Recognition competes with hydration in anion-triggered monolayer formation of cyanostar supra-amphiphiles at aqueous interfaces

Yan, Liwei; Saha, Ankur; Zhao, Wei; Neal, Jennifer F.; Chen, Yusheng; Flood, Amar H.; Allen, Heather C.

doi:10.1039/D2SC00986B

Title: Recognition competes with hydration in anion-triggered monolayer formation of cyanostar supra-amphiphiles at aqueous interfaces

Journal Article · Wed Apr 13 00:00:00 EDT 2022 · Chemical Science

DOI:https://doi.org/10.1039/D2SC00986B· OSTI ID:1860264

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^[1]; Chen, Yusheng ^[2];

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Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, USA
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA

The triggered self-assembly of surfactants into organized layers at aqueous interfaces is important for creating adaptive nanosystems and understanding selective ion extraction. While these transformations require molecular recognition, the underlying driving forces are modified by the local environment in ways that are not well understood. Herein, we investigate the role of ion binding and ion hydration using cyanosurf, which is composed of the cyanostar macrocycle, and its binding to anions that are either size-matched or mis-matched and either weakly or highly hydrated. We utilize the supra-amphiphile concept where anion binding converts cyanosurf into a charged and amphiphilic complex triggering its self-organization into monolayers at the air–water interface. Initially, cyanosurf forms aggregates at the surface of a pure water solution. When the weakly hydrated and size-matched hexafluorophosphate (PF₆^-) and perchlorate (ClO₄^-) anions are added, the macrocycles form distinct monolayer architectures. Surface-pressure isotherms reveal significant reorganization of the surface-active molecules upon anion binding while infrared reflection absorption spectroscopy show the ion-bound complexes are well ordered at the interface. Vibrational sum frequency generation spectroscopy shows the water molecules in the interfacial region are highly ordered in response to the charged monolayer of cyanosurf complexes. Consistent with the importance of recognition, we find the smaller mis-matched chloride does not trigger the transformation. However, the size-matched phosphate (H₂PO₄^-) also does not trigger monolayer formation indicating hydration inhibits its interfacial binding. These studies reveal how anion-selective recognition and hydration both control the binding and thus the switching of a responsive molecular interface.

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Research Organization:: Indiana Univ., Bloomington, IN (United States); The Ohio State University, Columbus, OH (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0002728; SC0022099; FG02-09ER16068

OSTI ID:: 1860264

Alternate ID(s):: OSTI ID: 1904538

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 13 Journal Issue: 15; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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