Nanoscale Helical Optical Force for Determining Crystal Chirality.

The deterministic control of material chirality has been a sought-after goal. As light possesses intrinsic chirality, light-matter interactions offer promising avenues for achieving non-contact, enantioselective optical induction, assembly, or sorting of chiral entities. However, experimental validations are confined to the microscale due to the limited strength of asymmetrical interactions within sub-diffraction limit ranges. In this study, a novel approach is presented to facilitate chirality modulation through chiral crystallization using a helical optical force field originating from localized nanogap surface plasmon resonance. The force field emerges near a gold trimer nanogap and is propelled by linear and angular momentum transfer from the incident light to the resonant nanogap plasmon. By employing Gaussian and Laguerre-Gaussian incident laser beams, notable enantioselectivity is achieved through low-power plasmon-induced chiral crystallization of an organic compound-ethylenediamine sulfate. The findings provide new insights into chirality transmission orchestrated by the exchange of linear and angular momentum between light and nanomaterials.

Enantioselective control in chiral crystallization of ethylenediamine sulfate using optical trapping with circularly polarized laser beams.

In this study, we conducted successful experiments on ethylenediamine sulfate (EDS), an organic compound, to investigate its enantioselectivity in chiral crystallization. We employed optical trapping with circularly polarized laser beams, using a continuous wave laser at 1064 nm. By focusing the laser at the air-solution interface of a heavy water-saturated EDS solution, the formation of sub-micrometer-sized chiral EDS crystals was verified. Two generated enantiomorphs (d-crystal and l-crystal) were identified by the rotating analyzer method. The enantioselectivity in the chiral crystallization of EDS was assessed through 30 to 60 times experiments conducted under various conditions of laser powers and polarization modes, utilizing the count of generated crystals for each enantiomorph in the evaluation. Circularly polarized lasers at a specific power created an imbalance in the generation probability of the enantiomorphs, resulting in crystal enantiomeric excess values of 23% and -30%. The enantioselectivity mechanism was explored from two perspectives: refractive index differences of two enantiomorphs and 3D helical optical forces. Study of the thermodynamic mechanism was insufficient to explain the outcomes. Conversely, the 3D helical optical force mechanism revealed that the forces acting on EDS clusters in solution induced helical fluid motion, driving EDS nucleation, with the helicity of fluid motion determining the crystal's chirality. This approach will present new insights into chirality in industrial and research fields, with potential applications in regard to improving optical resolution and addressing the origin of homochirality.

Spatially Uniform and Quantitative Surface-Enhanced Raman Scattering under Modal Ultrastrong Coupling Beyond Nanostructure Homogeneity Limits.

We developed a substrate that enables highly sensitive and spatially uniform surface-enhanced Raman scattering (SERS). This substrate comprises densely packed gold nanoparticles (d-AuNPs)/titanium dioxide/Au film (d-ATA). The d-ATA substrate demonstrates modal ultrastrong coupling between localized surface plasmon resonances (LSPRs) of AuNPs and Fabry-Pérot nanocavities. d-ATA exhibits a significant enhancement of the near-field intensity, resulting in a 78-fold increase in the SERS signal for crystal violet (CV) compared to that of d-AuNP/TiO2 substrates. Importantly, high sensitivity and a spatially uniform signal intensity can be obtained without precise control of the shape and arrangement of the nanoscale AuNPs, enabling quantitative SERS measurements. Additionally, SERS measurements of rhodamine 6G (R6G) on this substrate under ultralow adsorption conditions (0.6 R6G molecules/AuNP) show a spatial variation in the signal intensity within 3%. These findings suggest that the SERS signal under modal ultrastrong coupling originates from multiple plasmonic particles with quantum coherence.

Quantum-Coherence-Enhanced Hot-Electron Injection under Modal Strong Coupling.

Modal strong coupling between localized surface plasmon resonance and a Fabry-Pérot nanocavity has been studied to improve the quantum efficiency of artificial photosynthesis. In this research, we employed Au nanodisk/titanium dioxide/Au film modal strong coupling structures to investigate the mechanism of quantum efficiency enhancement. We found that the quantum coherence within the structures enhances the apparent quantum efficiency of the hot-electron injection from the Au nanodisks to the titanium dioxide layer. Under near-field mapping using photoemission electron microscopy, the existence of quantum coherence was directly observed. Furthermore, the coherence area was quantitatively evaluated by analyzing the relationship between the splitting energy and the particle number density of the Au nanodisks. This quantum-coherence-enhanced hot-electron injection is supported by our theoretical model. Based on these results, applying quantum coherence to photochemical reaction systems is expected to effectively enhance reaction efficiencies.

