Enantioselective sensing by collective circular dichroism.

Quantitative determination and in situ monitoring of molecular chirality at extremely low concentrations is still challenging with simple optics because of the molecular-scale mismatch with the incident light wavelength. Advances in spectroscopy1-4 and nanophotonics have successfully lowered the detection limit in enantioselective sensing, as it can bring the microscopic chiral characteristics of molecules into the macroscopic scale5-7 or squeeze the chiral light into the subwavelength scale8-17. Conventional nanophotonic approaches depend mainly on the optical helicity density8,9 by localized resonances within an individual structure, such as localized surface plasmon resonances (LSPRs)10-16 or dielectric Mie resonances17. These approaches use the local chiral hotspots in the immediate vicinity of the structure, whereas the handedness of these hotspots varies spatially. As such, these localized resonance modes tend to be error-prone to the stochasticity of the target molecular orientations, vibrations and local concentrations18,19. Here we identified enantioselective characteristics of collective resonances (CRs)20 arising from assembled 2D crystals of isotropic, 432-symmetric chiral gold nanoparticles (helicoids)21,22. The CRs exhibit a strong and uniform chiral near field over a large volume above the 2D crystal plane, resulting from the collectively spinning, optically induced dipoles at each helicoid. Thus, energy redistribution by molecular back action on the chiral near field shifts the CRs in opposite directions, depending on the handedness of the analyte, maximizing the modulation of the collective circular dichroism (CD).

Investigating chiral morphogenesis of gold using generative cellular automata.

Homochirality is an important feature in biological systems and occurs even in inorganic nanoparticles. However, the mechanism of chirality formation and the key steps during growth are not fully understood. Here we identify two distinguishable pathways from achiral to chiral morphologies in gold nanoparticles by training an artificial neural network of cellular automata according to experimental results. We find that the chirality is initially determined by the nature of the asymmetric growth along the boundaries of enantiomeric high-index planes. The deep learning-based interpretation of chiral morphogenesis provides a theoretical understanding but also allows us to predict an unprecedented crossover pathway and the resulting morphology.

Photochemical tuning of dynamic defects for high-performance atomically dispersed catalysts.

Developing active and stable atomically dispersed catalysts is challenging because of weak non-specific interactions between catalytically active metal atoms and supports. Here we demonstrate a general method for synthesizing atomically dispersed catalysts via photochemical defect tuning for controlling oxygen-vacancy dynamics, which can induce specific metal-support interactions. The developed synthesis method offers metal-dynamically stabilized atomic catalysts, and it can be applied to reducible metal oxides, including TiO2, ZnO and CeO2, containing various catalytically active transition metals, including Pt, Ir and Cu. The optimized Pt-DSA/TiO2 shows unprecedentedly high photocatalytic hydrogen evolution activity, producing 164 mmol g-1 h-1 with a turnover frequency of 1.27 s-1. Furthermore, it generates 42.2 mmol gsub-1 of hydrogen via a non-recyclable-plastic-photoreforming process, achieving a total conversion of 98%; this offers a promising solution for mitigating plastic waste and simultaneously producing valuable energy sources.

Kink-Controlled Gold Nanoparticles for Electrochemical Glucose Oxidation.

Enzymes in nature efficiently catalyze chiral organic molecules by elaborately tuning the geometrical arrangement of atoms in the active site. However, enantioselective oxidation of organic molecules by heterogeneous electrocatalysts is challenging because of the difficulty in controlling the asymmetric structures of the active sites on the electrodes. Here, we show that the distribution of chiral kink atoms on high-index facets can be precisely manipulated even on single gold nanoparticles; and this enabled stereoselective oxidation of hydroxyl groups on various sugar molecules. We characterized the crystallographic orientation and the density of kink atoms and investigated their specific interactions with the glucose molecule due to the geometrical structure and surface electrostatic potential.

Chiral-Induced Surface-Enhanced Raman Optical Activity on a Single-Particle Substrate.

Surface-enhanced Raman optical activity (SEROA) is a promising method for analyzing chiral molecules' molecular chirality and structural changes. However, conventional SEROA measurements face challenges related to substrate stability, signal uniformity, and interference from electronic circular dichroism (ECD). Therefore, in this study, we present a uniform and stable substrate for SEROA measurements by utilizing Au nanoparticles on the Au nanofilm structure to confine hotspots to the film-particle junctions and minimize ECD interference. This method also uses the induction of chirality from chiral molecules to achiral molecules to overcome the limitation of chiral molecules in SEROA measurements, specifically their lower signal efficiency. Successful chirality transfer is demonstrated through distinguishable SEROA signals when the l/d-alanine mixture is present. Enantiomeric discrimination of different l/d-alanine ratios was achieved with linear responses in the circular intensity difference (CID). Altogether, the proposed chiral-induced SEROA on the AuNP_on_AuNF substrate shows promising potential for detecting and characterizing structural changes in biomolecules, thus making it a valuable tool for various research applications.

