Wavelength-selective light-responsive DASA-functionalized polymersome nanoreactors

Omar Rifaie-Graham, Sebastian Ulrich, Nikolas F.B. Galensowske, Sandor Balog, Mohamed Chami, Daniel Rentsch, James R. Hemmer, Javier Read De Alaniz, Luciano F. Boesel, Nico Bruns

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Transient activation of biochemical reactions by visible light and subsequent return to the inactive state in the absence of light is an essential feature of the biochemical processes in photoreceptor cells. To mimic such light-responsiveness with artificial nanosystems, polymersome nanoreactors were developed that can be switched on by visible light and self-revert fast in the dark at room temperature to their inactive state. Donor-acceptor Stenhouse adducts (DASAs), with their ability to isomerize upon irradiation with visible light, were employed to change the permeability of polymersome membranes by switching polarity from a nonpolar triene-enol form to a cyclopentenone with increased polarity. To this end, amphiphilic block copolymers containing poly(pentafluorophenyl methacrylate) in their hydrophobic block were synthesized by reversible addition-fragmentation chain-transfer (RAFT) radical polymerization and functionalized either with a DASA that is based on Meldrum's acid or with a novel fast-switching pyrazolone-based DASA. These polymers were self-assembled into vesicles. Release of hydrophilic payload could be triggered by light and stopped as soon as the light was turned off. The encapsulation of enzymes yielded photoresponsive nanoreactors that catalyzed reactions only if they were irradiated with light. A mixture of polymersome nanoreactors, one that switches in green light, the other switching in red light, permitted specific control of the individual reactions of a reaction cascade in one pot by irradiation with varied wavelengths, thus enabling light-controlled wavelength-selective catalysis. The DASA-based nanoreactors demonstrate the potential of DASAs to switch permeability of membranes and could find application to switch reactions on and off, on demand, e.g., in microfluidics or in drug delivery.

LanguageEnglish
Pages8027-8036
Number of pages10
JournalJournal of the American Chemical Society
Volume140
Issue number25
DOIs
Publication statusPublished - 27 Jun 2018

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Nanoreactors
Light
Wavelength
Switches
Permeability
Biochemical Phenomena
Irradiation
Nanosystems
Membranes
Methyl Green
Photoreceptor Cells
Microfluidics
Free radical polymerization
Catalysis
Drug delivery
Encapsulation
Polymerization
Block copolymers
Polymers
Chemical activation

Keywords

  • biochemistry
  • photoreceptors
  • drug delivery

Cite this

Rifaie-Graham, O., Ulrich, S., Galensowske, N. F. B., Balog, S., Chami, M., Rentsch, D., ... Bruns, N. (2018). Wavelength-selective light-responsive DASA-functionalized polymersome nanoreactors. Journal of the American Chemical Society , 140(25), 8027-8036. https://doi.org/10.1021/jacs.8b04511
Rifaie-Graham, Omar ; Ulrich, Sebastian ; Galensowske, Nikolas F.B. ; Balog, Sandor ; Chami, Mohamed ; Rentsch, Daniel ; Hemmer, James R. ; Read De Alaniz, Javier ; Boesel, Luciano F. ; Bruns, Nico. / Wavelength-selective light-responsive DASA-functionalized polymersome nanoreactors. In: Journal of the American Chemical Society . 2018 ; Vol. 140, No. 25. pp. 8027-8036.
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Rifaie-Graham, O, Ulrich, S, Galensowske, NFB, Balog, S, Chami, M, Rentsch, D, Hemmer, JR, Read De Alaniz, J, Boesel, LF & Bruns, N 2018, 'Wavelength-selective light-responsive DASA-functionalized polymersome nanoreactors' Journal of the American Chemical Society , vol. 140, no. 25, pp. 8027-8036. https://doi.org/10.1021/jacs.8b04511

Wavelength-selective light-responsive DASA-functionalized polymersome nanoreactors. / Rifaie-Graham, Omar; Ulrich, Sebastian; Galensowske, Nikolas F.B.; Balog, Sandor; Chami, Mohamed; Rentsch, Daniel; Hemmer, James R.; Read De Alaniz, Javier; Boesel, Luciano F.; Bruns, Nico.

In: Journal of the American Chemical Society , Vol. 140, No. 25, 27.06.2018, p. 8027-8036.

Research output: Contribution to journalArticle

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T1 - Wavelength-selective light-responsive DASA-functionalized polymersome nanoreactors

AU - Rifaie-Graham, Omar

AU - Ulrich, Sebastian

AU - Galensowske, Nikolas F.B.

AU - Balog, Sandor

AU - Chami, Mohamed

AU - Rentsch, Daniel

AU - Hemmer, James R.

AU - Read De Alaniz, Javier

AU - Boesel, Luciano F.

AU - Bruns, Nico

PY - 2018/6/27

Y1 - 2018/6/27

N2 - Transient activation of biochemical reactions by visible light and subsequent return to the inactive state in the absence of light is an essential feature of the biochemical processes in photoreceptor cells. To mimic such light-responsiveness with artificial nanosystems, polymersome nanoreactors were developed that can be switched on by visible light and self-revert fast in the dark at room temperature to their inactive state. Donor-acceptor Stenhouse adducts (DASAs), with their ability to isomerize upon irradiation with visible light, were employed to change the permeability of polymersome membranes by switching polarity from a nonpolar triene-enol form to a cyclopentenone with increased polarity. To this end, amphiphilic block copolymers containing poly(pentafluorophenyl methacrylate) in their hydrophobic block were synthesized by reversible addition-fragmentation chain-transfer (RAFT) radical polymerization and functionalized either with a DASA that is based on Meldrum's acid or with a novel fast-switching pyrazolone-based DASA. These polymers were self-assembled into vesicles. Release of hydrophilic payload could be triggered by light and stopped as soon as the light was turned off. The encapsulation of enzymes yielded photoresponsive nanoreactors that catalyzed reactions only if they were irradiated with light. A mixture of polymersome nanoreactors, one that switches in green light, the other switching in red light, permitted specific control of the individual reactions of a reaction cascade in one pot by irradiation with varied wavelengths, thus enabling light-controlled wavelength-selective catalysis. The DASA-based nanoreactors demonstrate the potential of DASAs to switch permeability of membranes and could find application to switch reactions on and off, on demand, e.g., in microfluidics or in drug delivery.

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Rifaie-Graham O, Ulrich S, Galensowske NFB, Balog S, Chami M, Rentsch D et al. Wavelength-selective light-responsive DASA-functionalized polymersome nanoreactors. Journal of the American Chemical Society . 2018 Jun 27;140(25):8027-8036. https://doi.org/10.1021/jacs.8b04511