Circular Dichroism Peak Research Articles

Intense Circular Dichroism and Spin Selectivity in AgBiS2 Nanocrystals by Chiral Ligand Exchange.

Chiral semiconducting nanomaterials offer many potential applications in photodetection, light emission, quantum information, and so on. However, it is difficult to achieve a strong circular dichroism (CD) signal in semiconducting nanocrystals (NCs) due to the complexity of chiral ligand surface engineering and multiple, uncertain mechanisms of chiroptical behavior. Here, a chiral ligand exchange strategy with cysteine on the ternary metal chalcogenide AgBiS2 NCs is developed, and a strong, long-lasting CD signal in the near-UV region is achieved. By carefully optimizing the ligand concentration, the CD peaks are observed at 260 and 320nm, respectively, giving insight into the different ligand binding mechanisms influencing the CD signal of AgBiS2 NCs. Using density-functional theory, a large degree of crystal distortion by the bidentate mode of ligand chelation, and efficient ligand-NC electron transfer, synergistically resulting in the strongest CD signal (g-factor over 10-2) observed in chiral ligand-exchanged semiconductor NCs to date, is demonstrated. To demonstrate the effective chiral properties of these AgBiS2 NCs, a spin-filter device with over 86% efficiency is fabricated. This work represents a considerable leap in the field of chiral semiconductor NCs and points toward their future applications.

Passively Broadband Tunable Dual Circular Dichroism via Bound States in the Continuum in Topological Chiral Metasurface.

Dynamic control for a strong circular dichroism (CD) response is essential in engineering applications such as polarization manipulation, sensing, and imaging. Here, we propose and experimentally demonstrate a broadband tunable dual CD response via bound states in the continuum (BICs) in two-dimensional topologically protected metasurfaces composed of all-dielectric Si chiral grating structures that generate a pair of mixed and degenerated BIC mode and circular dichroic mode (CDM) as an additional degree of freedom in CD manipulation. It is found that a singular CD peak of nearly 100% at 1.6 μm can be achieved by CDM when BIC is hidden under normal incidence, while the CD peak can be split into two in which peak wavelengths can be precisely and linearly tuned over a bandwidth of 180 nm by the incident angle when the BIC mode is excited under oblique incidence. Additionally, dynamic modulation of output polarization states from linear to circular can be arbitrarily achieved at the split CD peaks by controlling the incident angle when asymmetry perturbations on chiral gratings are introduced due to the decoupling of various polarization states at Γ point by BIC to different positions in K space. The proposed chiral grating metasurface exhibits unique angle-sensitive tunable CD spectral characteristics, making it ideal for hyperspectral and spin-selective wavefront shaping, and holds significant promise in various applications such as optical security, angle sensors, chiral lasers, nonlinear filters, and other active chiral optical devices.

Nature-Inspired Helicoidal Nanocellulose-Based Multi-Compartment Assemblies with Tunable Chiroptical Properties.

Cellulose-based nanocomposites are highly appealing for the development of next-generation sustainable functional materials. Although many advances have been made in this direction, the true potential of fibrillar nanocomposites has yet to be realized because available fabrication approaches are inadequate for achieving precise structural control at the sub-micrometer scale. Here a spray-assisted alignment methodology of cellulose nanofibrils is combined with the layer-by-layer assembly into an additive manufacturing process in which the alignment direction of each cellulose layer is rationally selected to achieve thin films with a helicoidal arrangement of the nanofibrils. The helicoidal structure of the films is verified by measuring the circular dichroism (CD) of the samples. The sign and position of the structural CD peak show that the handedness and the pitch of the chiral structures can be easily tuned by deliberately selecting simple parameters, such as the number of consecutive cellulose layers sprayed in the same direction, and the angle of rotation between successive stacks of layers. To the authors' knowledge, this approach is unique as it offers the possibility to prepare complex nanocomposite architectures with various nanoscale-controlled sub-structures from different anisometric objects, which is enabling novel designs of composite films with damage-resistant and/or optical filtering functionalities.

Magnetochiroptical nanocavities in hyperbolic metamaterials enable sensing down to the few-molecule level.

