Single-Particle Photothermal Circular Dichroism and Photothermal Magnetic Circular Dichroism Microscopy.

Recent advances in single-particle photothermal circular dichroism (PT CD) and photothermal magnetic circular dichroism (PT MCD) microscopy have shown strong promise for diverse applications in chirality and magnetism. Photothermal circular dichroism microscopy measures direct differential absorption of left- and right-circularly polarized light by a chiral nanoobject and thus can measure a pure circular dichroism signal, which is free from the contribution of circular birefringence and linear dichroism. Photothermal magnetic circular dichroism, which is based on the polar magneto-optical Kerr effect, can probe the magnetic properties of a single nanoparticle (of sizes down to 20 nm) optically. Single-particle measurements enable studies of the spatiotemporal heterogeneity of magnetism at the nanoscale. Both PT CD and PT MCD have already found applications in chiral plasmonics and magnetic nanomaterials. Most importantly, the advent of these microscopic techniques opens possibilities for many novel applications in biology and nanomaterial science.

The N-Oscillator Born-Kuhn Model: An In-Depth Analysis of Chiro-Optical Properties in Complex Chiral Systems.

A comprehensive theory is developed for the chiral optical response of two configurations of the N-oscillator Born-Kuhn model (NOBK): the helically stacked and the corner stacked models. In the helical NOBK model, there is always a chiral response regardless of the value of N, whereas in the corner NOBK, only configurations with even N demonstrate a chiral response. Generally, the magnitudes of optical rotatory dispersion (ORD) and circular dichroism (CD) increase with N when the parameters of each oscillator are fixed. In cases of weak coupling, the spectral shapes of ORD and CD remain invariant, while strong coupling significantly alters the spectral shapes. For large damping, the spectral amplitude becomes smaller, and the spectral features become broader. In the presence of small damping, strong coupling introduces degeneracy in the coupled oscillator system, leading to multiple spectral features in both ORD and CD across the entire spectral region. This simple model can not only help in the design of tunable chiral metamaterials but also enhance our understanding of chiro-optical responses in structures with different configurations.

Universal Chiral-Plasmon-Induced Upward and Downward Transfer of Circular Dichroism to Achiral Molecules.

Electromagnetic chirality transfer represents an effective means of the nanoscale manipulation of optical chirality. While most of the previous reports have exclusively focused on the circular dichroism (CD) transfer from UV-responsive chiral molecules toward visible-resonant achiral colloidal nanoparticles, here we demonstrate a reverse process in which plasmonic chirality can be transferred to achiral molecules, either upward from visible to UV or downward from visible to near infrared (NIR). By hybridizing achiral UV- or NIR-responsive dye molecules with chiral metal nanoparticles in solution, we observe a chiral-plasmon-induced CD (CPICD) signal at the intrinsically achiral molecular absorption bands. Full-wave electromagnetic modeling reveals that both near-field Coulomb interaction and far-field radiative coupling contribute to the observed CPICD, indicating that the mechanism considered here is universal for different material systems and types of optical resonances. Our study provides a set of design guidelines for broadband nanophotonic chiral sensing from the UV to NIR spectral regime.

Electron Beam Induced Circularly Polarized Light Emission of Chiral Gold Nanohelices.

Chiral plasmonic nanostructures possess a chiroptical response orders of magnitude stronger than that of natural biomolecular systems, making them highly promising for a wide range of biochemical, medical, and physical applications. Despite extensive efforts to artificially create and tune the chiroptical properties of chiral nanostructures through compositional and geometrical modifications, a fundamental understanding of their underlying mechanisms remains limited. In this study, we present a comprehensive investigation of individual gold nanohelices by using advanced analytical electron microscopy techniques. Our results, as determined by angle-resolved cathodoluminescence polarimetry measurements, reveal a strong correlation between the circular polarization state of the emitted far-field radiation and the handedness of the chiral nanostructure in terms of both its dominant circularity and directional intensity distribution. Further analyses, including electron energy-loss measurements and numerical simulations, demonstrate that this correlation is driven by longitudinal plasmonic modes that oscillate along the helical windings, much like straight nanorods of equal strength and length. However, due to the three-dimensional shape of the structures, these longitudinal modes induce dipolar transverse modes with charge oscillations along the short axis of the helices for certain resonance energies. Their radiative decay leads to observed emission in the visible range. Our findings provide insight into the radiative properties and underlying mechanisms of chiral plasmonic nanostructures and enable their future development and application in a wide range of fields, such as nano-optics, metamaterials, molecular physics, biochemistry, and, most promising, chiral sensing via plasmonically enhanced chiral optical spectroscopy techniques.

