Second Harmonic Generation in Bis Typed Organic Compounds

In systematic research on a series of new nonlinear organic materials, we found that Bis (4-nitrophenoxy) methane (BNPM) showed a large intensity of second harmonic light, which was 4.4 times as large as that of urea crystal by powder technique and easily crystallized from a solution. The crystal structure of BNPM, obtained by the X-ray diffraction method, was orthorhombic, space group P2₁2₁2 (point group 222), with unit-sell dimension a = 10.205 Å; b = 12.854 Å; c = 4.8822 Å. In addition, we found that the absorption edge of BNPM was 430 nm with a 0.9-mm-thick crystal, and we observed the second harmonic light with BNPM single crystal at the wavelength of 1064 nm and in the range from 906 nm to 990 nm.     

A charge-transfer host system composed of a chiral 1,1′-bi-2-naphthol cluster and benzylviologen

Chiral charge-transfer (CT) complexes composed of a chiral 1,1′-bi-2-naphthol cluster as the electron donor and 1,1′-dibenzyl-4,4′-bipyridinium dichloride as the electron acceptor serve as a host system for molecular recognition. CT complexes that include guest alcohols show different diffuse reflectance spectra (DRS) depending on the included guest.     

Supported lipid bilayer formation by the giant vesicle fusion induced by vesicle–surface electrostatic attractive interaction

The effect of the electrostatic attractive force between giant unilamellar vesicles (GUVs) and the SiO₂ surface on the formation of a Ca²⁺-free supported lipid bilayer (SLB) was investigated by atomic force microscopy and fluorescence microscopy. When negatively charged GUVs were incubated for 1 h without Ca²⁺, the surface coverage of lipid bilayer was <1% on the SiO₂ surface. In contrast, a high coverage was obtained without addition of Ca²⁺ on the positively charged surface modified by aminopropyldimethylethoxysilane, and the coverage of SLBs decreased with increasing KCl concentrations. The thickness of the water layer under SLB was reduced by modification of APS.     

Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization

Polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) was successfully synthesized through the combination of metallocene catalysis with living radical polymerization. Terminally hydroxylated polyethylene, prepared by ethylene/allyl alcohol copolymerization with a specific zirconium metallocene/methylaluminoxane/triethylaluminum catalyst system, was treated with 2‐bromoisobutyryl bromide to produce terminally esterified polyethylene (PE‐Br). With the resulting PE‐Br as an initiator for transition‐metal‐mediated living radical polymerization, methyl methacrylate polymerization was subsequently performed with CuBr or RuCl₂(PPh₃)₃ as a catalyst. Then, PE‐b‐PMMA block copolymers of different poly(methyl methacrylate) (PMMA) contents were prepared. Transmission electron microscopy of the obtained block copolymers revealed unique morphological features that depended on the content of the PMMA segment. The block copolymer possessing 75 wt % PMMA contained 50–100‐nm spherical polyethylene lamellae uniformly dispersed in the PMMA matrix. Moreover, the PE‐b‐PMMA block copolymers effectively compatibilized homopolyethylene and homo‐PMMA at a nanometer level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3965–3973, 2003     

Selective retention of some polyaromatic hydrocarbons by highly crosslinked polymer networks

Highly crosslinked polymer networks were characterized in terms of structural differences based on the crosslinked network structures with their chromatographic molecular retentivity for some polyaromatic hydrocarbons (PAHs). Because PAHs and some sterically bulky solutes were used in the chromatographic characterization, tiny differences in the crosslinked polymer networks were observed in terms of the chromatographic molecular retentivity. Ethylene dimethacrylate afforded molecular retentivity for anthracene, and this recognition ability changed with the polymerization time. In addition, 1,4‐butanediol dimethacrylate afforded molecular retentivity for pyrene, and this retentivity was larger than that for anthracene. The polymerization methods also affected the resulting polymer networks drastically. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2556–2566, 2005     

Asymptotic distribution of maximal autoregressive process with weight tending to 1

The maximal operator plays the similar role as the summation operator in the sense of stability of operation. So, we could discussARMA processes in the maximal operation by the same way as in the summation operation. However, many papers already treated with moving order statistics. In this paper, we discuss asymptotic behaviors of maximal autoregressive (MAR) processes with the weight tending to 1.     

Development and features of hydro-membrane gas chromatography.

