Masayuki Naya

Reproducible fabrication of a fiber probe with a nanometric protrusion for near-field optics

We propose a new type of fiber probe with a nanometric protruding tip emerging from a metal film and describe a novel method, called the selective resin-coating method, for fabricating such probes. It is a reproducible etching process consisting of four steps and can be applied to silica fibers sharpened by selective chemical etching. With this method, we obtained tips with the apex diameter and the foot diameter of the protrusion being less than 10 and 30 nm, respectively, when the gold film was ~120 nm thick.

Large-Area Surface-Enhanced Raman Spectroscopy Imaging of Brain Ischemia by Gold Nanoparticles Grown on Random Nanoarrays of Transparent Boehmite

Although SERS spectroscopy, which is sensitive to molecular vibration states, offers label-free visualization of molecules, identification of molecules and their reliable large-area imaging remains to be developed. Limitation comes from difficulties in fabricating a SERS-active substrate with homogeneity over a large area. Here, we overcome this hurdle by utilizing a self-assembled nanostructure of boehmite that is easily achieved by a hydrothermal preparation of aluminum as a template for subsequent gold (Au) deposition. This approach brought about random arrays of Au-nanostructures with a diameter of ∼125 nm and a spacing of <10 nm, ideal for the hot-spots formation. The substrate, which we named gold nanocoral (GNC) after its coral reef-like shape, exhibited a small variability of signal intensities (coefficient value <11.2%) in detecting rhodamine 6G molecule when 121 spots were measured over an area of 10 × 10 mm(2), confirming high uniformity. The transparent nature of boehmite enabled us to conduct the measurement from the back-side of the substrate as efficiently as that from the front-side. We then conducted tissue imaging using the mouse ischemic brain adhered on the GNC substrate. Through nontargeted construction of two-dimensional-Raman-intensity map using differential bands from two metabolically distinct regions, that is, ischemic core and contralateral-control areas, we found that mapping using the adenine ring vibration band at 736 cm(-1) clearly demarcated ischemic core where high-energy adenine phosphonucleotides were degraded as judged by imaging mass spectrometry. Such a detection capability makes the GNC-based SERS technology especially promising for revealing acute energy derangement of tissues.

Imaging of biological samples by a collection-mode photon scanning tunneling microscope with an apertured probe

We report on high resolution imaging by a collection-mode photon scanning tunneling microscope (c-mode PSTM). In our PSTM system, we have used a novel probe with a nanometric protrusion formed from a metal coated sharpened fiber. By using this probe, flagellar filaments of salmonella of diameter 25 nm could be imaged to have a full width at half maximum of 50 nm. Obtained images strongly depended on the separation of the sample to the probe, the diameter of the aperture, and polarization of the irradiated light. Comments on the origins of these dependencies are given.

Near-field optical imaging of flagellar filaments of salmonella in water with optical feedback control

We report on the high-resolution observation of biological samples in water with a collection-mode near-field optical microscope (c-mode NOM) operating under optical feedback control. With rapidly decreasing evanescent field power used as the feedback signal, for the first time to our knowledge, an image of straight-type flagellar filaments of salmonella in water has been obtained. The estimated diameter of a single filament is around 55 nm with a pixel size of 10 nm. A comparison with its nominal value of 25 nm obtained from electron microscope observations under high vacuum confirms that our c-mode NOM performs high-resolution imaging in water.

Randomness in highly reflective silver nanoparticles and their localized optical fields

Reflection of near-infrared light is important for preventing heat transfer in energy saving applications. A large-area, mass-producible reflector that contains randomly distributed disk-shaped silver nanoparticles and that exhibits high reflection at near-infrared wavelengths was demonstrated. Although resonant coupling between incident light and the nanostructure of the reflector plays some role, what is more important is the geometrical randomness of the nanoparticles, which serves as the origin of a particle-dependent localization and hierarchical distribution of optical near-fields in the vicinity of the nanostructure. Here we show and clarified the unique optical near-field processes associated with the randomness seen in experimentally fabricated silver nanostructures by adapting a rigorous theory of optical near-fields based on an angular spectrum and detailed electromagnetic calculations.

TOF-SIMS imaging of halide/thiocyanate anions and hydrogen sulfide in mouse kidney sections using silver-deposited plates

In vivo imaging of reactive small molecule metabolites with high spatial resolution and specificity could give clues to understanding pathophysiology of various diseases. We herein applied time of flight-secondary ion mass spectrometry (TOF-SIMS) to newly developed silver-deposited plates that were stamped on mouse tissues, and succeeded in visualization of halide (Cl−, Br−, and I−) and pseudohalide thiocyanate (SCN−) anions, a class of substrates for neutrophils/eosinophil peroxidases to produce hypohalous acids (HOX/OX− mixture; X: (pseudo)halides), as well as hydrogen sulfide (H2S). Forty-micrometer frozen mouse kidney sections on cover glasses were attached to 37xa0°C preheated silver-deposited plates and incubated at −10xa0°C for 1xa0h. After sputter cleaning to remove surface contaminants, the plates were analyzed by TOF-SIMS to identify distribution of Br−, AgBr2−, I−, AgI2−, SCN−, as well as S2− and AgS− as products of tissue-derived H2S. Br−, AgBr2−, I−, and SCN− anions were mainly distributed in core regions including the inner medulla and inner stripe of the outer medulla (except for I−), rather than outer regions such as the cortex and outer stripe of the outer medulla. AgI2− anion was spread over the whole kidney, although its levels were relatively low. In contrast, S2− and AgS− anions were mainly present in the outer regions. To our knowledge, this is the first imaging study to reveal the distribution of (pseudo)halides and H2S in animal tissue sections.

