Quasicrystalline electronic states of a one-dimensionally modulated Ag film

Ag films on GaAs(110) exhibit a one-dimensional quasiperiodic modulation, resulting in a Fibonacci sequence of parallel stripes with two different widths. Valence level photoemission shows that the Ag electronic states acquire a unique character along the quasiperiodic direction, distinctively manifested by a hierarchy of energy level replicas and avoided crossings at characteristic intervals in reciprocal space. These observations demonstrate the strong influence of the one-dimensional quasiperiodic potential on the Ag film states.     

Anomalous behavior of linear resistivity arising in intergrain ordering process of weak-sintered ceramic system YBa2Cu4O8

Faint electric resistivity behavior is searched experimentally near and below intergrain ordering temperature of weakly sintered ceramic YBa₂Cu₄O₈ (Y124). For this purpose, a new method to detect linear and nonlinear resistivity sensitively by combination of pulse delta method and numerical Fourier-transformation has been designed. Making use of the experimental system for several weak sintered Y124 samples, it is revealed that linear resistivity just above the intergrain ordering point first drops toward zero steeply with decreasing temperature, and then turns abruptly upward to forms faint maximum at lower temperature. Such a novel behavior of ‘revival of resistivity’ is confirmed to be reproducible, and considered to be an essential frustration effect for d-wave type grain system with irregular or inhomogeneous ceramic structure.     

Frequency dependence of H2O2 generation from distilled water

The frequency dependence of H2O2 generation from H2O by a sonochemical reaction was detected experimentally. The results are in good agreement with previous experimental results, which indicate that in sonochemical reactions, frequencies higher than 90 kHz are more effective than frequencies of several tens of kilohertz. The phonon concept of acoustic waves makes it clear that energy depends on frequency, i.e. on the condition of equal phonon density; higher frequency means higher energy. The concentration and accumulation of acoustic energy will be performed through a bubble surface. From the analogy of photoelectric effects, the frequency dependence of the sonochemical reaction was discussed using the phonon concept.     

How well can we reconstruct the $t\bar{t}$ system near its threshold at future ee linear colliders?

We developed a new method for the full kinematical reconstruction of the system near its threshold at future linear e ⁺ e ^- colliders. In the core of the method lies likelihood fitting which is designed to improve measurement accuracies of the kinematical variables that specify the final states resulting from decays. The improvement is demonstrated by applying this method to a Monte Carlo sample generated with various experimental effects including beamstrahlung, finite acceptance and resolution of the detector system, etc. In most cases the fit takes a broad non-Gaussian distribution of a given kinematical variable to a nearly Gaussian shape, thereby justifying phenomenological analyses based on simple Gaussian smearing of the parton-level momenta. The standard deviations of the resultant distributions of various kinematical variables are given in order to facilitate such phenomenological analyses. A possible application of the kinematical fitting method and its expected impact are also discussed. Received: 4 March 2003 / Published online: 23 May 2003 RID="a" ID="a" e-mail: ikematsu@post.kek.jp RID="b" ID="b" e-mail: fujiik@jlcuxf.kek.jp RID="c" ID="c" e-mail: hioki@ias.tokushima-u.ac.jp RID="d" ID="d" e-mail: sumino@tuhep.phys.tohoku.ac.jp RID="e" ID="e" e-mail: tohrut@hiroshima-u.ac.jp     

Single-crystal-to-single-crystal photocyclization of 4-(2,4,6-triisopropylbenzoyl)benzoic acid in the salt crystal with (S)-phenylethylamine

Ultraviolet irradiation of a salt crystal of 4-(2,4,6-triisopropylbenzoyl)benzoic acid with (S)-phenylethylamine promoted single-crystal-to-single-crystal photocyclization to give an enantiopure (R,R)-cyclopentenol and almost racemic cyclobutenol. The reaction paths were elucidated by X-ray crystallographic analysis of the crystal before and after irradiation.     

Chiral distortion in a Mn(IV)(salen)(N3)2 derived from Jacobsen's catalyst as a possible conformation model for its enantioselective reactions

The Mn (IV)(salen)(N 3) 2 complex ( 3) from Jacobsen's catalyst is synthesized, and the X-ray crystal structures of 3 as well as the starting Mn (III)(salen)(N 3)(CH 3OH) complex ( 2) are determined in order to investigate the conformation of the high-valent Mn (IV)(salen) molecule in comparison with that of Mn (III)(salen). The asymmetric unit of the crystal of 3 contains four complexes, all of which adopt a nonplanar stepped conformation effectively distorted by the chirality of the diimine bridge. The asymmetric unit of 2 also contains four complexes. Two of them show a stepped conformation of a lesser degree, but the other two adopt a bowl-shaped conformation. Comparison of the structural parameters shows that the Mn center in 3 is coordinated from both sides by two external axial N 3 ligands with significantly shorter bond lengths, which could induce greater preference for the stepped conformation in 3. The CH 3CN solution of 3 shows circular dichroism with a significantly strong band at 275 nm as compared to 2, suggesting that 3 may adopt a more chirally distorted conformation also in solution. The circular dichroism spectrum of 3 is slightly altered with isodichroic points from 298 to 253 K and shows no further change at temperatures lower than 253 K, suggesting that the solution of 3 contains an equilibrium between two conformers, where a low-energy conformer with more chiral distortion is predominantly favored even at room temperature. Complexes 2 and 3 are thoroughly characterized using various techniques including cyclic voltammetry, magnetic susceptibility, UV-vis, electron paramagnetic resonance, (1)H NMR, infrared spectroscopy, and electrospray ionization mass spectrometry.     

