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

Margulis, Katherine; Zhang, Xiangyi; Joubert, Lydia -Marie; Bruening, Karsten; Tassone, Christopher J.; Zare, Richard N.; Waymouth, Robert M.

doi:10.1002/anie.201709564

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

Journal Article · Fri Oct 27 00:00:00 EDT 2017 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201709564· OSTI ID:1439109

^[1]; ^[1]; ^[1]; Bruening, Karsten ^[2]; Tassone, Christopher J. ^[2]; ^[1]; ^[1]

Stanford Univ., Stanford, CA (United States)
Stanford Univ., Menlo Park, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1439109

Alternate ID(s):: OSTI ID: 1410360

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 51 Vol. 56; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Cubical Shape Enhances the Interaction of Layer-by-Layer Polymeric Particles with Breast Cancer Cells Alexander, Jenolyn F.; Kozlovskaya, Veronika; Chen, Jun Advanced Healthcare Materials, Vol. 4, Issue 17 https://doi.org/10.1002/adhm.201500537	journal	October 2015
Nanoparticle Shape Improves Delivery: Rational Coarse Grain Molecular Dynamics (rCG-MD) of Taxol in Worm-Like PEG-PCL Micelles Loverde, Sharon M.; Klein, Michael L.; Discher, Dennis E. Advanced Materials, Vol. 24, Issue 28 https://doi.org/10.1002/adma.201103192	journal	November 2011
Formkontrolle bei der Synthese von Metallnanokristallen: einfache Chemie, komplexe Physik? Xia, Younan; Xiong, Yujie; Lim, Byungkwon Angewandte Chemie, Vol. 121, Issue 1 https://doi.org/10.1002/ange.200802248	journal	December 2008
Funktionale Blockcopolymere: nanostrukturierte Materialien mit neuen Anwendungsmöglichkeiten Schacher, Felix H.; Rupar, Paul A.; Manners, Ian Angewandte Chemie, Vol. 124, Issue 32 https://doi.org/10.1002/ange.201200310	journal	July 2012
Anisotropic Polymer Nanoparticles with Tunable Emission Wavelengths by Intersegmental Chain Packing Ruiz Perez, Julian D.; Mecking, Stefan Angewandte Chemie, Vol. 129, Issue 22 https://doi.org/10.1002/ange.201701000	journal	April 2017
Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics? Xia, Younan; Xiong, Yujie; Lim, Byungkwon Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103 https://doi.org/10.1002/anie.200802248	journal	December 2008
Functional Block Copolymers: Nanostructured Materials with Emerging Applications Schacher, Felix H.; Rupar, Paul A.; Manners, Ian Angewandte Chemie International Edition, Vol. 51, Issue 32 https://doi.org/10.1002/anie.201200310	journal	July 2012
Anisotropic Polymer Nanoparticles with Tunable Emission Wavelengths by Intersegmental Chain Packing Ruiz Perez, Julian D.; Mecking, Stefan Angewandte Chemie International Edition, Vol. 56, Issue 22 https://doi.org/10.1002/anie.201701000	journal	April 2017
Shape- and Size-Specific Chemistry of Ag Nanostructures in Catalytic Ethylene Epoxidation Christopher, Phillip; Linic, Suljo ChemCatChem, Vol. 2, Issue 1 https://doi.org/10.1002/cctc.200900231	journal	January 2010
Sidechain Engineering in Cell-Penetrating Poly(disulfide)s Morelli, Paola; Matile, Stefan Helvetica Chimica Acta, Vol. 100, Issue 3 https://doi.org/10.1002/hlca.201600370	journal	February 2017
Block Copolymers: Past Successes and Future Challenges Lodge, Timothy P. Macromolecular Chemistry and Physics, Vol. 204, Issue 2 https://doi.org/10.1002/macp.200290073	journal	February 2003
Differential scanning calorimetry studies on poly(ethylene glycol) with different molecular weights for thermal energy storage materials Pielichowski, Krzysztof; Flejtuch, Kinga Polymers for Advanced Technologies, Vol. 13, Issue 10-12 https://doi.org/10.1002/pat.276	journal	October 2002
Phase separation in polystyrene latex interpenetrating polymer networks Sheu, H. R.; El-Aasser, M. S.; Vanderhoff, J. W. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 28, Issue 3 https://doi.org/10.1002/pola.1990.080280314	journal	February 1990
Stability of curcumin in buffer solutions and characterization of its degradation products Wang, Ying-Jan; Pan, Min-Hsiung; Cheng, Ann-Lii Journal of Pharmaceutical and Biomedical Analysis, Vol. 15, Issue 12 https://doi.org/10.1016/S0731-7085(96)02024-9	journal	August 1997
Structural properties of self-assembled polymeric micelles Mortensen, Kell Current Opinion in Colloid & Interface Science, Vol. 3, Issue 1 https://doi.org/10.1016/S1359-0294(98)80036-8	journal	February 1998
Phagocytosis Dynamics Depends on Target Shape Paul, Debjani; Achouri, Sarra; Yoon, Young-Zoon Biophysical Journal, Vol. 105, Issue 5 https://doi.org/10.1016/j.bpj.2013.07.036	journal	September 2013
The effect of shape on the margination dynamics of non-neutrally buoyant particles in two-dimensional shear flows Gentile, F.; Chiappini, C.; Fine, D. Journal of Biomechanics, Vol. 41, Issue 10 https://doi.org/10.1016/j.jbiomech.2008.03.021	journal	July 2008
