Demand for the transfer of chirality from a preengineered nanoparticle to any other metal is of fundamental importance for developing a wide range of chirality-related applications. Herein, we show that binary alloy chiral nanoparticles (CNPs) with an engineerable composition can be formed from metallic CNPs with intrinsic structural chirality serving as sacrificial templates (STs), via a galvanic replacement reaction (GRR). This GRR-mediated chirality transfer is a general phenomenon and results in the formation of Cu−Ag CNPs with solid morphology and mesoporous CNPs made of Ag−Au, Ag−Pt, and Ag−Pd. Our study imposes a new component, i.e., structural chirality, on the GRR. The insights from our study improve our fundamental understanding of the GRR principle and devise a versatile method to generate mesoporous alloy CNPs for developing prominent chirality-related applications in asymmetric catalysis, enantiodifferentiation, enantioseparation, biodetection, and bioimaging.

Metallic chiral nanoparticles (CNPs) with a nominal helical pitch (P) of sub‐10 nm contain inherent chirality and are promisingly applied to diverse prominent enantiomer‐related applications. However, the sub‐wavelength P physically results in weak optical activity (OA) to prohibit the development of these applications. Herein, a facile method to amplify the CNPs' OA by alloying the host CNPs with metals through a three‐step layer‐by‐layer glancing angle deposition (GLAD) method is devised. Promoted by the GLAD‐induced heating effect, the solute metallic atoms diffuse into the host CNPs to create binary alloy CNPs. Chiral alloying not only induces the plasmonic OA of the diffused solute and the created alloys but also amplifies that of the host CNPs, generally occurring for alloying Ag CNPs with diverse metals (including Cu, Au, Al, and Fe) and alloying Cu CNPs with Ag. Furthermore, the chiral alloying leads to an enhancement of refractive index sensitivity of the CNPs. The alloy CNPs with amplified plasmonic OA pave the way for potentially developing important chirality‐related applications in the fields of heterogeneous asymmetric catalysis, enantiodifferentiation, enantioseparation, biosensing, and bioimaging.

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We suggest a new strategy for creating stimuliresponsive bio-integrated optical nanostructures based on Mieresonant silicon nanoparticles covered by an ensemble of similarity negatively charged polyelectrolytes (heparin and sodium polystyrene sulfonate). The dynamic tuning of the nanostructures optical response is due to light-induced heating of the nanoparticles and swelling of the polyelectrolyte shell. The resulting hydrophilic/hydrophobic transitions significantly change the shell thickness and reversible shift of the scattering spectra for individual nanoparticles up to 60 nm. Our findings bring novel opportunities for the application of smart nanomaterials in nanomedicine and bio-integrated nanophotonics.

Anisotropic metal nanoparticles (NPs), such as high-aspect-ratio Au nanorods (NRs), play an important role for applications in photocatalysis, sensing, and drug delivery because of their adjustable plasmon resonances. Their performance for these applications can be further improved by fine-tuning their morphologies. Achieving desired NP architectures requires insight into their formation mechanisms. Here, liquid-phase transmission electron microscopy is used to directly follow the overgrowth of Au NR seeds into nanoarrows (NAs) with fourfold symmetric wings along the sides. Adding thiol molecules like L-cysteine to the growth solution can lead to the formation of NAs with periodic prismatic teeth instead of the straight side wings. These observations suggest that this transition is controlled by binding of L-cysteine to the NR surface, which in turn, slows down the metal deposition rate, switching the overgrowth from the kinetically to thermodynamically controlled process. Furthermore, simulations demonstrate that these prismatic teeth enhance the NPs' plasmonic properties. The study describes how thiol additives control the morphological evolution of metal NPs, which is important for the fabrication of NPs with tailored shapes for a broad range of applications.