Fluorous-tagged indolylboron for the diversity-oriented synthesis of biologically-attractive bisindole derivatives

The diversity-oriented synthesis of bisindole derivatives to construct concise libraries using consecutive cross-coupling reactions and prepare new sulfonamide type fluorous protecting groups is presented.     

Study on suitability of KOD DNA polymerase for enzymatic production of artificial nucleic acids using base/sugar modified nucleoside triphosphates

Recently, KOD and its related DNA polymerases have been used for preparing various modified nucleic acids, including not only base-modified nucleic acids, but also sugar-modified ones, such as bridged/locked nucleic acid (BNA/LNA) which would be promising candidates for nucleic acid drugs. However, thus far, reasons for the effectiveness of KOD DNA polymerase for such purposes have not been clearly elucidated. Therefore, using mutated KOD DNA polymerases, we studied here their catalytic properties upon enzymatic incorporation of nucleotide analogues with base/sugar modifications. Experimental data indicate that their characteristic kinetic properties enabled incorporation of various modified nucleotides. Among those KOD mutants, one achieved efficient successive incorporation of bridged nucleotides with a 2'-ONHCH?CH?-4' linkage. In this study, the characteristic kinetic properties of KOD DNA polymerase for modified nucleoside triphosphates were shown, and the effectiveness of genetic engineering in improvement of the enzyme for modified nucleotide polymerization has been demonstrated.     

Resonant two photon spectrum in a Doppler broadened line

The line shape in the resonant and near resonant two photon absorption spectra in the $\text{Na 3S}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{?3P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{?5S}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ transition was investigated using two single frequency dye lasers. Two types of Doppler-free peaks for resonant case and Doppler-broadened normal two photon peaks were observed. They were different in the width, selection rule and the laser power dependence in agreement with theory.     

Thermally induced changes in amorphous indium-tin-oxide thin films

Amorphous indium-tin-oxide (ITO) transparent conducting film (15 at% Sn; thickness, 150–190 nm) was deposited on silicon wafer at room temperature by RF magnetron sputtering for temperature programmed desorption (TPD) in vacuum. The thermal crystallization was accompanied by evolution of water vapor (the main gas), argon and carbon dioxide. The total amount of evolved water vapor (H₂O [mol]/(In [mol]+Sn [mol])>0.2) was one or two orders of magnitude more than that from the nanocrystalline ITO films reported in our previous papers. The thermal change of amorphous ITO film was remarkably affected by the position of the substrate. An abrupt gas evolution was characteristic of the amorphous ITO films deposited on the position near the target center. The evolution temperature (548–563 K) was higher than the gas evolution temperature from the crystalline films. The far from center positioned films crystallized at higher temperature with relatively slower evolution of the gases.     

Infrared reflection absorption spectroscopic study of the adsorption structures of dimethyl ether and methyl ethyl ether on Cu(1 1 1) and Ag(1 1 1)

