Uniform biodegradable fiber-like micelles and block comicelles via “living” crystallization-driven self-assembly of poly(L-lactide) block copolymers : the importance of reducing unimer self-nucleation via hydrogen bond disruption

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Uniform biodegradable fiber-like micelles and block comicelles via “living” crystallization-driven self-assembly of poly(L-lactide) block copolymers  : the importance of reducing unimer self-nucleation via hydrogen bond disruption. / He, Yunxiang; Eloi, Jean-Charles; Harniman, Robert L ; Richardson, Robert M.; Whittell, George R; Mathers, Robert T.; Dove, Andrew; O'Reilly, Rachel; Manners, Ian.

In: Journal of the American Chemical Society, Vol. 141, No. 48, 04.12.2019, p. 19088-19098.

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@article{a01d77e916004f45b299a7acb4222c7d,
title = "Uniform biodegradable fiber-like micelles and block comicelles via “living” crystallization-driven self-assembly of poly(L-lactide) block copolymers : the importance of reducing unimer self-nucleation via hydrogen bond disruption",
abstract = "Fiber-like micelles based on biodegradable and biocompatible polymers exhibit considerable promise for applications in nanomedicine, but until recently no convenient methods were available to prepare samples with uniform and controllable dimensions and spatial control of functionality. “Living” crystallization-driven self-assembly (CDSA) is a seeded growth method of growing importance for the preparation of uniform 1D and 2D core–shell nanoparticles from a range of crystallizable polymeric amphiphiles. However, in the case of poly(L-lactide) (PLLA), arguably the most widely utilized biodegradable polymer as the crystallizable core-forming block, the controlled formation of uniform fiber-like structures over a substantial range of lengths by “living” CDSA has been a major challenge. Herein, we demonstrate that via simple modulation of the solvent conditions via the addition of trifluoroethanol (TFE), DMSO, DMF and acetone, uniform fiber-like nanoparticles from PLLA diblock copolymers with controlled lengths up to 1 μm can be prepared. The probable mechanism involves improved unimer solvation by a reduction of hydrogen bonding interactions among PLLA chains. We provide evidence that this minimizes undesirable unimer aggregation which otherwise favors self-nucleation that competes with epitaxial crystallization from seed termini. This approach has also allowed the formation of well-defined segmented block comicelles with PLLA cores via the sequential seeded-growth of PLLA block copolymers with different corona-forming blocks.",
keywords = "living CDSA, crystallisation driven self assembly, copolymers, fiber-like micelles, seeded growth, amphiphilic block copolymers",
author = "Yunxiang He and Jean-Charles Eloi and Harniman, {Robert L} and Richardson, {Robert M.} and Whittell, {George R} and Mathers, {Robert T.} and Andrew Dove and Rachel O'Reilly and Ian Manners",
year = "2019",
month = dec,
day = "4",
doi = "10.1021/jacs.9b09885",
language = "English",
volume = "141",
pages = "19088--19098",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "48",

}

RIS

TY - JOUR

T1 - Uniform biodegradable fiber-like micelles and block comicelles via “living” crystallization-driven self-assembly of poly(L-lactide) block copolymers 

T2 - the importance of reducing unimer self-nucleation via hydrogen bond disruption

AU - He, Yunxiang

AU - Eloi, Jean-Charles

AU - Harniman, Robert L

AU - Richardson, Robert M.

AU - Whittell, George R

AU - Mathers, Robert T.

AU - Dove, Andrew

AU - O'Reilly, Rachel

AU - Manners, Ian

PY - 2019/12/4

Y1 - 2019/12/4

N2 - Fiber-like micelles based on biodegradable and biocompatible polymers exhibit considerable promise for applications in nanomedicine, but until recently no convenient methods were available to prepare samples with uniform and controllable dimensions and spatial control of functionality. “Living” crystallization-driven self-assembly (CDSA) is a seeded growth method of growing importance for the preparation of uniform 1D and 2D core–shell nanoparticles from a range of crystallizable polymeric amphiphiles. However, in the case of poly(L-lactide) (PLLA), arguably the most widely utilized biodegradable polymer as the crystallizable core-forming block, the controlled formation of uniform fiber-like structures over a substantial range of lengths by “living” CDSA has been a major challenge. Herein, we demonstrate that via simple modulation of the solvent conditions via the addition of trifluoroethanol (TFE), DMSO, DMF and acetone, uniform fiber-like nanoparticles from PLLA diblock copolymers with controlled lengths up to 1 μm can be prepared. The probable mechanism involves improved unimer solvation by a reduction of hydrogen bonding interactions among PLLA chains. We provide evidence that this minimizes undesirable unimer aggregation which otherwise favors self-nucleation that competes with epitaxial crystallization from seed termini. This approach has also allowed the formation of well-defined segmented block comicelles with PLLA cores via the sequential seeded-growth of PLLA block copolymers with different corona-forming blocks.

AB - Fiber-like micelles based on biodegradable and biocompatible polymers exhibit considerable promise for applications in nanomedicine, but until recently no convenient methods were available to prepare samples with uniform and controllable dimensions and spatial control of functionality. “Living” crystallization-driven self-assembly (CDSA) is a seeded growth method of growing importance for the preparation of uniform 1D and 2D core–shell nanoparticles from a range of crystallizable polymeric amphiphiles. However, in the case of poly(L-lactide) (PLLA), arguably the most widely utilized biodegradable polymer as the crystallizable core-forming block, the controlled formation of uniform fiber-like structures over a substantial range of lengths by “living” CDSA has been a major challenge. Herein, we demonstrate that via simple modulation of the solvent conditions via the addition of trifluoroethanol (TFE), DMSO, DMF and acetone, uniform fiber-like nanoparticles from PLLA diblock copolymers with controlled lengths up to 1 μm can be prepared. The probable mechanism involves improved unimer solvation by a reduction of hydrogen bonding interactions among PLLA chains. We provide evidence that this minimizes undesirable unimer aggregation which otherwise favors self-nucleation that competes with epitaxial crystallization from seed termini. This approach has also allowed the formation of well-defined segmented block comicelles with PLLA cores via the sequential seeded-growth of PLLA block copolymers with different corona-forming blocks.

KW - living CDSA

KW - crystallisation driven self assembly

KW - copolymers

KW - fiber-like micelles

KW - seeded growth

KW - amphiphilic block copolymers

UR - http://www.scopus.com/inward/record.url?scp=85075451025&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b09885

DO - 10.1021/jacs.9b09885

M3 - Article

VL - 141

SP - 19088

EP - 19098

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 48

ER -