In this work, we combine the concepts of magnetic circular dichroism, nanocavities, and magneto-optical hyperbolic metamaterials (MO-HMMs) to demonstrate an approach for sensing down to a few molecules. Our proposal comprises a multilayer MO-HMM with a square, two-dimensional arrangement of nanocavities. The magnetization of the system is considered in polar configuration, i.e., in the plane of polarization and perpendicular to the plane of the multilayer structure. This allows for magneto-optical chirality to be induced through the polar magneto-optical Kerr effect, which is exhibited by reflected light from the nanostructure. Numerical analyses under the magnetization saturation condition indicate that magnetic circular dichroism peaks can be used instead of reflectance dips to monitor refractive index changes in the analyte region. Significantly, we obtained a relatively high sensitivity value of S = 40 nm/RIU for the case where refractive index changes are limited to the volume inside nanocavities, i.e., in the limit of a few molecules (or ultralow concentrations), while a very large sensitivity of S = 532 nm/RIU is calculated for the analyte region distributed along the entire superstrate layer.

Large and active circular dichroism in a photosensitive silicon based metasurface

Active circular dichroism (CD) is highly required for flexible polarization control in modern terahertz (THz) systems. In this work, we numerically achieve large and active CD in THz region by optically controlling photosensitive silicon in a gold/silicon hybrid cross-shape metasurface. At the incident angle of 75°, the proposed metasurface exhibits large CD. By tuning the conductivity of photosensitive silicon with an optical pump, the large CD (0.89) can be dynamically switched to 0.06 and the peak frequency is blue shifted around 0.09 THz. The simultaneous switching of CD strength and peak frequency is attributed to the variation of resonance modes between electric and magnetic dipole resonances. Our proposed active metasurface with dynamic CD has profound potential in the fields of reconfigurable THz devices.

Chiroptical properties of cyanine aggregates: hierarchical modelling from monomers to bundles.

Some achiral cyanine dyes form well-ordered chiral assemblies exhibiting pronounced Circular Dichroism (CD) and Circularly Polarized Luminescence (CPL). Notably, achiral C8O3 cyanines self-assemble into tubular J-aggregates, which further organize into bundles displaying bisignate CD spectrum - hallmark of an exciton coupled system - and an unusual bisignated CPL. In contrast, the tubular aggregates display a monosignate CD spectrum. The mechanism underlying these intriguing features remains elusive. In the present work, a quantum-mechanical exciton model is proposed to elucidate the (chir)optical behaviour of C8O3 aggregates. A herringbone arrangement of C8O3 dyes within the tubular aggregates well reproduces the observed spectral signatures. The anomalous observation of a singular CD peak in tubular aggregates is ascribed to the intrinsic chirality of the monomeric units inside the aggregate, whereas the CD doublet characterizing the bundles is attributed to the exciton coupling between the constituent tubes. The bisignated CPL signal observed in bundles reveals significant anti-Kasha emission at room temperature and is quantitatively addressed accounting for a very tiny exciton splitting leading to a sizable thermal population of both exciton states. This study provides crucial insights on the complexity of C8O3 aggregation and on the origin of chiroptical response at various aggregation stages.

Tunable Chiral Plasmonic Activities Enabled via Stimuli Responsive Micro-Origami.

Chiral plasmonic nanomaterials with distinctive circularly polarized light-dependent optical responses over a broad range of frequency have great potential for photonic and biomedical applications. However, it still remains challenging to fabricate 3D plasmonic chiral micro-constructs with readily modulated chiroptical properties over the magnitude of ellipticity, mode frequency, and switchable handedness, especially in the vis-NIR range. In this study, polymeric micro-origami-based 3D plasmonic chiral structures are constructed through self-rolling of gold nanospheres (AuNSs)-decorated polymeric micro-sheets. Spherical AuNSs are assembled as highly ordered linear chains on 2D rectangular micro-sheets by polydimethylsiloxane-wrinkle assisted assembly. Upon rolling the micro-sheets to micro-tubules, the AuNS chains transform into 3D helices. The AuNS-assembled helices induce collective plasmonic modes propagating in a helical manner, leading to a strong chiral response over the vis-NIR range. The circular dichroism (CD) is measured to be as high as hundreds of millidegree, and the position and sign of CD peaks are actively modulated by controlling the orientated angle of AuNS chains, enabled by tuning the collective plasmonic modes. This micro-origami-based strategy incorporates the incompatible 2D assembly technique with 3D chiral structures, opening up an intriguing way toward constructing chiral plasmonic structures and modulating chiroptical effects based on responsive polymeric materials.

Dual-Responsive Fe3O4@Polyaniline Chiral Superstructures for Information Encryption.

