Structural analysis of bottlebrush block copolymer micelles using small-angle X-ray Scattering
Abstract
We present structural analysis of spherical diblock copolymer micelles where core blocks have bottlebrush architecture. The dependence of the core radius ( R core ) and the corona thickness ( L corona ) on the core block length ( N core ) is investigated using small-angle X-ray scattering (SAXS) and discussed in terms of the stiffness of a core-forming polymer posed by its long fluoroalkyl side chains. The conformation of the core block is strongly stretched, and the measured exponents α and β from power-law correlations, R core ∼ N core α and L corona ∼ N core β, respectively, are greater than those from any scaling predictions for block copolymer micelles with a flexible, linear core-block. Such deviations are attributed to the appreciable chain stiffness of the bottlebrush core block, and a simple model is suggested to understand how the core block stiffness influences both the dimensions of core and corona.
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Star shaped polymers : a model for the conformation and its concentration dependence
Daoud, M., & Cotton, J. P. (1982) · Journal de physique · doi:10.1051/jphys:01982004303053100 · Cited by 1,285 · see citing works
Tailored Assemblies of Block Copolymers in Solution: It Is All about the Process
Hayward, R. C., & Pochan, D. J. (2010) · Macromolecules · doi:10.1021/ma9026806 · Cited by 526 · see citing works
Micellization of strongly segregated block copolymers
Förster, S., Zisenis, M., Wenz, E., & Antonietti, M. (1996) · The Journal of Chemical Physics · doi:10.1063/1.471723 · Cited by 436 · see citing works
Consequences of Nonergodicity in Aqueous Binary PEO−PB Micellar Dispersions
Jain, S., & Bates, F. S. (2004) · Macromolecules · doi:10.1021/ma035467j · Cited by 406 · see citing works
Block copolymer self-assembly in selective solvents: Spherical micelles with segregated cores
Nagarajan, R., & Ganesh, K. (1989) · The Journal of Chemical Physics · doi:10.1063/1.456390 · Cited by 311 · see citing works
Diblock Copolymer Micelles in a Dilute Solution
Zhulina, E. B., Adam, M. A., LaRue, I., Sheiko, S. S., & Rubinstein, M. (2005) · Macromolecules · doi:10.1021/ma048102n · Cited by 307 · see citing works
Application of Bottlebrush Block Copolymers as Photonic Crystals
Liberman‐Martin, A. L., Chu, C. K., & Grubbs, R. H. (2017) · Macromolecular Rapid Communications · doi:10.1002/marc.201700058 · Cited by 277 · see citing works
Miyake, G. M., Weitekamp, R. A., Piunova, V. A., & Grubbs, R. H. (2012) · Journal of the American Chemical Society · doi:10.1021/ja306430k · Cited by 266 · see citing works
Fenyves, R., Schmutz, M., Horner, I. J., Bright, F. V., & Rzayev, J. (2014) · Journal of the American Chemical Society · doi:10.1021/ja503283r · Cited by 249 · see citing works
Theory of Block Polymer Micelles: Recent Advances and Current Challenges
Zhulina, E. B., & Borisov, O. V. (2012) · Macromolecules · doi:10.1021/ma300195n · Cited by 225 · see citing works
Mechanism of Molecular Exchange in Diblock Copolymer Micelles: Hypersensitivity to Core Chain Length
Choi, S., Lodge, T. P., & Bates, F. S. (2010) · Physical Review Letters · doi:10.1103/physrevlett.104.047802 · Cited by 209 · see citing works
Self-citationBottlebrush Block Polymers: Quantitative Theory and Experiments
Dalsin, S. J., Rions-Maehren, T. G., Beam, M. D., Bates, F. S., Hillmyer, M. A., & Matsen, M. W. (2015) · ACS Nano · doi:10.1021/acsnano.5b05473 · Cited by 191 · see citing works
Molecular Exchange in PEO−PB Micelles in Water
Won, Y., DAVIS, H. T., & Bates, F. S. (2003) · Macromolecules · doi:10.1021/ma021439+ · Cited by 185 · see citing works
Self-Assembled Nanostructure of a Novel Coil−Rod Diblock Copolymer in Dilute Solution
Tu, Y., Wan, X., Zhang, D., et al. (2000) · Journal of the American Chemical Society · doi:10.1021/ja002163t · Cited by 185 · see citing works
Theory of micelle formation in block copolymer-homopolymer blends
Whitmore, M. D., & Noolandi, J. (1985) · Macromolecules · doi:10.1021/ma00146a014 · Cited by 176 · see citing works
Equilibrium Chain Exchange Kinetics of Diblock Copolymer Micelles: Tuning and Logarithmic Relaxation
Lund, R., Willner, L., Richter, D., & Dormidontova, E. E. (2006) · Macromolecules · doi:10.1021/ma060328y · Cited by 176 · see citing works
Pesek, S. L., Li, X., Hammouda, B., et al. (2013) · Macromolecules · doi:10.1021/ma401246b · Cited by 174 · see citing works
Zhou, L., Ma, J., Cheng, C., et al. (2010) · Macromolecules · doi:10.1021/ma902513n · Cited by 157 · see citing works
Self-Assembly of Symmetric Brush Diblock Copolymers
Gu, W., Huh, J., Hong, S. W., Sveinbjörnsson, B. R., Park, C., Grubbs, R. H., & Russell, T. P. (2013) · ACS Nano · doi:10.1021/nn305867d · Cited by 157 · see citing works
Combs and Bottlebrushes in a Melt
Liang, H., Cao, Z. H., Wang, Z., et al. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b00364 · Cited by 151 · see citing works
