Integrating redox-response in crown ethers by disulfide incorporation: a computational approach

Jayasree, Elambalassery G.; Sukumar, C.

doi:10.1007/s11224-021-01761-7

Cited by 2 publications

(2 citation statements)

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“…For example, thia-crown ethers have been employed as extractants for heavy metal ions [12][13][14][15]. Redox responses as well as catalytic functions of some thia-and selena-crown ethers were investigated [16][17][18][19][20][21]. Molecular assemblies through chalcogen bonding interactions have also been studied recently for telluro-ether heterocycles [22].…”

Section: Introductionmentioning

confidence: 99%

Controlling the Redox Catalytic Activity of a Cyclic Selenide Fused to 18-Crown-6 by the Conformational Transition Induced by Coordination to an Alkali Metal Ion

2023

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trans-3,4-Dihydroxyselenolane (DHS), a water-soluble cyclic selenide, exhibits selenoenzyme-like unique redox activities through reversible oxidation to the corresponding selenoxide. Previously, we demonstrated that DHS can be applied as an antioxidant against lipid peroxidation and a radioprotector by means of adequate modifications of the two hydroxy (OH) groups. Herein, we synthesized new DHS derivatives with a crown-ether ring fused to the OH groups (DHS-crown-n (n = 4 to 7), 1–4) and investigated their behaviors of complex formation with various alkali metal salts. According to the X-ray structure analysis, it was found that the two oxygen atoms of DHS change the directions from diaxial to diequatorial by complexation. The similar conformational transition was also observed in solution NMR experiments. The 1H NMR titration in CD3OD further confirmed that DHS-crown-6 (3) forms stable 1:1 complexes with KI, RbCl and CsCl, while it forms a 2:1 complex with KBPh4. The results suggested that the 1:1 complex (3·MX) exchanges the metal ion with metal-free 3 through the formation of the 2:1 complex. The redox catalytic activity of 3 was evaluated using a selenoenzyme model reaction between H2O2 and dithiothreitol. The activity was significantly reduced in the presence of KCl due to the complex formation. Thus, the redox catalytic activity of DHS could be controlled by the conformational transition induced by coordination to an alkali metal ion.

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Section: Introductionmentioning

confidence: 99%

Controlling the Redox Catalytic Activity of a Cyclic Selenide Fused to 18-Crown-6 by the Conformational Transition Induced by Coordination to an Alkali Metal Ion

2023

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“…More than 10,000 crown ether molecules have been reported to date [1][2][3][4][5] since the original discovery of crown ethers accidentally happened in 1967 by Pedersen. [6][7] However, the concept of crown ethers remains fascinating due to the potential applications of these molecules in various fields including (but not limited to) phase transfer catalysis, [8] ionsensing, [9,10] nuclear waste management, [11][12][13] and analytical methods. [14] The ability of crown ethers to recognize and trap different metal ions depending on the size of the macrocyclic ring, type of the donor atom (N, O, and S and thus hard-soft interactions), and polarity of the medium strengthened their utility in various aspects.…”

Section: Introductionmentioning

confidence: 99%

Organomagnesium Crown Ethers and Their Binding Affinities with Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ Ions – A Theoretical Study

et al. 2021

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Novel organomagnesium crown ether molecules have been computationally characterized using density functional theory (DFT). Monomer units of MgC 6 are used as building blocks. Isomers of MgC 6 H 2 have been extensively explored using both DFT and coupled-cluster methods in the past by some of us. It had been concluded that the seven-membered ring isomer, 1magnesacyclohept-4-en-2,6-diyne, was the thermodynamically most stable molecule at all levels. Thus, the latter has been used as the building block for designing new organomagne-sium crown ethers. Both alkali (Li + , Na + , and K + ) and alkalineearth (Be 2 + , Mg 2 + , and Ca 2 + ) metal ions selective complexes have been theoretically identified. Theoretical binding energies (~E at 0 K) and thermally corrected Gibbs free energies (~G at 298.15 K) have been computed for these molecules with MgC 6 -6-crown-2, MgC 6 -9-crown-3, and MgC 6 -12-crown-4 hosts. Higher binding affinity values obtained for Be 2 + indicate that these new crown ether molecules could effectively be used for Be 2 + encapsulation.

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Integrating redox-response in crown ethers by disulfide incorporation: a computational approach

Cited by 2 publications

References 45 publications

Controlling the Redox Catalytic Activity of a Cyclic Selenide Fused to 18-Crown-6 by the Conformational Transition Induced by Coordination to an Alkali Metal Ion

Controlling the Redox Catalytic Activity of a Cyclic Selenide Fused to 18-Crown-6 by the Conformational Transition Induced by Coordination to an Alkali Metal Ion

Organomagnesium Crown Ethers and Their Binding Affinities with Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ Ions – A Theoretical Study

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Integrating redox-response in crown ethers by disulfide incorporation: a computational approach

Cited by 2 publications

References 45 publications

Controlling the Redox Catalytic Activity of a Cyclic Selenide Fused to 18-Crown-6 by the Conformational Transition Induced by Coordination to an Alkali Metal Ion

Controlling the Redox Catalytic Activity of a Cyclic Selenide Fused to 18-Crown-6 by the Conformational Transition Induced by Coordination to an Alkali Metal Ion

Organomagnesium Crown Ethers and Their Binding Affinities with Li+, Na+, K+, Be2+, Mg2+, and Ca2+ Ions – A Theoretical Study

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Organomagnesium Crown Ethers and Their Binding Affinities with Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ Ions – A Theoretical Study