCl. A new transferable coarse grained MARTINI model for [P44414]Cl was developed, validated and applied to provide a molecular understanding of the experimental results. It is shown that the presence of large aliphatic moieties around the central phosphorus atoms of [P44414]Cl results in a decrease in the electrostatic repulsion between the cationic moieties, leading the [P44414]+ cation to present a behaviour conventionally associated with non-ionic surfactants. This difference in behaviour between HCl and NaCl was shown to result from the greater interaction of the hydronium cation with the micelle surface, thereby enhancing the [P44414]Cl aggregation.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.













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