Molecular design of crown ethers. 12. Complexation thermodynamics of 12- to 16-crown-4: thermodynamic origin of high lithium selectivity of 14-crown-4

Inoue, Yoshihisa; Hakushi, Tadao; Liu, Yu; Tong, Lin

doi:10.1021/jo00072a024

Cited by 36 publications

(27 citation statements)

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“…In contrast to the permeability results, 12C4-functionalized polynorbornene membranes consistently showed higher solubility for NaCl than LiCl. This suggests that Na + exhibits stronger affinity for 12C4 groups than Li + , which qualitatively agrees with binding-constant measurements in some solution-phase 12C4 systems in polar solvents (55).…”

Section: Resultssupporting

confidence: 87%

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Engineering Li/Na selectivity in 12-Crown-4–functionalized polymer membranes

Warnock

Sujanani

Zofchak

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

111

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Lithium is widely used in contemporary energy applications, but its isolation from natural reserves is plagued by time-consuming and costly processes. While polymer membranes could, in principle, circumvent these challenges by efficiently extracting lithium from aqueous solutions, they usually exhibit poor ion-specific selectivity. Toward this end, we have incorporated host–guest interactions into a tunable polynorbornene network by copolymerizing 1) 12-crown-4 ligands to impart ion selectivity, 2) poly(ethylene oxide) side chains to control water content, and 3) a crosslinker to form robust solids at room temperature. Single salt transport measurements indicate these materials exhibit unprecedented reverse permeability selectivity (∼2.3) for LiCl over NaCl—the highest documented to date for a dense, water-swollen polymer. As demonstrated by molecular dynamics simulations, this behavior originates from the ability of 12-crown-4 to bind Na+ ions more strongly than Li+ in an aqueous environment, which reduces Na+ mobility (relative to Li+) and offsets the increase in Na+ solubility due to binding with crown ethers. Under mixed salt conditions, 12-crown-4 functionalized membranes showed identical solubility selectivity relative to single salt conditions; however, the permeability and diffusivity selectivity of LiCl over NaCl decreased, presumably due to flux coupling. These results reveal insights for designing advanced membranes with solute-specific selectivity by utilizing host–guest interactions.

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Section: Resultssupporting

confidence: 87%

“…S14-S23). A complex between a crown ether and a cation (M + ) is typically depicted as the ion occupying the central cavity of the crown ether, which in the case of 12C4, corresponds to a cation coordinated with four oxygens (55,59,60). Another possibility is the formation of an M(12C4) 2…”

Section: Resultsmentioning

confidence: 99%

Engineering Li/Na selectivity in 12-Crown-4–functionalized polymer membranes

Warnock

Sujanani

Zofchak

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

111

View full text Add to dashboard Cite

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“…It is believed that the large slope, as shown in Figure 4, is caused by the rearrangement of the peripheral network of hydrogen bonds with the accompanying conformational changes in the skeleton [59]. It means, that only a fraction of the enthalpy effect, equal to the difference (1 − α), contributes to increasing the stability of the complex.…”

Section: Isothermal Titration Calorimetry (Itc)mentioning

confidence: 99%

Thermodynamic Studies of Interactions between Sertraline Hydrochloride and Randomly Methylated β-Cyclodextrin Molecules Supported by Circular Dichroism Spectroscopy and Molecular Docking Results

Belica-Pacha

Daśko

Buko

et al. 2021

IJMS

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The interaction between sertraline hydrochloride (SRT) and randomly methylated β-cyclodextrin (RMβCD) molecules have been investigated at 298.15 K under atmospheric pressure. The method used—Isothermal Titration Calorimetry (ITC) enabled to determine values of the thermodynamic functions like the enthalpy (ΔH), the entropy (ΔS) and the Gibbs free energy (ΔG) of binding for the examined system. Moreover, the stoichiometry coefficient of binding (n) and binding/association constant (K) value have been calculated from the experimental results. The obtained outcome was compared with the data from the literature for other non-ionic βCD derivatives interacting with SRT and the enthalpy-entropy compensation were observed and interpreted. Furthermore, the connection of RMβCD with SRT was characterized by circular dichroism spectroscopy (CD) and complexes of βCD derivatives with SRT were characterized through the computational studies with the use of molecular docking (MD).

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“…The interest arises from the high affinity of 12-crown-4 ether towards Li + ions. [6][7][8] Previous studies have revealed that lithium ions can intercalate or get strongly adsorbed onto the TiO 2 surface, inducing a shift of the semiconductor conduction band. [9][10][11] The nanoscopic effect of Li + at the nanoparticle surface has a macroscopic consequence, which is the improvement of the DSC current.…”

Section: Introductionmentioning

confidence: 99%