Probing the Structure of the Crystalline Core of Field-Aligned, Monodisperse, Cylindrical Polyisoprene-block-Polyferrocenylsilane Micelles in Solution Using Synchrotron Small- and Wide-Angle X-ray Scattering

Gilroy, Joe B.; Rupar, Paul A.; Whittell, George R.; Chabanne, Laurent; Terrill, Nicholas J.; Winnik, Mitchell A.; Manners, Ian; Richardson, Robert M.

doi:10.1021/ja207417z

Cited by 97Block Copolymer Self-AssemblyAdvanced Polymer Synthesis and CharacterizationPolymer crystallization and properties

Probing the Structure of the Crystalline Core of Field-Aligned, Monodisperse, Cylindrical Polyisoprene-block-Polyferrocenylsilane Micelles in Solution Using Synchrotron Small- and Wide-Angle X-ray Scattering

Gilroy, Joe B., Rupar, Paul A., Whittell, George R., Chabanne, Laurent, Terrill, Nicholas J., Winnik, Mitchell A., Manners, Ian, Richardson, Robert M.·2011·Journal of the American Chemical Society

DOI 10.1021/ja207417z

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Abstract

The self-assembly of block copolymers in selective solvents represents a powerful approach to functional core-shell nanoparticles. Crystallization of the core can play a critical role in directing self-assembly toward desirable, nonspherical morphologies with low mean interfacial curvature. Moreover, epitaxial growth processes have been implicated in recent advances that permit access to monodisperse cylinders, cylindrical block comicelles with segmented cores and/or coronas, and complex hierarchical architectures. However, how the core-forming block crystallizes in an inherently curved nanoscopic environment has not been resolved. Herein we report the results of synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) studies of well-defined, monodisperse crystalline-coil polyisoprene-block-polyferrocenylsilane cylindrical micelles aligned in an electric field. WAXS studies of the aligned cylinders have provided key structural information on the nature of the PFS micelle core together with insight into the role of polymer crystallinity in the self-assembly of these and potentially related crystalline-coil block copolymers.

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Phase structure identification, FCC or BCC, and the lattice parameter could be identified from the sequence of intensity peaks measured by SAXS.
“The phase structure identification, FCC (face-centered cubic) or BCC (bodycentered cubic), and the lattice parameter could be identified from the sequence of intensity peaks measured by SAXS.”
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Thompson et al. investigated cubic structures formed in Pluronics P104, P105, and F108 solutions at 31% (mass/vol) both neat and coformulated with cisplatin (0.02% to 0.1%, mass/vol).
“Thompson and coworkers [204] investigated the cubic structures formed in Pluronics® P104, P105, and F108 solutions at 31% (mass/vol) both neat and coformulated with the drug cisplatin (0.02% to 0.1%, mass/vol).”
From Polymeric micelles in drug delivery: An insight of the techniques for their characterization and assessment in biorelevant conditions (2021) · cites this paper as [204]

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Rasburn, J., Petersen, R., Jahr, T., Rulkens, R., Ian Manners, A., & Vancso, G. J. (1995) · Chemistry of Materials · doi:10.1021/cm00053a010 · Cited by 71 · see citing works
Polar Assembly in a Designed Protein Fiber
Smith, A. M., Acquah, S. F. A., Bone, N. M., Kroto, H. W., Ryadnov, M. G., Stevens, M. S. P., Walton, D. R. M., & Woolfson, D. N. (2004) · Angewandte Chemie International Edition · doi:10.1002/anie.200461599 · Cited by 70 · see citing works
Hockey‐Puck Micelles from Oligo(p‐benzamide)‐b‐PEG Rod–Coil Block Copolymers
Schleuss, T. W., Abbel, R., Gross, M. F., Schollmeyer, D., Frey, H., Maskos, M., Berger, R., & Kilbinger, A. F. M. (2006) · Angewandte Chemie International Edition · doi:10.1002/anie.200503514 · Cited by 67 · see citing works
Electroactive Linear–Hyperbranched Block Copolymers Based on Linear Poly(ferrocenylsilane)s and Hyperbranched Poly(carbosilane)s
