Raman and infrared spectra of the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers of β-carotene: Key bands distinguishing stretched or terminal-bent configurations form central-bent configurations

Raman and infrared spectra in the region of 1800-150 cm⁻¹ were recorded for a set of cis-trans isomers of d̃-carotene, i.e. the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers. Spectral comparison revealed Raman and infrared key bands which (1) distinguish stretched or terminal-bent configurations (all-trans, 7-cis and 9-cis) from central-bent configurations (13-cis and 15-cis), and (2) distinguish unmethylated 7-cis and 15-cis configuratios. Keybands (1) include Raman bands at 1160 and 1140 cm⁻¹ and infrared bands at 825 and 775 cm⁻¹ (the intensity varies with the position of the cis-bend) Key bands (2) include Raman bands at 1274 and 962 cm⁻¹ and an infrared band at 741 cm⁻¹ (characteristic of the 7-cis configuration), and also a Raman band at 1247 cm⁻¹ and an infrared band at 775 cm⁻¹ (characteristic of the 15-cis configuration). The normal modes for the key bands were determined by a set of normal coordinate calculations for the isomeric configurations of a simplified model of d̃-carotene. The key bands were mainly related to the C H in-plane bendings, coupled with the CC or C C stretching, or to the C H out-of-plane wagging vibrations, some of which coupled with the CC torsion.     

The pion velocity at chiral restoration and the vector manifestation

We study the effects of Lorentz non-invariance on the physical pion velocity at the critical temperature T_c in an effective theory of hidden local symmetry (HLS) with the “vector manifestation” fixed point. We match at a “matching scale” Λ_M the axial-vector current correlator in the HLS with the one in the operator product expansion for QCD, and present the matching condition to determine the bare pion velocity. We find that the physical pion velocity, which is found to be one at T=T_c when starting from the Lorentz invariant bare HLS, remains close to one with the Lorentz non-invariance, v_π(T_c)=0.83–0.99. This result is quite similar to the pion velocity in dense matter.     

Fabrication of oxide base nanostructures using pulsed laser ablation in aqueous solutions

Nanoparticles of TiO₂ and SnO₂ were obtained by laser ablation of Ti and Sn targets in both deionized water and sodium dodecyl sulfate (SDS) solutions. The crystallinity of the nanoparticles strongly depended on the SDS concentration in the solution. Well-crystallized oxide nanoparticles were most abundantly fabricated in SDS solution with around the critical micelle concentration. An inorganic/organic layered nanocomposite consisting of a zinc hydroxide layer and a SDS lamellar interlayer was obtained by the ablation of Zn in SDS solutions. The oxide and/or hydroxide can be formed by the rapid reactive quenching with water in the liquid–plasma interface, where ablated species can be oxidized by aqueous oxidation. The surfactant in the liquid medium could affect the aggregation and growth of nuclei after the oxidation. The preparation of Pt/TiO₂ nanocomposite particles by PLA of the bi-combinant target of Pt and TiO₂ is also reported. PACS 81.16.Mk; 81.10.Dn; 81.07.Bc     

High-energy quasi-phase-matched optical parametric oscillation in a 3-mm-thick periodically poled MgO:LiNbO3 device

We have demonstrated high-energy quasi-phase-matched optical parametric oscillation in a 3-mm-thick periodically poled 5-mol. % MgO-doped LiNbO3 device with a 32.1-microm grating period and a 30-mm length. With a large-spot-size pump laser of 2.2-mm diameter, we obtained a total output pulse energy of 22 mJ for both the signal (wavelength 1.82 microm) and the idler (2.56 microm) waves at an input pump energy of 46 mJ.     

Inhomogeneous superconducting state in the overdoped regime of La2−xSrxCuO4: Comparison with the superconducting state of NbSe2

We have measured the temperature dependence of the magnetic susceptibility, χ vs. T, and the magnetization curve, M vs. H, for NbSe₂ single crystals, in order to compare the superconducting (SC) state in the overdoped regime of La_2−xSr_xCuO₄ (LSCO) with the SC state of the layered conventional superconductor NbSe₂. While a plateau in χ vs. T in a moderate magnetic field and a so-called second peak in M vs. H, which is due to the marked enhancement of vortex pinning, have been observed in the overdoped regime of LSCO, these behaviors have not been observed in NbSe₂. The present results indicate that the anomalously marked enhancement of vortex pinning is a characteristic feature in the overdoped LSCO where a microscopic phase separation into SC and normal-state regions takes place.     

