In situ AFM studies on self-assembled monolayers of adsorbed surfactant molecules on well-defined H-terminated Si(111) surfaces in aqueous solutions

The formation of self-assembled monolayers (SAMs) of adsorbed cationic or anionic surfactant molecules on atomically flat H-terminated Si(111) surfaces in aqueous solutions was investigated by in situ AFM measurements, using octyl trimethylammonium chloride (C8TAC), dodecyl trimethylammonium chloride (C12TAC), octadecyl trimethylammonium chloride (C18TAC)) sodium dodecyl sulfate (STS), and sodium tetradecyl sulfate (SDS). The adsorbed surfactant layer with well-ordered molecular arrangement was formed when the Si(111) surface was in contact with 1.0x10(-4) M C18TAC, whereas a slightly roughened layer was formed for 1.0x10(-4) M C8TAC and C12TAC. On the other hand, the addition of alcohols to solutions of 1.0x10(-4) M C8TAC, C12TAC, or SDS improved the molecular arrangement in the adsorbed surfactant layer. Similarly, the addition of a salt, KCl, also improved the molecular arrangement for both the cationic and anionic surfactant layers. Moreover, the adsorbed surfactant layer with a well-ordered structure was formed in a solution of mixed cationic (C12TAC) and anionic (SDS) surfactants, though each surfactant alone did not form the well-ordered layer. These results were all explained by taking into account electrostatic repulsion between ionic head groups of adsorbed surfactant molecules as well as hydrophobic interaction between their alkyl chains, which increases with the increasing chain length, together with the increase in the hydrophobic interaction or the decrease in the electrostatic repulsion by incorporating alcohol molecules into the adsorbed surfactant layer, the decrease in the electrostatic repulsion by increasing the concentration of counterions, and the decrease in the electrostatic repulsion by alternate arrangement of cationic and anionic surfactant molecules. The present results have revealed various factors to form the well-ordered adsorbed surfactant layers on the H-Si(111) surface, which have a possibility of realizing the third generation surfaces with flexible structures and functions easily adaptable to circumstances.     

High-field 1H MAS and 15N CP-MAS NMR studies of alanine tripeptides and oligomers: distinction of antiparallel and parallel beta-sheet structures and two crystallographically independent molecules

beta-Strand peptides are known to assemble into either antiparallel (AP) or parallel (P) beta-sheet forms which are very important motifs for protein folding and fibril formations occurring in silk fibroin or amyloid proteins. Well-resolved 1H NMR signals including NH protons were observed for alanine tripeptides (Ala)3 with the AP and P structures as well as (Ala)n (n = 4-6) by high-field/fast magic-angle spinning NMR. Amide NH and amino NH3+ 1H signals of (Ala)3 with the P structure were well resonated at 7.5 and 8.9 ppm, respectively, whereas they were not resolved for the AP structure. Notably, NH 1H signals of (Ala)3 and (Ala)4 taking the P structure are resonated at higher field than those of the AP structure by 1.0 and 1.1 ppm, respectively. Further, NH 15N signals of (Ala)3 with the AP structure were resonated at lower field by 2 to 5 ppm than those of (Ala)3 with the P structure. These relative 1H and 15N hydrogen bond shifts of the P structure with respect to those of the AP structure are consistent with the relative hydrogen bond lengths of the interstrand N-H...O=C bonds. Distinction between the two crystallographically independent chains present in the AP and P structures was feasible by 15N chemical shifts but not by 1H chemical shifts because of insufficient spectral resolution in the latter. Calculated 1H and 15N shielding constants by density functional theory are generally consistent with the experimental data, although some discrepancies remain depending upon the models used.     

Microscopic study of Gamow-Teller and spin-dipole states in 208Bi

Gamow-Teller (GT) and spin-dipole (SD) states in ²⁰⁸Bi are studied by using self-consistent Hartree-Fock + Tamm-Dancoff approximation taking into account the coupling to the continuum. Most of SD strength is found at the excitation energy E _x≈ 25MeV with a very broad width, which agrees with recent experimental observations. It is shown that Landau damping effect is responsible for the large width of SD peak, while the escape width is found to be at most 1MeV. We study also electric dipole (E1) transitions between GT and SD states in ²⁰⁸Bi. Main E1 transitions for 0^- and 1^- states are found near excitation energy expected from Brink's hypothesis in which SD states are considered as E1 resonances built on the GT state. Calculated E1 transition strengths between GT and SD states are compared with the analytic sum rules within one-particle one-hole (1p-1h) configuration space and within both 1p-1h and 2p-2h model space. Received: 11 April 2000 / Accepted: 30 August 2000     

Sinusoidal Phase-Modulating Superluminescent Diode Interferometer with Fabry-Perot Etalone for Step-Profile Measurement

In this paper we use a superluminescent diode (SLD) as the light source of an interferometer and extract a narrow spectrum from a wide spectrum of the SLD with a Fabry-Perot Etalone (FPE). By varying sinusoidally the distance between the two mirrors of FPE, the central wavelength of the narrow spectrum is scanned sinusoidally. The distance between the mirrors is exactly set by a feedback control system, and sinusoidal phase-modulated SLD light that has a large scanning width of about 10 nm can be obtained with high stability and spatial uniformity. The phase of the interference signal has two different components. One is amplitude Z_b of sinusoidal phase modulation, which is proportional to the optical path difference (OPD) and the scanning width. The other is conventional phase α, which provides a fractional value of the OPD in the range of the wavelength. By combining the two values of the OPD obtained from Z_b and α, an exact OPD larger than the wavelength can be measure with ment accuracy in α. Characteristics of the interferometer are made clearly through step-profile measurements.     