AlCl3-catalyzed tandem acetylation of hydroarylated [60]fullerenes

The AlCl3-catalyzed acetylation of 1,2-hydrophenylated [60]fullerenes, HC60-Ar, proceeded via a sequential manner involving the acetylation at the hydrogenated fullerene carbon, the following intramolecular cyclization with the adjacent aryl group, the facile loss of water, and the second acetylation of the generated indenylidene double bond. However, the similar reaction of the hydrobiphenylated analogue brought about the normal acetylation at the terminal aromatic ring prior to the same sequential reactions as did hydrophenylated fullerenes.     

Simultaneous determination of the binding of amantadine and its analogues to synthetic melanin by liquid chromatography after precolumn derivatization with dansyl chloride

For the determination of amantadine (1-ADA), 2-adamantanamine (2-ADA), memantine (MEM), and rimantadine (RIM) in melanin binding studies, the simultaneous determination of 1-ADA or 2-ADA, MEM, and RIM is investigated by high-performance liquid chromatographic assay with dansyl chloride as a fluorescent derivative reagent. Dansyl derivatives with fluorescent intensity are detected at an excitation wavelength of 370 nm and an emission wavelength of 506 nm. Retention times of 1-ADA, 2-ADA, MEM, and RIM derivatives are 12.2, 12.2, 15.2, and 16.6 min, respectively. The peak of 1-ADA derivative coelutes with the 2-ADA derivative. The limits of detection for 1-ADA, 2-ADA, MEM, and RIM are 0.014, 0.007, 0.012, and 0.020microM, respectively (signal-to-noise ratio of 3:1). In the intra- and interday assay, the range of standard deviation to the average of 1-ADA, 2-ADA, MEM, and RIM is 4.6-12.7%. Their recovery is also good. The ranking order for synthetic melanin binding among these compounds is RIM > MEM > 2-ADA = 1-ADA. The method is simple, sensitive, and reproducible for simultaneously measuring 1-ADA or 2-ADA, MEM, and RIM. Also, it is useful to investigate their binding kinetics to melanin.     

Conformation of solvent N,N-dimethylpropionamide in the coordination sphere of the zinc(II) ion studied by Raman spectroscopy and DFT calculations

Solvation structure of the zinc(II) ion in N,N-dimethylpropionamide (DMPA) was studied by Raman spectroscopy at varying temperature and by quantum mechanical calculations. No significant ion-pair formation was found for the Zn(ClO4)2 solution in the molality range m(Zn) < 1.5 mol kg(-1), and the solvation number of the zinc(II) ion was determined to be 4, indicating that 6-coordination of DMPA is sterically hindered. Interestingly, DMPA molecules are under equilibrium between planar cis and nonplanar staggered conformers, and the latter is more preferred in the coordination sphere, while the reverse is the case in the bulk. The DeltaG degrees , DeltaH degrees , and TDeltaS degrees values of conformational change from planar cis to nonplanar staggered in the coordination sphere were obtained to be -0.9, -8.5, and -7.5 kJ mol(-1), respectively. Density functional theory (DFT) calculations show that the planar cis conformer is more favorable than the nonplanar staggered one in the 1:2 cluster, as is the case for a single DMPA molecule and H(DMPA)+, indicating that there hardly occurs solvent-solvent interaction through the metal ion in the Zn2+-DMPA 1:2 cluster. On the other hand, the SCF energy of [Zn(planar cis-DMPA)4-n(nonplanar staggered DMPA)n]2+ (n = 0-4) decreases with increasing n, implying that the nonplanar staggered conformer is preferred in the solvate ion. It is thus concluded that solvent-solvent interaction through space, or solvation steric effect, plays a crucial role in the conformational equilibrium in the coordination sphere of the four-solvate metal ion.     

Mode change in the self-motion of a benzoquinone disk coupled with a NADPH system

The self-motion of a benzoquinone (BQ) disk on NADPH was investigated as the coupling of an autonomous motor and an enzyme reaction. In the absence of the enzyme reaction, features of motion changed depending on the concentration of NADPH, that is, continuous motion→ intermittent oscillatory motion→ no motion. When the reverse reaction from NADP(+) to NADPH was introduced into the system with the addition of an enzyme reaction, continuous motion changed to intermittent oscillatory motion with small amplitude. The mechanism of this mode change is discussed in relation to the surface tension as a driving force and the time course of UV spectra as a window to the progress of the reaction. Characteristic features of the mode change were qualitatively reproduced by a numerical calculation.