Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors

Kuepfert, Michael; Qu, Peiyuan; Cohen, Aaron E.; Hoyt, Caroline B.; Jones, Christopher W.; Weck, Marcus

doi:10.1002/chem.202000179

Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors

Journal Article · Wed Apr 08 00:00:00 EDT 2020 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202000179· OSTI ID:1657170

Kuepfert, Michael ^[1]; Qu, Peiyuan ^[2]; Cohen, Aaron E. ^[2]; Hoyt, Caroline B. ^[3]; Jones, Christopher W. ^[3]; ^[2]

New York University, NY (United States); NYU
New York University, NY (United States)
Georgia Institute of Technology, Atlanta, GA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Georgia Institute of Technology, Atlanta, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Organization:: NYU and GeorgiaTech

Grant/Contract Number:: FG02-03ER15459

OSTI ID:: 1657170

Alternate ID(s):: OSTI ID: 1651215

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 51 Vol. 26; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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