Wurm, F. R., Hilf, S., & Frey, H. (2009) · Chemistry - A European Journal · doi:10.1002/chem.200900666 · Cited by 67 · see citing works
Water-Dispersible Polymer/Pd/Ni Hybrid Magnetic Nanofibers
Yan, X., Liu, G., Häußler, M., & Tang, B. Z. (2005) · Chemistry of Materials · doi:10.1021/cm051548d · Cited by 65 · see citing works
Self-Assembly of Poly(ferrocenyldimethylsilane-b-methyl methacrylate) Block Copolymers in a Selective Solvent
Korczagin, I., Hempenius, M. A., Fokkink, R. G., Stuart, M. A. C., Al‐Hussein, M., Bomans, P. H. H., Frederik, P. M., & Vancso, G. J. (2006) · Macromolecules · doi:10.1021/ma052521i · Cited by 64 · see citing works
Stable Dispersions of Highly Anisotropic Nanoparticles Formed by Cocrystallization of Enantiomeric Diblock Copolymers
Portinha, D., Boué, F., Bouteiller, L., Carrot, G., Chassenieux, C., Pensec, S., & Reiter, G. (2007) · Macromolecules · doi:10.1021/ma070467v · Cited by 64 · see citing works
Cross-Linked Nanospheres of Poly(2-cinnamoylethyl methacrylate) with Immediately Attached Surface Functional Groups
Tao, J. W., Liu, G., Ding, J., & Yang, M. (1997) · Macromolecules · doi:10.1021/ma9700237 · Cited by 54 · see citing works
Structure and transport in nanotubes
de Heer, W. A. (2002) · Nature Materials · doi:10.1038/nmat759 · Cited by 7 · see citing works

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Polymeric micelles in drug delivery: An insight of the techniques for their characterization and assessment in biorelevant conditions
Ghezzi, M., Pescina, S., Padula, C., Santi, P., Del Favero, E., Cantù, L., & Nicoli, S. (2021) · Journal of Controlled Release · doi:10.1016/j.jconrel.2021.02.031 · Cited by 1,135 · see citing works
50th Anniversary Perspective: Functional Nanoparticles from the Solution Self-Assembly of Block Copolymers
Tritschler, U., Pearce, S., Gwyther, J., Whittell, G. R., & Ian Manners, A. (2017) · Macromolecules · doi:10.1021/acs.macromol.6b02767 · Cited by 375 · see citing works
Polyferrocenylsilanes: synthesis, properties, and applications
Hailes, R. L. N., Oliver, A. M., Gwyther, J., Whittell, G. R., & Ian Manners, A. (2016) · Chemical Society Reviews · doi:10.1039/c6cs00155f · Cited by 318 · see citing works
Colour-tunable fluorescent multiblock micelles
Hudson, Z. M., Lunn, D. J., Winnik, M. A., & Ian Manners, A. (2014) · Nature Communications · doi:10.1038/ncomms4372 · Cited by 278 · see citing works
Emerging applications for living crystallization-driven self-assembly
MacFarlane, L. R., Zhao, C., Cai, J., Qiu, H., & Ian Manners, A. (2021) · Chemical Science · doi:10.1039/d0sc06878k · Cited by 254 · see citing works
Two-dimensional assemblies from crystallizable homopolymers with charged termini
He, X., Hsiao, M.-S., Boott, C. E., Harniman, R. L., Nazemi, A., Li, X., Winnik, M. A., & Ian Manners, A. (2017) · Nature Materials · doi:10.1038/nmat4837 · Cited by 238 · see citing works
Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly
Boott, C. E., Gwyther, J., Harniman, R. L., Hayward, D. W., & Ian Manners, A. (2017) · Nature Chemistry · doi:10.1038/nchem.2721 · Cited by 212 · see citing works
Metallopolymers for advanced sustainable applications
Wang, Y., Astruc, D., & Abd‐El‐Aziz, A. S. (2018) · Chemical Society Reviews · doi:10.1039/c7cs00656j · Cited by 192 · see citing works
Uniform Biodegradable Fiber-Like Micelles and Block Comicelles via “Living” Crystallization-Driven Self-Assembly of Poly( l -lactide) Block Copolymers: The Importance of Reducing Unimer Self-Nucleation via Hydrogen Bond Disruption
He, Y., Eloi, J., Harniman, R. L., Richardson, R. M., Whittell, G. R., Mathers, R. T., Dove, A. P., O’Reilly, R. K., & Ian Manners, A. (2019) · Journal of the American Chemical Society · doi:10.1021/jacs.9b09885 · Cited by 147 · see citing works
Complex and Hierarchical 2D Assemblies via Crystallization-Driven Self-Assembly of Poly( l -lactide) Homopolymers with Charged Termini
