AI帮你理解科学

AI 生成解读视频

AI抽取解析论文重点内容自动生成视频


pub
生成解读视频

AI 溯源

AI解析本论文相关学术脉络


Master Reading Tree
生成 溯源树

AI 精读

AI抽取本论文的概要总结


微博一下
We have found that the PFS crystallites obtained act as efficient initiators for crystallization-driven living self-assembly to allow the formation of monodisperse cylindrical micelles with a PFS PFS50 core

Monodisperse cylindrical micelles by crystallization-driven living self-assembly

NATURE CHEMISTRY, no. 7 (2010): 566.0-570

被引用298|浏览12
WOS NATURE
下载 PDF 全文
引用
微博一下

摘要

Non-spherical nanostructures derived from soft matter and with uniform size-that is, monodisperse materials-are of particular utility and interest, but are very rare outside the biological domain. We report the controlled formation of highly monodisperse cylindrical block copolymer micelles (length dispersity <= 1.03; length range, simila...更多

代码

数据

0
简介
  • Non-spherical nanostructures derived from soft matter and with uniform size—that is, monodisperse materials—are of particular utility and interest, but are very rare outside the biological domain.
  • The authors show that by using very small and uniform sterically stabilized PFS crystallites as seeds, this crystallization-driven living self-assembly process can be used to fabricate highly monodisperse nanocylinders of controlled length (Fig. 1).
  • The short length of the core-forming PFS block and the long sonication time drive the scission of the cylinders down to very small crystallites, with minimal degradation of the block copolymer (Supplementary Figs
重点内容
  • Non-spherical nanostructures derived from soft matter and with uniform size—that is, monodisperse materials—are of particular utility and interest, but are very rare outside the biological domain
  • This process is driven by the epitaxial crystallization of the core-forming PFS block and allows for their length to be increased by the addition of PFS block-copolymer unimers by means of a process termed crystallization-driven living self-assembly
  • By using cylindrical seed micelles formed by sonication of longer structures as initiators, we have shown that polydisperse cylinders (length dispersity (Lw/Ln) . 1.4 where Lw is the weight-average length and Ln the number-average length) with controlled lengths of up to 2 mm can be formed
  • We have found that the PFS crystallites obtained act as efficient initiators for crystallization-driven living self-assembly to allow the formation of monodisperse cylindrical micelles (Lw/Ln ≤ 1.03) with a PFS PFS50 core
  • We have explored the alignment behaviour of two samples of highly monodisperse nanocylinders of lengths 188 and 731 nm prepared by the aforementioned crystallite-initiated living self-assembly method by using small-angle X-ray scattering (SAXS) techniques
  • The SAXS data collected for the sample in a 4.7 V mm[21] electric field illustrate the alignment of the cylindrical micelles in the direction parallel to the electric field (Fig. 4b, Table 1 | Contour length data for stub-like PFS-b-PDMS
结果
  • The authors have found that the PFS crystallites obtained act as efficient initiators for crystallization-driven living self-assembly to allow the formation of monodisperse cylindrical micelles (Lw/Ln ≤ 1.03) with a PFS PFS50 core.
  • The resulting colloidal solutions were studied by TEM, and the micrographs (Fig. 3) showed cylindrical micelles with average lengths Ln between 236 and 1,787 nm, very narrow length dispersities (Table 1) and an average core width of 12 nm.
  • The length of the resulting cylinders is linearly dependent on the unimer-to-seed ratio, and yields Gaussian length distributions for each sample of cylindrical micelles (Fig. 3e; see Supplementary Fig. S6 and Table S3).
  • The seed crystallites serve as initiators for the crystallization-driven living self-assembly of added unimers into cylindrical micelles, in analogy to the small initiator molecules used in the most well-behaved classical living polymerization reactions.
  • The authors have explored the alignment behaviour of two samples of highly monodisperse nanocylinders of lengths 188 and 731 nm prepared by the aforementioned crystallite-initiated living self-assembly method by using small-angle X-ray scattering (SAXS) techniques.
  • The origin of this signal can be attributed to alignment of the cylinders with the vertical long axis of the capillary tube to minimize the interaction energy of the rigid rod-like micelles with the curved surface.
