The rational regulation of the pK(a) of an ionizable group in a synthetic device could be achieved by controlling the entropy of the linker connecting the hydrogen bond forming domains. We demonstrate this by designing a set of pH-responsive synthetic DNA-based nanoswitches that share the same hydrogen bond forming domains but differ in the length of the linker. The observed acidic constant (pK(a)) of these pH-dependent nanoswitches is linearly dependent on the entropic cost associated with loop formation and is gradually shifted to more basic pH values when the length of the linker domain is reduced. Through mathematical modeling and thermodynamic characterization we demonstrate that the modulation of the observed pK(a) is due to a purely entropic contribution. This approach represents a very versatile strategy to rationally modulate the pK(a) of synthetic devices in a highly predictable and accurate way.

Mariottini, D., Idili, A., Nijenhuis, M., Ercolani, G., Ricci, F. (2019). Entropy-based rational modulation of the p Ka of a synthetic pH-dependent nanoswitch. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 141(29), 11367-11371 [10.1021/jacs.9b04168].

Entropy-based rational modulation of the p Ka of a synthetic pH-dependent nanoswitch

Mariottini D.;Idili A.;Ercolani G.;Ricci F.
2019-01-01

Abstract

The rational regulation of the pK(a) of an ionizable group in a synthetic device could be achieved by controlling the entropy of the linker connecting the hydrogen bond forming domains. We demonstrate this by designing a set of pH-responsive synthetic DNA-based nanoswitches that share the same hydrogen bond forming domains but differ in the length of the linker. The observed acidic constant (pK(a)) of these pH-dependent nanoswitches is linearly dependent on the entropic cost associated with loop formation and is gradually shifted to more basic pH values when the length of the linker domain is reduced. Through mathematical modeling and thermodynamic characterization we demonstrate that the modulation of the observed pK(a) is due to a purely entropic contribution. This approach represents a very versatile strategy to rationally modulate the pK(a) of synthetic devices in a highly predictable and accurate way.
2019
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/01 - CHIMICA ANALITICA
Settore CHIM/06 - CHIMICA ORGANICA
English
Con Impact Factor ISI
This work was supported by the European Research Council, ERC (project no. 336493, FR), by Associazione Italiana per la Ricerca sul Cancro, AIRC (project no. 21965, FR) and by the Italian Ministry of Health (project no. GR-2013-02356714).
Mariottini, D., Idili, A., Nijenhuis, M., Ercolani, G., Ricci, F. (2019). Entropy-based rational modulation of the p Ka of a synthetic pH-dependent nanoswitch. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 141(29), 11367-11371 [10.1021/jacs.9b04168].
Mariottini, D; Idili, A; Nijenhuis, Mad; Ercolani, G; Ricci, F
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/218989
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