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

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. In conclusion, 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]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Menlo Park, CA (United States)
Publication Date:
Grant/Contract Number:
DMR-1407658; AC02-76SF00515
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
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dithiolane crosslinking; micelle aggregation; nanocubes; self-assembly; triblock copolymers
OSTI Identifier:
1439109
Alternate Identifier(s):
OSTI ID: 1410360

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., Web. doi:10.1002/anie.201709564.
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. doi:10.1002/anie.201709564.
Margulis, Katherine, Zhang, Xiangyi, Joubert, Lydia -Marie, Bruening, Karsten, Tassone, Christopher J., Zare, Richard N., and Waymouth, Robert M.. 2017. "Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers". United States. doi:10.1002/anie.201709564. https://www.osti.gov/servlets/purl/1439109.
@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 = {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. In conclusion, 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 = {2017},
month = {10}
}

Works referenced in this record:

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008
  • Xia, Younan; Xiong, Yujie; Lim, Byungkwon
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The effect of particle design on cellular internalization pathways
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