2D and 3D Self-Assembly of Fluorine-Free Pillar-[5]-Arenes and Perfluorinated Diacids at All-Aqueous Interfaces

Lawrence W. Honaker; Tu Nan Gao; Kelsey R. de Graaf; Tessa V.M. Bogaardt; Pim Vink; Tobias Stürzer; Gabriele Kociok-Köhn; Han Zuilhof; Fedor M. Miloserdov; Siddharth Deshpande

doi:10.1002/advs.202401807

2D and 3D Self-Assembly of Fluorine-Free Pillar-[5]-Arenes and Perfluorinated Diacids at All-Aqueous Interfaces

Lawrence W. Honaker, Tu Nan Gao, Kelsey R. de Graaf, Tessa V.M. Bogaardt, Pim Vink, Tobias Stürzer, Gabriele Kociok-Köhn, Han Zuilhof, Fedor M. Miloserdov, Siddharth Deshpande

Research output: Contribution to journal › Article › peer-review

3 Citations (SciVal)

Abstract

The interaction of perfluorinated molecules, also known as “forever chemicals” due to their pervasiveness, with their environment remains an important yet poorly understood topic. In this work, the self-assembly of perfluorinated molecules with multivalent hosts, pillar-[5]-arenes, is investigated. It is found that perfluoroalkyl diacids and pillar-[5]-arenes rapidly and strongly complex with each other at aqueous interfaces, forming solid interfacially templated films. Their complexation is shown to be driven primarily by fluorophilic aggregation and assisted by electrostatic interactions, as supported by the crystal structure of the complexes, and leads to the formation of quasi-2D phase-separated films. This self-assembly process can be further manipulated using aqueous two-phase system microdroplets, enabling the controlled formation of 3D micro-scaffolds.

Original language	English
Article number	2401807
Number of pages	10
Journal	Advanced Science
Volume	11
Issue number	29
Early online date	24 May 2024
DOIs	https://doi.org/10.1002/advs.202401807
Publication status	Published - 7 Aug 2024

Data Availability Statement

The data that support the ﬁndings of this study are available in the sup-plementary material of this article

Acknowledgements

The authors thank Mr. Thijmen van Voorthuizen and Mr. Jorik Schaap for performing some of the preliminary conceptual and experimental work associated with this project as well as Dr. Sylvia Brugman, Mr. Ketan Ganar, Mr. Chang Chen, Mr. Raoul Fix, Mr. Remco Fokkink, Mr. Robin van der Krieken, Dr. Sidharam Pujari, Prof. Mangala Srinivas, Ms. Alvja Mali, Dr. Guanna Li, Dr. Gert Salentijn, Ms. Si Huang, and Mr. Jelmer Vroom for technical assistance, providing materials, and fruitful discussions.

Funding

L.W.H. and S.D. acknowledge funding from the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (OCENW.XS21.4.116 and OCENW.XS22.3.069). T.N.G. acknowledges funding from the VLAG graduate school of Wageningen University.

Funders	Funder number
Nederlandse Organisatie voor Wetenschappelijk Onderzoek	OCENW.XS22.3.069, OCENW.XS21.4.116

Keywords

aqueous two-phase systems
electrospray
fluorophilic aggregation
microfluidics
PFAS
pillar-[5]-arenes
supramolecular assembly

ASJC Scopus subject areas

Medicine (miscellaneous)
General Chemical Engineering
General Materials Science
Biochemistry, Genetics and Molecular Biology (miscellaneous)
General Engineering
General Physics and Astronomy

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10.1002/advs.202401807Licence: CC BY

Cite this

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title = "2D and 3D Self-Assembly of Fluorine-Free Pillar-[5]-Arenes and Perfluorinated Diacids at All-Aqueous Interfaces",

abstract = "The interaction of perfluorinated molecules, also known as “forever chemicals” due to their pervasiveness, with their environment remains an important yet poorly understood topic. In this work, the self-assembly of perfluorinated molecules with multivalent hosts, pillar-[5]-arenes, is investigated. It is found that perfluoroalkyl diacids and pillar-[5]-arenes rapidly and strongly complex with each other at aqueous interfaces, forming solid interfacially templated films. Their complexation is shown to be driven primarily by fluorophilic aggregation and assisted by electrostatic interactions, as supported by the crystal structure of the complexes, and leads to the formation of quasi-2D phase-separated films. This self-assembly process can be further manipulated using aqueous two-phase system microdroplets, enabling the controlled formation of 3D micro-scaffolds.",

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AU - Gao, Tu Nan

AU - de Graaf, Kelsey R.

AU - Bogaardt, Tessa V.M.

AU - Vink, Pim

AU - Stürzer, Tobias

AU - Kociok-Köhn, Gabriele

AU - Zuilhof, Han

AU - Miloserdov, Fedor M.

AU - Deshpande, Siddharth

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AB - The interaction of perfluorinated molecules, also known as “forever chemicals” due to their pervasiveness, with their environment remains an important yet poorly understood topic. In this work, the self-assembly of perfluorinated molecules with multivalent hosts, pillar-[5]-arenes, is investigated. It is found that perfluoroalkyl diacids and pillar-[5]-arenes rapidly and strongly complex with each other at aqueous interfaces, forming solid interfacially templated films. Their complexation is shown to be driven primarily by fluorophilic aggregation and assisted by electrostatic interactions, as supported by the crystal structure of the complexes, and leads to the formation of quasi-2D phase-separated films. This self-assembly process can be further manipulated using aqueous two-phase system microdroplets, enabling the controlled formation of 3D micro-scaffolds.

KW - aqueous two-phase systems

KW - electrospray

KW - fluorophilic aggregation

KW - microfluidics

KW - PFAS

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KW - supramolecular assembly

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2D and 3D Self-Assembly of Fluorine-Free Pillar-[5]-Arenes and Perfluorinated Diacids at All-Aqueous Interfaces

Abstract

Data Availability Statement

Acknowledgements

Funding

Keywords

ASJC Scopus subject areas

Access to Document

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