Biomimicry means literally ‘imitation of life’ and is providing sustainable solutions for challenges that are occurring in the human lives. To date, the biomimic research reports that wettability in nature, e.g. self-cleaning effect on a lotus leaf and a striking water strider’s leg, is related to the cooperation between the chemical composition and the topography of the surface. Moreover, this study is developing a textile substrate that goes one step further than biomimic, called ‘Biomimicking beyond nature’. The focus of this study is establishing a 100% polyamide-66 textile substrate that is switchable and reversible between hydrophobic and hydrophilic states under stimulation of UV. In this study the behaviour of a polyamide-66 textile substrate, coated with three individual photoresponsive materials (azobenzene, titanium dioxide and zinc oxide), was investigated, under stimulation of 24 hours UV and one-week of storage period in dark conditions. Silicone was added to enhance the hydrophobicity of a titanium dioxide coated substrate. A switchability effect was detected, but no reversibility effect could be observed. The only organic photoresponsive material, azobenzene, obtained no significant results to conclude that an alternation between hydrophobic and hydrophilic was even present after 24 hours of UV radiation. However, azobenzene obtained more promising results on a 100% polyester textile substrate. Even though, the H0 cannot be rejected for all three individual photoresponsive materials, the zinc oxide coated polyamide-66 substrate, did exhibit the strongest results in switchability and reversibility. Based on the characterization measurements, a switchability effect from a hydrophobic surface (ca. 120°) to a hydrophilic surface (0°) can be observed after 24 hours of UV radiation. Moreover, a reversibility effect was only reported on a zinc oxide coated polyamide-66 substrate. The substrate partially reversed back to its original state with ca. 50%. Fabricating intelligent substrates could enhance many challenges confiscating today’s life. For instance, the development of smarts membranes or microfluidic switches, that alternate their wettability upon light radiation, could improve the exhausting manual labour in watering the harvest good in the agricultural industry. Therefore, it is of great importance that further research will be conducted upon the photoresponsive material, zinc oxide, in order to achieve more stable results. This study can be added to the relatively small area of knowledge around switchability phenomenon on textile substrates and can even been reported as one of the first attempts on developing a textile substrate with switchable and reversible characteristics, by use of a facile and possibly industrialized method.

A avaliação da ocorrência de interações hidrofóbicas em substâncias húmicas toma-se importante pois este tipo de interação pode afetar a dinâmica e a reatividade de contaminantes apoIares no ambiente e influenciar no controle biogeoquímico do carbono no solo, podendo contribuir para a mitigação do efeito estufa. Entretanto, devido à heterogeneidade química das substâncias húmicas associada à baixa energia envolvida neste tipo de interação, evidências ou detecções experimentais são difíceis. Neste trabalho avaliou-se a ocorrência de interações hidrofóbicas em substâncias húmicas e também em alguns componentes do solo utilizando a metodologia de marcador de spin, detectável por ressonância paramagnética eletrônica, e a supressão de fluorescência. A utilização de diferentes marcadores de spin (TEMPO, 5-SASL, 16-SASL e 5-MSSL) possibilitou avaliar que a interação estabelecida com o ácido húmico é predominantemente hidrofóbica. A forte imobilização do marcado r 5SASL no ácido húmico foi confirmada pela diminuição dos valores da taxa de difusão rotacional obtida por simulação espectral (109 s-1 em água e 106 s-1 em presença do ácido húmico). Da análise do comportamento espectral do marcador de spin, observou-se que a conformação estrutural do ácido húmico depende, além do pH, da concentração iônica. Em pH 7,5, foi observado que a utilização de concentrações iônicas acima de 0,1 moI L-1 de c1oreto de sódio favoreceu a formação de sítios hidrofóbicos menos expostos ao meio aquoso (internos). O tempo de hidratação e a concentração de ácido húmico também influenciaram na formação destes sítios. Os experimentos com variação de concentração de ácido húmico e de marcador de spin sugeriram que a estruturação de sítios hidrofóbicos internos, observados