Nanoimprint lithography based fabrication of shape-specific, enzymatically-triggered smart nanoparticles Glangchai, Luz Cristal; Caldorera-Moore, Mary; Shi, Li Journal of Controlled Release, Vol. 125, Issue 3 https://doi.org/10.1016/j.jconrel.2007.10.021	journal	February 2008
Role of nanoparticle size, shape and surface chemistry in oral drug delivery Banerjee, Amrita; Qi, Jianping; Gogoi, Rohan Journal of Controlled Release, Vol. 238 https://doi.org/10.1016/j.jconrel.2016.07.051	journal	September 2016
Polymerization-induced self-assembly of block copolymer nanoparticles via RAFT non-aqueous dispersion polymerization Derry, Matthew J.; Fielding, Lee A.; Armes, Steven P. Progress in Polymer Science, Vol. 52 https://doi.org/10.1016/j.progpolymsci.2015.10.002	journal	January 2016
Surface Composition of Silver Nanocubes and Their Influence on Morphological Stabilization and Catalytic Performance in Ethylene Epoxidation Sangaru, Shiv Shankar; Zhu, Haibo; Rosenfeld, Devon C. ACS Applied Materials & Interfaces, Vol. 7, Issue 51 https://doi.org/10.1021/acsami.5b09927	journal	December 2015
Polymerized-depolymerized vesicles. A reversible phosphatidylcholine-based membrane Regen, Steven L.; Yamaguchi, Kazuo; Samuel, N. K. P. Journal of the American Chemical Society, Vol. 105, Issue 20 https://doi.org/10.1021/ja00358a050	journal	September 1983
Direct Fabrication and Harvesting of Monodisperse, Shape-Specific Nanobiomaterials Rolland, Jason P.; Maynor, Benjamin W.; Euliss, Larken E. Journal of the American Chemical Society, Vol. 127, Issue 28 https://doi.org/10.1021/ja051977c	journal	July 2005
Synthesis of Monodisperse Pt Nanocubes and Their Enhanced Catalysis for Oxygen Reduction Wang, Chao; Daimon, Hideo; Lee, Youngmin Journal of the American Chemical Society, Vol. 129, Issue 22 https://doi.org/10.1021/ja070440r	journal	June 2007
Polymerization-Induced Self-Assembly of Block Copolymer Nano-objects via RAFT Aqueous Dispersion Polymerization Warren, Nicholas J.; Armes, Steven P. Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja502843f	journal	July 2014
Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu Journal of the American Chemical Society, Vol. 131, Issue 16 https://doi.org/10.1021/ja809936n	journal	April 2009
Structurally Dynamic Hydrogels Derived from 1,2-Dithiolanes Barcan, Gregg A.; Zhang, Xiangyi; Waymouth, Robert M. Journal of the American Chemical Society, Vol. 137, Issue 17 https://doi.org/10.1021/jacs.5b02161	journal	April 2015
1,2-Dithiolane-Derived Dynamic, Covalent Materials: Cooperative Self-Assembly and Reversible Cross-Linking Zhang, Xiangyi; Waymouth, Robert M. Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.7b00039	journal	February 2017
Evaporation-Induced Aggregation of Polystyrene- block -poly(acrylic acid) Micelles to Microcubic Particles Zhang, Wangqing; Shi, Linqi; An, Yingli Langmuir, Vol. 19, Issue 15 https://doi.org/10.1021/la034300g	journal	July 2003
Synthesis and Self-Assembly of Amphiphilic Polymeric Microparticles Dendukuri, Dhananjay; Hatton, T. Alan; Doyle, Patrick S. Langmuir, Vol. 23, Issue 8 https://doi.org/10.1021/la062512i	journal	April 2007
Phase Behavior of Reverse Poloxamers and Poloxamines in Water Larrañeta, Eneko; Isasi, José Ramón Langmuir, Vol. 29, Issue 4 https://doi.org/10.1021/la304245p	journal	January 2013
Tuning the Formation and Degradation of Layer-by-Layer Assembled Polymer Hydrogel Microcapsules ^† Becker, Alisa L.; Zelikin, Alexander N.; Johnston, Angus P. R. Langmuir, Vol. 25, Issue 24 https://doi.org/10.1021/la901687a	journal	December 2009
Structural study on the micelle formation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer in aqueous solution Mortensen, Kell; Pedersen, Jan Skov Macromolecules, Vol. 26, Issue 4 https://doi.org/10.1021/ma00056a035	journal	July 1993
Phase Diagrams and Aggregation Behavior of Poly(oxyethylene)-Poly(oxypropylene)-Poly(oxyethylene) Triblock Copolymers in Aqueous Solutions Wanka, G.; Hoffmann, H.; Ulbricht, W. Macromolecules, Vol. 27, Issue 15 https://doi.org/10.1021/ma00093a016	journal	July 1994
Tailored Assemblies of Block Copolymers in Solution: It Is All about the Process Hayward, Ryan C.; Pochan, Darrin J. Macromolecules, Vol. 43, Issue 8 https://doi.org/10.1021/ma9026806	journal	April 2010
Cubic Phase in a Connected Micellar Network of Poly(propylene oxide)−Poly(ethylene oxide)−Poly(propylene oxide) Triblock Copolymers in Water Mortensen, Kell Macromolecules, Vol. 30, Issue 3 https://doi.org/10.1021/ma960457m	journal	February 1997
Evaluation of the Microstructure of Semicrystalline Solid Dispersions Zhu, Qing; Taylor, Lynne S.; Harris, Michael T. Molecular Pharmaceutics, Vol. 7, Issue 4 https://doi.org/10.1021/mp1000907	journal	June 2010
Polymeric Nanocubes Spontaneously Formed from Poly(ε-caprolactone) Tu, Song; Wang, Bei-lei; Chen, Yuan-wei ACS Macro Letters, Vol. 1, Issue 8 https://doi.org/10.1021/mz300194p	journal	July 2012
