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1.上海交通大学化学化工学院 上海 200240
2.浙江大学高分子科学与工程系 杭州 310027
Published:20 February 2017,
Received:26 October 2016,
Revised:27 November 2016,
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Qi Mei-wei, Huang Wei, Xiao Gu-yu, Zhu Xin-yuan, Gao Chao, Zhou Yong-feng. Synthesis and Self-assembly of Hyperbranched Polymers. [J]. Acta Polymerica Sinica (2):214-228(2017)
Qi Mei-wei, Huang Wei, Xiao Gu-yu, Zhu Xin-yuan, Gao Chao, Zhou Yong-feng. Synthesis and Self-assembly of Hyperbranched Polymers. [J]. Acta Polymerica Sinica (2):214-228(2017) DOI: 10.11777/j.issn1000-3304.2017.16324.
超支化聚合物作为树形聚合物的一种,具有独特的结构和性能,受到了科学界和工业界的广泛关注.本文简要总结了研究者们在超支化聚合物的合成、组装及应用方面的部分工作成果.主要包括以下3方面的内容:第一部分介绍了超支化聚合物的合成方法;第二部分介绍了超支化聚合物多维多尺度的自组装结构和组装机理,包括纳米球形胶束,纳米、微米级囊泡,大的复合囊泡,纳米纤维,纳米、微米及宏观管和多孔膜等;第三部分介绍了超支化聚合物在生物医药、细胞模拟及纳米粒子模拟制备等方面的应用.
Hyperbranched polymers (HBPs)
comprising of dendritic units
linear units and terminal units
are highly branched macromolecules with three-dimensional dendritic globular architecture. Compared with linear polymers
HBPs have shown the characteristics of a large population of terminal functional groups
low or no chain entanglement
small hydrodynamic diameter
low solution or melt viscosity and good solubility. Due to these characteristics
HBPs have attracted global interest from science to industry. In this paper
we review some progress in the synthesis
self-assembly and application of HBPs. The paper includes three parts. In the first part
a short history on the development of HBPs focusing on the introduction of "couple-monomer methodology (CMM)" to prepare HBPs was discussed. A typical example of CMM named as "AA'+B'B
2
" method was described. In addition
the synthesis of a hyperbranched oxetanemethanol through ring-opening polymerization was also presented. In the second part
the self-assembly of amphiphilic HBPs was summarized according to the morphology of the self-assemblies from the spherical micelles
the vesicles
the sheets or films
the fibers or tubes
to complex supramolecular structures. The mechanism for the self-assembly of the micelles from HBPs was discussed in details. HBPs form unimolecular micelles (UMs) around 10 nm below the critical micellar concentration (CMC). Above the CMC
there are two possibilities for the formation of micelles:one is that HBPs undergo microphase separation and then form micelles with the diameter of the length of two HBPs (around 20 nm or larger)
which is named as "microphase-separated small micelles" (ms-SMs) and similar to the star micelles of linear block copolymers in structure; the other is that HBPs form multimolecular micelles (
>
50 nm) through a mechanism of "multimicelle aggregate" (MMA). The MMA mechanism can also be divided into two mechanisms of "unimolecular micelle aggregate" (UMA) and "small micelle aggregate" (SMA). The MAA mechanism is general and can also be used to explain the large multimolecular micelles self-assembled from other polymers or even small molecules. In the third part of this review
we introduced the applications of HBP self-assemblies in drug delivery
cytomimetic chemistry and monodisperse nanoparticle preparation. The HBP vesicles (named as branched-polymersomes) have displayed good properties like the simple preparation
good membrane fluidity and stability
and the facilely tuned and micrometer-scaled size
which make them the ideal model systems to mimic cell behaviors like fusion
fission
aggregation and so on. All these cytomimetic behaviors can be observed in real time under an optical microscope since the branched-polymersomes have a cell-like size.
超支化聚合物自组装药物传输胶束囊泡
Hyperbranched polymersSelf-assemblyDrug deliveryMicellesVesicles
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