Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers
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. In conclusion, the ability to solubilize a model hydrophobic drug, curcumin, was also explored.
- Authors:
-
- Stanford Univ., Stanford, CA (United States)
- Stanford Univ., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., 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.
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
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.
@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}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Direct Fabrication and Harvesting of Monodisperse, Shape-Specific Nanobiomaterials
journal, July 2005
- Rolland, Jason P.; Maynor, Benjamin W.; Euliss, Larken E.
- Journal of the American Chemical Society, Vol. 127, Issue 28
Synthesis and phase transition energy storage capability of a cross-linked PEG/LACE copolymer
journal, January 2015
- Maimaiti, Halidan; Xu, Sumei; Aerken, Xuekelaiti
- RSC Advances, Vol. 5, Issue 26
Synthesis of Monodisperse Pt Nanocubes and Their Enhanced Catalysis for Oxygen Reduction
journal, June 2007
- Wang, Chao; Daimon, Hideo; Lee, Youngmin
- Journal of the American Chemical Society, Vol. 129, Issue 22
1,2-Dithiolane-Derived Dynamic, Covalent Materials: Cooperative Self-Assembly and Reversible Cross-Linking
journal, February 2017
- Zhang, Xiangyi; Waymouth, Robert M.
- Journal of the American Chemical Society, Vol. 139, Issue 10
Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly
journal, February 2017
- Boott, Charlotte E.; Gwyther, Jessica; Harniman, Robert L.
- Nature Chemistry, Vol. 9, Issue 8
Nanostructure in block copolymer solutions: Rheology and small-angle neutron scattering
journal, December 2004
- Habas, Jean-Pierre; Pavie, Emmanuel; Perreur, Christelle
- Physical Review E, Vol. 70, Issue 6
Polymerization-induced self-assembly of block copolymer nanoparticles via RAFT non-aqueous dispersion polymerization
journal, January 2016
- Derry, Matthew J.; Fielding, Lee A.; Armes, Steven P.
- Progress in Polymer Science, Vol. 52
Investigation of processing parameters of spray freezing into liquid to prepare polyethylene glycol polymeric particles for drug delivery
journal, June 2003
- Barron, Melisa K.; Young, Timothy J.; Johnston, Keith P.
- AAPS PharmSciTech, Vol. 4, Issue 2
Self-assembly of block copolymers
journal, January 2012
- Mai, Yiyong; Eisenberg, Adi
- Chemical Society Reviews, Vol. 41, Issue 18
Tailored Assemblies of Block Copolymers in Solution: It Is All about the Process
journal, April 2010
- Hayward, Ryan C.; Pochan, Darrin J.
- Macromolecules, Vol. 43, Issue 8
Shape- and Size-Specific Chemistry of Ag Nanostructures in Catalytic Ethylene Epoxidation
journal, January 2010
- Christopher, Phillip; Linic, Suljo
- ChemCatChem, Vol. 2, Issue 1
Lithographically defined uniform worm-shaped polymeric nanoparticles
journal, January 2010
- Tao, L.; Zhao, X. M.; Gao, J. M.
- Nanotechnology, Vol. 21, Issue 9
Structural properties of self-assembled polymeric micelles
journal, February 1998
- Mortensen, Kell
- Current Opinion in Colloid & Interface Science, Vol. 3, Issue 1
Gold Nanoparticles as a Vaccine Platform: Influence of Size and Shape on Immunological Responses in Vitro and in Vivo
journal, May 2013
- Niikura, Kenichi; Matsunaga, Tatsuya; Suzuki, Tadaki
- ACS Nano, Vol. 7, Issue 5
The shape of things to come: importance of design in nanotechnology for drug delivery
journal, February 2012
- Liu, Yaling; Tan, Jifu; Thomas, Antony
- Therapeutic Delivery, Vol. 3, Issue 2
Nanoimprint lithography based fabrication of shape-specific, enzymatically-triggered smart nanoparticles
journal, February 2008
- Glangchai, Luz Cristal; Caldorera-Moore, Mary; Shi, Li
- Journal of Controlled Release, Vol. 125, Issue 3
Surface Composition of Silver Nanocubes and Their Influence on Morphological Stabilization and Catalytic Performance in Ethylene Epoxidation
journal, December 2015
- Sangaru, Shiv Shankar; Zhu, Haibo; Rosenfeld, Devon C.
- ACS Applied Materials & Interfaces, Vol. 7, Issue 51
Role of nanoparticle size, shape and surface chemistry in oral drug delivery
journal, September 2016
- Banerjee, Amrita; Qi, Jianping; Gogoi, Rohan
- Journal of Controlled Release, Vol. 238
Cubical Shape Enhances the Interaction of Layer-by-Layer Polymeric Particles with Breast Cancer Cells
journal, October 2015
- Alexander, Jenolyn F.; Kozlovskaya, Veronika; Chen, Jun
- Advanced Healthcare Materials, Vol. 4, Issue 17
Monodisperse cylindrical micelles by crystallization-driven living self-assembly
journal, May 2010
- Gilroy, Joe B.; Gädt, Torben; Whittell, George R.