Infrared reflection absorption (IRA) spectra measured for dimethyl ether (DME) adsorbed at 80 K on Cu(1 1 1) and Ag(1 1 1) give IR bands belonging only to the A₁ and B₂ species, indicating that the adsorbate takes on an orientation in which the C₂ axis bisecting the COC bond angle tilts away from the surface normal within the plane perpendicular to the substrates. The DFT method was applied to simulate the IRA spectra, indicating that the tilt angles of DME on Cu(1 1 1) and Ag(1 1 1) are about 50° and 55°, respectively, at submonolayer coverages. The results are in contrast to the case of DME on Cu(1 1 0) and Ag(1 1 0), where the C₂ axis is perpendicular to the substrates [T. Kiyohara et al., J. Phys. Chem. A 106 (2002) 3469]. Methyl ethyl ether (MEE) adsorbed at 80 K on Cu(1 1 1) gives IRA bands mainly ascribable to the gauche (G) form, whereas the IRA spectra measured for MEE on Ag(1 1 1) are characterized by the trans (T) form. The rotational isomers are identical with those on Cu(1 1 0) and Ag(1 1 0); i.e., MEE on Cu(1 1 0) takes the G form and the adsorbate on Ag(1 1 0) the T form [T. Kiyohara et al., J. Phys. Chem. B 107 (2003) 5008]. The simulation of the IRA spectra indicated that (i) the G form adsorbate on Cu(1 1 1) takes an orientation, in which the axis bisecting the COC bond angle tilts away from the surface normal by ca. 30° within the plane perpendicular to the surface to make the CH₃-CH₂ bond almost parallel to the surface, and (ii) the T form adsorbate on Ag(1 1 1) takes an orientation, in which the bisecting axis tilts away by ca. 60° from the surface normal within the perpendicular plane. Comparison of these adsorption structures of MEE on the (1 1 1) substrates with those of MEE on Cu(1 1 0) and Ag(1 1 0) indicates that the structures are mainly determined by a coordination interaction of the oxygen atom to the surface metals and an attractive van der Waals interaction between the ethyl group of MEE and the substrate surfaces. The coordination interaction plays an important role on Cu(1 1 1) and Cu(1 1 0), which makes the adsorbate on the Cu substrates to take the orientations with the bisecting axis near parallel to the surface normal and to assume the G form in order to make the ethyl group parallel to the surface, which is favorable for the van der Waals interaction. In the case of MEE on the Ag substrates the attractive van der Waals interaction plays a dominant role, resulting in the T form which is more favorable for the interaction than the G form.     

Asymmetric autocatalysis induced by chiral hydrocarbon [2.2]paracyclophanes

Chiral hydrocarbon [2.2]paracyclophanes act as chiral initiators in asymmetric autocatalysis in the addition of diisopropylzinc to pyrimidine-5-carbaldehyde and give highly enantiomerically enriched 5-pyrimidyl alkanol with a reversed sense of the enantioselectivity to that of other [2.2]paracyclophanes with heteroatoms.     

Search for Lorentz invariance and CPT violation with the MINOS far detector

We searched for a sidereal modulation in the MINOS far detector neutrino rate. Such a signal would be a consequence of Lorentz and CPT violation as described by the standard-model extension framework. It also would be the first detection of a perturbative effect to conventional neutrino mass oscillations. We found no evidence for this sidereal signature, and the upper limits placed on the magnitudes of the Lorentz and CPT violating coefficients describing the theory are an improvement by factors of 20-510 over the current best limits found by using the MINOS near detector.     

Quasiparticle scattering induced by charge doping of iron-pnictide superconductors probed by collective vortex pinning

Charge doping of iron-pnictide superconductors leads to collective pinning of flux vortices, whereas isovalent doping does not. Moreover, flux pinning in the charge-doped compounds is consistently described by the mean-free path fluctuations introduced by the dopant atoms, allowing for the extraction of the elastic quasiparticle scattering rate. The absence of scattering by dopant atoms in isovalently doped BaFe2(As(1-x)P(x))(2) is consistent with the observation of a linear temperature dependence of the low-temperature penetration depth in this material.     

Membrane filters for the concentration of trace elements in water: distribution of ion pairs between membrane filter and aqueous phases

The sorption of ion pairs on membrane filters (MFs) has been studied by taking the membrane filter as one of the homogeneous phases. The sorbability of some ionic species and the sorption abilities of different types of MF were evaluated in terms of the sorption constant defined by Ksor,CA = [(C+,A-)f]/[C+][A-], where C+, A- and (C+,A-) refer to the cation, anion and the ion pair, respectively, and f refers to the filter phase. The values of Ksor,CA were determined for many combinations of ionic complexes of cobalt(III) with pyridylazophenols, either as cations or anions, and oppositely charged organic ions having different alkyl chain lengths, with MFs made of different materials: nitrocellulose (NC; Toyo Advantec), acetylcellulose (AC; Fuji Film), regenerated cellulose (RC; Toyo Advantec) and polyethersulphone (PS; Toyo Advantec). For a given cobalt complex ion, the value of log Ksor,CA increased linearly with the increasing number of carbons in the counter ion. Membrane filters made of different materials showed different sorption abilities, the order being NC greater than PS greater than RC greater than AC. It was shown that the surface area of the MF is of greater significance than the volume of the matrix of the MF in determining the sorption constant.