Gold-catalysed alkenyl- and arylsilylation reactions forming 1-silaindenes

In the presence of gold(I)-phosphine catalysts, alkenyl- and arylsilanes undergo intramolecular cyclisation reactions onto appendant alkyne moieties to afford 1-silaindene derivatives. The reaction pathways vary depending on the substituent on silicon.     

Side chain effect on the double helix formation of ethynylhelicene oligomers

Three series of ethynylhelicene oligomers with different side chains were synthesized: (P)-bD-n (n = 2-6) with branched alkyloxycarbonyl side chains; (P)-S-n (n = 2-7) with decylsulfanyl side chains; and (P)-DF-n (n = 4, 6, 8, 10) with alternating decyloxycarbonyl and perfluorooctyl side chains. The double helix formation of these side chain derivatives was compared to that of (P)-D-n with decyloxycarbonyl side chains. CD, UV-vis, and vapor pressure osmometry (VPO) studies showed that (P)-bD-n formed double helices as well as (P)-D-n. CD studies in trifluoromethylbenzene at different temperatures and concentrations indicated that the stability of the aggregate of (P)-bD-6 was similar to that of (P)-D-6. Bulkiness of side chains had little effect on aggregation, which indicated that π-π interactions of the aromatic moiety were essential for double helix formation. (P)-S-n were random coils in all solvents examined except in trifluoromethylbenzene. Whereas (P)-D-7 formed a double helix at 1 × 10(-3) M in toluene, (P)-S-7 was a random coil. This result indicated that the double helix forming ability of (P)-S-n was substantially lower than that of (P)-D-n. Based on the previous observation that (P)-F-n formed a more stable double helix than (P)-D-n, the order of stability may be summarized as follows: (P)-F-n > (P)-D-n and (P)-bD-n >(P)-S-n. The lower stability of (P)-S-n compared to that of (P)-F-n was ascribed to the softness and/or the electron-rich nature at the m-phenylene moiety. (P)-DF-n did not form a stable double helix. It was speculated that a regular alternating arrangement of soft/hard or electron-rich/deficient moieties is important for stable double helix formation. Side chains of ethynylhelicene oligomers can play significant roles in determining the stability of double helices.     

Anchoring effects in audiovisual speech perception

Two experiments were conducted to investigate whether or not anchoring and selective adaptation induce basically the same psychological effects. The purpose of the first experiment is to show how an audiovisual anchor modifies the perception of consonant-vowel (CV) syllables. The anchors were two purely acoustical, two purely optical, and three audiovisual CV syllables. The results were compared with those of audiovisual speech selective-adaptation experiments conducted by Roberts and Summerfield [Percept. Psychophys. 30, 309-314 (1981)] and Salda?a and Rosenblum [J. Acoust. Soc. Am. 95, 3658-3661 (1994)]. The audiovisual anchoring effects were found to be very similar to the audiovisual selective-adaptation effects, but the incompatible audiovisual anchor produced more auditory-based contrast than the purely acoustical anchor or the compatible audiovisual anchor. This difference in contrast had not been found in the previous selective-adaptation experiments. The second experiment was conducted to directly compare audiovisual anchoring and selective-adaptation effects under the same stimuli and with the same subjects. It was found that the compatible audiovisual syllable (AbVb) caused more contrast in selective adaptation than in anchoring, although the discrepant audiovisual syllable (AbVg) caused no difference between anchoring and selective adaptation. It was also found that the anchor AbVg caused more auditory-based contrast than the anchor AbVb. It is suggested that the mechanisms behind these results are different.     

Detection of electron paramagnetic resonance absorption using frequency modulation

A frequency modulation (FM) method was developed to measure electron paramagnetic resonance (EPR) absorption. The first-derivative spectrum of 1,1-diphenyl-2-picrylhydrazyl (DPPH) powder was measured with this FM method. Frequency modulation of up to 1.6 MHz (peak-to-peak) was achieved at a microwave carrier frequency of 1.1 GHz. This corresponds to a magnetic field modulation of 57microT (peak-to-peak) at 40.3 mT. By using a tunable microwave resonator and automatic control systems, we achieved a practical continuous-wave (CW) EPR spectrometer that incorporates the FM method. In the present experiments, the EPR signal intensity was proportional to the magnitude of frequency modulation. The background signal at the modulation frequency (1 kHz) for EPR detection was also proportional to the magnitude of frequency modulation. An automatic matching control (AMC) system reduced the amplitude of noise in microwave detection and improved the baseline stability. Distortion of the spectral lineshape was seen when the spectrometer settings were not appropriate, e.g., with a lack of the open-loop gain in automatic tuning control (ATC). FM is an alternative to field modulation when the side-effect of field modulation is detrimental for EPR detection. The present spectroscopic technique based on the FM scheme is useful for measuring the first derivative with respect to the microwave frequency in investigations of electron-spin-related phenomena.     

Nonequivalent spectra of unpaired electrons in field and frequency modulation

We report a difference in the spectral lineshapes of continuous-wave (CW) electron paramagnetic resonance (EPR) spectroscopy between field and frequency modulation. This finding addresses the long-standing question of the effect of modulation in EPR absorption. We compared the first-derivative EPR spectra at 1.1 GHz for lithium phthalocyanine crystals, which have a single narrow linewidth in the EPR absorption spectrum, using field and frequency modulation. The experimental findings suggest that unpaired electrons have different behaviors under perturbation due to field and frequency modulation.     

Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation

We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).     

Energy Aspects of Thermal Molecular Switching: Molecular Thermal Hysteresis of Helicene Oligomers

Molecular switching is a phenomenon by which a molecule reversibly changes its structure and state in response to external stimuli or energy. Herein, molecular switching is discussed from thermodynamic and kinetic aspects in terms of energy supply with an emphasis on the thermal switching exhibited by helicene oligomers. It includes the inversion of relative thermodynamic stability induced by temperature changes and molecular thermal hysteresis in a closed system. The thermal phenomenon associated with the oligomers involves population/concentration changes between metastable states under nonequilibrium thermodynamic control.     

One-dimensional band-edge absorption in a doped quantum wire

Low-temperature photoluminescence-excitation spectra are studied in an n-type modulation-doped T-shaped single quantum wire with a gate to tune electron densities. With a nondegenerate one-dimensional (1D) electron gas, the band-edge absorption exhibits a sharp peak structure induced by the 1D density of states. When the dense 1D electron gas is degenerate at a low temperature, we observe a Fermi-edge absorption onset without many-body modifications.     

Biexciton gain and the Mott transition in GaAs quantum wires

Optical gain and the Mott transition in GaAs quantum wires were studied via simultaneous measurements of absorption and photoluminescence (PL). We observed well-separated PL peaks assigned to excitons (X) and biexcitons (XX) even at densities where optical gain existed. A sharp optical gain first appeared when the XX peak overtook the X peak, indicating the gain origin of biexciton-exciton population inversion. The XX peak eventually changed to a broad peak of plasma, and a broad gain due to plasma was observed as the Mott transition was completed.