Hybrid Anapole Induced Chirality in Metasurfaces.

The interaction between light and matter, particularly chirality, plays a pivotal role in modern science and technology. Typically, metasurfaces achieve chiro-optical effects by coupling electric and magnetic dipoles in specific orientations. In this work, the design and optimization of an asymmetric H-shaped metasurface is explored to induce hybrid anapole (HA) for optical activity. When the symmetry of the metasurface structure is disrupted, the design can simultaneously excite first-order and pseudo high-order HA under illumination with a specific circular polarization, both occurring within the same spectral regime. This results in high reflection for one circular polarization and a significant reduction in reflection for the orthogonal polarization, thereby exhibiting exceptional chiro-optical activity. Moreover, the HA-based chiral metasurface demonstrates strong polarization control capabilities, as verified by Stokes parameter analysis, revealing high birefringence and a pronounced dependence on the incident polarization angle. These results provide valuable insights for the design and optimization of HA metasurfaces for advanced optical applications and polarization control, paving the way for new developments in chiral nanophotonics.

Intrinsic Superchirality in Planar Plasmonic Metasurfaces.

Plasmonic metasurfaces with spatial symmetry breaking are crucial materials with significant applications in fields such as polarization-controlled photonic devices and nanophotonic platforms for chiral sensing. In this paper, we introduce planar plasmonic metasurfaces, less than one-tenth of a wavelength thick, featuring nanocavities formed by three equilateral triangles. This configuration creates uniform, thin metasurfaces. Through a combination of experimental measurements and numerical modeling, we demonstrate the inherent superchirality of these plasmonic metasurfaces. We address the challenge of achieving a strong enhancement of optical chirality in the visible spectrum, reaching levels comparable to those of 3D chiral metasurfaces.

Ultrasensitive Raman Detection of Biomolecular Conformation at the Attomole Scale using Chiral Nanophotonics.

Understanding the function of a biomolecule hinges on its 3D conformation or secondary structure. Chirally sensitive, optically active techniques based on the differential absorption of UV-vis circularly polarized light excel at rapid characterisation of secondary structures. However, Raman spectroscopy, a powerful method for determining the structure of simple molecules, has limited capacity for structural analysis of biomolecules because of intrinsically weak optical activity, necessitating millimolar (mM) sample quantities. A breakthrough is presented for utilising Raman spectroscopy in ultrasensitive biomolecular conformation detection, surpassing conventional Raman optical activity by 15 orders of magnitude. This strategy combines chiral plasmonic metasurfaces with achiral molecular Raman reporters and enables the detection of different conformations (α-helix and random coil) of a model peptide (poly-L/D-lysine) at the ≤attomole level (monolayer). This exceptional sensitivity stems from the ability to detect local, molecular-scale changes in the electromagnetic (EM) environment of a chiral nanocavity induced by the presence of biomolecules using molecular Raman reporters. Further signal enhancement is achieved by incorporating achiral Au nanoparticles. The introduction of the nanoparticles creates highly localized regions of extreme optical chirality. This approach, which exploits Raman, a generic phenomenon, paves the way for next-generation technologies for the ultrasensitive detection of diverse biomolecular structures.

Chirally Selective and Switchable Luminescence from Achiral Quantum Emitters on Suspended Twisted Stacking Metasurfaces.

Dynamic control of circularly polarized photoluminescence has aroused great interest in quantum optics and nanophotonics. Chiral plasmonic metasurfaces enable the manipulation of the polarization state via plasmon-photon coupling. However, current plasmonic light-emitting metasurfaces for effective deterministic modulation of spin-dependent emission at near-infrared wavelengths are underexplored in terms of dissymmetry and tunability. Here, we demonstrate a microfluidic hybrid emitting system of a suspended twisted stacking metasurface coated with PbS quantum dots. The suspended metasurface is fabricated with a single step of electron beam exposure, exhibiting a strong optical chirality of 309° µm-1 with a thickness of less than λ/10 at key spectral locations. With significant chiral-selective interactions, enhanced photoluminescence is achieved with strong dissymmetry in circular polarization. The dissymmetry factor of the induced circularly polarized emission can reach 1.54. More importantly, altering the refractive index of the surrounding medium at the bottom surface of the metasurface can effectively manipulate the chiroptical responses of the hybrid system, hence leading to chirality-reversed emission. This active hybrid emitting system could be a resultful platform for chirality-switchable light emission from achiral quantum emitters, holding great potential for anticounterfeiting, biosensing, light sources, imaging, and displays.

