Spatial arrangement of the ruthenium dipyridyl complex and ferrocene derivative in hetero-deposited redox polymer Langmuir-Blodgett (LB) films was carried out for direction control of photocurrent flow produced by photoinduced electron transfer reaction and for high quantum efficiency. Two hetero-deposited structures were obtained by varying the deposition order of the redox polymer monolayers by the LB technique. Cyclic voltammograms of hetero-deposited redox polymer LB films exhibited current rectifying and charge storage properties. Light irradiation led to anodic photocurrent of hetero-deposited redox polymer LB films consisting of Ru copolymer LB film as an inner layer and Fc copolymer LB film as an outer layer on the ITO (Fc/Ru/ITO) electrodes. On the other hand, cathodic current was observed at the reverse layered structure (Ru/Fc/ITO) electrodes. The direction of photocurrent flow depended on the deposition order of redox polymer LB films on the ITO electrode. Photocurrent quantum efficiency of 5.9% of the hetero-deposited redox polymer LB film was achieved. High photocurrent conversion efficiency is explained by inhibition of recombination of photoinduced charge separation due to hetero-deposited LB film structures.
{"title":"Photoinduced Electrochemical Properties of Organized Assembly of Amphiphilic Redox Polymers by Langmuir-Blodgett Technique","authors":"A. Aoki, T. Miyashita","doi":"10.5650/JOS1996.49.1217","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1217","url":null,"abstract":"Spatial arrangement of the ruthenium dipyridyl complex and ferrocene derivative in hetero-deposited redox polymer Langmuir-Blodgett (LB) films was carried out for direction control of photocurrent flow produced by photoinduced electron transfer reaction and for high quantum efficiency. Two hetero-deposited structures were obtained by varying the deposition order of the redox polymer monolayers by the LB technique. Cyclic voltammograms of hetero-deposited redox polymer LB films exhibited current rectifying and charge storage properties. Light irradiation led to anodic photocurrent of hetero-deposited redox polymer LB films consisting of Ru copolymer LB film as an inner layer and Fc copolymer LB film as an outer layer on the ITO (Fc/Ru/ITO) electrodes. On the other hand, cathodic current was observed at the reverse layered structure (Ru/Fc/ITO) electrodes. The direction of photocurrent flow depended on the deposition order of redox polymer LB films on the ITO electrode. Photocurrent quantum efficiency of 5.9% of the hetero-deposited redox polymer LB film was achieved. High photocurrent conversion efficiency is explained by inhibition of recombination of photoinduced charge separation due to hetero-deposited LB film structures.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74610870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This article reviews applications of surface forces measurement for characterizing interactions of molecular assemblies with overview given in Table 1. Measurement techniques using a surface force apparatus and a colloidal probe atomic force microscope described in a concise manner, and the results of detailed researches on functionalized surfactant assemblies are presented. 1) Surface forces measurement provided evidence for spontaneous vesicle formation of an ammonium surfactant with an acetate counterion. 2) The mechanism of fusion and aggregation of surfactant vesicles in the presence of salt (NaCl) was clarified. 3) Interactions between bilayers of various biological phospholipids were found to be attractive van der Waals and repulsive steric hydration forces in pure water and monovalent salt solutions. 4) Hydrogen-bonding interactions between glycine head groups were directly demonstrated. 5) Interactions between LB films of metal-chelating lipids ; pH dependence reflected different protonation states of iminodiacetic acid groups, and Cu2+ complexation with them. 6) The effects of surfactant on the particle bubble interactions between hydrophilic and hydrophobic silica particles and an air bubble were examined .
{"title":"Surface Force Measurement and Characterization of Functionalized Molecular Assemblies","authors":"K. Kurihara, Y. Nakai","doi":"10.5650/JOS1996.49.1191","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1191","url":null,"abstract":"This article reviews applications of surface forces measurement for characterizing interactions of molecular assemblies with overview given in Table 1. Measurement techniques using a surface force apparatus and a colloidal probe atomic force microscope described in a concise manner, and the results of detailed researches on functionalized surfactant assemblies are presented. 1) Surface forces measurement provided evidence for spontaneous vesicle formation of an ammonium surfactant with an acetate counterion. 2) The mechanism of fusion and aggregation of surfactant vesicles in the presence of salt (NaCl) was clarified. 3) Interactions between bilayers of various biological phospholipids were found to be attractive van der Waals and repulsive steric hydration forces in pure water and monovalent salt solutions. 4) Hydrogen-bonding interactions between glycine head groups were directly demonstrated. 5) Interactions between LB films of metal-chelating lipids ; pH dependence reflected different protonation states of iminodiacetic acid groups, and Cu2+ complexation with them. 6) The effects of surfactant on the particle bubble interactions between hydrophilic and hydrophobic silica particles and an air bubble were examined .","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80206561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A new cholesteric liquid crystals that respond quickly to stimuli such as temperature change or photoreaction of a doped compound in a liquid crystalline phase were found and stable molecular ordering below 80°C in the solid state brought about by rapid cooling from the liquid crystalline phase was noted. By changing the temperature at which rapid cooling start or degree of photoisomerization of photochromic compounds, colors from the visible spectral region reversibly fixed as interference colors. The compounds exhibited surface-directed self-assembly in a helical molecular ordering to form optically reflecting solid film on spin-coating from solution. All these may be considered properties of liquid crystals of medium-molecular-weight with over 1000 mass units. Through these properties, it is possible to obtain a re-writable full color recording in a photon or thermal mode.
