Surfactant-mixing effects on the interfacial tension and the microemulsion formation in water/supercritical CO2 system

The effects of surfactant mixing on interfacial tension and on microemulsion formation were examined for systems of air/water and water/supercritical CO2 (scCO2) interfaces and for water/scCO2 microemulsions. A fluorinated surfactant, sodium bis(1H,1H,2H,2H-heptadecafluorodecyl)-2-sulfosuccinate (8FS(EO)2), was mixed with the three hydrocarbon surfactants, Pluronic L31, Tergitol TMN-6, and decyltrimethylammonium chloride (DeTAC), at equimolar ratio. For all the cases, the interfacial tension was significantly lowered by the mixing. The positive synergistic effect suggests that the mixed surfactants tend to pack more closely on the interface than the pure constituents. It was found, however, that the microemulsion formation in scCO2 was never facilitated by the mixing, except for the case of TMN-6. This is probably due to the segregation of the surfactants into hydrocarbon-rich and fluorocarbon-rich phases on the microemulsion surface.     

Highly specific affinities of short peptides against synthetic polymers

We investigated polymer-binding 7-mer peptides that recognize differences in the polymer stereoregularity of all-purpose poly(methyl methacrylate)s (PMMAs) with simple chemical structures. Quantitative surface plasmon resonance measurements detected association/dissociation processes of the peptides against PMMA film surfaces, followed by an estimation of kinetic parameters such as association/dissociation rate constants and affinity constants. Greater association and smaller dissociation constants of the peptides were observed against a target isotactic PMMA than the structurally similar reference syndiotactic PMMA, followed by greater affinity constants against the target. A c02 peptide composed of the Glu-Leu-Trp-Arg-Pro-Thr-Arg sequence showed the greatest affinity constant (2.8x10(5) M(-1)) for the target, which was 41-fold greater than that for the reference, thus demonstrating extremely high peptide specificities. The substitution of each amino acid of the c02 peptide to Ala (Ala scanning) clearly revealed the essential amino acids for the affinity constants; the essential order was Pro5>Thr6>Arg7>Glu1>Arg4. In fact, the shorter 4-mer peptide composed of the C-terminal Arg-Pro-Thr-Arg sequence of the c02 peptide still demonstrated strong target specificity, although the N-terminal 4-mer peptide Glu-Leu-Trp-Arg completely lost its specificity. The possible conformations modeled with Molecular Mechanics supported the significance of the Arg-Pro-Thr-Arg sequence. The thermodynamic parameters of the c02 peptide suggested an induced fit mechanism for the specific affinity. The present affinity analyses of polymer-recognizing peptides revealed significant and general information that was essential for potential applications in peptidyl nanomaterials.     

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.     

Application of Solid Immersion Lens to Submicron Resolution Imaging of Nano-Scale Quantum Wells

We have discussed the resolution of submicron photoluminescence (PL) imaging using a solid immersion lens (SIL), which collects an evanescent light field. We apply the SIL microscope to measure PL image of a strip-line-patterned GaAs quantum well structure at low temperature. An improved resolution beyond diffraction limit and high collection efficiency of PL are realized.This paper was originally presented at the 5th International Conference on NEAR FIELD OPTICS and RELATED TECHNOLOGIES (NFO-5), which was held on December 6–10, 1998 at Coganoi Bay Hotel, Shirahama, Japan, in cooperation with the Japan Society of Applied Physics and Mombusho Grant-in Aid for Scientific Research on Priority Areas “Nearfield Nano-optics” Project, sponsored by Japan Society for the Promotion of Science.     

Biological properties of opioid peptides replacing Tyr at position 1 by 2,6-dimethyl-Tyr.