Tuning the CO2 Reduction Selectivity of an Immobilized Molecular Ag Complex beyond CO.

The electrochemical reduction of carbon dioxide (CO2) to produce fuels and chemicals has garnered significant attention. However, achieving control over the selectivity of the resulting products remains a challenging task, particularly within molecular systems. In this study, we employed a molecular silver complex immobilized on graphitized mesoporous carbon (GMC) as a catalyst for converting CO2 into CO, achieving an impressive selectivity of over 90% at -1.05 V vs RHE. Notably, the newly formed silver nanoparticles emerged as the active sites responsible for this high CO selectivity rather than the molecular system. Intriguingly, the introduction of copper ions into the restructured Ag-nanoparticle-decorated carbon altered the product selectivity. At -1.1 V vs RHE in 0.1 M KCl, we achieved a high C2 selectivity of 75%. Furthermore, not only the Ag-Cu bimetallic nanoparticle but also the small-sized Ag-Cu nanocluster decorated over GMC was proposed as active sites during catalytic reactions. Our straightforward approach offers valuable insights for fine-tuning the product selectivity of immobilized molecular systems, extending beyond C1 products.

Circular polarization sensitive opto-neuromorphic operation at plasmonic hot electron transistor using chiral gold nanoparticles.

Opto-neuromorphic operation is critical for biological system to recognize the visual objects and mimicking such operation is important for artificial prosthesis as well as machine vision system for industrial applications. To sophisticatedly mimic biological system, regulation of learning and memorizing efficiency is needed, however engineered synthetic platform has been lack of controllability, which makes huge gap between biological system and synthetic platform. Here we demonstrated controllable learning and memorizing opto-neuromorphic operation at plasmonic hot electron transistor. Especially, circularly polarized light (CPL) sensitive synaptic characteristics and learning experience capability are enabled by incorporating chiral plasmonic nanoparticle. Furthermore, gate voltage gives rise to controllable neuromorphic operation due to hot electron injection and trapping effect, resulting in high remaining synaptic weight of ∼70% at negative gate voltage under CPL excitation. We believe that this discovery makes significant leap toward on-demand in-sensor computing as well as toward bio-realistic device.

Enhancement of second-harmonic generation in a 64° stacked WSe2/WS2heterobilayer with local strain.

Transition metal dichalcogenides (TMDs) are actively studied in various fields of optics and optoelectronics, including nonlinear optics of second-harmonic generation (SHG). By stacking two different TMD materials to form a heterobilyaer, unique optical properties emerge, with stronger SHG at a twist angle of 0° between TMDs and weaker SHG at a twist angle of 60°. In this work, we demonstrate the enhancement of SHG in a heterobilayer consisting of WSe2and WS2monolayers stacked at a twist angle of 64.1°, using a nanoparticle to induce local strain. The interatomic spacing of the heterobilayer is deformed by the nanoparticle, breaking the inversion symmetry, resulting in a substantial increase in the SHG of the heterobilayer at room temperature. The SHG increases depending on the polarization of the pump laser: 15-fold for linear polarization, 9-fold for right-circular polarization, and up to 100-fold for left-circular polarization. In addition, the SHG enhanced in the heterobilayer with local strain satisfies the same chiral selection rule as in the unstrained TMD region, demonstrating that the chiral selection rule of SHG is insensitive to local strain. Our findings will increase the applicability of TMD heterobilayers in nonlinear optoelectronics and valleytronics.

Amino-acid- and peptide-directed synthesis of chiral plasmonic gold nanoparticles.