principalmente abaixo de pH 5, seja devida à agregação de várias estruturas húmicas menores. Embora tenha sido observada a existência de sítios hidrofóbicos no ácido fúlvico, este apresentou maior dificuldade de agregação em comparação ao ácido húmico, o que foi atribuído ao seu caráter mais hidrofílico. Dos experimentos de supressão de fluorescência, observou-se que a interação do pireno foi influenciada pelas características químicas dos ácidos húmicos extraídos de diferentes solos e sistemas de manejo. Os dados mostraram que quanto maior a aromaticidade do ácido húmico maior foi a interação, sugerindo que as interações estabelecidas ocorrem predominantemente por meio de forças de van der Waals. Não se obteve correlações significativas entre a porcentagem estimada de moléculas de marcadores de spin imobilizadas nos sítios hidrofóbicos internos com as características químicas dos ácidos húmicos. Este comportamento sugeriu que estes sítios podem estar mais associados à conformação estrutural do que à composição química dos ácidos húmicos. Também foi analisado o comportamento espectral do marcador de spin na presença de alguns componentes do solo (fração argila, solo tratado com ácido fluorídrico e ácido húmico). Pelos resultados não se observou imobilização do marcador de spin na fração argila (caulinita), diferentemente do que foi observado para o solo tratado com ácido fluorídrico e ácido húmico. As diferenças na imobilização dos marcadores de spin foram atribuídas aos diferentes teores de carbono de cada amostra. / Hydrophobic interactions can play an important role on the dynamics and reactivity of the apoIar organic compounds in the environrnent as well as the organic carbon dynamic in the global system, and eventually contribute to mitigation of greenhouse effect. However, due to the chemical heterogeneity of humic substances and the low energy involved in the hydrophobic interactions experimental evidences are very difficult to be obtained. ln this work, hydrophobic interactions in the humic substances and some soil components were evaluated through spin labeling, detected by electronic paramagnetic resonance, and fluorescence quenching. Using different spin labels (TEMPO, 5-SASL, 16-SASL and 5-MSSL), it was possible to observe that the interactions established with humic acids are mainly hydrophobic. The decrease of the values of the rotational diffusion rates, obtained from spectral simulation, from 109 s-1 Iin water to 106 s-1 in the presence of humic acid indicated that the spin label was strongly immobilized in the humic acid. The results from the analysis of spectral anisotropy of the spin label showed that conformational aspects of the humic acid are dependent on pH value and ionic strength. For pH around 7.5 and using ionic strength above 0.1 moI L-1 of sodium chloride was noticed an increase in the formation of inner hydrophobic sites. It was noticed that the formation of inner hydrophobic sites also was influenced by hydration time and humic acid concentration. Data obtained using different humic acids and spin label concentration suggested that the inner hydrophobic sites formation (mainly at pH below 5) is due to the aggregation of small humic structures. The existence of inner hydrophobic sites was noticed in the fulvic acid. However, the fulvic acid presented more difficulty to form aggregates, in comparison with humic acid, due to its major hydrophilic characteristic. From data obtained by fluorescence quenching it was observed that the interaction of pyrene was influenced by chemical composition of humic acid samples extracted from different soils and tillage systems. An increase of interactionin samples with higher aromaticity degree was shown, which indicates that the van der Waals forces are prevailing. No correlation between the estimated percentages of spin label molecules immobilized in the inner hydrophobic sites and the chemical characteristics of humic acid samples was obtained. This behavior suggested that the hydrophobic sites in the humic acid are mainly related to structural conformation instead of chemical composition. The mobility trend of spin label in the presence of soil components (clay fraction, fluoridric acid treated soil and humic acid) was also analyzed. No spin label immobilization was noticed in the clay fraction (kaolinite). On the other hand strongly immobilized spin label in the fluoridric acid treated soil and humic acid were observed. The differences in the immobilization were attributed to the carbon content.

