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Title: Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers

Abstract

Abstract Template‐free fabrication of non‐spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self‐assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self‐assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solid cubic particle formation. An approach for preserving the structures of these cubes in water by thiol‐ or photo‐induced crosslinking was developed. The ability to solubilize a model hydrophobic drug, curcumin, was also explored.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1439109
Alternate Identifier(s):
OSTI ID: 1410360
Grant/Contract Number:  
DMR-1407658; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 51; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dithiolane crosslinking; micelle aggregation; nanocubes; self-assembly; triblock copolymers

Citation Formats

Margulis, Katherine, Zhang, Xiangyi, Joubert, Lydia -Marie, Bruening, Karsten, Tassone, Christopher J., Zare, Richard N., and Waymouth, Robert M. Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers. United States: N. p., 2017. Web. doi:10.1002/anie.201709564.
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Margulis, Katherine, Zhang, Xiangyi, Joubert, Lydia -Marie, Bruening, Karsten, Tassone, Christopher J., Zare, Richard N., & Waymouth, Robert M. Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers. United States. https://doi.org/10.1002/anie.201709564
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Margulis, Katherine, Zhang, Xiangyi, Joubert, Lydia -Marie, Bruening, Karsten, Tassone, Christopher J., Zare, Richard N., and Waymouth, Robert M. Fri . "Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers". United States. https://doi.org/10.1002/anie.201709564. https://www.osti.gov/servlets/purl/1439109.
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@article{osti_1439109,
title = {Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers},
author = {Margulis, Katherine and Zhang, Xiangyi and Joubert, Lydia -Marie and Bruening, Karsten and Tassone, Christopher J. and Zare, Richard N. and Waymouth, Robert M.},
abstractNote = {Abstract Template‐free fabrication of non‐spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self‐assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self‐assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solid cubic particle formation. An approach for preserving the structures of these cubes in water by thiol‐ or photo‐induced crosslinking was developed. The ability to solubilize a model hydrophobic drug, curcumin, was also explored.},
doi = {10.1002/anie.201709564},
journal = {Angewandte Chemie (International Edition)},
number = 51,
volume = 56,
place = {United States},
year = {Fri Oct 27 00:00:00 EDT 2017},
month = {Fri Oct 27 00:00:00 EDT 2017}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/anie.201709564
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Cited by: 23 works
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Figures / Tables:

Figure 1 Figure 1: Self-assembly of dithiolane-containing triblock copolymers in water.
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    Works referencing / citing this record:

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    Reduction-Triggered Transformation of Disulfide-Containing Micelles at Chemically Tunable Rates
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    • DOI: 10.1002/anie.201802909
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