Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors
Abstract
This contribution reports light responsive catalytic nanoreactors based on poly(2-oxazoline) diblock copolymers. The hydrophobic block of the copolymer is a random copolymer consisting of a spiropyran functionalized 2-oxazoline (SPOx) and 2-(but-3-yn-1-yl)-4,5-dihydrooxazole (ButynOx), while the hydrophilic block is based on 2-methyl-2-oxazoline (MeOx). The block copolymer is terminated with tris(2-aminoethyl) amine (TREN) that serves as catalyst in a Knoevenagel condensation. Four block copolymers with different ButynOx/SPOx and hydrophilic/hydrophobic ratios are synthesized and self-assembled through solvent exchange. Micelles and vesicles of various sizes are observed by TEM, which undergo morphological and size changes in response to irradiation with UV light. We hypothesize that these transformations in the nanostructures are caused by increases in the hydrophilicity of the hydrophobic block when spiropyran (SP) isomerizes to merocyanine (MC) in the presence of UV light. The reversible transition from micellar to vesicular nanoreactors resulted in increased reaction kinetics through improved substrate accessibility to the catalytic site, or termination of the catalytic reaction due to polymer precipitation. Furthermore, these nanoreactors present a promising platform towards photoregulating reaction outcomes based on changes in nanostructure morphology.
- Authors:
-
[1]
- New York University, NY (United States)
- Georgia Institute of Technology, Atlanta, GA (United States)
- Publication Date:
- Research Org.:
- Georgia Institute of Technology, Atlanta, GA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- NYU and GeorgiaTech
- OSTI Identifier:
- 1657170
- Alternate Identifier(s):
- OSTI ID: 1651215
- Grant/Contract Number:
- FG02-03ER15459
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 26; Journal Issue: 51; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Kuepfert, Michael, Qu, Peiyuan, Cohen, Aaron E., Hoyt, Caroline B., Jones, Christopher W., and Weck, Marcus. Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors. United States: N. p., 2020.
Web. doi:10.1002/chem.202000179.
Kuepfert, Michael, Qu, Peiyuan, Cohen, Aaron E., Hoyt, Caroline B., Jones, Christopher W., & Weck, Marcus. Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors. United States. https://doi.org/10.1002/chem.202000179
Kuepfert, Michael, Qu, Peiyuan, Cohen, Aaron E., Hoyt, Caroline B., Jones, Christopher W., and Weck, Marcus. Wed .
"Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors". United States. https://doi.org/10.1002/chem.202000179. https://www.osti.gov/servlets/purl/1657170.
@article{osti_1657170,
title = {Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors},
author = {Kuepfert, Michael and Qu, Peiyuan and Cohen, Aaron E. and Hoyt, Caroline B. and Jones, Christopher W. and Weck, Marcus},
abstractNote = {This contribution reports light responsive catalytic nanoreactors based on poly(2-oxazoline) diblock copolymers. The hydrophobic block of the copolymer is a random copolymer consisting of a spiropyran functionalized 2-oxazoline (SPOx) and 2-(but-3-yn-1-yl)-4,5-dihydrooxazole (ButynOx), while the hydrophilic block is based on 2-methyl-2-oxazoline (MeOx). The block copolymer is terminated with tris(2-aminoethyl) amine (TREN) that serves as catalyst in a Knoevenagel condensation. Four block copolymers with different ButynOx/SPOx and hydrophilic/hydrophobic ratios are synthesized and self-assembled through solvent exchange. Micelles and vesicles of various sizes are observed by TEM, which undergo morphological and size changes in response to irradiation with UV light. We hypothesize that these transformations in the nanostructures are caused by increases in the hydrophilicity of the hydrophobic block when spiropyran (SP) isomerizes to merocyanine (MC) in the presence of UV light. The reversible transition from micellar to vesicular nanoreactors resulted in increased reaction kinetics through improved substrate accessibility to the catalytic site, or termination of the catalytic reaction due to polymer precipitation. Furthermore, these nanoreactors present a promising platform towards photoregulating reaction outcomes based on changes in nanostructure morphology.},
doi = {10.1002/chem.202000179},
journal = {Chemistry - A European Journal},
number = 51,
volume = 26,
place = {United States},
year = {Wed Apr 08 00:00:00 EDT 2020},
month = {Wed Apr 08 00:00:00 EDT 2020}
}
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