{"title":"Novel Optical Functions of Compounds Derived from Cholesterol","authors":"N. Tamaoki","doi":"10.5650/JOS1996.49.1041","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1041","url":null,"abstract":"A new cholesteric liquid crystals that respond quickly to stimuli such as temperature change or photoreaction of a doped compound in a liquid crystalline phase were found and stable molecular ordering below 80°C in the solid state brought about by rapid cooling from the liquid crystalline phase was noted. By changing the temperature at which rapid cooling start or degree of photoisomerization of photochromic compounds, colors from the visible spectral region reversibly fixed as interference colors. The compounds exhibited surface-directed self-assembly in a helical molecular ordering to form optically reflecting solid film on spin-coating from solution. All these may be considered properties of liquid crystals of medium-molecular-weight with over 1000 mass units. Through these properties, it is possible to obtain a re-writable full color recording in a photon or thermal mode.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85241414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Phase transition from a positive to negative-curved self-organized structure was noted to occur in a binary water/polyoxyethylene-type nonionic surfactant system with decrease in the number of ethyleneoxide (EO) units at constant temperature. Effective cross sectional area per each surfactant decreased with reduction in the EO chain length. The mechanism for phase transition is discussed based on the revised packing parameter theory. The effects of oil type on the surfactant layer curvature are explained as due to penetration and/or swelling of oil. Due to the oil effect, surfactant changes from waterto oil-soluble in a narrow range of temperature or EO-chain length in the presence of oil. This is the reason for the appearance of HLB temperature or PIT in water-oil system.
{"title":"Correlation of HLB with Self-Organized Structure","authors":"H. Kunieda, K. Aramaki","doi":"10.5650/JOS1996.49.1123","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1123","url":null,"abstract":"Phase transition from a positive to negative-curved self-organized structure was noted to occur in a binary water/polyoxyethylene-type nonionic surfactant system with decrease in the number of ethyleneoxide (EO) units at constant temperature. Effective cross sectional area per each surfactant decreased with reduction in the EO chain length. The mechanism for phase transition is discussed based on the revised packing parameter theory. The effects of oil type on the surfactant layer curvature are explained as due to penetration and/or swelling of oil. Due to the oil effect, surfactant changes from waterto oil-soluble in a narrow range of temperature or EO-chain length in the presence of oil. This is the reason for the appearance of HLB temperature or PIT in water-oil system.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"9 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86182988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aggregate properties of aqueous solutions of surfactants, characterization of model membranes, methods for the preparation of vesicles and vesicle-forming surfactants are reviewed in the present study. Nonionic amphiphiles are widely regarded as synthetic tailor-made lipids in consideration of their safty and ease of molecular structural design. In search for vesicle-forming substances with safe physiological properties, good storage stability and ease of preparation, poly (oxyethylene) (10) hydrogenated castor oil was found to meet these requirements. Vesicle formation of poly (oxyethylene) hydrogenated castor oil and physico-chemical properties in aqueous dispersion are discussed in the following.
