We developed a statistical method for detecting discontinuous phase changes (phase shifts) in fluctuating alpha rhythms in the human brain from electroencephalogram (EEG) data obtained in a single trial. This method uses the state space models and the line process technique, which is a Bayesian method for detecting discontinuity in an image. By applying this method to simulated data, we were able to detect the phase and amplitude shifts in a single simulated trial. Further, we demonstrated that this method can detect phase shifts caused by a visual stimulus in the alpha rhythm from experimental EEG data even in a single trial. The results for the experimental data showed that the timings of the phase shifts in the early latency period were similar between many of the trials, and that those in the late latency period were different between the trials. The conventional averaging method can only detect phase shifts that occur at similar timings between many of the trials, and therefore, the phase shifts that occur at differing timings cannot be detected using the conventional method. Consequently, our obtained results indicate the practicality of our method. Thus, we believe that our method will contribute to studies examining the phase dynamics of nonlinear alpha rhythm oscillators.
Competitive cross-/homo-photocyclodimerization of anthracene (AN) and 2-anthracenecarboxylic acid (AC) mediated by a chiral hydrogen-bonding template (TKS) was investigated under various conditions. The cross-photocyclodimerization was favored by a factor of 4-5 at all temperatures and wavelengths examined to afford the AC-AN cross-dimer in 80-84% yield even at AN/AC = 1 and in 98% yield at AN/AC = 10. The enantiomeric excesses (ee's) obtained were 27-47% for the homo-dimers and 21-24% for the cross-dimer. The absolute configuration of the cross-dimer was determined by comparing the experimental and theoretical circular dichroism spectra and further correlated with the re/si enantiotopic-face selectivity upon AC-TKS complexation in the ground state. Detailed analyses of the complexation behavior and the fluorescence lifetime and cyclodimerization rate of excited re/si complexes revealed that the product's ee is critically controlled not only by the relative abundance of the re/si complexes in the ground and excited states but also by their relative photocyclodimerization rate. Crucially, the ground-state thermodynamics and the excited-state kinetics are not synergistic but offsetting in enantiotopic-face selectivity, and the latter overwhelms the former to give the homo- and cross-dimers in modest ee's. Finally, some practical strategies for enhancing the enantioselectivity in chiral template-mediated photochirogenesis have been proposed.
2-Hydroxyanthracene (HA) in its neutral form smoothly photocyclodimerized to four stereoisomeric [4 + 4]-cyclodimers, which were isolated and characterized for the first time, whereas the anionic form of HA turned out to be photochemically inert. Enantiodifferentiating photocyclodimerization of HA in the presence of a chiral hydrogen-bonding template (TKS159), γ-cyclodextrin (γ-CDx) and bovine serum albumin (BSA) was examined to afford chiral syn-head-to-tail and anti-head-to-head cyclodimers in modest enantiomeric excesses with TKS159 and γ-CDx, but practically no photocyclodimerization proceeded in the presence of BSA probably due to the ionization of HA in the binding sites.
Previous studies suggest that the left inferior frontal cortex is involved in the resolution of lexical ambiguities for language comprehension. In this study, we hypothesized that processing of lexical ambiguities is improved when the excitability of the left inferior frontal cortex is enhanced. To test the hypothesis, we conducted an experiment with transcranial direct current stimulation (tDCS). We investigated the effect of anodal tDCS over the left inferior frontal cortex on behavioral indexes for semantic judgment on lexically ambiguous and unambiguous words within a context. Supporting the hypothesis, the RT was shorter in the anodal tDCS session than in the sham session for ambiguous words. The results suggest that controlled semantic retrieval and contextual selection were facilitated by anodal tDCS over the left inferior frontal cortex.
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