He, X., He, Y., Hsiao, M.-S., Harniman, R. L., Pearce, S., Winnik, M. A., & Ian Manners, A. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.7b03172 · Cited by 145 · see citing works
Monodisperse Cylindrical Micelles of Controlled Length with a Liquid‐Crystalline Perfluorinated Core by 1D “Self‐Seeding”
Li, X., Jin, B., Gao, Y., Hayward, D. W., Winnik, M. A., Luo, Y., & Ian Manners, A. (2016) · Angewandte Chemie International Edition · doi:10.1002/anie.201604551 · Cited by 131 · see citing works
Self-Seeding in One Dimension: A Route to Uniform Fiber-like Nanostructures from Block Copolymers with a Crystallizable Core-Forming Block
Qian, J., Lu, Y., Chia, A., Zhang, M., Rupar, P. A., Gunari, N., Walker, G. C., Cambridge, G., He, F., Guérin, G., et al. (2013) · ACS Nano · doi:10.1021/nn400124x · Cited by 124 · see citing works
Branched Micelles by Living Crystallization-Driven Block Copolymer Self-Assembly under Kinetic Control
Qiu, H., Gao, Y., Du, V. A., Harniman, R. L., Winnik, M. A., & Ian Manners, A. (2015) · Journal of the American Chemical Society · doi:10.1021/ja5126808 · Cited by 122 · see citing works
Uniform “Patchy” Platelets by Seeded Heteroepitaxial Growth of Crystallizable Polymer Blends in Two Dimensions
Nazemi, A., He, X., MacFarlane, L. R., Harniman, R. L., Hsiao, M.-S., Winnik, M. A., Faul, C. F. J., & Ian Manners, A. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.6b12503 · Cited by 111 · see citing works
Fiber-like Micelles via the Crystallization-Driven Solution Self-Assembly of Poly(3-hexylthiophene)-block-Poly(methyl methacrylate) Copolymers
Gilroy, J. B., Lunn, D. J., Patra, S. K., Whittell, G. R., Winnik, M. A., & Ian Manners, A. (2012) · Macromolecules · doi:10.1021/ma3008114 · Cited by 108 · see citing works
Recent applications of synchrotron radiation and neutrons in the study of soft matter
Narayanan, T., Wacklin, H. P., Konovalov, O., & Lund, R. (2017) · Crystallography Reviews · doi:10.1080/0889311x.2016.1277212 · Cited by 105 · see citing works
“SAXS/WAXS investigations of crystalline-coil block copolymer cylindrical micelles aligned in an electric field provided key structural information about the 2D pseudohexagonal chain packing in the micellar core perpendicular to the long axis of the cylinder and it helped to gain insight into the role of polymer crysta…”
Background
Dimensional Control of Block Copolymer Nanofibers with a π‐Conjugated Core: Crystallization‐Driven Solution Self‐Assembly of Amphiphilic Poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine)
Gwyther, J., Gilroy, J. B., Rupar, P. A., Lunn, D. J., Kynaston, E. L., Patra, S. K., Whittell, G. R., Winnik, M. A., & Ian Manners, A. (2013) · Chemistry - A European Journal · doi:10.1002/chem.201300463 · Cited by 104 · see citing works
Crystallization-Driven Self-Assembly of Block Copolymers with a Short Crystallizable Core-Forming Segment: Controlling Micelle Morphology through the Influence of Molar Mass and Solvent Selectivity
Hsiao, M.-S., Yusoff, S. F. M., Winnik, M. A., & Ian Manners, A. (2014) · Macromolecules · doi:10.1021/ma402429d · Cited by 104 · see citing works
Monodisperse Cylindrical Micelles and Block Comicelles of Controlled Length in Aqueous Media
Nazemi, A., Boott, C. E., Lunn, D. J., Gwyther, J., Hayward, D. W., Richardson, R. M., Winnik, M. A., & Ian Manners, A. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.5b13416 · Cited by 103 · see citing works
Extending the Scope of “Living” Crystallization-Driven Self-Assembly: Well-Defined 1D Micelles and Block Comicelles from Crystallizable Polycarbonate Block Copolymers
Finnegan, J. R., He, X., Street, S. T. G., Garcia-Hernandez, J. D., Hayward, D. W., Harniman, R. L., Richardson, R. M., Whittell, G. R., & Ian Manners, A. (2018) · Journal of the American Chemical Society · doi:10.1021/jacs.8b09861 · Cited by 103 · see citing works
“79,80 The rectangular core characteristic of the PFTMC fiber-like micelles leads to the interesting phenomenon where they can lie in two different orientations on a substrate, either on their largest face or on their edge (Figure 2).”
