CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, 230026, Hefei, Anhui, China.
Department of Chemistry, Boston University, Boston, MA, USA.
Nat Commun. 2020 Mar 4;11(1):1188. doi: 10.1038/s41467-020-15082-6.
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.
手性贵金属纳米粒子由于其潜在的应用而受到了广泛关注，包括超灵敏的手性识别和不对称合成。我们预计它们可以用于诱导具有高对映选择性和反应性的不对称光聚合反应。在这里，我们报告了这样一个系统。通过使用半胱氨酸修饰的银纳米粒子作为手性诱导剂，从非手性二乙炔单体出发，在非偏振紫外光的引发下，得到了具有高手性不对称性的聚二乙炔（PDA）。此外，通过改变紫外光的照射波长，可以控制螺旋手性的手性。这为制备具有定制手性分布的可编程二维手性 PDA 图案提供了一种可行且经济的方法，例如手性的平滑梯度和具有可定制圆偏振发光的微图案。我们的发现不仅为制备可编程的手性光学微图案开辟了一条途径，而且对于深入理解对映选择性光化学反应中的对称破缺也具有重要意义。
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