京都大学 / 新制・課程博士 / 博士(理学) / 甲第24443号 / 理博第4942号 / 新制||理||1706(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 若宮 淳志, 教授 依光 英樹, 教授 畠山 琢次 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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The reduction of CO2 emission has been a worldwide mission to resolve global warming predicament. Mesoporous silsesquioxanes, which stabilized by organobridges and has high content aminon absorption site, can serve as a potential CO2 adsorbent. Synthesis of such material is done by hydrolysis and polycondensation of trialkoxysilane. The fastest gelation was observed at reaction in the absence of acids or bases. However, addition of surfactant to the reaction mixture catalyzed formation of silsesquioxanes in acidic media. Obtained materials are strongly hydrophilic and possess a high thermostability. Study of particle size distributions showed that in all cases it was bimodal. The largest particles formed in basic media. Mesoporous silsesquioxanes were obtained from bridged alkyltrimethoxysilanes in the presence of surfactants.

Luminescence techniques are sensitive, selective, and widely used in analysis. Luminescence intensity is attenuated by quenchers. This research has focused on the use of surfactants such as CTAB, SDS, and TX-100 singly or together with TiO2 nanoparticles to evaluate their individual and combined effects on some fluorescent aromatic compounds such as pyrene, fluoranthene, anthracene, phenanthrene, and carbazole. Rutile phase TiO2 was synthesized using the low temperature sol-gel method. Carbazole and phenanthrene were severely quenched by all surfactants singly or in combination with TiO2. Anthracene and fluoranthene showed some enhancement in their luminescence intensity. The most dramatic effect was observed on the fluorescence intensity of pyrene. Pyrene showed enhanced fluorescence after degassing the solution alone or with the addition of the surfactants alone or in combination with TiO2 after degassing. These results showed that surfactants and TiO2 nanoparticles either singly or in combination should be useful for analysis employing luminescence techniques.

A simple and economical fluorometer using blue LEDs excitation sources and simple PMT detection had been built, assembled, optimized, and employed for measurement of fluorescence from riboflavin (vitamin B2). Surfactants have been known to enhance the intensity of fluorescence of fluorescent compounds. Fluorescence analysis of riboflavin in the presence of various anionic, cationic, and nonionic surfactants was also conducted to determine if they could improve analysis. However, the surfactants employed did not seem to have any meaningful enhancement; in fact, some actually diminished the fluorescence intensity of riboflavin. The procedure was linear for riboflavin from 0.01 to 2.5 μg/mL. Reproducibility expressed as relative standard deviation was about 2%. The recoveries obtained range from 91.3% to 100.21% for the samples determined. The proposed method was successfully applied to the analysis of riboflavin in commercial vitamin tablets and cereal products. The results obtained were consistent with expected values as provided by the manufacturers. The method is simple, sensitive, economical, and rapid.

An intrinsic link exists between soil moisture and soil nitrogen. Factors that increase or decrease soil moisture can have a profound effect on soil nitrogen cycling, which may have later repercussions in the plant community. Post-fire soil water repellency is one factor that can limit soil moisture acquisition and may indirectly affect nitrogen cycling and weed invasion in woody islands of fertility. Plots centered on burned Juniperus osteosperma trees were either left untreated or treated with a surfactant to ameliorate water repellency. Two years later, soils were excavated from the untreated and treated field plots. In the greenhouse, half of each soil type received a surfactant treatment while the other half was left untreated. Pots were seeded with either Bromus tectorum or Pseudoroegneria spicata. Analysis of field soil prior to the greenhouse trial showed that untreated, repellent soils had inorganic nitrogen levels an order of magnitude higher than wettable, surfactant-treated soils. Greenhouse pots that had received a surfactant treatment in the field and/or greenhouse had similar soil water content, plant density, and above ground biomass, which were, respectively, 55-101%, 31 to 34 -fold, and 16 to 18 -fold greater than pots without a surfactant treatment. No species effects were found. This study indicates that water repellency can reduce wetting and retention of water in the soil while promoting the retention of high levels of inorganic nitrogen. However, the effects of soil water repellency on inorganic nitrogen appeared to have a minimal effect on plant growth compared to the effect of soil water repellency on water availability.

<p>Surfactant is a type of surface-active molecule with wide industrial applications, such as personal care products, antibacterial products, surface modification, etc. Due to environmental concerns, biobased surfactants derived from renewable sources are of great interest. In the first part of this work, biobased quaternary ammonium (QA) amphiphiles are synthesized from soybean oil via a two-step reaction. For example, fatty acid amides (FAAms) were first synthesized through direct amidation of soybean oil. The FAAms exhibited different liquid-solid phase transition behavior depending on their saturation and chain length. A general trend of increasing enthalpy of fusion, narrower phase transition temperature range, higher melting temperature, and better thermal stability was observed with increasing chain length and saturation. Overall, fifteen green, organic PCMs were synthesized with the comparable latent heat of fusion to petroleum based PCMs. </p> <p>Biobased QA surfactants were successfully synthesized with comparable surface activity to cetyltrimethylammonium bromide (C16TAB) by alkylating FAAms into quaternary ammonium (QA) compounds.  The water solubility of long-chain (C18) QA surfactants was improved by introducing two or more QA groups in the headgroup, or unsaturation in the tail group. All the surfactants exhibited positive charge with high stability against varying pH. Surfactants derived from fully hydrogenated soybean oil (FHS) and diethylenetriamine (DETA) showed lower critical micelle concentration (CMC) and surface tension in water (SFT) than C16TAB. All the other five surfactants had surface activity comparable to C16TAB and C12TAB. These biobased surfactants are potential alternatives to commercial petroleum-derived QA surfactants. </p> <p>The second part of this work is devoted to understanding the effect of mixed surfactant composition on emulsion stability, and formation is beneficial for optimizing the wastewater treatment process. Emulsion behavior in a saline environment was studied with mixed anionic and nonionic surfactants: sodium laureth sulfate (SLES) and Triton X-100. It was found 500 ppm total surfactant concentration was sufficient to stabilize 5 wt. % mineral oil against coalescence, regardless of the surfactant ratio. Compared to Triton X-100-rich emulsions, SLES-rich ones had higher stability against flocculation and creaming. SLES-rich emulsions had twice as much remnant oil in the subnatant as Triton X-100-rich samples, which is undesirable in wastewater treatments. The relation between spontaneous emulsion behavior and the HLD model was studied with SLES-Span-80 surfactant mixtures. The influence of salinity, oil type, and surfactant composition was investigated. Spontaneous emulsification could only be observed when the systems have HLD values close to 0 (-0.96 ~ 1.04). A combined effect of bicontinuous-phase formation and ultra-low interfacial tension led to spontaneous emulsification. This work proposes a practical approach to predict emulsion compositions that result in spontaneous emulsification.</p>

[pt] Os surfactantes derivados de aminoácidos são moléculas que apresentam interesse tanto acadêmico quanto industrial por apresentarem características como baixa toxicidade e alta biodegradabilidade. Dentro dessa classe destaca-se o N-Lauril Sarcosinato de Sódio que vem sendo cada vez mais utilizado para substituir surfactantes aniônicos, como o dodecil sulfato de sódio, principalmente na área de cosméticos. Entretanto, estudos sobre seu comportamento de fases ainda são escassos, principalmente envolvendo a sua interação com outras moléculas, como o caso dos polímeros. Polímeros e surfactantes são utilizados juntos em diversos processos industriais, e conhecer o resultado de suas interações é de extrema importância para controlar as propriedades da mistura, já que se diferem totalmente das propriedades individuais de seus componentes. Neste trabalho, realizou-se o estudo das estruturas e termodinâmica de autoassociação de sistemas contendo o N-Lauril Sarcosinato de Sódio (LS) e polímeros com diferentes naturezas químicas: (PEG), (PSS), (PAA) e (PDADMAC). utilizando-se as técnicas de calorimetria, tensiometria, titulação calorimétrica isotérmica (ITC), espalhamento de luz dinâmico (DLS) e de raios X a baixos ângulos (SAXS). Os resultados mostraram que a micelização do LS ocorre na faixa de 10 a 14,6 nm a 298 K, tendo seu valor dependente da sensibilidade da técnica utilizada para sua determinação. A caracterização da estrutura das micelas em água indicou que elas possuem formato elipsoide e se alongam com o aumento da concentração, mas são muito dependentes do pH do meio. Além disso, este surfactante não apresentou formação de fases líquido-cristalinas na faixa de concentração estudada. Os polímeros PEG e PSS não afetam significativamente a termodinâmica de micelização do LS. Enquanto o PEG não apresentou indícios de interação alguma com LS, o PSS pode atuar como um sal levando ao crescimento unidimensional das micelas. O PAA pode ou não interagir fortemente com o LS dependendo do pH da solução, e inclusive induzir a formação de agregados em concentrações inferiores à concentração micelar crítica (CMC). Já o PDAMAC, que apresenta carga oposta ao LS, apresenta uma forte atração eletrostática com o surfactante, levando à separação de fases, em concentrações muito menores do que a CMC. O precipitado formado apresentou a mesma estrutura encontrada para altas concentrações de surfactante puro. Este estudo mostra como a natureza química de diferentes polímeros – neutro, aniônico e catiônico – influencia nas interações com o N-Lauril Sarcosinato de Sódio e, consequentemente, nos seus processos de micelização e estruturas de autoassociação. Portanto, permite uma melhor previsão e maior controle das propriedades de formulações em que se deseja combinar polímeros e surfactantes. / [en] Surfactants derived from amino acids are molecules that exhibit a great interest in academic and industrial research, as they present characteristics such as low toxicity and high biodegradability. Within this class, N-Lauryl Sarcosinate stands out as an anionic surfactant whose application has been increasingly used to replace other anionic surfactants, such as sodium dodecyl sulfate, mainly in cosmetics. However, studies on its behavior are still scarce, mainly involving its interaction with other molecules, such as polymers. Polymers and surfactants are used together in several industrial processes and, knowing the result of their interactions is extremely important to control the properties of the mixture since they totally differ from the individual properties of its components. In this work, the study of the structures and thermodynamics of self-assembly of systems containing N-Lauryl Sarcosinate (LS) and polymers with different chemical nature: (PEG), (PSS), (PAA) and (PDADMAC) was performed using the techniques of calorimetry, tensiometry, isothermal calorimetric titration (ITC), dynamic light scattering (DLS) and Small-angle X-ray Scattering (SAXS).The results showed that the micellization of the LS occurs in the range from 10 to 14.6 nm to 298 K, with its value being dependent on the sensitivity of the technique used for its determination. The characterization of the micelle structure in water indicated that they have an ellipsoid shape and elongate with increasing concentration, but are very dependent on the pH of the medium. Also, this surfactant showed no signs of liquid-crystalline phases formation in the studied concentration range. The polymers PEG and PSS do not significantly affect the LS micellization thermodynamics. While PEG showed no evidence of any interaction with LS, PSS can act as a salt leading to the unidimensional growth of micelles. PAA may or may not interact strongly with LS depending on the solution s pH, and even induce the formation of aggregates at concentrations below the critical micellar concentration (CMC). PDADMAC, which has a charge opposite to LS, has a strong electrostatic attraction with the surfactant, leading to phase separation, in much lower concentrations than CMC. The precipitate formed had the same structure found for high concentrations of pure surfactant. This study shows how the chemical nature of different polymers - neutral, anionic, and cationic - influences interactions with N-Lauryl Sarcosinate and, consequently, in their micellization processes and self-assembly structures. Therefore, it allows a better forecast and greater control of formulations properties in which it is desired to combine polymers and surfactants.

Rheology modifiers such as hydrophobically-modified ethoxylated urethane (HEUR)thickeners are included in waterborne latex coatings to optimize shear-rate dependent viscosity and other rheological properties. While these HEUR polymers are commonly used in industry, the complex chemical interactions that contribute to rheological properties are still not completely understood. Prior work in this area has focused on understanding latex-HEUR and latex-surfactant-HEUR interactions that affect rheological properties. Additionally, studies have been previously conducted to understand the relaxation mechanisms of complex interactions present in HEUR-thickened waterborne latex coatings under various dynamic conditions. The objective of this work is to extend the experimental work to fully-formulated coatings and determine the effects of additional ingredients in a fully-formulated system. Coating formulations were prepared with a target 90 KU (Kreb Units) viscosity, having 0.23wt% HEUR. The pigment volume concentration (PVC) and non-volatiles by volume (NVV) were kept constant at 19.87% and 30.47%, respectively. An analysis of phase stability (presence or absence of syneresis), flow sweep (10-2 to 103 s-1), oscillatory strain (10-2 to 102 %), and oscillatory frequency (10-2 to 102 Hz) data was carried out in an attempt to determine connections among these properties. Furthermore, brief comparisons were made with previous results on latex-HEUR and latex-HEUR-surfactant systems that utilized the same HEUR thickener and latex used in this study. In the fully-formulated system, 0.23wt% HEUR was found to be in excess of what is needed to saturate latex surfaces. This HEUR level is less than half of the level needed to saturate latex surfaces in simpler latex-HEUR systems in previous studies. Fully-formulated coatings, in addition to having TiO2 and other ingredients are more crowded than the previous systems. It appeared that a depletion flocculation mechanism dominated at low surfactant concentrations for fully-formulated systems in this study as evident from syneresis; large HEUR aggregates appear to build enough osmotic pressure to drive aggregation of latex and pigment particles resulting in depletion flocculation. At increasing surfactant levels, the depletion flocculation mechanism was negated allowing the associative HEUR bridge networks to dominate and stabilize the system. Phase stability for fully-formulated systems in this study were associated with Newtonian viscosity plateaus on flow sweeps, strain hardening on oscillatory strain sweeps, and formation of high frequency moduli plateaus in frequency sweeps. Further increase of surfactant concentration appeared to disrupt the stable latex-HEUR network due to competitive adsorption of surfactant on latex particles, resulting in syneresis from bridging flocculation. Possible correlations between phase stability and high relaxation times were seen, although further analysis of relaxation time data and simulations will need to be carried out to better understand the behavior of HEUR in fully-formulated systems.