Gold Nanoparticles as a Vaccine Platform: Influence of Size and Shape on Immunological Responses in Vitro and in Vivo Niikura, Kenichi; Matsunaga, Tatsuya; Suzuki, Tadaki ACS Nano, Vol. 7, Issue 5 https://doi.org/10.1021/nn3057005	journal	May 2013
Tailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensions Hudson, Zachary M.; Boott, Charlotte E.; Robinson, Matthew E. Nature Chemistry, Vol. 6, Issue 10 https://doi.org/10.1038/nchem.2038	journal	September 2014
Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly Boott, Charlotte E.; Gwyther, Jessica; Harniman, Robert L. Nature Chemistry, Vol. 9, Issue 8 https://doi.org/10.1038/nchem.2721	journal	February 2017
Monodisperse cylindrical micelles by crystallization-driven living self-assembly Gilroy, Joe B.; Gädt, Torben; Whittell, George R. Nature Chemistry, Vol. 2, Issue 7 https://doi.org/10.1038/nchem.664	journal	May 2010
Physical approaches to biomaterial design Mitragotri, Samir; Lahann, Joerg Nature Materials, Vol. 8, Issue 1 https://doi.org/10.1038/nmat2344	journal	January 2009
Shape effects of filaments versus spherical particles in flow and drug delivery Geng, Yan; Dalhaimer, Paul; Cai, Shenshen Nature Nanotechnology, Vol. 2, Issue 4 https://doi.org/10.1038/nnano.2007.70	journal	March 2007
Computer simulation of the translocation of nanoparticles with different shapes across a lipid bilayer Yang, Kai; Ma, Yu-Qiang Nature Nanotechnology, Vol. 5, Issue 8 https://doi.org/10.1038/nnano.2010.141	journal	July 2010
A dynamic covalent polymer driven by disulfidemetathesis under photoirradiation Otsuka, Hideyuki; Nagano, Shinsuke; Kobashi, Yasuharu Chem. Commun., Vol. 46, Issue 7 https://doi.org/10.1039/B916128G	journal	January 2010
Synthesis and phase transition energy storage capability of a cross-linked PEG/LACE copolymer Maimaiti, Halidan; Xu, Sumei; Aerken, Xuekelaiti RSC Advances, Vol. 5, Issue 26 https://doi.org/10.1039/C4RA15984E	journal	January 2015
Shape effect in cellular uptake of PEGylated nanoparticles: comparison between sphere, rod, cube and disk Li, Ying; Kröger, Martin; Liu, Wing Kam Nanoscale, Vol. 7, Issue 40 https://doi.org/10.1039/C5NR02970H	journal	January 2015
Self-assembly of block copolymers Mai, Yiyong; Eisenberg, Adi Chemical Society Reviews, Vol. 41, Issue 18 https://doi.org/10.1039/c2cs35115c	journal	January 2012
Role of target geometry in phagocytosis Champion, J. A.; Mitragotri, S. Proceedings of the National Academy of Sciences, Vol. 103, Issue 13 https://doi.org/10.1073/pnas.0600997103	journal	March 2006
The effect of particle design on cellular internalization pathways Gratton, S. E. A.; Ropp, P. A.; Pohlhaus, P. D. Proceedings of the National Academy of Sciences, Vol. 105, Issue 33, p. 11613-11618 https://doi.org/10.1073/pnas.0801763105	journal	August 2008
Particle shape enhances specificity of antibody-displaying nanoparticles Barua, Sutapa; Yoo, Jin-Wook; Kolhar, Poornima Proceedings of the National Academy of Sciences, Vol. 110, Issue 9 https://doi.org/10.1073/pnas.1216893110	journal	February 2013
Lithographically defined uniform worm-shaped polymeric nanoparticles Tao, L.; Zhao, X. M.; Gao, J. M. Nanotechnology, Vol. 21, Issue 9 https://doi.org/10.1088/0957-4484/21/9/095301	journal	January 2010
Improving the Solubility and Pharmacological Efficacy of Curcumin by Heat Treatment Kurien, Biji T.; Singh, Anil; Matsumoto, Hiroyuki ASSAY and Drug Development Technologies, Vol. 5, Issue 4 https://doi.org/10.1089/adt.2007.064	journal	August 2007
Nanostructure in block copolymer solutions: Rheology and small-angle neutron scattering Habas, Jean-Pierre; Pavie, Emmanuel; Perreur, Christelle Physical Review E, Vol. 70, Issue 6 https://doi.org/10.1103/PhysRevE.70.061802	journal	December 2004
Multiple Morphologies of "Crew-Cut" Aggregates of Polystyrene-b-poly(acrylic acid) Block Copolymers Zhang, L.; Eisenberg, A. Science, Vol. 268, Issue 5218 https://doi.org/10.1126/science.268.5218.1728	journal	June 1995
Uniform patchy and hollow rectangular platelet micelles from crystallizable polymer blends Qiu, H.; Gao, Y.; Boott, C. E. Science, Vol. 352, Issue 6286 https://doi.org/10.1126/science.aad9521	journal	May 2016
Modeling Particle Shape-Dependent Dynamics in Nanomedicine Shah, Samar; Liu, Yaling; Hu, Walter Journal of Nanoscience and Nanotechnology, Vol. 11, Issue 2 https://doi.org/10.1166/jnn.2011.3536	journal	February 2011
Investigation of processing parameters of spray freezing into liquid to prepare polyethylene glycol polymeric particles for drug delivery Barron, Melisa K.; Young, Timothy J.; Johnston, Keith P. AAPS PharmSciTech, Vol. 4, Issue 2 https://doi.org/10.1208/pt040212	journal	June 2003
The shape of things to come: importance of design in nanotechnology for drug delivery Liu, Yaling; Tan, Jifu; Thomas, Antony Therapeutic Delivery, Vol. 3, Issue 2 https://doi.org/10.4155/tde.11.156	journal	February 2012

