Formation of Polymeric Yolk/Shell Nanomaterial by Polymerization-Induced Self-Assembly and Reorganization
Formation of Polymeric Yolk/Shell Nanomaterial by Polymerization-Induced Self-Assembly and Reorganization
复制标题
通过聚合诱导自组装和重组形成聚合物蛋黄/壳纳米材料
DOI：
10.1021/ma100021a
复制
发表时间：
2010-02
期刊：
影响因子：
5.5
通讯作者：
Pan, Cai-Yuan
中科院分区：
文献类型：
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作者：
Wan, Wen-Ming;Pan, Cai-Yuan
在过去的十年中，具有移动的功能核的中空粒子由于在药物输送、催化、人工细胞等方面显示出潜在的应用前景而受到人们的广泛关注。1这些颗粒具有伪三层结构，称为蛋黄/壳纳米颗粒。用于制备这种类型的材料的一般且有效的方法是基于通过化学溶解或热分解去除三层纳米颗粒的中间层。2但目前的脱膜方法存在一些问题，如对包封剂的破坏和合成步骤多、复杂等。为了避免去除步骤，已经开发了微乳液方法，其通过在水滴表面上的正硅酸乙酯与功能性纳米颗粒（例如Fe 3 O 4）的缩聚或通过在表面活性剂的水性混合物中用SiO2壳包覆纳米颗粒来进行。3然而，这些方法都是基于模板辅助的方法，可用的模板是有限的，因此报道的蛋黄/壳纳米颗粒主要是由无机材料制备的。自组装是制备纳米结构材料的常用方法，嵌段共聚物、聚苯乙烯-b-聚丙烯酸和均聚苯乙烯（homo-PS）的自组装可以形成三层结构。不幸的是，蛋黄/壳纳米颗粒没有形成。4因此，需要开发制备聚合物蛋黄/壳纳米材料的策略。在我们以前的结果的基础上，球形胶束可以通过聚合诱导自组装来制备，5并且通过调节进料摩尔比和反应条件，囊泡可以通过聚合诱导自组装和重组（PISR）来实现，因为核心聚合物链的连续增长可以改变涉及核心链拉伸的力平衡，核与外部溶剂之间的表面张力以及冠链之间的排斥力。6我们可以想象，在通过球形胶束的融合和重组形成囊泡的过程中，存在于反应介质中的纳米颗粒可能被封装在囊泡中，形成蛋黄/壳纳米材料（方案1）。根据聚合体系中纳米颗粒的类型和性质，可以制备各种蛋黄/壳纳米颗粒。因此，我们提出了通过PISR制备高分子蛋黄/壳纳米材料的设想。
In the past decade, the hollow particles with a mobile functional core have gained great attention because they displayed potential applications in drug delivery, catalysis, and artificial cell. 1 These particles are of a pseudo-triple-layer structure which is called yolk/shell nanoparticles. A general and efficient method for preparing this type of material is based on removing the intermediate layer of the trilayer nanoparticles by chemical dissolution or thermal decomposition. 2 However, the removing methods displayed some problems, such as destruction of the encapsulated agents and multistep and complicated synthetic procedure. For keeping away from the removal step, a microemulsion method has been developed, which was performed by polycondensation of tetraethoxysilane on the surface of a water droplet with functional nanoparticles, such as Fe3O4 inside, or by encapsulation of nanoparticles with SiO2 shell in aqueous mixtures of surfactants. 3 However, all these methods are based on the template-assisted approach, the available templates are limited, and so the yolk/shell nanoparticles reported are mainly prepared from inorganic materials. Hitherto, the preparation of yolk/shell nanoparticles with the polymer yolk and the polymer shell is not successful, and investigation on their synthesis should be valuable in polymer chemistry.Generally, self-assembly is a common strategy to prepare nanostructural materials; self-assembling of the block copolymer, polystyrene-b-poly (acrylic acid), and homopolystyrene (homo-PS) may form a trilayer structure. Unfortunately, the yolk/shell nanoparticles were not formed. 4 Thus, a strategy for preparation of polymer yolk/shell nanomaterials needs to be developed. On the basis of our previous results, the spherical micelles could be prepared by polymerization-induced self-assembling, 5 and by tuning feed molar ratio and reaction conditions, the vesicles can be achieved via polymerization-induced self-assembly and reorganization (PISR) because continuous propagation of the core polymer chains can alter the force balance involving stretching of the core chains, the surface tension between the core and outside solvent, and repulsion among the corona chains. 6 We can imagine, during the formation process of vesicles via fusion and reorganization of the spherical micelles, the nanoparticles existed in the reaction media may be encapsulated in the vesicles, forming yolk/shell nanomaterials (Scheme 1). Based on the type and the properties of nanoparticles in the polymerization system, various yolk/shell nanoparticles can be prepared. So, we raised an idea for preparation of the polymeric yolk/shell nanomaterials via PISR.