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Kaoru Tamada

Publications and source records attributed to Kaoru Tamada.

7 recordsLinked to original sources

Dynamic and collective electrochemical responses of tetrathiafulvalene derivative self-assembled monolayers.

Electroactive tetrathiafulvalene (TTF)-containing alkanethiol self-assembled monolayers (SAMs) were designed and synthesized to elucidate the relationship between electrochemical responses and film structures. Two TTF derivative molecules having one alkanethiol chain (1) and two alkanethiol chains (2) were utilized to modulate the molecular packing arrangements in the SAMs, and the formation and structure of the SAMs were characterized by surface plasmon resonance spectroscopy (SPR). SPR measurements in various contacting media demonstrated loose packing of SAM 1 and close packing of SAM 2 due to the different space fillings of the molecules. Two successive one-electron redox waves were observed for both SAMs by cyclic voltammetry. The peak widths of the redox waves were strongly dependent on the oxidation states of the TTF moieties, the packing arrangement of the SAMs, and the contacting medium. We found that TTF-based SAMs exhibited collective electrochemical responses induced by dynamic structural changes, depending on the degree of freedom for the component molecules in the SAMs. These results imply that the molecular design, taking into account the electrochemical responses, extends the available range of molecular-based functionalities in TTF-based SAMs.

Journal Article↗

Estimation of dielectric function of biotin-capped gold nanoparticles via signal enhancement on surface plasmon resonance.

Biotin-capped gold nanoparticles assembled on flat gold with volume fraction f are studied by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy (AFM) in order to estimate the dielectric function of the gold nanoparticles based on the Maxwell-Garnett (MG) theory. The complex dielectric function (epsilon',epsilon'') of the spherical nanoparticles at three representative wavelengths in the vis-near-IR region, i.e., lambda = 543, 632.8, and 1152 nm, is estimated for a surface homogeneously covered with nanoparticles in order to discuss the wavelength dependence of the dielectric function. The SPR response of a surface covered with particles in 2D aggregates is also analyzed. The experimental SPR curve of the particle aggregates deviates from the theoretical predictions, suggesting dipole interactions between particles.

Adsorption↗

Studies of human hair by friction force microscopy with the hair-model-probe.

We employed a cantilever modified with a self-assembled monolayer (SAM) as a "hair-model-probe" for friction force microscopy (FFM) to measure friction acting between hair and hair-like surfaces. The "hair-model-probe" was prepared by forming a SAM of octadecanethiol on a gold-coated cantilever. We investigated frictional properties of human hair at both root and tip, and the dependency on applied load, influence of scanning direction, and local frictional distribution. The friction coefficient of the hair tip was greater than that of the hair root. Load dependency of friction at the hair tip was clearly observed, while friction at the hair root was less dependent on applied load. At the hair root, an anisotropic frictional property was observed: friction force along the long axis of the hair fiber was about 1.5-2 times larger than that along the short axis. Atomic force microscopy (AFM) images showed striations on the cuticle cells that have about 6 nm depth and their long axis oriented in the direction of the hair fiber. The frictional distribution images revealed that the local areas showing strong shear corresponded to striations. Since such distribution of friction was not observed at the hair tip, it is suggested that the anisotropic frictional property at the hair root was caused mainly by the striations. The frictional distribution in regions that excluded the striations also showed the anisotropic frictional property that friction parallel to the long axis of the hair fiber is greater than that along the short axis. This result suggests that the orientation of fatty acid molecules comprising the fat layer (F-layer) may also contribute to the anisotropic frictional property. We have concluded that loss of the F-layer is a dominant cause of strong friction detected at the hair tip, and at the striations of the hair root.

Friction↗

Formation of chiral surface with enantiomeric tartaric acid on gemini-structured self-assembled monolayers.

Chiral surfaces were prepared by L, D, and Meso-tartaric acids (TAs) adsorbed on gemini-structured self-assembled monolayers (SAMs) composed of ethylenebis [(12-mercaptododecyl) dimethyl ammonium bromide] (HS-gQA-SH). The formation and structure of the chiral surfaces were characterized by surface plasmon resonance spectroscopy (SPR) and Fourier transform infrared-reflection adsorption spectroscopy (FTIR-RAS). The thickness of enantiomeric TA layers on the HS-gQA-SH SAM was estimated to be c.a. 5-6 angstroms regardless of their chirality, in good agreement with the height of TA molecules anchoring on the surface with two COOH groups. All the TAs on the HS-gQA-SH SAM exhibit the same ionization state independent of their chirality in their vibration bands of carboxylic groups. We attempted a second-layer adsorption of the enantiomeric TAs on L-TA monomolecular layer (L-TA SAM) precomposed on the HS-gQA-SH. A strong affinity between first and second TA layers resulted in the film growth when their chirality is identical (i.e., L-TA on L-TA SAM). We found the structure of second L-TA layer was completely different from that of the first layer, where a crystalline-like L-TA phase was found as a predominant component. Our results imply a preferential crystalline growth of chiral molecules on the same chiral surface, which may lead to a work for optical resolution into two enantiomers at a solid-liquid interface.

Adsorption↗

Thickness measurements on transparent substrates based on reflection ellipsometry. I. Optical effects of high-refractive-index additional layers.

Theoretical studies were conducted for thickness measurements using transparent substrates on the external and internal reflection configurations. For three-phase systems consisting of ambient, film, and substrate, the refractive index of the substrate could be optimized to obtain the high sensitivity of an ellipsometric quantity delta to the film thickness and the small susceptibility of delta to errors in the incident angle. It was shown that the combination of an ordinary glass substrate and an additional dielectric layer with an appropriate layer thickness works as a synthetic high-index single substrate (SHIS). The optical effect of the combination was approximately described by use of the effective refractive index of SHIS. A method to select the refractive index of the additional layer was also given.

Journal Article↗

Wavelength-scanning surface plasmon resonance imaging.

A new surface plasmon resonance (SPR) imaging technique was proposed. After measurements were conducted at varying wavelengths, the wavelength affording the minimum brightness (SPR wavelength) was determined at each pixel of the image. A two-dimensional map of the SPR wavelength could be converted to a thickness profile by use of a nonlinear calibration curve, which was obtained by Fresnel calculation. An array of protein thin layers on a gold film was evaluated in air to present the layers' surface structure in nanometer scale.

Algorithms↗

Two-dimensional thickness measurements based on internal reflection ellipsometry.

An imaging ellipsometer technique on internal reflection geometry that can measure the thickness distribution of a thin film possessing an assumed refractive index is described. Because a prism is used for the internal reflection geometry, it was theoretically predicted that angular derivation from the normal incidence on the prism surface affects only the psi value by a factor of 0.97 at maximum. Measurements were carried out for an optical system of silica substrate-TiO2 layer-silica layer-protein film-air, with a thin-film array of dried protein as the sample film. Thickness of the protein films was two-dimensionally estimated only from the measured map of the delta value by use of the simulated relationship between the thickness and the delta value. The thickness map obtained was coincident on the whole with the results according to a mechanical scanning. The detection limit was approximately +/- 0.2 nm. These findings validate the optical effect of a high-index additional layer to improve the sensitivity and precision of thickness measurements of the sample film on transparent substrates.

Coated Materials, Biocompatible↗