STM/TERS observation of (M)-type diphenyl[7]thiaheterohelicene on Ag(111).

The chiral recognition of a self-assembled structure of enantiopure (M)-type 2,13-diphenyl[7]thiaheterohelicene ((M)-Ph-[7]TH) was investigated on a Ag(111) substrate by scanning tunnelling microscopy (STM) and tip-enhanced Raman spectroscopy (TERS). In contrast to previous research of thiaheterohelicene and its derivatives showing zigzag row formation on the Ag(111) substrate, the hexagonal ordered structure was observed by STM. The obtained TERS spectra of (M)-Ph-[7]TH were consistent with the Raman spectra calculated on the basis of density functional theory (DFT), which suggests that (M)-Ph-[7]TH was adsorbed on the substrate without decomposition. The sample bias voltage dependence of STM images combined with the calculated molecular orbitals of (M)-Ph-[7]TH indicates that a phenyl ring was observed as a protrusion at +3.0 V, whereas the helicene backbone was observed at +0.5 V. From these results, a possible model of the hexagonal structure was proposed. Owing to the phenyl ring, the van der Waals interaction between (M)-Ph-[7]TH and the substrate becomes strong. This leads to the formation of the hexagonal structure with the same symmetry as the substrate.

Light Emission from M-Type Enantiomer of 2,13-bis(hydroxymethyl)[7]-thiaheterohelicene Molecules Adsorbed on Au(111) and C60/Au(111) Surfaces Investigated by STM-LE.

Light emission from the M-type enantiomer of a helicene derivative (2,13-bis(hydroxymethyl)[7]-thiaheterohelicene) adsorbed on the clean Au(111) and the C60-covered Au(111) surfaces were investigated by tunneling-current-induced light-emission technique. Plasmon-originated light emission was observed on the helicence/Au(111) surface and it was strongly suppressed on the area where the helicene molecules were adsorbed at the edges of the Au(111) terraces. To avoid luminescence quenching of excited helicene molecules and to suppress strong plasmon light emission from the Au(111) surface, C60 layers were used as decoupling buffer layers between helicene molecules and the Au(111) surface. Helicene molecules were adsorbed preferentially on the Au(111) surface rather than on the C60 buffer layers due to the small interaction of the molecules and C60 islands. This fact motivated us to deposit a multilayer of helicene molecules onto the C60 layers grown on the Au(111) surface, leading to the fact that the helicene/C60 multilayer showed strong luminescence with the molecules character. We consider that such strong light emission from the multilayer of helicene molecules has a plasmon origin strongly modulated by the molecular electronic states of (M)-[7]TH-diol molecules.

Assessment of heavy metal pollution in the coastal sediments of an urbanized atoll in the central Pacific: Majuro Atoll, the Marshall Islands.

Pacific atolls are extremely vulnerable to the effects of climate change. Coral reef ecosystems, which are responsible for the island formation and maintenance, can potentially keep pace with rising sea levels. Such ecosystems are sensitive to pollution; however, the sources and levels of atoll pollutants caused by urbanization have rarely been investigated. In this study, we assessed the heavy metal pollution (Cr, Mn, Ni, Cu, Zn, Cd, and Pb) of coastal sediments to evaluate the effects of urbanization on Majuro Atoll, the Marshall Islands. The densely populated area had the most significant pollution with high levels of Pb, Mn, Zn, and Cu due to road traffic activity. Domestic wastewater, a major pollution source in Pacific atolls, was not identified. Remarkably, the Zn and Pb levels in the lagoonal coasts of the remote island area were 697 - 1539 and 22 - 337 times higher, respectively, than in the natural area of Funafuti Atoll, Tuvalu. Thus, the remote island and sparsely populated areas were significantly polluted because of the maritime traffic activity in the lagoon and debris accumulation in/around the lagoon. This pollution resulted from improper municipal solid waste management of the main island. The contamination factor, pollution load index, and geo-accumulation index indicated high levels of heavy metal pollution in these areas. Urbanization of the atoll clearly resulted in a distinct heavy metal composition and high pollution levels compared with Funafuti Atoll. These findings emphasize the importance of pollution management in the conservation and rehabilitation of urbanized atolls threatened by future sea-level rises.

