Catalytically Active Multicompartment Micelles
Abstract
This article presents the self-assembly behavior of multicompartment micelles (MCMs) in water into morphologies with multiple segregated domains and their use as supports for aqueous catalysis. A library of poly(norbornene)-based amphiphilic bottlebrush copolymers containing covalently attached l-proline in the hydrophobic, styrene, and pentafluorostyrene domains and a poly(ethylene glycol)-containing repeat unit as the hydrophilic block have been synthesized using ring-opening metathesis polymerization. Interaction parameter (χ) values between amphiphilic blocks were determined using a Flory–Huggins-based computational model. The morphologies of the MCMs are observed via cryogenic transmission electron microscopy and modeled using dissipative particle dynamic simulations. The catalytic activities of these MCM nanoreactors were systematically investigated using the aldol addition between 4-nitrobenzaldehyde and cyclohexanone in water as a model reaction. MCMs present an ideal environment for catalysis by providing control over water content and enhancing interactions between the catalytic sites and the aldehyde substrate, thereby forming the aldol product in high yields and selectivities that is otherwise not possible under aqueous conditions. Catalyst location, block ratio, and functionality have substantial influences on micelle morphology and, ultimately, catalytic efficiency. “Clover-like” and “core–shell” micelle morphologies displayed the best catalytic activity. Our MCM-based catalytic system expands the application of these nanostructures beyond selective storage ofmore »
- Authors:
-
[1]
- Molecular Design Institute and Department of Chemistry, New York University, New York, New York 10003, United States
- School of Materials Science and Engineering, Georgia Institute of Technology, 771 Ferst Dr., Atlanta, Georgia 30332-0245, United States
- Publication Date:
- Research Org.:
- Georgia Institute of Technology, Atlanta, GA (United States); New York Univ. (NYU), NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1888080
- Alternate Identifier(s):
- OSTI ID: 1894023; OSTI ID: 1894450
- Grant/Contract Number:
- FG02-03ER15459
- Resource Type:
- Published Article
- Journal Name:
- JACS Au
- Additional Journal Information:
- Journal Name: JACS Au Journal Volume: 2 Journal Issue: 10; Journal ID: ISSN 2691-3704
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; multicompartment micelles; bottlebrush copolymers; asymmetric aldol addition; supported catalysis; compartmentalization; amphiphilic bottlebrush copolymer; site location; micelle morphology; catalysts; copolymers; morphology; polymers; multicompartment micelles, amphiphilic bottlebrush copolymer, site isolation, asymmetric aldol addition, micelle morphology, supported catalysis
Citation Formats
Ahmed, Eman, Cho, Jinwon, Friedmann, Lulu, Jang, Seung Soon, and Weck, Marcus. Catalytically Active Multicompartment Micelles. United States: N. p., 2022.
Web. doi:10.1021/jacsau.2c00367.
Ahmed, Eman, Cho, Jinwon, Friedmann, Lulu, Jang, Seung Soon, & Weck, Marcus. Catalytically Active Multicompartment Micelles. United States. https://doi.org/10.1021/jacsau.2c00367
Ahmed, Eman, Cho, Jinwon, Friedmann, Lulu, Jang, Seung Soon, and Weck, Marcus. Mon .
"Catalytically Active Multicompartment Micelles". United States. https://doi.org/10.1021/jacsau.2c00367.
@article{osti_1888080,
title = {Catalytically Active Multicompartment Micelles},
author = {Ahmed, Eman and Cho, Jinwon and Friedmann, Lulu and Jang, Seung Soon and Weck, Marcus},
abstractNote = {This article presents the self-assembly behavior of multicompartment micelles (MCMs) in water into morphologies with multiple segregated domains and their use as supports for aqueous catalysis. A library of poly(norbornene)-based amphiphilic bottlebrush copolymers containing covalently attached l-proline in the hydrophobic, styrene, and pentafluorostyrene domains and a poly(ethylene glycol)-containing repeat unit as the hydrophilic block have been synthesized using ring-opening metathesis polymerization. Interaction parameter (χ) values between amphiphilic blocks were determined using a Flory–Huggins-based computational model. The morphologies of the MCMs are observed via cryogenic transmission electron microscopy and modeled using dissipative particle dynamic simulations. The catalytic activities of these MCM nanoreactors were systematically investigated using the aldol addition between 4-nitrobenzaldehyde and cyclohexanone in water as a model reaction. MCMs present an ideal environment for catalysis by providing control over water content and enhancing interactions between the catalytic sites and the aldehyde substrate, thereby forming the aldol product in high yields and selectivities that is otherwise not possible under aqueous conditions. Catalyst location, block ratio, and functionality have substantial influences on micelle morphology and, ultimately, catalytic efficiency. “Clover-like” and “core–shell” micelle morphologies displayed the best catalytic activity. Our MCM-based catalytic system expands the application of these nanostructures beyond selective storage of guest molecules and demonstrates the importance of micelle morphology on catalytic activity.},
doi = {10.1021/jacsau.2c00367},
journal = {JACS Au},
number = 10,
volume = 2,
place = {United States},
year = {Mon Sep 19 00:00:00 EDT 2022},
month = {Mon Sep 19 00:00:00 EDT 2022}
}
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