Understanding chirality, or handedness, in molecules is important because of the enantioselectivity that is observed in many biochemical reactions 1 , and because of the recent development of chiral metamaterials with exceptional light-manipulating capabilities, such as polarization control2-4, a negative refractive index 5 and chiral sensing 6 . Chiral nanostructures have been produced using nanofabrication techniques such as lithography 7 and molecular self-assembly8-11, but large-scale and simple fabrication methods for three-dimensional chiral structures remain a challenge. In this regard, chirality transfer represents a simpler and more efficient method for controlling chiral morphology12-18. Although a few studies18,19 have described the transfer of molecular chirality into micrometre-sized helical ceramic crystals, this technique has yet to be implemented for metal nanoparticles with sizes of hundreds of nanometres. Here we develop a strategy for synthesizing chiral gold nanoparticles that involves using amino acids and peptides to control the optical activity, handedness and chiral plasmonic resonance of the nanoparticles. The key requirement for achieving such chiral structures is the formation of high-Miller-index surfaces ({hkl}, h ≠ k ≠ l ≠ 0) that are intrinsically chiral, owing to the presence of 'kink' sites20-22 in the nanoparticles during growth. The presence of chiral components at the inorganic surface of the nanoparticles and in the amino acids and peptides results in enantioselective interactions at the interface between these elements; these interactions lead to asymmetric evolution of the nanoparticles and the formation of helicoid morphologies that consist of highly twisted chiral elements. The gold nanoparticles that we grow display strong chiral plasmonic optical activity (a dis-symmetry factor of 0.2), even when dispersed randomly in solution; this observation is supported by theoretical calculations and direct visualizations of macroscopic colour transformations. We anticipate that our strategy will aid in the rational design and fabrication of three-dimensional chiral nanostructures for use in plasmonic metamaterial applications.

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.

Iridium-Cooperated, Symmetry-Broken Manganese Oxide Nanocatalyst for Water Oxidation.

The water oxidation reaction, the most important reaction for hydrogen production and other sustainable chemistry, is efficiently catalyzed by the Mn4CaO5 cluster in biological photosystem II. However, synthetic Mn-based heterogeneous electrocatalysts exhibit inferior catalytic activity at neutral pH under mild conditions. Symmetry-broken Mn atoms and their cooperative mechanism through efficient oxidative charge accumulation in biological clusters are important lessons but synthesis strategies for heterogeneous electrocatalysts have not been successfully developed. Here, we report a crystallographically distorted Mn-oxide nanocatalyst, in which Ir atoms break the space group symmetry from I41/amd to P1. Tetrahedral Mn(II) in spinel is partially replaced by Ir, surprisingly resulting in an unprecedented crystal structure. We analyzed the distorted crystal structure of manganese oxide using TEM and investigated how the charge accumulation of Mn atoms is facilitated by the presence of a small amount of Ir.

Hyperreflective foci distribution in eyes with dry age-related macular degeneration with subretinal drusenoid deposits.

PURPOSE: To investigate the distribution of hyperreflective foci (HRF) in eyes with dry age-related macular degeneration (AMD). METHODS: We retrospectively reviewed optical coherence tomography (OCT) images of 58 dry AMD eyes presenting HRF. The distribution of HRF according to the early treatment diabetic retinopathy study area was analyzed according to the presence of subretinal drusenoid deposits (SDDs). RESULTS: We classified 32 eyes and 26 eyes into the dry AMD with SDD group (SDD group) and dry AMD without SDD group (non-SDD group), respectively. The non-SDD group had higher prevalence and density of HRF at the fovea (65.4% and 1.71 ± 1.48) than the SDD group (37.5% and 0.48 ± 0.63, P = 0.035 and P < 0.001, respectively). However, the prevalence and density of HRF in the outer circle area of the SDD group (81.3% and 0.11 ± 0.09) were greater than those of the non-SDD group (53.8% and 0.05 ± 0.06, p = 0.025 and p = 0.004, respectively). The SDD group showed higher prevalence and mean densities of HRF in the superior and temporal area than in the non-SDD group (all, p < 0.05). CONCLUSION: HRF distributions in dry AMD varied according to the presence of SDDs. This might support that the degenerative features may be different between dry AMD eyes with and without SDDs.

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.

Clinical features associated with the atrophy of fellow eyes in patients with unilateral type 3 macular neovascularization.

