Dispersity within brushes plays a major role in determining their interfacial properties : the case of oligoxazoline-based graft polymers

Romio, Matteo; Grob, Benjamin; Trachsel, Lucca; Mattarei, Andrea; Morgese, Giulia; Ramakrishna, Shivaprakash N.; Niccolai, Francesca; Guazzelli, Elisa; Paradisi, Cristina; Martinelli, Elisa; Spencer, Nicholas D.; Benetti, Edmondo M.

doi:10.1021/jacs.1c08383

Please use this identifier to cite or link to this item: https://doi.org/10.21256/zhaw-28405

Publication type:	Article in scientific journal
Type of review:	Peer review (publication)
Title:	Dispersity within brushes plays a major role in determining their interfacial properties : the case of oligoxazoline-based graft polymers
Authors:	Romio, Matteo Grob, Benjamin Trachsel, Lucca Mattarei, Andrea Morgese, Giulia Ramakrishna, Shivaprakash N. Niccolai, Francesca Guazzelli, Elisa Paradisi, Cristina Martinelli, Elisa Spencer, Nicholas D. Benetti, Edmondo M.
et. al:	No
DOI:	10.1021/jacs.1c08383 10.21256/zhaw-28405
Published in:	Journal of the American Chemical Society
Volume(Issue):	143
Issue:	45
Page(s):	19067
Pages to:	19077
Issue Date:	5-Nov-2021
Publisher / Ed. Institution:	American Chemical Society
ISSN:	0002-7863 1520-5126
Language:	English
Subjects:	Adsorption; Gold; Physical and chemical properties; Polymer brushes; Polymers
Subject (DDC):	540: Chemistry 620.11: Engineering materials
Abstract:	Many synthetic polymers used to form polymer-brush films feature a main backbone with functional, oligomeric side chains. While the structure of such graft polymers mimics biomacromolecules to an extent, it lacks the monodispersity and structural purity present in nature. Here we demonstrate that side-chain heterogeneity within graft polymers significantly influences hydration and the occurrence of hydrophobic interactions in the subsequently formed brushes and consequently impacts fundamental interfacial properties. This is demonstrated for the case of poly(methacrylate)s (PMAs) presenting oligomeric side chains of different length (n) and dispersity. A precise tuning of brush structure was achieved by first synthesizing oligo(2-ethyl-2-oxazoline) methacrylates (OEOXMAs) by cationic ring-opening polymerization (CROP), subsequently purifying them into discrete macromonomers with distinct values of n by column chromatography, and finally obtaining poly[oligo(2-ethyl-2-oxazoline) methacrylate]s (POEOXMAs) by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Assembly of POEOXMA on Au surfaces yielded graft polymer brushes with different side-chain dispersities and lengths, whose properties were thoroughly investigated by a combination of variable angle spectroscopic ellipsometry (VASE), quartz crystal microbalance with dissipation (QCMD), and atomic force microscopy (AFM) methods. Side-chain dispersity, or dispersity within brushes, leads to assemblies that are more hydrated, less adhesive, and more lubricious and biopassive compared to analogous films obtained from graft polymers characterized by a homogeneous structure.
URI:	https://digitalcollection.zhaw.ch/handle/11475/28405
Fulltext version:	Published version
License (according to publishing contract):	CC BY 4.0: Attribution 4.0 International
Departement:	School of Engineering
Organisational Unit:	Institute of Materials and Process Engineering (IMPE)
Appears in collections:	Publikationen School of Engineering

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Romio, M., Grob, B., Trachsel, L., Mattarei, A., Morgese, G., Ramakrishna, S. N., Niccolai, F., Guazzelli, E., Paradisi, C., Martinelli, E., Spencer, N. D., & Benetti, E. M. (2021). Dispersity within brushes plays a major role in determining their interfacial properties : the case of oligoxazoline-based graft polymers. Journal of the American Chemical Society, 143(45), 19067–19077. https://doi.org/10.1021/jacs.1c08383

Romio, M. et al. (2021) ‘Dispersity within brushes plays a major role in determining their interfacial properties : the case of oligoxazoline-based graft polymers’, Journal of the American Chemical Society, 143(45), pp. 19067–19077. Available at: https://doi.org/10.1021/jacs.1c08383.

M. Romio et al., “Dispersity within brushes plays a major role in determining their interfacial properties : the case of oligoxazoline-based graft polymers,” Journal of the American Chemical Society, vol. 143, no. 45, pp. 19067–19077, Nov. 2021, doi: 10.1021/jacs.1c08383.

ROMIO, Matteo, Benjamin GROB, Lucca TRACHSEL, Andrea MATTAREI, Giulia MORGESE, Shivaprakash N. RAMAKRISHNA, Francesca NICCOLAI, Elisa GUAZZELLI, Cristina PARADISI, Elisa MARTINELLI, Nicholas D. SPENCER und Edmondo M. BENETTI, 2021. Dispersity within brushes plays a major role in determining their interfacial properties : the case of oligoxazoline-based graft polymers. Journal of the American Chemical Society. 5 November 2021. Bd. 143, Nr. 45, S. 19067–19077. DOI 10.1021/jacs.1c08383

Romio, Matteo, Benjamin Grob, Lucca Trachsel, Andrea Mattarei, Giulia Morgese, Shivaprakash N. Ramakrishna, Francesca Niccolai, et al. 2021. “Dispersity within Brushes Plays a Major Role in Determining Their Interfacial Properties : The Case of Oligoxazoline-Based Graft Polymers.” Journal of the American Chemical Society 143 (45): 19067–77. https://doi.org/10.1021/jacs.1c08383.

Romio, Matteo, et al. “Dispersity within Brushes Plays a Major Role in Determining Their Interfacial Properties : The Case of Oligoxazoline-Based Graft Polymers.” Journal of the American Chemical Society, vol. 143, no. 45, Nov. 2021, pp. 19067–77, https://doi.org/10.1021/jacs.1c08383.