"Cross" Supermicelles via the Hierarchical Assembly of Amphiphilic Cylindrical Triblock Comicelles

被引:65
作者
Li, Xiaoyu [1 ,4 ]
Gao, Yang [1 ]
Boott, Charlotte E. [1 ]
Hayward, Dominic W. [1 ]
Harniman, Robert [1 ]
Whittell, George R. [1 ]
Richardson, Robert M. [2 ]
Winnik, Mitchell A. [3 ]
Manners, Ian [1 ]
机构
[1] Univ Bristol, Sch Chem, Cantocks Close, Bristol BS8 1TS, Avon, England
[2] Univ Bristol, Sch Phys, Bristol BS8 1TS, Avon, England
[3] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada
[4] Beijing Inst Technol, Sch Mat Sci & Technol, Dept Polymer Mat, Beijing 100081, Peoples R China
基金
英国工程与自然科学研究理事会; 英国生物技术与生命科学研究理事会; 加拿大自然科学与工程研究理事会;
关键词
BLOCK-COPOLYMER MICELLES; CONJUGATED POLYTHIOPHENE CORE; POLYMERIC JANUS PARTICLES; DIBLOCK COPOLYMERS; MULTICOMPARTMENT MICELLES; PHOTONIC CRYSTALS; CONTROLLED LENGTH; CRYSTALLIZATION; ARCHITECTURES; NANOPARTICLES;
D O I
10.1021/jacs.5b12735
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Self-assembled "cross" architectures are well-known in biological systems (as illustrated by chromosomes, for example); however, comparable synthetic structures are extremely rare. Herein we report an in depth study of the hierarchical assembly of the amphiphilic cylindrical P-H-P triblock comicelles with polar (P) coronal ends and a hydrophobic (H) central periphery in a selective solvent for the terminal segments which allows access to "cross" supermicelles under certain conditions. Well-defined P-H-P triblock comicelles M(PFS-b-PtBA)-b-M(PFS-b-PDMS)-b-M(PFS-b-PtBA) (M = micelle segment, PFS = polyferrocenyldimethylsilane, PtBA = poly(tert-butyl acrylate), and PDMS = polydimethylsiloxane) were created by the living crystallization-driven self-assembly (CDSA) method. By manipulating two factors in the supermicelles, namely the H segment-solvent interfacial energy (through the central H segment length, L-1) and coronal steric effects (via the PtBA corona chain length in the P segment, L-2 related to the degree of polymerization DP2) the aggregation of the triblock comicelles could be finely tuned. This allowed a phase-diagram to be constructed that can be extended to other triblock comicelles with different coronas on the central or end segment where "cross" supermicelles were exclusively formed under predicted conditions. Laser scanning confocal microscopy (LSCM) analysis of dye-labeled "cross" supermicelles, and block "cross" supermicelles formed by addition of a different unimer to the arm termini, provided complementary characterization to transmission electron microscopy (TEM) and dynamic light scattering (DLS) and confirmed the existence of these "cross" supermicelles as kinetically stable, micron-size colloidally stable structures in solution.
引用
收藏
页码:4087 / 4095
页数:9
相关论文
共 83 条
[1]  
Aliprandi A, 2016, NAT CHEM, V8, P10, DOI [10.1038/nchem.2383, 10.1038/NCHEM.2383]
[2]  
Brandrup J., 1999, Polymer handbook, VII
[3]   Janus Particles Templated from Double Emulsion Droplets Generated Using Mcrofluidics [J].
Chen, Chia-Hung ;
Shah, Rhutesh K. ;
Abate, Adam R. ;
Weitz, David A. .
LANGMUIR, 2009, 25 (08) :4320-4323
[4]   Directed self-assembly of a colloidal kagome lattice [J].
Chen, Qian ;
Bae, Sung Chul ;
Granick, Steve .
NATURE, 2011, 469 (7330) :381-384
[5]   Supracolloidal Reaction Kinetics of Janus Spheres [J].
Chen, Qian ;
Whitmer, Jonathan K. ;
Jiang, Shan ;
Bae, Sung Chul ;
Luijten, Erik ;
Granick, Steve .
SCIENCE, 2011, 331 (6014) :199-202
[6]   Structure of poly(ferrocenyldimethylsilane) in electrospun nanofibers [J].
Chen, ZH ;
Foster, MD ;
Zhou, WS ;
Fong, H ;
Reneker, DH ;
Resendes, R ;
Manners, I .
MACROMOLECULES, 2001, 34 (18) :6156-6158
[7]   Nanoscale Tubular and Sheetlike Superstructures from Hierarchical Self-Assembly of Polymeric Janus Particles [J].
Cheng, Lin ;
Zhang, Guangzhao ;
Zhu, Lei ;
Chen, Daoyong ;
Jiang, Ming .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (52) :10171-10174
[8]   Block copolymer assembly via kinetic control [J].
Cui, Honggang ;
Chen, Zhiyun ;
Zhong, Sheng ;
Wooley, Karen L. ;
Pochan, Darrin J. .
SCIENCE, 2007, 317 (5838) :647-650
[9]   Self-Assembled ABC Triblock Copolymer Double and Triple Helices [J].
Dupont, John ;
Liu, Guojun ;
Niihara, Ken-ichi ;
Kimoto, Ryuhei ;
Jinnai, Hiroshi .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (33) :6144-6147
[10]   Amphiphilic Janus micelles with polystyrene and poly(methacrylic acid) hemispheres [J].
Erhardt, R ;
Zhang, MF ;
Böker, A ;
Zettl, H ;
Abetz, C ;
Frederik, P ;
Krausch, G ;
Abetz, V ;
Müller, AHE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (11) :3260-3267