Incorporating stimuli-responsive mechanisms into chiral assemblies of nanostructures offers numerous opportunities to create optical materials capable of dynamically modulating their chiroptical properties. In this study, we demonstrate the formation of chiral superstructures by assembling Fe3O4@polyaniline hybrid nanorods by using a gradient magnetic field. The resulting superstructures exhibit a dual response to changes in both the magnetic field and solution pH, enabling dynamic regulation of the position, intensity, and sign of its circular dichroism peaks. Such responsiveness allows for convenient control over the optical rotatory dispersion properties of the assemblies, which are further integrated into the design of a chiroptical switch that can display various colors and patterns when illuminated with light of different wavelengths and polarization states. Finally, an optical information encryption system is constructed through the controlled assembly of the hybrid nanorods to showcase the potential opportunities for practical applications brought by the resulting responsive chiral superstructures.

Multipole resonances-mediated dual-band tunable circular dichroism via vanadium dioxide chiral metamaterials

Chiral response based on phase transition metamaterial of vanadium dioxide (VO2) is a promising candidate for chirality-related applications such as biochemical sensing, spectral detection, and advanced imaging. However, chiroptical peaks of VO2 chiral metamaterials are usually vanished after VO2 undergoes the phase transition from metallic state to dielectric state, which limits the dynamic control of their chiral properties. Herein, we propose a complementary z-shaped VO2 chiral metamaterial to achieve dual-band circular dichroism (CD) responses, and the two resonant CD peaks can be maintained in both metallic and dielectric states of VO2. The mechanisms of the novel robust CD responses are associated with the excitations of hybrid multipole resonances according to the far-field multipole decomposition and the near-field distribution of the device, and their peak values as well as their resonance locations can be dynamically tuned in the mid-infrared region by changing the volume fraction. In addition, the variations of the length and the width of the proposed device slightly alter the CD responses particular the resonance location, but the CD responses are almost immune to the variation of its height. Highlights The concept of multipole resonances-mediated tunable CD is proposed via the VO2-based chiral metamaterials. Robust dual-band CD responses associated with the excitation of hybrid multipole resonances are demonstrated. The peak value, frequency and bandwidth of CD response can be dynamically tuned by changing volume fraction. Good CD performances can be maintained even if the geometrical parameters are significantly altered.

Photonically active bowtie nanoassemblies with chirality continuum.

Chirality is a geometrical property described by continuous mathematical functions1-5. However, in chemical disciplines, chirality is often treated as a binary left or right characteristic of molecules rather than a continuity of chiral shapes. Although they are theoretically possible, a family of stable chemical structures with similar shapes and progressively tuneable chirality is yet unknown. Here we show that nanostructured microparticles with an anisotropic bowtie shape display chirality continuum and can be made with widely tuneable twist angle, pitch, width, thickness and length. The self-limited assembly of the bowties enables high synthetic reproducibility, size monodispersity and computational predictability of their geometries for different assembly conditions6. The bowtie nanoassemblies show several strong circular dichroism peaks originating from absorptive and scattering phenomena. Unlike classical chiral molecules, these particles show a continuum of chirality measures2 that correlate exponentially with the spectral positions of the circular dichroism peaks. Bowtie particles with variable polarization rotation were used to print photonically active metasurfaces with spectrally tuneable positive or negative polarization signatures for light detection and ranging (LIDAR) devices.

Spin polarization through axially chiral linkers: Length dependence and correlation with the dissymmetry factor.

The chiral-induced spin selectivity (CISS) effect relates to the spin-selective electron transport through chiral molecules; therefore, the chiral molecules act as spin filters. In past studies, correlation was found between the magnitude of the spin filtering and the intensity of the circular dichroism (CD) spectrum (the first Compton peak) of the molecules. Since the intensity of the CD peak relates to both the magnitude of the electric and magnetic dipole transitions, it was not clear which of these properties correlate with the CISS effect. This work aims at addressing this question. By studying the spin-dependent conduction and the CD spectra of the thiol-functionalized enantiopure binaphthalene (BINAP) and ternaphthalene (TERNAP), we found that both BINAP and TERNAP exhibit a similar spin polarization of 50%, despite the first Compton peak in TERNAP being almost twice as intense as the peak in BINAP. These results can be explained by the similar values of their anisotropy (or dissymmetry) factor, gabs , which is proportional to the magnetic transition dipole moment. Hence, we concluded that the CISS effect is proportional to the transition dipole moment in chiral molecules, namely, to the dissymmetry factor.

Enhancement and sensing applications of ultra-narrow band circular dichroism of the chiral nanopore films based on Bragg reflector.

