Tuning the Surface Activity of Gemini Amphiphile by the Host–Guest Interaction of Cucurbit[7]uril

This research is aimed to develop an effective supramolecular route for tuning the surface activity of the surfactant. To this end, cationic gemini amphiphiles and cucurbit[7]­uril (CB[7]) were complexed in water, and each hydrophobic chain of the gemini amphiphiles was bound with a CB[7]. The steric hindrance of CB[7] prevented the two hydrophobic chains from getting closed to each other, leading a significant change of surface activity. Before supramolecular complexation, the surface activity of the gemini amphiphile is relatively high, which can generate the foams easily. However, the foam generated by gemini amphiphile can be destructed by adding CB[7], suggesting that the suface activity is lowed after the supramolecular complexation. The surface activity can recover after adding 1-adamantanamine hydrochloride, which has a stronger ability to bind CB[7]. Therefore, a controllable foaming and defoaming process can be realized. It is highly anticipated that supramolecular chemistry for tuning amphiphilicity of surfactants may find application in the fields that fast foaming and defoaming are needed

Photoswitchable Quadruple Hydrogen-Bonding Motif

Multiple hydrogen-bonding motifs serve as important building blocks for molecular recognition and self-assembly. Herein, a photoswitchable quadruple hydrogen-bonding motif featuring near-complete, reversible, and thermostable conversion between DADA and AADD arrays associated with an alteration of their dimerization constants by over 3 orders of magnitude is reported. The system is based on a diarylethene featuring a ureidopyrimidin-4-ol moiety, which upon photoinduced ring closure and associated loss of aromaticity undergoes enol–keto tautomerization to a ureidopyrimidinone moiety. The latter causes a transformation of the hydrogen-bonding arrays and significantly weakens the free energy of dimerization in the case of the closed isomer. This photoswitchable quadruple hydrogen-bonding motif should allow us to spatially and temporarily direct self-assembly and supramolecular polymerization processes by light

Cucurbit[7]uril-Modulated H/D Exchange of α‑Carbonyl Hydrogen: Deceleration in Alkali and Acceleration in Acid Conditions

Supramolecular catalysis based on host–guest interactions has aroused much attention in past decades. Among the various strategies, modulation of the reactivity of key intermediates is an effective strategy to achieve high-efficiency supramolecular catalysis. Here, we report that by utilizing the host–guest interaction of cucurbit[7]­uril (CB[7]), the reactivity of anionic enolate and cationic oxonium, the intermediates of H/D exchange of the α-carbonyl hydrogen in alkali and acid conditions, respectively, could be modulated effectively. On one hand, in alkaline conditions, both the electrostatic effect and the steric hindrance effect of CB[7] disfavored formation of the enolate anion intermediate. On the other hand, in acidic conditions, the oxonium was stabilized and the solvent effect was weakened by the electrostatic effect of CB[7]. As a result, the H/D exchange of 1-(4-acetylphenyl)-N,N,N-trimethylmethanaminium bromide is decelerated in alkaline and accelerated in acidic conditions. It is promising that the highly polar portals of CB­[n] molecules together with their well-defined host–guest chemistry may be applied to modulate the reactivity of other kinds of ionic intermediates in an effective and convenient way, thus enriching the toolkit of supramolecular catalysis