Demonstration of a diffraction-based optical diffuser inspired by the Morpho butterfly.

Optical diffusers are widely used in a variety of light sources to create uniform illumination over a wide field of view. Inspired by the diffraction-based light diffusion of the Morpho butterfly, here we demonstrate a novel diffuser which fulfils (i) high transmittance, (ii) wide angular spread, and (iii) low color dispersion. Two-dimensional nanopatterns were designed using optical simulations to enable simple fabrication. By introducing anisotropy into the surface nanopatterns, we achieved control of anisotropic light diffusion, which has been challenging for conventional diffusers. Next, the designed diffuser was implemented over a large area (100 × 100 mm2) via nanoimprint lithography. The obtained diffuser demonstrated a high transmittance of ∼85% and full width at half maximum (FWHM) of >60° with low color dispersion, outperforming conventional diffusers. Since the presented diffuser has the controllable diffusion properties with low light loss, it has many applications including LED lighting, displays, and daylight harvesting systems.

Long- and Short-Term Conductance Control of Artificial Polymer Wire Synapses.

Networks in the human brain are extremely complex and sophisticated. The abstract model of the human brain has been used in software development, specifically in artificial intelligence. Despite the remarkable outcomes achieved using artificial intelligence, the approach consumes a huge amount of computational resources. A possible solution to this issue is the development of processing circuits that physically resemble an artificial brain, which can offer low-energy loss and high-speed processing. This study demonstrated the synaptic functions of conductive polymer wires linking arbitrary electrodes in solution. By controlling the conductance of the wires, synaptic functions such as long-term potentiation and short-term plasticity were achieved, which are similar to the manner in which a synapse changes the strength of its connections. This novel organic artificial synapse can be used to construct information-processing circuits by wiring from scratch and learning efficiently in response to external stimuli.

Behavior of eukaryotic symbionts in large benthic foraminifers Calcarina gaudichaudii and Baculogypsina sphaerulata under exposure to wastewater.

Large benthic foraminifers (LBFs) are significant contributors to coral island formation in the Pacific Ocean. In recent years, the population of LBFs has decreased because of the increase in anthropogenic influences, such as wastewater (WW) discharge. To implement efficient mitigation measures, pollution tolerance in LBFs should be understood. However, the effects of WW on LBFs and their symbionts have not yet been demonstrated. This study examined the changes in the photosynthetic efficiency (Y[II]) of Calcarina gaudichaudii and Baculogypsina sphaerulata in response to WW by using a pulse-amplitude-modulation fluorometer. These LBFs were exposed to WW with different dilution levels for 22 days. The Y(II) values of the LBFs were found to deteriorate within 1-2 days. However, the Y(II) values both deteriorated and were enhanced in the experiments, thus indicating that WW contains both harmful and beneficial components. Baculogypsina sphaerulata showed an earlier response and greater sensitivity to WW and a higher epibiont infestation than C. gaudichaudii. This result can be attributed to the differences in the physiological and morphological responses of distinct LBFs. A sequencing analysis of 18S rDNA confirmed that the dominant eukaryotic symbionts in the two LBFs studied were Ochrophyta and Labyrinthulomycetes. These eukaryotic symbionts were released and attached as epibionts onto LBFs that were exposed to WW, thus leading to an increase in inactive LBFs. The Shannon-Weaver and Simpson diversity indices revealed that eukaryotic symbiont communities decreased in biodiversity after exposure to WW because of the abundance of algal symbionts. On the basis of these results, we conclude that WW, even with 10,000 × dilution, causes a decrease in active LBF populations owing to the release of eukaryotic symbionts, the decrease in biodiversity, and the infestation of epibionts even though Y(II) is temporarily enhanced. These responses are more significant in B. sphaerulata than in C. gaudichaudii.