PURPOSE: We sought to investigate the clinical features of eyes with unilateral type 3 macular neovascularization (MNV) according to the degenerative features of fellow eyes. METHODS: We retrospectively reviewed 55 patients with unilateral type 3 MNV and identified degenerative features including geographic atrophy (GA) in fellow eyes using multimodal imaging. Then, the clinical features of eyes with type 3 MNV at baseline and during follow-up with anti-vascular endothelial growth factor treatment and an as-needed regimen were compared according to the degenerative features of fellow eyes. RESULTS: Eighteen patients (32.7%) had GA in fellow eyes; initial disease manifestations of type 3 MNV eyes including stage, best-corrected visual acuity, and choroidal thickness (CT) did not vary between groups (all P > 0.05). During follow-up, a rate of complete fluid resolution after three monthly loading injections was not associated with GA in fellow eyes (P = 0.703), while a lower rate of early recurrence within 3 months after loading treatment was associated with thinner CT in type 3 MNV eyes and GA over one disc area in fellow eyes (P = 0.025 and P = 0.021). CONCLUSION: Degenerative features of fellow eyes in patients with unilateral type 3 MNV may be associated with the clinical characteristics of affected eyes.

Chorioretinal thickness and retinal pigment epithelial degeneration of fellow eyes in patients with unilateral neovascular age-related macular degeneration with subretinal drusenoid deposits.

BACKGROUND: We sought to investigate the chorioretinal thickness and retinal pigment epithelial (RPE) degenerative features of eyes with early age-related macular degeneration (AMD) and subretinal drusenoid deposits (SDDs) according to the presence of macular neovascularization (MNV) in the fellow eyes. METHODS: We classified 70 eyes into two groups of 47 eyes with non-neovascular AMD and 23 eyes with neovascular AMD, respectively, according to the presence of MNV in the fellow eyes. The mean macular retinal, ganglion cell-inner plexiform layer (GCIPL), and choroidal thickness values and RPE features of the 6-mm-diameter zone were compared. RPE degeneration was defined as a lesion with an incomplete RPE and outer retinal atrophy (iRORA) or attenuated RPE reflectivity with diffuse basal laminar deposits, which was defined as when the eye showed an attenuated RPE line with granular features and mixed reflectivity in combination with sub-RPE deposits with a lesion ≥ 1,000 µm in length. RESULTS: Mean retinal, GCIPL, and choroidal thickness values (286.69 ± 15.02 µm, 64.36 ± 4.21 µm, and 156.11 ± 33.10 µm) of the neovascular AMD group were greater than those (278.61 ± 13.96 µm, 61.44 ± 4.63 µm, and 133.59 ± 34.33 µm) of the non-neovascular AMD group (all P < 0.05). RPE degeneration was more prevalent in the neovascular AMD group (65.2%) than the non-neovascular AMD group (38.3%; P = 0.034). Greater mean GCIPL and choroidal thickness values and the presence of RPE degeneration were associated with type 3 MNV in fellow eyes (all P < 0.05). CONCLUSIONS: Different degenerative features according to MNV in fellow eyes of patients with AMD and SDDs suggest that variable degenerative features might be present during disease progression and have an association with the phenotype.

Synergistic Effects of Nonmagnetic Carbon Nanotubes on the Performance and Stability of Magnetorheological Fluids Containing Carbon Nanotube-Co0.4Fe0.4Ni0.2 Nanocomposite Particles.

We investigated the magnetorheological (MR) properties of the carbon nanotube (CNT)-Co0.4Fe0.4Ni0.2 composite suspension to find a high-performance MR fluid with excellent stability. The composites were fabricated by chemical reduction of Co0.4Fe0.4Ni0.2 on the surface of amine-functionalized CNTs. A synergistic effect between the high aspect ratio of the CNTs and the strong magnetic polarization of the Co0.4Fe0.4Ni0.2 led to stronger MR performance of the nanocomposite particle suspension. The MR fluid exhibits an unexpected high yield stress value that is 13 times greater than that of a CNT-Fe3O4 suspension at a magnetic field strength of 343 kA/m. Nonmagnetic CNTs form a three-dimensional networklike structure, imparting surprisingly large additional yield stress to the CNT-Co0.4Fe0.4Ni0.2 nanocomposite MR suspension. The low density of the CNTs resulted in much better long-term stability for the CNT-Co0.4Fe0.4Ni0.2 nanocomposite suspension than the MR fluid containing only Co0.4Fe0.4Ni0.2.

Inorganic Hollow Nanocoils Fabricated by Controlled Interfacial Reaction and Their Electrocatalytic Properties.