Background
Seeded Self-Assembly of Charge-Terminated Poly(3-hexylthiophene) Amphiphiles Based on the Energy Landscape
Fukui, T., Garcia-Hernandez, J. D., MacFarlane, L. R., Lei, S., Whittell, G. R., & Ian Manners, A. (2020) · Journal of the American Chemical Society · doi:10.1021/jacs.0c06185 · Cited by 87 · see citing works
Design of block copolymer micelles via crystallization
Crassous, J. J., Schurtenberger, P., Ballauff, M., & Mihut, A. M. (2015) · Polymer · doi:10.1016/j.polymer.2015.02.030 · Cited by 82 · see citing works
Probing the Growth Kinetics for the Formation of Uniform 1D Block Copolymer Nanoparticles by Living Crystallization-Driven Self-Assembly
Boott, C. E., Leitao, E. M., Hayward, D. W., Laine, R. F., Mahou, P., Guérin, G., Winnik, M. A., Richardson, R. M., Kaminski, C. F., Whittell, G. R., et al. (2018) · ACS Nano · doi:10.1021/acsnano.8b01353 · Cited by 82 · see citing works
Hierarchical Assembly of Cylindrical Block Comicelles Mediated by Spatially Confined Hydrogen-Bonding Interactions
Li, X., Gao, Y., Harniman, R. L., Winnik, M. A., & Ian Manners, A. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.6b05973 · Cited by 78 · see citing works
In-plane aligned assemblies of 1D-nanoobjects: recent approaches and applications
Hu, H., Wang, S., Feng, X., Pauly, M., Decher, G., & Long, Y. (2019) · Chemical Society Reviews · doi:10.1039/c9cs00382g · Cited by 77 · see citing works
Uniform 1D Micelles and Patchy & Block Comicelles via Scalable, One-Step Crystallization-Driven Block Copolymer Self-Assembly
Song, S., Liu, X., Nikbin, E., Howe, J. Y., Yu, Q. Y., Ian Manners, A., & Winnik, M. A. (2021) · Journal of the American Chemical Society · doi:10.1021/jacs.1c02395 · Cited by 75 · see citing works
“Cross” Supermicelles via the Hierarchical Assembly of Amphiphilic Cylindrical Triblock Comicelles
Li, X., Gao, Y., Boott, C. E., Hayward, D. W., Harniman, R. L., Whittell, G. R., Richardson, R. M., Winnik, M. A., & Ian Manners, A. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.5b12735 · Cited by 75 · see citing works
Supramolecular Nanosheets Assembled from Poly(ethylene glycol)-b-poly(N-(2-phenylethyl)glycine) Diblock Copolymer Containing Crystallizable Hydrophobic Polypeptoid: Crystallization Driven Assembly Transition from Filaments to Nanosheets
Wei, Y., Tian, J., Zhang, Z., Zhu, C., Sun, J., & Li, Z. (2019) · Macromolecules · doi:10.1021/acs.macromol.8b02230 · Cited by 73 · see citing works
Cylindrical crystalline-core micelles: pushing the limits of solution self-assembly
Schmelz, J., Schacher, F. H., & Schmalz, H. (2012) · Soft Matter · doi:10.1039/c2sm27259h · Cited by 70 · see citing works
Branched Cylindrical Micelles via Crystallization-Driven Self-Assembly
Qiu, H., Du, V. A., Winnik, M. A., & Ian Manners, A. (2013) · Journal of the American Chemical Society · doi:10.1021/ja410176n · Cited by 66 · see citing works
Crystallization-Driven Self-Assembly of Coil–Comb-Shaped Polypeptoid Block Copolymers: Solution Morphology and Self-Assembly Pathways
Jiang, N., Yu, T., Darvish, O. A., Qian, S., Tsengam, I. K. M., John, V. T., & Zhang, D. (2019) · Macromolecules · doi:10.1021/acs.macromol.9b01546 · Cited by 63 · see citing works
Formation of Lenticular Platelet Micelles via the Interplay of Crystallization and Chain Stretching: Solution Self-Assembly of Poly(ferrocenyldimethylsilane)-block-poly(2-vinylpyridine) with a Crystallizable Core-Forming Metalloblock
Yusoff, S. F. M., Hsiao, M.-S., Schacher, F. H., Winnik, M. A., & Ian Manners, A. (2012) · Macromolecules · doi:10.1021/ma2027726 · Cited by 57 · see citing works
AIE-Active, Stimuli-Responsive Fluorescent 2D Block Copolymer Nanoplatelets Based on Corona Chain Compression
