Mechanism of the hydroperoxide destruction in the oxidized methyl oleate,oleyl alcohol,and oleic acid

The differentiated mechanism of destruction of hydroperoxides derived from methyl oleate, oleyl alcohol and oleic acid was explained with the influence of the hydrogen-bond interactions. The evidence for the proposed models was given through the quantitative yields of the five classes of the secondary products of autoxidation: monohydroxy-, dihydroxy-, keto-, ketohydroxyderivatives and monofunctional products of degradation of the oxidized molecules.     

The influence of hydrogen-bond association on the destruction of hydroperoxides in the autoxidation process of oleyl alcohol, oleic acid, and methyl oleate

The autoxidation process of oleyl alcohol, oleic acid, and methyl oleate at 40, 50, and 60 °C was considered with the special stress laid upon the mechanism of cumulating and destruction of peroxidic products. Interpretation of the observed differences was based on the hydrogen-bond association patterns.     

Spectroscopic and dielectric examination of the oleyl alcohol-oleic acid system

The comparison of association was made for the oleyl alcohol-oleic acid systems composed in several molar ratios. The ir spectroscopy and dielectric constant measurements were applied as analytical techniques. It was stated that oleyl alcohol and oleic acid interact in a number of molar ratios giving the hydrogen-bonded associates. In the range of temparatures 30–60 °C the most stable hydrogen-bonded associate is formed in a ratio of alcohol to acid of 9:1.     

Optical activity in the isotropic and blue phases of two cholesterics

Optical activity measurements were performed in the isotropic phase and blue phases of two short-pitch cholesteric liquid crystals (cholesteryl oleate and cholesteryl oleyl carbonate). The data in the isotropic phase are interpreted in terms of five structural modes of the order parameter. Coupling between these modes gives rise to an extremum and a change of sign in the pretransitional optical rotation. The intensities of the polarized and depolarized component of the transmitted beam were measured as an extral tool to locate the phase transitions.     

Synthesis of the p-toluenesulfonate of oleyl acohol under conditions of phase-transfer catalysis

The tosylation of oleyl alcohol under the conditions of phase-transfer catalysis has been studied. In this process oleyl p-toluenesulfonate of formed with a yield of up to 80%.Institute of Bioorganic Chemistry, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, 443–445, May–June, 1988.     

Optical activity in the isotropic and blue phases of two cholesterics

Optical activity measurements were performed in the isotropic phase and blue phases of two short-pitch cholesteric liquid crystals (cholesteryl oleate and cholesteryl oleyl carbonate). The data in the isotropic phase are interpreted in terms of five structural modes of the order parameter. Coupling between these modes gives rise to an extremum and a change of sign in the pretransitional optical rotation. The intensities of the polarized and depolarized component of the transmitted beam were measured as an extral tool to locate the phase transitions.     

Characteristics of the oxidation process in the methyl oleate-propionic acid system by means of dielectric constant measurements

In our paper the influence of association in the methyl oleate-propionic acid system on the course of autoxidation of this system was discussed. The course of autoxidation of the a/m system was characterized with the help of peroxide number and dielectric constant measurements.     

Mixed micelles containing sodium oleate: the effect of the chain length and the polar head group

We have investigated the mixing behavior of binary mixtures of the alkylglucosides (CnG) octyl beta-D-glucoside and decyl D-glucoside in combination with sodium oleate (NaOl), and the amine oxide surfactants (AO) N,N-dimethyldodecylamine oxide, N,N-bis (2-hydroxyethyl)dodecylamine oxide, and 3-lauramidopropyl-N,N-dimethylamine oxide in combination with NaOl. From the equilibrium surface tension measurements, the critical micelle concentration (cmc) data were obtained as functions of the composition. Values of the cmc were analyzed according to both the regular solution model developed by Rubingh for mixed micelles and Maeda's formulation for ionic/nonionic mixed micelles. Two interaction parameters, beta and B1, were estimated from the regular solution model and Maeda's formulation, respectively. For NaOl/CnG mixed systems, a decrease in the hydrocarbon chain length of CnG resulted in a stronger interaction with NaOl from both beta and B1 values. For NaOl/AO mixed systems, the bulkiness of a polar head group of AO surfactants influenced the interaction between NaOl and AO. The dynamic surface tension measurements show that all surface tension values of surfactant solutions examined decreased with the time. We found that the time dependence of surface tension values for NaOl mixed systems was greatly influenced by the presence of NaOl rather than the other component.     

Mixed saturated-unsaturated alkyl-chain assemblies: solid solutions of zinc stearate and zinc oleate

The linear saturated stearic acid and the bent mono-unsaturated oleic acid do not mix and form solid solutions. However, the zinc salts of these acids can. From X-ray diffraction and DSC measurements we show that the layered zinc stearate and zinc oleate salts form a homogeneous solid solution at all composition ratios. The solid solutions exhibit a single melting endotherm, with the melting temperature varying linearly with composition but with the enthalpy change showing a minimum. By monitoring features in the infrared spectra that are characteristic of the global conformation of the hydrocarbon chain, and hence can distinguish between stearate and oleate chains, it is shown that solid solution formation is realized by the introduction of gauche defects in a fraction of the stearate chains that are then no longer linear. This fraction increases with oleate concentration. It has also been possible from the spectroscopic measurements to establish a quantitative relation between molecular conformational order and the thermodynamic enthalpy of melting of the solid solutions.     