Direct Monitoring of Thickness and Refractive Index of Optical Thin Film Deposited on Fiber End-face

We propose a system for depositing thin films on waveguides which enables low-temperature deposition and precise control of the refractive index and film thickness. It is composed of a conventional ion-beam sputtering (IBS) system and a new system for directly monitoring film characteristics during deposition. We controlled refractive indices over a wide range from 1.52 to 1.97 by moving the sputtering targets (SiO₂ and Si₃N₄) in the IBS system. The refractive index or film thickness was in-situ monitored by observing the optical power reflected from the end-face of a monitoring fiber set in the deposition chamber. Antireflection coating films were successfully deposited on a fiber end-face and a laser diode chip facet with low reflectivity from 0.05 to 0.07%. This deposition system is attractive for constructing highly functional optical devices for future photonic networks.     

Direct conversion to 2-phenyl-4-quinolones via a 4-alkoxyflavylium salt from a naturally occurring flavanone

A flavanone, in which a hydroxyl group at the 5-position was protected with a methyl group, converted to the corresponding 5-methoxy-2-phenyl-4-quinolone via flavylium salt under mild conditions. Flavanone-O-rhamnoglucoside, naringin, was also converted to 5-methoxy-2-phenyl-4-quinolon-7-O-rhamnoglucoside in the same way in an overall 25% yield.     

A theoretical study of the dehydration and the dehydrogenation processes of alcohols on metal oxides using MOPAC

Using a semi-empirical molecular orbital method, PM3, and 2-propanol as an example, the dehydration and the dehydrogenation processes of alcohol on oxide catalysts were studied. The catalysts addressed here were four kinds of oxides (Al₂O₃, SiO₂, ZnO, CdO) whose reaction selectivities had been experimentally determined. The usual models consisting of a surface metal ion, several oxide ions and an isopropoxy group were used in calculations. For the dehydration, heats of formation of the models were calculated at each point of the process where the distance between a β-hydrogen of the group and a basic site (i.e. oxygen of the group or a surface oxide ion) or a metal ion was gradually shortened, or where the length of the C–O bond of the group was gradually increased. A reasonable dehydration mechanism was estimated by comparing activation energies calculated from the transitions of the heats of formation. The most probable dehydrogenation mechanism was also estimated in a similar way by gradually making an -hydrogen close to a surface oxide ion, the metal ion or a surface proton. It was concluded that the dehydration proceeds by scission of the C–O bond of the group after its oxygen was attacked by some electrophile on the surface and that the dehydrogenation proceeds by a mechanism in which an -hydrogen of the group was extracted by the metal ion.

Based on the dehydration mechanism thus deduced, alkoxy groups generated by adsorption of the primary, secondary and tertiary alcohols on SiO₂ were calculated in order to estimate the activation energies of their decompositions. In result, the order of the energies was found to be in good agreement with that of the decomposition rates experimentally determined by Kitahara. This agreement gives support to the validity of the mechanism deduced for the dehydration of alcohol.     

Photoemission study of Ag nanofilm grown on pseudomorphic fcc Fe(1 0 0)

An angle-resolved photoemission study for Ag nanofilm grown on pseudomorphic metastable-fcc-phase Fe(1 0 0) has been done in order to investigate in detail the quantized electronic structures. From the low-energy electron-diffraction and angle-resolved photoemission spectra, it is found that the present Ag nanofilms were grown in the direction of [1 1 1] on pseudomorphic fcc Fe(1 0 0) substrates. The angle-resolved photoemission spectra of Ag nanofilms grown on pseudomorphic fcc Fe(1 0 0) exhibit the features derived from Shockley-type surface state and additional fine-structures derived from the quantized state of Ag sp valence electron. The experimental nanofilm-thickness dependence of binding energies of these quantized states is compared with the theoretical calculation based on the phase accumulation model, taking into account the phase shifts of electron reflection at both interfaces of the Ag nanofilm. From these results, we discuss the quantized electronic structure in Ag nanofilm grown on pseudomorphic fcc Fe(1 0 0).     

Spin polarization of β-emitting fragments in high energy heavy ions on Be collisions

The degrees of nuclear spin polarization of ^8,12B, ⁹C, ¹²N, ¹³O, ^20,21F, ²³Mg, ²⁷Si and ³⁹Ca produced in the high energy ^12,13C, ¹⁶O, ²²Ne, ²⁴Mg, ²⁸Si and ⁴⁰Ca ions on Be collisions have been measured systematically, for the technical developments of the nuclear moment studies as well as the hyperfine interaction studies by means of β-NMR technique. The fragment momentum dependences were well reproduced by the simple kinematical model. Incident energy dependence and the mass dependence as well as the reaction angle dependences were qualitatively explained by the mixing of the near and far side collisions. This revised version was published online in August 2006 with corrections to the Cover Date.