Shigeo Hayano

High-performance liquid chromatographic studies on non-mercapt α mercapt conversion of human serum albumin. II

Abstract High-performance liquid chromatographic (HPLC) analysis of human serum albumin (HSA) on a GS-520 column with 0.03 M sodium phosphate buffer—0.15 M sodium sulphate (pH 6.87) showed three peaks, the principal component corresponding to human mercaptalbumin (HMA) and the secondary and tertiary components to nonmercaptalbumin (HNA). Using HPLC analysis, the nonmercapt → mercapt conversion of HSA during haemodialysis and the mercapt → nonmercapt conversion after haemodialysis in chronic renal failure were re-confirmed, indicating that HMA is a covalent carrier protein for sulphur-containing amino acids. Fractions of HMA in various liver diseases were significantly lower than those of healthy male adults.

Effect of alcohols on the critical micelle concentration decrease in the aqueous sodium dodecyl sulfate solution

The critical micelle concentration (CMC) of aqueous sodium dodecyl sulfate (SDS) solutions decreases, upon the addition of 1-alcohols. There is a linear relation between the carbon number of the alcohols and the slope of the CMC decrease with alcohol concentration. The slope of the CMC decrease with alcohol concentration is found to relate linearly to ΔGp° for the standard free energy change of penetration of the alcohol from the aqueous to the micellar phases. For the alcohols the following equation was obtained. In CMC = −0.82Xa − 8.84, where Xa is the mole fraction of the alcohol in the micellar phase. The coefficient −0.82 is related to the interaction of surfactants and additives. The factor which governs the CMC is the mole fraction of alcohol in the micellar phase independent of the kind of alcohol. The chemical potential of the micelle decreases because the electrical potential of the micelle decreases when alcohol moves from the aqueous to the micellar phase. The effect of the alcohols on the CMC decrease has been elucidated numerically.

Effects of temperature on the distribution of 1-alcohols in aqueous SDS micellar solutions and ISA (Interaction of Surfactant and Additive) Coefficients

Abstract The distribution coefficients (K) of alcohols (1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol) between the aqueous and sodium dodecyl sulfate (SDS) micellar phases at 40 and 55°C were determined in addition to that at 25°C. The standard free energy change (ΔG°p) of penetration of the alcohol from the aqueous to the micellar phase was obtained using the equation ΔG°p = -RT ln(K). There is a linear relation between ΔG°p and the carbon number of the alcohols, and the increment in ΔG°p per methylene group slightly decreases with increasing temperature. The standard enthalpy change (ΔH°p) and entropy change (ΔS°p) of penetration of the alcohol were estimated at 10, 25, 40, and 55°C by the use of temperature variation of the K and the Gibbs-Helmholtz equation. The fact that both ΔH°p and ΔS°p become less positive with the increase in temperature indicates that at lower temperature the penetration of the alcohol into micelle exhibits a greater entropy dependence. Estimated values of ΔH°p were compared with calorimetrical values. At 40 and 55°C, similar to that at 25°C, linear relations are observed between K and critical micelle concentration (CMC) decrease upon the addition of the alcohols. From the linear relations, ISA (interaction of surfactant and additive) coefficients defined as d ln(CMC)/dYa = (ISA)K were obtained to be −0.95 and −0.56 at 40 and 55°C, respectively, where Ya is the mole fraction of the alcohol in the aqueous phase, d ln(Q)/dXa was estimated from ISA, where Q is the degree of ionization of ionic micelles, and Xa is the mole fraction of the alcohol in the micellar phase. The theoretical value of d ln(Q)/dXa from ISA was compared with the experimental one, and a good agreement was obtained between them.

Accelerating effect of additives on the penetration rate of an anthraquinoid acidic dye into cationic micelle

Abstract Penetration rates of an anthraquinoid acidic dye into the micelle of a cationic surfactant, hexadecyltrimethylammonium bromide (HTAB), were measured in the presence of potassium salts and 1-alcohols using the stopped-flow method. The rate constant, k , increases linearly with the increase in the concentration of added salt, and this accelerating effect varies with the nature of the added anion. This variation seems to arise from the difference in the counterion binding ability of the anion. The following two parameters regarding the anion are defined in this study; the acceleration ( a ) as the increase in k with the increase in the concentration of added anion, and the relative counterion parameter (α) as the CMC depression effect of the anion relative to the bromide ion. Then, there is a linear relationship between these parameters. The alcohol addition also increases k , and its effect is in proportion to the carbon number of alcohol. However, based on the concept of the distribution of alcohol between the aqueous and the micellar phases, k was found to a function of the molar fraction of alcohol in the micellar phase ( Y a ) independent of its carbon number. Therefore, it was suggested that the surface potential reduction of the micelle, which made the dye penetration smooth, was a main factor of the acceleration effect.

