To follow the progress of biodegradation of anionic surfactants, the methylene blue method is the most widely employed for quantitative analysis. But, there is unaccountably the case in which the activity to methylene blue disappeared even before surfactant has not yet completely been biodegraded into inorganic compounds. And so, we examined the biodegradability of several surfactants by measuring the residual carbonaceous materials in comparison with the colorimetric analysis. Sodium α-olefin sulfonates (AOS) and other ten anionic and three nonionic surfactants were taken as test materials. In the shake culture test method, it was found that surfactants containing straight alkyl chain such as AOS, alcohol sulfate and soap were degraded in shorter period necessary for the disappearance of the carbonaceous materials during biodegradation. However, surfactants having benzene ring or ethoxylate chain in their molecules were slow in decrease of the concentration of organic carbon during biodegradation, and there was a large discrepancy between the biodegradation rates obtained by colorimetric analysis and measurement of organic carbon.
The addition reactions of maleic anhydride to linolic acid were carried out in the presence of activated clay at 180°C. The methyl ester of reaction products was fractionated by TLC. Then, each fraction was identified by mol. wt., saponif. V., and from the GLC, NMR, IR, and UV spectral characteristics. The activated clay acts as a catalyst for the maleic anhydride addition reaction to linolic acid giving monomaleinized compounds with the structure of cyclohexenic type in more than 50% yield. In the absence of activated clay the reaction products include compounds of various type containing monomaleinized compounds of succinic anhydride type.
The present work aims at the development of fractionation technique for the products obtained by the reaction of tung oil with maleic anhydride at 120°C for 14 hrs. Samples of maleinized tung oil were fractionated by TLC on adsorbent layers of Silica Gel G developed in a solvent system of petroleum ether-diethyl ether-formic acid 5 : 5 : 0.1 (vol/vol/vol). Six fractions were separated and hydrolyzed followed by methylation. The resulting methyl esters were analyzed by GLC, obtaining the following conclusions with the structure of each fraction. Fr. 1 (Rf=0.93) : Unreacted glycerides. Fr. 2 (Rf=0.88) : Maleic anhydride mono-adducts of glycerides. Fr. 3 (Rf=0.74) : By-products of unknown structure (very small amounts). Fr. 4 (Rf=0.71) : Maleic anhydride di-adducts of glycerides. Fr. 5 (Rf=0.41) : Maleic anhydride tri-adducts of glycerides with small amounts of by-products. Fr. 6 (Rf=0.00) : Mainly by-products including polymerized products. Further, it was found that the separation of the mono-adducts of succinic type derived from oleic acid and those of cyclohexenic type derived from α-and β-eleostearic acids is attainable by use of GLC for their methyl ester.
The isomerization of safflower oil in the presence of 5% alkali and alkaline earth metals such as LiI, Nal, KI, MgI2, CaI2, SrI2 and BaI2, at 200 and 220°C was studied.The results show that LiI, MgI2, CaI2 and SrI2 promote the isomerization. In the case of MgI2 and LiI catalysts which having the strong isomerization activity, it is found that much octadecenoic acid forms and on the other hand, the content of saturated acids does not increase during the reaction. Also, the formation of small amounts of dimers and some compounds having lower molecular weight are observed.
Six terpenyl hydroxyethyl ethers (terpenyl-HEE) [isobornyl-HEE , 1-β-fenchyl-HEE , n-bornyl-HEE , α-terpinyl-HEE , myrcenyl-HEE  and dihydro-myrcenyl-HEE ] and six terpenyl hydroxypropyl ethers (terpenyl-HPE) [isobornyl-HPE , 1-β-fenchyl-HPE , n-bornyl-HPE , α-terpinyl-HPE , myrcenyl-HPE  and dihydromyrcenyl-HPE ] were prepared by the reaction of camphene , tricyclene , 2-pinene , 2 (10) -pinene , 1, 8-p-menthadiene , myrcene  or dihydromyrcene  with ethylene glycol  or propylene glycol  in the presence of cation exchange resin at 50°±2°C. These structures were confirmed by physical constants, MS, IR and NMR spectra.
The dissolution state of polyoxyethylene (n) nonylphenylether-water-cyclohexane system was studied as a function of temperature. The phase inversion temperature (PIT) and the temperature range over which W/O type emulsions are stable were determined. As a result, the relation between the PIT and the oxyethylene chain length of emulsifiers which will give the stable W/O type emulsions was obtained, thereby an emulsifier which will yield stable emulsion at a given temperature can be selected. Emulsions are most stable, if we select emulsifiers whose oxyethylene chain length is shorter by about two as compared with the emulsifier whose PIT (HLB-temperature) is equal to an experimental temperature. Thus, the procedures for the emulsifier selection of W/O type became clear by HLB-temperature method.