Room-temperature discrete-charge-fluctuation dynamics of a single molecule adsorbed on a carbon nanotube.

Detection and use of physical noise fluctuations in a signal provides significant advantages in the development of bio- and neuro-sensing and functional mimicking devices. Low-dimensional carbon nanomaterials are a good candidate for use in noise generation due to the high surface sensitivity of these materials, which may themselves serve as the main building blocks of these devices. Here, we demonstrate that the addition of a molecule with high redox activity to a carbon nanotube (CNT) field-effect transistor provides tunable current fluctuation noise. A unique charge-trap state in the vicinity of the CNT surface due to the presence of the single molecule is the origin of the noise, which generates a prominent and unique slow discrete random telegraph signal in the device current. The power spectral density reveals the peculiar frequency limit of the fluctuation for different types of molecules depending on their redox activity and adsorption configuration. These results indicate that the detected noise will provide new opportunities to obtain electronic information for a single molecule combined with a nanotube surface, and that controllability of the noise may contribute to the expansion of noise utilization in future bio-inspired devices.

Anomalous hexagonal superstructure of aluminum oxide layer grown on NiAl(110) surface.

A modified method for the fabrication of a highly crystallized layer of aluminum oxide on a NiAl(110) surface is reported. The fabrication method involves the multistep selective oxidation of aluminum atoms on a NiAl(110) surface resulting from successive oxygen deposition and annealing. The surface morphology and local electronic structure of the novel aluminum oxide layer were investigated by high-resolution imaging using scanning tunneling microscopy (STM) and current imaging tunneling spectroscopy. In contrast to the standard fabrication method of aluminum oxide on a NiAl(110) surface, the proposed method produces an atomically flat surface exhibiting a hexagonal superstructure. The superstructure exhibits a slightly distorted hexagonal array of close-packed bright protrusions with a periodicity of 4.5 ± 0.2 nm. Atomically resolved STM imaging of the aluminum oxide layer reveals a hexagonal arrangement of dark contrast spots with a periodicity of 0.27 ± 0.02 nm. On the basis of the atomic structure of the fabricated layer, the formation of α-Al2O3(0001) on the NiAl(110) surface is suggested.

Heavy metal contamination of coastal lagoon sediments: Fongafale Islet, Funafuti Atoll, Tuvalu.

To evaluate contamination of coastal sediments along Fongafale Islet, Central Pacific, a field survey was conducted in densely populated, sparsely populated, open dumping and undisturbed natural areas. Current measurements in shallow water of the lagoon indicated that contaminants from the densely populated area would only be transported for a small proportion of a tidal cycle. Acid-volatile sulfides were detected in both the intertidal beach and nearshore zones of the densely populated area, whereas these were no detection in the other areas. This observation lends support to argument that the coastal pollution mechanism that during ebb tide, domestic wastewater leaking from poorly constructed sanitary facilities seeps into the coast. The total concentrations of Cr, Mn, Ni, Cu, Zn, Cd and Pb were relatively high in all of the areas except the undisturbed natural area. The indices of contamination factor, pollution load index and geoaccumulation index were indicative of heavy metal pollution in the three areas. The densely populated area has the most significant contamination; domestic wastewater led to significant contamination of coastal sediments with Cr, Zn, Cu, Pb and Cd. The open dumping area is noteworthy with respect to Mn and Ni, which can be derived from disposed batteries.

Bis(tert-butylpyrene) nanotweezers and nanocalipers: enhanced extraction and recognition abilities for single-walled carbon nanotubes.