{"title":"Supramolecular Structures of Functionality Vesicles","authors":"T. Horiuchi, K. Tajima","doi":"10.5650/JOS1996.49.1107","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1107","url":null,"abstract":"Aggregate properties of aqueous solutions of surfactants, characterization of model membranes, methods for the preparation of vesicles and vesicle-forming surfactants are reviewed in the present study. Nonionic amphiphiles are widely regarded as synthetic tailor-made lipids in consideration of their safty and ease of molecular structural design. In search for vesicle-forming substances with safe physiological properties, good storage stability and ease of preparation, poly (oxyethylene) (10) hydrogenated castor oil was found to meet these requirements. Vesicle formation of poly (oxyethylene) hydrogenated castor oil and physico-chemical properties in aqueous dispersion are discussed in the following.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"14 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76381666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fluoroalkanoyl peroxide was found useful for the synthesis of fluoroalkyl end-capped oligomers having COOH, SO3H, O=C-NR1R2, OH, betaine segments, phosphorous segments and blocked-isocyanato segments. The fluoroalkyl end-capped oligomers were generally soluble not only in water but common organic solvents as well. These oligomers were highly surface active, showing very low surface tensions and clear break points, as in the case of low molecular weight fluorinated surfactants. Self-organization thus occurs to form molecular aggregates. Based on light scattering studies, fluoroalkyl end-capped oligomers having COOH formed ellipsoidal micelles. Fluoroalkyl end-capped oligomers with hydroxy or betaine segments gave rise to gelation owing to hydrophobic interaction of end-capped fluoroalkyl segments in addition to the hydrogen bonding and/or the ionic interaction of betaine segments. Moreover, as some examples of interesting properties of fluoroalkyl end-capped acrylamide type oligomers, the unique binding power of Ca2+ or Cr3+, selective recognition of organic color material having -NH2 or -NMe2 groups such as methylene blue and/or luminol, and the immobilization of cytochrome c are discussed. These features may be due to molecular aggregates produced by the interaction between end-capped fluoroalkyls.
{"title":"Novel Fluorinated Oligo-Surfactants Imparted by the Aggregation of Fluoroalkyl Segments","authors":"H. Sawada, T. Kawase","doi":"10.5650/JOS1996.49.1021","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1021","url":null,"abstract":"Fluoroalkanoyl peroxide was found useful for the synthesis of fluoroalkyl end-capped oligomers having COOH, SO3H, O=C-NR1R2, OH, betaine segments, phosphorous segments and blocked-isocyanato segments. The fluoroalkyl end-capped oligomers were generally soluble not only in water but common organic solvents as well. These oligomers were highly surface active, showing very low surface tensions and clear break points, as in the case of low molecular weight fluorinated surfactants. Self-organization thus occurs to form molecular aggregates. Based on light scattering studies, fluoroalkyl end-capped oligomers having COOH formed ellipsoidal micelles. Fluoroalkyl end-capped oligomers with hydroxy or betaine segments gave rise to gelation owing to hydrophobic interaction of end-capped fluoroalkyl segments in addition to the hydrogen bonding and/or the ionic interaction of betaine segments. Moreover, as some examples of interesting properties of fluoroalkyl end-capped acrylamide type oligomers, the unique binding power of Ca2+ or Cr3+, selective recognition of organic color material having -NH2 or -NMe2 groups such as methylene blue and/or luminol, and the immobilization of cytochrome c are discussed. These features may be due to molecular aggregates produced by the interaction between end-capped fluoroalkyls.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87102296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Adsorption-induced self-organization is a new concept for “wet process” techniques for preparing highly ordered molecular adlayers by spontenious adsorption in aqueous solution. The essential step is a controlled “mild” adsorption, which makes possible rapid surface diffusion and adsorption/desorption equilibrium. To conduct “mild” adsorption, the choice of substrate and setting of electrode potential are most possible. STM visualization of highly ordered molecules provides fundamental data on intermolecular interactions.
{"title":"Two-Dimensional Highly Ordered Molecular Layers Prepared by Adsorption-Induced Self-Organization","authors":"M. Kunitake","doi":"10.5650/JOS1996.49.1225","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1225","url":null,"abstract":"Adsorption-induced self-organization is a new concept for “wet process” techniques for preparing highly ordered molecular adlayers by spontenious adsorption in aqueous solution. The essential step is a controlled “mild” adsorption, which makes possible rapid surface diffusion and adsorption/desorption equilibrium. To conduct “mild” adsorption, the choice of substrate and setting of electrode potential are most possible. STM visualization of highly ordered molecules provides fundamental data on intermolecular interactions.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81131654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Physico-chemical properties of sugar-based surfactants, such as alkyl glucosides, alkyl maltosides, sucrose monoalkanoates, and alkanoylglucosides, were reviewed with attention directed primarily to anomeric effects of the head group sugar. Phase behaviors of surfactant solid and surfactant-water 2-component systems for α-anomer of alkyl glucosides differed considerably from that of β-anomer. Chain length effects of the hydrophobic group on phase behavior of alkyl glucoside-water system were studied for β-anomers and a liquid-liquid phase separation region was confirmed to exist for decyl β-glucoside (0.1-17 wt%) but for octyl and nonyl β-glucoside. The growth of micelles of decyl β-glucoside would thus appear to be promoted by increse in surfactant concentration and micellar network structure was noted to form at above 17 wt% solution. The size and shape of micellar aggregates for octyl glucoside, dodecyl maltoside, and octanoylglucoside demonstrated significant anomeric effects.
{"title":"Sugar-based Surfactants","authors":"K. Fukada","doi":"10.5650/JOS1996.49.1035","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1035","url":null,"abstract":"Physico-chemical properties of sugar-based surfactants, such as alkyl glucosides, alkyl maltosides, sucrose monoalkanoates, and alkanoylglucosides, were reviewed with attention directed primarily to anomeric effects of the head group sugar. Phase behaviors of surfactant solid and surfactant-water 2-component systems for α-anomer of alkyl glucosides differed considerably from that of β-anomer. Chain length effects of the hydrophobic group on phase behavior of alkyl glucoside-water system were studied for β-anomers and a liquid-liquid phase separation region was confirmed to exist for decyl β-glucoside (0.1-17 wt%) but for octyl and nonyl β-glucoside. The growth of micelles of decyl β-glucoside would thus appear to be promoted by increse in surfactant concentration and micellar network structure was noted to form at above 17 wt% solution. The size and shape of micellar aggregates for octyl glucoside, dodecyl maltoside, and octanoylglucoside demonstrated significant anomeric effects.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91032902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Interactions of liposomes with detergents and physicochemical properties of liposomes were reviewed. Several amphiphiles that produce liposomes by themselves or form liposomes only by mixing two amphiphiles are initially discussed and then solubilization of liposomes by detergents, formation of liposomes from mixed micelles on removal of the detergents, mechanism of micelle-vesicle transition, and method for regulating vesicular size are considered in regard to the micelle-vesicle transition mechanism. ESR spectroscopy, hyperfine splitting of 2, 2, 6, 6-tetramethylpiperidine-N-oxyl dissolved in octylglucoside-containing vesicles and order parameters of 5-doxylstearic acid incorporated in vesicles, was useful for obtaining the properties of detergent-containing liposomes. 1H NMR spectra of the choline N-methyl group in internal and external monolayers of phosphatidylethanolamine/lysophosphatidylcholine (LPC) vesicles indicated LPC to possibly prefer external monolayers of lipid and the presence of internal monolayers to be essential for vesicle stabilization.
综述了脂质体与洗涤剂的相互作用以及脂质体的理化性质。本文首先讨论了几种自行产生脂质体或仅通过两种两亲性物质混合形成脂质体的两亲性物质，然后讨论了洗涤剂对脂质体的增溶作用、洗涤剂去除后混合胶束形成脂质体、胶束-囊泡转变机理以及调节囊泡大小的方法。ESR光谱法、2,2,6,6 -四甲基哌啶- n -氧基溶解在辛基葡萄糖苷囊泡中的超精细分裂和5-羟基硬脂酸在囊泡中的有序参数，有助于获得含洗涤剂脂质体的性质。磷脂酰乙醇胺/溶血磷脂酰胆碱(LPC)囊泡内外单分子层中胆碱n -甲基的1H NMR谱表明，LPC可能更倾向于外部单分子脂质层，而内部单分子脂质层的存在对囊泡的稳定至关重要。
{"title":"Interaction of Liposomes with Detergents","authors":"M. Ueno, H. Kashiwagi","doi":"10.5650/JOS1996.49.1131","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1131","url":null,"abstract":"Interactions of liposomes with detergents and physicochemical properties of liposomes were reviewed. Several amphiphiles that produce liposomes by themselves or form liposomes only by mixing two amphiphiles are initially discussed and then solubilization of liposomes by detergents, formation of liposomes from mixed micelles on removal of the detergents, mechanism of micelle-vesicle transition, and method for regulating vesicular size are considered in regard to the micelle-vesicle transition mechanism. ESR spectroscopy, hyperfine splitting of 2, 2, 6, 6-tetramethylpiperidine-N-oxyl dissolved in octylglucoside-containing vesicles and order parameters of 5-doxylstearic acid incorporated in vesicles, was useful for obtaining the properties of detergent-containing liposomes. 1H NMR spectra of the choline N-methyl group in internal and external monolayers of phosphatidylethanolamine/lysophosphatidylcholine (LPC) vesicles indicated LPC to possibly prefer external monolayers of lipid and the presence of internal monolayers to be essential for vesicle stabilization.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"56 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86030037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. Okano, Y. Abe, Daisuke Hotta, T. Nakano, G. Sugihara, Seong-Geun Oh