To understand the effect of the replacement of Tyr residue at position 1 in opioid peptides by 2,6-dimethyl-Tyr (Dmt) on the biological property, chiral (D or L) Dmt1 analogs of Leu-enkephalin (Enk) and Tyr-D-Arg-Phe-beta Ala-NH2 (YRFB) were synthesized and their enzymatic stabilities, in vitro bioactivities and receptor binding affinities compared with those of parent peptides. [L-Dmt1]Enk (1) exhibited 4-fold higher stability against aminopeptidase-M and possessed dramatically increased activities in guinea pig ilium (GPI) (187-fold) and mouse vas deferens (MVD) (131-fold) assays, and in rat brain receptor binding assays (356-fold at mu receptor and 46-fold at delta receptor) as compared to Enk. [L-Dmt1]YRFB (3) also exhibited increased activities in GPI (46-fold) and MVD (177-fold) assays, and in the binding assays (69-fold at mu receptro and 341-fold at delta receptor) as compared to the parent peptide. [D-Dmt1]Enk (2) and [D-Dmt1]YRFB (4) exhibited activities with diminished or lesser potency than the parent peptide in all assays. These results indicate that there is a tendency for mu affinity to be enhanced more than delta affinity with introduction of L-Dmt into delta ligand peptide (Enk), and for delta affinity to be enhanced more than mu affinity in case of mu ligand peptide (YRFB), resulting in reduced receptor selectivities at the receptors.     

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.     

Synthesis of hybrid resins via polysiloxane with methacryloyloxy groups

A polysiloxane derivative with methacryloyloxy groups (MPS) that was obtained from the reaction of polymeric tributylstannyl ester of silicic acid and (3‐methacryloyloxypropyl)dimethylchlorosilane was demonstrated to be a useful inorganic component for the preparation of organic–inorganic hybrid resins as nanocomposites. The copolymerizations of MPS with common monomers such as styrene, acrylonitrile, and methyl methacrylate proceeded readily at room temperature under UV irradiation to give the corresponding resins in good yields. The resins obtained from MPS and methyl methacrylate showed good transparency, hardness in a scratch test, and resistance to toluene but had poor flexibility. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1–7, 2001     

Amphiphilic block and statistical copolymers with pendant glucose residues: Controlled synthesis by living cationic polymerization and the effect of copolymer architecture on their properties

Amphiphilic block and statistical copolymers of vinyl ethers (VEs) with pendant glucose residues were synthesized by the living cationic polymerization of isobutyl VE (IBVE) and a VE carrying 1,2:5,6‐di‐O‐isopropylidene‐D ‐glucose (IpGlcVE), followed by deprotection. The block copolymer was prepared by a two‐stage sequential block copolymerization, whereas the statistical copolymer was obtained by the copolymerization of a mixture of the two monomers. The monomer reactivity ratios estimated with the statistical copolymerization were r₁ (IBVE) = 1.65 and r₂ (IpGlcVE) = 1.15. The obtained statistical copolymers were nearly uniform with the comonomer composition along the main chain. Both the block and statistical copolymers had narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight ∼ 1.1). Gel permeation chromatography, static light scattering, and spin–lattice relaxation time measurements in a selective solvent revealed that the block copolymer formed multimolecular micelles, possibly with a hydrophobic poly(IBVE) core and a glucose‐carrying poly(VE) shell, whereas the statistical copolymer with nearly the same molecular weight and segment composition was molecularly dispersed in solution. The surface properties of the solvent‐cast films of the block and statistical copolymer were also investigated with the contact‐angle measurement. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 459–467, 2001     

Structural analysis of polyhydroxyurethane obtained by polyaddition of bifunctional five‐membered cyclic carbonate and diamine based on the model reaction

This article focuses on the structural analysis of polyhydroxyurethane obtained by the reaction of 2,2‐bis[p‐(1,3‐dioxolan‐2‐one‐4‐yl‐methoxy)phenyl]propane with a diamine based on the model reaction. The compounds obtained in the model reaction could be separated into hydroxyurethanes containing primary and secondary alcohol groups by preparative gel permeation chromatography with a recycling technique to determine the structures by ¹H NMR, ¹³C NMR, distortionless enhancement by polarization transfer (DEPT) and C H correlation spectroscopy to obtain hydroxyurethane carrying the primary alcohol structure moiety dominantly. The ratios were independent of the reaction temperature but somewhat dependent on the solvents and amines. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 851–859, 2001