Neste trabalho propomos uma investigação através de simulações de dinâmica molecular da água em contato com superfícies hidrofóbicas e hidrofílicas, tanto dentro de nanotubos funcionalizados quanto em membranas bi-dimensionais para dessalinização. No caso da água em contato com superfícies hidrofóbicas e hidrofílicas de nanotubos nós encontramos uma quebra na relação de Stokes-Einstein para a difusão e a viscosidade da água. Essa quebra ocorre para os menores nanotubos − em que pelo menos duas camadas de água formam-se, condição para deslizamento de camadas necessária para o cálculo da viscosidade. O mecanismo por trás deste comportamento é ditado pela estrutura da água confinada. Esse resultado indica que algumas das características observadas para a água dentro de nanotubos hidrofóbicos, como nanotubos de carbono na natureza, são únicas. Encontramos uma grande dependência da dinâmica e estrutura da água confinada com as características polares do nanotubo, principalmente para nanotubos com diâmetros menores que 1 nm. Ao variarmos a temperatura do sistema, observamos ainda uma forte dependência da estruturação das moléculas de água com a temperatura, a ponto de apresentar transições entre estados mais e menos ocupados Nossos resultados de dinâmica molecular também mostram que membranas contendo nanoporos com sítios hidrofílicos entre regiões hidrofóbicas podem apresentar grande fluxo de água e reduzido transporte de íons, o que torna esses materiais excelentes candidatos para sistemas de dessalinização e limpeza de metais pesados. Ao acrescentarmos um químico floculante (cloreto de ferro) à água salgada, encontramos resultados ainda melhores para a rejeição de sal pelas membranas nanoporosas. Todos esses resultados demonstram a importância do estudo das propriedades hidrofóbicas e hidrofílicas em interfaces aquosas. Em todos os casos, encontramos uma dependência inerente das propriedades de transporte da água com a característica polar da superfície de contato. / In this work we have proposed an investigation through molecular dynamics (MD) simulations of the water behavior at hydrophobic and hydrophilic surfaces in both functionalyzed nanotubes and two-dimensional nanpores. In the case of water at hydrophobic and hydrophilic nanotube surfaces, we have found a breakdown of the Stokes-Einstein relation for diffusion and viscosity of water confined in narrow hydrophobic nanopores. The mechanism underlying this behavior is dictated by the structure of water under confinement. This result indicates that some of the features observed for water inside hydrophobic carbon nanotubes cannot be observed in other nanopores. We have also found an important dependence of the water dynamics with the polar character of the nanotube, mostly for small diameters. By varying the temperature, both the dynamics and the water structuration are affected, presenting transitions between dense-packed and low-density states. Our results also shows that nanoporous membranes, with hydrophilic sites sandwiched between hydrophobic regions, can present an important flux of water molecules and reduced ion transportation, making these structures promising for desalination processes. By adding a flocculant ingredient (ferric chloride) to the salt water, we found even larger ion rejection rates. All the results point out the importance of studying hydrophilic and hydrophobic interfaces for water transport. In all the cases, we have found an ubiquitous dependence of water dynamic properties on the surface polarity.

Using the classical molecular dynamics simulations, the interfacial partitioning of selected aromatic species, namely benzoic acid and neutral and zwitterionic form of L-phenylalanine, was studied in the three slab systems: a) aqueous organics solution, b) palmitic acid monolayer in tilted condensed phase at aqueous organics solution and c) palmitic acid monolayer in tilted condensed - 2D gas phase coexistence at aqueous organics solution. The surface activity and the tendency to aggregate in particular at the air- aqueous and palmitic acid-aqueous interface was confirmed for all of the investigated aromatic species. The results of the simulation performed for the system of palmitic acid monolayer at benzoic acid solution were compared with the literature results of a similar simulation that employed a different parametrization. The comparison showed that the behaviour of the aromatic species at the fatty acid monolayer-aqueous interface strongly depends on the force field. The structural properties of the palmitic acid Langmuir monolayers were evaluated by means of the chain tilt angle and the headgroup region dihedral angle distributions analysis depending on the surface film density and the adsorbed aromatic species. The simulations mimicking the isothermal compression of the mixed monolayer in the...

In frame work of this diploma thesis, monolithic stationary phases based on hydroxymethylmethacrylate were prepared in fused silica capillaries of 320 μm innerdiameter. Monolithic columns were synthesized by a simple procedure using a polymerization mixture, consisting of a monomer N-(hydroxymethyl) methacrylamide (HMMAA), a croslinking agent ethylene dimethacrylate (EDMA), porogenic solvents butane- 1,4-diol, propane-1-ol and an initiator α,α′-azobisisobutyronitrile (AIBN). Prepared HMMA monolithic columns were utilized for separation of mixtures of biologically active compounds, namely peptides with small number of amino acids. Mechanical strength and specific permeability were determined for selected monolithic columns. Keywords: HPLC, HILIC mechanism, hydroxymethyl methacrylate (HMMA) monolithic columns, amino acid, enkephalins.

Studies of dietary fat absorption are generally conducted by using an animal model equipped with a lymph cannula. Although this animal model is widely accepted as the in vivo model of dietary fat absorption, the surgical techniques involved are challenging and expensive. Genetic manipulation of the animal model is also costly and time consuming. The alternative in vitro model is arguably more affordable, timesaving, and less challenging. Importantly, the in vitro model allows investigators to examine the enterocytes as an isolated system, reducing the complexity inherent in the whole organism model. This paper describes how human colon carcinoma cells (Caco-2) can serve as an in vitro model to study the enterocyte transport of lipids, and lipid-soluble drugs and vitamins. It explains the proper maintenance of Caco-2 cells and the preparation of their lipid mixture; and it further discusses the valuable option of using the permeable membrane system. Since differentiated Caco-2 cells are polarized, the main advantage of using the permeable membrane system is that it separates the apical from the basolateral compartment. Consequently, the lipid mixture can be added to the apical compartment while the lipoproteins can be collected from the basolateral compartment. In addition, the effectiveness of the lentivirus expression system in upregulating gene expression in Caco-2 cells is discussed. Lastly, this paper describes how to confirm the successful isolation of intestinal lipoproteins by transmission electron microscopy (TEM).

