title: Biomimetic Hierarchical Assembly of Helical Supraparticles from Chiral Nanoparticles.
abstract: 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.
authors.affiliation: Wenzhou Institute of Biomaterials and Engineering, CNITECH.CAS-Wenzhou Medical University , Wenzhou, Zhejiang 325011, People's Republic of China.
authors.forename: Yunlong
authors.initials: Y
authors.lastname: Zhou
authors.forename: Ryan L
authors.initials: RL
authors.lastname: Marson
authors.forename: Greg
authors.initials: G
authors.lastname: van Anders
authors.forename: Jian
authors.initials: J
authors.lastname: Zhu
authors.forename: Guanxiang
authors.initials: G
authors.lastname: Ma
authors.affiliation: National Center for Electron Microscopy, the Molecular Foundry, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Peter
authors.initials: P
authors.lastname: Ercius
authors.forename: Kai
authors.initials: K
authors.lastname: Sun
authors.affiliation: Department of Chemical Engineering, Myongji University , Yongin, Gyeonggido 17058, South Korea.
authors.forename: Bongjun
authors.initials: B
authors.lastname: Yeom
authors.forename: Sharon C
authors.initials: SC
authors.lastname: Glotzer
authors.forename: Nicholas A
authors.initials: NA
authors.lastname: Kotov
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D032701:Biomimetics / Q000379:methods; D019187:Cadmium Compounds / Q000737:chemistry*; D003545:Cysteine / Q000737:chemistry*; D008958:Models, Molecular; D053758:Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure*; D036103:Nanotechnology / Q000379:methods; D013237:Stereoisomerism; D013691:Tellurium / Q000737:chemistry*; D014780:Viruses / Q000737:chemistry*
chemical_list: D019187:Cadmium Compounds; D003545:Cysteine; D013691:Tellurium; C028337:cadmium telluride
keywords: biomimetic nanoparticles; chirality; helices; self-assembly; supraparticles; virus-like nanostructures