Defect-Free Synthesis of a Fully π-Conjugated Helical Ladder Polymer and Resolution into a Pair of Enantiomeric Helical Ladders**

Fully π-conjugated ladder polymers with a spiral geometry represent a new class of helical polymers with great potential for organic nanodevices, but there is no precedent for an optically active helical ladder polymer totally composed of achiral units. We now report the defect-free synthesis and resolution of a fully π-conjugated helical ladder polymer with a rigid helical cavity, which has been achieved by quantitative and chemoselective acid-promoted alkyne benzannulations of a rationally designed, random-coil achiral polymer followed by chromatographic enantioseparation. Because of a sufficiently high helix-inversion barrier, the isolated excess one-handed helical ladder polymer with a degree of polymerization of more than 15 showed a strong circular dichroism with a dissymmetry factor of up to 1.7×10⁻² and is thermally stable, maintaining its optical activity in solution even at 100 °C, as well-supported by molecular dynamics simulation.     

The Transition State of Free Radical SH2′ Reaction of Allyl Chloride with Organomercurial Study by Inverse Secondary α‐Deuterium Kinetic Isotope Effect

The concerted mechanism of free radical S_H2′ reaction of 2‐substituted allyl chloride was suggested again by inverse secondary α‐deuterium isotope effect. The transition state of free radical S_H2′ reaction of allyl chlorides seems to be symmetrical and is not as early as that of a free radical addition reaction.     

Synthesis of 2‐[4‐(Imidazolin‐2‐Ylideneamino)Benzyl]‐Indan‐1‐Ones as Novel Potent Prostacyclin Antagonists

Prostacyclin is involved in many pathological conditions, such as sensitization of inflammation induced pain and isovolumetic distention. Therefore, antagonism of prostacyclin action may be useful in the alleviation of these conditions. In this study, novel potent prostacyclin antagonists, 2‐[4‐(imidazolin‐2‐ylideneamino)benzyl]‐indan‐1‐ones were synthesized from their respective substituted indanones in three steps. The construction of the amino‐imidazole moiety of these derivatives is achieved by using in situ generation of chloro‐imidazole and reaction with their respective anilines. Thus, these N‐substituted 2‐imidazolines can be prepared safely and efficiently. Moreover, these compounds show potent prostacyclin antagonistic activity by inhibition of prostacyclin agonist induced ERK_1/2 phosphorylation in human erythroleukemia cells. Moreover, we observed an increase in activity with the increase in electro‐donating property of the substitution on the indanone aromatic ring. Prostacyclin antagonists with increased potency may be designed based on these findings. These compounds may also be invaluable tools for the study of the physiological functions of prostacyclin.     

Calibration of a compact XUV soft X‐ray monochromator with a digital autocollimator in situ

A digital autocollimator of resolution 0.1 µrad (0.02 arcsec) serves as a handy correction tool for calibrating the angular uncertainty during angular and lateral movements of gratings inside a monochromator chamber under ultra‐high vacuum. The photon energy dispersed from the extreme ultraviolet (XUV) to the soft X‐ray region of the synchrotron beamline at the Taiwan Light Source was monitored using molecular ionization spectra at high resolution as energy references that correlate with the fine angular steps during grating rotation. The angular resolution of the scanning mechanism was <0.3 µrad, which results in an energy shift of 80 meV at 867 eV. The angular uncertainties caused by the lateral movement during a grating exchange were decreased from 2.2 µrad to 0.1 µrad after correction. The proposed method provides a simple solution for on‐site beamline diagnostics of highly precise multi‐axis optical manipulating instruments at synchrotron facilities and in‐house laboratories.     

A two‐scale low‐Reynolds number turbulence model

In this study, a two‐scale low‐Reynolds number turbulence model is proposed. The Kolmogorov turbulence time scale, based on fluid kinematic viscosity and the dissipation rate of turbulent kinetic energy (ν, ε), is adopted to address the viscous effects and the rapid increasing of dissipation rate in the near‐wall region. As a wall is approached, the turbulence time scale transits smoothly from a turbulent kinetic energy based (k, ε) scale to a (ν, ε) scale. The damping functions of the low‐Reynolds number models can thus be simplified and the near‐wall turbulence characteristics, such as the ε distribution, are correctly reproduced. The proposed two‐scale low‐Reynolds number turbulence model is first examined in detail by predicting a two‐dimensional channel flow, and then it is applied to predict a backward‐facing step flow. Numerical results are compared with the direct numerical simulation (DNS) budgets, experimental data and the model results of Chien, and Lam and Bremhorst respectively. It is proved that the proposed two‐scale model indeed improves the predictions of the turbulent flows considered. Copyright © 2000 John Wiley & Sons, Ltd.     

