Aggregation in Aqueous Solutions of 2-(Tetrafluoro(trifluoromethyl)-λ(6)-sulfanyl-ethan-1-ol (CF(3)SF(4)-ethanol)): A Comparison with Aqueous Trifluoroethanol and Hexafluoroisopropanol Using Molecular Dynamics Simulations and Dynamic Light Scattering Experiments

2-(四氟(三氟甲基)-λ(6)-硫基-1-醇(CF(3)SF(4)-乙醇)水溶液中的聚集:与三氟乙醇和六氟异丙醇水溶液的比较:分子动力学模拟和动态光散射实验

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Abstract

2-Tetrafluoro(trifluoromethyl)-λ(6)-sulfanylethan-1-ol (CF(3)SF(4)-ethanol) combines the polar hydrophobicity of tetrafluoro(trifluoromethyl)-λ(6)-sulfanyl (CF(3)SF(4)) group with the polarity of simple alcohols. The properties of aqueous solutions of the well-known fluorinated alcohols 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) were compared with those of aqueous solutions of the novel CF(3)SF(4)-ethanol. Those properties were computed using all atom molecular dynamics simulations with OPLS-compatible parameters. DFT ab initio calculations were used to accurately describe the nonsymmetrical, hypervalent sulfur in CF(3)SF(4)-ethanol. Although the molecular and conformational characteristics of CF(3)SF(4)-ethanol are like those of both TFE and HFIP, the greater hydrophobicity and lower polarity of CF(3)SF(4)-ethanol resulted in solution phase aggregation at a much lower concentration. The properties computed for TFE and HFIP in this work were consistent with published computational and experimental studies. CF(3)SF(4)-ethanol is predicted to be environmentally benign and hence an excellent green solvent candidate while possessing many of the same properties as TFE or HFIP.

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