Extrinsic Chirality by Interference between Two Plasmonic Modes on an Achiral Rectangular Nanostructure.

The optical near field (NF) induced by circularly polarized light (CPL) is a hot scientific topic. We observed a chiral NF intensity distribution on a series of achiral gold nanorectangular structures (Au-NRs) under CPL irradiation by using multiphoton photoemission electron microscopy (MP-PEEM). Additionally, the differential NF spectra under left and right CPL irradiation, which represent the asymmetry of the NF intensity distribution, were investigated. We propose an interpretation that the chiral NF intensity distribution on an achiral metallic nanostructure is extrinsically generated by the interference between two plasmonic modes by combining state-of-the-art MP-PEEM techniques and the classical oscillator model. Our interpretation well explains both the experimental and simulation results. Furthermore, the intensity of the NF and its phase angle of each mode under linearly polarized light irradiation were revealed to be critical factors for the generation of extrinsic chirality in the NF intensity distribution.

Spin-Orbit Angular-Momentum Transfer from a Nanogap Surface Plasmon to a Trapped Nanodiamond.

The ability to control the motion of single nanoparticles or molecules is currently one of the major scientific and technological challenges. Despite tremendous progress in the field of plasmonic nanotweezers, controlled nanoscale manipulation of nanoparticles trapped by a plasmonic nanogap antenna has not been reported yet. Here, we demonstrate the controlled orbital rotation of a single fluorescent nanodiamond trapped by a gold trimer nanoantenna irradiated by a rotating linearly polarized light or circularly polarized light. Remarkably, the rotation direction is opposite to the light's polarization rotation. We numerically show that this inversion comes from sequential excitation of individual nanotriangles in the reverse order when the linear polarization is rotated, whereas using a circular polarization, light-nanoparticle angular momentum transfer occurs via the generation of a Poynting vector vortex of reversed handedness. This work provides a new path for the control of light-matter angular momentum transfer using plasmonic nanogap antennas.

Optical selection and sorting of nanoparticles according to quantum mechanical properties.

Optical trapping and manipulation have been widely applied to biological systems, and their cutting-edge techniques are creating current trends in nanomaterial sciences. The resonant absorption of materials induces not only the energy transfer from photons to quantum mechanical motion of electrons but also the momentum transfer between them, resulting in dissipative optical forces that drive the macroscopic mechanical motion of the particles. However, optical manipulation, according to the quantum mechanical properties of individual nanoparticles, is still challenging. Here, we demonstrate selective transportation of nanodiamonds with and without nitrogen-vacancy centers by balancing resonant absorption and scattering forces induced by two different-colored lasers counterpropagating along a nanofiber. Furthermore, we propose a methodology for precisely determining the absorption cross sections for single nanoparticles by monitoring the optically driven motion, which is called as "optical force spectroscopy." This method provides a novel direction in optical manipulation technology toward development of functional nanomaterials and quantum devices.

Near-field engineering for boosting the photoelectrochemical activity to a modal strong coupling structure.

Near-field engineering is considered a significant strategy in constructing plasmonic nanostructures for efficient plasmonic chemistry. We demonstrate interfacial near-field engineering on a Au-NP/TiO2/Au-film (ATA) photoanode to improve the water oxidation efficiency. To tailor the near-field distribution, postdeposited Au on an ATA electrode (Au@ATA) is implemented using a facile constant potential electrolysis technique. As a result, the average photocurrent conversion efficiency of Au@ATA is approximately 1.3-fold higher than that of ATA.

Plasmonic Manipulation-Controlled Chiral Crystallization of Sodium Chlorate.

Plasmonic manipulation using well-designed triangular trimeric gold nanostructures achieves a giant (greater than 50%) crystal enantiomeric excess (CEE) of sodium chlorate (NaClO3). Stronger asymmetric interactions between molecule and light are pursued to reach high enantiomeric excess. The well-designed gold nanostructures immersed in a saturated NaClO3 D2O solution were irradiated with linear, left-hand, and right-hand circular polarizations of a 1064 nm continuous-wave laser. Within seconds of the start of the irradiation, an achiral metastable crystal was formed at the laser focus, and further irradiation induced a subsequent polymorphic transition to the chiral crystal. The crystal chirality is sensitive to the handedness of circular polarization, allowing for efficient enantioselectivity. The mechanisms to achieve this giant CEE are proposed based on the results of electromagnetic field analysis generated near the nanostructure by the finite element method.

Localized ZnO Growth on a Gold Nanoantenna by Plasmon-Assisted Hydrothermal Synthesis.

