Peculiar Aqueous Solubility Trend in Cucurbiturils Unraveled by Atomistic Simulations

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dc.contributor.authorMalaspina, Thaciana [UNIFESP]
dc.contributor.authorFileti, Eudes [UNIFESP]
dc.contributor.authorChaban, Vitaly V. [UNIFESP]
dc.date.accessioned2019-07-22T15:46:55Z
dc.date.available2019-07-22T15:46:55Z
dc.date.issued2016
dc.description.abstractCucurbiturils (CBs) compose a family of macrocycles whose elementary unit is glycouril (GLYC). CBs are of high interest in chemistry and biology due to their versatile applications, ranging from sensors to advanced drug-delivery systems. Here, we report a systematic hydration study of all currently known CBs by classical molecular dynamics simulations to understand their different aqueous solubilities, as revealed in the experiments. Water readily penetrates CBs, including the smallest CB, that is, CB[5]. The number of CB[n]-water hydrogen bonds can be assessed as 2 x n. The hydration enthalpies of the CBs were found to be significantly favorable, due to a number of strong hydrogen bonds with water. However, these enthalpy gains are not enough to compensate for an even larger entropic penalty due to modifying a. genuine bulk arrangement of water molecules. We found that the free energy of hydration moderately but uniformly increases with the number of GLYCs. Therefore, the better solubility of odd-numbered CBs is independent of the CB-water interactions, either an enthalpic or entropic contribution. The higher solubilities of CB[n]s with n = 5, 7, or 9 occur exclusively because of their amorphous solid states. Our results allow the prognosis of the aqueous solubilities of not-yet-synthesized CBs.en
dc.description.affiliationUniv Fed Sao Paulo, Inst Ciencia & Tecnol, BR-12247014 Sao Jose Dos Campos, SP, Brazil
dc.description.affiliationUnifespUniv Fed Sao Paulo, Inst Ciencia & Tecnol, BR-12247014 Sao Jose Dos Campos, SP, Brazil
dc.description.sourceWeb of Science
dc.description.sponsorshipCNPq
dc.description.sponsorshipCAPES
dc.description.sponsorshipFAPESP
dc.format.extent7511-7516
dc.identifierhttp://dx.doi.org/10.1021/acs.jpcb.6b05425
dc.identifier.citationJournal Of Physical Chemistry B. Washington, v. 120, n. 30, p. 7511-7516, 2016.
dc.identifier.doi10.1021/acs.jpcb.6b05425
dc.identifier.issn1520-6106
dc.identifier.urihttp://repositorio.unifesp.br/handle/11600/51175
dc.identifier.wosWOS:000381235800021
dc.language.isoeng
dc.publisherAmer Chemical Soc
dc.rightsAcesso aberto
dc.titlePeculiar Aqueous Solubility Trend in Cucurbiturils Unraveled by Atomistic Simulationsen
dc.typeArtigo
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