Laser-Induced Chirality of Plasmonic Nanoparticles Embedded in Porous Matrix.

Chiral plasmonic nanostructures have emerged as promising objects for numerous applications in nanophotonics, optoelectronics, biosensing, chemistry, and pharmacy. Here, we propose a novel method to induce strong chirality in achiral ensembles of gold nanoparticles via irradiation with circularly-polarized light of a picosecond Nd:YAG laser. Embedding of gold nanoparticles into a nanoporous silicate matrix leads to the formation of a racemic mixture of metal nanoparticles of different chirality that is enhanced by highly asymmetric dielectric environment of the nanoporous matrix. Then, illumination with intense circularly-polarized light selectively modifies the particles with the chirality defined by the handedness of the laser light, while their "enantiomers" survive the laser action almost unaffected. This novel modification of the spectral hole burning technique leads to the formation of an ensemble of plasmonic metal nanoparticles that demonstrates circular dichroism up to 100 mdeg. An unforeseen peculiarity of the chiral nanostructures obtained in this way is that 2D and 3D nanostructures contribute almost equally to the observed circular dichroism signals. Thus, the circular dichroism is neither even nor odd under reversal of direction of light propagation. These findings will help guide the development of a passive optical modulator and nanoplatform for enhanced chiral sensing and catalysis.

Site-Selective Chiral Growth of Anisotropic Au Triangular Nanoplates for Tuning the Optical Chirality.

Site-selective chiral growth of anisotropic nanoparticles is of great importance to realize the plasmonic nanostructures with delicate geometry and desired optical chirality; however, it remains largely unexplored. This work demonstrates a controlled site-selective chiral growth system based on the seed-mediated growth of anisotropic Au triangular nanoplates. The site-selective chiral growth involves two distinct underlying pathways, faceted growth and island growth, which are interswitchable upon maneuvering the interplay of chiral molecules, surfactants, and reducing agents. The pathway switch governs the geometric and chirality evolution of Au triangular nanoplates, giving rise to tailorable circular dichroism spectra. The ability to tune the optical chirality in a controlled manner by manipulating the site-selective chiral growth pathway opens up a promising strategy for exploiting chiral metamaterials with increasing architectural complexity in chiroptical applications.

Transformable Plasmonic Helix with Swinging Gold Nanoparticles.

Control over multiple optical elements that can be dynamically rearranged to yield substantial three-dimensional structural transformations is of great importance to realize reconfigurable plasmonic nanoarchitectures with sensitive and distinct optical feedback. In this work, we demonstrate a transformable plasmonic helix system, in which multiple gold nanoparticles (AuNPs) can be directly transported by DNA swingarms to target positions without undergoing consecutive stepwise movements. The swingarms allow for programmable AuNP translocations in large leaps within plasmonic nanoarchitectures, giving rise to tailored circular dichroism spectra. Our work provides an instructive bottom-up solution to building complex dynamic plasmonic systems, which can exhibit prominent optical responses through cooperative rearrangements of the constituent optical elements with high fidelity and programmability.

Chirality in Light-Matter Interaction.

The scientific effort to control the interaction between light and matter has grown exponentially in the last 2 decades. This growth has been aided by the development of scientific and technological tools enabling the manipulation of light at deeply sub-wavelength scales, unlocking a large variety of novel phenomena spanning traditionally distant research areas. Here, the role of chirality in light-matter interactions is reviewed by providing a broad overview of its properties, materials, and applications. A perspective on future developments is highlighted, including the growing role of machine learning in designing advanced chiroptical materials to enhance and control light-matter interactions across several scales.

Magnetic Control of the Plasmonic Chirality in Gold Helicoids.