We developed a host-guest methodology for separation of single-walled carbon nanotubes (SWNTs) according to the handedness, diameter and metallicity by the use of diporphyrin nanotweezers and nanocalipers. Although the pyrene has been frequently used to replace porphyrin, due to a similar affinity to the surface of SWNTs and better availability, the extraction and recognition abilities of dipyrene nanotweezers were not so good as those of diporphyrin ones as we reported previously. However, introduction of a tert-butyl substituent at the 7'-position of 2-pyrene is found to enhance the extraction and recognition abilities of dipyrene nanotweezers and nanocalipers. That is, (6,5)-SWNTs were obtained in high purity by use of bis(tert-butylpyrene) nanotweezers with a phenanthrene spacer and metallic SWNTs were highly enriched by use of bis(tert-butylpyrene) nanocalipers with a carbazole-anthracene-carbazole spacer.

Simultaneous discrimination of diameter, handedness, and metallicity of single-walled carbon nanotubes with chiral diporphyrin nanocalipers.

We have been developing the methodology to discriminate the handedness and diameter of single-walled carbon nanotubes (SWNTs) through molecular recognition using chiral diporphyrin nanotweezers. Although relatively small diameters of SWNTs (<1.0 nm) were recognized well, nanotweezers were not able to form stable complexes with the SWNTs having the diameters >1.0 nm. In this context, we designed chiral diporphyrin with a much larger cavity, namely, "nanocalipers". The feature of the newly designed host molecule is: (1) long spacer with more than 1.4 nm consisting of three aromatic moieties; (2) nearly parallel orientation of the two porphyrins; (3) restricted conformation by biaryl linkages of the porphyrin-carbazole and carbazole-anthracene; (4) strong interaction of two porphyrins and anthracene with the surface of a SWNT through π-π stacking; and (5) stereogenic centers at the periphery of porphyrins discriminating helicity of SWNTs. As expected, we obtained optically active SWNTs with >1.0 nm in diameter and, unexpectedly, enriched metallic SWNTs over semiconducting ones. The optically active metallic SWNTs are identified for the first time, in addition to the optically active semiconducting SWNTs with such large diameters. The nanocalipers are found to recognize the diameter, handedness, and metallicity of SWNTs simultaneously.

Controlled chain polymerisation and chemical soldering for single-molecule electronics.

Single functional molecules offer great potential for the development of novel nanoelectronic devices with capabilities beyond today's silicon-based devices. To realise single-molecule electronics, the development of a viable method for connecting functional molecules to each other using single conductive polymer chains is required. The method of initiating chain polymerisation using the tip of a scanning tunnelling microscope (STM) is very useful for fabricating single conductive polymer chains at designated positions and thereby wiring single molecules. In this feature article, developments in the controlled chain polymerisation of diacetylene compounds and the properties of polydiacetylene chains are summarised. Recent studies of "chemical soldering", a technique enabling the covalent connection of single polydiacetylene chains to single functional molecules, are also introduced. This represents a key step in advancing the development of single-molecule electronics.

Development and application of multiple-probe scanning probe microscopes.

In the research of advanced materials based on nanoscience and nanotechnology, it is often desirable to measure nanoscale local electrical conductivity at a designated position of a given sample. For this purpose, multiple-probe scanning probe microscopes (MP-SPMs), in which two, three or four scanning tunneling microscope (STM) or atomic force microscope (AFM) probes are operated independently, have been developed. Each probe in an MP-SPM is used not only for observing high-resolution STM or AFM images but also for forming an electrical contact enabling nanoscale local electrical conductivity measurement. The world's first double-probe STM (DP-STM) developed by the authors, which was subsequently modified to a triple-probe STM (TP-STM), has been used to measure the conductivities of one-dimensional metal nanowires and carbon nanotubes and also two-dimensional molecular films. A quadruple-probe STM (QP-STM) has also been developed and used to measure the conductivity of two-dimensional molecular films without the ambiguity of contact resistance between the probe and sample. Moreover, a quadruple-probe AFM (QP-AFM) with four conductive tuning-fork-type self-detection force sensing probes has been developed to measure the conductivity of a nanostructure on an insulating substrate. A general-purpose computer software to control four probes at the same time has also been developed and used in the operation of the QP-AFM. These developments and applications of MP-SPMs are reviewed in this paper.

