Plasmon dephasing time and optical field enhancement in a plasmonic nanobowl substrate studied by scanning near-field optical microscopy.

Plasmonic substrates have been extensively investigated due to their potential applications in fluorescence microscopy, chemical sensing, and photochemical reactions. The optical properties of the substrate depend on the spatial and temporal features of the plasmon excited. Hence, the ability to directly visualize plasmon dynamics is crucial. In this study, we investigated the spatial and temporal properties of plasmon excitation in a plasmonic nanobowl substrate consisting of a periodic hexagonal array of nanoscale bowl-like structures developed with self-assembly. Near-field transmission imaging revealed that multiple plasmon resonance bands are observed from visible to near-infrared spectral region, and the optical contrast of the image is dependent on the observed band. Near-field two-photon photoluminescence microscopy revealed that the probability of excitation inside each nanoscale bowl-like structure is greater than that in the surrounding area. Near-field time-resolved imaging revealed that the nanobowl substrate exhibited a substantially long plasmon dephasing time, exceeding 12 fs. Based on the spectral features of the near-field and far-field spectra, we found that optically dark plasmon mode is excited by the near-field illumination and only partly contributes to the long dephasing time observed. This fact indicates that the dephasing time is extended by some other mechanism in the periodic substrate. We revealed from this study that the enhanced optical fields induced in the nanobowl structure originate from the photosynergetic effect of the cavity mode and plasmon mode excited.

Switching nanoscale temperature fields with high-order plasmonic modes in transition metal nanorods.

Depending on the photoirradiation conditions, metal nanostructures exhibit various plasmonic modes, including dipolar, quadrupolar, and hexapolar modes. This work demonstrates numerically that these high-order plasmonic modes can be used to switch nanoscale temperature distributions during the plasmonic heating of a manganese (Mn) nanorod. The key feature of Mn is its low thermal conductivity. Generally, when noble metal nanostructures are used for plasmonic heating, the nanostructure surface will be almost isothermal regardless of the order of the excited plasmonic modes because of the high thermal conductivity of noble metals, e.g., the thermal conductivity of gold is 314 W m-1 K-1. However, unlike noble metals, Mn has a significantly lower thermal conductivity of 7.8 W m-1 K-1. Due to this lower thermal conductivity, the distinct spatial characteristics of the high-order plasmonic modes can be transcribed clearly into nanoscale temperature fields, which are achieved by generating polarization currents by high-order plasmons within the nanorod. These findings strongly suggest that high-order plasmonic modes hold significant potential for the advanced and precise manipulation of heat generation at the nanometer scale in thermoplasmonics.

Ultrafast sensitivity-controlled and specific detection of extracellular vesicles using optical force with antibody-modified microparticles in a microflow system.

Extracellular vesicles (EVs), including nanoscale exosomes and ectosomes, hold promise as biomarkers that provide information about the cell of origin through their cargo of nucleic acids and proteins, both on their surface and within. Here, we develop a detection method of EVs based on light-induced acceleration of specific binding between their surface and antibody-modified microparticles, using a controlled microflow with three-dimensional analysis by confocal microscopy. Our method successfully detected 103-104 nanoscale EVs in liquid samples as small as a 500 nanoliters within 5 minutes, with the ability to distinguish multiple membrane proteins. Remarkably, we achieved the specific detection of EVs secreted from living cancer cell lines with high linearity, without the need for a time-consuming ultracentrifugation process that can take several hours. Furthermore, the detection range can be controlled by adjusting the action range of optical force using a defocused laser, consistent with the theoretical calculations. These findings demonstrate an ultrafast, sensitive, and quantitative approach for measuring biological nanoparticles, enabling innovative analyses of cell-to-cell communication and early diagnosis of various diseases, including cancer.

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.

Light-Induced Condensation of Biofunctional Molecules around Targeted Living Cells to Accelerate Cytosolic Delivery.

The light-induced force and convection can be enhanced by the collective effect of electrons (superradiance and red shift) in high-density metallic nanoparticles, leading to macroscopic assembly of target molecules. We here demonstrate application of the light-induced assembly for drug delivery system with enhancement of cell membrane accumulation and penetration of biofunctional molecules including cell-penetrating peptides (CPPs) with superradiance-mediated photothermal convection. For induction of photothermal assembly around targeted living cells in cell culture medium, infrared continuous-wave laser light was focused onto high-density gold-particle-bound glass bottom dishes exhibiting plasmonic superradiance or thin gold-film-coated glass bottom dishes. In this system, the biofunctional molecules can be concentrated around the targeted living cells and internalized into them only by 100 s laser irradiation. Using this simple approach, we successfully achieved enhanced cytosolic release of the CPPs and apoptosis induction using a pro-apoptotic domain with a very low peptide concentration (nM level) by light-induced condensation.

