Experimental evidence for the p-d hybridization in the Cd-Ca quasicrystal: origin of the pseudogap

Ca 2p-3d resonant photoemission spectroscopy of a Cd6Ca crystalline approximant unambiguously demonstrates that the low-lying unoccupied 3d levels of calcium are lowered below the Fermi energy by the formation of the approximant, as suggested from electronic structure calculations [Phys. Rev. Lett. 87, 206408 (2001)]]. Moreover, the Ca 3d partial density of states (DOS) obtained near the Fermi energy is in reasonable agreement with theoretical Ca 3d DOS. These results verify the unconventional picture that the origin of the pseudogap in the Cd-based quasicrystals is due to hybridization of the Ca 3d band with the Cd 5p band.     

Strongly red-fluorescent novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazoles with enhanced two-photon absorption cross-sections

Novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazole fluorescent dyes connected to the N,N-diarylamino terminus via various type pi-conjugate spacers exhibits large two-photon absorption cross-sections and high fluorescent quantum yields in orange-red color.     

Time-resolved Auger decay in CsBr using high harmonics

The temperature-dependent decay dynamics of innershell holes in CsBr was measured by using high harmonics. The measured lifetime was as short as 1.5 ps at 340 K due to increasing the Auger-allowed final state density in the Urbach exciton tail, whereas it is 1.1 ns at 10 K, determined by radiative recombination. The temperature-dependent Auger lifetime extrapolated to a high temperature corresponds to the fully energy-allowed Auger decay. In the model to be presented, this yields an interatomic Auger decay lifetime of 2.4+3.8/-1.5 fs, in line with a theoretical calculation for NaF.     

Frequency-resolved optical gating of femtosecond pulses in the extreme ultraviolet

Femtosecond extreme ultraviolet (XUV) pulses were fully characterized for the first time by using a newly developed cross-correlation frequency-resolved optical gating (FROG) technique in the XUV region. This method utilizes laser-assisted two-photon ionization as a nonlinear optical process. Near-infrared pulses characterized by FROG were used as a reference. The amplitude and phase of XUV pulses with a pulse duration of 10 fs were found to be in good agreement with a model analysis, taking into account phase modulation by ionization, self-phase modulation, and the atomic dipole phase.     

Laser-driven vehicles – from inner-space to outer-space

Laser-supported propulsion of a micro-airplane with a water-covered ablator is demonstrated. The repetitive use of an overlay structure is experimentally demonstrated with a specially designed water supply. Various transparent overlays are investigated by the CIP-based hydrodynamic code and by experiments using a pendulum and using a semi-conductor load cell. A momentum-coupling efficiency of ∼10⁴ N s/MJ is achieved by water–exotic-target experiments, in agreement with the simulation code, which predicts a maximum efficiency of ∼10⁵ N s/MJ. The concept of laser-supported propulsion can also be used for driving a Mach 5 airplane in the stratosphere, a micro-ship inside the human body, and a robot in a nuclear power reactor accident, during which large numbers of neutrons make electronic devices useless. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-3/5734-2165, E-mail: yabe@mech.titech.ac.jp     

Synthesis and evaluation of 6-nitro-7-(1-piperazino)quinazolines: dual-acting compounds with inhibitory activities toward both tumor necrosis factor-alpha (TNF-alpha) production and T cell proliferation

We investigated the chemical modifications of the nitroquinazoline derivative (1) through the replacement of the NH group at the C(4)-position with several N-alkyl groups to increase the lipophilicity at the C(4)-position. Among them, we found that the N-methyl analogue (5a) showed a 2-fold loss in the inhibitory activity toward tumor necrosis factor-alpha (TNF-alpha) production in vitro as compared with the NH analogue (1); however, 5a exhibited an oral inhibitory activity on TNF-alpha production with an ED50 value of 26 mg/kg, whereas 1 did not. Moreover, the oral bioavailability of 5a was higher than that of 1 (1, F=1%; 5a, F=21%), and the calculated ClogP value for 5a was higher than that for 1. These results suggest that the improved lipophilicity of 5a compared with that of 1 reflects its greater inhibitory activity on TNF-alpha production in vivo as well as oral bioavailability.     

Molecular numbers in core and shell: structural dependence of reactivity of alkylcarboxylate-stabilized silver nanoparticles

Spectroscopic, chemical, thermal, and voltammetric analyses on six kinds of alkylcarboxylate-stabilized silver nanoparticles 4.7 nm in diameter were carried out with an aim to reveal the effect of alkylcarboxylates on the optical, thermal, geometric, and electrochemical properties of the nanoparticles. These nanoparticles are composed of silver atoms and silver alkylcarboxylates having even numbers, m, of carbon atoms from 8 to 18. As a measure of the structure of the nanoparticles, the ratio of the number of silver atoms (nAg) to that of alkylcarboxylates (ns) per nanoparticle was evaluated by means of titration through chemical oxidation, voltammetric currents, and thermal gravimetric analysis. It increased with an increase in m and ranged from 1.3 to 9.8. Properties of the nanoparticle have been exhibited in absorbance of the UV-vis spectra at the point of the proportionality to n(Ag), voltammetric currents of which values were close to the theoretical values at the diffusion of particle itself, and the m-independent kinetic energy of the thermal decomposition and the overpotential of the reduction. They are not observed for the composed species, that is, silver atoms and silver alkylcarboxylate molecules.     

Wolfram

Ohne Zusammenfassung     

Quadruple Decker [3.3][3.3][3.3]Orthocyclophane Acetal—An Orthocyclophane Ladder

Through clever bridging of orthocyclophanes (in this case by acetalization), molecules such as 1 can be formed with four benzene rings in a stacked face-to-face arrangement. UV/Vis spectroscopic and electrochemical properties of 1 are governed by π–π through-space interactions within the molecule.