Uncovering Maximum Chirality in Resonant Nanostructures.

Chiral nanostructures allow engineering of chiroptical responses; however, their design usually relies on empirical approaches and extensive numerical simulations. It remains unclear if a general strategy exists to enhance and maximize the intrinsic chirality of subwavelength photonic structures. Here, we suggest a microscopic theory and uncover the origin of strong chiral responses of resonant nanostructures. We reveal that the reactive helicity density is critically important for achieving maximum chirality at resonances. We demonstrate our general concept on the examples of planar photonic crystal slabs and metasurfaces, where out-of-plane mirror symmetry is broken by a bilayer design. Our findings provide a general recipe for designing photonic structures with maximum chirality, paving the way toward many applications, including chiral sensing, chiral emitters and detectors, and chiral quantum optics.

Trace-Amount Detection of Chiral Molecules Based on Plasmonic Racemic Arrays Fabricated via Direct Laser Writing.

Superchiral fields, supported by chiral plasmonic structures, have shown outstanding performance for chiral molecule sensing via enhanced chiral light-matter interaction. However, this sensing capability cannot fully reveal the chiral origin of the molecules as the chiroptic response of the molecules is intertwined with the chiroptic response of the chiral plasmonic nanostructures, which can potentially be excluded by using a plasmonic racemic mixture. Such a plasmonic racemic mixture is not easily attainable, as it normally requires complex fabrication and expensive instrumentation, whose structural fineness is limited by the fabrication precision. Here, we demonstrate trace-amount chiral molecule detection with plasmonic racemic arrays fabricated by direct laser writing with vector beams, which is facile, cost-effective, and highly controllable. The racemic arrays present no inherent circular differential scattering but a large local superchiral field, which reflects the intrinsic chiral features of the chiral molecules. They are further applied to discriminate enantiomers of phenylalanine with a limit of detection (LOD) of 10.0 ± 2.8 µM, which is an order of magnitude smaller than the LOD of conventional circular dichroism spectroscopy. The strong local superchiral field provided by the plasmonic racemic arrays enlightens the design of a superior sensing platform, which holds promising applications for biomedical detection and enantioselective drug development.

Room-Temperature Geometrical Circular Photocurrent in Few-Layer MoS2.

Valleytronics, i.e., the manipulation of the valley degree of freedom, offers a promising path for energy-efficient electronics. One of the key milestones in this field is the room-temperature manipulation of the valley information in thick-layered material. Using scanning photocurrent microscopy, we achieve this milestone by observing a geometrically dependent circular photocurrent in a few-layer molybdenum disulfide (MoS2) under normal incidence. Such an observation shows that the system symmetry is lower than that of bulk MoS2 material, preserving the optical chirality-valley correspondence. Moreover, the circular photocurrent polarity can be reversed by applying electrical bias. We propose a model where the observed photocurrent results from the symmetry breaking and the built-in field at the electrode-sample interface. Our results show that the valley information is still retained even in thick-layered MoS2 at room temperature and opens up new opportunities for exploiting the valley index through interface engineering in multilayer valleytronics devices.

Self-Assembly for Creating Vertically-Aligned Graphene Micro Helices with Monolayer Graphene as Chiral Metamaterials.

Graphene's emergence enables creating chiral metamaterials in helical shapes for terahertz (THz) applications, overcoming material limitations. However, practical implementation remains theoretical due to fabrication challenges. This paper introduces a dual-component self-assembly technique that enables creating vertically-aligned continuous monolayer graphene helices at microscale with great flexibility and high controllability. This assembly process not only facilitates the creation of 3D microstructures, but also positions the 3D structures from a horizontal to a vertical orientation, achieving an aspect ratio (height/width) of ≈2700. As a result, an array of vertically-aligned graphene helices is formed, reaching up to 4 mm in height, which is equivalent to 4 million times the height of monolayer graphene. The benefit of these 3D chiral structures made from graphene is their capability to infinitely extend in height, interacting with light in ways that are not possible with traditional 2D layering methods. Such an impressive height elevates a level of interaction with light that far surpasses what is achievable with traditional 2D layering methods, resulting in a notable enhancement of optical chirality properties. This approach is applicable to various 2D materials, promising advancements in innovative research and diverse applications across fields.

