Brush-First and ROMP-Out with Functional (Macro)monomers: Method Development, Structural Investigations, and Applications of an Expanded Brush-Arm Star Polymer Platform
Brush-First and ROMP-Out with Functional (Macro)monomers: Method Development, Structural Investigations, and Applications of an Expanded Brush-Arm Star Polymer Platform
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DOI：
10.1021/acs.macromol.8b01966
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发表时间：
2018-12-11
期刊：
影响因子：
5.5
通讯作者：
Johnson, Jeremiah A.
中科院分区：
文献类型：
--
作者：
Golder, Matthew R.;Nguyen, Hung V. -T.;Johnson, Jeremiah A.
复杂功能高分子纳米材料的高效合成往往是一个挑战。钌引发的开环复分解聚合（ROMP）多价单体，然后交联形成电刷臂星形（BASP）聚合物，可以获得具有多种功能的明确的纳米结构。这种“刷先”的方法在BASP微凝胶核心中留下活性Ru，这可能会在随后的“ROMP-out”（RO）步骤中使用，通过添加（宏）单体来进一步修饰BASP结构。在这里，我们深入研究了这种RO方法。利用电感耦合等离子体质谱法和凝胶渗透色谱法的组合，评估了RO对各种BASP成分的效率。为了证明反渗透过程的模块化，制备了芳基硼酸功能化的basp；流式细胞术和荧光显微镜检测发现，相对于非功能化的BASPs，这些RO-BASPs被高唾液化的癌细胞吸收。此外，还证明了通过刷先和反渗透制备的mitoarm basp与不同的大单体之间的自组装。电刷优先ROMP与RO的结合提供了一种简单的模块化策略，可以访问各种功能纳米材料。
The efficient synthesis of complex functional polymeric nanomaterials is often challenging. Ru-initiated ring opening metathesis polymerization (ROMP) of multivalent macromonomers followed by cross-linking to form brush-arm star (BASP) polymers enables access to well-defined nano structures with diverse functionality. This "brush-first" method leaves active Ru in the BASP microgel core, which could potentially be used in a subsequent "ROMP-out" (RO) step to introduce further modifications to the BASP structure via the addition of (macro)monomers. Here, we study this RO approach in depth. The efficiency of RO is assessed for a variety of BASP compositions using a combination of inductively coupled plasma mass spectrometry and gel permeation chromatography. To demonstrate the modularity of the RO process, arylboronic acid-functionalized BASPs were prepared; uptake of these RO-BASPs into hypersialylated cancer cells was enhanced relative to non-functionalized BASPs as determined by flow cytometry and fluorescence microscopy. In addition, the self assembly of miktoarm BASPs prepared via brush-first and RO with different macromonomers is demonstrated. The combination of brush-first ROMP with RO provides a simple, modular strategy for access to a wide array of functional nanomaterials.