Intramolecular Folding of Coil‐Helix Block Copolymers Induced by Quadrupole Interactions
Intramolecular Folding of Coil‐Helix Block Copolymers Induced by Quadrupole Interactions
复制标题
四极相互作用诱导的螺旋-螺旋嵌段共聚物的分子内折叠
DOI：
10.1002/marc.202100368
复制
发表时间：
2021
影响因子：
4.6
通讯作者：
Weck, Marcus
中科院分区：
文献类型：
--
作者：
Wang, Chengyuan;Weck, Marcus
在合成体系中，具有确定的局部二级结构的真正三级结构是罕见的。调整成熟的合成结构单元并通过不同的相互作用控制它们的折叠可以是实现这一目标的一般方法。在这方面的贡献，合成3D层次组装体与不同的二级域形成通过分子内折叠的嵌段共聚物含有线圈状聚（苯乙烯）（PS）嵌段与螺旋聚（异氰化物）嵌段诱导苯基-五氟苯基四极相互作用。PS嵌段通过原子转移自由基聚合制备，并用镍络合物末端官能化，所述镍络合物用作用于聚合带有五氟苯基侧基的手性异腈的大分子引发剂。通过动态光散射、NMR光谱、广角X射线散射和差示扫描量热法研究了卷曲-螺旋嵌段共聚物的折叠行为。
True tertiary architectures with defined local secondary structures are rare in synthetic systems. Adapting well‐developed synthetic building blocks and controlling their folding through diverse interactions can be a general approach toward this goal. In this contribution, the synthesis of 3D hierarchical assemblies with distinct secondary domains formed through the intramolecular folding of a block copolymer containing a coil‐like poly(styrene) (PS) block with a helical poly(isocyanide) block induced by phenyl‐pentafluorophenyl quadrupole interactions is reported. The PS block is prepared via atom‐transfer radical polymerization and end functionalized with a nickel complex that serves as a macroinitiator for the polymerization of chiral isocyanides bearing pentafluorophenyl pendants. The folding behavior of the coil‐helix block copolymers is investigated by dynamic light scattering, NMR spectroscopy, wide‐angle X‐ray scattering, and differential scanning calorimetry.