Blázquez-Martín Agustín, Ruiz-Bardillo Ainara, Verde-Sesto Ester, Iturrospe Amaia, Arbe Arantxa, Pomposo José A
Centro de Física de Materiales (CSIC, UPV/EHU)-Materials Physics Center (MPC), 20018 Donostia-San Sebastián, Spain.
IKERBASQUE-Basque Foundation for Science, 48009 Bilbao, Spain.
Nanomaterials (Basel). 2023 Apr 18;13(8):1394. doi: 10.3390/nano13081394.
We report herein on a new platform for synthesizing stable, inert, and dispersible metal-free single-chain nanoparticles (SCNPs) via intramolecular metal-traceless azide-alkyne click chemistry. It is well known that SCNPs synthesized via Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) often experience metal-induced aggregation issues during storage. Moreover, the presence of metal traces limits its use in a number of potential applications. To address these problems, we selected a bifunctional cross-linker molecule, -dibenzo-1,5-cyclooctadiene-3,7-diyne (DIBOD). DIBOD has two highly strained alkyne bonds that allow for the synthesis of metal-free SCNPs. We demonstrate the utility of this new approach by synthesizing metal-free polystyrene (PS)-SCNPs without significant aggregation issues during storage, as demonstrated by small-angle X-ray scattering (SAXS) experiments. Notably, this method paves the way for the synthesis of long-term-dispersible, metal-free SCNPs from potentially any polymer precursor decorated with azide functional groups.
我们在此报告一种通过分子内无痕金属叠氮化物-炔烃点击化学合成稳定、惰性且可分散的无金属单链纳米颗粒（SCNP）的新平台。众所周知，通过铜（I）催化的叠氮化物-炔烃环加成反应（CuAAC）合成的SCNP在储存期间经常会出现金属诱导的聚集问题。此外，金属痕迹的存在限制了其在许多潜在应用中的使用。为了解决这些问题，我们选择了一种双功能交联剂分子，即 -二苯并-1,5-环辛二烯-3,7-二炔（DIBOD）。DIBOD具有两个高度张力的炔键，可用于合成无金属的SCNP。我们通过合成无金属的聚苯乙烯（PS）-SCNP证明了这种新方法的实用性，小角X射线散射（SAXS）实验表明，该SCNP在储存期间没有明显的聚集问题。值得注意的是，这种方法为从潜在的任何带有叠氮官能团的聚合物前体合成长期可分散的无金属SCNP铺平了道路。
