Fundamental aspects of light scattering and optical Kerr effect spectroscopy

We describe the principles of two spectroscopic methods of non-resonance light scattering (LS) and optical-Kerr-effect (OKE) spectroscopies in detail, and review basic but truly important phenomena observed by these two methods. Particularly, we focus on the following three experiments: 1) Response functions determined by frequency-domain LS and time-domain OKE spectroscopies, almost completely agree with each other, indicating that the quantum-mechanical fluctuation-dissipation theorem (QM-FDT) holds well in this system. 2) Femtosecond time responses of liquids clearly show an initial rise process even though they show an exponential response at a later time. This indicates that the Debye relaxation model does not hold in such an early time region. 3) From the measurement of the Stokes and anti-Stokes LS intensity ratios, it is found that the LS spectra of relaxation modes in liquids and solids are symmetric with respect to the spectral origin of the scattered light and hence the ratio does not satisfy the Boltzmann distribution rule expected from QM-FDT. These experimental results which contain apparently contradictory data are closely related with the nature of relaxation modes examined, which more or less assume a macroscopic character, and also with the physical basis of relaxation, which is inevitably connected to the observation problem of quantum mechanics. We discuss these points in relation to the physical reality of macroscopic quantity.     

Amycolamicin: A Novel Broad‐Spectrum Antibiotic Inhibiting Bacterial Topoisomerase

The abuse of antibacterial drugs imposes a selection pressure on bacteria that has driven the evolution of multidrug resistance in many pathogens. Our efforts to discover novel classes of antibiotics to combat these pathogens resulted in the discovery of amycolamicin (AMM). The absolute structure of AMM was determined by NMR spectroscopy, X‐ray analysis, chemical degradation, and modification of its functional groups. AMM consists of trans‐decalin, tetramic acid, two unusual sugars (amycolose and amykitanose), and dichloropyrrole carboxylic acid. The pyranose ring named as amykitanose undergoes anomerization in methanol. AMM is a potent and broad‐spectrum antibiotic against Gram‐positive pathogenic bacteria by inhibiting DNA gyrase and bacterial topoisomerase IV. The target of AMM has been proved to be the DNA gyrase B subunit and its binding mode to DNA gyrase is different from those of novobiocin and coumermycin, the known DNA gyrase inhibitors.     

Improving syllable identification by a preprocessing method reducing overlap-masking in reverberant environments

Overlap-masking degrades speech intelligibility in reverberation [R. H. Bolt and A. D. MacDonald, J. Acoust. Soc. Am. 21(6), 577-580 (1949)]. To reduce the effect of this degradation, steady-state suppression has been proposed as a preprocessing technique [Arai et al., Proc. Autumn Meet. Acoust. Soc. Jpn., 2001; Acoust. Sci. Tech. 23(8), 229-232 (2002)]. This technique automatically suppresses steady-state portions of speech that have more energy but are less crucial for speech perception. The present paper explores the effect of steady-state suppression on syllable identification preceded by /a/ under various reverberant conditions. In each of two perception experiments, stimuli were presented to 22 subjects with normal hearing. The stimuli consisted of mono-syllables in a carrier phrase with and without steady-state suppression and were presented under different reverberant conditions using artificial impulse responses. The results indicate that steady-state suppression statistically improves consonant identification for reverberation times of 0.7 to 1.2 s. Analysis of confusion matrices shows that identification of voiced consonants, stop and nasal consonants, and bilabial, alveolar, and velar consonants were especially improved by steady-state suppression. The steady-state suppression is demonstrated to be an effective preprocessing method for improving syllable identification by reducing the effect of overlap-masking under specific reverberant conditions.     

CLV3/ESR-related (CLE) peptides as intercellular signaling molecules in plants

For many years, the plant hormones auxin, cytokinin, ethylene, gibberellin, abscisic acid, brassinosteroid, jasmonic acid, and salicylic acid have been extensively studied as key regulators of plant growth and development. However, recent biochemical and genetic analyses have revealed that secretory peptides are also responsible for intercellular signaling in plants and regulate various events including wound response, cell division control, and pollen self-incompatibility. We discovered two natural CLAVATA3 (CLV3)/ESR-related (CLE) peptides: tracheary elements differentiation inhibitory factor (TDIF) and CLV3, which are dodecapeptides with two hydroxyproline residues that regulate vascular development and meristem formation, respectively. This discovery enabled us to predict the chemical form of CLE gene products. In the Arabidopsis genome, there are 31 CLE genes that correspond to 26 CLE peptides. The application of all 26 chemically synthesized peptides to plants revealed the existence of distinctive functional groups. From these results, we discuss the functions of CLE peptides in plant development and plant-parasite interactions.     