Chiral plasmonic nanostructures have facilitated a promising method for manipulating the polarization state of light. While a precise structural modification at the nanometer-scale-level could offer chiroptic responses at various wavelength ranges, a system that allows fast response control of a given structure has been required. In this study, we constructed uniformly arranged chiral gold helicoids with cobalt thin-film deposition that exhibited a strong chiroptic response with magnetic controllability. Tunable circular dichroism (CD) values from 0.9° to 1.5° at 550 nm wavelength were achieved by reversing the magnetic field direction. In addition, a magnetic circular dichroism (MCD) study revealed that the gap structure and size-related surface plasmon resonance induced MCD peaks. We demonstrated the transmitted color modulation, where the color dynamically changed from green-to-red, by controlling the field strength and polarizer axis. We believe current work broadens our understanding of magnetoplasmonic nanostructure and expands its potential applicability in optoelectronics or optical-communications.

Morphological and Optical Transitions during Micelle-Seeded Chiral Growth on Gold Nanorods.

Chiral plasmonics is a rapidly developing field where breakthroughs and unsolved problems coexist. We have recently reported binary surfactant-assisted seeded growth of chiral gold nanorods (Au NRs) with high chiroptical activity. Such a seeded-growth process involves the use of a chiral cosurfactant that induces micellar helicity, in turn driving the transition from achiral to chiral Au NRs, from both the morphological and the optical points of view. We report herein a detailed study on both transitions, which reveals intermediate states that were hidden so far. The correlation between structure and optical response is carefully analyzed, including the (linear and CD) spectral evolution over time, electron tomography, the impact of NR dimensions on their optical response, the variation of the absorption-to-scattering ratio during the evolution from achiral to chiral Au NRs, and the near-field enhancement related to chiral plasmon modes. Our findings provide further understanding of the growth process of chiral Au NRs and the associated optical changes, which will facilitate further study and applications of chiral nanomaterials.

Tunable Reversal of Circular Dichroism in the Seed-Mediated Growth of Bichiral Plasmonic Nanoparticles.

Plasmonic nanoparticles with an intrinsic chiral structure have emerged as a promising chiral platform for applications in biosensing, medicine, catalysis, separation, and photonics. Quantitative understanding of the correlation between nanoparticle structure and optical chirality becomes increasingly important but still represents a significantly challenging task. Here we demonstrate that tunable signal reversal of circular dichroism in the seed-mediated chiral growth of plasmonic nanoparticles can be achieved through the hybridization of bichiral centers without inverting the geometric chirality. Both experimental and theoretical results demonstrated the opposite sign of circular dichroism of two different bichiral geometries. Chiral molecules were found to not only contribute to the chirality transfer from molecules to nanoparticles but also manipulate the structural evolution of nanoparticles that synergistically drive the formation of two different chiral centers. By deliberately adjusting the concentration of chiral molecules and other synthetic parameters, such as the reducing agent concentration, the capping surfactant concentration, and the amount of Au precursor, we have been able to fine-tune the circular dichroism reversal of bichiral Au nanoparticles. We further demonstrate that the structure of chiral molecules and the crystal structure of Au seeds play crucial roles in the formation of Au nanoparticles with bichiral centers. The insights gained from this work not only shed light on the underlying mechanisms dictating the intriguing geometric and chirality evolution of bichiral plasmonic nanoparticles but also provide an important knowledge framework that guides the rational design of bichiral plasmonic nanostructures toward chiroptical applications.

Nanohelix-Induced Optical Activity of Liquid Metal Nanoparticles.

Liquid metals (such as gallium or Ga) exist in liquid states under ambient conditions and are hardly sculpted in chiral structures. Herein, through electron-beam evaporation of Ga, hemispherical achiral Ga nanoparticles (NPs) are randomly immobilized along helical surfaces of SiO2 nanohelices (NHs), functioning as a chiral template. Helical assembly of Ga NPs shows chiroplasmonic optical activity owing to collective plasmon-plasmon interactions, which can be tuned as a function of a helical SiO2 pitch (P) and the amount of Ga evaporated. At a P of ≈150 nm, the chiroplasmonic optical activity, evaluated with anisotropic g-factor, can be as large as ≈0.1. Because the SiO2 NHs and Ga NPs have high environmental stability of nanostructures, the chiroplasmonic optical activity shows excellent anti-aging stability, despite slight blue shift and chiroplasmonic degradation for the first 2 weeks. Spontaneous oxidation of the Ga NPs enables the formation of dense Ga2 O3 layers covering Ga cores to prevent further oxidation and thus to stabilize the chiroplasmonic optical activity. This work devises an alternative approach to impose optical activity onto Ga NPs, providing an additional degree of freedom (i.e., chirality) for Ga-based flexible electronic devices to develop advanced applications of 3D display, circular polarizers, bio-imaging, and bio-detection.

