Anger Christian, Deubel Frank, Salzinger Stephan, Stohrer Jürgen, Halbach Tobias, Jordan Rainer, Veinot Jonathan G C, Rieger Bernhard
Institut für Siliciumchemie, TU München Lichtenbergstraße 4, 85748 Garching, Germany.
ACS Macro Lett. 2013 Feb 19;2(2):121-124. doi: 10.1021/mz3006439. Epub 2013 Jan 15.
Photoacid-induced siloxane cross-linking of stimuli-responsive copolymer micelles allows the synthesis of well-defined organic-inorganic hybrid nanoparticles. Two conceptually different synthetic approaches are presented, both via photoinduced cross-linking of poly(4-hydroxystyrene--styrene) micelles and via photoacid-catalyzed micelle formation and siloxane cross-linking of poly(4--butoxystyrene--styrene). The synthetic route showed intermicellar cross-linking leading to agglomerates. In contrast to this, the formation of the nanoparticles via the one-pot synthesis yielded well-defined structures. The use of different siloxane cross-linking agents and their effects on the properties of the cross-linked micellar structures have been evaluated. Scanning electron microscopy and differential scanning calorimetry indicate rigid core cross-linked nanoparticles. Their size, molar mass, and swelling behavior were analyzed by dynamic and static light scattering. Cyclic siloxane cross-linking agents lead to residual C═C double bonds within the nanoparticle core that allow postsynthetic modification by, e.g., thiol-ene click reactions.
光酸诱导的刺激响应性共聚物胶束的硅氧烷交联可实现结构明确的有机-无机杂化纳米粒子的合成。本文介绍了两种概念上不同的合成方法，均通过聚（4-羟基苯乙烯-苯乙烯）胶束的光诱导交联以及聚（4-丁氧基苯乙烯-苯乙烯）的光酸催化胶束形成和硅氧烷交联来实现。合成路线显示出胶束间交联导致团聚。与此相反，通过一锅法合成纳米粒子可得到结构明确的结构。已评估了不同硅氧烷交联剂的使用及其对交联胶束结构性能的影响。扫描电子显微镜和差示扫描量热法表明形成了刚性核交联纳米粒子。通过动态和静态光散射分析了它们的尺寸、摩尔质量和溶胀行为。环状硅氧烷交联剂会在纳米粒子核内产生残留的C═C双键，从而允许通过例如硫醇-烯点击反应进行合成后修饰。