Hydro-membrane gas chromatography (HMGC) is achieved by the annular condensation of water in a capillary column at less than 70 degrees C. The annular membrane of water is formed as a result of the wettability of the stationary phase, which is induced at a water contact angle ranging from 75 degrees to 79 degrees, as derived from a solubility parameter (delta) range of 15.7 +/- 0.3 MPa(1/2) of the coated resin. The range of the liquid to gas volume ratio (beta) required to support the annular membrane should be kept between 0.00005 and 0.0003. In the case of a 0.25-mm i.d. column, the ratio can be set by the combination of a 0.1 to 0.2 microl min(-1) water supply rate and helium gas flow rate. Separation by HMGC develops not only a gas-solid partition but also a focusing effect on the water membrane. One feature of HMGC is that it gives a non-adsorption chromatogram based on the blocking effect of pre-adsorbed water; furthermore, despite the presence of a relatively large quantity of water, the electron impact ionization efficiency is kept the same as in the usual GC/MS condition. The detection limit with the injection of 1 microl of aquatic solution was estimated to be less than 0.1 ppb of low-molecular-weight fatty acids with s/n = 5 on a mass chromatogram at m/z 45. The HMGC/EI-MS system can be applied to the trace analysis of C1 to C3 volatile acids, volatile inorganic acids, and halogenated organic acids in water.     

Highly efficient formation of metal and metal alloy particles from methyl metal compounds by a single pulse laser irradiation

Highly efficient processes for fine particle formation of metal alloys and metal oxides were developed using a high-power laser. In these processes, laser light was used only for the ignition of a thermal chain reaction. This reaction was suppressed by adding inert gases, and the suppression effect was in the order C₃H₈ > C₂H₆ > CH₄ > He > Ar > Xe. Oxygen accelerated the reaction because of the large exothermicity of the reaction of oxygen with methyl metal compounds.     

Conversion of molecular information by luminescent nanointerface self-assembled from amphiphilic Tb(III) complexes

A novel amphiphilic Tb(3+) complex (TbL(+)) having anionic bis(pyridine) arms and a hydrophobic alkyl chain is developed. It spontaneously self-assembles in water and gives stable vesicles that show sensitized luminescence of Tb(3+) ions at neutral pH. This TbL(+) complex is designed to show coordinative unsaturation, i.e., water molecules occupy some of the first coordination spheres and are replaceable upon binding of phosphate ions. These features render TbL(+) self-assembling receptor molecules which show increase in the luminescence intensity upon binding of nucleotides. Upon addition of adenosine triphosphate (ATP), significant amplification of luminescent intensity was observed. On the other hand, ADP showed moderately increased luminescence and almost no enhancement was observed for AMP. Very interestingly, the increase in luminescence intensity observed for ATP and ADP showed sigmoidal dependence on the concentration of added nucleotides. It indicates positive cooperative binding of these nucleotides to TbL(+) complexes preorganized on the vesicle surface. Self-assembly of amphiphilic Tb(3+) receptor complexes provides nanointerfaces which selectively convert and amplify molecular information of high energy phosphates linked by phosphoanhydride bonds into luminescence intensity changes.     

Polarized near-edge x-ray-absorption fine structure spectroscopy of C60-functionalized 11-amino-1-undecane thiol self-assembled monolayer: molecular orientation and evidence for C60 aggregation

Near-edge x-ray-absorption fine structure (NEXAFS) spectroscopy was adopted to probe the unoccupied electronic states of C60 anchored onto an organized assembly of 11-amino-1-undecane thiol on Au(111). The polarization dependence of the intensity of pi* resonance associated with C60 pi network revealed the self-assembled monolayer (SAM) system to be oriented with an average molecular tilt angle of 57 degrees with respect to the surface normal. Invoking the absence of solid-state band dispersion effects and in comparison to solid C60 and /or 1-ML C60/Au(111), the electronic structure of the resulting assembly was found dominated by spectral position shift and linewidth and intensity changes of the lowest unoccupied molecular orbital (LUMO), LUMO+1, and LUMO+2 orbitals. The latter implied hybridization between N Pz of -NH2 group of thiolate SAM and pi levels of C60, resulting in a nucleophilic addition with a change in the symmetry of C60 from Ih to C1 in the SAM. Occurrence of a new feature at 285.3 eV in the NEXAFS spectrum, assigned previously to pi* graphitic LUMO, signified the formation of aggregated clusters, (C60)n of C60 monomer. Low tunneling current scanning tunneling microscopy confirmed them to be spherical and stable aggregates with n approximately 5.