Narrow-band circular dichroism (CD) has attracted considerable attention in the high-sensitivity detection of chiral molecules and chiral catalysis. However, achieving dynamic adjustment of narrow-band CD signals is challenging. In this study, we introduce a disruption layer (DL) and molybdenum disulfide (MoS2) into an L-shaped chiral nanohole array based on a distributed Bragg reflector (DBR), forming L-shaped chiral nanoholes (LCNAs/DL-DBR/MoS2), and investigate the mechanism of CD signal generation. Simulation results show that LCNAs/DL-DBR/MoS2 generate three narrow-band CD signals in the visible region. Analysis of the near-field electric field maps reveals that the three CD peaks of LCNAs/DL-DBR/MoS2 are caused by three Tamm resonances in the DBR layer. The producing and adjusting mechanisms of the CD signals are achieved by changing the structural parameters and the number of MoS2 layers. Dynamic adjustment of the CD signals of LCNAs/DL-DBR/MoS2 can be achieved by changing the environmental temperature. Furthermore, by altering the refractive index of the environment and the DBR layer, it is demonstrated that LCNAs/DL-DBR/MoS2 has a high-quality factor. Our theoretical simulations aid in the design of UNB chiral devices, opening up new avenues for environmental monitoring and the detection of chiral molecules with exceptional sensitivity.

Enhancement and Sensing Application of Ultra-Narrowband Circular Dichroism in the Chiral Nanostructures Based on Monolayer MoS2 and a Distributed Bragg Reflector.

Narrowband circular dichroism (CD) has aroused wide concerns in high-sensitivity detections of chiral molecular and chiral catalysis. Nevertheless, the dynamical adjustment of ultra-narrowband (UNB) CD signals is hard to achieve. In this work, single-layer molybdenum disulfide (MoS2), vanadium dioxide (VO2), and a distributed Bragg reflector (DBR) are introduced into X-shaped chiral nanostructures (XCNs) for overcoming the above challenge. The simulation results show that XCNs can generate four strong UNB CD signals in the near-infrared band, and XCNs/MoS2 can further enhance the UNB CD signals. The full width at half-minimum of UNB CD signals can reach 0.14 nm. The electric field distributions of XCNs/MoS2 show that the four CD signals originate from the coupling between the guided mode resonances along the x and y axes in the VO2 layer and the Tamm plasmon polaritons along the x and y axes in the DBR layer. Four UNB CD peaks can be actively tuned by varying the structural parameters, the number of MoS2 layers, and the environmental temperature. The FOM of XCNs/MoS2 can reach 1487 by changing the refractive index of the DRB layers. These findings contribute to the design of UNB chiral devices and provide new possibilities for environmental monitoring and ultrasensitive detection of chiral molecules.

Flexible engineering of circular dichroism enabled by chiral surface lattice resonances

Engineering the chiroptical responses of artificial nanostructures is vital for realizing applications in the fields of optical devices, enantioselective separation, and bio-sensing. Here, by utilizing the nano-kirigami based meta-molecule arrays, the flexible engineering of circular dichroism (CD) is achieved in the near-infrared wavelength region by the excitation of chiral surface lattice resonances (SLRs). It is found that the chiral SLRs can be flexibly tailored by a tiny structural perturbation. As a result, the wavelength, intensity, and sign of CD peak/dip can be abruptly engineered. Specifically, a CD peak with the value of +0.44 is evolved into a CD dip with an intensity of −0.66 when the etching silt length of the meta-molecules is simply decreased by 190 nm. Importantly, such CD reversal is experimentally demonstrated with the nano-kirigami method without requiring the inversion of geometric chirality. Moreover, it is found that the asymmetric dielectric environment around the meta-molecules can significantly suppress the chiral SLRs, providing an insightful understanding of the chiral SLR. Such flexible tailoring of the CD with chiral SLRs paves a versatile way toward the manipulation of chiral light–matter interactions and chiroptical functional devices.

Enantiomeric NIR-II Emitting Rare-Earth-Doped Ag2 Se Nanoparticles with Differentiated In Vivo Imaging Efficiencies.

Here, chiral second near-infrared (NIR-II) emitting rare-earth doped silver selenide nanoparticles (R- or S-Ag2 Se:Nd/Yd/Er NPs) were fabricated, exhibiting circular dichroism peak at 850 nm and fluorescence peak at 1550 nm, with 145.7-fold enhanced intensity compared to the reported Ag2 Se NPs. Compared with S-Ag2 Se:Nd/Yd/Er NPs, imaging efficiency of R-Ag2 Se:Nd/Yd/Er NPs in living cells was significantly improved due to a higher cellular uptake rate and 927.7-fold higher affinity. Furthermore, R-Ag2 Se:Nd/Yd/Er NPs reached at the tumor 2-fold faster than S type of NPs in vivo. We discover that chirality leads to differences in the affinity between chiral Ag2 Se:Nd/Yd/Er NPs and cluster of differentiation 44 (CD44) onto the surface of murine mammary carcinoma cell to cause different in vivo imaging efficiency. These results reveal that chiral Ag2 Se:Nd/Yd/Er NPs have high photoluminescence intensity and high in vivo imaging efficiency reflecting wide applications in biomedical diagnosis.

