Control over Aspect Ratio and Polymer Spatial Distribution of 2D Platelets via Living Crystallization-Driven Self-Assembly

Tianlai Xia; Laihui Xiao; Kaiwen Sun; Julia Y. Rho; Yujie Xie; Sam J. Parkinson; Leire Sangroniz; Jian Zhang; Jiaping Lin; Alejandro J. Müller; Liang Gao; Andrew P. Dove; Rachel K. O’Reilly

doi:10.1021/acs.macromol.4c02496

Control over Aspect Ratio and Polymer Spatial Distribution of 2D Platelets via Living Crystallization-Driven Self-Assembly

Tianlai Xia
, Laihui Xiao
, Kaiwen Sun
, Julia Y. Rho
, Yujie Xie
, Sam J. Parkinson
, Leire Sangroniz
, Jian Zhang
, Jiaping Lin
, Alejandro J. Müller
, Liang Gao
, Andrew P. Dove
, Rachel K. O’Reilly

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

11 Citations (Scopus)

10 Downloads (Pure)

Abstract

The aspect ratios of nano- and micrometer-sized features in nature have evolved to enable specific characteristics that are finely tuned for optimizing strength, surface area, optics, and heat dissipation. Despite the importance of aspect ratios, precise control over the aspect ratios of anisotropic polymeric nanoparticles is challenging to achieve and the formation mechanisms by which they occur are not fully understood. In this study, using the crystallization-driven self-assembly (CDSA) process, we achieved two-dimensional (2D) platelets with precisely controlled aspect ratios through the rational compositional adjustment of various polycaprolactone (PCL)-based homopolymers (HP) and block copolymers (BCP). These polymer compositions exhibit distinct polymer crystallization rates, which allow for highly controlled aspect ratios and polymer spatial distribution in 2D platelets. Brownian dynamics (BD) simulations provided an in-depth understanding of the formation of 2D platelets. The BD simulations help us further confirm the nature of living epitaxial growth, simulate the structural order of polymer chains during the CDSA process, and demonstrate the influence of PCL length on the aspect ratio. Our work opens up new possibilities for a nuanced understanding of the interplay between polymer composition, crystallization rate, and morphology, providing a method for the controlled synthesis of 2D nanostructures.

Original language	English
Pages (from-to)	11210-11220
Number of pages	11
Journal	Macromolecules
Volume	57
Issue number	23
Early online date	29 Nov 2024
DOIs	https://doi.org/10.1021/acs.macromol.4c02496
Publication status	Published - 10 Dec 2024

Bibliographical note

Funding

T.X., J.Y.R., S.J.P., A.P.D., and R.K.O.R. thank the University of Birmingham for financial support. L.X. and J.Z. thank the China Scholarship Council for support. K.S., L.G., and J.L. thank the National Natural Science Foundation of China for financial support (22103025). Y.X. would like to thank the National Natural Science Foundation of China for financial support (22205133). L.S. and A.J.M. would like to acknowledge funding from the project MAT2017-83014-C2-1-P by MCIN/AEI/10.13039/501100011033 and by the Basque Government through grant IT1503-22.

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10.1021/acs.macromol.4c02496Licence: CC BY 4.0

xia-et-al-2024-control-over-aspect-ratio-and-polymer-spatial-distribution-of-2d-platelets-via-living-crystallization
Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/).
Final published version, 11.7 MBLicence: CC BY 4.0

Cite this

Xia, T., Xiao, L., Sun, K., Rho, J. Y., Xie, Y., Parkinson, S. J., Sangroniz, L., Zhang, J., Lin, J., Müller, A. J., Gao, L., Dove, A. P., & O’Reilly, R. K. (2024). Control over Aspect Ratio and Polymer Spatial Distribution of 2D Platelets via Living Crystallization-Driven Self-Assembly. Macromolecules, 57(23), 11210-11220. https://doi.org/10.1021/acs.macromol.4c02496

