Direct evidence has been presented for condensed phase formation in adsorbed monolayers at surfactant solution surfaces, which is quite the same as phase transitions from expanded to condensed phases in spread monolayers by compression. It thus follows that there is no clear boundary between adsorbed and spread monolayers. However, there are many different modes of relaxation in spread monolayers ouing to the greater non-equilibrium nature of spread monolayers during compression compared to adsorbed monolayers.
{"title":"Morphological Changes and Relaxations in Monolayers","authors":"Teiji Kato","doi":"10.5650/JOS1996.49.1089","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1089","url":null,"abstract":"Direct evidence has been presented for condensed phase formation in adsorbed monolayers at surfactant solution surfaces, which is quite the same as phase transitions from expanded to condensed phases in spread monolayers by compression. It thus follows that there is no clear boundary between adsorbed and spread monolayers. However, there are many different modes of relaxation in spread monolayers ouing to the greater non-equilibrium nature of spread monolayers during compression compared to adsorbed monolayers.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87233309","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}
Examination was made of the development and properties of chemically cleavable surfactants. Chemically cleavable surfactants possessing dioxolane, dioxane ring, noncyclic acetal group and carbon-nitrogen double bond were synthesized and found to easily undergo hydrolytic decomposition by acid. Many of these surfactants were noted to have good surface activity and undergo biodegradation in addition to acid-sensitivity. Bis (sodium sulfonated ester) and bis (ammonium bromide) surfactants were synthesized and found to exhibit alkali-sensitivity, surface activity and biodegradability. Ozon-cleavable surfactants bearing carbon-carbon double bonds were also produced and noted to have good surface active properties and biodegradability.
{"title":"Molecular Design and Properties of Chemically Cleavable Surfactants","authors":"T. Takeda","doi":"10.5650/JOS1996.49.1051","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1051","url":null,"abstract":"Examination was made of the development and properties of chemically cleavable surfactants. Chemically cleavable surfactants possessing dioxolane, dioxane ring, noncyclic acetal group and carbon-nitrogen double bond were synthesized and found to easily undergo hydrolytic decomposition by acid. Many of these surfactants were noted to have good surface activity and undergo biodegradation in addition to acid-sensitivity. Bis (sodium sulfonated ester) and bis (ammonium bromide) surfactants were synthesized and found to exhibit alkali-sensitivity, surface activity and biodegradability. Ozon-cleavable surfactants bearing carbon-carbon double bonds were also produced and noted to have good surface active properties and biodegradability.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86790602","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}
Intercalation of inorganic materials into organized organic assemblies provides possibility for developing new functional materials possessing superior physicochemical properties. A composite material consisting of Prussian blue intercalated into photo-responsive organic molecules (azobenzene-containing multibilayer vesicles) was made. Photoisomerization of the film was attended with geometrically confined structural change within the vesicles as reflefted by changes in dipole moment and electrostatic field. It was consequently possible to control the magnetic properties of the new material by photo-illumination, as well as magnetic properties of photo-isomerizable nano-film containing iron oxide particle by photoillumination at room temperature.
{"title":"Optical Control of Magnetic Properties by Use of Self-Assembled Films","authors":"Y. Einaga, O. Sato, A. Fujishima, K. Hashimoto","doi":"10.5650/JOS1996.49.1245","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1245","url":null,"abstract":"Intercalation of inorganic materials into organized organic assemblies provides possibility for developing new functional materials possessing superior physicochemical properties. A composite material consisting of Prussian blue intercalated into photo-responsive organic molecules (azobenzene-containing multibilayer vesicles) was made. Photoisomerization of the film was attended with geometrically confined structural change within the vesicles as reflefted by changes in dipole moment and electrostatic field. It was consequently possible to control the magnetic properties of the new material by photo-illumination, as well as magnetic properties of photo-isomerizable nano-film containing iron oxide particle by photoillumination at room temperature.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81383392","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}
The solubilization of organic molecules in surfactant molecular assemblies may be controlled effectively by electrochemical reactions using redox-active surfactants. In this study, several aromatic compounds were solubilized in aqueous micellar solution of ferrocene-modified nonionic surfactant (11-ferrocenylundecyl polyoxyethylene ether : FPEG) and the effects of redox reactions on solubilization were examined. The solubilization equilibrium constant (K) of the solutes in FPEG micelles, which represents the distribution of solubilizates between micelles and bulk solution, was noted to decrease with the oxidation of ferrocenyl moieties of FPEG molecules, but increase with reduction of ferrocenyl moieties. Electrochemical control of vesicle formation and applications for solubilization control were investigated using aqueous mixtures of a ferrocene-modified cationic surfactant (FTMA) and anionic sodium dodecylbenzene sulfonate (SDBS).
{"title":"Electrochemical Control of Solubilization by Redox-Active Surfactants","authors":"H. Sakai, M. Abe","doi":"10.5650/JOS1996.49.1279","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1279","url":null,"abstract":"The solubilization of organic molecules in surfactant molecular assemblies may be controlled effectively by electrochemical reactions using redox-active surfactants. In this study, several aromatic compounds were solubilized in aqueous micellar solution of ferrocene-modified nonionic surfactant (11-ferrocenylundecyl polyoxyethylene ether : FPEG) and the effects of redox reactions on solubilization were examined. The solubilization equilibrium constant (K) of the solutes in FPEG micelles, which represents the distribution of solubilizates between micelles and bulk solution, was noted to decrease with the oxidation of ferrocenyl moieties of FPEG molecules, but increase with reduction of ferrocenyl moieties. Electrochemical control of vesicle formation and applications for solubilization control were investigated using aqueous mixtures of a ferrocene-modified cationic surfactant (FTMA) and anionic sodium dodecylbenzene sulfonate (SDBS).","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79887706","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}
Various amphiphilic block copolymers (polymer surfactants) possessing hydrophilic and hydrophobic segments were designed, prepared, and examined for stimuli-responsive selforganization in water. New polymer micelles or physical gels that would have this property were made by intermolecular hydrophobic interaction. Recent advances and related topics are initially summarized in this paper. Well-controlled block copoly (vinyl ether) s were synthesized in this study by living cationic polymerization of vinyl ethers with various functional groups. Not only hydrophilic polyalcohols and hydrophobic poly (alkyl vinyl ether) s, but thermally-responsive polymers with oxyethylene units as well were used as segments of diblock copolymers. When aqueous polymer solution was heated, characteristic physical gelation occurred in a certain temperature range corresponding to the particular properties of the segments. As other stimuli, the addition of selected organic compounds and H+ to the solution containing diblock copolymers was also examined as a means for obtaining physical gels via a mechanism similar to that in thermally-responsive systems.
{"title":"Stimuli-Responsive Polymer Surfactants","authors":"S. Aoshima, S. Sugihara","doi":"10.5650/JOS1996.49.1061","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1061","url":null,"abstract":"Various amphiphilic block copolymers (polymer surfactants) possessing hydrophilic and hydrophobic segments were designed, prepared, and examined for stimuli-responsive selforganization in water. New polymer micelles or physical gels that would have this property were made by intermolecular hydrophobic interaction. Recent advances and related topics are initially summarized in this paper. Well-controlled block copoly (vinyl ether) s were synthesized in this study by living cationic polymerization of vinyl ethers with various functional groups. Not only hydrophilic polyalcohols and hydrophobic poly (alkyl vinyl ether) s, but thermally-responsive polymers with oxyethylene units as well were used as segments of diblock copolymers. When aqueous polymer solution was heated, characteristic physical gelation occurred in a certain temperature range corresponding to the particular properties of the segments. As other stimuli, the addition of selected organic compounds and H+ to the solution containing diblock copolymers was also examined as a means for obtaining physical gels via a mechanism similar to that in thermally-responsive systems.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88975063","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}
Photoreactions in Langmuir-Blodgett (LB) films were studied with special attention directed to structural changes of LB films accompanied by the photoreactions. First, a counter concept of free volume is presented. Three-dimensional cone-shaped structures were developed with trans-to-cis photoisomerization in polyion complex LB film of a water-soluble amphiphilic azobenzene. The structures alternately appeared and disappeared by illumination with UV and then visible light. The concept of free volume was found not to hold in the present case. Photoinduced J-aggregate formation of non-photochromic and photochromic dyes is discussed. Reversible photoisomerization of azobenzene in mixed LB films of azobenzene and dyes triggered irreversible J-aggregate dye formation. J-aggregate formation was accompanied by irreversible large morphological changes of the films. The photoisomerization of azobenzene served to induce self-organization of dye molecules. The photopolymerization of amphiphilic diacetylenes was investigated in LB films. This process was found to consist of blue-red, red, and yellow phases based on the spectral change. This change was found to depend on molecular orientation in the LB films. During the blue-to-red transition, the LB films showed considerable morphological change.
{"title":"Photoreactions in Langmuir-Blodgett Films","authors":"M. Matsumoto","doi":"10.5650/JOS1996.49.1099","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1099","url":null,"abstract":"Photoreactions in Langmuir-Blodgett (LB) films were studied with special attention directed to structural changes of LB films accompanied by the photoreactions. First, a counter concept of free volume is presented. Three-dimensional cone-shaped structures were developed with trans-to-cis photoisomerization in polyion complex LB film of a water-soluble amphiphilic azobenzene. The structures alternately appeared and disappeared by illumination with UV and then visible light. The concept of free volume was found not to hold in the present case. Photoinduced J-aggregate formation of non-photochromic and photochromic dyes is discussed. Reversible photoisomerization of azobenzene in mixed LB films of azobenzene and dyes triggered irreversible J-aggregate dye formation. J-aggregate formation was accompanied by irreversible large morphological changes of the films. The photoisomerization of azobenzene served to induce self-organization of dye molecules. The photopolymerization of amphiphilic diacetylenes was investigated in LB films. This process was found to consist of blue-red, red, and yellow phases based on the spectral change. This change was found to depend on molecular orientation in the LB films. During the blue-to-red transition, the LB films showed considerable morphological change.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83810127","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}
The synthesis of fluorinated silane coupling agents having methoxy, ethoxy, or isocyanate groups was conducted in the present study and their applications to surface modification of glass and dental material (bovine tooth) are discussed. Methoxy-type silane coupling agents were prepared by hydrosilylation of trichlorosilane with fluoroalkylated olefins, followed by reaction with sodium methoxide. Isocyanate-type coupling agents were obtained by reactions of chloro-type coupling agents with silver cyanate in benzene. Glasses modified with fluorinated coupling agents showed high repellency toward water and oleic acid. Fluorinated silane coupling agents possessing three methoxy or isocyanate groups formed fluorocarbon layers having high stability in acid and oxidant on glass surfaces. In vivo and in vitro experiments indicated very little plaque to accumulate on bovine tooth surfaces modified with the isocyanate-type coupling agent. Fluorinated silane coupling agents should thus prove useful as surface modifiers for the promotion of oral health.
{"title":"Fluorinated Surface-modifiers","authors":"N. Yoshino, Y. Kondo","doi":"10.5650/JOS1996.49.1081","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1081","url":null,"abstract":"The synthesis of fluorinated silane coupling agents having methoxy, ethoxy, or isocyanate groups was conducted in the present study and their applications to surface modification of glass and dental material (bovine tooth) are discussed. Methoxy-type silane coupling agents were prepared by hydrosilylation of trichlorosilane with fluoroalkylated olefins, followed by reaction with sodium methoxide. Isocyanate-type coupling agents were obtained by reactions of chloro-type coupling agents with silver cyanate in benzene. Glasses modified with fluorinated coupling agents showed high repellency toward water and oleic acid. Fluorinated silane coupling agents possessing three methoxy or isocyanate groups formed fluorocarbon layers having high stability in acid and oxidant on glass surfaces. In vivo and in vitro experiments indicated very little plaque to accumulate on bovine tooth surfaces modified with the isocyanate-type coupling agent. Fluorinated silane coupling agents should thus prove useful as surface modifiers for the promotion of oral health.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79748126","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}
Scanning probe microscopy (SPM) is widely used for characterizing surface morphology and properties. In the SPM family, atomic force microscopy (AFM) is useful for insulating materials under various atmospheres. And AFM facilitates the study of aggregation structures of surfactants on solid surfaces. In this review, SPM, especially AFM, are briefly explained and AFM images of surfactants are presented. Molecular arrangements of surfactant single crystals were visualized and found consistent with the results of x-ray diffraction. Heterogeneous growth and self-repair of surfactant aggregates at an aqueous solution/silica interface could be observed by in situ AFM. The morphology of various surfactants aggregate on solid surfaces was studied by soft contact AFM under various conditions.
{"title":"Scanning Probe Microscopy","authors":"Masatoshi Fujii","doi":"10.5650/JOS1996.49.1181","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1181","url":null,"abstract":"Scanning probe microscopy (SPM) is widely used for characterizing surface morphology and properties. In the SPM family, atomic force microscopy (AFM) is useful for insulating materials under various atmospheres. And AFM facilitates the study of aggregation structures of surfactants on solid surfaces. In this review, SPM, especially AFM, are briefly explained and AFM images of surfactants are presented. Molecular arrangements of surfactant single crystals were visualized and found consistent with the results of x-ray diffraction. Heterogeneous growth and self-repair of surfactant aggregates at an aqueous solution/silica interface could be observed by in situ AFM. The morphology of various surfactants aggregate on solid surfaces was studied by soft contact AFM under various conditions.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77122090","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}
The basic concept of small-angle X-ray and neutron scattering (SAXS, SANS) has been described by way of applications of polymer micelle systems. SAXS and SANS provide information on the size, shape and surface nanostructure of micelles. Based on model calculations and contrast variation in SANS, density inhomogeneity within the particle can be assessed. SAXS and SANS are highly useful for the study of surfactant micelle.
{"title":"Introduction to Small-angle X-ray and Neutron Scattering","authors":"H. Matsuoka","doi":"10.5650/JOS1996.49.1163","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1163","url":null,"abstract":"The basic concept of small-angle X-ray and neutron scattering (SAXS, SANS) has been described by way of applications of polymer micelle systems. SAXS and SANS provide information on the size, shape and surface nanostructure of micelles. Based on model calculations and contrast variation in SANS, density inhomogeneity within the particle can be assessed. SAXS and SANS are highly useful for the study of surfactant micelle.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73333267","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}
Hyperbranched polymers or dendrimers have been of considerable interest since the mid 1980s. Nanocomposites consisting of dendrimers and various metal nanoparticles have been synthesized for use in the preparation of highly functional materials such as substrate-selective catalysts and chemical sensors. The synthesis and applications of dendrimer-metal nanocomposites mainly for poly (amidoamine) dendrimers are discussed in this paper.
{"title":"Synthesis of Dendrimer-Metal Nanocomposites and Physicochemical Properties","authors":"K. Torigoe, K. Esumi","doi":"10.5650/JOS1996.49.1271","DOIUrl":"https://doi.org/10.5650/JOS1996.49.1271","url":null,"abstract":"Hyperbranched polymers or dendrimers have been of considerable interest since the mid 1980s. Nanocomposites consisting of dendrimers and various metal nanoparticles have been synthesized for use in the preparation of highly functional materials such as substrate-selective catalysts and chemical sensors. The synthesis and applications of dendrimer-metal nanocomposites mainly for poly (amidoamine) dendrimers are discussed in this paper.","PeriodicalId":16191,"journal":{"name":"Journal of Japan Oil Chemists Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2000-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73402873","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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