Spin Unlocked Vortex Beam Generation on Nonlinear Chiroptical Metasurfaces.

Optical vortices with spin and orbital angular momentum (SAM and OAM) states offer multiple degrees of freedom for manipulating optical fields and thus enable great potentials in optical information processing. Recently, the optical metasurface has become an important platform for vortex beam generation and steering. However, the strong spin-orbit interaction on such metasurfaces usually leads to spin locked OAM generation, which limits the complete control of the angular momentum state of light. Here, we propose to solve this constraint using geometric phase controlled nonlinear chiroptical metasurfaces. The metasurface consists of two types of plasmonic meta-atoms which have opposite handedness and exhibit a strong spin-dependent circular dichroism effect. By encoding specific phase singularities and phase gradients to different channels, we experimentally demonstrate the spin unlocked second harmonic beam steering. The proposed nonlinear chiroptical metasurfaces may have important applications in developing multifunctional nonlinear optical devices.

Enantioselective Optical Trapping of Multiple Pairs of Enantiomers by Focused Hybrid Polarized Beams.

Enantiomers (opposite chiral molecules) usually exhibit different effects when interacting with chiral agents, thus the identification and separation of enantiomers are of importance in pharmaceuticals and agrochemicals. Here an optical approach is proposed to enantioselective trapping of multiple pairs of enantiomers by a focused hybrid polarized beam. Numerical results indicate that such a focused beam shows multiple local optical chirality of opposite signs in the focal plane, and can trap the corresponding enantiomers near the extreme value of optical chirality density according to the handedness of enantiomers. The number and positions of trapped enantiomers can be changed by altering the value and sign of polarization orders of hybrid polarized beams, respectively. The key to realizing enantioselective optical trapping of enantiomers is that the chiral optical force exerted on enantiomers in this focused field is stronger than the achiral optical force. The results provide insight into the optical identification and separation of multiple pairs of enantiomers and will find applications in chiral detection and sensing.

Tuning the Plexcitonic Optical Chirality Using Discrete Structurally Chiral Plasmonic Nanoparticles.

Constructing chiral plexcitonic systems with tunable plasmon-exciton coupling may advance the scientific exploitation of strong light-matter interactions. Because of their intriguing chiroptical properties, chiral plasmonic materials have shown promising applications in photonics, sensing, and biomedicine. However, the strong coupling of chiral plasmonic nanoparticles with excitons remains largely unexplored. Here we demonstrate the construction of a chiral plasmon-exciton system using chiral AuAg nanorods and J aggregates for tuning the plexcitonic optical chirality. Circular dichroism spectroscopy was employed to characterize chiral plasmon-exciton coupling, in which Rabi splitting and anticrossing behaviors were observed, whereas the extinction spectra exhibited less prominent phenomena. By controlling the number of molecular excitons and the energy detuning between plasmons and excitons, we have been able to fine-tune the plexcitonic optical chirality. The ability to fine-tune the plexcitonic optical chirality opens up unique opportunities for exploring chiral light-matter interactions and boosting the development of emerging chiroptical devices.

Controlling Valley-Specific Light Emission from Monolayer MoS2 with Achiral Dielectric Metasurfaces.

Excitons in two-dimensional transition metal dichalcogenides have a valley degree of freedom that can be optically manipulated for quantum information processing. Here, we integrate MoS2 monolayers with achiral silicon disk array metasurfaces to enhance and control valley-specific absorption and emission. Through the coupling to the metasurface electric and magnetic Mie modes, the intensity and lifetime of the emission of neutral excitons, trions, and defect bound excitons can be enhanced and shortened, respectively, while the spectral shape can be modified. Additionally, the degree of polarization (DOP) of exciton and trion emission from the valley can be symmetrically enhanced at 100 K. The DOP increase is attributed to both the metasurface-enhanced chiral absorption of light and the metasurface-enhanced exciton emission from the Purcell effect. Combining Si-compatible photonic design with large-scale 2D materials integration, our work makes an important step toward on-chip valleytronic applications approaching room-temperature operation.

Nanophotonic Chirality Transfer to Dielectric Mie Resonators.