Interparticle gap geometry effects on chiroptical properties of plasmonic nanoparticle assemblies.

Chiral linear assemblies of plasmonic nanoparticles with chiral optical activity often show low asymmetry factors. Systematic understanding of the structure-property relationship in these systems must be improved to facilitate rational design of their chiroptical response. Here we study the effect of large area interparticle gaps in chiral linear nanoparticle assemblies on their chiroptical properties using a tetrahelix structure formed by a linear face-to-face assembly of nanoscale Au tetrahedra. Using finite-difference time-domain and finite element methods, we performed in-depth evaluation of the extinction spectra and electric field distribution in the tetrahelix structure and its dependence on various geometric parameters. The reported structure supports various plasmonic modes, one of which shows a strong incident light handedness selectivity that is associated with large face-to-face junctions. This works highlights the importance of gap engineering in chiral plasmonic assemblies to achieveg-factors greater than 1 and produce structures with a handedness-selective optical response.

DNA Programmable Self-Assembly of Planar, Thin-Layered Chiral Nanoparticle Superstructures with Complex Two-Dimensional Patterns.

Planar, thin-layered chiral plasmonic superstructures with complex two-dimensional (2D) patterns, namely, double-layered binary stars (bi-stars) and pinwheels, were realized through DNA programmable 2D supramolecular self-assembly of gold nanorods (AuNRs). The chirality of the chiral superstructures was defined by a finite number of AuNR pairs as enantiomeric motifs, and their sizes (∼240 nm) were precisely defined by the underlying DNA template. These planar, thin-layered chiral nanoparticle superstructures exhibited prescribed shapes and sizes at the dried state on the substrate surface and are characteristic of giant anisotropy of chiroptical responses, with enhanced g-factors from the axial incident excitation as compared to the in-plane excitation. This work will inspire possibilities for the construction of 2D chiral materials, for example, chiral metasurfaces, for the on-chip manipulation of chiral light-matter interactions via programmable self-assembly of nanoparticles.

Chiral Photomelting of DNA-Nanocrystal Assemblies Utilizing Plasmonic Photoheating.

Chiral plasmonic nanostructures exhibit anomalously strong chiroptical signals and offer the possibility to realize asymmetric photophysical and photochemical processes controlled by circularly polarized light. Here, we use a chiral DNA-assembled nanorod pair as a model system for chiral plasmonic photomelting. We show that both the enantiomeric excess and consequent circular dichroism can be controlled with chiral light. The nonlinear chiroptical response of our plasmonic system results from the chiral photothermal effect leading to selective melting of the DNA linker strands. Our study describes both the single-complex and collective heating regimes, which should be treated with different models. The chiral asymmetry factors of the calculated photothermal and photomelting effects exceed the values typical for the chiral molecular photochemistry at least 10-fold. Our proposed mechanism can be used to develop chiral photoresponsive systems controllable with circularly polarized light.

Femtomolar Biodetection by a Compact Core-Shell 3D Chiral Metamaterial.

Advanced sensing tools, detecting extremely low concentrations of circulating biomarkers, can open unexplored routes toward early diagnostics and diseases progression monitoring. Here, we demonstrate the sensing capabilities of a chip-based metamaterial, combining 3D chiral geometry with a functional core-shell nanoarchitecture. The chiral metamaterial provides a circular polarization-dependent optical response, allowing analysis in a complex environment without significant background interferences. The functional nanoarchitecture, based on the conformal coating with a polymer shell, modifies the chiral metamaterial near- and far-field optical response because of the energy transfer between dielectric shell polarization charges and plasmonic core free electrons, leading to efficient interaction with biomolecules. The system sensitivity slope is 27 nm/pM, in the detection of TAR DNA-binding protein 43, clinically relevant for neurodegenerative diseases. Measurements were performed in spiked solution and in human serum with concentrations from 1 pM down to 10 fM, which is a range not accessible with common immunological assays, opening new perspectives for next-generation biomedical systems.

Revealing the Chiroptical Response of Plasmonic Nanostructures at the Nanofemto Scale.

