Analytical high-performance affinity chromatography of ovalbumin-derived glycopeptides on columns of concanavalin A-and wheat germ agglutinin-immobilized gels

Concanavalin A (Con A) or wheat germ agglutinin (WGA) was immobilized on a silica-based support, and the chromatographic behaviours of a series of dansylated ovalbumin-derived glycopeptides on small columns of the resultant gels were compared. These columns had high contents of lectins, and allowed differentiation of these glycopeptides. This method was rapid and reproducible, and enabled sensitive detection of these fluorescent glycopeptides. The structural requirement of these glycopeptides to manifest affinity to the immobilized lectins is also discussed, based on binding constants obtained from their retention times.     

Furan derivatives. Part 8 On substituent effects in the synthesis of 4,5-dihydro-3H-naphtho[1,8-bc]furans

4,5-Dihydro-3H-naphtho[1,8-bc]furans 4 and 6 which have various substituents (R¹ and R²) have been synthesized from 8-oxo-5,6,7,8-tetrahydro-1-naphthyloxyacetic acids 1 and 3 or their ethyl esters 2 . The reaction of acids 1 and 3 with sodium acetate in acetic anhydride gave a mixture of furans 4 and 6 and lactones 5 and 7 . The ratios of the products were varied according to the types of substituents (R¹ and R²) in acids 1 and 3 . As the substituent R¹ (R² = hydrogen) in acids 1 was changed from hydrogen to a methyl, ethyl or isopropyl group, production of furans 4 became more difficult. However, when a phenyl group was used as the substituent, furan 4 was obtained in good yield. Similarly, as the substituent R² (R¹ = hydrogen) in acids 1 was changed from hydrogen to a methyl, ethyl or isopropyl group, furan formation was more difficult. In contrast, acids 3 which had electron-withdrawing substituents such as chlorine, bromine or a nitro group at the 4-position afforded furans 6 in good yield. 4,5-Dihydro-3H-naphtho[1,8-bc]furans 4 and 4,5-dihydro-3H-naphtho[1,8-bc]furan-2-carbocylic acids 8 were synthesized from the reaction of esters 2 and potassium hydroxide in dioxane. When the substituents R¹ or R² in esters 2 were varied from hydrogen to a methyl, ethyl or isopropyl group the total yields of furans 4 and furancarboxylic acids 8 were reduced.     

Regiospecific α-dialkoxymethylation of preformed enolates

Reaction of a preformed lithium enolate and trimethyl orthoformate with added boron trifluoride leads to the corresponding α-dimethoxymethyl ketone.     

Evaluation of thallium-201 myocardial emission computed tomography based on a comparison with postmortem findings

The correlative study of myocardial perfusion assessed by 201Tl myocardial ECT with the pathological finding of the heart was performed in 10 autopsied cases with mean age of 77 years old (range: 60-90 y). In 6 cases with myocardial infarction (MI) 7 perfusion defects were observed, that was, 3 in anteroseptal wall, 1 in anterolateral wall and 3 in posterior wall on the images of SPECT. Seven MIs were also found in postmortem examination. Six MIs were observed at autopsy corresponding to perfusion defect on SPECT images. In one myocardial perfusion defect at inferoposterior portion on SPECT, a non-transmural MI was found at anteroseptum. In one case with valvular disease a false positive result was obtained at posterior wall where neither myocardial necrosis nor fibrosis was observed at autopsy. This case had aortic stenosis due to bicuspid aortic valve by autopsy. The ventricle was divided into 16 segments in each of 4 short axial images to evaluate extent of MI. SPECT for extent of MI showed sensitivity of 81.9%, specificity of 96.0% and diagnostic accuracy of 92.5%. False negative segment was apt to be observed at the surrounding of non-transmural MI or basal half of left ventricle (LV) with transmural MI, while false positive segment was at posterior portion of basal half of LV. It was concluded that myocardial ECT was useful for evaluation of the site and extent of MI.     

