Kinetic analysis of cis-trans thermal isomerization of polyacetylene

A single broad exothermic peak due to cis-trans isomerization appears near 140°C in the differential scanning calorimetry (DSC) curve of polyacetylene (PA) films, polymerized by a nonsolvent method using a high-temperature-aged catalyst. This exothermic peakis described by a two-state model, in which population probabilities for cis and trans states are assumed to change through the forward and backward reactions. The enthalpy difference between the two states is 1.69 kcal/mol, which was derived from the slope of the plot of heat of isomerization versus cis content. The activation energy was determined experimentally from the heating-rate dependence of the peak temperature. A single activated process with an activation energy of 28 kcal/mol was observed for the PA film. Other parameters such as the preexponential factor were estimated by comparing theoretical and experimental DSC curves.     

Optogalvanic detection of negative ions in discharges

With the aid of rf, microwave and dc discharges, an optogalvanic (OG) signal, due to the photodetachment of negative oxygen ions, has been observed. The OG signal intensity in an rf discharge was successfully estimated from the discharge parameters. Thus, the OG technique may be potentially useful as a plasma diagnostic method. Furthermore, the OG signal from negative oxygen ions is found to be strong in the diffusion-controlled positive column, while the OG signal due to the excited levels of atomic oxygen is strong in the cathode fall region. Preliminary results for the observation of the OG signal in discharges of H₂, CO, H₂O₂, and (COCH₃)₂ are also described.     

Direct monitoring of enzymatic glucan hydrolysis on a 27-MHz quartz-crystal microbalance

By using a highly sensitive 27-MHz glucan-immobilized quartz-crystal microbalance, we could follow kinetically all processes (enzyme binding and release, kon and koff, and intramolecular hydrolysis rates, kcat) of glucan hydrolysis by glucoamylase by detecting directly the formation and decay of the enzyme-substrate complex as mass changes.     

Biosynthesis of lambertellols based on the high specific incorporation of the 13C-labeled acetates and their biological properties

Biosyntheses of lambertellols A (1) and B (2) as well as lambertellin (3) were investigated by isotope labeling experiments. Nearly 40% of specific incorporation of [1,2-(13)C(2)]acetate was achieved, and all the carbons in 1 and 2 were labeled. This high incorporation of the labeled acetate was realized by providing INADEQUATE spectra by employing only 0.4 and 0.7 mg of 1 and 2, respectively. Our studies revealed that 1-3 are biogenetically synthesized via loss of two carbons from octameric acetate. A biological assay against Monilinia fructicola revealed those remarkably inhibited hyphal germinations. However, neither of them killed the spores immediately, even in high concentration. These conditions induced the formation of microconidia.     

Positive homotropic allosteric binding of benzenediols in a hydrindacene-based exoditopic receptor: cooperativity in amide hydrogen bonding

The preparation and complexation properties of a hydrindacene-based exoditopic receptor, that exhibits a positive homotropic allosteric binding process toward benzenediols, are described. The exoditopic receptors form 1:2 complexes with resorcinols, catechol, and 3-hydroxybenzyl alcohol with K2/K1 = 3-33. Both the entropy and the enthalpy terms are important in this allosteric system; the crystallographic studies provide the first clear evidence that the cooperativity in amide hydrogen bonding by polarization contributes to the positive homotropic allosteric binding property.     

Estimation of HRTFs on the horizontal plane using physical features

Sound localization can be controlled by using head related transfer functions (HRTFs), which are related to the size of the head, the ears and so on. Since HRTFs are characterized by source directions and subjects, it is necessary to conduct measurements in all directions for all subjects. However, such measurement is expensive and time-consuming. In this paper, we propose a simpler and more useful method that investigates the relationship between HRTFs and physical size by multiple regression analysis. The estimated HRTFs are evaluated by objective and subjective measures. For objective results, the average spectral distortion score is 4.0 dB in a bandwidth ranging from 0 to 8 kHz. Subjective results indicate no significant difference between the measured and the estimated HRTFs in that frequency range. These results support the hypothesis that the proposed method is effective for estimating HRTFs.