This communication will demonstrate the existence of a thermodynamic molecular switch in the pairwise, sequence-specific hydrophobic interaction of Ile-Ile, Leu-Ile, Val-Leu, or Ala-Leu over the temperature range of 273-333 K reported by Nemethy and Scheraga in 1962. Based on Chun's development of the Planck-Benzinger methodology, the change in inherent chemical bond energy at 0 K, ΔH°(T0), is 3.0 kcal mol-1 for Ile-Ile, 2.4 for Leu-Ile, 1.8 for Val-Leu, and 1.2 kcal mol-1 for Ala-Leu. The value of ΔH°(T0) decreases as the length of the hydrophobics side chain decreases. It is clear that the strength and stability of the hydrophobic interaction is determined by the packing density of the side chains, with Ala-Leu being the most stable. At , the thermal agitation energy, ∫0T ΔCp°(T)dT, is about five times greater than ΔH°(T0) in each case. Additionally, the thermal agitation energy for the same series, evaluated at , decreases in the same order, that is, as the length of the side chain decreases. This pairwise, sequence-specific hydrophobic interaction is highly similar in its thermodynamic behavior to that of other biological systems, except that the negative Gibbs free energy change minimum at occurs at a considerably higher temperature, 355 K compared to about 300 K. The melting temperature, , is also high, 470K compared to 343 K in a biological system. The implication is that the negative Gibbs free energy minimum at a well-defined >Ts> has it origin in the hydrophobic interactions, which are highly dependent on details of molecular structure. In addition to the four specific dipeptide interactions described, we have shown in our unpublished work the existence of a thermodynamic molecular switch in the interactions of 32 dipeptides wherein a change of sign in ΔCp°(T)reaction leads to a true negative minimum in the Gibbs free energy of reaction, and hence, a maximum in the related Keq. Indeed, all interacting biological systems that we have thus far examined using the Planck-Benzinger approach point to the universality of thermodynamic molecular switches.

Granulation, the process of formation of granules from a combination of base powders and binder liquids, has been a subject of research for almost 50 years, studied extensively for its vast applications, primarily to the pharmaceutical industry sector. The principal aim of granulation is to form granules comprised of the active pharmaceutical ingredients (API’s), which have more desirable handling and flowability properties than raw powders. It is also essential to ensure an even distribution of active ingredients within a tablet with the goal of achieving time-controlled release of drugs. Due to the product-specific nature of the industry, however, data is largely empirical [1]. For example, the raw powders used can vary in size by two orders of magnitude with narrow or broad size distributions. The physical properties of the binder liquids can also vary significantly depending on the powder properties and required granule size. Some significant progress has been made to better our understanding of the overall granulation process [1] and it is widely accepted that the initial nucleation / wetting stage, when the binder liquid first wets the powders, is key to the whole process. As such, many experimental studies have been conducted in attempt to elucidate the physics of this first stage [1], with two main mechanisms being observed – classified by Ivenson [1] as the “Traditional description” and the “Modern Approach”. See Figure 1 for a graphical definition of these two mechanisms. Recent studies have focused on the latter approach [1] and a new, exciting development in this field is the Liquid Marble. This interesting formation occurs when a liquid droplet interacts with a hydrophobic (or superhydrophobic) powder. The droplet can become encased in the powder, which essentially provides a protective “shell” or “jacket” for the liquid inside [2]. The liquid inside is then isolated from contact with other solids or liquids and has some fascinating physical properties, which will be described later on. The main potential use for these liquid marbles appears to be for the formation of novel, hollow granules [3], which may have desirable properties in specific pharmaceutical applications (e.g. respiratory devices). They have also been shown to be a highly effectively means of water recovery and potentially as micro-transporters and micro-reactors [4]. However, many studies in the literature are essentially proof-of-concept approaches for applications and a systematic study of the dynamics of the marble formation and the first interactions of the liquid droplet with the powder is lacking. This is the motivation for this research project, where we aim to provide such information from an experimental study of drop impact onto hydrophobic powders with the use of high-speed imaging.