Electronic structure of the organic conductors based on BMDT-TTF (BIS(methylenedithio)tetrathiafulvalene)

In the crystals of the cation radical salts based on the organic donor BMDT-TTF, the charge separation is observed. This comes from (1) nonequivalency of the site potential and (2) the long range electron-electron interaction, which are related to the two-dimensional nature of the molecular arrangement. The effects of the charge separation on the elctronic structure are discussed.     

Infrared and Raman Spectra and lattice Vibrations of Some Ionic Crystals: Fluorides and Oxides

The infrared and Raman spectra of so-called ionic crystals have been subjects of many investigations by chemists as well as by physicists. These spectra have been interpreted on the basis of a dynamical theory on the long-lattice vibrations of the optical branches by Born and Huang [l]. An interpretation of the optically active lattice vibrations of crystals yields important information regarding the interionic interactions in the crystal. The interatomic interactions in the ionic crystals are divided into the short-range repulsive and long-range electrostatic interactions, while those in the molecular crystals arise primarily from the short-range repulsive ones.     

Generation and detection of the radical cation and the dication derived from 4,9‐diethyl[1,4]dihydrodithiino[5,6‐f]benzotrithiole and its 5‐oxide

4,9‐Diethyl[1,4]dihydrodithiino[5,6‐f]benzotrithiole (DTBT) gave a radical cation, DTBT(•+), and a dication, DTBT(2+), on treatment with a single‐electron oxidizing reagent. Both compounds showed an ESR signal, whereas the dication, generated by this procedure, was silent for ¹H NMR. Hydrolysis of DTBT(2+) gave DTBT 1‐oxide (DTBT 1‐O) and 2‐oxide (DTBT 2‐O) together with DTBT and a mixture of several dioxides. A singlet‐state dication, DTBT(2+)‐S, which was generated upon treatment of DTBT 5‐oxide (DTBT 5‐O) with concentrated D₂SO₄, was detected by ¹H and ¹³C NMR. After 20 h, the NMR signals disappeared while the solution was active for ESR. The results suggest that (i) a species generated from DTBT by oxidation with the single‐electron oxidizing reagent is a triplet‐state dication, DTBT(2+)‐T, and (ii) DTBT(2+)‐S, initially generated, gradually isomerizes to DTBT(2+)‐T in the solution, and DTBT(2+)‐T forms a partial spin pair. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:394–401, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20445     

Hg(OAc)(2).0.1Sc(OTf)(3)-catalyzed cycloisomerization of 2-(4-pentynyl)furan

[structure: see text]. Although the Hg(OTf)2.3TMU-catalyzed Friedel-Crafts-type reaction of 3-(4-pentynyl)furan afforded the exo cyclization product, the reaction of 2-(4-pentynyl)furan furnished a very low yield. We found a 10:1 mixed reagent of Hg(OAc)2 and Sc(OTf)3 showed remarkable catalytic activity for the latter transformation. The actual reacting species is presumed to be Hg(OAc)(OTf), which is efficiently generated in situ by mixing the two reagents.     

Platelet Graphite Nanofibers for Electrochemical Sensing and Biosensing: The Influence of Graphene Sheet Orientation

Here, we demonstrate that platelet graphite nanofibers (PGNFs) exhibit fast heterogeneous electron‐transfer rates for a wide variety of compounds such as FeCl₃, ferrocyanide, dopamine, uric acid, ascorbic acid, and the reduced form of β‐nicotinamide adenine dinucleotide. The electrochemical properties of PGNFs are superior to those of multiwalled carbon nanotubes (MWCNTs) or graphite microparticles (GMPs). Transmission electron microscopy and Raman spectroscopy reveal that this arises from the unique graphene sheet orientation of such platelet nanofibers, which accounts for their unparalleled high ratio of graphene edge planes versus basal planes.