Self‐Assembled Columnar Triazole Quartets: An Example of Synergistic Hydrogen‐Bonding/Anion–π Interactions

Abstract

The self-assembly of triazole amphiphiles was examined in solution, the solid state,and in bilayer membranes. Single-crystal X-ray diffraction experiments show that stacked protonated triazole quartets (T 4 )a re stabilized by multiple strong interactions with two anions.H ydrogen bonding/ion pairing of the anions are combined with anion-p recognition to produce columnar architectures.I nb ilayer membranes,l ow transport activity is observed when the T 4 channels are operated as H + /X À translocators,b ut higher transport activity is observed for X À in the presence of the K + -carrier valinomycin. These self-assembled superstructures,presenting intriguing structural behaviors such as directionality,a nd strong anion encapsulation by hydrogen bonding supported by vicinal anion-p interactions can serve as artificial supramolecular channels for transporting anions across lipid bilayer membranes.

Biomimetic Artificial Proton Channels

“…A series of experiments were performed by using an H + selective carrier (FCCP) or a K + -selective carrier (valinomycin). There was no significant difference in the transport activity, confirming that these artificial triazole channels have no cation selectivity ( Figure 21 ) [ 63 ].…”

“…A selective anion recognition has to be combined with fast anion translocation along the directional pathways in channels. A series of protonated amino-triazole amphiphiles were synthesized and characterized by Barboiu et al to form self-assembled channels of stacked triazole quartets ( Figure 20 ) [ 63 ].…”

“… The molecular structure of the self-assembled amino-triazole amphiphiles and their protonated counterparts. Adapted with permission from Reference [ 63 ] Copyright © 2019, Wiley publishing. …”

“… The proposed transport mechanism through the self-assembled columnar triazole channels and the comparison of the transport activity of one protonated molecule ( a ) in the absence and the presence of 50 μm FCCP (H + carrier) and ( b ) in the absence and the presence of 50 μm valinomycin (K + carrier). Adapted with permission from Reference [ 63 ] Copyright © 2019, Wiley publishing. …”

Anion-Responsive Manganese Porphyrin Facilitates Chloride Transport and Induces Immunogenic Cell Death

“…[4][5] Barboiu et al reported self-assembled columnar triazole quartets as artificial channels in lipid vesicles. 6 However, it remains to be seen whether successful self-assembly and chloride transport can be achieved under physiological conditions.…”