Sidewall functionalization of single-walled carbon nanotubes through electrophilic addition

Electrophilic addition of chloroform to SWNTs followed by hydrolysis resulted in the addition of hydroxy groups to the surface of the nanotubes; further esterification with propionyl chloride led to the corresponding ester derivatives, which allowed us to identify their structure, also providing better solubility in organic solvents.     

Ultrasonic butt welding of aluminum,aluminum alloy and stainless steel plate specimens

Welding characteristics of aluminum, aluminum alloy and stainless steel plate specimens of 6.0 mm thickness by a 15 kHz ultrasonic butt welding system were studied. There are no detailed welding condition data of these specimens although the joining of these materials are required due to anticorrosive and high strength characteristics for not only large specimens but small electronic parts especially. These specimens of 6.0 mm thickness were welded end to end using a 15 kHz ultrasonic butt welding equipment with a vibration source using eight bolt-clamped Langevin type PZT transducers and a 50 kW static induction thyristor power amplifier. The stainless steel plate specimens electrolytically polished were joined with welding strength almost equal to the material strength under rather large vibration amplitude of 25 microm (peak-to-zero value), static pressure 70 MPa and welding time of 1.0-3.0 s. The hardness of stainless steel specimen adjacent to a welding surface increased about 20% by ultrasonic vibration.     

Determination of optical isomers for left-handed or right-handed chiral double-wall carbon nanotubes

The handedness relationship between adjacent layers in nested double-wall carbon nanotubes (DWNTs) has been investigated for the first time. Our high-resolution electron microscopy analysis on a series of specimen tilts can successfully tell the handedness of each constituent nanotube in a DWNT, and therefore the chiral indices (n, m) including their optical isomers [(n, m) or (m, n)] of inner and outer nanotubes can be uniquely determined. It is shown that right-handed and left-handed nanotubes are equally distributed for both the inner and outer nanotubes in the examined specimens and a preferable handedness relationship between the adjacent layers in DWNT may exist.     

Direct observation of excitons and a continuum of one-dimensional Mott insulators: a reflection-type third-harmonic-generation study of Ni-halogen chain compounds

The third-harmonic-generation (THG) spectrum was measured for a NiBr-chain compound, which is a one-dimensional Mott insulator, in a reflection configuration. A sharp peak and a shoulder structure in the THG spectrum are attributed to three-photon resonance to an exciton and a continuum, respectively. The band-edge energy, the exciton binding energy, and the spectral weights for the exciton and the continuum were determined from comparative studies of linear absorption, THG, and electroreflectance spectra. The excitonic effect is more pronounced in the NiCl chain than in the NiBr chain.     

A convenient synthesis of the beraprost intermediate: a useful method for introducing a C3 unit at the benzyl position

[reaction: see text] The Heck reaction is a more efficient and reliable method than previous ones for introducing a C3 unit at the benzyl position for the synthesis of Beraprost. Especially, trialkylated long-chain amines such as (n-C(8)H(17))(3)N and (n-C(12)H(25))(3)N resulted in good yields. This development will be used for the industrial synthesis of Beraprost.     

Pentagonal-Dodecahedral La2 Charge Density in [80-Ih]Fullerene: La2@C80

No Abstract     

Metallic behavior and periodical valence ordering in a MMX chain compound, Pt(2)(EtCS(2))(4)I.

A new one-dimensional (1-D) halogen-bridged mixed-valence diplatinum(II,III) compound, Pt(2)(EtCS(2))(4)I (3), has been successfully synthesized from [Pt(2)(EtCS(2))(4)] (1) and [Pt(2)(EtCS(2))(4)I(2)] (2). These three compounds have been examined using UV-visible-near-IR, IR, polarized Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray crystal structure analyses (except for 1). Compound 3 was further characterized through electrical transport measurements, determination of the temperature dependence of lattice parameters, X-ray diffuse scattering, and SQUID magnetometry. 3 crystallizes in the monoclinic space group C2/c and exhibits a crystal structure consisting of neutral 1-D chains with a repeating -Pt-Pt-I- unit lying on the crystallographic 2-fold axis parallel to the b axis. The Pt-Pt distance at 293 K is 2.684 (1) A in the dinuclear unit, while the Pt-I distances are essentially equal (2.982 (1) and 2.978 (1) A). 3 shows relatively high electrical conductivity (5-30 S cm(-1)) at room temperature and undergoes a metal-semiconductor transition at T(M-S) = 205 K. The XPS spectrum in the metallic state reveals a Pt(2+) and Pt(3+) mixed-valence state on the time scale of XPS spectroscopy ( approximately 10(-17) s). In accordance with the metal-semiconductor transition, anomalies are observed in the temperature dependence of the crystal structure, lattice parameters, X-ray diffuse scattering, and polarized Raman spectra near T(M-S). In variable-temperature crystal structure analyses, a sudden and drastic increase in the Pt-I distance near the transition temperature is observed. Furthermore, a steep increase in U(22) of iodine atoms in the 1-D chain direction has been observed. The lattice parameters exhibit significant temperature dependence with drastic change in slope at about 205-240 K. This was especially evident in the unit cell parameter b (1-D chain direction) as it was found to lengthen rapidly with increasing temperature. X-ray diffraction photographs taken utilizing the fixed-film and fixed-crystal method for the metallic state revealed the presence of diffuse scattering with line shapes parallel to the a* axis indexed as (-, n + 0.5, l) (n; integer). Diffuse scattering with k = n + 0.5 is considered to originate from the 2-fold periodical ordering corresponding to -Pt(2+)-Pt(2+)-I-Pt(3+)-Pt(3+)-I- or -Pt(2+)-Pt(3+)-I-Pt(3+)-Pt(2+)-I- in an extremely short time scale. Diffuse lines corresponding to 2-D ordering progressively decrease in intensity below 252 K and are converted to the diffuse planes corresponding to 1-D ordering near T(M-S). Furthermore, diffuse planes condensed into superlattice reflections below T(M-S). Polarized Raman spectra show temperature dependence through a drastic low-energy shift of the Pt-I stretching mode and also through broadening of bands above T(M-S).     

Mechanism of alternating copolymerization of 4-hydroxy-4′-vinylbiphenyl with α-chloromaleic anhydride

The copolymerization of 4-hydroxy-4′-vinylbiphenyl (HVB) with α-chloromaleic anhydride (CMAn) was investigated in THF, 1,4-dioxane, and acetonitrile. The formation of the 1:1 charge transfer complex between HVB and CMAn was confirmed spectroscopically, and the corresponding equilibrium constant (K_eq) was determined as follows: K_eq = 0.19, 0.11, and 0.058 mol/L in THF, 1,4-dioxane, and CH₃CN, respectively. The copolymer composition is affected by the solvent, i.e., the content of HVB in the copolymer obtained in THF or 1,4-dioxane is lower than 50 mol % whereas the copolymer obtained in CH₃CN has excess of HVB units. The maximum rate of copolymerization was observed at a 1:1 initial comonomer mole ratio, irrespective of the solvent polarity. Plots of R_p/[HVB] vs. [HVB] gave a straight line with a slope and an intercept for the copolymerization in THF whereas a straight line in CH₃CN has no slope. On the basis of these results and ¹³C-NMR spectra of the copolymers, the mechanism of the predominant formation of alternating copolymers is discussed.