  • The SAXS data collected for the sample in a 4.7 V mm[21] electric field illustrate the alignment of the cylindrical micelles in the direction parallel to the electric field (Fig. 4b, Table 1 | Contour length data for stub-like PFS-b-PDMS
结论
  • The electric field alignment behaviour studied by SAXS indicates that at a cylindrical micelle concentration of 25 mg ml[21] the colloidal solution of 731 nm nanocylinders is isotropic, and neither the capillary surface nor an electric field can impose a preferred direction.
  • The authors have demonstrated that by using very small ( 20 nm) uniform crystallites as seed initiators, monodisperse nanocylinders of variable length are accessible using a crystallization-driven living self-assembly process.
  • The ability to prepare different nanocylinder samples with narrow dispersities in length has allowed them to identify length-dependent, field-responsive liquid-crystalline behaviour of monodisperse cylindrical nanostructures.
总结
  • Non-spherical nanostructures derived from soft matter and with uniform size—that is, monodisperse materials—are of particular utility and interest, but are very rare outside the biological domain.
  • The authors show that by using very small and uniform sterically stabilized PFS crystallites as seeds, this crystallization-driven living self-assembly process can be used to fabricate highly monodisperse nanocylinders of controlled length (Fig. 1).
  • The short length of the core-forming PFS block and the long sonication time drive the scission of the cylinders down to very small crystallites, with minimal degradation of the block copolymer (Supplementary Figs
  • The authors have found that the PFS crystallites obtained act as efficient initiators for crystallization-driven living self-assembly to allow the formation of monodisperse cylindrical micelles (Lw/Ln ≤ 1.03) with a PFS PFS50 core.
  • The resulting colloidal solutions were studied by TEM, and the micrographs (Fig. 3) showed cylindrical micelles with average lengths Ln between 236 and 1,787 nm, very narrow length dispersities (Table 1) and an average core width of 12 nm.
  • The length of the resulting cylinders is linearly dependent on the unimer-to-seed ratio, and yields Gaussian length distributions for each sample of cylindrical micelles (Fig. 3e; see Supplementary Fig. S6 and Table S3).
  • The seed crystallites serve as initiators for the crystallization-driven living self-assembly of added unimers into cylindrical micelles, in analogy to the small initiator molecules used in the most well-behaved classical living polymerization reactions.
  • The authors have explored the alignment behaviour of two samples of highly monodisperse nanocylinders of lengths 188 and 731 nm prepared by the aforementioned crystallite-initiated living self-assembly method by using small-angle X-ray scattering (SAXS) techniques.
  • The origin of this signal can be attributed to alignment of the cylinders with the vertical long axis of the capillary tube to minimize the interaction energy of the rigid rod-like micelles with the curved surface.
  • The SAXS data collected for the sample in a 4.7 V mm[21] electric field illustrate the alignment of the cylindrical micelles in the direction parallel to the electric field (Fig. 4b, Table 1 | Contour length data for stub-like PFS-b-PDMS
  • The electric field alignment behaviour studied by SAXS indicates that at a cylindrical micelle concentration of 25 mg ml[21] the colloidal solution of 731 nm nanocylinders is isotropic, and neither the capillary surface nor an electric field can impose a preferred direction.
  • The authors have demonstrated that by using very small ( 20 nm) uniform crystallites as seed initiators, monodisperse nanocylinders of variable length are accessible using a crystallization-driven living self-assembly process.
  • The ability to prepare different nanocylinder samples with narrow dispersities in length has allowed them to identify length-dependent, field-responsive liquid-crystalline behaviour of monodisperse cylindrical nanostructures.
表格
  • Table1: Contour length data (nm) for stub-like PFS-b-PDMS
Download tables as Excel
基金
  • I.M. thanks the European Union for a Marie Curie Chair, a Reintegration Grant and an Advanced Investigator Grant, and also the Royal Society for a Wolfson Research Merit Award
  • M.A.W. also thanks NSERC for financial support
引用论文
  • Mann, S. Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions. Nature Mater. 8, 781–792 (2009).
    Google ScholarLocate open access versionFindings
  • Douglas, T. & Young, M. Viruses: making friends with old foes. Science 312, 873–875 (2006).
    Google ScholarLocate open access versionFindings
  • Mao, C. et al. Virus-based toolkit for the directed synthesis of magnetic and semiconducting nanowires. Science 303, 213–217 (2004).
    Google ScholarLocate open access versionFindings
  • Aldaye, F. A., Palmer, A. L. & Sleiman, H. F. Assembling materials with DNA as the guide. Science 321, 1795–1799 (2008).
    Google ScholarLocate open access versionFindings
  • Nie, Z., Petukhova, A. & Kumacheva, E. Properties and emerging applications of self-assembled structures made from inorganic nanoparticles. Nature Nanotech. 5, 15–25 (2010).
    Google ScholarLocate open access versionFindings
  • Tseng, R. J. et al. Digital memory device based on tobacco mosaic virus conjugated with nanoparticles. Nature Nanotech. 1, 72–77 (2006).
    Google ScholarLocate open access versionFindings
  • Aldaye, F. A. & Sleiman, H. F. Dynamic DNA templates for discrete gold nanoparticle assemblies: control of geometry, modularity, write/erase and structural switching. J. Am. Chem. Soc. 129, 4130–4131 (2007).
    Google ScholarLocate open access versionFindings
  • Zha, L., Zhang, Y., Yang, W. & Fu, S. Monodisperse temperature-sensitive microcontainers. Adv. Mater. 14, 1090–1092 (2002).
    Google ScholarLocate open access versionFindings
  • Yi, G.-R. et al. Generation of uniform colloidal assemblies in soft microfluidic devices. Adv. Mater. 15, 1300–1304 (2003).
    Google ScholarLocate open access versionFindings
  • Fernandez-Nieves, A. et al. Optically anisotropic colloids of controllable shape. Adv. Mater. 17, 680–684 (2005).
    Google ScholarLocate open access versionFindings
  • Zoldesi, C. I. & Imhof, A. Synthesis of monodisperse colloidal spheres, capsules and microballoons by emulsion templating. Adv. Mater. 17, 924–928 (2005).
    Google ScholarLocate open access versionFindings
  • Yuan, J. et al. Water-soluble organo–silica hybrid nanowires. Nature Mater. 7, 718–722 (2008).
    Google ScholarLocate open access versionFindings
  • Qian, J., Zhang, M., Manners, I. & Winnik, M. A. Nanofiber micelles from the self-assembly of block copolymers. Trends Biotechnol. 28, 84–92 (2010).
    Google ScholarLocate open access versionFindings
  • Gohy, J.-F. Block copolymer micelles. Adv. Polym. Sci. 190, 65–136 (2005).
    Google ScholarLocate open access versionFindings
  • Alexandridis, P. & Lindman, B. Amphiphilic Block Copolymers: Self-Assembly and Applications (Elsevier, 2000).
    Google ScholarFindings
  • Zhang, L. & Eisenberg, A. Multiple morphologies of ‘crew-cut’ aggregates of polystyrene-b-poly(acrylic acid) block copolymers. Science 268, 1728–1731 (1995).
    Google ScholarLocate open access versionFindings
  • Liu, G. et al. Polystyrene-block-poly(2-cinnamoylethyl methacrylate) nanofibers—preparation, characterization and liquid crystalline properties. Chem. Eur. J. 5, 2740–2749 (1999).
    Google ScholarLocate open access versionFindings
  • Jain, S. & Bates, F. S. On the origins of morphological complexity in block copolymer surfactants. Science 300, 460–464 (2003).
    Google ScholarLocate open access versionFindings
  • Pochan, D. J. et al. Toroidal triblock copolymer assemblies. Science 306, 94–97 (2004).
    Google ScholarLocate open access versionFindings
  • Cui, H. et al. Block copolymer assembly via kinetic control. Science 317, 647–650 (2007).
    Google ScholarLocate open access versionFindings
  • Hu, J., Liu, G. & Nijkang, G. Hierarchical interfacial assembly of ABC triblock copolymer. J. Am. Chem. Soc. 130, 3236–3237 (2008).
    Google ScholarLocate open access versionFindings
  • Walther, A. et al. Self-assembly of janus cylinders into hierarchical superstructures. J. Am. Chem. Soc. 131, 4720–4728 (2009).
    Google ScholarLocate open access versionFindings
  • Geng, Y. et al. Shape effects of filaments versus spherical particles in flow and drug delivery. Nature Nanotech. 2, 249–255 (2007).
    Google ScholarLocate open access versionFindings
  • Thio, Y. S., Wu, J. & Bates, F. S. Epoxy toughening using low molecular weight poly(hexylene oxide)–poly(ethylene oxide) diblock copolymers. Macromolecules 39, 7187–7189 (2006).
    Google ScholarLocate open access versionFindings
  • Cao, L. et al. Reactive ion etching of cylindrical polyferrocenylsilane block copolymer micelles: fabrication of ceramic nanolines on semiconducting substrates. Adv. Funct. Mater. 13, 271–276 (2003).
    Google ScholarLocate open access versionFindings
  • Yu, S. M. et al. Smectic ordering in solutions and films of a rod-like polymer owing to monodispersity of chain length. Nature 389, 167–170 (1997).