Enantiomeric NIR‐II Emitting Rare‐Earth‐Doped Ag2Se Nanoparticles with Differentiated In Vivo Imaging Efficiencies

AbstractHere, chiral second near‐infrared (NIR‐II) emitting rare‐earth doped silver selenide nanoparticles (R‐ or S‐Ag2Se:Nd/Yd/Er NPs) were fabricated, exhibiting circular dichroism peak at 850 nm and fluorescence peak at 1550 nm, with 145.7‐fold enhanced intensity compared to the reported Ag2Se NPs. Compared with S‐Ag2Se:Nd/Yd/Er NPs, imaging efficiency of R‐Ag2Se:Nd/Yd/Er NPs in living cells was significantly improved due to a higher cellular uptake rate and 927.7‐fold higher affinity. Furthermore, R‐Ag2Se:Nd/Yd/Er NPs reached at the tumor 2‐fold faster than S type of NPs in vivo. We discover that chirality leads to differences in the affinity between chiral Ag2Se:Nd/Yd/Er NPs and cluster of differentiation 44 (CD44) onto the surface of murine mammary carcinoma cell to cause different in vivo imaging efficiency. These results reveal that chiral Ag2Se:Nd/Yd/Er NPs have high photoluminescence intensity and high in vivo imaging efficiency reflecting wide applications in biomedical diagnosis.

One-Pot Synthesis of Magnetoplasmonic Au@FexOy Nanowires: Bioinspired Bouligand Chiral Stack.

One-dimensional hybrid nanostructures composed of a plasmonic gold nanowire core covered by a shell of magnetic oxide nanoparticles (Au@FexOy NWs) were synthesized by a one-pot solvothermal synthesis process. The effects of reaction temperature, time, reducing agent, and precursor as well as postsynthesis treatment were optimized to produce highly uniform NWs with a diameter of 226 ± 25 nm and a plasmonic core aspect ratio of 25 to 82. By exploiting the interaction of NWs with an external magnetic field, precise arrangements into highly periodic photonic structures were achieved, which can generate distinctive structural colors that are vividly iridescent and polarization-sensitive. Furthermore, a Bouligand-type chiral nematic film consisting of multistacked unidirectional layers of achiral NWs was fabricated using a modified layer-by-layer deposition method, which displays circular dichroism (CD) and chiral sensing capability. The addition of bovine serum albumin (BSA) as a model protein analyte induced a concentration-dependent wavelength shift of CD peaks. These intriguing properties of magnetoplasmonic anisotropic NWs and their self-assemblies could be consequently valuable for developing nature-inspired structural color imprints as well as solid-state chiral sensing devices.

Chirality Transfer from Chiral Mesoporous Silica to Perovskite CsPbBr 3 Nanocrystals: The Role of Chiral Confinement

Chirality Transfer from Chiral Mesoporous Silica to Perovskite CsPbBr ₃ Nanocrystals: The Role of Chiral Confinement

Supramolecular Nanohelix Fabricated by Pillararene-Based Host–Guest System for Chirality Amplification, Transfer, and Circularly Polarized Luminescence in Water

Supramolecular Nanohelix Fabricated by Pillararene-Based Host–Guest System for Chirality Amplification, Transfer, and Circularly Polarized Luminescence in Water

Engineering Strongly Chiral Plasmonic Lattices with Achiral Unit Cells for Sensing and Photodetection

AbstractAlthough the concept of chirality has its origin in chemistry, the field of photonics is actively exploring and utilizing it. A new family of 2D chiral lattices constructed from fully achiral unit cells is introduced here. This type of chiral structure differs fundamentally from previously reported arrays made of chiral unit cells. In this system, circular dichroism (CD) appears due to the electromagnetic interaction between unit cells and the formation of lattice plasmons (LP). Importantly, the CD is strongly enhanced for anisotropic rectangular lattices, whereas the chiral signal in square lattices is found to be relatively weak. The results cover two configurations. The first has an index‐matched environment, and the second includes an asymmetric arrangement of refractive indices. The index‐matched model is preferable and supports ultrasharp LP resonances. Overall, excellent control of the spectral position and broadening of the CD peaks is also demonstrated by tuning the geometry and matrix refractive indices. These results can be useful for engineering polarization filters and chiral biosensors.