Synthesis, π‐Face‐Selective Aggregation,and π‐Face Chiral Recognition of Configurationally Stable C3‐Symmetric Propeller‐Chiral Molecules with a π‐Core

The C₃‐symmetric propeller‐chiral compounds (P,P,P)‐ 1 and (M,M,M)‐ 1 with planar π‐cores perpendicular to the C₃‐axis were synthesized in optically pure states. (P,P,P)‐ 1 possesses two distinguishable propeller‐chiral π‐faces with rims of different heights named the (P/L)‐face and (P/H)‐face. Each face is configurationally stable because of the rigid structure of the helicenes contained in the π‐core. (P,P,P)‐ 1 formed dimeric aggregates in organic solutions as indicated by the results of ¹H NMR, CD, and UV/Vis spectroscopy and vapor pressure osmometry analyses. The (P/L)/(P/L) interactions were observed in the solid state by single‐crystal X‐ray analysis, and they were also predominant over the (P/H)/(P/H) and (P/L)/(P/H) interactions in solution, as indicated by the results of ¹H and 2D NMR spectroscopy analyses. The dimerization constant was obtained for a racemic mixture, which showed that the heterochiral (P,P,P)‐ 1 /(M,M,M)‐ 1 interactions were much weaker than the homochiral (P,P,P)‐ 1 /(P,P,P)‐ 1 interactions. The results indicated that the propeller‐chiral (P/L)‐face interacts with the (P/L)‐face more strongly than with the (P/H)‐face, (M/L)‐face, and (M/H)‐face. The study showed the π‐face‐selective aggregation and π‐face chiral recognition of the configurationally stable propeller‐chiral molecules.     

Preparation of α-trialkylsilyl ketones from α-phenylseleno derivatives via their silyl enol ethers

On treatment with metallic lithium in the presence of dimethylaminonaphthalene, trialkylsilyl enol ethers of α-phenylseleno ketones were converted into the corresponding α-trialkylsilyl ketones in good yields.     

Acceptable range of speech level in noisy sound fields for young adults and elderly persons

The acceptable range of speech level as a function of background noise level was investigated on the basis of word intelligibility scores and listening difficulty ratings. In the present study, the acceptable range is defined as the range that maximizes word intelligibility scores and simultaneously does not cause a significant increase in listening difficulty ratings from the minimum ratings. Listening tests with young adult and elderly listeners demonstrated the following. (1) The acceptable range of speech level for elderly listeners overlapped that for young listeners. (2) The lower limit of the acceptable speech level for both young and elderly listeners was 65 dB (A-weighted) for noise levels of 40 and 45 dB (A-weighted), a level with a speech-to-noise ratio of +15 dB for noise levels of 50 and 55 dB, and a level with a speech-to-noise ratio of +10 dB for noise levels from 60 to 70 dB. (3) The upper limit of the acceptable speech level for both young and elderly listeners was 80 dB for noise levels from 40 to 55 dB and 85 dB or above for noise levels from 55 to 70 dB.     

Hydrolysis of ionized deoxycholic acid in the aqueous phase and rate analysis for transfer of neutralized deoxycholic acid into the benzene phase across the benzene/water interface

Sodium deoxycholate in water dissociates into sodium cation and deoxycholate anion in the aqueous phase, and then, the latter anions partially hydrolyze to form deionized deoxycholic acids. The acids move into the benzene phase, when liquid benzene is placed upon the aqueous phase, and finally the partition equilibrium is reached. The above processes were traced by pH change in the aqueous phase by a pH meter or the change in [OH-] with time, from which the rate for transfer of neutralized acid to the organic phase was analyzed. From the trace, the rate constants for hydrolysis of acid anion ( kf), neutralization of acid ( kb), transfer of neutralized acid from the aqueous phase to the organic phase ( kin*), and its back-transfer from the organic phase to the aqueous phase ( kut*) were evaluated; kf = 2.18 x 10 (-4) mol (-1) dm (3) min (-1), kb = 1.24 x 10 (5) mol (-1) dm (3) min (-1), kin* = 4.06 x 10 (-1) min (-1) cm (-2), and kout*) = 8.00 x 10 (-2) min (-1) cm (-2). The above values are supported by the partition constant of deoxycholic acid between the benzene phase and the aqueous phase.     

Electrooptics of beta-FeOOH particle in aqueous media 2. Field-strength dependence of decay and steady-state birefringence, and the hydrodynamic and electrooptic properties

Steady-state and decay birefringence, expressed in terms of the optical phase retardation per cell length delta/d, was measured on beta-FeOOH in aqueous ionic media at 633 nm and at 25 degrees C by an electric square-pulse technique over a wide range of field strength E to ca. 6 kV/cm. The field-strength dependence of both delta/d and field-free rotational relaxation time tau was determined at the sample concentrations between 0.0011 and 0.055 g/L and in the 0.02-2.0 mM NaCl concentration range. Extrapolation of both delta/d and tau values to infinitely high fields (E(2)-->infinity) could yield birefringence- and weight-average quantities, respectively. Observed tau values were decreased at weak fields but leveled off to ca. 0.3 ms at very high fields due to a slight polydispersity regarding the length and volume of particles. The weight-average relaxation time tau(w) was calculated with Perrin's expressions theoretically from the length, width, and volume of beta-FeOOH particles estimated in the dried state from electron micrograph. These quantities were variously averaged. The size distribution was discussed in terms of observed discrete histogram and theoretical (Weibull and Lansing-Kraemer) distribution functions. The sign of observed delta/d value was always positive. The infinitely high-field (delta/d)(infinity) values and the reduced optical anisotropy factor Delta g/n were evaluated by fitting to theoretical orientation functions. The intrinsic birefringence (n3-n1) could be estimated with the mean refractive index n(p) reported in the literature. For the spindle-shaped particle with an axial ratio of ca. 4, the sign of Delta g/n is always positive, whereas the quantity (n3-n1) was either negative (n(p) > 2.35) or positive (n(p) < 2.05) in sign or nearly zero (ca. n(p) = 2.26), depending critically on the n(p) values.