The protonation of aromatic hydrocarbon radical anions

Summary The rates of protonation of aromatic hydrocarbon radical anions with water in the DMF—water systems were measured by the stopped flow method. Apparent first-order rate constants of the order of 10 s−1 were obtained by this method. These rate constants were compared with those calculated from the polarographic limiting currents on the basis of two possible mechanisms, i.e. the e.c.e. mechanism: R + e ⇌ R ⨪ R ⨪ + H 2 O → R H ⋅ + O H − R H ⋅ + e ⇌ R H − and the regeneration mechanism: R + e ⇌ R ⨪ R ⨪ + H 2 O → k R H ⋅ + O H − R H ⋅ + R ⨪ → fast R H − + R Good agreement was found between the rate constants of protonation measured by the stopped flow method and those calculated on the basis of the regeneration mechanism. The regeneration mechanism was justified also by the observation that it leads to rate constants which are independent of drop-time.

Distribution of oxygen-containing functional groups and elements in humic acids from marine sediments

The elemental composition and oxygen-containing functional groups contents in the marine humic acids from the five sediment samples from Sagami Bay and Suruga Bay were determined. Kumadas method of classification of soil humic acids was applied to the marine humic acids. The carbon, nitrogen, hydrogen, oxygen and sulfur contents of the marine humic acids were, on average, 52.96, 5.12, 5.79, 34.99 and 1.13%, respectively, without wide variation. In comparison with terrestrial humic acids, the marine ones had relatively lower carbon content and higher hydrogen and nitrogen contents. It is suggested that the marine humic acids have more aliphatic and less aromatic character, as expected from their possible origins, e.g., phytoplankton. The total acidity, carboxyl, phenolic and alcoholic hydroxyl, carbonyl and methoxyl group contents in the marine humic acids were, on average, 5.80, 3.27, 2.53, 2.53, 3.09 and 0.41 milliequivalents per gram of dry ash-free humic acid (me g−1), respectively. From quantitative data on the elemental composition and functional groups of the average marine humic acid, its empirical formula was calculated to be C107H138O20(COOH)9(OH)7phenolic (OH)7alcoholic (CO)9(OCH)3N10S. The marine humic acids were similar to the so-called B type of soil humic acids with regard to the distribution of functional groups and spectroscopic properties.

Kinetics of partition between aqueous solutions of salts and bulk liquid membranes containing neutral carriers

The relationship between the rates of transport of alkali metal cations through a bulk chloroform liquid membrane containing polynactin or dibenzo-18-crown-6 as neutral carrier and the rates of uptake and release of cation at the interfaces between aqueous phase and membrane phase were investigated. The fluxes of cations through the membranes and cation-distribution ratios between aqueous solution and membrane were strongly dependent on the anions present. The distribution ratio increased in the following order: Cl− < NO3− < SCN− < ClO4−, and the flux increased in the same order as the distribution ratio, except for the fluxes of KSCN and KClO4 with polynactin. In the case of polynactin, the flux of KSCN was comparable to that of KClO4 in spite of the fact that KSCN was less soluble in the membrane than was KClO4. In order to clarify the cause of this apparently contradictory behavior, the apparent rate constants of uptake and release of potassium were determined independently using an equation derived from Ficks first law of diffusion. From the rates of uptake and release, it was suggested that the overall rate of cation transport through the membrane was dependent on the rate of release rather than that of uptake.

Polarographic determination of critical micelle concentration of anionic surfactants

SummaryCritical micelle concentrations of four anionic surfactants were determined by DC polarographic desorption waves of the surfactants without supporting electrolyte. The linear plot obtained between the potentials of the desorption waves and the logarithmic concentrations of the surfactant had an inflection point which corresponded to the CMC. The CMC values obtained are in good agreement with those in the literature.ZusammenfassungEs wurden die kritischen Mizellbildungskonzentrationen (KMK) von anionischen Tensiden durch Gleichstrompolarographie in Abwesenheit von Leitelektrolyten bestimmt.

Formation of hazardous substances and mutagenicity of PAH produced during the combustion process in a diesel engine

Abstract Gaseous and particulate components, emitted from each stage of the combustion process in a diesel engine using light oil and n -decane fuels, were analyzed by a combination of gas chromatography, chemiluminescence spectrometry, gas chromatography-mass spectrometry and thin layer chromatography. CO 2 , NO and SO 2 increased with the advance of crank angle, while CO, H 2 S, gaseous hydrocarbons, polycyclic aromatic hydrocarbons (PAH), mutagenicity, and particulates gave maximum concentrations at a crank angle of 15°. The PAH concentration measured directly from the combustion chamber was two to three orders of magnitude higher than that measured in the exhaust gas. The mutagenicity of the exhaust gas particulates was almost one order of magnitude less than that of the combustion chamber gas particulates.

Characterization of humic and fulvic acids isolated from marine sediments of Sagami and Suruga Bays with C-13 and proton nuclear magnetic resonance

The C-13 and proton NMR spectra of marine humic and fulvic acids isolated from sediments of Sagami and Suruga Bays and Aldrich humic acid were obtained using pulse Fourier transform mode. The C-13 and proton NMR spectra, which clarified the differences in chemical characteristics among the various humic substances, showed that the marine humic acids had more aliphatic and less aromatic character than the Aldrich humic acid, and the marine fulvic acids had polysaccharide-like character. The C-13 NMR spectra of the marine humic substances, in particular, had many relatively well-resolved peaks with significant intensities, indicating the presence of variously bonded carbon atoms in them.