Synthesis of Chiral Ag, Pd, and Pt Helicoids inside Chiral Silica Mold.

Chiral inorganic nanomaterials hold significant promise for various applications, including enantioselective catalysis, polarization-controlling optical devices, metamaterials, and enantioselective molecular sensors. In our previous work, we presented a method for synthesizing chiral Au 432 helicoid III (Au helicoids) from peptides and amino acids, where helical gaps are intricately arranged with 432 symmetry within single cubic nanoparticles. In this study, we have achieved the fabrication of chiral silica molds through Au etching subsequent to the silica coating of Au helicoids. We demonstrate that these molds serve as geometrically confined reactors capable of producing chiral Ag, Pd, and Pt 432 helicoid III (Ag, Pd, and Pt helicoids). The morphology of the synthesized Ag, Pd, and Pt helicoids closely resembles that of the Au helicoids, exhibiting a superior g-factor compared to other reported chiral structures of each material. Notably, the Ag and Pd helicoids are found to be single-crystalline, with high-index planes exposed within the gaps. We believe that this silica mold-based approach can be generalized to synthesize chiral nanomaterials of various metal and even oxide materials.

Chiral plasmonic sensing: From the perspective of light-matter interaction.

Molecular chirality is represented as broken mirror symmetry in the structural orientation of constituent atoms and plays a pivotal role at every scale of nature. Since the discovery of the chiroptic property of chiral molecules, the characterization of molecular chirality is important in the fields of biology, physics, and chemistry. Over the centuries, the field of optical chiral sensing was based on chiral light-matter interactions between chiral molecules and polarized light. Starting from simple optics-based sensing, the utilization of plasmonic materials that could control local chiral light-matter interactions by squeezing light into molecules successfully facilitated chiral sensing into noninvasive, ultrasensitive, and accurate detection. In this Review, the importance of plasmonic materials and their engineering in chiral sensing are discussed based on the principle of chiral light-matter interactions and the theory of optical chirality and chiral perturbation; thus, this Review can serve as a milestone for the proper design and utilization of plasmonic nanostructures for improved chiral sensing.

Enantioselective Molecular Detection by Surface Enhanced Raman Scattering at Chiral Gold Helicoids on Grating Surfaces.

Distinct advantages of surface enhanced Raman scattering (SERS) in molecular detection can benefit the enantioselective discrimination of specific molecular configurations. However, many of the recent methods still lack versatility and require customized anchors to chemically interact with the studied analyte. In this work, we propose the utilization of helicoid-shaped chiral gold nanoparticles arranged in an ordered array on a gold grating surface for enantioselective SERS recognition. This arrangement ensured a homogeneous distribution of chiral plasmonic hot spots and facilitated the enhancement of the SERS response of targeted analytes through plasmon coupling between gold helicoid multimers (formed in the grating valleys) and adjacent regions of the gold grating. Naproxen enantiomers (R(+) and S(-)) were employed as model compounds, revealing a clear dependence of their SERS response on the chirality of the gold helicoids. Additionally, propranolol and penicillamine enantiomers were used to validate the universality of the proposed approach. Finally, numerical simulations were conducted to elucidate the roles of intensified local electric field and optical helicity density on the SERS signal intensity and on the chirality of the nanoparticles and enantiomers. Unlike previously reported methods, our approach relies on the excitation of a chiral plasmonic near-field and its interaction with the chiral environment of analyte molecules, obviating the need for the enantioselective entrapment of targeted molecules. Moreover, our method is not limited to specific analyte classes and can be applied to a broad range of chiral molecules.

Spatiotemporally modulated full-polarized light emission for multiplexed optical encryption.

Spatiotemporal control of full freedoms of polarized light emission is crucial in multiplexed optical computing, encryption and communication. Although recent advancements have been made in active emission or passive conversion of polarized light through solution-processed nanomaterials or metasurfaces, these design paths usually encounter limitations, such as small polarization degrees, low light utilization efficiency, limited polarization states, and lack of spatiotemporal control. Here, we addressed these challenges by integrating the spatiotemporal modulation of the LED device, the precise control and efficient polarization emission through nanomaterial assembly, and the programmable patterning/positioning using 3D printing. We achieved an extremely high degree of polarization for both linearly and circularly polarized emission from ultrathin inorganic nanowires and quantum nanorods thanks to the shear-force-induced alignment effect during the protruding of printing filaments. Real-time polarization modulation covering the entire Poincaré sphere can be conveniently obtained through the programming of the on-off state of each LED pixel. Further, the output polarization states can be encoded by an ordered chiral plasmonic film. Our device provides an excellent platform for multiplexing spatiotemporal polarization information, enabling visible light communication with an exceptionally elevated level of physical layer security and multifunctional encrypted displays that can encode both 2D and 3D information.

Selective Targeting of Nanobody-Modified Gold Nanoparticles to Distinct Cell Types.

Nanobody-modified gold nanoparticles were used to explore their ability to achieve selective targeting in vitro and in vivo to distinct cell type(s), based on the specificity of the nanobody that was installed. We developed conjugation methods that exploit click chemistry for octahedral ∼50 nm gold nanoparticles and chiral ∼180 nm gold nanoparticles. We determined that each of these particles could be modified with ∼75 and ∼330 nanobodies, respectively. Particle-bound nanobodies retain their antigen binding capacity. After conjugation of the mouse Class II MHC-specific nanobody VHH7 to chiral gold nanoparticles, selective targeting of Class II MHC-positive cell types was observed in vitro by fluorometric assays and by dark-field microscopy. Upon installation of the positron emission tomography (PET) isotopes 89Zr or 64Cu on nanobody-modified gold nanoparticles and retro-orbital injection of the radiolabeled particles, we observed accumulation predominantly in the liver and to a far lesser extent in the spleen, regardless of the size of the gold nanoparticles and the identity of the attached nanobody. We observed a striking difference in the distribution of radioisotope-labeled gold nanoparticles by changing the route of administration to intraperitoneal delivery. Significantly reduced accumulation in the liver and spleen was observed by intraperitoneal injection of nanoparticles. In the case of nanobody-modified gold nanoparticles injected intraperitoneally, prominent and persistent signals from the parathymic lymph nodes were observed in the PET/computed tomography images.