    Google ScholarLocate open access versionFindings
  • Joannic, R., Auvray, L. & Lasic, D. D. Monodisperse vesicles stabilized by grafted polymers. Phys. Rev. Lett. 78, 3402–3405 (1997).
    Google ScholarLocate open access versionFindings
  • Yan, X., Liu, G., Haeussler, M. & Tang, B. Z. Water-dispersible polymer/Pd/Ni hybrid magnetic nanofibers. Chem. Mater. 17, 6053–6059 (2005).
    Google ScholarLocate open access versionFindings
  • Nam, K. T. et al. Virus-enabled synthesis and assembly of nanowires for lithium ion battery electrodes. Science 312, 885–888 (2006).
    Google ScholarLocate open access versionFindings
  • Massey, J. A. et al. 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. J. Am. Chem. Soc. 122, 11577–11584 (2000).
    Google ScholarLocate open access versionFindings
  • Wang, X. et al. Cylindrical block copolymer micelles and co-micelles of controlled length and architecture. Science 317, 644–647 (2007).
    Google ScholarLocate open access versionFindings
  • Guerin, G., Wang, H., Manners, I. & Winnik, M. A. Fragmentation of fiber-like structures: sonication studies of cylindrical block copolymer micelles and behavioral comparisons to biological fibrils. J. Am. Chem. Soc. 130, 14763–14771 (2008).
    Google ScholarLocate open access versionFindings
  • Israelachvili, J. Intermolecular and Surface Forces, 2nd edn (Academic Press, 1992).
    Google ScholarFindings
  • Kato, T., Mizoshita, N. & Kishimoto, K. Functional liquid-crystalline assemblies: self-organized soft materials. Angew. Chem. Int. Ed. 45, 38–68 (2006).
    Google ScholarLocate open access versionFindings
  • Oldenbourg, R., Wen, X., Meyer, R. B. & Caspar, D. L. D. Orientational distribution function in nematic tobacco-mosaic-virus liquid-crystals measured by X-ray diffraction. Phys. Rev. Lett. 61, 1851–1854 (1988).
    Google ScholarLocate open access versionFindings
  • Onsager, L. The effects of shape on the interaction of colloidal particles. Ann. NY Acad. Sci. 51, 627–659 (1949).
    Google ScholarLocate open access versionFindings
  • Fu, J. et al. Self-assembly of crystalline-coil diblock copolymer in solvents with varying selectivity: from spinodal-like aggregates to spheres, cylinders and lamellae. Macromolecules 37, 976–986 (2004).
    Google ScholarLocate open access versionFindings
  • Zhang, J., Wang, L.-Q., Wang, H. & Tu, K. Micellization phenomena of amphiphilic block copolymers based on methoxy poly(ethylene glycol) and either crystalline or amorphous poly(caprolactone-b-lactide). Biomacromolecules 7, 2492–2500 (2006).
    Google ScholarLocate open access versionFindings
  • Portinha, D. et al. Stable dispersions of highly anisotropic nanoparticles formed by cocrystallization of enantiomeric diblock copolymers. Macromolecules 40, 4037–4042 (2007).
    Google ScholarLocate open access versionFindings
  • Schmalz, H. et al. Thermo-reversible formation of wormlike micelles with a microphase-separated corona from a semicrystalline triblock terpolymer. Macromolecules 41, 3235–3242 (2008).
    Google ScholarLocate open access versionFindings
  • Lazzari, M., Scalarone, D., Vazquez-Vazquez, C. & Lopez-Quintela, M. A. Cylindrical micelles from the self-assembly of polyacrylonitrile-based diblock copolymers in nonpolar selective solvents. Macromol. Rapid Commun. 29, 352–357 (2008).
    Google ScholarLocate open access versionFindings
  • Du, Z.-X., Xu, J.-T. & Fan, Z.-Q. Regulation of micellar morphology of PCL-bPEO block copolymers by crystallization temperature. Macromol. Rapid Commun. 29, 467–471 (2008).
    Google ScholarLocate open access versionFindings
  • Mihut, A. M., Drechsler, M., Moller, M. & Ballauff, M. Sphere-to-rod transitions of micelles formed by the semicrystalline polybutadiene-block-poly(ethylene oxide) block copolymer in a selective solvent. Macromol. Rapid Commun. 31, 449–453 (2010).
    Google ScholarLocate open access versionFindings
  • Gadt, T. et al. Complex and hierarchical micelle architectures from diblock copolymers using living, crystallization-driven polymerizations. Nature Mater. 8, 144–150 (2009).
    Google ScholarLocate open access versionFindings
  • Wang, H. et al. Cylindrical block co-micelles with spatially selective functionalization by nanoparticles. J. Am. Chem. Soc. 129, 12924–12925 (2007).
    Google ScholarLocate open access versionFindings
您的评分 :
0

 

标签
评论
数据免责声明
页面数据均来自互联网公开来源、合作出版商和通过AI技术自动分析结果,我们不对页面数据的有效性、准确性、正确性、可靠性、完整性和及时性做出任何承诺和保证。若有疑问,可以通过电子邮件方式联系我们:report@aminer.cn
小科