The study of electron beam flue gas treatment for coal-fired thermal plant in Japan

The fundamental research work with simulated coal-fired flue gas was performed in JAERI to get basic data for electron beam treatment of flue gas from thermal power plants in Japan. The standard condition of the experiments was set to be the same as that of next large scale pilot test in Nagoya. The concentrations of NO_x and SO_x were 225 ppm and 800 ppm, respectively. The temperature of the system was 65°C. The effect of multiple irradiation was observed for NO_x removal. The target SO_x and NO_x removals (94% and 80%, respectively) with low NH₃ leakage (less than 10 ppm) were achieved at 9 kGy irradiation with 0.9 NH₃ stoichiometry during 7 hours continuous operation. The facility for the pilot plant (12,000 Nm³/hr) has just built at the site of Shin-Nagoya power plant of Chubu Electric Power Company and will be started in full operation in November 1992.     

Enantioselective ring cleavage of dioxane acetals mediated by a chiral Lewis acid: application to asymmetric desymmetrization of meso-1,3-diols

[reaction: see text]. Phenylalanine-derived B-aryl-N-tosyloxazaborolidinones selectively activate one of two enantiotopic oxygen atoms in prochiral anti dioxane acetals derived from meso-1,3-diols, leading to enantioselective formation of ring-cleavage products. The reaction is utilized as a key step in asymmetric desymmetrization of meso-1,3-diols.     

Sol–gel preparation and properties of hydroxypropylcellulose–titania hybrid thin films

Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC₃H₇ ⁱ )₄ was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO₂/(HPC + TiO₂) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC₃H₇ ⁱ )₄ is converted into TiO₂. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where cracking did not occur at higher HPC contents even when the substrate was bent.     

Three novel quassinoids, javanicolides A and B, and javanicoside A, from seeds of Brucea javanica

Two novel quassinoids, javanicolides A and B, and one novel quassinoid glucoside, javanicoside A were isolated from the seeds of Brucea javanica Merr. (Simaroubaceae), along with four known quassinoids, yadanziolides A and D, and bruceins D and E, and two known quassinoid glucosides, yadanziosides D and L. Their structures were elucidated by the analysis of spectral data and chemical evidence.     

Determination of the specific interaction of disubstituted aromatic compounds on hydrous zirconium oxide-loaded porous polymer resin

Summary A porous polymer resin loaded with hydrous zirconium oxide (Zr-gel) was evaluated as a stationary phase for the liquid chromatographic separation of disubstituted aromatic compounds. The prepared Zr-gel was used to separate disubstituted phenols andortho-substituted benzoic acid derivatives in reversed-phase mode. The retention time of catechol was greater than those of other disubstituted phenols; this implies that the Zr-gel has specificity for the phenolic hydroxyl group. The retention behavior ofortho-substituted benzoic acid derivatives on the Zr-gel was also evaluated in reversedphase mode using buffer. Phthalic acid was specifically retained in the vicinity of pH 6.0, which has been regarded as the equal adsorbic point. Similar behavior was also observed for salicylic acid, although the retention time of salicylic acid was less than that of phthalic acid. It seems that the specific retention behavior of hydrous zirconium oxide is a result of complexation with ligands such as hydroxyl and carboxyl groups. The results of this study have revealed that the retention mechanism of hydrous zirconium oxide is a combination of ion exchange and interaction based on complexation with ligands.     

Efficient photochemical oxetane formation from 1-methyl-2,4,5-triphenylimidazole and benzophenones

In contrast to simple imidazoles, 1-methy1–2,4,5-triphenylimidazole ($\text{1}$) produced stable oxetane photoadducts $\text{3b}$ - $\text{e}$ with good efficiency upon irradiation in the presence of benzophenone derivatives $\text{2b}$ - $\text{e}$ in acetonitrile solution. Irradiation in the solid-phase was also studied. The oxetanes $\text{3b}$ - $\text{e}$ readily underwent cycloreversion by acid catalysis or by heating.