Solution Structure and Scaling Laws of Cylindrical and Tapered Bottlebrush Polymers

Mohammed Alaboalirat; Samantha J. Scannelli; Hadi Rahmaninejad; Jan Michael Carrillo; Changwoo Do; John B. Matson; Rana Ashkar

doi:10.1021/acs.macromol.3c01412

Solution Structure and Scaling Laws of Cylindrical and Tapered Bottlebrush Polymers

Mohammed Alaboalirat, Samantha J. Scannelli, Hadi Rahmaninejad, Jan Michael Carrillo, Changwoo Do, John B. Matson, Rana Ashkar

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Bottlebrush polymers are a unique class of macromolecular architectures with a plethora of potential industrial and pharmaceutical applications that critically depend on the bottlebrush shape and dimensions. Here, a systematic series of 12 cylindrical and 12 cone-shaped (tapered) bottlebrush polymers with poly(tert-butyl acrylate) (PtBA) or polystyrene (PS) side chains were synthesized using the sequential addition of macromonomers ring-opening metathesis polymerization (SAM-ROMP) grafting-through method. Small-angle neutron scattering (SANS) studies on dilute solutions of the two types of bottlebrush polymers provided noninvasive characterization of their structural dimensions and chain conformations. Simulated SANS traces, generated using coarse-grained molecular dynamics simulations, reproduced the distinctive features observed in the experimental SANS signals and provided necessary validation for data modeling. The combined analysis of experimental and simulated SANS signals yielded key structural and conformational parameters, including the bottlebrush radius, length, and Kuhn length as well as the excluded volume parameter and the correlation length of the polymer side chains. Importantly, the obtained structural parameters followed well-defined scaling laws as a function of the backbone and side chain degrees of polymerization, as predicted by mean field theories. These findings provide clear experimental and computational evidence of the interdependence of structural and conformational properties in an important class of polymer architectures.

Original language	English
Pages (from-to)	9264-9276
Number of pages	13
Journal	Macromolecules
Volume	56
Issue number	22
DOIs	https://doi.org/10.1021/acs.macromol.3c01412
State	Published - Nov 28 2023

Funding

This work was supported by Saudi Aramco (fellowship to MAA), the Army Research Office (W911NF-19-1-0331), and a joint grant between the National Science Foundation and the Binational Science Foundation (DMR-2104602). A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This work benefited from the use of the SasView application, originally developed under NSF Award DMR-0520547. SasView also contains code developed with funding from the EU Horizon 2020 program under the SINE2020 project Grant No. 654000. Molecular dynamics simulations and computational aspects of this research were supported by the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. This research used resources at the Oak Ridge Leadership Computing Facility, which is supported by the Office of Science of the U.S. Department of Energy under Contract DE-AC05-00OR22725. This work was supported by Saudi Aramco (fellowship to MAA), the Army Research Office (W911NF-19-1-0331), and a joint grant between the National Science Foundation and the Binational Science Foundation (DMR-2104602). A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This work benefited from the use of the SasView application, originally developed under NSF Award DMR-0520547. SasView also contains code developed with funding from the EU Horizon 2020 program under the SINE2020 project Grant No. 654000. Molecular dynamics simulations and computational aspects of this research were supported by the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. This research used resources at the Oak Ridge Leadership Computing Facility, which is supported by the Office of Science of the U.S. Department of Energy under Contract DE-AC05-00OR22725.

Funders	Funder number
Center for Nanophase Materials Sciences
EU Horizon 2020 program	654000
National Science Foundation	DMR-0520547
U.S. Department of Energy	DE-AC05-00OR22725
Army Research Office	W911NF-19-1-0331
Office of Science
Oak Ridge National Laboratory
United States-Israel Binational Science Foundation	DMR-2104602
Saudi Arabian Oil Company

