Selective DNP Signal Amplification To Probe Structures of Core–Shell Polymer Hybrid Nanoparticles

Selective DNP Signal Amplification To Probe Structures of Core–Shell Polymer Hybrid Nanoparticles
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选择性 DNP 信号放大探测核壳聚合物杂化纳米粒子的结构

DOI:
10.1021/acs.jpcc.8b07969
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发表时间:
2019
期刊:
The Journal of Physical Chemistry C
影响因子:
--
通讯作者:
Gutmann
Gutmann
中科院分区:
--
文献类型:
--
作者:
Schäfer;Vowinkel;Breitzke;Gallei;Gutmann

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提出了一种表征核壳聚合物杂化纳米粒子的有效方法。采用动态核极化(DNP)选择性信号放大技术,进一步揭示了粒子表面和壳层的分子结构。用dnp增强的29si固态核磁共振清楚地证明了纳米颗粒的核壳结构,以及它们与低量三甲基硅氧基的成功功能化。结合dnp增强1h→29Si和1h→13C交叉极化魔角纺丝实验,研究了不同取代的烷氧基硅烷基团,即甲基丙烯氧基丙基三乙氧基硅烷、3-甲基丙烯氧基丙基三异丙基硅烷和3-甲基丙烯氧基丙基(甲氧基乙氧基)硅烷,揭示了粒子壳的不同交联能力。这种关于表面功能化和交联位点效率的知识强烈地影响了核-壳聚合物杂化颗粒的应用和性质,例如,作为光子晶体、颗粒膜形成和涂层的材料。这对于设计量身定制的核壳粒子结构具有重要意义。
An efficient approach for the characterization of core–shell polymer hybrid nanoparticles is presented. Selective signal amplification by dynamic nuclear polarization (DNP) is employed to shed more light on the molecular structure of surface sites and shell of the particles. DNP-enhanced29Si solid-state NMR is used to clearly prove the core–shell structure of the nanoparticles as well as the success of their functionalization with low amounts of trimethylsiloxy groups. By combination of DNP-enhanced1H →29Si and1H →13C cross-polarization magic-angle-spinning experiments, differently substituted alkoxysilane moieties, namely, methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriisopropoxysilane, and 3-methacryloxypropyltris(methoxyethoxy)silane, are investigated, revealing various cross-linking capabilities of the particle shell. This knowledge about efficiency of surface functionalization and cross-linking sites strongly influences the application and properties of the core–shell polymer hybrid particles, for instance, as materials for photonic crystals, particle film formation, and coatings. This is of high importance for the design of tailor-made core–shell particle architectures.
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