Kaihang Zhang,David Kujawski,Chris Spurrell,Bing Wang,John C. Crittenden
Liquid-liquid extraction (LLE) using ionic liquids (ILs)-based methods to remove perfluoroalkyl chemicals (PFACs), such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), from wastewater, is an important strategy. However, the lack of physicochemical and LLE data limits the selection of the most suitable ILs for the extraction of PFACs. In this work, 1763 ILs for PFACs extraction from water were systematically screened using COSMOtherm to estimate the infinite dilution activity coefficient ( ln γ ∞ )of PFOA and PFOS in water and ILs. To evaluate the accuracy of COSMOtherm, 8 ILs with various ln γ ∞ values were selected, and their extraction efficiency ( E ) and distribution coefficient ( D exp ) were measured experimentally. The results showed that the predicted ln γ ∞ decreased as the increase of experimental extraction efficiency of PFOA or PFOS, while the tendency of predicted distribution coefficient ( D pre ) was consistent with the experimental ( D exp ) results. This work provides an efficient basis for selecting ILs for the extraction of PFACs from wastewater.
Cytosolic delivery of peptides remains a challenging task owing to their susceptibility to enzymatic degradation and the existence of multiple intracellular barriers. Here, we report a new strategy to address these issues by decoration of a fluorous tag on the terminal of cargo peptides. The fluorous-tagged peptides were assembled into nanostructures, efficiently internalized by cells via several endocytic pathways and released into the cytosol after endosomal escape. They were relatively stable against enzymatic degradation and showed much higher efficiency than nonfluorinated analogs and cell penetrant peptide–conjugated ones. The proposed strategy also efficiently delivered a proapoptotic peptide into specific sites in the cells and restored the function of cargo peptide after cytosolic delivery. The fluorous-tagged proapoptotic peptide efficiently inhibited tumor growth in vivo. This study provides an efficient fluorination strategy to promote the cytosolic delivery of peptides.