The excitation of localized surface plasmon resonances (LSPRs) in metal nanostructures enables subwavelength photon localization and large electric field enhancement, which can be advantageously used to strongly enhance light-matter interactions at the nanoscale. For this purpose, efficient methods for deterministically handling and arranging nanomaterials at the exact position of the localized electric field are required. In this Letter, we propose a novel method based on a hydrothermal synthesis reaction to locally and selectively synthesize zinc oxide in a plasmonic nanoantenna. We first make evident the role of LSPR for achieving efficient heating of gold nanostructures. Then, by selectively addressing one of the LSPRs of a gold antenna, we demonstrate that localized zinc oxide formation at the targeted location of the antenna can be achieved due to the nanoscale confinement of the heat production.

Enhanced water splitting under modal strong coupling conditions.

Strong coupling between plasmons and optical modes, such as waveguide or resonator modes, gives rise to a splitting in the plasmon absorption band. As a result, two new hybrid modes are formed that exhibit near-field enhancement effects. These hybrid modes have been exploited to improve light absorption in a number of systems. Here we show that this modal strong coupling between a Fabry-Pérot nanocavity mode and a localized surface plasmon resonance (LSPR) facilitates water splitting reactions. We use a gold nanoparticle (Au-NP)/TiO2/Au-film structure as a photoanode. This structure exhibits modal strong coupling between the Fabry-Pérot nanocavity modes of the TiO2 thin film/Au film and LSPR of the Au NPs. Electronic excitation of the Au NPs is promoted by the optical hybrid modes across a broad range of wavelengths, followed by a hot electron transfer to TiO2. A key feature of our structure is that the Au NPs are partially inlaid in the TiO2 layer, which results in an enhancement of the coupling strength and water-oxidation efficiency. We observe an 11-fold increase in the incident photon-to-current conversion efficiency with respect to a photoanode structure with no Au film. Also, the internal quantum efficiency is enhanced 1.5 times under a strong coupling over that under uncoupled conditions.

Low sense of coherence is associated with anxiety among adults: Results based on data from all 47 prefectures of Japan.

BACKGROUND: Anxiety disorder is a major societal, economic, and healthcare burden, so it is essential to identify underlying risk factors. Sense of coherence (SOC), defined as an individual's perceived ability to control events and cope with challenges, is strongly associated with healthcare outcomes. METHODS: This study investigated the association between SOC and anxiety among adults in all 47 prefectures of Japan using a cross-sectional online panel survey. SOC was assessed using the University of Tokyo Health Sociology version of the SOC Scale and anxiety was assessed using the Generalized Anxiety Disorder-7 (GAD-7) scale. RESULTS: Among 2100 participants (1051 males and 1049 females), 475 (22.6%) were identified with anxiety (scoring 8 points or higher on the GAD-7 scale). Before adjustment for potential confounders, there was a significant negative association between SOC and presence of anxiety. Even after adjustment, the presence of anxiety was significantly higher among the lower SOC subgroup than the higher SOC subgroup. CONCLUSIONS: These results indicate that approximately one-fifth of adults in Japan suffer from anxiety and that low SOC is a significant risk factor.

Nanofocusing of structured light for quadrupolar light-matter interactions.

The spatial structure of an electromagnetic field can determine the characteristics of light-matter interactions. A strong gradient of light in the near field can excite dipole-forbidden atomic transitions, e.g., electric quadrupole transitions, which are rarely observed under plane-wave far-field illumination. Structured light with a higher-order orbital angular momentum state may also modulate the selection rules in which an atom can absorb two quanta of angular momentum: one from the spin and another from the spatial structure of the beam. Here, we numerically demonstrate a strong focusing of structured light with a higher-order orbital angular momentum state in the near field. A quadrupole field was confined within a gap region of several tens of nanometres in a plasmonic tetramer structure. A plasmonic crystal surrounding the tetramer structure provides a robust antenna effect, where the incident structured light can be strongly coupled to the quadrupole field in the gap region with a larger alignment tolerance. The proposed system is expected to provide a platform for light-matter interactions with strong multipolar effects.

Stereodivergent Hydroboration of Allenes.

Full details of a stereodivergent hydroboration of allenes are reported. While hydroboration of an allene with 9-BBN provided a thermodynamically stable (E)-allylic alcohol after oxidative work-up, the reaction of an identical allene with HB(Sia)2 (disiamylborane) formed a (Z)-allylic alcohol as the kinetic product. The developed conditions allowed for the synthesis of trisubstituted olefins in a highly stereoselective fashion, which is known to be challenging. The method was also applied to the stereodivergent synthesis of structural motifs such as skipped dienes and allylbenzenes, which are often embedded in biologically active natural products.