Nanophotonics can boost the weak circular dichroism of chiral molecules. One mechanism for enhanced chiral sensing relies on using a resonator to create fields with high optical chirality at the molecular position. Here, we elucidate how the reverse interaction between molecules and the resonator, called chirality transfer, can produce stronger circular dichroism. The chiral analyte modifies the electric and magnetic dipole moments of the resonator, imprinting a chiral response on an otherwise achiral resonance. We demonstrate that silicon nanoparticles and metasurfaces tailored for chirality transfer generate chiroptical signals orders of magnitude higher than the contribution from optical chirality alone. We derive closed-form equations for the dependence of chirality transfer on molecular chirality, molecule-resonator distance, and Mie coefficients. We propose a dielectric metasurface for a 900-fold circular dichroism enhancement on the basis of these principles. Finally, we identify a fundamental limit to chirality transfer. Our findings thus establish key concepts for nanophotonic chiral sensing.

Magnetic/Plasmonic Hybrid Nanodisks with Dynamically Tunable Mechano-Chiroptical Responses.

Chiral plasmonic nanostructures have promising applications in optoelectronics due to their chiroptical responses. However, achieving active tuning of optical chirality remains challenging. Here, we develop stretchable chiroptical films with mechanically tunable extrinsic chirality by assembling hexagonal magnetic/plasmonic hybrid nanodisks in magnetic fields. The nanodisks, synthesized using a space-confined growth method, display three distinct plasmonic resonance modes at the UV-vis-NIR region, which red shift with increasing size as demonstrated by simulation and experimental results. The coupled magnetic and plasmonic anisotropy allows convenient control over the plasmonic resonance modes by altering the strength or direction of external magnetic fields. Further, magnetically aligning the nanodisks in a stretchable polymer film produces superstructures with extrinsic chirality, displaying selective absorption of circularly polarized light and inverted circular dichroism due to the linear dichroism-linear birefringence effect. Reversible mechanical stretching allows for continuous switching of circular dichroism in a wide range (from -1° to +1°). The efficient magnetic alignment of hybrid nanodisks in the hydrogel provides a simple and effective strategy for designing stretchable optical devices with tunable extrinsic chirality.

Plasmonic Chiral Metasurface-Induced Upconverted Circularly Polarized Luminescence from Achiral Upconversion Nanoparticles.

Chirality induction, transfer, and manipulation have aroused great interest in achiral nanomaterials. Here, we demonstrate strong upconverted circularly polarized luminescence from achiral core-shell upconversion nanoparticles (UCNPs) via a plasmonic chiral metasurface-induced optical chirality transfer. The Yb3+-sensitized core-shell UCNPs with good dispersity exhibit intense upconversion luminescence of Tm3+ and Nd3+ through the energy transfer process. By spin-coating the core-shell UCNPs on this chiral metasurface, strong enhancement and circular polarization modulation of upconversion luminescence can be achieved due to resonant coupling between surface plasmons and upconversion nanoparticles. In the UCNPs-on-metasurface composite, a significant upconversion luminescence enhancement can be achieved with a maximum enhancement factor of 32.63 at 878 nm and an overall enhancement factor of 11.61. The luminescence dissymmetry factor of the induced upconverted circularly polarized luminescence can reach 0.95 at the emission wavelength of 895 nm. The UCNPs-on-metasurface composite yields efficient modulation for the emission intensity and polarization of UCNPs, paving new pathways to many potential applications in imaging, sensing, and anticounterfeiting fields.

Four-Component Ugi Reaction for Optical Chirality Sensing and Surface Nanoengineering of Chiral Self-Assemblies.

Using green chemistry to control chirality at hierarchical levels as well as chiroptical activities endows with new opportunities to the development of multiple functions. Here, the four-component Ugi reaction is introduced for the general and precise optical chirality sensing of amines as well as the surface nanoengineering of chiral soft self-assemblies. To overcome the relatively weak Cotton effects, direct synthesis of a folded peptide structure on a rotatable ferrocene core with axial chirality was accomplished from chiral amine, 1,1'-ferrocenyl dicarboxylic acid, formaldehyde and isocyanide. Enhanced Cotton effects benefiting from the folded structure allow for the precise and quantitative sensing of natural and synthetic chiral amines covering alkyl, aromatic amines and amino acid derivatives. In addition, aqueous reaction enables the modification of amine-bearing dye to microfibers self-assembled from π-conjugated amino acids. Surface dye-modification via Ugi reaction barely changes the pristine morphology, showing non-invasive properties in contrast to dye staining, which is applicable in soft nano/microarchitectures from self-assembly. This work which combines the four-component Ugi reaction to enable precise ee% detection and surface nanoengineering of soft chiral assemblies sheds light on the advanced application of green chemistry to chirality science.