Comparison of oleyl and elaidyl isomer surfactant-counterion systems in drag reduction, rheological properties and nanostructure

Compared with quaternary ammonium cationic surfactants with saturated alkyl chains, quaternary ammonium cationic surfactants with one double-bond in their alkyl chains, when mixed with appropriate counterions (in certain molar concentration ratios, ξ), can reach much lower effective drag-reduction temperatures, while maintaining the upper drag-reduction temperature limit of the corresponding saturated drag reducing surfactant solutions. No previous study has compared the effects of cis- vs. trans-unsaturated alkyl hydrocarbon tail configurations (oleyl vs. elaidyl) trimethyl ammonium chloride cationic surfactants at different counterion/surfactant concentration ratios on micellar nanostructures, (1)H NMR spectra and on rheological and drag-reduction behavior of their solutions. Since neither pure oleyl (cis-) nor elaidyl (trans-) trimethyl ammonium chloride surfactants are commercially available, they were synthesized and their 5mM solutions with NaSal counterion at concentrations of 5mM, 7.5mM and 12.5mM were studied.     

Solubilization of oleyl alcohol by pure and mixtures of surfactants

The solubilization behavior of oleyl alcohol by pure and mixtures of surfactants systems have been studied in terms of the maximum additive concentration (MAC), the solubilizing power, and the particle sizes of micelles with or without oleyl alcohol. The surfactants used are amphoteric (N,N-dimethyl-N-lauroyl lysine, DMLL; N,N,N-trimethyl-N-lauroyl lysine, TMLL; N,N-dimethyl-N-(carboxymethyl)-lauryl ammonium, DMCL), anionic (sodium dodecyl sulfate, SDS) and nonionic (alkyl polyoxyethylene ethers).The maximum additive concentration of oleyl alcohol by pure surfactants is larger by nonionic surfactants than by others.For a nonionic surfactant system mixed with DMLL, the mixing effect of surfactant on the increase in the MAC is not recognized. While, for DMLL mixed with SDS, the MAC becomes larger than that by pure surfactants. This may be attributed to the fact that the large micellar size will result in increasing the maximum additive concentration.     

CO2-Responsive wormlike micelles based on sodium oleate and hydrophobic tertiary amines

We reported two simple and novel CO₂-responsive surfactant wormlike micellar systems consisting of commercial anionic surfactant sodium oleate (NaOA) and common hydrophobic tertiary amine N,N-dimethylcyclohexylamine (DMCHA), N,N-dimethylbenzylamine (DMBA). The conductivity, pH, and rheological measurements demonstrated the CO₂-sensitive flowing behavior and property, which were attributed to the spherical-wormlike micelles transition, verified by cryogenic transmission electron microscopy (Cryo-TEM) and dynamic laser light scattering (DLS) measurements. Moreover, the transition can be easily cycled more than three times without deterioration of viscosity. Combined with the species distribution curve and ¹H NMR spectra, a mechanism of the intermolecular electrostatic interaction and hydrophobic effects was proposed.     

Characteristics of the oxidation process in the oleic acid-propionic acid system by means of dielectric constant measurements

The influence of the hydrogen-bond association on the course of autoxidation of oleic acid in the binary system oleic acid-propionic acid was discussed. The association was characterized with the help of dielectric constant measurements.     

Forces and friction between hydrophilic and hydrophobic surfaces: influence of oleate species

The atomic force microscope has been used to investigate normal surface forces and lateral friction forces at different concentrations of sodium oleate, a frequently used fatty acid in the deinking process. The measurements have been performed using the colloidal probe technique with bead materials consisting of cellulose and silica. Cellulose was used together with a printing ink alkyd resin and mica, whereas silica was used with a hydrophobized silica wafer. The cellulose-alkyd resin system showed stronger double layer repulsion and the friction was reduced with increasing surfactant concentration. The adhesive interaction disappeared immediately on addition of sodium oleate. The normal surface forces for cellulose-mica indicated no apparent adsorption of the sodium oleate however, the friction coefficient increased on addition of sodium oleate, which we ascribe to some limited adsorption increasing the effective surface roughness. The silica-hydrophobic silica system showed a completely different surface force behavior at the different concentrations. An attractive hydrophobic interaction was evident since the surfaces jumped into adhesive contact at a longer distance than the van der Waals forces would predict. The strong adhesion was reflected in the friction forces as a nonlinear relationship between load and friction and a large friction response at zero applied load. Indirect evidence of adsorption to the hydrophilic silica surface was also observed in this case, and QCM studies were performed to confirm the adsorption of material to both surfaces.     

