Synthesis and structure-activity relationships in a series of ethenesulfonamide derivatives, a novel class of endothelin receptor antagonists.

In the previous paper, we described a series of the 2-arylethenesulfonamide derivatives, a novel class of ETA-selective endothelin (ET) receptor antagonists, including the compounds 1a, b. Compound 1a showed excellent oral antagonistic activities and pharmacokinetic profiles, and the monopotassium salt of 1 (YM-598 monopotassium) is in clinical trials. In this paper, we wish to report the investigation of the further details of structure-activity relationships (SARs) of the 2-phenylethenesulfonamide region in 1a. It was found that methyl substitutions at the 2-, 4- and 6-positions of the phenyl group in 1a led to the discovery of the ET(A)/ET(B) mixed antagonist (6s) with an IC50 of 2.2 nM for the ET(A) receptor. We also found that introduction of an ethyl group to the 1-position of the ethenyl group in 1a gave the ET(A) selective antagonist (6u) with an oral endothelin antagonistic activity in rats.     

An anthracene-based Cd fluorescent chemosensor with a 4,7-bis(2-hydroxyethyl)-9-hydroxy-1,4,7-triazanonyl group as a highly selective chelator to Cd over Zn

We have developed a Cd²⁺ fluorescent chemosensor with high selectivity as well as sensitivity by tethering a 4,7-bis(2-hydroxyethyl)-9-hydroxy-1,4,7-triazanonyl chelator to anthracene. This sensor features the ability to discriminate Cd²⁺ from Zn²⁺ to a high degree (K_dZn/K_dCd = 560) in a pH 7.2 buffer.     

Photoconductive properties of titanium dioxide film modified by femtosecond laser irradiation

Titanium dioxide (TiO₂) films were irradiated with a femtosecond laser to alter their photoconductive properties. The laser wavelength and pulse duration were 775 nm and 150 fs, respectively. The TiO₂ films irradiated with the femtosecond laser were darkened without changing the topography of the TiO₂ film surface. The electrical resistances of the films as a function of time were measured under visible-light illumination. The transient electrical resistances decreased as time was increased after turning on the light. There were two stages in the reduction process of the electrical resistance.     

A novel disaccharide,wilforibiose from cynanchum wilfordi h(=emsl)

The structure of a novel disaccharide, wilforibiose, isolated from the root of $\text{Cynanchum wilfordi}$ H(=emsl), has been established by spectral data.     

Cyclic strength of imperfectly saturated sands and analysis of liquefaction

The simplified method of analysis to assess liquefaction potential of a given sand deposit is briefly introduced in the first part of this paper. Then, recent advances in the laboratory testing for evaluating liquefaction resistance are described with a particular emphasis on the sand partly saturated with water. As a means to identify the degree of saturation which is applicable for both field deposits and laboratory samples, the use of the longitudinal wave (P-wave) is proposed based on a suite of data obtained from the triaxial tests in the laboratory. It is recommended that the non-destructive P-wave measurements be carried out first to determine the degree of saturation, and then the cyclic triaxial tests involving large destructive strains should be performed to determine the cyclic strength on the same sample of the sand. In order to demonstrate usefulness of the proposed approach, two sets of undisturbed samples were secured from two sites; one is located in Sakai-minato city which has suffered severe liquefaction at the time of the 2000 Tottoriken-Seibu earthquake and the other site is located in Koshigaya city, Saitama, where likelihood of liquefaction to occur in a future earthquake is of major concern. Penetration tests and in-situ velocity logging were also conducted at these two sites. By adjusting the P-wave velocity of the undisturbed samples in the laboratory so as to have the same velocity in the field, the in-situ state of saturation was reproduced in the laboratory samples. Then, the cyclic loading tests were conducted to determine the cyclic strength of intact samples. The results of the laboratory tests as above were incorporated into the simple method of liquefaction analysis described in the first section of this paper. The analysis seems to yield results which are in reasonably good agreement with what was observed at the time of the earthquake.     