The fabrication of 3D hollow nanostructures not only allows the tactical provision of specific physicochemical properties but also broadens the application scope of such materials in various fields. The synthesis of 3D hollow nanocoils (HNCs), however, is limited by the lack of an appropriate template or synthesis method, thereby restricting the wide-scale application of HNCs. Herein, a strategy for preparing HNCs by harnessing a single sacrificial template to modulate the interfacial reaction at a solid-liquid interface that allows the shape-regulated transition is studied. Furthermore, the triggering of the Kirkendall effect in 3D HNCs is demonstrated. Depending on the final state of the transition metal ions reduced during the electrochemical preparation of HNCs, the surface states of the binding anions and the composition of the HNCs can be tuned. In a single-component CrPO4 HNC with a clean surface, the Kirkendall effect of the coil shape is analyzed at various points throughout the reaction. The rough-surface multicomponent MnOx P0.21 HNCs are complexed with ligand-modified BF4 -Mn3 O4 nanoparticles. The fabricated nanocomposite exhibits an overpotential decrease of 25 mV at neutral pH compared to pure BF4 -Mn3 O4 nanoparticles because of the increased active surface area.

Effects of paramagnetic fluctuations on the thermochemistry of MnO(100) surfaces in the oxygen evolution reaction.

We investigated the effects of paramagnetic (PM) fluctuations on the thermochemistry of the MnO(100) surface in the oxygen evolution reaction (OER) using the "noncollinear magnetic sampling method plus U" (NCMSM+U). Various physical properties, such as the electronic structure, free energy, and charge occupation, of the MnO(100) surface in the PM state with several OER intermediates, were reckoned and compared to those in the antiferromagnetic (AFM) state. We found that PM fluctuation enhances charge transfer from a surface Mn ion to each of the intermediates and strengthens the chemical bond between them, while not altering the overall features, such as the rate determining step and resting state, in reaction pathways. The enhanced charge transfer can be attributed to the delocalized nature of valence bands observed in the PM surface. In addition, it was observed that chemical-bond enhancement depends on the intermediates, resulting in significant deviations in reaction energy barriers. Our study suggests that PM fluctuations play a significant role in the thermochemistry of chemical reactions occurring on correlated oxide surfaces.

GANGLION CELL-INNER PLEXIFORM LAYER THICKNESS IN EYES WITH NONEXUDATIVE AGE-RELATED MACULAR DEGENERATION OF DIFFERENT DRUSEN SUBTYPES.

PURPOSE: We sought to investigate the ganglion cell-inner plexiform layer (GCIPL) thickness in eyes with nonexudative age-related macular degeneration. METHODS: We classified eyes into four categories-pachydrusen, soft drusen, subretinal drusenoid deposit (SDD), and soft drusen with SDD-and compared the baseline mean macular GCIPL thickness according to the Early Treatment Diabetic Retinopathy Study grid and its change between groups. RESULTS: We classified 53, 29, 36, and 34 eyes into the four categories, respectively. The mean GCIPL thickness values in the 3-mm area were 82.61 ± 9.54 µm for the pachydrusen group, 79.11 ± 10.26 µm for the soft drusen group, 77.72 ± 6.04 µm for the SDD group, and 71.63 ± 8.69 µm for the soft drusen with SDD group (P < 0.001). The soft drusen with the SDD group showed a greater change in GCIPL thickness (-2.50 ± 0.29 µm/year) in the 3-mm area as compared with the pachydrusen group (-0.18 ± 0.35 µm/year), soft drusen group (-0.55 ± 0.36 µm/year), and SDD group (-0.55 ± 0.37) (all P < 0.001). CONCLUSION: The GCIPL thickness varied according to the type of nonexudative age-related macular degeneration. The thinner baseline GCIPL and its greater change in eyes with soft drusen with SDD may suggest that these eyes are experiencing more prominent neuroretinal degeneration in the central 3-mm area than those in the other groups.

Single Nanoparticle Chiroptics in a Liquid: Optical Activity in Hyper-Rayleigh Scattering from Au Helicoids.

Linear optical methods of determining the chirality of organic and inorganic materials have relied on weak chiral optical (chiroptical) effects. Nonlinear chiroptical characterization holds the potential of much greater sensitivity and smaller interaction volumes. However, suitable materials on which to perform measurements have been lacking for decades. Here, we present the first nonlinear chiroptical characterization of crystallographic chirality in gold helicoids (≈150 nm size) and core/shell helicoids with the newly discovered hyper-Rayleigh scattering optical activity (HRS OA) technique. The observed chiroptical signal is, on average, originating from between ≈0.05 and ≈0.13 helicoids, i.e., less than a single nanoparticle. The measured HRS OA ellipticities reach ≈3°, for a concentration ≈109 times smaller than that of chiral molecules with similar nonlinear chiroptical response. These huge values indicate that the helicoids are excellent candidates for future nonlinear chiroptical materials and applications.