- Nature Chemistry, Vol. 2, Issue 7
Block Copolymers: Past Successes and Future Challenges
journal, February 2003
- Lodge, Timothy P.
- Macromolecular Chemistry and Physics, Vol. 204, Issue 2
Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008
- Xia, Younan; Xiong, Yujie; Lim, Byungkwon
- Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103
Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation
journal, April 2009
- Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu
- Journal of the American Chemical Society, Vol. 131, Issue 16
Nanoparticle Shape Improves Delivery: Rational Coarse Grain Molecular Dynamics (rCG-MD) of Taxol in Worm-Like PEG-PCL Micelles
journal, November 2011
- Loverde, Sharon M.; Klein, Michael L.; Discher, Dennis E.
- Advanced Materials, Vol. 24, Issue 28
Phase Diagrams and Aggregation Behavior of Poly(oxyethylene)-Poly(oxypropylene)-Poly(oxyethylene) Triblock Copolymers in Aqueous Solutions
journal, July 1994
- Wanka, G.; Hoffmann, H.; Ulbricht, W.
- Macromolecules, Vol. 27, Issue 15
Functional Block Copolymers: Nanostructured Materials with Emerging Applications
journal, July 2012
- Schacher, Felix H.; Rupar, Paul A.; Manners, Ian
- Angewandte Chemie International Edition, Vol. 51, Issue 32
Improving the Solubility and Pharmacological Efficacy of Curcumin by Heat Treatment
journal, August 2007
- Kurien, Biji T.; Singh, Anil; Matsumoto, Hiroyuki
- ASSAY and Drug Development Technologies, Vol. 5, Issue 4
Physical approaches to biomaterial design
journal, January 2009
- Mitragotri, Samir; Lahann, Joerg
- Nature Materials, Vol. 8, Issue 1
Synthesis and Self-Assembly of Amphiphilic Polymeric Microparticles
journal, April 2007
- Dendukuri, Dhananjay; Hatton, T. Alan; Doyle, Patrick S.
- Langmuir, Vol. 23, Issue 8
Phagocytosis Dynamics Depends on Target Shape
journal, September 2013
- Paul, Debjani; Achouri, Sarra; Yoon, Young-Zoon
- Biophysical Journal, Vol. 105, Issue 5
Differential scanning calorimetry studies on poly(ethylene glycol) with different molecular weights for thermal energy storage materials
journal, October 2002
- Pielichowski, Krzysztof; Flejtuch, Kinga
- Polymers for Advanced Technologies, Vol. 13, Issue 10-12
The effect of shape on the margination dynamics of non-neutrally buoyant particles in two-dimensional shear flows
journal, July 2008
- Gentile, F.; Chiappini, C.; Fine, D.
- Journal of Biomechanics, Vol. 41, Issue 10
Shape effect in cellular uptake of PEGylated nanoparticles: comparison between sphere, rod, cube and disk
journal, January 2015
- Li, Ying; Kröger, Martin; Liu, Wing Kam
- Nanoscale, Vol. 7, Issue 40
Polymerized-depolymerized vesicles. A reversible phosphatidylcholine-based membrane
journal, September 1983
- Regen, Steven L.; Yamaguchi, Kazuo; Samuel, N. K. P.
- Journal of the American Chemical Society, Vol. 105, Issue 20
Tuning the Formation and Degradation of Layer-by-Layer Assembled Polymer Hydrogel Microcapsules †
journal, December 2009
- Becker, Alisa L.; Zelikin, Alexander N.; Johnston, Angus P. R.
- Langmuir, Vol. 25, Issue 24
Polymeric Nanocubes Spontaneously Formed from Poly(ε-caprolactone)
journal, July 2012
- Tu, Song; Wang, Bei-lei; Chen, Yuan-wei
- ACS Macro Letters, Vol. 1, Issue 8
Role of target geometry in phagocytosis
journal, March 2006
- Champion, J. A.; Mitragotri, S.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 13
Anisotropic Polymer Nanoparticles with Tunable Emission Wavelengths by Intersegmental Chain Packing
journal, April 2017
- Ruiz Perez, Julian D.; Mecking, Stefan
- Angewandte Chemie International Edition, Vol. 56, Issue 22
Evaporation-Induced Aggregation of Polystyrene- block -poly(acrylic acid) Micelles to Microcubic Particles
journal, July 2003
- Zhang, Wangqing; Shi, Linqi; An, Yingli
- Langmuir, Vol. 19, Issue 15
Phase Behavior of Reverse Poloxamers and Poloxamines in Water
journal, January 2013
- Larrañeta, Eneko; Isasi, José Ramón
- Langmuir, Vol. 29, Issue 4
Computer simulation of the translocation of nanoparticles with different shapes across a lipid bilayer
journal, July 2010
- Yang, Kai; Ma, Yu-Qiang
- Nature Nanotechnology, Vol. 5, Issue 8
The effect of particle design on cellular internalization pathways
journal, August 2008
- Gratton, S. E. A.; Ropp, P. A.; Pohlhaus, P. D.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 33, p. 11613-11618
Funktionale Blockcopolymere: nanostrukturierte Materialien mit neuen Anwendungsmöglichkeiten
journal, July 2012
- Schacher, Felix H.; Rupar, Paul A.; Manners, Ian
- Angewandte Chemie, Vol. 124, Issue 32
Formkontrolle bei der Synthese von Metallnanokristallen: einfache Chemie, komplexe Physik?