Three series of new types of nonionics (PEE) having a general formula, (ROCH2) xC [CH2O (C2H4O) nH] 4-x (x=13, R=n-C3n-C16), have been prepared by polyaddition of ethylene oxide (EO) to higher alkyl ethers of pentaerythritol. Some gross effects of PEE were examined in comparison with those of n-alkanol-EO (S type) and α, α'-glyceryl-dialkylether-EO (GDE) adducts. Nonionics having the multi-chain type hydrophobe were superior to S type in interfacial tension lowering ability, wetting and emulsifying efficiencies. While, their foaming and suspending powers were less effective than those of S types. These trends appeared unequivocally rather in case of the comparison among the higher homologues. For nonionics having three polyoxyethylene chains in the hydrophile, it was observed that the lower members (R=C12) were excellent in interfacial tension lowering and foaming, while the higher members (R=C16) were excellent in suspending and emulsifying. The higher GDE were rather superior to the corresponding S and PEE types in detergency. Nonionics having each two chains in both hydorophobic and hydrophilic parts exhibited the higher efficiencies for most of the gross effects examined. Based on these results, a connection between the basic properties reported previously (ref. 6) and the gross effects in the multi-chain type nonionics was discussed.
Ceramide 2-aminoethylphosphonate (CAEP) was found to be the principal phospho-sphingolipids in the shellfish. The presence of CAEP as a major lipid constituent in these organism is unique, since this phospholipid has been not found or only trace in all other animals investigated so far. In this paper authors report the isolation and characterization of CAEP from ova of a fresh-water bivalve, Hyriopsis schlegelii. Total lipid (0.5g) from the ova was subjected to alkaline methanolysis according to a modified procedure of Dawson. An alkali-stable lipid fraction (200mg) was fractionated on a silicic acid column with chloroform-methanol mixture. CAEP (32mg) was eluted from the column with 350ml of chloroform-methanol (80 : 20, by vol) and the homogeneity of the isolated CAEP was determined on thin-layer plates developed in chloroform-methanol-water (65 : 25 : 4, by vol) and chloroform-methanol-acetic acid-water (100 : 20 : 12 : 5, by vol). Enzymatic degradation of CAEP by phospholipase C from Cl. perfringens yielded ceramide and 2-aminoethylphosphonic acid, and the former was purified by chromatography on a silicic acid column using chloroform, chloroform-methanol (98 : 2, by vol). The chloroform-methanol eluate contained only one component as revealed by thin-layer chromatography. Acid hydrolysis of ceramide derived from CAEP was performed by heating for 18hr at 70°C in aqueous 1N-methanolic HCl. The fatty acid methyl esters produced by the acid hydrolysis were extracted with n-hexane and estimated by gas-liquid chromatography at 160°C on a 15% DEGS column. The fatty acids identified were C14 : 0, C15 : 0, C16 : 0 (predominant), C17 : 0 and C18 : 0. After removal of fatty acid components by extraction with n-hexane the remaining aqueous solution was adjusted to pH 11.0 by adding 1N-NaOH. The long-chain bases were extracted with diethyl ether from the remaining solution, converted to their trimethylsilyl derivatives and analyzed by gas-liquid chromatograph-mass spectrometer at 200°C on a 1% OV-1 column. Octadeca-4-sphingenine (predominant), and presumable branched octadeca- and nonadeca-4-sphingenine were the principal long-chain bases of CAEP. To determine 2-aminoethylphosphonic acid obtained as one of the enzymatic hydrolyzates, a small portion of the hydrolyzates was converted to a trimethylsilyl derivative with bis (trimethylsilyl) acetamide-pyridine-trimethyl chlorosilane (1hr, 60°C), and analyzed by gas-liquid chromatograph-mass spectrometer. 2-Aminoethylphosphonic acid was identified by a reference to the mass spectrum of the synthetic compound. The occurrence of CAEP in nature is well documented. However, this is the first finding of this compound in the lipids of shellfish ova.
Refractive indices of the hexagonal urea adducts were measured by the polarizing microscope, and they were compared with that of the tetragonal crystal of urea. In the tetragonal crystal of urea, the planes of the Y-shaped molecules are perpendicular to each other but parallel to the c axis; consequently this crystal is uniaxially positive (ω=1.483, ε=1.593). In the hexagonal urea adducts, although the oxygen atoms of urea molecules are superimposed along a vertical edges axis, the urea molecules are oriented 120° with respect to one another forming a helix spiral. The guest molecules are packed along c axis. As a result, the urea adducts are also uniaxially positive, and ω were constant (=1.492), but ε were changed by the forms of guest molecules (paraffins=1.566, saturated fatty acids =1.577, unsaturated fatty acids=1.5827). For the birefringence, therfore, the tetragonal urea was stronger than the hexagonal urea adducts.
Authors have studied on the synthesis of new type of chelate surfactants having very good dispersing power for TiO2 in organic solvents. Within these chelates. C, C'-bisdecyl EDTA Al chelate (BDe), C-decyl, C'-dodecyl EDTA Al chelate (DeDo) and C, C'-bisdodecyl EDTA Al chelate (BDo) were added to the aminoalkyd resin enamels for improvement the properties of coating films. These coating films were tested on the chemical resistance (acid, alkali and detergent) and were measured for Dupon impact resistance, gloss and bending resistance after weathering. It was found that these surfactants improved much the chemical resistance, namely, softening of the coating films containing some of the dispersants did not take place even after immersing in 2% NaOH or 0.2% detergent solution for 3 days. Also, these dispersants effectively prevented the gloss drop and the embrittling of coating films under weathering.