Chiral inorganic nanomaterials are of great interest because of their excellent optical properties. Most of the attention has been focused on the utilization of biomolecules or their derivatives as linkers or templates to control the chiral structure of assembled inorganic nanoparticles. Chiral polymers are promising synthetic materials that can be used to replace their biological counterparts. Here, by using poly(methacrylate hydroxyethyl-3-indole propionate) (PIPEMA) and poly(2-hydroxyethyl methacrylate) (PHEMA) synthesized via syndioselective reversible addition−fragmentation chain transfer polymerization, we successfully realized chiral self-assembly of gold nanorods with strong circular dichroism response in the vis−NIR region. Moreover, the intensity of the chiral signal of the assemblies can be regulated by the molecular weight of the polymers. Notably, although the monomers are achiral and no chiral reagents are involved in their synthesis, the main chains of PIPEMA and PHEMA exhibit a preferredhanded helical conformation, which is the origin of chirality of the nanorod assemblies. The preferred-handed helical conformation of polymers is attributed to their syndiotacticity and stabilized by the steric hindrance of the side groups. The addition of chiral carbon atoms at the side groups does not change the preferred-handedness of the polymer main chain, resulting in the assembled nanorod structures with the same chirality. This strategy provides inspiration for the rational design and synthesis of optically active functional synthetic polymers for the preparation of promising chiral nanomaterials.

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The coupling between an inorganic nanostructure and a chiral molecule can give rise to a strong chiroptical response in a range from the UV to visible spectrum. In this work, novel plasmonic Ag@Ag 3 PO 4 core−shell hybrid nanorods (CSHNRs) have been prepared via a wet chemical method. The cysteine molecules can adsorb on the surface of the plasmonic hybrid nanorods, leading to the appearance of new circular dichroism (CD) signals in the UV region. The Ag@Ag 3 PO 4 −cysteine CSHNRs show a similar CD spectrum to the Ag 3 PO 4 −cysteine polyhedral nanocrystals (PNCs), although they have different morphology and structure. The Ag@Ag 3 PO 4 −cysteine CSHNRs and Ag 3 PO 4 −cysteine PNCs have a stronger chiroptical response than the Ag−cysteine nanorods (NRs) attributed to the effect of phosphate groups. This indicates that the Ag + ions on the surface of nanostructures can promote the formation of S−S bonds of oxidized cysteine under acidic conditions, rendering the uniformity of molecular conformation on the surface of nanostrucures, thus giving rise to the strong chiroptical response. Furthermore, the Ag@Ag 3 PO 4 CSHNRs can spontaneously form a chiral liquid crystalline phase upon dispersion in the ethylene glycol solution owing to their large aspect ratio and the optimum solvating effect of ethylene glycol.