Amino acids and peptides. XIII. Synthetic studies on N-terminal tripeptide amide analogs of fibrin alpha-chain

N-Terminal tripeptide analogs of fibrin alpha-chain were synthesized and their inhibitory effect on fibrinogen/thrombin clotting was examined. A new water-soluble active ester, 3-pyridinium ester, was used for the synthesis. Among the synthetic peptides, H-Gly-Pro-Arg-hexamethyleneimine exhibited the highest inhibitory effect on fibrinogen-thrombin clotting.     

Analysis method of the angiotensin-I converting enzyme inhibitory activity based on micellar electrokinetic chromatography.

A micellar electrokinetic chromatography (MEKC) method was developed for estimating the angiotensin-I converting enzyme (ACE) inhibitory activity by separating the hippuric acid liberated in the ACE reaction mixture in the presence of an inhibitor, captopril. The hippuric acid was successfully separated and detected by MEKC with a 25 mM sodium dodecyl sulfate solution in a 25 mM phosphate-50 mM borate buffer at pH 7.0; the total analysis took about 5 min. A good linear relationship was observed between the inhibitor and the peak area of hippuric acid release. No significant difference in the ACE inhibitory activity (IC50) of captopril (an antihypertensive medicine) or autolyzed-mushrooms (functional foods) was observed between the conventional method and the MEKC method. The MEKC method was found to be a useful technique for a rapid assay of the ACE inhibitory activity.     

Hydration Structure Around the Carboxyl Group Studied by Neutron Diffraction with 12C/13C and H/D Isotopic Substitution Methods

Time-of-Flight (TOF) neutron diffraction measurements have been carried out on aqueous 8 mol% sodium acetate solutions in D₂O. Scattering cross sections that were observed for sample solutions involving ¹²C/¹³C and H/D isotopically substituted acetate ions were used to derive the first-order difference functions, Δ_H(Q) and Δ_C(Q), and corresponding distribution functions, G _H(r;r) and G _C(r;r), which describe the environmental structure around the methyl and the carboxyl groups within the acetate ion, respectively. Structural parameters concerning the first hydration shell of the carboxyl group within the acetate ion were obtained through the least squares fit to the observed intermolecular difference function, Δ_C ^inter(Q). The nearest neighbor C _O...D _W1 (C_O: carboxyl carbon atom, D_W1: water deuterium atom) distance, r(C _O...D _W1 ), and the angle, ∠ C _O ...D _W1 -O _W (O _W : water oxygen atom), were determined to be 2.63(1) Å and 120(1)°, respectively. The coordination number, n(C _O ...D _W1 ), was obtained to be 4.0(1). These results are consistent with the hydration structure in which water molecules in the first hydration shell of the carboxyl group are hydrogen-bonded with oxygen atoms of the carboxyl group.     

Synthesis of novel organoselenium as catalyst for Baeyer-Villiger oxidation with 30% H2O2

A novel diselenide was synthesized in good yield via only four steps from phenol, and was employed as the catalyst for the Baeyer-Villiger oxidation with 30% H₂O₂ to obtain lactones in good yields.     

Vacancy ion-exclusion chromatography of carboxylic acids on a weakly acidic cation-exchange resin

In this preliminary study, a new approach to ion-exclusion chromatography is proposed to overcome the relatively poor conductivity detection response which occurs in ion-exclusion chromatography when acids are added to the eluent in order to improve peak shape. This approach, termed vacancy ion-exclusion chromatography, requires the sample to be used as eluent and a sample of water to be injected onto a weakly acidic cation-exchange column (TSKgel OApak-A). Vacancy peaks for each of the analytes appear at the retention times of these analytes. Highly sensitive conductivity detection is possible and sharp, well-shaped peaks are produced, leading to efficient separations. Retention times were found to be affected by the concentration of the analytes in the eluent, and also by the presence of an organic modifier such as methanol in the eluent. Detection limits for oxalic, formic, acetic, propionic, butyric and valeric acids were 0.1, 0.2, 0.3, 0.3, 0.4 and 0.5 microM, respectively, and linear ranges for some acids extended over two orders of magnitude. Precision values for retention times were 0.21% and for peak areas were <1.90%. The vacancy ion-exclusion chromatography method was found to give detection responses four to 10 times higher than conventional ion-exclusion chromatography using sulfuric acid eluent and two to five times higher than conventional ion-exclusion chromatography using benzoic acid eluent.     

Homogeneous palladium catalyst suppressing Pd black formation in air oxidation of alcohols

In homogeneous catalyst systems, there is the persistent problem that metal aggregation and precipitation cause catalyst decomposition and considerable loss of catalytic activity. Pd black formation is a typical example. Pd catalysts are known to easily aggregate and form Pd black, although they realize a wide variety of useful reactions in organic synthesis. In order to overcome this intrinsic problem of homogeneous Pd catalysis, we explored a new class of Pd catalyst by adopting aerobic oxidation of alcohols as a probe reaction. Herein we report a new catalyst system that suppresses the Pd black formation even under air and with a high substrate to catalyst molar ratio (S/C: more than 1000) in oxidation of alcohols. The novel pyridine derivatives having a 2,3,4,5-tetraphenylphenyl substituent and its higher dendritic unit at the 3-position of the pyridine ring were found to be excellent ligands with Pd(OAc)2 in the palladium-catalyzed air (balloon) oxidation of alcohols in toluene at 80 degrees C. Comparison with structurally related pyridine ligands revealed that introduction of the 2,3,4,5-tetraphenylphenyl substituent at the 3-position of pyridine ring effectively suppresses the Pd black formation, maintaining the catalytic activity for a long time to give aldehydes or ketones as products in high yields.     

Unique Reactivity of a Diphenyldisilane Unit Incorporated into the Bicyclic Ring System: Generation of a Disilanyllithium via Silicon-Phenyl Bond Cleavage with Lithium

A bicyclic diphenyldisilane bearing two tetramethylene tethers reacts with lithium to form predominantly the disilanyllithium as a result of Si-C_Ph bond fission, while the pentamethylene homolog undergoes ordinary Si-Si bond cleavage to afford the expected phenylsilyllithium. The compressed Si-Si bond incorporated in the bicyclic ring system may be kinetically stabilized (compression effect), resulting in the unusual Si-C bond fission. When the reaction is carried out in the presence of chlorotrimethylsilane, a Calas-type reaction takes place on the phenyl rings. This result suggests that electron transfer to the phenyl group is the primary process in these bicyclic disilanes, followed by Si-Si or Si-C bond cleavage to afford the corresponding silyllithium species.     

Electron spin resonance study of ethylene–acrolein copolymer irradiated with ultraviolet light

When ethylene–acrolein copolymer was irradiated at ?196°C with ultraviolet light, a sharp singlet spectrum with a g value of about 2.001 was predominant. This spectrum is attributed to acyl radicals, which are produced by dissociation of a hydrogen atom from an aldehyde group. At the same time it is supposed that dissociation of formyl groups also took place to give alkyl radicals, CO, and H₂. The alkyl radicals reacted with CO molecules to give acyl radicals at ?78°C under vacuum. Peroxy radicals were produced when the sample irradiated at ?196°C in the presence of air was treated at ?78°C. The sample irradiated at ?196°C was warmed to near 0°C and an apparent singlet spectrum with a g value of about 2.004 was observed. This spectrum was tentatively assigned as due to free radicals of the type