Tailored coupled cluster singles and doubles method applied to calculations on molecular structure and harmonic vibrational frequencies of ozone

To assess the separation of dynamic and nondynamic correlations and orbital choice, we calculate the molecular structure and harmonic vibrational frequencies of ozone with the recently developed tailored coupled cluster singles and doubles method (TCCSD). We employ the Hartree-Fock and complete active space (CAS) self-consistent field (SCF) orbitals to perform TCCSD calculations. When using the Hartree-Fock orbitals, it is difficult to reproduce the experimental vibrational frequency of the asymmetric stretching mode. On the other hand, the TCCSD based on the CASSCF orbitals in a correlation consistent polarized valence triple zeta basis yields excellent results with the two symmetric vibrations differing from the experimental harmonic values by 2 cm(-1) and the asymmetric vibration differing by 9 cm(-1).     

Changes in thermodynamic quantities upon contact of two solutes in solvent under isochoric and isobaric conditions

The changes in excess thermodynamic quantities upon the contact of two solutes immersed in a solvent are analyzed using the radial-symmetric and three-dimensional versions of the integral equation theory. A simple model mimicking a solute in water is employed. The solute-solute interaction energy is not included in the calculations. Under the isochoric condition, the solute contact always leads to a positive entropy change irrespective of the solute solvophobicity or solvophilicity. The energy change is negative for solvophobic solutes while it is positive for solvophilic ones. Under the isobaric condition, the contact of solvophobic solutes results in system-volume compression but that of solvophilic ones gives rise to expansion. Effects of the compression and expansion on the changes in enthalpy and entropy are enlarged with rising temperature. When the solute solvophobicity is sufficiently high, the entropy change (multiplied by the absolute temperature) can become negative due to the compression, except at low temperatures with the result of an even larger, negative enthalpy change. The expansion in the case of solvophilic solutes leads to a large, positive entropy change accompanied by an even larger, positive enthalpy change. The changes in enthalpy and entropy are strongly dependent on the temperature. However, the changes in enthalpy and entropy are largely cancelled out and the temperature dependency of the free-energy change is much weaker. The authors also discuss possible relevance to the enthalpy-entropy compensation experimentally known for a variety of physicochemical processes in aqueous solution such as protein folding.     

Status of pump-probe time-resolved photoemission electron microscopy at SPring-8

The present status and the recent progress of pump-probe time-resolved photoemission electron microscopy at SPring-8 are introduced. Combining the variety of bunch operation modes available at the SPring-8 storage ring with ultra-short excitation sources including pulsed magnetic fields, electric fields and lasers, the element-specific time evolution of materials in response to the excitation can be observed with spatial and temporal resolutions of (50–300) nm and (40–100) ps, respectively, with repetition frequencies of up to 42 MHz. By using the magnetic circular dichroism effect, the domain motion of sub-micron sized magnetic areas can be observed. The time evolution of electronic structures in local areas can also be studied. The experimental setups and representative activities are described.     

Development of scattering near-field optical microspectroscopy apparatus using an infrared synchrotron radiation source

We report the status of a scattering near-field microspectroscopy apparatus developed at SPring-8 using an infrared synchrotron radiation (IR-SR) source. It consists of a scattering type scanning near-field optical microscope and a Fourier transform infrared spectrometer. The IR-SR is used as a highly brilliant and broad-band IR source. This apparatus has potential for application in near-field spectroscopy with high spatial resolution beyond the diffraction limit. In order to eliminate background scatterings from the probe shaft and/or sample surface, we used higher harmonic demodulation method. The near-field spectra were observed by 2nd harmonic components using the lock-in detection. The spatial resolution of about 300 nm was achieved at around 1000 cm^? 1 (10 μm wavelength).