Shining light on chiral inorganic nanomaterials for biological issues.

The rapid development of chiral inorganic nanostructures has greatly expanded from intrinsically chiral nanoparticles to more sophisticated assemblies made by organics, metals, semiconductors, and their hybrids. Among them, lots of studies concerning on hybrid complex of chiral molecules with achiral nanoparticles (NPs) and superstructures with chiral configurations were accordingly conducted due to the great advances such as highly enhanced biocompatibility with low cytotoxicity and enhanced penetration and retention capability, programmable surface functionality with engineerable building blocks, and more importantly tunable chirality in a controlled manner, leading to revolutionary designs of new biomaterials for synergistic cancer therapy, control of enantiomeric enzymatic reactions, integration of metabolism and pathology via bio-to nano or structural chirality. Herein, in this review our objective is to emphasize current research state and clinical applications of chiral nanomaterials in biological systems with special attentions to chiral metal- or semiconductor-based nanostructures in terms of the basic synthesis, related circular dichroism effects at optical frequencies, mechanisms of induced optical chirality and their performances in biomedical applications such as phototherapy, bio-imaging, neurodegenerative diseases, gene editing, cellular activity and sensing of biomarkers so as to provide insights into this fascinating field for peer researchers.

Generation of circular dichroism from superposed porphyrin films.

Circular dichroism (CD) was observed from the superposed porphyrin deposited glass plates, which were prepared by the vapor deposition of achiral porphyrin molecules and oriented to one direction by rubbing parallel to the surface of plate. The CD spectra depended on the twisted angle between the plates and the number of plates superposed. The observed CD spectra agreed with the simulated ones by the Mueller matrices superposition calculation using the observed linear dichroism spectra and linear birefringence spectra of each plate.

Gigantic vortical differential scattering as a monochromatic probe for multiscale chiral structures.

Spin angular momentum of light is vital to investigate enantiomers characterized by circular dichroism (CD), widely adopted in biology, chemistry, and material science. However, to discriminate chiral materials with multiscale features, CD spectroscopy normally requires wavelength-swept laser sources as well as wavelength-specific optical accessories. Here, we experimentally demonstrate an orbital-angular-momentum-assisted approach to yield chiroptical signals with monochromatic light. The gigantic vortical differential scattering (VDS) of ∼120% is achieved on intrinsically chiral microstructures fabricated by femtosecond laser. The VDS measurements can robustly generate chiroptical properties on microstructures with varying geometric features (e.g., diameters and helical pitches) and detect chiral molecules with high sensitivity. This VDS scheme lays a paradigm-shift pavement toward efficiently chiroptical discrimination of multiscale chiral structures with photonic orbital angular momentum. It simplifies and complements the conventional CD spectroscopy, opening possibilities for measuring weak optical chirality, especially on mesoscale chiral architectures and macromolecules.

DNA Origami Guided Self-Assembly of Plasmonic Polymers with Robust Long-Range Plasmonic Resonance.

Plasmonic polymers consisting of metallic nanoparticles (NPs) are able to squeeze light into the deep-subwavelength space and transfer along a highly confined nanoscale path in long range. DNA nanotechnology, particularly benefiting from the molecular programmability of DNA origami, has provided otherwise nearly impossible platforms for constructing plasmonic nanoparticle polymers with designer configurations and nanoscale gaps. Here, we design and assemble a DNA origami hashtag tile that is able to polymerize into one-dimensional chains with high rigidity. The DNA origami hashtag chains are used as frames to enable robust, versatile, and precise arrangement of metallic NPs into micrometer-long chiral and magnetic plasmonic polymers, which are capable of efficiently transporting plasmonic angular momentum and magnetic surface plasmonic polaritons at the deep-subwavelength scale. Our work provides a molecular platform for the fabrication of long, straight, and structurally complex nanoparticle polymers with emerging plasmonic properties that are appealing to a variety of fields.