Cation recognition controlled by protonation or chemical reduction: a computational study.
Phys Chem Chem Phys
; 25(22): 15518-15530, 2023 Jun 07.
Article
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| ID: mdl-37249495
ABSTRACT
To control biochemical processes, non-covalent interactions involving cations are activated by protons or electrons. In the present study, the bonding situation between (i) carboxylic acid or (ii) ferrocene-functionalized crown ether derivatives and cations (Li+, Na+ or K+) has been elucidated and, mainly, tuned by the substitution of hydrogen atoms by electron donor (-NH2) or acceptor (-NO2) groups. The deprotonation of the carboxyl groups improves the interaction with the cations through more favorable electrostatic Oâ¯cation interactions. Reducing the ferrocene structures favors cationic recognition supported by a less unfavorable ironâ¯cation binding. The receptors preferably interact with smaller cations because of more attractive electrostatic and orbital (σ or π) Oâ¯cation interactions. The presence of electron donor or acceptor groups in the carboxylic acid-functionalized crown ethers promotes less attractive interactions with the cations, mainly due to the less favorable electrostatic Oâ¯Na+ interactions. The -H â -NH2 substitution in the ferrocene framework favors the cationic recognition. It is based on the strengthening of the electrostatic and σ Oâ¯Na+ and H2Nâ¯Na+ bonds. The (i) absence of repulsive electrostatic ironâ¯cation interactions, or (ii) the presence of oxygen atoms with large electron density, ensures carboxylic acid-functionalized crown ethers have more favorable interactions with cations than ferrocene compounds. Therefore, this work has demonstrated how cation recognition can be improved by structural changes in carboxylic acid- or ferrocene-functionalized crown ethers and has shown that the carboxylic acid molecules appear to be better candidates for cation recognition than ferrocene derivatives.
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MEDLINE
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En
Revista:
Phys Chem Chem Phys
Asunto de la revista:
BIOFISICA
/
QUIMICA
Año:
2023
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Article
País de afiliación:
Brasil