Nanoneedle formation via doughnut beam-induced Marangoni effects.

Recently, nanosecond pulsed optical vortices enables the production of a unique chiral and sharp needle-like nanostructure (nano-needle). However, the formation process of these structures has been unsolved although mass transport by angular momentum would contribute to the chirality. Here, we reveal that another key factor in the formation of a sharp nano-needle is the Marangoni effect during the melting condition at high temperature. Remarkably, the thickness and height of the nano-needle can be precisely controlled within 200 nm, corresponding to 1/25 of beam radius (5 µm) beyond the diffraction limit by ring-shaped inhomogeneous temperature rise. Our finding will facilitate the development of advanced nano-processing with a variety of structured light beams.

Attogram-level light-induced antigen-antibody binding confined in microflow.

The analysis of trace amounts of proteins based on immunoassays and other methods is essential for the early diagnosis of various diseases such as cancer, dementia, and microbial infections. Here, we propose a light-induced acceleration of antigen-antibody reaction of attogram-level proteins at the solid-liquid interface by tuning the laser irradiation area comparable to the microscale confinement geometry for enhancing the collisional probability of target molecules and probe particles with optical force and fluidic pressure. This principle was applied to achieve a 102-fold higher sensitivity and ultrafast specific detection in comparison with conventional protein detection methods (a few hours) by omitting any pretreatment procedures; 47-750 ag of target proteins were detected in 300 nL of sample after 3 minutes of laser irradiation. Our findings can promote the development of proteomics and innovative platforms for high-throughput bio-analyses under the control of a variety of biochemical reactions.

Plasmonic nanoscale temperature shaping on a single titanium nitride nanostructure.

Arbitrary shaping of temperature fields at the nanometre scale is an important goal in nanotechnology; however, this is challenging because of the diffusive nature of heat transfer. In the present work, we numerically demonstrated that spatial shaping of nanoscale temperature fields can be achieved by plasmonic heating of a single titanium nitride (TiN) nanostructure. A key feature of TiN is its low thermal conductivity (kTiN = 29 [W m-1 K-1]) compared with ordinary plasmonic metals such as Au (kAu = 314 [W m-1 K-1]). When the localised surface plasmon resonance of a metal nanostructure is excited, the light intensity is converted to heat power density in the nanostructure via the Joule heating effect. For a gold nanoparticle, non-uniform spatial distributions of the heat power density will disappear because of the high thermal conductivity of Au; the nanoparticle surface will be entirely isothermal. In contrast, the spatial distributions of the heat power density can be clearly transcribed into temperature fields on a TiN nanostructure because the heat dissipation is suppressed. In fact, we revealed that highly localised temperature distributions can be selectively controlled around the TiN nanostructure at a spatial resolution of several tens of nanometres depending on the excitation wavelength. The present results indicate that arbitrary temperature shaping at the nanometre scale can be achieved by designing the heat power density in TiN nanostructures for plasmonic heating, leading to unconventional thermofluidics and thermal chemical biology.

Damage-free light-induced assembly of intestinal bacteria with a bubble-mimetic substrate.

Rapid evaluation of functions in densely assembled bacteria is a crucial issue in the efficient study of symbiotic mechanisms. If the interaction between many living microbes can be controlled and accelerated via remote assembly, a cultivation process requiring a few days can be ommitted, thus leading to a reduction in the time needed to analyze the bacterial functions. Here, we show the rapid, damage-free, and extremely dense light-induced assembly of microbes over a submillimeter area with the "bubble-mimetic substrate (BMS)". In particular, we successfully assembled 104-105 cells of lactic acid bacteria (Lactobacillus casei), achieving a survival rate higher than 95% within a few minutes without cultivation process. This type of light-induced assembly on substrates like BMS, with the maintenance of the inherent functions of various biological samples, can pave the way for the development of innovative methods for rapid and highly efficient analysis of functions in a variety of microbes.

Near-field transmission and reflection spectroscopy for revealing absorption and scattering characteristics of single silver nanoplates.

Near-field optical microscopy visualizes spatial characteristics of elementary excitations induced in metal nanostructures. However, the microscopy is not able to reveal the absorption and scattering characteristics of the object simultaneously. In this study, we demonstrate a method for revealing the absorption and scattering characteristics of silver nanoplate by using near-field transmission and reflection spectroscopy. Near-field transmission and reflection images show characteristic spatial features attributable to the excited plasmon modes. The near-field refection image near the resonance shows a reversed contrast depending on the observed wavelength. Near-field reflection spectra show unique positive and negative resonant features. We reveal that the optical characteristics and the wavelength dependency of the optical contrast originate from the scattering and absorption properties of the plasmons, with the aid of the electromagnetic simulations.

