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Review
. 2023 Jan 20:11:1119240.
doi: 10.3389/fchem.2023.1119240. eCollection 2023.

The aqueous supramolecular chemistry of crown ethers

Zhenhui Qi  1 , Yao Qin  1 , Jijun Wang  1 , Maojin Zhao  1 , Zhuo Yu  1 , Qiangqiang Xu  1 , Hongqi Nie  2 , Qilong Yan  2 , Yan Ge  1
Affiliations
Review

The aqueous supramolecular chemistry of crown ethers

Zhenhui Qi et al. Front Chem. .

Abstract

This mini-review summarizes the seminal exploration of aqueous supramolecular chemistry of crown ether macrocycles. In history, most research of crown ethers were focusing on their supramolecular chemistry in organic phase or in gas phase. In sharp contrast, the recent research evidently reveal that crown ethers are very suitable for studying abroad range of the properties and applications of water interactions, from: high water-solubility, control of Hofmeister series, "structural water", and supramolecular adhesives. Key studies revealing more details about the properties of water and aqueous solutions are highlighted.

Keywords: crown ethers; hofmeister series; responsive materials; selenium; structural water.

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Conflict of interest statement

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Figures

FIGURE 1
FIGURE 1
Comparison of the water-solubility of CEs and their derivatives with α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin and cucurbit[7]urils. Adapted and reproduced from Dong et al. (2017a), Jin et al. (2019), Xu et al. (2021) with kind permission from American Chemical Society and Elsevier.
FIGURE 2
FIGURE 2
(A) The redox-controlled hydration of CE for design macrocyclic amphiphiles. (A1) the chemical structure of bolaamphiphile C7SeBola; (A2) C7SeBola exhibited rapid LCST behavior in water, (A3) The highly reversible LCST transition processes, (A4) turbid-to-clear and clear-to-turbid transitions can be controlled in an “ON-OFF” manner. (B) Hofmeister series reversal behavior. (B1) Hofmeister series reversal of anions for lysozyme reported by Cremer et al. The apparent association constants of anionic-lysozyme interaction for ClO4 −, SCN−, I−, NO3 −, Br− and Cl− are 0.10, 0.10, 0.09, 0.10, 0.18 and 0.12 M−1, respectively. (B2) Hofmeister series reversal of cation for a triple-CE-molecule (TC7). The inverse Hofmeister series at low salt concentration regimes should be the cation–solute interaction at wok. The charge density is initially dominant and then decays due to the increase of the ionic radius, then the enhanced “size-fitting” induced molecular recognition dominants the system. (B3) Ring-open counterpart (TC7-O) showed no Hofmeister series reversal. (C) TC7 generates structural water for fabricating supramolecular adhesive material. (C1) The dependence of DC conductivity σdc versus 1/T for TC7 n-H materials with different water content. (C2) Dielectric loss versus frequency for TC7 n-H materials with different water content at a temperature of −100°C; (C3) Averaged hydrogen-bond strengths (EHB) of CE-water systems with different number of water molecules (N water) as obtained from the density functional theory (DFT) calculations; (C4) Application of TC7 10-H 1 materials as supramolecular adhesive materials. Adapted and reproduced from Xu et al. (2021), Qi et al. (2018), Zhang and Cremer (2009), Dong et al. (2017b) with kind permission by the Elsevier, National Academy of Science, Wiley-VCH and American Association for the Advancement of Science.
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References

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