Adaptive Response to Solvation in Flexible Molecules: Oligo Hydrates of 4-Hydroxy-2-butanone

Research output: Contribution to journalArticleResearchpeer review

Authors

  • Meng Li
  • Wenqin Li
  • Cristóbal Pérez
  • Alberto Lesarri
  • Jens Uwe Grabow

External Research Organisations

  • Universidad de Valladolid
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Details

Original languageEnglish
Article numbere202404447
Number of pages8
JournalAngewandte Chemie - International Edition
Volume63
Issue number29
Early online date8 May 2024
Publication statusPublished - 8 Jul 2024

Abstract

Structural changes induced by water play a pivotal role in chemistry and biology but remain challenging to predict, measure, and control at molecular level. Here we explore size-governed gas-phase water aggregation in the flexible molecule 4-hydroxy-2-butanone, modeling the conformational adaptability of flexible substrates to host water scaffolds and the preference for sequential droplet growth. The experiment was conducted using broadband rotational spectroscopy, rationalized with quantum chemical calculations. Two different isomers were observed experimentally from the di- to the pentahydrates (4-hydroxy-2-butanone-(H2O)n=2–5), including the 18O isotopologues for the di- and trihydrates. Interestingly, to accommodate water molecules effectively, the heavy atom skeleton of 4-hydroxy-2-butanone reshapes in every observed isomer and does not correspond to the stable conformer of the free monomer. All solvates initiate from the alcohol group (proton donor) but retain the carbonyl group as secondary binding point. The water scaffolds closely resemble those found in the pure water clusters, balancing between the capability of 4-hydroxy-2-butanone for steering the orientation and position of the water molecules and the ability of water to modulate the monomer's conformation. The present work thus provides an accurate molecular description on how torsionally flexible molecules dynamically adapt to water along progressing solvation.

Keywords

    Conformational behavior, Hydrogen bonding, Non-covalent interactions, Rotational spectroscopy, Water clusters

ASJC Scopus subject areas

Cite this

Adaptive Response to Solvation in Flexible Molecules: Oligo Hydrates of 4-Hydroxy-2-butanone. / Li, Meng; Li, Wenqin; Pérez, Cristóbal et al.
In: Angewandte Chemie - International Edition, Vol. 63, No. 29, e202404447, 08.07.2024.

Research output: Contribution to journalArticleResearchpeer review

Li M, Li W, Pérez C, Lesarri A, Grabow JU. Adaptive Response to Solvation in Flexible Molecules: Oligo Hydrates of 4-Hydroxy-2-butanone. Angewandte Chemie - International Edition. 2024 Jul 8;63(29):e202404447. Epub 2024 May 8. doi: 10.1002/anie.202404447
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AU - Li, Wenqin

AU - Pérez, Cristóbal

AU - Lesarri, Alberto

AU - Grabow, Jens Uwe

N1 - Publisher Copyright: © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

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