Biomimetic Hierarchical Assembly of Helical Supraparticles from Chiral Nanoparticles

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• 作者：Yunlong Zhou ; Ryan L. Marson ; Greg van Anders ; Jian Zhu ; Guanxiang Ma ; Peter Ercius ; Kai Sun ; Bongjun Yeom ; Sharon C. Glotzer ; Nicholas A. Kotov
• 刊名：ACS Nano
• 出版年：2016
• 出版时间：March 22, 2016
• 年：2016
• 卷：10
• 期：3
• 页码：3248-3256
• 全文大小：582K
• ISSN：1936-086X

文摘

Chiroptical materials found in butterflies, beetles, stomatopod crustaceans, and other creatures are attributed to biocomposites with helical motifs and multiscale hierarchical organization. These structurally sophisticated materials self-assemble from primitive nanoscale building blocks, a process that is simpler and more energy efficient than many top-down methods currently used to produce similarly sized three-dimensional materials. Here, we report that molecular-scale chirality of a CdTe nanoparticle surface can be translated to nanoscale helical assemblies, leading to chiroptical activity in the visible electromagnetic range. Chiral CdTe nanoparticles coated with cysteine self-organize around Te cores to produce helical supraparticles. d-/l-Form of the amino acid determines the dominant left/right helicity of the supraparticles. Coarse-grained molecular dynamics simulations with a helical pair-potential confirm the assembly mechanism and the origin of its enantioselectivity, providing a framework for engineering three-dimensional chiral materials by self-assembly. The helical supraparticles further self-organize into lamellar crystals with liquid crystalline order, demonstrating the possibility of hierarchical organization and with multiple structural motifs and length scales determined by molecular-scale asymmetry of nanoparticle interactions.