Center of excellence for atomically controlled fabrication technology.

This short review aims to show the introduction of the educational and research program of "Center of excellence of atomically controlled fabrication technology" supported ministry of education, culture, sports, science and technology--Japan. We would like to introduce research activity and a unique trait of educational system.

Numerical analysis on the optical role of nano-randomness on the Morpho butterfly's scale.

The blue coloration of Morpho butterflies has anomalously low angular dependence despite the production of color with a selected wavelength based on an interference effect. A key to the mechanism of the specific Morpho-color was suggested to be the randomness of its scale. Using finite-difference time-domain (FDTD) analysis, the role of different kinds of randomness in the structure of the Morpho butterfly's scale was investigated, which was impossible by conventional analytical calculations. The results revealed that incoherence in the incident light plays an essential role, which cannot be realized only by structural randomness. On the other hand, the lateral and vertical randomness, and the number of random components were found each to have an independent role to realize the specific Morpho-color preventing the sharp reflective angular dependence. The direction obtained by the numerical simulations to analyze optically complex random structures will serve not only to understand the scientific principles, but also to design the optical properties of artificial materials.

Nanoscale control of reversible chemical reaction between fullerene C60 molecules using scanning tunneling microscope.

The nanoscale control of reversible chemical reactions, the polymerization and depolymerization between C60 molecules, has been investigated. Using a scanning tunneling microscope (STM), the polymerization and depolymerization can be controlled at designated positions in ultrathin films of C60 molecules. One of the two chemical reactions can be selectively induced by controlling the sample bias voltage (V(s)); the application of negative and positive values of V(s) results in polymerization and depolymerization, respectively. The selectivity between the two chemical reactions becomes extremely high when the thickness of the C60 film increases to more than three molecular layers. We conclude that STM-induced negative and positive electrostatic ionization are responsible for the control of the polymerization and depolymerization, respectively.

Charge-carrier injection into pentacene thin film formed on Si(111) probed by STM spectroscopy.

The injection of charge carriers into a pentacene thin film formed on a Si substrate was investigated by scanning tunneling microscopy (STM). Tip height versus bias voltage (z-V) spectroscopy reveals the characteristic charge transport properties of the molecular film, i.e., the conductivity and the threshold energy of charge injection. The abrupt descent of the tip into the film owing to the transition of film conductance, which depends on the degree of charge carrier injection, was observed for crystallized pentacene thin films. The lower film conductance at around zero bias voltage is still higher than that of a vacuum. This indicates that the carrier injection barrier between the pentacene and the semiconducting substrate is extremely low. The convergence of the carrier injection endpoints into a narrow range of electric-field intensity implies that the main factor contributing to barrier formation and collapse is not the bias voltage but the electric field.

Direct observation of X-ray induced atomic motion using scanning tunneling microscope combined with synchrotron radiation.

X-ray induced atomic motion on a Ge(111)-c(2 x 8) clean surface at room temperature was directly observed with atomic resolution using a synchrotron radiation (SR)-based scanning tunneling microscope (STM) system under ultra high vacuum condition. The atomic motion was visualized as a tracking image by developing a method to merge the STM images before and after X-ray irradiation. Using the tracking image, the atomic mobility was found to be strongly affected by defects on the surface, but was not dependent on the incident X-ray energy, although it was clearly dependent on the photon density. The atomic motion can be attributed to surface diffusion, which might not be due to core-excitation accompanied with electronic transition, but a thermal effect by X-ray irradiation. The crystal surface structure was possible to break even at a lower photon density than the conventionally known barrier. These results can alert X-ray studies in the near future about sample damage during measurements, while suggesting the possibility of new applications. Also the obtained results show a new availability of the in-situ SR-STM system.