Polymers with Strongly Interacting Groups: Theory for Nonspherical Multiplets
Semenov, A. N., Nyrkova, I. A., & Khokhlov, A. R. (1995) · Macromolecules · doi:10.1021/ma00126a029 · Cited by 149 · see citing works
Block Copolymer Nanocomposites with High Refractive Index Contrast for One-Step Photonics
Song, D., Li, C., Li, W., & Watkins, J. J. (2015) · ACS Nano · doi:10.1021/acsnano.5b06525 · Cited by 144 · see citing works
Elasticity of Comb Copolymer Cylindrical Brushes
Subbotin, A. V., Saariaho, M., Ikkala, O. T., et al. (2000) · Macromolecules · doi:10.1021/ma991031l · Cited by 129 · see citing works
Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush
Lin, T., Chang, A. B., Luo, S. L., et al. (2017) · ACS Nano · doi:10.1021/acsnano.7b06664 · Cited by 121 · see citing works
Hsu, H., Paul, W., Rathgeber, S., & Binder, K. (2010) · Macromolecules · doi:10.1021/ma902101n · Cited by 103 · see citing works
Access to the Superstrong Segregation Regime with Nonionic ABC Copolymers
Lodge, T. P., Hillmyer, M. A., Zhou, Z., et al. (2004) · Macromolecules · doi:10.1021/ma048708b · Cited by 96 · see citing works
Theodorakis, P. E., Hsu, H., Paul, W., & Binder, K. (2011) · The Journal of Chemical Physics · doi:10.1063/1.3656072 · Cited by 89 · see citing works
Alaboalirat, M., Qi, L., Arrington, K. J., et al. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b02366 · Cited by 77 · see citing works
Micellization Behavior of Complex Comblike Block Copolymer Architectures
Zamurovic, M., Christodoulou, S., Vazaios, A., Iatrou, E., Pitsikalis, M., & Hadjichristidis, N. (2007) · Macromolecules · doi:10.1021/ma0704919 · Cited by 72 · see citing works
Disk Micelles from Nonionic Coil−Coil Diblock Copolymers
Edmonds, W. F., Li, Z., Hillmyer, M. A., & Lodge, T. P. (2006) · Macromolecules · doi:10.1021/ma060633j · Cited by 62 · see citing works
Aggregation of a semifluorinated n-alkane in perfluorooctane
Nostro, P. L., & Chen, S. H. (1993) · The Journal of Physical Chemistry · doi:10.1021/j100126a033 · Cited by 61 · see citing works
Wessels, M. G., & Jayaraman, A. (2019) · Soft Matter · doi:10.1039/c9sm00375d · Cited by 60 · see citing works
Exchange Kinetics for a Single Block Copolymer in Micelles of Two Different Sizes
Zhao, D., Ma, Y., & Lodge, T. P. (2018) · Macromolecules · doi:10.1021/acs.macromol.7b02550 · Cited by 45 · see citing works
Castelletto, V., Hamley, I. W., & Pedersen, J. S. (2002) · The Journal of Chemical Physics · doi:10.1063/1.1509747 · Cited by 41 · see citing works
Graft Density Dependence of Main Chain Stiffness in Molecular Rod Brushes
Kikuchi, M., Nakano, R., Jinbo, Y., et al. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b01010 · Cited by 36 · see citing works
Ma, Y., & Lodge, T. P. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b00315 · Cited by 28 · see citing works
Micelle Morphology and Mechanical Response of Triblock Gels
Seitz, M. E., Burghardt, W. R., & Shull, K. R. (2009) · Macromolecules · doi:10.1021/ma901448x · Cited by 27 · see citing works
Schaeffel, D., Kreyes, A., Zhao, Y., et al. (2014) · ACS Macro Letters · doi:10.1021/mz500169n · Cited by 24 · see citing works
Association and Structure of Thermosensitive Comblike Block Copolymers in Aqueous Solutions
Cheng, G., Hua, F., Melnichenko, Y. B., et al. (2008) · Macromolecules · doi:10.1021/ma702580v · Cited by 22 · see citing works
Macromolecules and Liquid Crystals: Reflections on Certain Lines of Research
de Gennes, P. G. (1978) · Liquid Crystals · doi:10.1016/b978-0-12-607774-2.50006-9 · Cited by 22 · see citing works
Pitsikalis, M., Siakali‐Kioulafa, E., & Hadjichristidis, N. (2004) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.20258 · Cited by 18 · see citing works
Swelling-induced pore generation in fluorinated polynorbornene block copolymer films
Cho, Y., Kim, Y., Choi, T., et al. (2018) · Polymer Chemistry · doi:10.1039/c8py00646f · Cited by 16 · see citing works
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- Authors
- Kim, S., Cho, Y., Kim, J. H., Song, S., Lim, J., Choi, S.-H., & Char, K.
- Affiliations
- Seoul National University (KR)
- Kyung Hee University (KR)
- Hongik University (KR)
- Corresponding author
- Choi, Soo-Hyung
- Char, Kookheon
- Venue
- ACS Macro Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2020-08-18
- Volume
- 9
- Issue
- 9
- Pages
- 1261-1266
- ISSN
- 2161-1653 (ISSN-L)
- OpenAlex
- W3059249628
- Cited by
- 14
- References
- 42
- Citations by year
- 2026: 3 · 2024: 2 · 2023: 1 · 2022: 4 · 2021: 4
- FWCI
- 0.88
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- ACS Macro Letters (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Research Foundation of Korea (2010-0018290, 2016R1C1B3010402, 2017M2A2A6A01021244, 2017M3A9E4047246)
- Topics
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemistry › Organic Chemistry › Surfactants and Colloidal Systems
- Keywords
- bottlebrush block copolymers, diblock copolymer micelles, core radius, chain stiffness, power-law scaling, micelle structure
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