Lei, S., Tian, J., Kang, Y., Zhang, Y., & Ian Manners, A. (2022) · Journal of the American Chemical Society · doi:10.1021/jacs.2c07133 · Cited by 56 · see citing works
Stealth nanorods via the aqueous living crystallisation-driven self-assembly of poly(2-oxazoline)s
Finnegan, J. R., Pilkington, E. H., Alt, K., Rahim, M. A., Kent, S. J., Davis, T. P., & Kempe, K. (2021) · Chemical Science · doi:10.1039/d1sc00938a · Cited by 57 · see citing works
Crystallization-Driven Thermoreversible Gelation of Coil-Crystalline Cyclic and Linear Diblock Copolypeptoids
Lee, C., Lu, L., Chen, J., Garno, J. C., & Zhang, D. (2013) · ACS Macro Letters · doi:10.1021/mz300667n · Cited by 55 · see citing works
High-resolution cryo-electron microscopy structure of block copolymer nanofibres with a crystalline core
Tian, J., Xie, S., Borucu, U., Lei, S., Zhang, Y., & Ian Manners, A. (2023) · Nature Materials · doi:10.1038/s41563-023-01559-4 · Cited by 52 · see citing works
Efficient Energy Funneling in Spatially Tailored Segmented Conjugated Block Copolymer Nanofiber–Quantum Dot or Rod Conjugates
Zhang, Y., Shaikh, H., Sneyd, A. J., Tian, J., Xiao, J., Blackburn, A. M., Rao, A., Friend, R. H., & Ian Manners, A. (2021) · Journal of the American Chemical Society · doi:10.1021/jacs.1c01571 · Cited by 48 · see citing works
Role of Competitive Crystallization Kinetics in the Formation of 2D Platelets with Distinct Coronal Surface Patterns via Seeded Growth
Deng, R., Mao, X., Pearce, S., Tian, J., Zhang, Y., & Ian Manners, A. (2022) · Journal of the American Chemical Society · doi:10.1021/jacs.2c07962 · Cited by 46 · see citing works
Polyferrocenylsilane Block Copolymer Spherulites in Dilute Solution
Jiang, J., Nikbin, E., Hicks, G. E. J., Song, S., Liu, Y., Wong, E. C. N., Ian Manners, A., Howe, J. Y., & Winnik, M. A. (2023) · Journal of the American Chemical Society · doi:10.1021/jacs.2c11119 · Cited by 46 · see citing works
Tailored Energy Funneling in Photocatalytic π-Conjugated Polymer Nanofibers for High-Performance Hydrogen Production
Zhang, Y., Tian, J., Shaikh, H., MacKenzie, H. K., He, Y., Zhao, C., Lei, S., Ren, Y., & Ian Manners, A. (2023) · Journal of the American Chemical Society · doi:10.1021/jacs.3c07443 · Cited by 46 · see citing works
Fiber‐Like Micelles from the Crystallization‐Driven Self‐Assembly of Poly(3‐heptylselenophene)‐block‐Polystyrene
Kynaston, E. L., Gould, O. E. C., Gwyther, J., Whittell, G. R., Winnik, M. A., & Ian Manners, A. (2015) · Macromolecular Chemistry and Physics · doi:10.1002/macp.201400541 · Cited by 44 · see citing works
Toward Uniform Nanofibers with a π-Conjugated Core: Optimizing the “Living” Crystallization-Driven Self-Assembly of Diblock Copolymers with a Poly(3-octylthiophene) Core-Forming Block
Tritschler, U., Gwyther, J., Harniman, R. L., Whittell, G. R., Winnik, M. A., & Ian Manners, A. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b00488 · Cited by 42 · see citing works
Uniform, High-Aspect-Ratio, and Patchy 2D Platelets by Living Crystallization-Driven Self-Assembly of Crystallizable Poly(ferrocenyldimethylsilane)-Based Homopolymers with Hydrophilic Charged Termini
Pearce, S., He, X., Hsiao, M.-S., Harniman, R. L., MacFarlane, L. R., & Ian Manners, A. (2019) · Macromolecules · doi:10.1021/acs.macromol.9b00904 · Cited by 41 · see citing works
Deciphering Evolution, Function, and Observation of Crystallization-Driven Self-Assembly
Xia, T., Xiao, L., Xie, Y., Dove, A. P., & O’Reilly, R. K. (2025) · Chemical Reviews · doi:10.1021/acs.chemrev.5c00298 · Cited by 40 · see citing works
Hierarchical Polymer–Carbon Nanotube Hybrid Mesostructures by Crystallization-Driven Self-Assembly
Jia, L., Petretic, A., Molev, G., Guérin, G., Ian Manners, A., & Winnik, M. A. (2015) · ACS Nano · doi:10.1021/acsnano.5b01176 · Cited by 39 · see citing works
