128 research outputs found
Adaptation in Sound Localization Processing Induced by Interaural Time Difference in Amplitude Envelope at High Frequencies
<div><h3>Background</h3><p>When a second sound follows a long first sound, its location appears to be perceived away from the first one (the localization/lateralization aftereffect). This aftereffect has often been considered to reflect an efficient neural coding of sound locations in the auditory system. To understand determinants of the localization aftereffect, the current study examined whether it is induced by an interaural temporal difference (ITD) in the amplitude envelope of high frequency transposed tones (over 2 kHz), which is known to function as a sound localization cue.</p> <h3>Methodology/Principal Findings</h3><p>In <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0041328#s2">Experiment 1</a>, participants were required to adjust the position of a pointer to the perceived location of test stimuli before and after adaptation. Test and adapter stimuli were amplitude modulated (AM) sounds presented at high frequencies and their positional differences were manipulated solely by the envelope ITD. Results showed that the adapter's ITD systematically affected the perceived position of test sounds to the directions expected from the localization/lateralization aftereffect when the adapter was presented at ±600 µs ITD; a corresponding significant effect was not observed for a 0 µs ITD adapter. In <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0041328#s3">Experiment 2</a>, the observed adapter effect was confirmed using a forced-choice task. It was also found that adaptation to the AM sounds at high frequencies did not significantly change the perceived position of pure-tone test stimuli in the low frequency region (128 and 256 Hz).</p> <h3>Conclusions/Significance</h3><p>The findings in the current study indicate that ITD in the envelope at high frequencies induces the localization aftereffect. This suggests that ITD in the high frequency region is involved in adaptive plasticity of auditory localization processing.</p> </div
Proportion of “right” responses as a function of the ITD of the test stimuli of one participant (S3).
<p>The left panels show the results in AM adapter condition (128-Hz modulation frequency), and the right panels show those in tone adapter condition (128 Hz). Each row displays results in each test condition: The abbreviations P128 and P256 refer to the 128- and 256-Hz tone respectively. AM128 and AM256 refer to the AM sounds that were modulated with 128 and 256 Hz. Unfilled circles indicate the results in the no-adapter condition. Filled and unfilled triangles indicate the results in the −937 and 937 µs ITD conditions respectively. There is a relatively larger aftereffect when both the adapting and test stimuli are AM tones.</p
The average magnitude of the aftereffect in each adapter condition as a function of the type of test stimuli.
<p>See the caption of <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0041328#pone-0041328-g002" target="_blank">Figure 2</a> for explanation of abbreviations such as P128. There are relatively large aftereffects when the adapter and test stimuli are of the same type. Error bars show SEs.</p
Average normalized responses as a function of the ITD of the test stimulus.
<p>Error bars represent standard errors. After the adaptation at ±600 µs, the subjective midline shifted towards the position of the adapter. Error bars show SEs.</p
Development of a Sila-Friedel−Crafts Reaction and Its Application to the Synthesis of Dibenzosilole Derivatives
Development of a Sila-Friedel−Crafts Reaction and Its Application to the Synthesis of Dibenzosilole Derivative
A Potential Intermediate for the Aza-Corey−Chaykovsky Reaction: Synthesis, Structure, and Thermolysis of a Pentacoordinate 1,2-Thiazetidine 1-Oxide
Thermolysis of a pentacoordinate 1λ6,2-thiazetidine, which was synthesized for the first time and characterized by X-ray crystallographic
analysis, gave the corresponding aziridine and a cyclic sulfinate almost quantitatively. The potential intermediacy of a 1λ6,2-thiazetidine was
suggested in the aza-Corey−Chaykovsky reaction
Systematic Study on the Structures and Reactivity of Hydrazobenzenes and Azobenzenes Bearing a Chalcogenophosphoryl Group
Hydrazobenzenes 3−5 bearing a chalcogenophosphoryl group were synthesized by palladium-catalyzed cross-coupling reactions. Their X-ray crystallographic analyses and NMR and IR spectra showed the presence of
intramolecular hydrogen bonds between the N−H protons and the chalcogenophosphoryl groups. The intermolecular
hydrogen bonds in phosphine oxide 3 and selenide 5 were observed in the solid state. Phosphine oxide 3, sulfide
4, and selenide 5 constructed a dimeric structure, a discrete monomeric structure, and a chain structure, respectively.
