The reactions of N-succinimidyl benzoates (1) with various amino acids (2) to give the corresponding N- (arylcarbonyl) amino acids (3) were studied kinetically at 25°C and pH=pKa. The formation of (3) was competitive with the decomposition of (1) in aqueous solution; i.e., the rate may be expressed as V= (k_{1, d}+k₂ [2]) [1], where k_{1, d} is the first order rate constant for the N-arylcarbonylation of (2) by (1).
The second order rate constant, k₂, at pH= pKa, correlated with the nucleophilicity (pKa) of (2), giving slopes of 0.78 0.86 for log k₂ vs. pKa plots. The plot of log k₂ vs. σ for metasubstituted (1) showed a linear relationship with ρ=0.651.28. The rate of ortho-substituted (1) was smaller than that of meta-substituted (1), because of the steric hindrance of ortho-substituent in (1). The ratios, 10^-3k₂/k_{1, d} exceeded unity. The above observations demonstrate N-arylcarbonylation involving a nucleonphilic attack of a free amino group on the ester carbonyl carbon in (1) and the possibility of (1) as an N-arylcarbonyl reagent of proteins.

View full abstract

A simple quantitative method for the analysis of oxidized methyl linoleate and edible oils by TLC-FID has been developed. Oxidized methyl linoleate 10200 μg was developed on a Chro marod SII, first by n-hexane to 10 cm and then by n-hexane : diethylether, 8 : 2 vol/vol to 7 cm. This double developing method was found applicable to the quantitation of oxidation products from methyl linoleate. Moreover, the most suitable conditions for quatitating very small amounts of as many oxidized products as possible were determined. A 200μg sample (almost the maximum amount) was spotted on a Chromarod and developed first by η-hexane to 8 cm, then to 10 cm and finally by η-hexane : diethylether 9 : 1 vol/vol to 7 cm. By this triple developing method, 1% of the oxidation products containing in methyl linoleate were quantitated. Both methods are applicable to the analysis of oxidation products in edible oils such as corn and safflower oil.

View full abstract

A study was made of the transport through a 1, 2-dichloroethane liquid membrane of two kinds of zwitter ionic compounds, dodecyldimethylammoniododecaneimidate (AI) and (1-tetradecyl-2-pyridinio) -octanesulfonimidate (PY), as carrier molecules.
Halide ions were sym-ported with hydrogen ions, almost completely so by AI. The rate of transport of AI or trioctylamine (AM) was much faster than that of PY or perhydrodibenzo-18-crown-6. For iodide ions, the rate by AI was faster than that by AM.
Phenylalanine was counter-ported by AI, as well as AM, in the opposite direction to hydrogen and halide ions, against its concentration gradient. The flux was 2×10^-3mol·cm^-2·mol^-1·h^-1. This result along with the fact of permanganate ion extraction, indicate ion release to be the rate determining step for the transport of phenylalanine by AI.

View full abstract

The effects of builder action i.e., dispersion, calcium binding and alkaline buffer action, on the removal of Fe₂O₃ particulate soils were studied using various copolymers of sodium styrenesulfonate with sodium methacrylate and 2-hydroxyethylmethacrylate so as to find some substitute for a phosphate builder.
The calcium binding capacity of builders was measured by the calcium electrode method. Particle size in suspension, deposition, redeposition and removal efficiency were investigated as functions of builder concentration under fixed conditions of 50 ppm hard water, pH 10 and 30°C. The ζ-potentials of particles and fabrics were also measured by microelectrophoresis and streaming potential, respectively.
The most important function of a builder should be its ability to adsorb polyelectrolyte with electric and steric barrior effects, since removal behavior of particulate soil is influenced more electrokinetic phenomena than chelating phenomena.
Sodium styrenesulfonate-sodium methacrylate copolymer having multi-functional builder action, i.e., dispersion, calcium binding and alkaline buffer action was found to be an excellent new builder.

View full abstract

The ability of a lipase and surfactant in combined form in solution to remove fatty soil was investigated. The specific conductivities, binding isotherms, surface tensions, solubilization of Yellow OB were measured using Chromobacterium vicosum (Chr) and sodium dodecyl sulfate (SDS) as the lipase and surfactant, respectively. The removal of squalane soil by this means was also examined.
SDS interacts with the protein of Chr to afford a Chr-SDS complex (cluster). The surface tension of the combined lipase-surfactant solution reaches a plateau at a lower concentration than when SDS is present alone. As the concentration of SDS increases, oily materials solubilize in the hydrophobic region as a result of interaction between the cluster and free surfactant. The data of the present study indicate solubilization to be quite important for the removal of fatty soil in a Chr-SDS combined system.

View full abstract

The reaction of α-pinene-2, 3-epoxide (1), d-limonene-1, 2-epoxide (2) and styrene oxide (3) by the potassium permanganate coated molecular sieve catalyst (KMnO₄/sieve) were investagated. Epoxide (1) was easily isomerized to 2, 2, 3-trimethyl-3-cyclopenten-1-acetaldehyde (5) with a high selectivity of 78.6%. 1-Methyl-3-isopropenyl--cyclopentyl-1-carboxaldehyde (10) was obtained as the main product from (2). Benzaldehyde (15) was produced preferentially when the reaction of (3) was conducted in the presence of toluene at 110°C for 3 h.

View full abstract

A substance which accelerates the amidase activity of trypsin by more than three times that of intact trypsin was separated from autoxidized methyl linolenate by gel chromatography on Sephadex LH- 20, silicic acid chromatography on Silica gel 60, and by high-performance liquid chromatography on μ-Porasil. This substance isolated from the highly active fraction was identified as methyl 12-oxo-9-hydroxy-10-dodecenoate by GLC and GC-MS analyses.

View full abstract