Synthetic approach toward antibiotic tunicamycins — VI total synthesis of tunicamycins

Tunicamycins and their eight analogs have been synthesized by condensation of a N-acetyl-D-glucosamine derivative and an anomeric chloride of tunicaminyl uracil, followed by deprotections and N-acylation.     

Chamaechromone,a novel rearranged biflavonoid from Stellera chamaejasme L.

A novel biflavonoid, chamaechromone was isolated from $\text{Stellera chamaejasme}$ L. (Thymelaeaceae) and its structure elucidated by spectroscopic and chemical methods.     

Application of pattern recognition to structure-activity problems: Use of minimal spanning tree

A graph-theoretical algorithm based on the minimal spanning tree (MST) is applied to structure—activity problems. The method is helpful in interpreting the results of cluster analysis, and becomes useful by combining with the mapping method that illustrates approximations of a multidimensional data structure. The antibacterial spectra of cephalosporins are analyzed by the MST approach and a linear mapping method. The main diameter obtained by MST gives the representative data set and clarifies the substituent effect on the antibacterial spectra. Relations between the central nervous system activity of benzodiazepine derivatives and their physicochemical parameters are also analyzed by MST and nonlinear mapping methods. These results for cephalosporins and benzodiazepines prove that MST is very useful in understanding the position of compounds in feature space and their activities.     

Further studies on palytoxin. II. structure of palytoxin

The full structure of palytoxin, a potent coelenterate toxin, is reported.     

Biomimetic transformation of dehydrocurdione into curcumenol and isocurcumenol and their stereochemistries

Dehydrocurdione, a sesquiterpene isolated from $\text{Curcuma zedoaria}$, was converted to curcumenol, isocurcumenol or new spirolactones in a highly selective manner and their absolute configurations were determined.     

Absolute stereostructures of halenaquinol and halenaquinol sulfate,pentacyclic hydroquinones from the okinawan marine sponge xestospongia sapra, as determined by theoretical calculation of CD spectra

The absolute stereostructures of two pentacyclic hydroquinones, halenaguinol ($\text{1}$) and halenaquinol sulfate ($\text{2}$) from the Okinawan marine sponge Xestospongia sapra, have been determined by means of theoretical calculation of CD spectra.     

Photographic measurements of propagation speeds of the conducting zone in polyaniline films during electrochemical switching

In order to observe the propagation of a conducting zone of a polyaniline film in response to anodic switching, propagation perpendicular to the film surface was simulated by propagation along the film by mounting the film on an insulated plate. A polyaniline film electrochemically deposited on an indium tin oxide (ITO) electrode was reinforced by casting polymethylmethacrylate solution on the film. It was peeled off the ITO, chemically reduced and then potentiostatically oxidized at one end in 1 mol dm⁻³ H₂SO₄ solution. Dynamic growth of the conducting zone was observed through an optical microscope. A well-defined boundary between the conducting zone and the insulating zone was seen. The contrast of the boundary did not vary with the electrolysis time, the growth length or the applied potential. The growth rate decreased slightly with the electrolysis time as a result of IR drop across the film. A differential equation for growth rate involving the effect of the IR drop was presented and solved to give more accurate values of the rate. The logarithmic growth ratio exhibited a linear relation with the applied potential, indicating a charge-transfer rate of the Tafel type. The anodic transfer coefficient was 0.2 and the rate constant was 5 × 10⁻⁵ m s⁻¹. The propagation on a molecular scale was discussed on the basis of the experimental results.     

Purealin,a novel enzyme activator from the Okinawan marine sponge Psammaplysilla purea

Purealin , a novel secondary metabolite, which modurates enzymic reactions of ATPases, has been isolated from the okinawan marine sponge $\text{Psammaplysilla}$$\text{purea}$ and the structure has been determined by the ¹H-¹H homonuclear and ¹H-¹³C heteronuclear NMR chemical shift correlations and CD spectra.     

Configurational stabilization of mixed-valence states in the star-burst tetranuclear ruthenium complex bridged with acetylene links

A new tetranuclear ruthenium complex in which a metal was bridged radially to three identical metals with acetylene links showed a mixed-valence state in cyclic voltammograms. The peak potential difference for the mixed-valence state was twice the potential difference for a mixed-valence state of the corresponding binuclear complex. This fact suggests stabilization of the mixed-valence state twice by configurational modification of redox centers. However, this is inconsistent with the prediction from the additive pair model of the redox interaction. A quantum chemical model of the redox interaction was presented, in which the potential difference was expressed by the overlap integral S and the nearest neighbor interaction energy between the reduced center and the oxidized one. Application of the theory gave a negative value of S, which demonstrated reasonably the stabilization of the mixed-valence state from a quantum chemical viewpoint.     

Conformation of dithia[3.3]- and [2.2] azuleno(2,6)pyridinophanes

Four azuleno(2,6)pyridinophanes (1–4) were synthesized and their conformations were found by NMR spectroscopy to be very similar to those of the corresponding azulenometacyclophanes. A transverse conformational change was observed for [2.2](5,7)azuleno(2,6)pyridinophane.