Light-induced assembly of living bacteria with honeycomb substrate.

Some bacteria are recognized to produce useful substances and electric currents, offering a promising solution to environmental and energy problems. However, applications of high-performance microbial devices require a method to accumulate living bacteria into a higher-density condition in larger substrates. Here, we propose a method for the high-density assembly of bacteria (106 to 107 cells/cm2) with a high survival rate of 80 to 90% using laser-induced convection onto a self-organized honeycomb-like photothermal film. Furthermore, the electricity-producing bacteria can be optically assembled, and the electrical current can be increased by one to two orders of magnitude simply by increasing the number of laser irradiations. This concept can facilitate the development of high-density microbial energy conversion devices and provide new platforms for unconventional environmental technology.

Interparticle-Interaction-Mediated Anomalous Acceleration of Nanoparticles under Light-Field with Coupled Orbital and Spin Angular Momentum.

Spin-orbit interaction is a crucial issue in the field of nanoscale physics and chemistry. Here, we theoretically demonstrate that the spin angular momentum (SAM) can accelerate and decelerate the orbital motion of nanoparticles (NPs) via light-induced interparticle interactions by a circularly polarized optical vortex. The Laguerre-Gaussian beam as a conventional optical vortex with orbital angular momentum (OAM) induces the orbital and spinning motion of a trapped object depending on the spatial configuration. On the contrary, it is not clear whether circularly polarized light induces the orbital motion for the particles trapped off-axis. The present study reveals that the interparticle light-induced force due to the SAM enhances or weakens the orbital torque and modulates rotational dynamics depending on the number of NPs, where the rotation speed of NPs in the optical field with both positive SAM and OAM can be 4 times faster than that in the optical field with negative SAM and positive OAM. The obtained results will not only clarify the principle for the control of NPs based on OAM-SAM coupling via light-matter interaction but also contribute to the unconventional laser processing technique for nanostructures with various chiral symmetries.

Mesoscopic Motion of Optically Trapped Particle Synchronized with Photochromic Reactions of Diarylethene Derivatives.

Not only the energy but also the momentum of photons transfers to material via photoabsorption; this momentum transfer, known as radiation pressure, can induce motions of small particles. It can therefore be expected to induce mechanical motions of mesoscopic materials synchronized with the reversible change of their absorption coefficient by external stimuli. We demonstrated quantitative photomechanical motions in mesoscopic regions by combining optical tweezer and photochromic reactions of diarylethene (DAE). A microparticle including DAE was optically trapped with 532 nm laser and the absorption band of the DAE was photoswitched with UV laser, resulting in the modulation of the radiation force through the change in the complex dielectric constant of the particle. In this process, mesoscopic mechanical motions were successfully induced by the photochromic reaction. The present approach is potentially applicable in a wide variety of nano/micromechanical devices and also paves the way for monitoring the absorption of photons by molecules via photomechanical response.

Mechanism in External Field-mediated Trapping of Bacteria Sensitive to Nanoscale Surface Chemical Structure.

Molecular imprinting technique enables the selective binding of nanoscale target molecules to a polymer film, within which their chemical structure is transcribed. Here, we report the successful production of mixed bacterial imprinted film (BIF) from several food poisoning bacteria by the simultaneous imprinting of their nanoscale surface chemical structures (SCS), and provide highly selective trapping of original micron-scale bacteria used in the production process of mixed BIF even for multiple kinds of bacteria in real samples. Particularly, we reveal the rapid specific identification of E. coli group serotypes (O157:H7 and O26:H11) using an alternating electric field and a quartz crystal microbalance. Furthermore, we have performed the detailed physicochemical analysis of the specific binding of SCS and molecular recognition sites (MRS) based on the dynamic Monte Carlo method under taking into account the electromagnetic interaction. The dielectrophoretic selective trapping greatly depends on change in SCS of bacteria damaged by thermal treatment, ultraviolet irradiation, or antibiotic drugs, which can be well explained by the simulation results. Our results open the avenue for an innovative means of specific and rapid detection of unknown bacteria for food safety and medicine from a nanoscale viewpoint.

Optical Trap-Mediated High-Sensitivity Nanohole Array Biosensors with Random Nanospikes.

We clarify an unconventional principle of the light-driven operation of a biosensor for enhanced sensitivity with the help of random nanospikes added to the surface of a nanohole array. Such a system is capable of optically guiding viruses and trapping them in the vicinity of a highly sensitive site by an anomalous light-induced force arising from random-nanospike-modulated extraordinary optical transmission and the plasmonic mirror image in a virus as a dielectric submicron object. In particular, after guiding the viruses near the apex of nanospikes, there are conditions where the spectral peak shift of extraordinary optical transmission can be greatly increased and reach several hundred nanometers in comparison with that of a conventional nanohole array without random nanospikes. These results will allow for the development of a simple, rapid, and highly sensitive virus detection method based on optical trapping with the help of random-nanospike-modulated extraordinary optical transmission, facilitating convenient medical diagnosis and food inspection.