Trapping and Deposition of Dye-Molecule Nanoparticles in the Nanogap of a Plasmonic Antenna.

Plasmonic nanostructures, which allow light focusing at the deep subwavelength scale, and colloidal nanoparticles with unique optoelectronic properties are nowadays fabricated with nanometer precision. However, to fully control and exploit nanoscale light-matter interactions in hybrid plasmonic-nanophotonic devices, both materials must be assembled in heterostructures with similar precision. Near-field optical forces have recently attracted much attention, as they can precisely trap and position nanoparticles at plasmonic hotspots. However, long-range attraction and the surface bonding of nanoparticles usually require other specific techniques, such as electrothermal heating and surface chemical treatments. This Letter reports on the optical trapping and deposition of dye-molecule nanoparticles in the nanogap of a gold antenna. The nanoparticles are captured by focusing a near-infrared laser beam on a targeted plasmonic antenna. This single-step deposition process requires only a few seconds under 1.4-1.8 MW·cm-2 continuous-wave illumination and shows a polarization dependence smaller than expected. Fluorescence and electronic microscopy observations suggest that nanoparticle deposition arises from a trade-off between optical and thermal effects.

Quadrupole lattice resonances in plasmonic crystal excited by cylindrical vector beams.

We report a scheme to exploit low radiative loss plasmonic resonance by combining a dark (subradiant) mode and a lattice resonance. We theoretically demonstrate that such dark-mode lattice resonances in periodic arrays of nanodisks or plasmonic crystals can be excited by vertically incident light beams. We investigate the excitation of lattice resonances in a finite sized, square-lattice plasmonic crystal by two types of cylindrical vector beams and a linearly polarized Gaussian beam. Quadrupole lattice resonances are excited by all three beams, and the largest peak intensity is obtained by using a specific type of cylindrical vector beam. Because of their lower radiative losses with many hotspots, the quadrupole lattice resonances in plasmonic crystal may pave the way for photonic research and applications that require strong light-matter interactions.

Detailed Observation of Multiphoton Emission Enhancement from a Single Colloidal Quantum Dot Using a Silver-Coated AFM Tip.

The enhancement of multiphoton emission from a single colloidal nanocrystal quantum dot (NQD) interacting with a plasmonic nanostructure was investigated using a silver-coated atomic force microscopy tip (AgTip) as the plasmonic nanostructure. Using the AgTip, which exhibited a well-defined localized surface plasmon (LSP) resonance band, we controlled the spectral overlap and the distance between the single NQD and the AgTip. The emission behavior of the single NQD when approaching the AgTip at the nanometer scale was measured using off-resonance (405 nm) and resonance (465 nm) excitation of the LSP. We directly observed the conversion of the single-photon emission from a single NQD to multiphoton emission with reduction of the emission lifetime at both excitation wavelengths as the NQD-AgTip distance decreased, whereas a decrease and increase in the emission intensity were observed at 405 and 465 nm excitation, respectively. By combining theoretical analysis and the numerical simulation of the AgTip, we deduced that the enhancement of the multiphoton emission was caused by the quenching of the single-exciton state due to the energy transfer from the NQD to the AgTip and that the emission intensity was increased by enhancement of the excitation rate due to the electric field of the LSP on the AgTip. These results provide evidence that the photon statistics and the photon flux from the single NQD can be manipulated by the plasmonic nanostructure through control of the spectral overlap and the distance.

Nanoscale Color Sorting of Surface Plasmons in a Double-Nanogap Structure with Multipolar Plasmon Excitation.

We demonstrated a new plasmonic nanodevice that spatially sorts photons according to their colors on the nanoscale while maintaining their nanoconcentration. The properties of this nanoscale color sorting based on constructive and destructive interferences between different multipolar plasmon modes are controlled by tuning the incidence angle of the incoming photons. The added ability of color sorting and its manipulation could significantly influence the development of possible photonic applications, including nanoscale spectroscopy and sensing.

Two-photon excited fluorescence from a pseudoisocyanine-attached gold tip via a plasmonic-photonic hybrid system.

A plasmonic-photonic hybrid system with efficient coupling of light from a fiber-coupled microspherical cavity to localized surface plasmon (LSP) modes of a gold-coated tip was proposed, which was composed of a fiber-coupled microspherical cavity and a pseudoisocyanine (PIC)-attached gold tip. To prove efficient excitation of LSP at the gold-coated tip, we experimentally demonstrated two-photon excited fluorescence from the PIC-attached gold-coated tip via a fiber-coupled microspherical cavity under a weak continuous wave excitation condition. This hybrid system could focus the incident light with coupling efficiency of around 64% into a nanoscale domain of the metal tip with an effective area of a 79-nm circle.