Willenbacher Johannes, Wuest Kilian N R, Mueller Jan O, Kaupp Michael, Wagenknecht Hans-Achim, Barner-Kowollik Christopher
Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76131 Karlsruhe, Germany.
Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
ACS Macro Lett. 2014 Jun 17;3(6):574-579. doi: 10.1021/mz500292e. Epub 2014 Jun 2.
We report the facile ambient temperature generation of size tunable and well-defined (pro)fluorescent single-chain nanoparticles (SCNPs) via the photoinduced nitrile imine intramolecular cross-ligation of linear precursor polymers, constituting a platform technology as novel imaging agents. A set of three linear precursor polymers ( ≈ 14000 g mol, ≈ 1.25) was synthesized via nitroxide-mediated statistical copolymerization of styrene and 4-(chloromethyl)styrene (CMS), followed by a postpolymerization modification of the resulting copolymer installing protected maleimide (PG-Mal) as well as tetrazole (Tet) moieties. The tetrazole content (% Tet) along the lateral polymer chains was varied between 12 and 24% in order to preselect not only the size of the corresponding SCNPs, but also their fluorescence and reactive properties. Finally, the applicability of the profluorescent SCNPs for fluorescence labeling was demonstrated utilizing residual surface expressed Tet moieties on the SCNPs surface in a reaction with maleimide functional polymeric microspheres. The (pro)fluorescent single-chain nanoparticles were in-depth characterized by H NMR spectroscopy, dynamic light scattering (DLS), size exclusion chromatography (SEC), and atomic force microscopy (AFM), as well as UV/vis and fluorescence spectroscopy.
我们报道了通过线性前体聚合物的光诱导腈亚胺分子内交叉连接，在环境温度下轻松生成尺寸可调且定义明确的（前）荧光单链纳米颗粒（SCNP），这构成了一种作为新型成像剂的平台技术。通过苯乙烯和4-（氯甲基）苯乙烯（CMS）的氮氧化物介导的统计共聚反应，合成了一组三种线性前体聚合物（≈14000 g/mol，≈1.25），随后对所得共聚物进行后聚合改性，引入受保护的马来酰亚胺（PG-Mal）以及四唑（Tet）部分。沿聚合物侧链的四唑含量（% Tet）在12%至24%之间变化，以便不仅预先选择相应SCNP的尺寸，还选择它们的荧光和反应特性。最后，利用SCNP表面残留的表面表达四唑部分与马来酰亚胺功能化聚合物微球反应，证明了前荧光SCNP用于荧光标记的适用性。通过1H NMR光谱、动态光散射（DLS）、尺寸排阻色谱（SEC）、原子力显微镜（AFM）以及紫外/可见光谱和荧光光谱对（前）荧光单链纳米颗粒进行了深入表征。