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abstract = "The aspect ratios of nano- and micrometer-sized features in nature have evolved to enable specific characteristics that are finely tuned for optimizing strength, surface area, optics, and heat dissipation. Despite the importance of aspect ratios, precise control over the aspect ratios of anisotropic polymeric nanoparticles is challenging to achieve and the formation mechanisms by which they occur are not fully understood. In this study, using the crystallization-driven self-assembly (CDSA) process, we achieved two-dimensional (2D) platelets with precisely controlled aspect ratios through the rational compositional adjustment of various polycaprolactone (PCL)-based homopolymers (HP) and block copolymers (BCP). These polymer compositions exhibit distinct polymer crystallization rates, which allow for highly controlled aspect ratios and polymer spatial distribution in 2D platelets. Brownian dynamics (BD) simulations provided an in-depth understanding of the formation of 2D platelets. The BD simulations help us further confirm the nature of living epitaxial growth, simulate the structural order of polymer chains during the CDSA process, and demonstrate the influence of PCL length on the aspect ratio. Our work opens up new possibilities for a nuanced understanding of the interplay between polymer composition, crystallization rate, and morphology, providing a method for the controlled synthesis of 2D nanostructures.",

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AU - Xie, Yujie

AU - Parkinson, Sam J.

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AU - Zhang, Jian

AU - Lin, Jiaping

AU - Müller, Alejandro J.

AU - Gao, Liang

AU - Dove, Andrew P.

AU - O’Reilly, Rachel K.

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N2 - The aspect ratios of nano- and micrometer-sized features in nature have evolved to enable specific characteristics that are finely tuned for optimizing strength, surface area, optics, and heat dissipation. Despite the importance of aspect ratios, precise control over the aspect ratios of anisotropic polymeric nanoparticles is challenging to achieve and the formation mechanisms by which they occur are not fully understood. In this study, using the crystallization-driven self-assembly (CDSA) process, we achieved two-dimensional (2D) platelets with precisely controlled aspect ratios through the rational compositional adjustment of various polycaprolactone (PCL)-based homopolymers (HP) and block copolymers (BCP). These polymer compositions exhibit distinct polymer crystallization rates, which allow for highly controlled aspect ratios and polymer spatial distribution in 2D platelets. Brownian dynamics (BD) simulations provided an in-depth understanding of the formation of 2D platelets. The BD simulations help us further confirm the nature of living epitaxial growth, simulate the structural order of polymer chains during the CDSA process, and demonstrate the influence of PCL length on the aspect ratio. Our work opens up new possibilities for a nuanced understanding of the interplay between polymer composition, crystallization rate, and morphology, providing a method for the controlled synthesis of 2D nanostructures.

AB - The aspect ratios of nano- and micrometer-sized features in nature have evolved to enable specific characteristics that are finely tuned for optimizing strength, surface area, optics, and heat dissipation. Despite the importance of aspect ratios, precise control over the aspect ratios of anisotropic polymeric nanoparticles is challenging to achieve and the formation mechanisms by which they occur are not fully understood. In this study, using the crystallization-driven self-assembly (CDSA) process, we achieved two-dimensional (2D) platelets with precisely controlled aspect ratios through the rational compositional adjustment of various polycaprolactone (PCL)-based homopolymers (HP) and block copolymers (BCP). These polymer compositions exhibit distinct polymer crystallization rates, which allow for highly controlled aspect ratios and polymer spatial distribution in 2D platelets. Brownian dynamics (BD) simulations provided an in-depth understanding of the formation of 2D platelets. The BD simulations help us further confirm the nature of living epitaxial growth, simulate the structural order of polymer chains during the CDSA process, and demonstrate the influence of PCL length on the aspect ratio. Our work opens up new possibilities for a nuanced understanding of the interplay between polymer composition, crystallization rate, and morphology, providing a method for the controlled synthesis of 2D nanostructures.

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Control over Aspect Ratio and Polymer Spatial Distribution of 2D Platelets via Living Crystallization-Driven Self-Assembly

Abstract

Bibliographical note

Funding

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