Self‐Assembly of Copolymers Containing Crystallizable Blocks: Strategies and Applications
Shi, B., Shen, D., Li, W., & Wang, G. (2022) · Macromolecular Rapid Communications · doi:10.1002/marc.202200071 · Cited by 39 · see citing works
Uniform Toroidal Micelles via the Solution Self-Assembly of Block Copolymer–Homopolymer Blends Using a “Frustrated Crystallization” Approach
Qiu, H., Oliver, A. M., Gwyther, J., Cai, J., Harniman, R. L., Hayward, D. W., & Ian Manners, A. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b02227 · Cited by 37 · see citing works
“6a,c).(33-35,52) However, the toroidal micelles derived from the co-assembly of the PFDMS36-b-P2VP502/PFDMS20 blends in 1:5 v/v THF/IPA that had been quenched with water (50% v/v) in order to preserve the toroidal structure displayed an”
Method
Experimental and Theoretical Study of the Living Polymerization of N-Silylphosphoranimines. Synthesis of New Block Copolyphosphazenes
Suárez‐Suárez, S., Soto, D. P., Carriedo, G. A., Soto, A. P., & Staubitz, A. (2012) · Organometallics · doi:10.1021/om201012g · Cited by 36 · see citing works
Lateral Growth of 1D Core-Crystalline Micelles upon Annealing in Solution
Guérin, G., Rupar, P. A., Molev, G., Ian Manners, A., Jinnai, H., & Winnik, M. A. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b01487 · Cited by 36 · see citing works
Water‐Soluble Metallocene‐Containing Polymers
Alkan, A., & Wurm, F. R. (2016) · Macromolecular Rapid Communications · doi:10.1002/marc.201600205 · Cited by 33 · see citing works
Synthesis and crystallization-driven solution self-assembly of polyferrocenylsilane diblock copolymers with polymethacrylate corona-forming blocks
McGrath, N., Schacher, F. H., Qiu, H., Mann, S., Winnik, M. A., & Ian Manners, A. (2013) · Polymer Chemistry · doi:10.1039/c3py01383a · Cited by 32 · see citing works
Polyferrocenylsilane Crystals in Nanoconfinement: Fragmentation, Dissolution, and Regrowth of Cylindrical Block Copolymer Micelles with a Crystalline Core
Qian, J., Lu, Y., Cambridge, G., Guérin, G., Ian Manners, A., & Winnik, M. A. (2012) · Macromolecules · doi:10.1021/ma3014788 · Cited by 32 · see citing works
Defect-Induced Secondary Crystals Drive Two-Dimensional to Three-Dimensional Morphological Evolution in the Co-Self-Assembly of Polyferrocenylsilane Block Copolymer and Homopolymer
Jiang, J., Nikbin, E., Liu, Y., Lei, S., Ye, G., Howe, J. Y., Ian Manners, A., & Winnik, M. A. (2023) · Journal of the American Chemical Society · doi:10.1021/jacs.3c09791 · Cited by 30 · see citing works
Controlled thiol–ene post-polymerization reactions on polyferrocenylsilane homopolymers and block copolymers
Chabanne, L., Pfirrmann, S., Lunn, D. J., & Ian Manners, A. (2013) · Polymer Chemistry · doi:10.1039/c3py21129k · Cited by 30 · see citing works
Manipulation and Deposition of Complex, Functional Block Copolymer Nanostructures Using Optical Tweezers
Gould, O. E. C., Box, S. J., Boott, C. E., Ward, A. D., Winnik, M. A., Miles, M. J., & Ian Manners, A. (2019) · ACS Nano · doi:10.1021/acsnano.9b00342 · Cited by 29 · see citing works
Structure of the Crystalline Core of Fiber-like Polythiophene Block Copolymer Micelles
Hayward, D. W., Lunn, D. J., Seddon, A., Finnegan, J. R., Gould, O. E. C., Magdysyuk, O., Manners, I., Whittell, G. R., & Richardson, R. M. (2018) · Macromolecules · doi:10.1021/acs.macromol.7b02552 · Cited by 28 · see citing works
Beyond simple small-angle X-ray scattering: developments in online complementary techniques and sample environments
Bras, W., Koizumi, S., & Terrill, N. (2014) · IUCrJ · doi:10.1107/s2052252514019198 · Cited by 27 · see citing works
“As an example, the self-assembly of polyisoprene-blockpolyferrocenylsilane, PI550-b-PFS50, in decane solution can be mentioned (Gilroy et al., 2011) (Fig.”
