NMR Studies of Block Copolymer-Based Supramolecules in Solution

Chang, Boyce S.; Ma, Le; He, Mengdi; Xu, Ting

doi:10.1021/acsmacrolett.0c00434

NMR Studies of Block Copolymer-Based Supramolecules in Solution

Journal Article · Tue Jul 07 00:00:00 EDT 2020 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.0c00434· OSTI ID:1783111

^[1]; Ma, Le ^[1]; He, Mengdi ^[1]; ^[2]

Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Hierarchical assemblies from block copolymer (BCP)-based supramolecules have shown immense potential as programmable materials owing to their versatility for incorporating functional molecules and provide access to arrays of hierarchical structures. However, there remains a knowledge gap on the formation of the supramolecule in solution. Here, we applied NMR techniques to investigate the solution-phase behavior of the most studied supramolecular systems, polystyrene-block-poly(4-vinylpyridine)(3-pentadecylphenol) (PS-b-P4VP(PDP)_r). The results show that the supramolecule likely adopts a coil-comb conformation, despite the small molecule's (PDP) rapid exchange between the bonded and free states. The exchange rate (>10⁴ s^-1) exceeds the NMR time scale at the frequency of interest. The supramolecules form under dilute conditions (~2 vol %) and are attributed to the enthalpic gain of the hydrogen bonding between the PDP and 4VP. As the solute concentration increases (>10 vol %), the supramolecule forms micelle-like aggregates with PDP accumulated within the comb-block's pervaded volume based on analysis of the apparent molecular weight, viscosity, and chain dynamics. Overall, this work sheds light on the long-standing question regarding the evolution of the constituents in the BCP-based supramolecule in solution and provides valuable guidance toward their solution-based processing and morphological control.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1783111

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 7 Vol. 9; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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NMR Studies of Block Copolymer-Based Supramolecules in Solution

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