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title = "Solution Structure and Scaling Laws of Cylindrical and Tapered Bottlebrush Polymers",

abstract = "Bottlebrush polymers are a unique class of macromolecular architectures with a plethora of potential industrial and pharmaceutical applications that critically depend on the bottlebrush shape and dimensions. Here, a systematic series of 12 cylindrical and 12 cone-shaped (tapered) bottlebrush polymers with poly(tert-butyl acrylate) (PtBA) or polystyrene (PS) side chains were synthesized using the sequential addition of macromonomers ring-opening metathesis polymerization (SAM-ROMP) grafting-through method. Small-angle neutron scattering (SANS) studies on dilute solutions of the two types of bottlebrush polymers provided noninvasive characterization of their structural dimensions and chain conformations. Simulated SANS traces, generated using coarse-grained molecular dynamics simulations, reproduced the distinctive features observed in the experimental SANS signals and provided necessary validation for data modeling. The combined analysis of experimental and simulated SANS signals yielded key structural and conformational parameters, including the bottlebrush radius, length, and Kuhn length as well as the excluded volume parameter and the correlation length of the polymer side chains. Importantly, the obtained structural parameters followed well-defined scaling laws as a function of the backbone and side chain degrees of polymerization, as predicted by mean field theories. These findings provide clear experimental and computational evidence of the interdependence of structural and conformational properties in an important class of polymer architectures.",

author = "Mohammed Alaboalirat and Scannelli, {Samantha J.} and Hadi Rahmaninejad and Carrillo, {Jan Michael} and Changwoo Do and Matson, {John B.} and Rana Ashkar",

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AU - Alaboalirat, Mohammed

AU - Scannelli, Samantha J.

AU - Rahmaninejad, Hadi

AU - Carrillo, Jan Michael

AU - Do, Changwoo

AU - Matson, John B.

AU - Ashkar, Rana

PY - 2023/11/28

Y1 - 2023/11/28

N2 - Bottlebrush polymers are a unique class of macromolecular architectures with a plethora of potential industrial and pharmaceutical applications that critically depend on the bottlebrush shape and dimensions. Here, a systematic series of 12 cylindrical and 12 cone-shaped (tapered) bottlebrush polymers with poly(tert-butyl acrylate) (PtBA) or polystyrene (PS) side chains were synthesized using the sequential addition of macromonomers ring-opening metathesis polymerization (SAM-ROMP) grafting-through method. Small-angle neutron scattering (SANS) studies on dilute solutions of the two types of bottlebrush polymers provided noninvasive characterization of their structural dimensions and chain conformations. Simulated SANS traces, generated using coarse-grained molecular dynamics simulations, reproduced the distinctive features observed in the experimental SANS signals and provided necessary validation for data modeling. The combined analysis of experimental and simulated SANS signals yielded key structural and conformational parameters, including the bottlebrush radius, length, and Kuhn length as well as the excluded volume parameter and the correlation length of the polymer side chains. Importantly, the obtained structural parameters followed well-defined scaling laws as a function of the backbone and side chain degrees of polymerization, as predicted by mean field theories. These findings provide clear experimental and computational evidence of the interdependence of structural and conformational properties in an important class of polymer architectures.

AB - Bottlebrush polymers are a unique class of macromolecular architectures with a plethora of potential industrial and pharmaceutical applications that critically depend on the bottlebrush shape and dimensions. Here, a systematic series of 12 cylindrical and 12 cone-shaped (tapered) bottlebrush polymers with poly(tert-butyl acrylate) (PtBA) or polystyrene (PS) side chains were synthesized using the sequential addition of macromonomers ring-opening metathesis polymerization (SAM-ROMP) grafting-through method. Small-angle neutron scattering (SANS) studies on dilute solutions of the two types of bottlebrush polymers provided noninvasive characterization of their structural dimensions and chain conformations. Simulated SANS traces, generated using coarse-grained molecular dynamics simulations, reproduced the distinctive features observed in the experimental SANS signals and provided necessary validation for data modeling. The combined analysis of experimental and simulated SANS signals yielded key structural and conformational parameters, including the bottlebrush radius, length, and Kuhn length as well as the excluded volume parameter and the correlation length of the polymer side chains. Importantly, the obtained structural parameters followed well-defined scaling laws as a function of the backbone and side chain degrees of polymerization, as predicted by mean field theories. These findings provide clear experimental and computational evidence of the interdependence of structural and conformational properties in an important class of polymer architectures.

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Solution Structure and Scaling Laws of Cylindrical and Tapered Bottlebrush Polymers

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