Background
Liquid Crystalline Phase Behavior of Well-Defined Cylindrical Block Copolymer Micelles Using Synchrotron Small-Angle X-ray Scattering
Hayward, D. W., Gilroy, J. B., Rupar, P. A., Chabanne, L., Pizzey, C. L., Winnik, M. A., Whittell, G. R., Ian Manners, A., & Richardson, R. M. (2015) · Macromolecules · doi:10.1021/ma502222f · Cited by 27 · see citing works
Polystyrene-block-polyethylene-block-polystyrene triblock copolymers: Synthesis and crystallization-driven self-assembly behavior
Xu, S., Zhang, C., Li, L., & Zheng, S. (2017) · Polymer · doi:10.1016/j.polymer.2017.09.002 · Cited by 27 · see citing works
Formation of 2D and 3D multi-tori mesostructures via crystallization-driven self-assembly
Guérin, G., Cruz, M. V., & Yu, Q. Y. (2020) · Science Advances · doi:10.1126/sciadv.aaz7301 · Cited by 27 · see citing works
A Small-Angle Neutron Scattering Environment for In-Situ Observation of Chemical Processes
Hayward, D. W., Chiappisi, L., Prévost, S. F., Schweins, R., & Gradzielski, M. (2018) · Scientific Reports · doi:10.1038/s41598-018-24718-z · Cited by 25 · see citing works
Organometallic–Polypeptide Diblock Copolymers: Synthesis by Diels–Alder Coupling and Crystallization-Driven Self-Assembly to Uniform Truncated Elliptical Lamellae
Molev, G., Lu, Y., Kim, K. S., Chab‐Majdalani, I., Guérin, G., Petrov, S., Walker, G. C., Ian Manners, A., & Winnik, M. A. (2014) · Macromolecules · doi:10.1021/ma402441y · Cited by 25 · see citing works
Exploring the “Living” Growth of Block Copolymer Nanofibers from Surface-Confined Seeds by In Situ Solution-Phase Atomic Force Microscopy
Harniman, R. L., Pearce, S., & Ian Manners, A. (2022) · Journal of the American Chemical Society · doi:10.1021/jacs.1c11209 · Cited by 21 · see citing works
Evaluation of the Cross Section of Elongated Micelles by Static and Dynamic Light Scattering
Guérin, G., Qi, F., Cambridge, G., Ian Manners, A., & Winnik, M. A. (2012) · The Journal of Physical Chemistry B · doi:10.1021/jp210454z · Cited by 19 · see citing works
Novel thermosensitive telechelic PEGs with antioxidant activity: synthesis, molecular properties and conformational behaviour
Sergeeva, O. Y., Vlasov, P. S., Domnina, N. S., Bogomolova, A., Konarev, P. V., Svergun, D. I., Walterová, Z., Horský, J., Štěpánek, P., & Filippov, S. K. (2014) · RSC Advances · doi:10.1039/c4ra06978a · Cited by 18 · see citing works
Computational Reverse Engineering Analysis for Scattering Experiments (CREASE) on Vesicles Assembled from Amphiphilic Macromolecular Solutions
Ye, Z., Wu, Z., & Jayaraman, A. (2021) · JACS Au · doi:10.1021/jacsau.1c00305 · Cited by 17 · see citing works
Orientational Distribution Function of Aligned Elongated Molecules and Particulates Determined from Their Scattering Signature
Huang, G.-R., Wang, Y., Do, C., Shinohara, Y., Egami, T., Porcar, L., Liu, Y., & Chen, W. (2019) · ACS Macro Letters · doi:10.1021/acsmacrolett.9b00496 · Cited by 16 · see citing works
NMR Study of the Dissolution of Core-Crystalline Micelles
Yu, Q. Y., Pichugin, D., Cruz, M. V., Guérin, G., Ian Manners, A., & Winnik, M. A. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b00098 · Cited by 16 · see citing works
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Method
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Reorientation of the poly(3-hydroxybutyrate- co -3-hydroxyhexanoate) crystal in thin film induced by polyethylene glycol
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The interaction between fundamental and industrial research and experimental developments in the field of polymer crystallization
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Crystallization-Driven Self-Assembly of Polyferrocenyldimethylsilane Block Copolymers with the Corona Modified with Pendant Amino Groups
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Synthesis and Solution Self‐Assembly of Polyisoprene‐block‐poly(ferrocenylmethylsilane): A Diblock Copolymer with an Atactic but Semicrystalline Core‐Forming Metalloblock
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An exact inversion method for extracting orientation ordering by small-angle scattering
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Synthesis and solution self-assembly of block copolymers with a gradient, crystallizable polyferrocenylsilane core-forming metalloblock
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Block Copolymer Networks Composed of Poly(ε-caprolactone) and Polyethylene with Triple Shape Memory Properties
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Poly(γ-benzyl-l-glutamate) decorated with cyanoferrate complex: synthesis, characterization and electrochemical properties
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Thioether‐Facilitated Iridium‐Catalyzed Hydrosilylation of Steric 1,1‐Disubstituted Olefins
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A temperature-controlled electric field sample environment for small-angle neutron scattering experiments
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Probing the Heteroepitaxial Seeded Growth and Self‐Sorting Processes of Segmented Co‐Micelles with Chemically Distinct Crystalline Cores
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Semi-conductive micellar networks of all-conjugated diblock and triblock copolymer blends
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Elongated particles in flow: commentary on small-angle scattering investigations
Huang, G.-R., Porcar, L., Murphy, R. P., Shinohara, Y., Wang, Y., Carrillo, J. Y., Sumpter, B. G., Tung, C.-H., Ding, L., Do, C., et al. (2025) · Journal of Applied Crystallography · doi:10.1107/s1600576725002900 · Cited by 4 · see citing works
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An investigation into the hexagonal phases formed in high-concentration dispersions of well-defined cylindrical block copolymer micelles
Hayward, D. W., Whittell, G. R., Gilroy, J. B., Ian Manners, A., & Richardson, R. M. (2016) · Liquid Crystals · doi:10.1080/02678292.2016.1170217 · Cited by 3 · see citing works
“[6,7] A further advantage of the block copolymer selfassembly route is the potential to carefully tune the inter-particle interactions.”