The spatiotemporal origin of plasmonic chiroptical responses in nanostructures remains unexplored and unclear. Here, two orthogonally oriented Au nanorods as a prototype were investigated, with a giant chiroptical response caused by antisymmetric and symmetric mode excitations for obliquely incident left-handed circular polarization (LCP) and right-handed circular polarization (RCP) light. Time-resolved photoemission electron microscopy (PEEM) was employed to measure the near-field spatial distributions, spectra, and spatiotemporal dynamics of plasmonic modes associated with the chiroptical responses at the nanofemto scale, verifying the characteristic near-field distributions at the resonant wavelengths of the two modes and a very large spectral dichroism for LCP and RCP. More importantly, eigenmode excitations and their contributions to the ultrafast plasmonic chiroptical response in the space-time domain were directly revealed, promoting a full understanding of the ultrafast chiral origin in complex nanostructures. These findings open a way to design chiroptical nanophotonic devices for spatiotemporal control of chiral light-matter interactions.

Chiro-optical response of a wafer scale metamaterial with ellipsoidal metal nanoparticles.

We report a large chiro-optical response from a nanostructured film of aperiodic dielectric helices decorated with ellipsoidal metal nanoparticles. The influence of the inherent fabrication variation on the chiro-optical response of the wafer-scalable nanostructured film is investigated using a computational model which closely mimics the material system. From the computational approach, we found that the chiro-optical signal is strongly dependent on the ellipticities of the metal nanoparticles and the developed computational model can account for all the variations caused by the fabrication process. We report the experimentally realized dissymmetry factor ∼1.6, which is the largest reported for wafer scalable chiro-plasmonic samples till now. The calculations incorporate strong multipolar contributions of the plasmonic interactions to the chiro-optical response from the tightly confined ellipsoidal nanoparticles, improving upon the previous studies carried in the coupled dipole approximation regime. Our analyzes confirm the large chiro-optical response in these films developed by a scalable and simple fabrication technique, indicating their applicability pertaining to manipulation of optical polarization, enantiomer selective identification and enhanced sensing and detection of chiral molecules.

Light-Responsive Dynamic DNA-Origami-Based Plasmonic Assemblies.

DNA nanotechnology offers a versatile toolbox for precise spatial and temporal manipulation of matter on the nanoscale. However, rendering DNA-based systems responsive to light has remained challenging. Herein, we describe the remote manipulation of native (non-photoresponsive) chiral plasmonic molecules (CPMs) using light. Our strategy is based on the use of a photoresponsive medium comprising a merocyanine-based photoacid. Upon exposure to visible light, the medium decreases its pH, inducing the formation of DNA triplex links, leading to a spatial reconfiguration of the CPMs. The process can be reversed simply by turning the light off and it can be repeated for multiple cycles. The degree of the overall chirality change in an ensemble of CPMs depends on the CPM fraction undergoing reconfiguration, which, remarkably, depends on and can be tuned by the intensity of incident light. Such a dynamic, remotely controlled system could aid in further advancing DNA-based devices and nanomaterials.

Chirality Transfer from Sub-Nanometer Biochemical Molecules to Sub-Micrometer Plasmonic Metastructures: Physiochemical Mechanisms, Biosensing, and Bioimaging Opportunities.

Determining the structural chirality of biomolecules is of vital importance in bioscience and biomedicine. Conventional methods for characterizing molecular chirality, e.g., circular dichroism (CD) spectroscopy, require high-concentration specimens due to the weak electronic CD signals of biomolecules such as amino acids. Artificially designed chiral plasmonic metastructures exhibit strong intrinsic chirality. However, the significant size mismatch between metastructures and biomolecules makes the former unsuitable for chirality-recognition-based molecular discrimination. Fortunately, constructing metallic architectures through molecular self-assembly allows chirality transfer from sub-nanometer biomolecules to sub-micrometer, intrinsically achiral plasmonic metastructures by means of either near-field interaction or chirality inheritance, resulting in hybrid systems with CD signals orders of magnitude larger than that of pristine biomolecules. This exotic property provides a new means to determine molecular chirality at extremely low concentrations (ideally at the single-molecule level). Herein, three strategies of chirality transfer from sub-nanometer biomolecules to sub-micrometer metallic metastructures are analyzed. The physiochemical mechanisms responsible for chirality transfer are elaborated and new fascinating opportunities for employing plasmonic metastructures in chirality-based biosensing and bioimaging are outlined.