Gold-nanofève surface-enhanced Raman spectroscopy visualizes hypotaurine as a robust anti-oxidant consumed in cancer survival

Gold deposition with diagonal angle towards boehmite-based nanostructure creates random arrays of horse-bean-shaped nanostructures named gold-nanofève (GNF). GNF generates many electromagnetic hotspots as surface-enhanced Raman spectroscopy (SERS) excitation sources, and enables large-area visualization of molecular vibration fingerprints of metabolites in human cancer xenografts in livers of immunodeficient mice with sufficient sensitivity and uniformity. Differential screening of GNF-SERS signals in tumours and those in parenchyma demarcated tumour boundaries in liver tissues. Furthermore, GNF-SERS combined with quantum chemical calculation identified cysteine-derived glutathione and hypotaurine (HT) as tumour-dominant and parenchyma-dominant metabolites, respectively. CD44 knockdown in cancer diminished glutathione, but not HT in tumours. Mechanisms whereby tumours sustained HT under CD44-knockdown conditions include upregulation of PHGDH, PSAT1 and PSPH that drove glycolysis-dependent activation of serine/glycine-cleavage systems to provide one-methyl group for HT synthesis. HT was rapidly converted into taurine in cancer cells, suggesting that HT is a robust anti-oxidant for their survival under glutathione-suppressed conditions.Surface-enhanced Raman spectroscopy (SERS) visualizes fingerprints of intermolecular vibrations of many metabolites. Here the authors report a SERS imaging technique that enables the visualization of metabolites distribution and automated extraction of tumour boundaries in frozen tissues.

Anti-reflective coating for visible light using a silver nanodisc metasurface with a refractive index of less than 1.0

Suppression of visible-light reflection from material surfaces is an important technology for many applications such as flat-panel displays, camera lenses, and solar panels. In this study, we developed an anti-reflective coating design based on a silver nanodisc metasurface. The effective refractive index of a 10-nm-thick monolayer of silver nanodiscs was less than 1.0, which enabled strong suppression of reflection from the underlying substrate. The nanodisc structure was easy to fabricate using a conventional roll-to-roll wet-coating method. The anti-reflective structure was fabricated over a large area.Suppression of visible-light reflection from material surfaces is an important technology for many applications such as flat-panel displays, camera lenses, and solar panels. In this study, we developed an anti-reflective coating design based on a silver nanodisc metasurface. The effective refractive index of a 10-nm-thick monolayer of silver nanodiscs was less than 1.0, which enabled strong suppression of reflection from the underlying substrate. The nanodisc structure was easy to fabricate using a conventional roll-to-roll wet-coating method. The anti-reflective structure was fabricated over a large area.

DNA Brush-Directed Vertical Alignment of Extensive Gold Nanorod Arrays with Controlled Density

Control over the orientation of metal nanorods is important for both fundamental and applied research. We show that gold nanorods (GNRs) can be aligned in a single direction by adsorbing positively charged GNRs onto a double-strand DNA-grafted substrate through electrostatic interaction. The ordered structure can be optimized by controlling the density of the positive charges on the surface of the GNRs. We found, in agreement with the results of theoretical simulation, that the resultant structure exhibits plasmonic properties that are dependent on the GNR orientation relative to the direction of an oscillating electric field. Our approach provides new insights into the polymer-assisted self-assembly of rod-shaped nanoparticles utilizing electrostatic interactions.

Local circular polarizations in nanostructures induced by linear polarization via optical near-fields

We previously reported [Sci. Rep.4, 6077 (2014)10.1038/srep06077SRWSDA2045-2322] that the geometrical randomness of disk-shaped silver nanoparticles, which exhibit high reflection at near-infrared wavelengths, serves as the origin of a particle-dependent localization and hierarchical distribution of optical near-fields in the vicinity of the nanostructure. In this study, we show that the induced polarizations are circular, particularly at resonant wavelengths. We formulate optical near-field processes between nanostructures, accounting for their polarizations and geometries, and attribute circular polarization to the layout-dependent phase difference between the electrical susceptibilities associated with longitudinal and transverse-electric components. This study clarifies the fundamental optical properties of random nanostructured matter and offers generic theoretical concepts for implementing nanoscale polarizations of optical near-fields.