Irciformonins E – K,C22‐Trinorsesterterpenoids from the Sponge Ircinia formosana

Chemical investigation of the sponge Ircinia formosana resulted in the isolation of seven new linear C₂₂‐sesterterpenoids, irciformonins E–K ( 1 – 7 ) in addition to irciformonin A ( 8 ), a previously isolated furanosesterterpenoid (=a furan‐moiety‐containing sesterterpenoid) from the same species. The structures were determined by interpretation of HR‐ESI‐MS and 2D‐NMR spectra. The structure of irciformonin A ( 8 ) was revised. Compound 5 exhibited significant inhibition of peripheral blood mononuclear cell proliferation induced by phytohemaglutinin.     

Sidelobe suppression of spectral response in holographic optical filter

In order to suppress sidelobes of holographic filter’s spectral response we propose to use weighting of grating intensity distribution along light propagation. This can be realized in photorefractive material (for example in LiNbO₃:Fe) by using spatial selective decaying of conventional uniform grating by illumination of light through some transparent mask. Experimental results show that it is able to obtain 8 dB improvement of sidelobe level compared to uniform grating. But it is accompanied by 1.7 times expansion of main lobe and two times decrease of diffraction efficiency.     

Synthesis of the Chiral Pair of a Novel Thromboxane Antagonist, 3‐[2‐(3‐Benzenesulfonylamino‐7‐oxabicyclo[2.2.1]hept‐2‐yl‐methyl)phenyl] Propionic Acid

Preparation of the enantiomeric pair of 3‐[2‐(3‐benzenesulfonylamino‐7‐oxabicyclo[2.2.1]hept‐2‐yl‐methyl)phenyl] propionic acid, a novel thromboxane antagonist is reported. They are synthesized from either enantiomers of known (1R,2R,3R,4S)‐3‐[2‐(3‐carboxy‐7‐oxabicyclo[2,2,1]hept‐2‐yl‐methyl)phenyl]‐propionic acid methyl ester via epimerization, modified Curtius' rearrangement and sulfonylamino formation. Other derivatives may be prepared similarly.     

A Digital-Image-Processing-Based Computer System to Measure the Area Under Curves

Experimental Techniques -     

Lesions involving the fourth ventricle evaluated by CT and MR: A comparative study

A retrospective review of 21 patients with lesions involving the fourth ventricle was performed to determine the relative capability of computed tomography (CT) and MR for detection, characterization, localization, and diagnosis. Lesions involving the fourth ventricle included ependymoma (three), subependymoma (one), glioma (five), cysticercosis cyst (three), medulloblastoma (three), bleeding into the fourth ventricle (two), epidermoid cyst (two), “trapped” fourth ventricle (one), and lymphomatoid granuloma (one). Posterior fossa lesions that displaced but did not invade the fourth ventricle were excluded. Lesion detectability on CT was judged excellent in ten, good in 8, and fair or poor in 3. Detectability of lesions by MR was judged excellent in 16 and good in 5. There was complete agreement on lesion extension between CT and MR in 6 lesions, mild disagreement in 4, and moderate to significant disagreement in 11. Preoperatively, MR alone correctly diagnosed seven lesions, and CT alone correctly diagnosed three lesions. A review of the combined scans (after the correct diagnosis was given) showed both CT and MR were equal in the diagnosis of 14 lesions, MR better than CT in six, and CT better in one. There was complete agreement on both CT and MR with the surgical/pathologic findings in three lesions. Both studies proved disappointing in their ability to make the correct histologic diagnosis, probably because CT and MR characteristics may not always offer a definitive diagnosis and because of the wide spectrum of pathologic processes that may involve the fourth ventricle.