Mössbauer Spectroscopic Study of a Mural Painting from Morgadal Grande,Mexico

Hyperfine Interactions - In this study, 57Fe Mössbauer spectroscopy has been applied to fragments of a mural painting excavated at Morgadal Grande, Mexico, to characterize the pigments used. A...     

Trends of optically fed wireless communication systems

Mobile communication systems such as cellular radio and PHS are rapidly penetrating into our real life, and have gained many subscriber numbers. User demands will be growing to higher data rates that support multimedia mobile computing demands, such as graphics and motion pictures. These demands require more band width and/or spectrum utilization efficiency enhancement, and optically fed communication systems are considered to be one of the most powerful solutions. In this paper, the roles, technologies and application examples of optically fed communication systems are described. In the final part, prospects for systems and requirements for photonic devices are mentioned.     

Disposition of ipriflavone (TC-80) in rats and dogs

Oral 14C-ipriflavone was absorbed by rats to give a maximum plasma 14C level at 1.5 h and a half-life of 5.8 h. In dogs, after po dosing, the plasma 14C peaked at 0.5 h, followed by gradual decline. The plasma of both animals contained mostly metabolites, with small amounts of unchanged ipriflavone. In rats, 14C was distributed widely in tissues, with relatively high concns. in the liver, kidney and gut. Distribution in rat thigh bone of unmetabolized ipriflavone was also demonstrated. 14C-Ipriflavone was eliminated mostly as metabolites within 48 and 72 h, respectively, in rats and dogs. Rats excreted more 14C in urine than in feces, whereas the reverse was noted in dogs. Biliary excretion and reabsorption of 14C were also obvious in both animals.     

Unusual reaction of 2-trimethylsilylethylidenetriarylphosphoranes (seyferth-wittig reagent) with α-methylaldehydes: a novel method for highly cram-diastereoselective addition of vinyl anion equivalent

By the reaction of α-methylaldehydes with trimethylsilylethylidenetriarylphosphoranes the introduction of vinyl group is effected in highly Cram-selective manner.     

Mechanism of asymmetric hydrogenation of alpha-(acylamino)acrylic esters catalyzed by BINAP-ruthenium(II) diacetate

The mechanism of asymmetric hydrogenation of alpha-(acylamino)acrylic esters with Ru(CH(3)COO)(2)[(S)-binap] (BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl), giving the S saturated products in >90% ee, has been investigated by means of a kinetic study, deuterium labeling experiments, isotope effect measurements, and NMR and X-ray analysis of certain Ru complexes. The hydrogenation in methanol under a low H2 pressure proceeds via a monohydride-unsaturate mechanism that involves the initial RuH formation followed by a reaction with an olefinic substrate. The migratory insertion in the enamide-RuH chelate complex occurs reversibly and endergonically in an exo manner, giving a five-membered metallacycle intermediate. The cleavage of the Ru-C bond is achieved with either H2 (major) or CH3OH (minor). Both of the pathways result in overall cis hydrogenation products. The hydrogen at C3 is mainly from an H2 molecule, and the C2 hydrogen is from another H2 or protic CH3OH. The major S and minor R enantiomers are produced via the same mechanism involving diastereomeric intermediates. The turnover rate is limited by the step of hydrogenolysis of a half-hydrogenated metallacyclic intermediate. The participation of two different hydrogen donor molecules is in contrast to the pairwise dihydrogenation using a single H2 molecule in the RhI-catalyzed reaction which occurs via a dihydride mechanism. In addition, the sense of asymmetric induction is opposite to that observed with S-BINAP-RhI catalysts. The origin of this phenomenon is interpreted in terms of stereocomplementary models of the enamide/metal chelate complexes. A series of model stoichiometric reactions mimicking the catalytic steps has indicated that most NMR-observable Ru complexes are not directly involved in the catalytic hydrogenation but are reservoirs of real catalytic complexes or even side products that retard the reaction.