Highly enantioselective photo-polymerization enhanced by chiral nanoparticles and in situ photopatterning of chirality
Highly enantioselective photo-polymerization enhanced by chiral nanoparticles and in situ photopatterning of chirality
复制标题
手性纳米粒子增强的高度对映选择性光聚合和手性原位光图案化
DOI：
10.1038/s41467-020-15082-6
复制
发表时间：
2020-03-04
影响因子：
16.6
通讯作者：
Zou, Gang
中科院分区：
文献类型：
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作者：
He, Chenlu;Feng, Zeyu;Zou, Gang
手性贵金属纳米粒子因其在超灵敏手性识别和不对称合成等方面的潜在应用而受到人们的极大关注。我们期望它们能够被用来诱导具有高对映选择性和反应活性的不对称光聚合反应。在这里，我们报告这样一个系统。采用半胱氨酸修饰的银纳米粒子作为手性诱导剂，在未偏振的紫外光引发下，从非手性二乙炔单体中得到了具有高度手性不对称性的聚二乙炔(PDA)。此外，通过改变紫外光照射的波长可以控制螺旋手性的感觉。这使得一种可行和经济的方法来制造具有定制手性分布的手性PDA的可编程2D图案，例如手性的平滑梯度和具有可定制的圆偏振发光的微图案。我们的发现不仅为生产可编程手性微图案开辟了一条途径，而且对于深入理解对映体选择性光化学反应中的对称性破缺也是非常有价值的。
Chiral noble metal nanoparticles has recently gained great interest due to their potential applications including ultrasensitive chiral recognition and asymmetric synthesis. We anticipate that they could be utilized to induce asymmetric photo-polymerization reactions with high enantioselectivity and reactivity. Here, we report such a system. By employing silver nanoparticles modified with cysteine as the chiral inducer, polydiacetylene (PDA) with high chiral asymmetry was obtained from achiral diacetylene monomers triggered with unpolarized UV light. Furthermore, the helical sense of chirality can be controlled by varying the wavelength of UV irradiation. This enables a feasible and economical method to fabricate programmable 2D patterns of chiral PDA with tailored chirality distributions, such as smooth gradients in chirality and micropatterns with tailorable circularly polarized luminescence. Our finding not only opens a pathway for producing programmable chiroptical micropatterns, but also is highly valuable for deeper understanding of symmetry breaking in enantioselective photochemical reactions.