A naphtho-tri-t-butyltrisdehydro[16]annulene and related compounds

Synthesis of naphtho-tri-t-butyltrisdehydro[16]annulene containing a hexapentaene and an acetylene units has been described. It was found that the [16]annulene is less stable and the paratropicity is much stronger as compared with previously reported isomeric naphtho[16]-annulene containing a diacetylene and a butatriene linkage.     

Slow neutron scattering and intermolecular excitations in liquid hydrogen

A simple analytical model for inelastic neutron scattering in liquid hydrogen with the effects of delayed diffusion and intermolecular vibrations with a single frequency parameter is proposed. Calculated results show good agreements with experimental results of total and differential scattering cross sections as well as the energy spectra of neutrons in liquid hydrogen moderators, and thus indicate the importance of the consideration of intermolecular excitations in the dynamics of liquid hydrogen.     

Charge-order pattern of the low-temperature phase from a monoclinic single domain of NaV2O5 uniquely determined by resonant x-ray scattering

The present resonant x-ray scattering has been performed on a monoclinically split single domain of NaV(2)O(5). The observation of a critically enhanced contrast between V(4+) and V(5+) ions has led us to the unequivocal conclusion of the charge-order pattern of the low-temperature phase of NaV(2)O(5) below T(c) = 35 K. In spite of the possible four types of configuration of the zigzag-type charge-order patterns in the ab plane (A,A',B and B'), the stacking sequence along the c axis is determined as the AAA'A' type by comparison with model calculations.     

Direct imaging of the alkali metal site in K-doped fullerene peapods

The structure of K-doped fullerene peapods has been investigated by means of high-resolution transmission electron microscopy and electron energy-loss spectroscopy (EELS). It is proven that the potassium atoms can be doped at the intermolecular sites within C60 peapods. The EELS spectrum of potassium (K) L edge clearly exhibits the feature of K+ in the doped peapod and consequently suggests n-type doping. These results encourage the realization of a one-dimensional superconducting wire based on the nanotube peapods.     

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.     

Unambiguous detection of target DNAs by excimer-monomer switching molecular beacons

A new class of molecular beacons were developed in which pyrene fluorophores were connected both at 3' and 5' ends of a single-stranded oligonucleotide. The two pyrene-based fluorophores were synthesized from the same starting material, so that the preparation of the beacons was simplified. The detection strategy of the beacons for target DNAs is based on "excimer-monomer emission switching" of the pyrene fluorophores: excimer emission of the pyrene moieties changed to monomer one when the beacons hybridized with the targets. This type of two-state mode of fluorescence allows unambiguous detection of the target DNAs because strict 1:1 correlation between the nonhybridized and the hybridized beacons can be monitored by the presence of isoemissive points of the fluorescence changes. The beacons can detect target 19-mer DNAs and can discriminate the targets from their single-nucleotide mismatches at 1 nM concentration. Advantages of the excimer-monomer switching molecular beacons were discussed in comparison with conventional ones.     

Interactions of enzymes and a lectin with a chitin-based graft copolymer having polysarcosine side chains

The molecular-recognition abilities of a water-soluble chitin derivative, chitin-graft-polysarcosine (2) were investigated using chitinase, lysozyme, and wheat germ agglutinin (WGA). The enzymatic degradabilities of 2 were evaluated using chitinase and lysozyme. The molecular weight of those compounds of 2 with a higher affinity toward water decreased rapidly, as compared with partially deacetylated chitin (1). The 1H NMR spectrum of the low-molecular-weight fraction, yielded after lysozymic hydrolysis, indicated that saccharide residues in the chitinous backbone were specifically recognized by the lysozyme, then beta-glycosidic linkages in the backbone were selectively hydrolyzed. Furthermore, the molecular-recognition ability of the chitinous backbone of graft copolymer 2 toward the lectin WGA was elucidated by the enzyme-linked lectin-binding assay (ELLA). It was revealed that the graft copolymer with a lower degree of substitution (DS) value efficiently interacted with WGA. Interestingly, a graft copolymer having longer polysarcosine side chains showed higher recognition ability toward WGA than that having short side chains.     

Vibration analysis on electromagnetic-resonance-ultrasound microscopy (ERUM) for determining localized elastic constants of solids

In this paper we present a new acoustic-resonance microscopy, Electromagnetic-Resonance-Ultrasound Microscopy (ERUM), to measure the localized elastic stiffness of a solid material. It visualizes the resonance-frequency shift of vibrating piezoelectric crystal (langasite, La3Ga5SiO14) excited by an electric field from a solenoid coil. The acoustic coupling is made only at the tip of the crystal touching the specimen surface. Being based on the calibration for the specimen's effective stiffness, the local elasticity is determined from the resonance frequencies of the crystal with the Rayleigh-Ritz method. An approximate model for the specimen's effective stiffness predicts the shift of resonance frequencies, for which the conventional Hertz-contact model is improved. As an illustrating example, the mapping of Young's modulus of a duplex stainless steel is presented, which shows good agreement with the existing study.     

Non-destructive analysis of the two subspecies of African elephants, mammoth, hippopotamus, and sperm whale ivories by visible and short-wave near infrared spectroscopy and chemometrics

Visible (VIS) and short-wave near infrared (SW-NIR) spectroscopy was used for non-destructive analysis of ivories. VIS-SW-NIR (500-1000 nm) spectra were measured in situ for five kinds of ivories, that is two subspecies of African elephants, mammoth, hippopotamus, and sperm whale. Chemometrics analyses were carried out for the spectral data from 500 to 1000 nm region. The five kinds of ivories were clearly discriminated from each other on the scores plot of two principal components (PCs) obtained by principal component analysis (PCA). It was noteworthy that the ivories of the two subspecies of African elephants were discriminated by the scores of PC 1. The loadings plot for PC 1 showed that the discrimination relies on the intensity changes in bands due to collagenous proteins and water interacting with proteins. It was found that the scores plot of PC 2 is useful to distinguish between the ivories of the two subspecies of African elephants and the other ivories. We also developed a calibration model that predicted the specific gravity of five kinds of ivories from their VIS-SW-NIR spectral data using partial least squares (PLS)-1 regression. The correlation coefficient and root mean square error of cross validation (RMSECV) of this model were 0.960 and 0.037, respectively.