Properties of monoalkyl phosphate (MAP), including surface active properties, cutaneous effects, and applications to paste & liquid type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production of MAP, are reviewed. It has been found that MAP exhibit considerably high safety on skin in comparison with typical anionic surfactants. This is caracterlized by neutral pH, low skin irritation & roughness and small elution amount of natural moisturizing facters from the stratum corneum. In addition, C12 MAP shows adequate surface active properties for skin cleanser. The industrial production of MAP have been established by two phosphorylation methods, one is ROH/H2O/P2O5 and another is poly-phosphoric acid method. These findings have promoted the development of paste & liquid type skin cleansers composed of MAP.
The rate of capillary wetting in fibrous assemblies was measured by a newly developed device. The change in specific electric conductivity, λ/λc, with time, t, was measured using a plug of cellulose filter paper in a cylindrical Teflon cell. The yield time, t0, and initial slope, S, in λ/λc versus t curves were used as parameters of the wetting rate. The aqueous ionic surfactant solutions were used as wetting liquids. The effect of the alkyl chain length of alkyltrimethyl ammoniumchloride (ATAC) on the wetting rate was investigated. The effect of the electrolyte (KCl) was also examined for sodium dodecyl sulfate (SDS). The wetting rate was found to decrease with increasing ATAC concentration, and it decreased with increasing alkyl chain length for any given concentration of ATAC. In the case of SDS, the rate increased with increasing SDS concentration below the critical micelle concentration (cmc). Above the cmc, the wetting rate decreased with increasing concentration of SDS. The resultant maximum rate was found in the region of low SDS concentration by the addition of KCl. The results obtained below the cmc were discussed in terms of the Washburn equation; the wetting rate was affected by change in the surface free energies of liquids and in the advancing dynamic contact angle by the force balance at the interface due to adsorption of surfactants.
The synergistic antioxidant effects of tocopherol (Toc) and 20 kinds of methyl esters of amino acids on lard and palm oil were investigated by the oven and AOM tests. The amino acid derivatives were used in consideration of the insolubility of their free forms in fats. They were homogeniously dissolved using monoglyceride as the medium, as previously described. The antioxidant effects of them were also studied in the same manner. 1) The solubility of the amino acid derivatives was found in most cases to be less than 40ppm. 2) On lard, 14 amino acid derivatives had rather antioxidant effects according to the oven test, particularly so in the case of methyl L-tryptophan (L-Trp) and methyl lysine (Lys), but dimethyl L-glutamate (Glu-2) tended to accelate oxidation. However, such effects were not observed by the AOM test. All the derivatives except Glu-2 enhanced the antioxidant effect of Toc according to the oven and AOM tests, and the addition of L-Trp, Lys, methyl proline (Pro) or methyl tyrosine (Tyr) along with the mixture of d-Toc (m-Toc) was particularly effective for this. 3) On palm oil, 9 of the amino acid derivatives had rather antioxidant effects by the oven test. Pro and L-Trp did so markedly, but Glu-2 and methyl serine tended to accelate oxidation. With Toc, 12 derivatives showed synergistic effects and the addition of Pro, L-Trp, Try or dimethyl cystine along with m-Toc was particularly effective. Similar effects were observed by the AOM test.
The essential oil from leaves of Menamomi (Siegesbeckia pubescens Makino) has been studied. The constituents were separated by means of conbination of elution chromatography and preparative gas chromatography and were identified by MS, UV, IR and NMR. Six sesquiterpene hydrocarbones (60.8%), eight sesquiterpene alcohols (23.1%), ten acethylenic aldehydes and alcohols (9.7%) and cis-3-hexen-1-ol (3.8%) were recognized as the constituents of the essential oil. The main components were germacrene-D, δ-cadinene, spathulenol, copaborneol, T-muurolol α-cadinol, germacra-4 (15), 5 (E), 10 (14) -trien-1-ol (2), cis-7, trans-12, trans-14-hexadecatrien-10-ynal (1) and cis-9, trans-14, trans-16-octadecatrien-12-ynal.
Polymorphic behavior was studied for series of 1, 3-di (saturated acyl) -2-oleoylglycerols in which the saturated acyl groups were palmitoyl (POP), stearoyl (SOS), arachidoyl (AOA) and behenoyl (BOB). The purity of the samples employed was 90.4% (POP), 91.3% (SOS) 83.2% (AOA), and 71.5% (BOB). Attention was directed to the identification of an independent polymorph by subjecting the sample to two thermal treatments : transformation in a crystalline state at different temperatures after chilling the melt at 0°C, and solidification of more stable polymorphs after rapidly melting the less stable forms. The long and short spacing spectra, examined by X-ray diffractometry and the melting point were used to determine the polymorph. Five independent polymorphs were found to occur frequently in the four triacylglycerols examined : α, γ, pseudo-β', β2 and β1 at ambient temperatures. The melting points increased in the order described above, being α the lowest and β1, the highest. In addition, sub α appeared in SOS, AOA and BOB as a less stable form than α, where as β' was observed in POP, AOA and BOB with stability intermediate between α and γ. All the above polymorphs exhibited distinctively different short spacing spectra and melting points. The solid-state transformation occurred in a sequential way from (sub α) α to β1, implying the nature of the polymorphism to be monotropic. The chain length structure was a double chain for α and β' of the four triglycerides examined, and for pseudo-β', singly of POP. Triple chain length structure was found for γ, β2 and β1 in all the glycerides and pseudo-β' in SOS, AOA and BOB. Although rather complicated, the present findings showed good agreement with data in previous reports which have long been contradictory to each other. Taking the X-ray data and previous reports into account, the new nomenclature of the polymorphs discussed above was explained. Finally, the authors consider that the V-VI transformation of cocoa butter, responsible for the blooming phenomena of confectionery fats, may possibly be caused by polymorphic transformation from β2 to β1 of the solid fat fractions of cocoa butter.