journal, December 2008
- Xia, Younan; Xiong, Yujie; Lim, Byungkwon
- Angewandte Chemie, Vol. 121, Issue 1
Modeling Particle Shape-Dependent Dynamics in Nanomedicine
journal, February 2011
- Shah, Samar; Liu, Yaling; Hu, Walter
- Journal of Nanoscience and Nanotechnology, Vol. 11, Issue 2
Structurally Dynamic Hydrogels Derived from 1,2-Dithiolanes
journal, April 2015
- Barcan, Gregg A.; Zhang, Xiangyi; Waymouth, Robert M.
- Journal of the American Chemical Society, Vol. 137, Issue 17
Uniform patchy and hollow rectangular platelet micelles from crystallizable polymer blends
journal, May 2016
- Qiu, H.; Gao, Y.; Boott, C. E.
- Science, Vol. 352, Issue 6286
Sidechain Engineering in Cell-Penetrating Poly(disulfide)s
journal, February 2017
- Morelli, Paola; Matile, Stefan
- Helvetica Chimica Acta, Vol. 100, Issue 3
Structural study on the micelle formation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer in aqueous solution
journal, July 1993
- Mortensen, Kell; Pedersen, Jan Skov
- Macromolecules, Vol. 26, Issue 4
Shape effects of filaments versus spherical particles in flow and drug delivery
journal, March 2007
- Geng, Yan; Dalhaimer, Paul; Cai, Shenshen
- Nature Nanotechnology, Vol. 2, Issue 4
Tailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensions
journal, September 2014
- Hudson, Zachary M.; Boott, Charlotte E.; Robinson, Matthew E.
- Nature Chemistry, Vol. 6, Issue 10
Anisotropic Polymer Nanoparticles with Tunable Emission Wavelengths by Intersegmental Chain Packing
journal, April 2017
- Ruiz Perez, Julian D.; Mecking, Stefan
- Angewandte Chemie, Vol. 129, Issue 22
Evaluation of the Microstructure of Semicrystalline Solid Dispersions
journal, June 2010
- Zhu, Qing; Taylor, Lynne S.; Harris, Michael T.
- Molecular Pharmaceutics, Vol. 7, Issue 4
Particle shape enhances specificity of antibody-displaying nanoparticles
journal, February 2013
- Barua, Sutapa; Yoo, Jin-Wook; Kolhar, Poornima
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 9
Polymerization-Induced Self-Assembly of Block Copolymer Nano-objects via RAFT Aqueous Dispersion Polymerization
journal, July 2014
- Warren, Nicholas J.; Armes, Steven P.
- Journal of the American Chemical Society, Vol. 136, Issue 29
Multiple Morphologies of "Crew-Cut" Aggregates of Polystyrene-b-poly(acrylic acid) Block Copolymers
journal, June 1995
- Zhang, L.; Eisenberg, A.
- Science, Vol. 268, Issue 5218
A dynamic covalent polymer driven by disulfidemetathesis under photoirradiation
journal, January 2010
- Otsuka, Hideyuki; Nagano, Shinsuke; Kobashi, Yasuharu
- Chem. Commun., Vol. 46, Issue 7
Stability of curcumin in buffer solutions and characterization of its degradation products
journal, August 1997
- Wang, Ying-Jan; Pan, Min-Hsiung; Cheng, Ann-Lii
- Journal of Pharmaceutical and Biomedical Analysis, Vol. 15, Issue 12
Cubic Phase in a Connected Micellar Network of Poly(propylene oxide)−Poly(ethylene oxide)−Poly(propylene oxide) Triblock Copolymers in Water
journal, February 1997
- Mortensen, Kell
- Macromolecules, Vol. 30, Issue 3
Phase separation in polystyrene latex interpenetrating polymer networks
journal, February 1990
- Sheu, H. R.; El-Aasser, M. S.; Vanderhoff, J. W.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 28, Issue 3
Works referencing / citing this record:
Reduction-Triggered Transformation of Disulfide-Containing Micelles at Chemically Tunable Rates
journal, June 2018
- Deng, Zhengyu; Yuan, Shuai; Xu, Ronald X.
- Angewandte Chemie, Vol. 130, Issue 29
Reduction-Triggered Transformation of Disulfide-Containing Micelles at Chemically Tunable Rates
journal, June 2018
- Deng, Zhengyu; Yuan, Shuai; Xu, Ronald X.
- Angewandte Chemie International Edition, Vol. 57, Issue 29
Telechelic amphiphilic metallopolymers end-functionalized with platinum( ii ) complexes: synthesis, luminescence enhancement, and their self-assembly into flowerlike vesicles and giant flowerlike vesicles
journal, January 2019
- Meng, Weisheng; He, Qun; Yu, Manman
- Polymer Chemistry, Vol. 10, Issue 32
Figures / Tables found in this record: