Plasmonic nanoparticles, particularly gold nanoparticles (GNPs) hold a great potential as structural and functional building blocks for three-dimensional (3D) nanoarchitectures with specific optical applications. However, a rational control of their assembly into nanoscale superstructures with defined positioning and overall arrangement still remains challenging. Herein, we propose a solution to this challenge by using as building blocks: (1) nanometric silica helices with tunable handedness and sizes as a matrix and (2) GNPs with diameter varying from 4 to 10 nm to prepare a collection of helical GNPs superstructures (called Goldhelices hereafter). These nanomaterials exhibit well-defined arrangement of GNPs following the helicity of the silica template. Strong chiroptical activity is evidenced by circular dichroism (CD) spectroscopy at the wavelength of the surface plasmon resonance (SPR) of the GNPs with a anisotropy factor (g-factor) of the order of 1 × 10, i.e., 10-fold larger than what is typically reported in the literature. Such CD signals were simulated using a coupled dipole method which fit very well the experimental data. The measured signals are 1-2 orders of magnitude lower than the simulated signals, which is explained by the disordered GNPs grafting, the polydispersity of the GNPs, and the dimension of the nanohelices. These Goldhelices based on inorganic templates are much more robust than previously reported organic-based chiroptical nanostructures, making them good candidates for complex hierarchical organization, providing a promising approach for light management and benefits in applications such as circular polarizers, chiral metamaterials, or chiral sensing in the visible range.
Ligand-induced chirality in semiconductor nanocrystals (NCs) has attracted attention because of the tunable optical properties of the NCs. Induced circular dichroism (CD) has been observed in CdX (X = S, Se, Te) NCs and their hybrids, but circularly polarized luminescence (CPL) in these fluorescent nanomaterials has been seldom reported. Herein, we describe the successful preparation of l- and d-cysteine-capped CdSe-dot/CdS-rods (DRs) with tunable CD and CPL behaviors and a maximum anisotropic factor ( g) of 4.66 × 10. The observed CD and CPL activities are sensitive to the relative absorption ratio of the CdS shell to the CdSe core, suggesting that the anisotropic g-factors in both CD and CPL increase to some extent for a smaller shell-to-core absorption ratio. In addition, the molar ratio of chiral cysteine to the DRs is investigated. Instead of enhancing the chiral interactions between the chiral molecules and DRs, an excess of cysteine molecules in aqueous solution inhibits both the CD and CPL activities. Such chiral and emissive NCs provide an ideal platform for the rational design of semiconductor nanomaterials with chiroptical properties.
We constructed an intelligent cloud lab that integrates lab automation with cloud servers and artificial intelligence (AI) to detect chirality in perovskites. Driven by the materials acceleration operating system in cloud (MAOSIC) platform, on-demand experimental design by remote users was enabled in this cloud lab. By employing artificial intelligence of things (AIoT) technology, synthesis, characterization, and parameter optimization can be autonomously achieved. Through the remote collaboration of researchers, optically active inorganic perovskite nanocrystals (IPNCs) were first synthesized with temperature-dependent circular dichroism (CD) and inversion control. The inter-structure (structural patterns) and intrastructure (screw dislocations) dual-pattern-induced mechanisms detected by MAOSIC were comprehensively investigated, and offline theoretical analysis revealed the thermodynamic mechanism inside the materials. This self-driving cloud lab enables efficient and reliable collaborations across the world, reduces the setup costs of in-house facilities, combines offline theoretic analysis, and is practical for accelerating the speed of material discovery.
Hybrid organic–inorganic metal halides have emerged as highly promising materials for a wide range of applications in optoelectronics. Incorporating chiral organic molecules into metal halides enables the extension of their unique optical and electronic properties to chiral optics. By using chiral (R)‐ or (S)‐methylbenzylamine (R‐/S‐MBA) as the organic component, we synthesized chiral hybrid copper halides, (R‐/S‐MBA)2CuCl4, and investigated their optical activity. Thin films of this material showed a record anisotropic g‐factor as high as approximately 0.06. We discuss the origin of the giant optical activity observed in (R‐/S‐MBA)2CuCl4 by theoretical modeling based on density functional theory (DFT) and demonstrate highly efficient second harmonic generation (SHG) in these samples. Our study provides insight into the design of chiral materials by structural engineering, creating a new platform for chiral and nonlinear photonic device applications of the chiral hybrid copper halides.
All-inorganic lead halides, including CsPbX3 (X = Cl, Br, I), have become important candidate materials in the field of optoelectronics. However, the inherent toxicity of metal lead and poor material...
Ligand-induced chirality in asymmetric CdSe/CdS core-shell nanocrystals (NCs) has been extensively applied in chiral biosensors, regioselective syntheses and assemblies, circularly polarized luminescence (CPL) and chiroptic-based devices due to their excellent physiochemical properties, such as the tunable quantum confinement effects, surface functionality and chemical stability. Herein, we present CdSe/CdS NCs with various morphologies such as nanoflowers, tadpoles and dot/rods (DRs) with chirality induced by surface chiral ligands. The observed circular dichroism (CD) and CPL activities are closely associated with the geometrical characteristics of the nanostructures, such as the shell thickness and the aspect ratio of the CdSe/CdS NCs. Furthermore, in situ observations of the growth of tadpoles with a single tail indicate that the CD response is mainly attributed to the CdS shell, which has a maximum tail length of ~45 nm (approximately λ/10 of the incident light wavelength). On the other hand, the CPL activity is only related to the CdSe core, and the activity benefits from a thin CdS shell with a relatively high photoluminescence quantum yield (QY). Further theoretical models demonstrated the aspect-ratiodependent g-factor and QY variation in these asymmetric nanostructures. These findings provide insights into not only the asymmetric synthesis of CdSe/CdS NCs, but also the rational design of CdSe/CdS nanostructures with tunable CD and CPL activities.
Chirality‐based semiconducting nanocrystals, as an emerging area, are envisioned to have great potential in chiral sensing, biomedicine, and chiroptical devices. Herein, chiral substoichiometric molybdenum oxide (l/d‐Cys‐MoO3−x) nanoparticles are synthesized via step‐by‐step reduction treatment with chiral cysteine molecules. The obtained nanoparticles are used as visible‐ and near‐infrared‐light dual responsive photothermal therapy agent for tumor cell ablation. Notably, the chiral nanoparticles show chiral selectivity for incident light, i.e., when irradiated by left‐circularly polarized light, l‐Cys‐MoO3−x is the most sensitive agent giving the highest mortality for HeLa cell ablation in vitro, and vice versa for right‐circularly polarized light with d‐Cys‐MoO3−x. In comparison to traditional photothermal therapy with near‐field light source, the investigations with chiral visible light at 532 nm indicate the possibility of chiral Cys‐MoO3−x nanoparticles for visible light‐based phototherapy via metal–ligand charge transfer chirality, which provides insights for new methods in nanotechnology supported photothermal treatments.
Finely tuned chiral nanometric silica fibers were synthesized based on sol-gel chemistry using organic self-assembly as a template. The optimization of the sol-gel process in acidic conditions allowed us to reduce the transcription time by a factor of 10. These nanohelices were successfully fragmented while preserving the fine internal structures from several micrometers to several hundreds of nanometers in length by a sonication method previously reported for carbon nanotubes. By carefully choosing the nature of the solvent, the sonication power, pH in the case of water, and densification of the silica walls by freeze-drying, the homogeneous and stable colloidal suspensions of individualized chiral nanometric silica ribbons with controlled length were obtained.
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