Micelle formation in water and adsorbed film formation at air/water interface were studied by surface tension measurement for two mixed surfactant systems : combinations of sodium salts of α-sulfonatomyristic acid methyl ester (α-SMy·Me) and the propyl ester (α-SMy·Pr) with n-decanoyl-N-methyl glucamide (MEGA-10). The α-SMy·Pr/MEGA-10 and the α-SMy·Me/MEGA-10 mixed systems were found to synergistically enhance surface activity and form well-mixed micelles with the aid of strong interaction between head groups. Critical micellization concentration (CMC) as a function of mole fraction of MEGA-10 in the surfactant mixture (XMEGA-10) for both mixed systems was noted to deviate negatively from ideal mixing. Micellar phase (CMC vs YMEGA-10 relation) curves were simulated through use of the interaction parameter, ωR=-2.1 for α-SMy·Me/MEGA-10 and ωR=-2.0 for α-SMy·Pr/MEGA-10 and indicated the presence of azeotropes. Based on equations for estimating composition (Zi) and the interaction parameter (ωA) in adsorbed film equilibrated with monomers in bulk solution, phase diagrams were constructed that included the two relations of CMC vs XMEGA-10 and CMC vs ZMEGA-10. Adsorbed film of the respective mixed systems was formed through stronger interactions between anionic and nonionic surfactants compared to those of mixed micelles (-ωA>-ωR). The diagrams demonstrated that composition in micelles (Yi) differs from that in the adsorbed film (Zi). From the slope of surface tension (γ) vs logarithmic molality (ln mt) curve, just below CMC, surface excess (Γ) was determined and mean molecular area (Am) was computed as a function of XMEGA-10 or ZMEGA-10. From Am data, partial molecular area (PMA) of each component was determined as a function of ZMEGA-10; a large deviation from ideal mixing (the additivity rule) was observed for the respective mixed systems. Effects of differences in head group moiety, i.e., either methyl or propyl, were clearly evident with respect to hydrophobicity difference, but physicochemical behavior appeared essentially the same.
{"title":"Binary Mixed Systems of Anionic/Nonionic Surfactants","authors":"T. Okano, Y. Abe, Daisuke Hotta, T. Nakano, G. Sugihara, Seong-Geun Oh","doi":"10.5650/JOS1996.49.915","DOIUrl":"https://doi.org/10.5650/JOS1996.49.915","url":null,"abstract":"Micelle formation in water and adsorbed film formation at air/water interface were studied by surface tension measurement for two mixed surfactant systems : combinations of sodium salts of α-sulfonatomyristic acid methyl ester (α-SMy·Me) and the propyl ester (α-SMy·Pr) with n-decanoyl-N-methyl glucamide (MEGA-10). The α-SMy·Pr/MEGA-10 and the α-SMy·Me/MEGA-10 mixed systems were found to synergistically enhance surface activity and form well-mixed micelles with the aid of strong interaction between head groups. Critical micellization concentration (CMC) as a function of mole fraction of MEGA-10 in the surfactant mixture (XMEGA-10) for both mixed systems was noted to deviate negatively from ideal mixing. Micellar phase (CMC vs YMEGA-10 relation) curves were simulated through use of the interaction parameter, ωR=-2.1 for α-SMy·Me/MEGA-10 and ωR=-2.0 for α-SMy·Pr/MEGA-10 and indicated the presence of azeotropes. Based on equations for estimating composition (Zi) and the interaction parameter (ωA) in adsorbed film equilibrated with monomers in bulk solution, phase diagrams were constructed that included the two relations of CMC vs XMEGA-10 and CMC vs ZMEGA-10. Adsorbed film of the respective mixed systems was formed through stronger interactions between anionic and nonionic surfactants compared to those of mixed micelles (-ωA>-ωR). The diagrams demonstrated that composition in micelles (Yi) differs from that in the adsorbed film (Zi). From the slope of surface tension (γ) vs logarithmic molality (ln mt) curve, just below CMC, surface excess (Γ) was determined and mean molecular area (Am) was computed as a function of XMEGA-10 or ZMEGA-10. From Am data, partial molecular area (PMA) of each component was determined as a function of ZMEGA-10; a large deviation from ideal mixing (the additivity rule) was observed for the respective mixed systems. Effects of differences in head group moiety, i.e., either methyl or propyl, were clearly evident with respect to hydrophobicity difference, but physicochemical behavior appeared essentially the same.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":"57 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2000-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84877635","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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