Effect of preformed egg phosphatidylcholine vesicles on spontaneous vesiculation of oleate micelles

An addition of oleate micellar solution to two original sizes (180 nm and 50 nm) of preformed vesicles was studied using gel exclusion chromatography, dynamic light scattering and freeze fracture electron microscopy. The effect of molar ratios of phospholipid and oleate on size distribution of newly formed vesicles was investigated by varying molar concentrations of these two components. After adding an equiamount of oleate to 180 nm-preformed vesicles or 50 nm-preformed vesicles, a relatively monodisperse population of newly formed vesicles was detected. For the high amount of oleate addition to two original sizes of preformed vesicles, the results were quite different. New large vesicles and a number of new small vesicles were observed in samples of mixed EggPC/oleate suspension in the presence of preformed vesicles with 180 nm of size, whereas, only some new large vesicles were detected in samples of mixed EggPC/oleate suspension in the presence of preformed vesicles with 50 nm of size. We assumed that the number of new small vesicles, with size close to preformed vesicles, increased in the latter case. The transformation of mixed EggPC/oleate micelles to mixed vesicles was investigated. The results showed that transformation of mixed EggPC/oleate micelles to vesicles was remarkably faster than transformation of mere oleate micelles to vesicles. The above findings suggested that new mixed EggPC/oleate vesicles with small size were presumably formed by partial solubilization.     

New vesicle formation upon oleate addition to preformed vesicles

The size distribution of new vesicles formed after addition of oleate in different forms to preformed egg yolk phosphatidylcholine (EggPC) vesicles was studied by gel exclusion chromatography. The addition of oleate to preformed vesicles resulted in the formation of new small vesicles. Fission of preformed vesicles incorporated by oleate and partial solubilization of the vesicles by addition of oleate in micellar form were involved in the process of the new small vesicle formation.     

Synthesis and solution properties of gemini surfactants containing oleyl chains

Gemini surfactants 18:1-s-18:1, where s = 2, 3, and 6 methylene groups and 18:1 refers to oleyl carbon chains, have been synthesized, characterized and a number of micelle solution properties measured by using electrical conductance, fluorescence probe emission, light scattering (DLS), surface tension and isothermal titration calorimetry (ITC) methods at 25 degrees C. The cmc values of 18:1-2-18:1, 18:1-3-18:1, and 18:1-6-18:1 were found to be 26.9, 23.4, and 18.0 microM, respectively, using the electrical conductance method. Surface tension results suggest that in 0.01 N NaCl solutions, the s = 2 and 3 members of the series form multilayer rather than monolayer structures, while the s = 6 homologue adopts a close-packed arrangement. This is consistent with DLS and EM measurements which show vesicle formation for the s = 2 and 3 compounds, and micelle formation for the s = 6 compound. The enthalpies of micellization (deltaH degrees (M)) are more exothermic for the 18:1-s-18:1 series of surfactants, than for the 12-s-12 series. The differences are rationalized in terms of steric and configurational contributions to deltaH degrees (M) arising from difficulties associated with packing of the bulky cis-9-octadecene tails.     

Surface rheology and foaming properties of sodium oleate and C12(EO)6 aqueous solutions

The dynamic surface tension (DST) and the surface viscoelastic modulus of sodium oleate aqueous solutions at different concentrations were measured using an image analysis tensiometer based on the oscillating bubble technique. The diffusion coefficient of oleate moieties was calculated from DST measurements and the surface viscoelastic modulus using the Langmuir-Szyszkowski and the diffusion-controlled adsorption models. The viscoelastic moduli obtained from model calculations were compared with the corresponding experimental values. The diffusion coefficient of C(12)(EO)(6) in water and the parameters of the Langmuir-Szyszkowski adsorption isotherm were taken from the literature and used to calculate the surface viscoelastic modulus of its aqueous solutions at different concentrations. The foaming properties of both C(12)(EO)(6) and sodium oleate solutions, viz., the foam conductance and the water volume fraction in the foam, were measured using a commercial Foamscan device. Foaming experiments with C(12)(EO)(6) and sodium oleate solutions were carried out either under static conditions; i.e., the foam conductance and the water volume fraction were measured as a function of time after the generation of a fixed volume of foam, or under dynamic conditions; i.e., the foam conductance and the water volume fraction were measured during foam formation. The variations in the foam permeability as a function of surfactant concentration were related to the viscoelastic properties of the air/water interface and to the presence of micelles in the foam films. With foams in which the water volume fraction was higher than 0.05, the foam electrical conduction could be described using a simple parallel resistor model and their conductance measurements were related to the foam water volume fraction. The results related to water drainage under static conditions were used to interpret water drainage under dynamic conditions. Preliminary conjectures on the influence of foam permeability and water volume fraction on the yield of the flotation deinking process were drawn from these results.     

不同溶剂中酶催化合成油酸酯研究初探

对几种非水溶剂中脂肪酶催化合成油酸酯 (油酸乙酯、油酸正辛酯和油酸油酯 )进行了初步考察。结果表明 ,在环己烷、正庚烷和甲苯等有机溶剂中 ,上述酯化反应都有很高的转化率 ;在所考察的实验条件下 ,超临界CO2 中反应的转化率略比上述有机溶剂中的低 ,但该结果已初步显示以超临界CO2 替代有机溶剂合成油酸酯具有很大的应用潜力。