水中单链聚合物纳米颗粒的光化学诱导折叠
Photochemically Induced Folding of Single Chain Polymer Nanoparticles in Water.
作者信息
Heiler Carolin, Offenloch Janin T, Blasco Eva, Barner-Kowollik Christopher
机构信息
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.
出版信息
ACS Macro Lett. 2017 Jan 17;6(1):56-61. doi: 10.1021/acsmacrolett.6b00858. Epub 2016 Dec 29.
We pioneer the synthesis of fluorescent single chain nanoparticles (SCNPs) via UV-light induced folding based on tetrazole chemistry directly in pure water. Water-soluble photoreactive precursor polymers based on poly(acrylic acid) (PAA) bearing tetrazole, alkene and tetraethylene glycol monomethyl ether moieties, (PAA(Tet/p-Mal/TEG)), or simply tetrazoles moieties, PAA(Tet), were generated via RAFT polymerization. While tetrazole, ene, and acrylic acid containing polymers fold via dual nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) as well as nitrile imine-carboxylic acid ligation (NICAL), tetrazole and acrylic acid only functional prepolymers fold exclusively via NICAL. A detailed study of the underpinning photochemistry of NITEC and NICAL is also included. The resulting water-soluble SCNPs were carefully characterized via analytical techniques such as NMR, UV-vis, and fluorescence spectroscopy, as well as SEC and DLS.
我们率先基于四氮唑化学，通过紫外光诱导折叠，直接在纯水中合成荧光单链纳米颗粒（SCNP）。通过可逆加成-断裂链转移（RAFT）聚合反应，制备了基于聚（丙烯酸）（PAA）的水溶性光反应性前体聚合物，其带有四氮唑、烯烃和四甘醇单甲醚部分，即PAA（Tet/p-Mal/TEG），或简单地带有四氮唑部分的PAA（Tet）。含四氮唑、烯和丙烯酸的聚合物通过双腈亚胺介导的四氮唑-烯环加成反应（NITEC）以及腈亚胺-羧酸连接反应（NICAL）折叠，而仅含四氮唑和丙烯酸的功能性预聚物仅通过NICAL折叠。还包括对NITEC和NICAL基础光化学的详细研究。通过核磁共振（NMR）、紫外可见光谱和荧光光谱以及尺寸排阻色谱（SEC）和动态光散射（DLS）等分析技术，对所得水溶性SCNP进行了仔细表征。
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