As the chalcogen atom changed, the crystalline structures of the 2-chalcogenophosphorylhydrazobenzenes also
changed. The hydrogen bonds affected the oxidation reactions of the hydrazobenzenes, and oxidation of
hydrazobenzenes bearing a lighter chalcogen atom was more difficult. For azobenzenes bearing a chalcogenophosphoryl group, X-ray crystallographic analyses and NMR spectra showed little interaction between the azo
group and the chalcogenophosphoryl groups. However, in the UV−vis spectra, the red shifts of the absorption
maxima due to the n → π* transitions indicated intramolecular interactions in the excited state, in contrast to the
corresponding 4-substituted azobenzenes. In addition, photoirradiation of phosphine oxide (E)-7 gave (Z)-7, whereas
that of phosphine sulfide (E)-8 and phosphine selenide (E)-9 did not give (Z)-8 and (Z)-9, suggesting that heavy
chalcogen atoms quench excited states by through-space interactions. Introduction of a chalcogenophosphoryl
group at the 2-position had a significant effect on the structure, spectral properties, and reactivity of hydrazobenzenes
and azobenzenes. Although azobenzene (E)-10 bearing a hydroxyphosphoryl group at the 2-position did not show
hydrogen bonding in the crystalline state, its optical properties and photoisomerization ratio were different from
those of (E)-7
Reversible Photocontrol of the Coordination Number of Silicon in a Tetrafluorosilicate Bearing a 2-(Phenylazo)phenyl Group
Reversible Photocontrol of the Coordination Number
of Silicon in a Tetrafluorosilicate Bearing a
2-(Phenylazo)phenyl Grou
Isolation of a Metastable Geometrical Isomer of a Hexacoordinated Dihydrophosphate: Elucidation of Its Enhanced Reactivity in Umpolung of a Hydrogen Atom of Water
Two of five conceivable geometrical isomers of a hexacoordinated dihydrophosphate bearing two sets of a bidentate ligand were investigated. X-ray crystallographic analysis of both of isomers, 1a-TPP and 1b-TEA, revealed their octahedral geometries of C2 and C1 symmetry, respectively, which were consistent with the NMR spectra. The isomer 1b-TEA underwent both hydride reduction of an aldehyde and proton exchange with water at room temperature in DMSO without any additive. A one-pot reaction of both of the reactions of 1b-TEA with D2O and an aldehyde or a ketone under the above conditions proceeded successfully to give the deuterated alcohol. Thus, umpolung of a hydrogen atom of water with 1b-TEA was achieved under much milder conditions than those used in the reaction with another isomer, 1a-TEA. Quantitative isomerization of 1b-TEA to 1a-TEA occurred in methanol at room temperature. Calculations on the five conceivable geometrical isomers of the anionic part of the dihydrophosphate revealed their relative stability, which reasonably explained the isomerization, and the larger negative charge at the atoms located at the trans positions of the oxygen atoms. The smaller coupling constants of the P–H and P–C bonds located at the rear of an oxygen atom in the NMR spectra resulted in the smaller s character of these bonds. The differences in both hydride-donation and proton-exchange reactivities between 1a-TEA and 1b-TEA could be explained by the differences in the atomic charge of the hydrogen atom and the stability difference of the initially formed phosphorane intermediates, respectively
Thermal and Photocontrol of the Equilibrium between a 2-Phosphinoazobenzene and an Inner Phosphonium Salt
The reversible conversion between a phosphine and a phosphonium salt has been achieved by external stimuli of light and heat. Two 2-phosphinoazobenzenes were successfully synthesized by desulfurization of the corresponding phosphine sulfides. One of the phosphines bearing an azo group was in equilibrium with an inner phosphonium salt and showed thermochromism, which is derived from the change of the equilibrium constant depending on the temperature. While the 2-phosphinoazobenzene reacted as a usual triarylphosphine, its reaction with water gave phosphine oxide bearing a hydrazine moiety via a mechanism similar to the Mitsunobu reaction. The 2-phosphinoazobenzene bearing a methyl group at the 4‘-position of azobenzene was isomerized to the Z-isomer by irradiation. The Z-isomer was neither in equilibrium with an inner phosphonium salt nor hydrolyzed, in contrast to the E-isomer, because its geometry is difficult for an intramolecular nucleophilic attack. Photoisomerization caused the switching of the unique reactivity toward water. Such phosphines in equilibrium with the inner phosphonium salts are expected to be useful to control organic reactions by taking advantage of the photoisomerization of the azobenzene moiety
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