Background
Simple Preparation of Sophisticated Multiresponsive Core‐Crystalline Micelles via an Approach Reminiscent of the Division of Labor in Microorganisms
Zhao, J., Qi, F., Li, L., Jiang, J., Lei, S., Du, Y., Yu, Q. Y., Lin, J., Winnik, M. A., & Guérin, G. (2025) · Small Structures · doi:10.1002/sstr.202400641 · Cited by 2 · see citing works
Two-Dimensional Reversible Supramolecular Polymorphism Governed by Weak Solvent–Solute Interactions
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Synthesis and Properties of Poly(ferrocenylsilane)s Containing Si-Vinylene Units in the Main Chain
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Probing the Heteroepitaxial Seeded Growth and Self‐Sorting Processes of Segmented Co‐Micelles with Chemically Distinct Crystalline Cores
Pearce, S., MacKenzie, H. K., Shaikh, H., Liu, Z., Harniman, R. L., Eloi, J., Davis, S. A., Richardson, R. M., LaPierre, E. A., Ian Manners, A., et al. (2025) · Angewandte Chemie · doi:10.1002/ange.202506872
Living Crystallization-driven Self-assembly
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Liquid Crystalline Phase Behavior of Well-Defined Cylindrical Block Copolymer Micelles Using Synchrotron Small-Angle X-ray Scattering
Hayward, D. W., Gilroy, J. B., Rupar, P. A., Chabanne, L., Pizzey, C. L., Winnik, M. A., Whittell, G. R., Ian Manners, A., & Richardson, R. M. (2015) · Macromolecules · doi:10.1021/ma502222f · Cited by 27 · see citing works
Synthesis and solution self-assembly of block copolymers with a gradient, crystallizable polyferrocenylsilane core-forming metalloblock
Schacher, F. H., Bellas, V., Winnik, M. A., & Ian Manners, A. (2013) · Soft Matter · doi:10.1039/c3sm50859e · Cited by 11 · see citing works
Structure of the Crystalline Core of Fiber-like Polythiophene Block Copolymer Micelles
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Solution Self-Assembly of Blends of Crystalline-Coil Polyferrocenylsilane-block-polyisoprene with Crystallizable Polyferrocenylsilane Homopolymer
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Self-Assembly of Organometallic Block Copolymers: The Role of Crystallinity of the Core-Forming Polyferrocene Block in the Micellar Morphologies Formed by Poly(ferrocenylsilane-b-dimethylsiloxane) in n-Alkane Solvents
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Authors: Gilroy, J. B., Rupar, P. A., Whittell, G. R., Chabanne, L., Terrill, N. J., Winnik, M. A., Manners, I., & Richardson, R. M.
Affiliations: University of Bristol (GB)
Diamond Light Source (GB)
University of Toronto (CA)
School of Chemistry, University of Bristol, Bristol, United Kingdom, BS8 1TS
Corresponding author: Winnik, Mitchell A.
Richardson, Robert M.
ORCID: Gilroy, Joe B.
Rupar, Paul A.
Whittell, George R.
Terrill, Nicholas J.
Winnik, Mitchell A.
Richardson, Robert M.
Venue: Journal of the American Chemical Society
Publisher: American Chemical Society (ACS)
Published: 2011-09-30
Volume: 133
Issue: 42
Pages: 17056-17062
ISSN: 0002-7863 (ISSN-L)
1520-5126
DOI: 10.1021/ja207417z
OpenAlex: W1990943133
Cited by: 97
References: 94
Citations by year: 2026: 1 · 2025: 6 · 2024: 2 · 2023: 5 · 2022: 6 · 2021: 9 · 2020: 2 · 2019: 9 · 2018: 8 · 2017: 8 · 2016: 12 · 2015: 6 · 2014: 6 · 2013: 10 · 2012: 7
FWCI: 3.61
Type: journal article
Language: en
Open access: closed
Locations: Journal of the American Chemical Society (publishedVersion)
PubMed (publishedVersion)
Bristol Research (University of Bristol) (submittedVersion)
Explore Bristol Research (submittedVersion)
Topics: Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
Keywords: block copolymer self-assembly, cylindrical micelles, field alignment, polymer crystallization, core-shell nanoparticles, epitaxial growth, polymer crystallinity

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Probing the Structure of the Crystalline Core of Field-Aligned, Monodisperse, Cylindrical Polyisoprene-block-Polyferrocenylsilane Micelles in Solution Using Synchrotron Small- and Wide-Angle X-ray Scattering

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