Controlling the growth and shape of chiral supramolecular polymers in water

被引:185
作者
Besenius, Pol [1 ,2 ]
Portale, Giuseppe [3 ]
Bomans, Paul H. H. [4 ,5 ]
Janssen, Henk M. [6 ]
Palmans, Anja R. A. [1 ,2 ]
Meijer, E. W. [1 ,2 ]
机构
[1] Eindhoven Univ Technol, Inst Complex Mol Syst, NL-5600 MB Eindhoven, Netherlands
[2] Eindhoven Univ Technol, Lab Macromol & Organ Chem, NL-5600 MB Eindhoven, Netherlands
[3] European Synchrotron Radiat Facil, Dutch Belgian Beamline DUBBLE BM26 26, F-38043 Grenoble, France
[4] Eindhoven Univ Technol, Lab Mat & Interface Chem, Dept Chem & Chem Engn, NL-5600 MB Eindhoven, Netherlands
[5] Eindhoven Univ Technol, Soft Matter CryoTEM Res Unit, Dept Chem & Chem Engn, NL-5600 MB Eindhoven, Netherlands
[6] SyMO Chem, NL-5600 MB Eindhoven, Netherlands
关键词
aqueous self-assembly; controlled architecture; supramolecular polymerization; dynamic materials; BLOCK-COPOLYMER MICELLES; POLYELECTROLYTES; CONFORMATION; ASSEMBLIES; DENDRIMERS; MECHANISM; VESICLES; DILUTE; LENGTH; LAWS;
D O I
10.1073/pnas.1009592107
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
A challenging target in the noncovalent synthesis of nanostructured functional materials is the formation of uniform features that exhibit well-defined properties, e. g., precise control over the aggregate shape, size, and stability. In particular, for aqueous-based one-dimensional supramolecular polymers, this is a daunting task. Here we disclose a strategy based on self-assembling discotic amphiphiles that leads to the control over stack length and shape of ordered, chiral columnar aggregates. By balancing out attractive noncovalent forces within the hydrophobic core of the polymerizing building blocks with electrostatic repulsive interactions on the hydrophilic rim we managed to switch from elongated, rod-like assemblies to small and discrete objects. Intriguingly this rod-to-sphere transition is expressed in a loss of cooperativity in the temperature-dependent self-assembly mechanism. The aggregates were characterized using circular dichroism, UV and 1H-NMR spectroscopy, small angle X-ray scattering, and cryotransmission electron microscopy. In analogy to many systems found in biology, mechanistic details of the self-assembly pathways emphasize the importance of cooperativity as a key feature that dictates the physical properties of the produced supramolecular polymers.
引用
收藏
页码:17888 / 17893
页数:6
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