Submillimetre Network Formation by Light-induced Hybridization of Zeptomole-level DNA.

Macroscopic unique self-assembled structures are produced via double-stranded DNA formation (hybridization) as a specific binding essential in biological systems. However, a large amount of complementary DNA molecules are usually required to form an optically observable structure via natural hybridization, and the detection of small amounts of DNA less than femtomole requires complex and time-consuming procedures. Here, we demonstrate the laser-induced acceleration of hybridization between zeptomole-level DNA and DNA-modified nanoparticles (NPs), resulting in the assembly of a submillimetre network-like structure at the desired position with a dramatic spectral modulation within several minutes. The gradual enhancement of light-induced force and convection facilitated the two-dimensional network growth near the air-liquid interface with optical and fluidic symmetry breakdown. The simultaneous microscope observation and local spectroscopy revealed that the assembling process and spectral change are sensitive to the DNA sequence. Our findings establish innovative guiding principles for facile bottom-up production via various biomolecular recognition events.

Multiple Resonances Induced by Plasmonic Coupling between Gold Nanoparticle Trimers and Hexagonal Assembly of Gold-Coated Polystyrene Microspheres.

Optical properties of a gold nanoparticle trimer assembly coupled with gold-coated hexagonally close-packed polystyrene microspheres were investigated by linear and nonlinear spectroscopy. The observed reflection spectrum shows multiple peaks from the visible to near-infrared spectral regions. The spectroscopic properties were also examined by a finite-difference time-domain simulation. We found that the optical response of plasmons excited in the gold nanoparticle trimers was significantly modulated by strong coupling of the plasmons and the photonic mode induced in the gold-coated polystyrene assembly. Two-photon induced photoluminescence and Raman scattering from the sample were investigated, and both signals were significantly enhanced at the gold nanoparticle assembly. The simulations reveal that the electric fields can be enhanced site-selectively, not only at the interstitial sites in the nanoparticle assembly but also at the gaps between the particle and the gold film due to plasmonic interactions, by tuning the wavelength and are responsible for the strong optical responses.

Selective optical assembly of highly uniform nanoparticles by doughnut-shaped beams.

A highly efficient natural light-harvesting antenna has a ring-like structure consisting of dye molecules whose absorption band changes through selective evolutionary processes driven by external stimuli, i.e., sunlight depending on its territory and thermal fluctuations. Inspired by this fact, here, we experimentally and theoretically demonstrate the selective assembling of ring-like arrangements of many silver nanorods with particular shapes and orientations onto a substrate by the light-induced force of doughnut beams with different colours (wavelengths) and polarizations in conjunction with thermal fluctuations at room temperature. Furthermore, the majority of nanorods are electromagnetically coupled to form a prominent red-shifted collective mode of localized surface plasmons resonant with the wavelength of the irradiated light, where a spectral broadening also appears for the efficient broadband optical response. The discovered principle is a promising route for "bio-inspired selective optical assembly" of various nanomaterials that can be used in the wide field of nanotechnology.

Fluctuation-mediated optical screening of nanoparticles.

Inspired by biological motors, we propose a guiding principle for selectively separating nanoparticles (NPs) by efficiently using the light-induced force (LIF) and thermal fluctuations. We demonstrate the possibility of transporting metallic NPs of different sizes with a size-selection accuracy of less than 10 nm even at room temperature by designing asymmetric spatiotemporal light fields. This technique will lead to unconventional nanoextraction processes based on light and fluctuations.

"Triple Observation Method (TOM)" to discriminate optically autofluorescence from porphyrins versus that from copper-metallothioneins.

We propose a conclusive difference observed between the excitation conditions required to observe porphyrins and copper-metallothioneins in cells and/or tissues using an ordinary fluorescence microscope. We have emphasized the importance of examining the spectral properties of the emissions to avoid any serious mistakes such as confusing porphyrins with copper-metallothioneins in the liver and kidneys. However, microspectrophotometry is not a conventional method for either histochemical, cytochemical, or pathological studies because microspectrophotometers are both expensive and difficult to operate. Therefore, we demonstrate a simple comparative method using ordinary excitation filter arrangements. When using our technique, it becomes possible to optically discriminate more accurately between the autofluorescence properties arising from porphyrins and those arising from copper-metallothioneins. We would like to name our simple technique "Triple Observation Method (TOM)".