Mechanosensitive membrane probes: push-pull papillons

Heorhii V. Humeniuk; Giuseppe Licari; Eric Vauthey; Naomi Sakai; Stefan Matile

doi:10.1080/10610278.2019.1702193

Mechanosensitive membrane probes: push-pull papillons

Heorhii V. Humeniuk
, Giuseppe Licari
, Eric Vauthey
, Naomi Sakai
, Stefan Matile

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

6 Citations (Scopus)

Abstract

Design, synthesis and evaluation of push-pull N,N′-diphenyl-dihydrodibenzo[a,c]phenazines are reported. Consistent with theoretical predictions, donors and acceptors attached to the bent mechanophore are shown to shift absorption maxima to either red or blue, depending on their positioning in the chromophore. Redshifted excitation of push-pull fluorophores is reflected in redshifted emission of both bent and planar excited states. The intensity ratios of the dual emission in more and less polar solvents imply that excited-state (ES) planarization decelerates with increasing fluorophore macrodipole, presumably due to attraction between the wings of closed papillons. ES planarization of highly polarisable papillons is not observed in lipid bilayer membranes. All push-pull papillon amphiphiles excel with aggregation-induced emission (AIE) from bent ES as micelles in water and mechanosensitivity in viscous solvents. They are not solvatochromic and only weakly fluorescent (QY < 4%).

Original language	English
Pages (from-to)	106-111
Number of pages	6
Journal	Supramolecular Chemistry
Volume	32
Issue number	2
DOIs	https://doi.org/10.1080/10610278.2019.1702193
Publication status	Published - 1 Feb 2020
Externally published	Yes

Bibliographical note

Funding Information:
We thank the NMR and the MS platforms for services, and the University of Geneva, the Swiss National Centre of Competence in Research (NCCR) Chemical Biology, the NCCR Molecular Systems Engineering and the Swiss NSF for financial support.

Funding Information:
This work was supported by the University of Geneva; Swiss NSF [200020 175486]; National Centre of Competence in Research (NCCR) [Chemical Biology, Molecular Systems Engineering]. We thank the NMR and the MS platforms for services, and the University of Geneva, the Swiss National Centre of Competence in Research (NCCR) Chemical Biology, the NCCR Molecular Systems Engineering and the Swiss NSF for financial support.

Publisher Copyright:
© 2019, © 2019 Informa UK Limited, trading as Taylor & Francis Group.

Funding

We thank the NMR and the MS platforms for services, and the University of Geneva, the Swiss National Centre of Competence in Research (NCCR) Chemical Biology, the NCCR Molecular Systems Engineering and the Swiss NSF for financial support. This work was supported by the University of Geneva; Swiss NSF [200020 175486]; National Centre of Competence in Research (NCCR) [Chemical Biology, Molecular Systems Engineering]. We thank the NMR and the MS platforms for services, and the University of Geneva, the Swiss National Centre of Competence in Research (NCCR) Chemical Biology, the NCCR Molecular Systems Engineering and the Swiss NSF for financial support.

Keywords

bent aromatics
fluorescent probes
lipid bilayer membranes
Mechanochemistry
push–pull systems

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10.1080/10610278.2019.1702193

Cite this

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title = "Mechanosensitive membrane probes: push-pull papillons",

abstract = "Design, synthesis and evaluation of push-pull N,N′-diphenyl-dihydrodibenzo[a,c]phenazines are reported. Consistent with theoretical predictions, donors and acceptors attached to the bent mechanophore are shown to shift absorption maxima to either red or blue, depending on their positioning in the chromophore. Redshifted excitation of push-pull fluorophores is reflected in redshifted emission of both bent and planar excited states. The intensity ratios of the dual emission in more and less polar solvents imply that excited-state (ES) planarization decelerates with increasing fluorophore macrodipole, presumably due to attraction between the wings of closed papillons. ES planarization of highly polarisable papillons is not observed in lipid bilayer membranes. All push-pull papillon amphiphiles excel with aggregation-induced emission (AIE) from bent ES as micelles in water and mechanosensitivity in viscous solvents. They are not solvatochromic and only weakly fluorescent (QY < 4\%).",

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AU - Matile, Stefan

N1 - Funding Information: We thank the NMR and the MS platforms for services, and the University of Geneva, the Swiss National Centre of Competence in Research (NCCR) Chemical Biology, the NCCR Molecular Systems Engineering and the Swiss NSF for financial support. Funding Information: This work was supported by the University of Geneva; Swiss NSF [200020 175486]; National Centre of Competence in Research (NCCR) [Chemical Biology, Molecular Systems Engineering]. We thank the NMR and the MS platforms for services, and the University of Geneva, the Swiss National Centre of Competence in Research (NCCR) Chemical Biology, the NCCR Molecular Systems Engineering and the Swiss NSF for financial support. Publisher Copyright: © 2019, © 2019 Informa UK Limited, trading as Taylor & Francis Group.

PY - 2020/2/1

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N2 - Design, synthesis and evaluation of push-pull N,N′-diphenyl-dihydrodibenzo[a,c]phenazines are reported. Consistent with theoretical predictions, donors and acceptors attached to the bent mechanophore are shown to shift absorption maxima to either red or blue, depending on their positioning in the chromophore. Redshifted excitation of push-pull fluorophores is reflected in redshifted emission of both bent and planar excited states. The intensity ratios of the dual emission in more and less polar solvents imply that excited-state (ES) planarization decelerates with increasing fluorophore macrodipole, presumably due to attraction between the wings of closed papillons. ES planarization of highly polarisable papillons is not observed in lipid bilayer membranes. All push-pull papillon amphiphiles excel with aggregation-induced emission (AIE) from bent ES as micelles in water and mechanosensitivity in viscous solvents. They are not solvatochromic and only weakly fluorescent (QY < 4%).

AB - Design, synthesis and evaluation of push-pull N,N′-diphenyl-dihydrodibenzo[a,c]phenazines are reported. Consistent with theoretical predictions, donors and acceptors attached to the bent mechanophore are shown to shift absorption maxima to either red or blue, depending on their positioning in the chromophore. Redshifted excitation of push-pull fluorophores is reflected in redshifted emission of both bent and planar excited states. The intensity ratios of the dual emission in more and less polar solvents imply that excited-state (ES) planarization decelerates with increasing fluorophore macrodipole, presumably due to attraction between the wings of closed papillons. ES planarization of highly polarisable papillons is not observed in lipid bilayer membranes. All push-pull papillon amphiphiles excel with aggregation-induced emission (AIE) from bent ES as micelles in water and mechanosensitivity in viscous solvents. They are not solvatochromic and only weakly fluorescent (QY < 4%).

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KW - push–pull systems

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Mechanosensitive membrane probes: push-pull papillons

Abstract

Bibliographical note

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Keywords

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