Cited By (3)

Reduction-Triggered Transformation of Disulfide-Containing Micelles at Chemically Tunable Rates Deng, Zhengyu; Yuan, Shuai; Xu, Ronald X. Angewandte Chemie, Vol. 130, Issue 29 https://doi.org/10.1002/ange.201802909	journal	June 2018
Reduction-Triggered Transformation of Disulfide-Containing Micelles at Chemically Tunable Rates Deng, Zhengyu; Yuan, Shuai; Xu, Ronald X. Angewandte Chemie International Edition, Vol. 57, Issue 29 https://doi.org/10.1002/anie.201802909	journal	June 2018
Telechelic amphiphilic metallopolymers end-functionalized with platinum( ii ) complexes: synthesis, luminescence enhancement, and their self-assembly into flowerlike vesicles and giant flowerlike vesicles Meng, Weisheng; He, Qun; Yu, Manman Polymer Chemistry, Vol. 10, Issue 32 https://doi.org/10.1039/c9py00652d	journal	January 2019

Figures / Tables (7)

Similar Records

Formation of Polymeric Nanocubes by Self‐Assembly and Crystallization of Dithiolane‐Containing Triblock Copolymers

Journal Article · Thu Nov 23 19:00:00 EST 2017 · Angewandte Chemie · OSTI ID:1410359

Effects of Solvent Composition on the Assembly and Relaxation of Triblock Copolymer-Based Polyelectrolyte Gels

Journal Article · Mon Mar 26 00:00:00 EDT 2012 · Macromolecules · OSTI ID:1035382

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
dithiolane crosslinking
micelle aggregation
nanocubes
self-assembly
triblock copolymers

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

Citation Formats

References (60)

Cited By (3)

Figures / Tables (7)

Similar Records

Related Subjects