L’objectif de cette thèse était de concevoir denouveaux matériaux polymères hydrophobes pour la protectionde composants semi-conducteurs, résistants à hautetempérature, aux forts champs électriques et aux atmosphèresagressives. Dans ce contexte, les polyimides d’addition sontapparus comme la famille de polymères la mieux adaptée pourl’application envisagée. La synthèse de l’encapsulant étantréalisée directement dans les boîtiers des modules, elle ne peutdonc pas contenir de solvant organique exogène. Ainsi, nousavons développé de nouvelles voies de synthèse sans solvantde poly(aminobismaléimide)s et de poly(bismaléimide)s.Dans un premier temps, différentes diamines aliphatiques ontété utilisées comme solvant réactif lors de la synthèse depoly(aminobismaléimide)s à une température bien inférieure à latempérature de fusion du bismaléimide utilisé (Tf > 300 °C). Unepremière série de 3 nouveaux poly(aminobismaléimide)sréticulés de 70 à 95 % a ainsi été réalisée. A partir de cespremières synthèses, 10 nouveaux poly(aminobismaléimide)sont été élaborés. Pour 9 d’entre eux, des diamines aromatiquesont été utilisées et, pour le dernier, une diamine siloxane. Cesrésultats démontrent la possibilité de généraliser ce procédé desynthèse.Dans un second temps, des poly(bismaléimide)s ont étésynthétisés, toujours sans solvant. Pour cela, les synthèses dequatre nouveaux bismaléimides liquides à température ambianteont été mises au point. Ces composés ont une structurealiphatique ou siloxane dans laquelle un motif pyroméllitique aété, ou pas, introduit. Leur polymérisation amorcée avecl’amorceur radicalaire ad hoc, conduit à la formation desmatériaux sans l’usage de solvant.Selon le choix des réactifs, des matériaux thermodurcissablesou élastomères sont obtenus. Ces derniers semblent mieuxadaptés à l’application souhaitée car, d’une part, la faibleviscosité des mélanges réactionnels permet leur applicationsans difficulté dans un module de puissance et, d’autre part, leurcaractère hydrophobe est plus marqué. L’un d’eux présente unestabilité thermique à 250 °C particulièrement intéressante et unetempérature de relaxation mécanique quasi hors gamme detempérature de fonctionnement. Ce matériau peut doncvraisemblablement être utilisé comme encapsulant. / The aim of this work is to develop new hydrophobicpolymeric materials for the protection of semi-conductorcomponents. These materials must withstand high temperature,strong electric fields and aggressive atmospheres such asmoisture. In this context, addition polyimides emerged as themost suitable polymers for the intended application. Thesynthesis of the encapsulant being made directly in the powermodules, it must be solvent free. Thus, we have developed newsolvent free synthesis routes of poly(aminobismaleimide)s andpoly(bismaleimide)s.First of all, different aliphatic diamines were used as a reactivesolvent in the synthesis of poly(aminobismaleimide)s to atemperature well below the melting point of the usedbismaleimide (m.p. > 300 °C). A first series of 3 newpoly(aminobismaleimide)s, crosslinked from 70 to 95 %, hasthus been made. From these first syntheses, 10 newpoly(aminobismaleimide)s have been developed. For 9 of them,aromatic diamines were used and, for the latter, a siloxanediamine. These results demonstrate that this process can begeneralized.Secondly, poly(bismaleimide)s were synthesized, still withoutany solvent. In order to do so, the syntheses of four newbismaleimides, liquid at room temperature, have beendeveloped. These compounds have an aliphatic or siloxanestructure in which a pyromellitic pattern has been or notintroduced. Their polymerization initiated with the suitable radicalinitiator leads to the formation of materials without the use of anysolvent.Depending on the choice of reagents, thermosetting materials orelastomers are obtained. These latter seem more suitable for thedesired application because, on one hand, the low viscosity ofthe reaction mixtures enables their application in a powermodule without any difficulty and, on the other hand, theirhydrophobic behaviour is stronger. One of them has aparticularly attractive thermal stability at 250 ° C and amechanical relaxation temperature almost out of the workingtemperature range. Therefore, this material may be used asencapsulant.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18096号 / 理博第3974号 / 新制||理||1573(附属図書館) / 30954 / 京都大学大学院理学研究科化学専攻 / (主査)准教授 中西 和樹, 教授 北川 宏, 教授 竹腰 清乃理 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM