Dissertations / Theses on the topic 'Functional Gels'

Les alginates, des polysaccharides produits par les algues brunes, sont des copolymères à blocs linéaires, formés d’unités mannuronate (M) et guluronate (G). En raison de leur abondance naturelle, prix et propriétés physicochimiques avantageuses, les alginates représentent une classe de biopolymères très intéressante et relativement inexplorée pour des applications dans le domaine des matériaux avancés. Dans ce contexte, le présent travail vise à enrichir la gamme des applications des matériaux dérivés d’alginates, en exploitant les propriétés de cette classe de polysaccharides naturels. En particulier, la préparation de matériaux à base d'alginate pour la catalyse, l'adsorption et le domaine biomédical a été étudiée, avec des résultats encourageants dans toutes les applications testées. L'utilisation bénéfique de l'acide alginique en catalyse hétérogène a été démontrée, en tant que promoteur de réaction et support pour l’hétérogénéisation d'un organocatalyseur. L'activité du catalyseur a été trouvée très dépendante de l'accessibilité des groupes fonctionnels, mettant en évidence l’avantage de l’emploi de formulations plus accessibles. La texturation des alginates a été aussi avantageuse dans la préparation de matériaux pour applications en flux. Des mousses d'acide alginique, avec une structure hiérarchique macro-mésoporeuse, ont été développées à cet effet. Une caractérisation précise des matériaux a été réalisée, afin d'optimiser la procédure de préparation et de corréler les propriétés texturales obtenues avec les paramètres utilisés. L'intérêt dans l’utilisation de mousses à base d'acide alginique a été démontré dans une application modèle, l'adsorption de bleu de méthylène à partir de solutions aqueuses, à la fois en batch et en flux. La possibilité de modifier facilement les groupes fonctionnels de l’alginate, couplée avec la nature biocompatible et biodégradable de ces biopolymères, a finalement été exploitée pour le développement de gels auto-réparants, obtenus grâce à la formation de deux types d'interactions covalentes dynamiques : base de Schiff et ester de boronate. Les deux systèmes examinés ont présenté une remarquable habilité à se reconstruire après un dégât, même si l'ampleur de la reconstruction et la stabilité des gels étaient fortement dépendantes des paramètres de préparation des gels et des conditions environnementales utilisées. Les résultats obtenus dans le cadre de cette étude démontrent clairement comment la compréhension et un emploi conscient des propriétés physico-chimiques des alginates peuvent maximiser le potentiel que cette ressource durable dans le domaine de la chimie des matériaux<br>Alginates, polysaccharides produced by brown algae, are linear block-copolymers formed by mannuronate (M) and guluronate (G) units. Because of their huge natural abundance, cheapness and physicochemical properties, alginates represent a highly attractive and still relatively unexplored class of biopolymers for applications in the field of advanced materials. In this context, the present work aimed to enrich the range of possible applications of alginate-derived materials, making the most of the peculiar features of this class of natural polysaccharides. In particular, the preparation of alginate-based active materials to be employed in the catalysis, adsorption and biomedical field was studied, achieving encouraging results in all the tested applications. The beneficial use of alginic acid in heterogeneous catalysis, both as reaction promoter and as support for the heterogeneization of an organocatalyst, was demonstrated. The activity of the material was found highly dependent on the accessibility of the active functions, highlighting the advantage of employing more accessible alginate formulations. The texturation of alginates was further advantageous for the preparation of materials with improved flowability. Alginic acid foams, bearing a hierarchical macro-mesoporous structure were developed by means of a simple procedure. Accurate characterization was performed to optimize the preparation procedure and to correlate the textural properties of the obtained materials with the parameters used. The interest of the prepared alginic acid foams was demonstrated in a model application, the adsorption of methylene blue from aqueous solutions, both in batch and in flow conditions. The possibility to easily modify alginate functional groups, coupled with the biocompatible and biodegradable nature of alginates, was finally employed for the development of self-healing gels, thanks to the formation of two types of dynamic covalent interactions: Schiff base and boronate ester bonds. Both the examined systems presented a marked ability to recover after damage, even if the extent of the recovery and the stability of the gels was highly dependent on the preparation parameters and environmental conditions used. The results obtained in the course of this study clearly demonstrate how a full comprehension and conscious employment of alginate physicochemical properties can maximize the potential of this sustainable resource in the field of material chemistry

La industria alimentaria ha estudiado la encapsulación de compuestos bioactivos para su aplicación en el diseño de alimentos funcionales. El alginato ha sido utilizado como agente encapsulante debido a su matriz biodegradable, no tóxica y versátil que protege a éstos de las condiciones adversas del entorno, enmascara sabores y olores y, mejora su estabilidad y biodisponibilidad. En concreto, estudiar la obtención de geles de alginato como encapsulante a través de diferentes mecanismos de gelificación y técnicas derivadas para la encapsulación de compuestos activos permite determinar las condiciones más idóneas para su preparación, así como, la influencia del tipo de fuente de calcio y su concentración, pH, entre otras sobre las características viscoelásticas, tamaño, morfología y textura de los geles. Con este fin se caracteriza el alginato sódico utilizado y los geles de alginato cálcico preparados por gelificación externa (GE) y gelificación interna (GI), a partir de sus características reológicas se estudian las técnicas de encapsulación. En primer lugar, se estudian las condiciones para formar una emulsión estable que proporcione las microesferas de alginato de menor tamaño por GI, así como la encapsulación de compuestos activos polifenólicos del extracto de cacao en ellas, a través de un diseño experimental. En segundo lugar, se analizan las esferas obtenidas por extrusión con diferentes formulaciones, comparándose su tamaño, morfología y textura. También se estudia la liberación de los polifenoles desde los encapsulados hacia el medio que los rodea y el ajuste de la curva de liberación a varios modelos propuestos en la bibliografía. Finalizando con la incorporación de las esferas más idóneas según las características deseadas en un alimento para su evaluación sensorial. La estructura polimérica del alginato sódico sugiere una contribución equilibrada de sus monómeros con una distribución por bloques heterogénea que proporciona mayor flexibilidad al gel formado. Las características viscoelásticas de los geles obtenidos, en general, muestran que un incremento de la [Ca+2] proporciona geles más compactos. Las diferencias observadas entre sus propiedades indican una influencia de la fuente de calcio al utilizar GI y, del proceso de formación en el gel por GE. La distribución de tamaños de las microesferas obtenidas por GI a partir de las diferentes emulsiones y citrato cálcico indican que las microesferas de menor tamaño y polidispersidad se producen con tensioactivo polirricinoleato de poliglicerol (PGPR). Al encapsular el extracto de cacao en las microesferas, el diseño experimental muestra que la cantidad de fase dispersa influye significativamente en el porcentaje retenido de polifenoles y que la velocidad de agitación afecta al diámetro medio y la polidispersidad de las microesferas. Las esferas obtenidas por extrusión se ven afectadas por el aumento de la [Ca+2] al producirse una disminución en sus diámetros, la estructura interna de éstas confirma la influencia del tipo de gelificación, siendo las esferas obtenidas por GE heterogéneas, mientras que las formadas por GI se presentan más homogéneas. Sus propiedades texturales indican que son más duras las esferas preparadas por GE que las formadas por GI, y para todas las formulaciones que las esferas por GI son menos gomosas y, por tanto, requieren menor energía para su masticación. La liberación de los polifenoles desde los diferentes encapsulados muestra los mejores ajustes al modelo de Peppas-Sahlin, lo que sugiere una cinética dominada por la difusión del compuesto activo producto del mecanismo disolución/relajación de la matriz hinchada. La incorporación de esferas más suaves, menos gomosas con un alto contenido de extracto de cacao y [Ca+2] a un producto alimentario como la gelatina muestra a través de una evaluación sensorial que el sabor astringente y amargo del extracto natural es satisfactoriamente enmascarado.<br>Functional foods are beginning to play a major role in what consumers eat due that the encapsulation of active compounds is being studying by the food industry. Biopolymers as the alginate has been one of the most widely used in encapsulation due to the matrix forms a versatile, biocompatible and nontoxic barrier for the protection of those components sensitive to the factors which are exposed to foods during processing and storage. The structure of the sodium alginate used suggests a balanced contribution of their monomers with a heterogeneous distribution block that provides greater flexibility to the gel formed. Gels of calcium alginate are formed by external gelation (GE) and internal gelation (GI) mechanism using polyvalent cations, such as Ca+2. The viscoelastic properties of the gels obtained, in general, show that an increase in [Ca+2] provides more compact gels. The differences observed between their properties indicate an influence of the source of calcium by using GI and by the gelation mechanism when the GE is used. The size distribution of the microspheres obtained by GI from different emulsions and calcium citrate indicate that the microspheres with smaller size and polydispersity occur with the polyglycerol polyricinoleate emulsifier. By encapsulating the cocoa extract rich in polyphenols in the microspheres, the experimental design shows that the amount of dispersed phase significantly affects the percentage of polyphenols retained and that the stirring speed influences the mean diameter and the polydispersity of the microspheres. Moreover, the beads obtained by extrusion are affected by increased of [Ca+2] which cause a decrease in its diameter, the morphology of these confirms an influence of the type of gelation, where the spheres obtained by GE are heterogeneous, while those formed by GI are more homogeneous. For all formulations of the spheres prepared, the beads formed by GI are presented softer and less gummy respect to those obtained by GE. The incorporation of those beads also with a high cocoa extract and [Ca+2] contents into a food product such as the gelatin shows through a sensory evaluation that the astringent and bitter flavor of the natural extract is successfully masked.

It is well-known that production of a crystal matrix is as a rule accompanied by using hightemperature processing which considerably limits the area of applied use of the objects. In the present work, we consider new approaches aimed at formation of crystalline highly active oxide phases without using annealing stage by achieving deep intercomponent penetration of disperse particles at the nanolevel during the sol-gel process reactions. The use of these approaches was possible in a single stage for the first time: 1) entrapment of various biological objects in a ceramic biocompatible matrix necessary for obtaining vaccines of new generation; 2) doping a crystal lattice up to 10at. % usingsoft chemistry method; 3) chemical modification of biopolymers for the purpose of developing high-level operational characteristics. In this work, trends in forming crystals from solutions for existing ceramic matrices are analyzed for the first time. The main objects of study are materials of modified titania and alumina. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35209

Les organosilices sont des matériaux en plein essor, qui combinent les propriétés des fragments organiques et ceux de la matrice siliciée. Ces matériaux hybrides ont trouvé des applications dans les domaines de la catalyse, de l'optique, de l'électronique etc. Ils peuvent être préparés par le procédé sol-gel à partir d'organosilanes contenant des fragments organiques à propriétés désirées. Pour former ces matériaux, il est essentiel de simplifier la préparation des organosilanes fonctionnels en réduisant le nombre d'étapes réactionnelles. Aussi, l'un des buts de cette thèse est de développer une méthode de préparation sélective, universelle et à spectre large pour les organo(trialcoxy)silanes. Dans ce but, la réaction Click de CuAAC, connue comme une approche simple de couplage, a été adaptée pour les composés sensibles à l'eau. En utilisant des azotures ou des alcynes contenant la fonction triéthoxysilane avec des partenaires organiques, nous avons réussi à préparer des séries de précurseurs silylés par réaction Click. La réaction est rapide, quantitative et sélective, et tolère une gamme étendue de substrats. De plus, de nouveaux alcynes et azotures comportant deux fonctions triéthoxysilyle ont été préparés, afin d'être clickés sur différentes molécules organiques. Ces précurseurs bissilylés sont des organo(triéthoxy)silanes clickables, précurseurs de silsesquioxanes pontés. En utilisant des molécules fonctionnelles comportant un seul site de dérivatisation, des organosilanes pontés peuvent être obtenus, présentant un fragment organique pendant. De plus, un précurseur contenant une fonction alcyne protégée a été obtenu, ce qui permettra la formation de matériaux multifonctionnels. Certains des précurseurs sol-gel obtenus ont été transformés en matériaux hybrides par le procédé sol-gel. Ceux contenant des fragments organiques connus comme des ligands chiraux actifs ont été choisis pour des tests en catalyse asymétrique. Par ce biais, des ligands chiraux supportés ont été formés, et testés pour quelques réactions bien connues. De plus, cette thèse s'est intéressée à la nano-structuration de matériaux. Des molécules contenant des systèmes aromatiques et des fonctions urée, capables de s'auto-assembler grâce à des interactions non covalentes, ont été conçues et préparées. Dans certains cas, en particulier les systèmes à base de Binol avec des fonctions urée, des nanostructures régulières ont été observées sur des surfaces localisées. En conclusion, les travaux présentés dans cette thèse ont apporté de nouvelles possibilités pour la synthèse d'organo(triéthoxy)silanes, ainsi que des matériaux hybrides à propriétés et applications ciblées<br>Organosilicates are attracting considerable attention, owing to the combined properties of the organic fragment and inorganic silica matrix. These hybrid materials have found application in catalysis, optics, electronics, etc. They can be prepared by the sol-gel hydrolysis of functional organosilanes with the desired properties. To apply these materials in industry, it is essential to make the preparation of these silylated precursors easier and more efficient by reducing the number of reaction steps. Therefore one of the aims of this thesis is to develop a universal, wide scope and selective method of preparation for trialkoxyorganosilanes. For this purposes the “CuAAC reaction”, known for its simple approach, has been adapted for water-sensitive substrates. Using a silylated azide or silylated alkyne with an organic counterpart, we were able to prepare a series of clicked sol-gel precursors. The reaction is quantitative, fast, and selective and tolerates a wide range of substrates. Moreover, new bissilylated alkynes and azides which can be clicked to various organic molecules were prepared. They represent new families of bridged organotrialkoxysilanes to which a desired organic molecule, bearing only one bonding site, can be incorporated as a pending group with a targeted functionality. Furthermore, a bissilylated precursor bearing a protected alkyne function was prepared, allowing the synthesis of bifunctional materials. Some of the prepared precursors were transformed into hybrid silicas by the sol-gel process. Those containing organic molecules known as active chiral ligands for enantioselective reactions were chosen. By this way, supported chiral ligands were formed and we tested their activity according to known reactions. Additionally, in this thesis the structuring of the materials was also attempted. Molecules bearing aromatic systems and urea functions, which are capable of self-organization thanks to the weak non-covalent bonding interactions, were designed and prepared. In some cases, especially Binol systems with urea function, regular nanostructures on localized areas have been observed. Overall, this thesis brings new possibilities in the synthesis of both trialkoxyorganosilanes precursors and hybrid materials with desired properties and applications

Les structures d'acto-myosine sont impliquées dans de nombreuses fonctions cellulaires. Comprendre leur organisation et leur comportement collectif est toujours difficile. Nous avons étudié l'anneau cytokinétique dans les cellules de mammifères et dans les levures de fission, en orientant les cellules dans les microcavités, ce qui permet de voir l'anneau dans un seul plan focal. Avec cette configuration, nous révélons de nouvelles structures et des dynamiques distinctes pour les deux systèmes cellulaires. Dans les cellules de mammifères, nous trouvons des motifs réguliers de la myosine et la formine. Les caractéristiques de ces motifs sont stables tout au long de sa fermeture et leur apparition coïncide avec la constriction. Nous proposons que ce phénomène est une propriété inhérente du réseau d'acto-myosine et que la formation de ces motifs entraîne une augmentation du stress. Ces hypothèses sont confirmées par notre modèle en champ moyen. Par contraste, l'anneau de levure de fission montre des inhomogénéités tournantes de l'actine, de la myosine, des protéines de la construction de la paroi (Bgs) et d'autres protéines. La dynamique des inhomogénéités de myosine est inchangée, si la croissance de la paroi est inhibée. Cependant, l'inhibition du mouvement des inhomogénéités conduit à l'arrêt de la fermeture. Nous proposons que la fermeture de l'anneau est entraînée par la rotation de l'actine et de la myosine qui tirent des protéines Bgs, lesquelles construisent ainsi le septum. Cette hypothèse est confirmée par nos calculs et par des simulations numériques. Nous suggérons que la transition entre les états de différents ordres et dynamiques pourrait être une façon de réguler in vivo les systèmes d'acto-myosine<br>Actomyosin structures are involved in many cell functions. Understanding their organization and collective behavior is still challenging. We study the cytokinetic ring in mammalian cells and in fission yeasts, by orienting cells in microcavities. This allows seeing the ring in a single plane of focus. With this setup, we reveal new structures and distinct dynamics for both cellular systems. In mammalian cells we find a pattern of regular clusters of myosin and formin. The characteristics of this pattern are stable throughout closure and its formation coincides with the onset of constriction. We propose that its characteristic is an inherent property of the actomyosin network and that its formation leads to an increase in stress generation. These hypotheses are supported by our theoretical mean field model. In contrast, fission yeast rings show rotating inhomogeneities (speckles), i.e. rotations of actin, myosin, cell wall building proteins (Bgs) and other proteins. Myosin speckles dynamic is unchanged, if wall growth is inhibited. However, the inhibition of speckle motion leads to stalled closure. We propose that the ring closure is driven by the rotation of actin and myosin, which pull Bgs thereby building the septum. This model is supported by our calculations and by numerical simulations. We suggest that the transition between states of different orders and dynamics might be a way to regulate actomyosin systems in vivo

L'objectif de la thèse était d'étudier la mobilité de traceurs particulaires dans des milieuxcomplexes par microscopie confocale à balayage laser (CLSM) combinée avec le suivi demultiple particules (MPT) et le recouvrement de fluorescence après photoblanchiment (FRAP).Tout d'abord, nous avons étudié la diffusion de particules dans les gels formés par des protéinesglobulaires. Dans ce but, des gels avec structures variés ont été préparés en faisant varier lesconcentrations en protéine et en sel. La structure a été caractérisée par l'analyse des imagesobtenues par CLSM en termes de fonction de corrélation de paires. La mobilité de particulesavec une large gamme de tailles (2nm - 1 micron) a été étudiée à la fois dans des gels homogèneset hétérogènes et reliée à la structure du gel.Deuxièmement, nous avons étudié des émulsions eau dans eau préparées en mélangeant dessolutions aqueuses de PEO et de dextran. Il a été montré que lorsque des particules colloïdalessont ajoutées, elles sont emprisonnées à l'interface eau-eau, car elles réduisent la tensioninterfaciale. La structure et le déplacement des particules à l'interface ont été déterminés parCLSM combinée avec MPT<br>The objective of the thesis was to investigate the mobility of tracer particles in complex media byConfocal Laser Scanning Microscopy (CLSM) combined with multiple particle tracking (MPT)and fluorescence recovery after photobleaching (FRAP).First, we investigated the diffusion of tracer particles in gels formed by globular proteins. Gelswith a variety of structures were prepared by varying the protein and salt concentrations. Thestructure was characterized by analysis of the CLSM images in terms of the pair correlationfunction. The mobility of particles with a broad range of sizes (2nm - 1μm) was investigatedboth in homogeneous and heterogeneous gels and related to the gel structure.Second, we studied water-in-water-emulsions prepared by mixing aqueous solutions of PEO anddextran. It is shown that when colloidal particles are added they become trapped at the waterwaterinterface because they reduce the interfacial tension. The structure and the displacement ofthe particles at the interface were determined using CLSM combined with MPT

Dissertação para obtenção do Grau de Doutor em Química<br>This Ph.D. project is focused on the synthesis of functional inorganic materials, their formulation into inks and their deposition using inkjet printing on non-conventional substrates, such as paper, with the ultimate goal of advancing the state-of-the-art in the area of printed electrochromic displays. Other materials, inks,techniques and substrates were also explored. The first step in building a printed electrochromic display is to synthesize the functional materials necessary for the different layers of the device; this part of the work focused on inorganic electrochromic materials (tungsten oxide and vanadium oxide) and on transparent conductive oxides (TCO). ATO(antimony tin oxide) was synthesized using the Pechini method and the results obtained were promising. Tungsten oxide and vanadium oxide nanoparticles were also synthesized via a sol-gel route. FTIR,Raman and X-ray diffraction spectroscopic measurements showed that tungsten oxide nanoparticles synthesized via sol-gel are mainly in an amorphous state, with hexagonal crystalline domains, and allowed the analysis of the hydration extent of those nanoparticles. Vanadium oxide gel synthesized in this work is similar to those previously described in the literature, consisting of V2O5.6H2O, with microstructures similar to orthorhombic V2O5, while Raman spectroscopy also showed the presence of amorphous domains. The nanoparticle sizes were measured combining Dynamic Light Scattering, sedimentation and microscopic techniques (AFM and TEM). Tungsten oxide particles presented an average nanoparticle size between 160 and 200 nm, and vanadium oxide of 60 nm. The nanoparticles were used to produce ink formulations for application in inkjet printing. In addition to tungsten oxide and vanadium oxide, other electrochromic materials were printed. This part of the work examined the possibility of inkjet printing several organic (poly(thiophene)s) and inorganic electrochromic materials (metal oxides and metal hexacyanometallates) and also evaluated the performance of the resulting electrochromic devices. Poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate), poly(3-hexylthiophene), tungsten oxide, vanadium oxide and Prussian blue were inkjet printed on flexible substrates, such as plastic and paper. Solid-state electrochromic devices were assembled at room temperature on plastic and on paper substrates, without sintering the printed films, showing, in some cases, excellent contrast between the on and off state. The tungsten oxide and vanadium oxide devices were then tested through spectroelectrochemistry by Visible/NIR absorption spectroscopy. Tungsten oxide showed a dual spectroscopic response depending on the applied voltage and vanadium oxide presented several redox steps, which give rise to a variety of color transitions, also as a function of the applied voltage. Color space analysis was used to characterize the electrochromic transitions; monitorization of the color contrast and cycling tests, as well as techniques such as cyclic voltammetry, were also used to characterize device performance.

Various nano-fillers can introduce specific functions into polymer and expand their application areas. Myriad properties, such as mechanical, electrical, thermal, or magnetic properties can be combined with original polymer characteristics, including flexible, light weight, and ease of use. These composites can be used to produce multi-functional fibers as the next generation textile or fabrics. In this research, Polyacrylonitrile (PAN) is adopted as the main polymer with different nano-fillers, such as carbon nanotube (CNT), iron oxide nanoparticle, and graphene oxide nanoribbon (GONR). Using gel-spinning technology, PAN-based composite fibers are fabricated in single- or bi-component fibers. Fibers are also characterized for their structure, morphology, mechanical properties, as well as for their electrical, thermal, or magnetic properties. For example, bi-component fibers with polymer sheath and polymer-CNT core as well as polymer-CNT sheath and polymer core are processed. With electrical and thermal conductivity introduced by CNT, such bi-components fibers can be applied for wearable electronics or for thermal management. Joule-heating effect owing to applied electrical current on single component PAN/CNT fibers is also investigated. With controllable electrical conductivity and fiber temperature, this active functional fiber can be applied for temperature regulation fibers or new carbon fiber manufacturing process. Another example is magnetic fiber with superparamagnetic iron oxide nano-particles. These novel magnetic fibers with high strength can be used for actuator, inductors, EMI shielding, or microwave absorption. GONR is also discussed and used to reinforce PAN-based fibers. Several theoretical models are considered to analyze the observed results.

This thesis focuses on the use of hydrophilic polymers for bioanalytical applications, including several microanalytical techniques encompassing nanotechnology, microarray technology and DNA gel electrophoresis. The dissertation is divided in two parts, which share the employment of dimethylacrylamide-based copolymers, developed at the laboratory of Analytical Microsystems of the Institute of Chemistry for Molecular Recognition (National Research Council of Italy) where the thesis has been carried out. PART A introduces a novel approach for surface modification of quantum dots and gold nanoparticles, based on physi-/chemisorption of two different functional dimethylacrylamide copolymers. Beside developing innovative functionalization strategies, the goal is to demonstrate the application of coated nanoparticles in highly sensitive immunoassays based on microarray technology. PART B of the dissertation presents the results of an activity, conducted in collaboration with the company Agilent Technology (UK), aimed at developing an innovative gel sieving matrix for high performance DNA electrophoresis. We introduce a new hydrogel obtained by cross-linking an alkyne modified polymer with an azide one, exploiting a copper catalysed click chemistry reaction. The alkyne functionalized polymer is based on poly(dimethilacrylamide) and it was obtained by a post-polymerization modification approach from the parent copolymer poly(DMA-NAS-MAPS), extensively used in the first part of this dissertation. The azide polymer is a polyethylenglycol terminated with azide groups at both ends, and is commercially available. A considerable part of this work is devoted to the optimization of the characteristics of the new hydrogel, in particular to the extension of its shelf-life, an important parameter in view of its industrial application.

Dissertação(mestrado) - Universidade Federal do Rio Grande, Programa de Pós-Graduação em Engenharia e Ciência de Alimentos, Escola de Química e Alimentos, 2007.<br>Submitted by Caroline Silva (krol_bilhar@hotmail.com) on 2012-10-17T17:53:43Z No. of bitstreams: 1 avaliao das propriedades funcionais da anchoita engraulis anchoita e das modificaes produzidas durante o armazenamento em gelo e gua do mar e processamento.pdf: 1503082 bytes, checksum: 012f5e03de9242ddf39f8071e85d9acc (MD5)<br>Approved for entry into archive by Bruna Vieira(bruninha_vieira@ibest.com.br) on 2012-12-01T15:11:10Z (GMT) No. of bitstreams: 1 avaliao das propriedades funcionais da anchoita engraulis anchoita e das modificaes produzidas durante o armazenamento em gelo e gua do mar e processamento.pdf: 1503082 bytes, checksum: 012f5e03de9242ddf39f8071e85d9acc (MD5)<br>Made available in DSpace on 2012-12-01T15:11:10Z (GMT). No. of bitstreams: 1 avaliao das propriedades funcionais da anchoita engraulis anchoita e das modificaes produzidas durante o armazenamento em gelo e gua do mar e processamento.pdf: 1503082 bytes, checksum: 012f5e03de9242ddf39f8071e85d9acc (MD5) Previous issue date: 2007<br>O trabalho teve por objetivo estudar as propriedades funcionais da anchoita (Engraulis anchoita) e suas modificações quando armazenada em gelo e água do mar e processada como base protéica. A anchoita foi capturada em cruzeiros realizados a bordo do Navio Oceanográfico Atlântico Sul da Fundação Universidade Federal do Rio Grande(FURG), RS, Brasil, próximo a divisa Brasil-Uruguai. Logo após a captura o pescado foi acondicionado a bordo em recipiente de polietileno contendo gelo e água do mar na razão 1:1, de maneira que o pescado ficasse imerso e não em contato direto com o gelo. Parte do lote foi mantido como pescado inteiro e a outra parcela foi eviscerada e despolpada em uma indústria pesqueira local. Polpa e peixe inteiro foram então transportados para o Laboratório de Análise Sensorial e Controle de Qualidade da FURG. O trabalho está constituído por uma revisão bibliográfica, que enfatiza a importância do recurso pesqueiro em estudo como potencial a ser explorado, descorre sobre propriedades funcionais, métodos de avaliação da qualidade e formas de conservação. O desenvolvimento do trabalho é expresso por três artigos. O primeiro teve como objetivo caracterizar o odor da anchoita e verificar suas modificações durante o tempo de armazenamento nas mesmas condições de bordo. Os resultados definiram o frescor da anchoita pelos grupos de odor a maresia, grama e pescado assado, caracterizando-se a perda de frescor pela presença de odor a ácido, penetrante e pungente. O odor pungente passou a ser detectado pelos julgadores a partir do 8° dia de armazenamento. No segundo artigo foram discutidas as alterações sofridas pela matéria-prima em função do tempo de armazenamento em gelo e água do mar sob o ponto de vista da funcionalidade das proteínas, como solubilidade (SP), capacidade de retenção de água (CRA), de gordura (CRG) e capacidade de emulsificação (CE); as alterações do atributo odor (avaliadas sensorialmente) e o frescor (N-BVT, N-TMA e pH), analisados diariamente por um período de 9 dias. Os resultados indicaram redução nos valores médios das propriedades funcionais estudadas, com o tempo de armazenamento. Os parâmetros N-BVT e pH não demonstraram eficiência para serem utilizados como indicadores do limite de frescor da matéria-prima, nas condições experimentais. No entanto, o N-TMA demonstrou importante correlação com o atributo odor, o que o justifica como eficiente parâmetro de avaliação do frescor da anchoíta armazenada em gelo e água do mar. Foi possível indicar 7 dias como limite de aceitabilidade da anchoita, armazenada nas condições experimentais. No terceiro artigo a polpa e as bases protéicas de pescado, elaboradas a partir de diferentes solventes (H2O e H3PO4 0,05%), foram monitoradas quanto aos parâmetros de frescor (N-BVT, N-TMA e pH) e estabilidade das gorduras (índice de peróxido e número de ácido tiobarbitúrico) quando estes produtos são armazenados sob congelamento por 120 dias, bem como, microbiologicamente, no início e no final do período de armazenamento. Ainda neste capítulo foi avaliada a funcionalidade das proteínas das bases protéicas, quando submetidas a secagem a temperatura de 40, 60 e 70°C. Os resultados indicaram que o melhor solvente utilizado para extração de proteínas solúveis foi o H3PO4 e que não foram registradas variações importantes nos parâmetros de frescor, na estabilidade das gorduras e microbiológicos durante o armazenamento das amostras analisadas. O menor tempo e secagem foi obtido para a base protéica elaborada a partir de H3PO4, independente da temperatura utilizada. As maiores SP e CRA foram registradas para a secagem a temperatura de 60°C e para a CRG e CE, os melhores valores foram obtidos para 40°C.<br>This work aimed to study the functional properties of the anchovy (Engraulis anchoita) and its changing while stored in ice and sea water and processed as protein bases. The anchovy was captured in cruises on board of Navio Oceanográfico Atlântico Sul of Fundação Universidade Federal do Rio Grande (FURG), RS, Brazil, next to Brazil-Uruguay border. Soon after its capture the fish was conditioned on board into a polyethylene container containing ice and sea water in 1:1 ratio, so that the fish would be immerse avoiding direct contact with the ice. Part of the fish lot was kept entire while the other parcel was gutted and pulped at a local fishing industry. Pulp and entire fish were then carried to the FURG’s Laboratório de Análise Sensorial e Controle de Qualidade.The work is constituted by a bibliographical revision which emphasizes the importance of the studied fishing resource as a potential to be explored, talking about its functional properties, methods of quality evaluation and conservation forms. The work development is expressed by three articles. The first one had as an objective to characterize the anchovy’s odor in order to verify its changing according to the time while stored in the same on-board conditions. The results defined the freshness of anchovy in groups according the following odors: sea, grass and baked fish, characterizing freshness loss through the presence of acid, penetrating and pungent odor. The pungent odor started being detected by the judges from the 8th day of storage. In the second article the alterations suffered by the raw material due the storage time in ice and sea water under the point of view of proteins functionality, such as Solubility (PS), Water Holding Capacity (WHC), Oil Holding Capacity (OHC) and Emulsifying Capacity (EC), the alterations of the odor feature (sensorially evaluated) as well as its freshness (N-BVT, N-TMA and pH), analyzed daily during a period of 9 days. With the storage time the results indicated an average values reduction of the functional properties that were studied. N-BVT and pH parameters had not proved themselves efficient to be used in order to indicate the raw material freshness limit under experimental conditions. However, N-TMA demonstrated an important correlation with the odor feature showing itself as an efficient parameter to evaluate anchovy freshness while stored in ice and sea water. It was possible to indicate 7 days as the limit of anchovy acceptability when stored under experimental conditions. In the third article the protein pulp and fish protein bases, elaborated from different solvents (H2O and H3PO4 0,05%), had been monitored concerning the freshness parameters (NBVT, N-TMA and pH) and fat stability (peroxide index and number of thiobarbiturical acid) when such products are stored under freezing conditions for 120 days, as well as, microbiologically, in the beginning and at the end of storage time. Also, in this third chapter the functionality of proteins from protein bases, when submitted to a drying process at the temperatures of 40, 60 and 70°C. The results indicated H3PO4 as the best solvent used for soluble protein extraction. They also registered no important variations in freshness parameters, in fat stability and microbiologicals during the storage of the analysed samples. The shortest drying time was obtained by the protein bases elaborated from H3PO4, disregarding the temperature used. The highest SP and CRA were registered for the drying process at the temperature of 60°C and for CRG and CE, the best values were obtained for 40°C.

In this work, the question of how the structure-property relations of polyacrylamide flocculants relate to the flocculation of natural macromolecules and colloids is posed. The question requires an understanding of the chemical function of the polymers and, subsequently, an understanding of how the polymers are binding to the substrate that is flocculated.

The periderm is a complex structure that protects plants’ secondary organs and wounded tissues. This function is given by the phellem, a multilayered tissue formed by cells with suberized cell walls located on the outer part of the periderm. Suberin is a basic polymer for protection thanks to its lipid nature. Exceptionally, the cork oak has a great capacity to produce layers of phellem. Recently, transcriptomics studies, as well as reverse genetic approaches, have contributed to the knowledge of the formation and regulation of the periderm and the synthesis and transport of the suberin components. However, the molecular bases that control these processes are still quite unknown. For this reason, new regulatory and transport candidate genes have been characterized. In addition, a faster and less expensive roots transformation system has been developed. Finally, a global transcriptome analysis of the outer bark of cork oak during its growth has been performed<br>El periderma és una estructura complexa que protegeix els òrgans secundaris i els teixits cicatricials. Aquesta funció la dóna el fel·lema,teixit pluriestratificat format per cèl·lules amb parets suberificades situat a la part externa del periderma. La suberina és un polímer bàsic per la protecció gràcies a la seva naturalesa lipídica. De forma excepcional l’alzina surera té una gran capacitat per produir capes de fel·lema. En els últims anys, estudis transcriptòmics, així com de genètica inversa, han contribuït al coneixement de la formació i regulació del periderma i la síntesi i transport de la suberina. No obstant, les bases moleculars que controlen aquests processos són encara força desconegudes. Per aquest motiu s'han caracteritzat nous gens candidats reguladors i de transport. A més, s'ha posat a punt un sistema de transformació d'arrels més ràpid i menys costós. Per últim, s'ha realitzat un anàlisi global del transcriptoma de l'excorça externa de l'alzina surera durant el seu creixement

La pile à combustible est une solution d'avenir pour produire de l'électricité propre. Cependant des problèmes technologiques limitent pour le moment un déploiement à grande échelle. C’est au cœur de pile et plus particulièrement de la membrane conductrice ionique séparant l’anode et la cathode, que certaines difficultés se posent. Nous pouvons ainsi citer l’impossibilité d’améliorer l’efficacité du catalyseur et le rendement du dispositif en augmentant simplement la température de fonctionnement (100 - 120°C). En effet, la membrane de référence (Nafion) perd ses propriétés thermomécaniques au-delà de 80°C, alors que les membranes alternatives (offrant une meilleure stabilité thermomécanique) sont victimes d’un vieillissement chimique trop rapide qui induit un arrêt inopiné du dispositif. Pour lever ce verrou technologique, nous proposons une nouvelle stratégie qui repose sur le développement de membranes nano-composites constituées d'une matrice ionomère commerciale (non réticulée) dans laquelle nous introduirons des précurseurs aptes à former une phase sol-gel offrant une stabilisation chimique et thermomécanique (réticulée). C'est le contrôle de la chimie de ce réseau, de sa morphologie et de sa localisation dans la membrane hôte qui permettra l'amélioration des propriétés de la membrane hybride ainsi obtenue.Nous avons réalisé une analyse minutieuse de l'effet d’un traitement hydrothermique sur la microstructure des membranes sPEEK. Grâce à cette analyse nous pouvons relier la microstructure avec les propriétés fonctionnelles de l’ionomère pour obtenir des membranes sPEEK mieux nanostructurées et donc plus performantes. Le procédé sol-gel permet la croissance de la phase sol-gel sans perturbation de la nanostructuration initiale de l'ionomère. Cette stratégie permet donc de contrôler la distribution et la morphologie de la phase inorganique.Le processus d'élaboration des membranes hybrides a été étudié. Nous avons étudié l'influence des paramètres de fabrication sur les propriétés des membranes hybrides, et ainsi pu produire des membranes hybrides optimisées. Les propriétés physiques et chimiques de ces membranes ont été évaluées par de nombreuses techniques (SANS, IR, DMA, etc.). L'influence de la structure chimique (degré de réticulation) du réseau sol-gel des membranes hybrides et l'impact de la teneur en sol-gel et de sa distribution (morphologie) dans la membrane hôte sur les propriétés fonctionnelles sont présentés. Nous observons une grande influence du dégrée de réticulation et de la quantité de sol-gel présent dans la membrane qui conditionne les propriétés fonctionnelles de la membrane<br>Fuel cell is a promising solution for clean production of hydrogen based energy. However to achieve a large-scale deployment of this technology, issues remain to be addressed. One of the remaining problems concerns the heart of the cell (polymer membrane sandwiched between two electrodes). We can stress the fact that it is impossible to improve the catalyst efficiency and the cell performance by a simple increase of the operating temperature (100-120 °C). Indeed the reference membrane (Nafion) exhibit a step decrease of its thermomechanical properties beyond 80 °C, whereas alternative membranes (with a better thermomechanical stability) are victims of a much faster chemical aging resulting into unexpected failure of the device.Our main objective is to develop novel hybrid membranes consisting of a commercial ionomer matrix in which we will introduce precursors capable to form a sol-gel phase. It will result on membrane composed of two interpenetrating phases, an ion conductive non-crosslinked polymer phase and a crosslinked inorganic phase providing chemical and thermomechanical stabilization. The control of the chemistry of this sol-gel phase, its morphology and its location in the membrane, which will improve the membrane properties, are essential to consider the development of these membranes for fuel cells.A careful analysis of the hydrothermal treatment effect on the microstructure of sPEEK membranes has been performed. Thanks to this analyse we can relate the microstructure with the functional properties of the polymer. The sol-gel process enables the growth of the sol-gel phase without disturbance of the initial nanostructured membrane. This strategy makes possible to control the distribution and morphology of the inorganic phase.The elaboration process of hybrid membrane has been studied. We presented the influence of elaboration parameters regarding the best conditions to prepare an optimized hybrid membrane. The physical and chemical properties of the inorganic phase were evaluated by many techniques (SANS, IR, DMA, etc.). The influence of the chemical structure (cross-linking degree) of the sol-gel network andthe impact of the sol-gel content and its distribution (morphology) into the host membrane on their functional properties is presented. We observed the great influence of cross-linking degree and of the amount of sol-gel present in the membrane which determines the functional properties of the membrane

The paper describes the functionalization of planar ceramic membranes (Al2O3) with the active layer containing 3-mercaptopropyl complexing groups. The sol-gel method was used for that. There was analyzed the influence of the ratio of alkoxysilanes and the dilution of the original sol on the nanostructure of the produced surface layer. The work is aimed to develop the techniques for ceramic membranes functionalization by complexing groups, therefore, these membranes can be used for the removal of heavy metal ions from aqueous media in the process of filtration. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35342

Homogeneous single C-S-H gels have been prepared for the investigation of alkali binding potential and crystallisation. A distribution coefficient, R_d, was introduced to express the partition of alkali between solid and aqueous phases at 25°C. R_d is independent of alkali hydroxide concentration and depends only on Ca:Si ratio over wide ranges of alkali concentration. The trend of numerical values of R_d indicates that alkali bonding into the solid improves as its Ca:Si ratio decreases. Reversibility is demonstrated, indicating a possibility of constant R_d value of the material. Al has been introduced to form C-A-S-H gels and their alkali sorption properties also determined. Al substituted into C-S-H markedly increases R_d, indicating enhancement of alkali binding. However, the dependence of R_d on alkali concentration is non-ideal with composition. A two-site model for bonding is presented. Crystallisation both under saturated steam and 1 bar vapour pressure has been investigated. It has been shown that heat treatment by saturated steam causes crystallisation of gels. The principal minerals obtained were (i) C-S-H gel and Ca(OH)₂ at ~55°C, (ii) 1.1 nm tobermorite, jennite and afwillite at 85-130°C, and (iii) xonotlite, foshagite and hillebrandite at 150-180°C. Properties of crystalline C-S-H were also reported for reversible phase transformation, pH conditioning ability, seeding effect and solubility. At 1 bar pressure, crystallisation is slower than in saturated steam due to lower water activity. Tobermorite-like nanodomains develop during reaction at low Ca/Si ratios. In some Ca-rich compositions, Ca(OH)₂ is exsolved and occurs as nano-sized crystallites.

Orientador: Sidney José Lima Ribeiro<br>Resumo: Este trabalho descreve o desenvolvimento de membranas de cellulose bacterianas (BCM), econômicas e ecologicamente amigáveis com propriedades funcionais. Nanopartículas de sílica esféricas com tamanho de partícula de cerca de 51 ± 4 nm, obtidas pelo método sol-gel e nanopartículas de sílica com tamanho de partículas heterogêneo, extraídas da casca de arroz, foram preparadas e funcionalizadas pelas metodologias in situ e post-grafting, respectivamente, com alcoxisilanos com propriedades easy-cleaning e curcuma. Nanocompósito de anatase SiO2@TiO2 preparado pelo método sol-gel, também foi desenvolvido. Posteriormente, estes nanomateriais funcionais e os organosilanos 1,4 – bis(trietoxissilil)benzeno (BTEB), Bis(trietoxisililpropil)disulfeto (BTPD) and 1,2-Bis(trietoxissilil)etano (BTSE), foram imobilizados com sucesso na BCM, segundo as metodologias in situ e post-grafting. Na BCM funcionalizada com os organosilanos BTEB, BTPD e BTSE, nanopartículas de sílica esféricas com estrutura porosa e distribuição de tamanho de partícula heterogêneo, foram formados nas fibras de celulose. A repelência da BCM funcionalizado com nanopartículas de sílica contendo propriedades de limpeza facilmente melhorada notavelmente. BCM apresenta fobicidade à água, tolueno, cicloexano e solução de suor artificial. Especificamente, a BCM funcionalizada com a amostra SiO2@F13TES segundo as metodologias in situ e post-grafting, apresentam uma superfície quase superhidrofóbica (> 150°). As medições de decomp... (Resumo completo, clicar acesso eletrônico abaixo)<br>Abstract: This work reports the development of economic and environmentally friendly Bacterial Cellulose Membrane (BCM) with functional properties. The spherical mesoporous silica nanoparticles with average particle size around 51 ± 4 nm, obtained by sol-gel method and spherical silica nanoparticles with heterogeneous particles size distribution (20-40 nm) obtained through agro-industrial waste were prepared and functionalized by in situ and post-grafting methodology, respectively, with alkoxysilanes with easy-cleaning properties and natural dye obtained through natural extracts, namely curcuma. Anatase TiO2@SiO2 spherical nanocomposites prepared by the sol-gel method, have also been developed. Subsequently, these functional nanomaterials and the organosilanes 1,4 – bis(triethoxysilyl)benzene (BTEB), Bis(triethoxysilylpropyl)disulfide (BTPD) and 1,2-Bis(triethoxysilyl)ethane (BTSE), were successfully incorporated into BCM, by in situ and post-grafting methodologies. In the BCM functionalized with BTEB, BTPD and BTSE, spherical silica nanoparticles with porous structure and heterogeneous particle size, were formed on the cellulose fibers. The surface repellency of the functionalized BCM with silica nanoparticles containing easy-cleaning properties was remarkably enhanced. This BCM displaying phobicity to water, toluene, cyclohexane and artificial sweat. Specifically, the BCM functionalized by in situ and post-grafting with SiO2@F13TES, displayed a surface almost superhydrophobic (> 150°... (Complete abstract click electronic access below)<br>Doutor

Zum gegenwärtigen Kenntnisstand bezüglich Solvatochromie, Sol-Gel Prozesse, und der Synthese von Polyketonen wird eine kurze Einführung gegeben. Die Synthesekonzeptionen funktionalisierter aromatischer Aminoketone wereden vorgestellt. Die neun Verbindungen wurden mittels Elementaranalyse, Röntgenstrukturanalyse, und spektroskopischen (NMR, UV/Vis, MS) Methoden aufgeklärt. Im Mittelpunkt der Untersuchungen steht die Untersuchung des Einflusses von unterschiedlichen Medien (Lösungmittel, Oberflächen, Sol-Gel Materialien und Nachbarnmoleküle im Kristall) auf die Lage der UV/Vis-Absorptionsmaxima verschiedener aromatischer Aminoketone. Die Ergebnisse der Untersuchungen liefern Informationen in Bezug auf das spezifische Solvatationsvermögen, die Polarität von Feststoffoberflächen, der Einfluss funktionaler Gruppen in aromatischen Aminoketonen auf die intermolekulare Wasserstoffbrückenbindungen in Kristallen, und über die Natur der Gast-Host-Wechselwirkungen. Auf der Basis von nucleophilen Substitutionsreaktionen wurden zwei verschiedene Prozesse für die Synthese von Ploy(benzophenone-co-piperazin) und der Kompositform entwickelt. Molekulare Strukturen und Eigenschaften konnten durch Elementaranalyse, mehrere spektroskopische (IR, Festkörper-NMR, UV/Vis, MALDI-TOF) Methoden, Zetapotentialmessungen in wässeriger Phase und thermogravimetrischen Bestimmungen charakterisiert werden.

Mestrado em Engenharia Alimentar - Qualidade e Segurança Alimentar - Instituto Superior de Agronomia<br>Reestructurated fish products combining minced meagre and dietary fiber were developed in this work. In the first part of the work, the combination of microbial transglutaminase (MTGase) and dietary fibers (pea fiber, carrageenan fiber and konjac fiber) entailing the production of low-salt gel products from farmed meagre, was studied. MTGase addition improved gelation and had a favourable impact on texture, enabling the development of low-salt products. Inner pea dietary fiber also improved gel texture. The combination of carrageenan and konjac hardened meagre gels and enhanced water holding capacity. In the second part of the work, meagre sausages with antioxidant grape dietary fiber (FDAU) were developed, being the stability and antioxidant capacity, analysed during 98 days in refrigeration (2 ºC 2 ºC) and vacuum-packed. Sausages were remarkably stable over storage time. The FDAU had an effective antioxidant capacity and seemed to have some antimicrobial effect. The sensory assessment only pointed to some loss of textural quality, associated to the large granulometry of FDAU.

As fat is removed from Mozzarella cheese, the resulting increase in protein content causes the cheese to become tough, thus decreasing the desired physical characteristics of meltability and stretch. Low-fat (6% fat) Mozzarella cheese was manufactured with the addition of several levels of a Lactococcus lactis adjunct culture that was proteinase positive and lactose deficient in an attempt to improve these physical properties. During cheese manufacture , milk was acidified to pH 6.0, then inoculated with Lactobacillus helveticus and Streptococcus thermophilus. Experimental vats were also inoculated with either 0.25, 0.50, or 1.0% of the adjunct culture. Cheeses made with the adjunct culture had increased melt properties at d 1. During the first 14 d of storage, cheeses manufactured with 0.50% and 1.0% adjunct culture melted more readily than the control; by 28 d, the meltability of all cheeses was similar. Breakdown of cheese body was more rapid in the experimental cheeses and was particularly apparent during shredding. The increase in softness was presumed to be the result of increased proteolysis in the cheeses. There were no significant differences in melt viscosity between control and experimental cheeses. Storage time, however, was significant, and between d 14 and d 28, melt viscosity decreased for all cheeses. Protein hydrolysis was measured using SDS-PAGE, but no differences were observed in the disappearance of intact caseins. In the second part of this study, part-skim (18% fat) Mozzarella cheese was manufactured from milk standardized to a casein-to-fat ratio of 1.2 and inoculated with L. helveticus strain and S. thermophilus strain. Low-fat (6% fat) Mozzarella cheese was manufactured from milk with a casein-to-fat ratio of 4.2 and inoculated with the same starter culture with (or without) addition of the proteinase positive, lactose deficient adjunct culture. The cheese was molded into 1.5-lb blocks and stored at 4°C. Meltability and melt viscosity of the cheese were measured during 28 d storage. Disappearance of αs1-casein and ß-casein was measured using free solution capillary electrophoresis, which separated intact proteins and large peptides. Micellar electrokinetic capillary chromatography was used to study the appearance of small peptides (<30 >kDa) during storage. After 28 d storage, there were significant decreases in the amount of intact αs1-casein remaining after 28 d, but no measurable change in ß-casein in either the part-skim or low-fat cheeses. In part-skim cheese, 71% αs1-casein remained, but in the low-fat cheeses only 20% intact αs1-casein remained after 28 d. If adjunct culture was used in low-fat cheese, then only 14% a 5 1-casein was found after 28 d. A similar increase in proteolysis in the low-fat cheeses was observed based on the amount of small peptides produced. Part of these differences may be a function of increased moisture content of the low-fat cheese, 61% vs 51% in part-skim cheese. During storage, part-skim Mozzarella showed a typical increase in melt with a corresponding decrease in melt viscosity. Melt increased from 10.6 cm at d 1 to 16.9 cm at d 28; melt viscosity at 80°C decreased from 1.0 x 106 cP at d 1 to 2.1 x 105 cP at d 28. There was less change in melt in the low-fat cheese during storage, 8.9 cm at d 1 and 10.9 cm at d 28. Melt viscosity decreased from 4.8 x 105 cP at d 1 to 1.9 x 105cP at d 28. It appears that adding the adjunct culture increased initial meltability of the low-fat cheese by accelerating proteolysis during the first 14 d but caused an increase in viscosity and decrease in melt after 14 d of refrigerated storage.

京都大学<br>0048<br>新制・課程博士<br>博士(工学)<br>甲第22470号<br>工博第4731号<br>新制||工||1739(附属図書館)<br>京都大学大学院工学研究科高分子化学専攻<br>(主査)教授 大内 誠, 教授 秋吉 一成, 教授 竹中 幹人<br>学位規則第4条第1項該当<br>Doctor of Philosophy (Engineering)<br>Kyoto University<br>DGAM

Diffusive gradients in thin films technique (DGT) is a simple preconcetration method for in situ determination of labile metal ions in aquatic systems. It eliminates contamination problems associated with the sampling and transport into the laboratory. The DGT technique is based on a simple device that accumulates metal ions on a cation-exchange resin, immobilized in thin layer of hydrogel, after passage through the diffusion layer. The cation-exchanger, usually Chelex 100, is selective for binding free or weakly complexed metal ions in solution. This diploma thesis deals with the characterization of a new resin gel based on ion exchanger with anchored thiol-functional groups, Spheron-Thiol, for DGT technique. This new binding agent with a high selectivity for „heavy“ metal ions could provide more information on the labile metal species in water systems. The performance of DGT technique with utilization of Spheron-Thiol resin was investigated by the determination of Cd, Cu, Ni and Pb under laboratory conditions. Due to the strong adsorption of copper to the Spheron-Thiol, it is necessary to decompose the resin gel in nitric acid prior to the determination. New resin gel provides reliable information of trace metal concentrations within the pH range 6 – 8 typical for natural waters. The effect of competitive ligands, iminodiacetic and humic acids, on Cd, Cu, Ni a Pb sorption on Spheron-Thiol and Chelex 100 resin gels was determined.

We study the properties of the foreground galaxy of the Ruby, the brightest gravitationally lensed high-redshift galaxy on the sub-millimeter sky as probed by the Planck satellite, and part of our sample of Planck's dusty GEMS. The Ruby consists of an Einstein ring of 1.4" diameter at z = 3.005 observed with ALMA at 0.1" resolution, centered on a faint, red, massive lensing galaxy seen with HST/WFC3, which itself has an exceptionally high redshift, z = 1.525 +/- 0.001, as confirmed with VLT/X-shooter spectroscopy. Here we focus on the properties of the lens and the lensing model obtained with LENSTOOL. The rest-frame optical morphology of this system is strongly dominated by the lens, while the Ruby itself is highly obscured, and contributes less than 10% to the photometry out to the K band. The foreground galaxy has a lensing mass of (3.70 +/- 0.35) x 10(11) M-Theta Magnification factors are between 7 and 38 for individual clumps forming two image families along the Einstein ring. We present a decomposition of the foreground and background sources in the WFC3 images, and stellar population synthesis modeling with a range of star-formation histories for Chabrier and Salpeter initial mass functions (IMFs). Only the stellar mass range obtained with the latter agrees well with the lensing mass. This is consistent with the bottom-heavy IMFs of massive high-redshift galaxies expected from detailed studies of the stellar masses and mass profiles of their low-redshift descendants, and from models of turbulent gas fragmentation. This may be the first direct constraint on the IMF in a lens at z = 1.5, which is not a cluster central galaxy.

Doutoramento em Ciência e Engenharia de Materiais<br>Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.<br>Tantalatos e niobatos alcalinos, como K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, são uma família atrativa de compostos ferroeléctricos livres de chumbo com estrutura perosvquítica. As suas propriedades versáteis fazem destes potencialmente interessantes para aplicações em microelectrónica, foto catálise, energia e biomédica. Entre os compostos acima citados, os compostos de tantalato de potássio, KTaO3 (KTO), tem atraído bastante atenção como substitutos para o amplamente conhecido titanato de estrôncio, SrTiO3 (STO). KTO é um óxido perovsquítico com comportamento paraelétrico quântico, quando eletricamente estimulado, e elevada polaribilidade tornando viável engenhar as suas propriedades através de estímulos internos e externos. No entanto os problemas na sua produção, quer em macroescala quer em nanoestruturas 2D, tornam estes compostos numa alternativa pouco viável para a substituir o STO. Consequentemente, e de forma a contribuir cientificamente para aumentar o conhecimento sobre as aplicações dos tantalatos, os principais objectivos desta tese são: i) produzir e caracterizar filmes finos de tantalatos alcalinos através de deposição de solução química em substratos rígidos, à base de silício, e a baixas temperaturas de forma a serem compatíveis com a tecnologia de silício; ii) complementar o conhecimento científico sobre estes materiais funcionais relativamente às suas características termodinâmicas; iii) explorar aplicações alternativas para os tantalatos alcalinos, como a foto catálise. No que diz respeito à síntese, foi focalizada no entendimento da formação de fase no tantalato de potássio sintetizado por diferentes métodos, de modo a controlar a cristalização da estrutura perovsquítica desejada e evitar a formação da fase pirocloro a baixas temperaturas e fases deficientes em potássio. Em tantalatos alcalinos o processo de formação da fase desejada está longe de estar plenamente analisado, como é o caso das perovsquites que contêm chumbo, consequentemente o trabalho foi inicialmente focado na compreensão da relação processo-fase para identificar as forças motrizes responsáveis por regular o processo de síntese. Foi realizada um estudo comparativo da formação de fase via método convencional de reação do estado sólido e via método de sol-gel. A análise estrutural revelou que a estrutura piroclórica intermédia K2Ta2O6 não foi formada em nenhuma etapa da reação via método do estado sólido. Por outro lado em processos baseados em solução, como os baseados em alcóxidos, a cristalização perovsquítica ocorre através da indesejada fase pirocloro intermédia; a baixas temperaturas a fase pirocloro é dominante e sofre a transformação para perovsquite a >800 °C. A análise cinética efectuada usando o modelo Johnson-Mehl-Avrami-Kolmogorow e a difração de raio-X quantitativa (DRX), demonstraram que nos pós obtidos pelo método sol-gel, a cristalização ocorre em duas etapas: i) no estágio inicial a reação é denominada por nucleação primária, o mecanismo é controlado por fronteira de fase, e ii) no segundo estágio, o baixo valor do expoente de Avrami, n ~ 0.3, não segue nenhuma categoria reportada impossibilitando assim uma clara identificação do mecanismo. Posteriormente, e em colaboração com o grupo da Professora Alexandra Navrostky da Universidade da Califórnia, Davis, foram realizados estudos de termodinâmica, usando calorimetria de solução de óxidos fundidos a alta temperatura. Foram calculadas as entalpias de formação das três estruturas: pirocloro, perovsquite e tetragonal tungsténio bronze K6Ta10.8O30 (TTB). As entalpias de formação relativas aos óxidos correspondentes, ∆Hfox, para KTaO3, KTa2.2O6 e K6Ta10.8O30, são -203.63 ± 2.84 kJ/mol, 358.02 ± 3.74 kJ/mol e -1252.34 ± 10.10 kJ/mol, respectivamente; enquanto que as relativas aos elementos, ∆Hfel, para KTaO3, KTa2.2O6 e K6Ta10.8O30 são 1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol e -13393.04 ± 31.15 kJ/mol, respectivamente. As possíveis reações de decomposição, de KTa2.2O6 para KTaO3 e Ta2O5 (reação 1) ou para K6Ta10.8O30 e Ta2O5 (reação 2), foram propostas e o cálculo das entalpias resultou em 308.79 ± 4.41 kJ/mol e 895.79 ± 8.64 kJ/mol, respectivamente. As reações são fortemente endotérmicas, indicando que estas decomposições são energeticamente desfavoráveis, uma vez que é improvável que qualquer termo de entropia possa sobrepor-se a uma entalpia tão positiva. Os estudos termodinâmicos provaram que o pirocloro é energeticamente mais estável que a perovsquite para temperaturas baixas. Assim, a organização local dos precipitados amorfos canaliza a cristalização para a estrutura mais favorável, que é a pirocloro com uma organização local similar; a distância entre os vizinhos mais próximos na fase amorfa, ou na fase ordenada a baixo alcance, é similar à do pirocloro. Tendo em conta a derivação estequiométrica no sistema KTO, selecionar a técnica de fabricação / deposição de filmes finos mais apropriada é uma questão-chave, especialmente no que concerne aos óxidos ferroeléctricos complexos. A deposição por solução química tem sido o método de processamento mais reportado, para crescimento de filmes finos de KTO, mas o método clássico de alcóxidos permite cristalizar a fase perovsquite a temperaturas >800 °C enquanto que a temperatura máxima de estabilidade para os substratos de silício platinizado é ~700 °C. Portanto, foi usado um processo alternativo baseado em dióis, com precursores carboxilados de potássio, com o objectivo de estabilizar os precursores em solução, evitando assim o uso de solventes tóxicos e diminuindo a temperatura de cristalização da fase perovsquite. A análise dos pós revelou que no caso de KTOac (solução baseada em acetato de potássio), uma mistura de fase perovsquite e pirocloro foi detectada a uma temperatura de apenas 450 °C, e a transformação gradual em estrutura perovsquítica monofásica ocorre quando as temperaturas sobem acima de 750 °C, no entanto a fase KTaO3 monofásica não é obtida. No caso do KTOacac (solução com acetil-acetona de potássio, cadeia alquílica longa carboxilato de metal), um amplo pico é detectado a temperaturas <650 °C, característico de estruturas amorfas, enquanto que a elevadas temperaturas, os planos de difração das fases pirocloro e perovsquite são visíveis e a perovsquite KTaO3 monofásica é conseguida a temperaturas >700 °C. A análise de infravermelhos mostrou que estas diferenças acontecem devido à deformação da estrutura base dos carbonatos sob aquecimento. Uma série de filmes finos de tantalatos alcalinos foram depositados por spincoating em substratos de silício, usando a metodologia baseada em dióis. Filmes monofásicos de perovsquite KTaO3 depositados usando solução de KTOacac foram obtidos a uma temperatura de apenas 550 °C; os filmes foram recristralizados em fornos de aquecimento rápido em atmosfera de oxigénio durante 5 minutos com taxa de aquecimento de 30 °C/seg. Outras composições, LiTaO3 (LTO) e NaTaO3 (NTO), foram depositados com sucesso em substratos de silício a 650 °C. O carácter ferroeléctrico do LTO à temperatura ambiente foi provado. Infelizmente, não foi possível medir as propriedades eléctricas do KTO no condensador paralelo devido às interfaces filme-substrato ou filme-eléctrodo. Assim sendo, estudos futuros são necessários para compreender esta questão. Foram também conduzidos estudos com vista às possíveis aplicações; dois casos de estudo: i) estudo da atividade fotocatalítica de tantalatos e niobatos alcalinos para decomposição de poluentes, e ii) estudo de bioatividade de filmes ferroelétricos de tantalatos alcalinos como revestimento funcional para regeneração óssea. Recentemente, tem sido dedicada muita atenção ao desenvolvimento de novos materiais fotocatalíticos, e as composições à base de óxido de tântalo e nióbio tem demonstrado capacidade de fotocatálise na reação de separação da água devido ao elevado potencial das bandas de condução. Assim, várias composições das famílias dos tantalatos e niobatos alcalinos foram testadas como catalisadores para degradação do azul de metileno. Os resultados mostram valores de atividade promissores para alguns dos compostos, sendo o KNbO3 o mais ativo de entre os testados, alcançando valores acima de 50 % na degradação do pigmento após 7 h sob exposição a UVA. No entanto algumas modificações nas composições dos pós podem melhorar a sua performance. No que concerne à regeneração óssea, é importante obter plataformas que através de estímulos apropriados consigam assegurar a adesão e direcionar o crescimento, a proliferação e a diferenciação celular. Neste contexto, foi aqui explorada uma estratégia alternativa para revestimento de implantes ósseos, baseada na regeneração óssea mediada por sinais elétricos. Esta estratégia implica revestir substratos metálicos de aço inoxidável tipo 316L (316L-SST), com camadas de LiTaO3 ferroeléctrico, funcionalizadas através de polarização elétrica ou de irradiação com luz UV. Foi demonstrado que a formação de fosfato de cálcio na superfície e a adsorção de proteínas é consideravelmente melhorada quando o 316L-SST é revestido com filmes ferroelétricos funcionalizados. Esta estratégia pode ser encarada como um conjunto de orientações para o desenvolvimento de plataformas eletricamente funcionalizadas, capazes de estimular a regeneração de tecidos, promovendo a associação direta do implante com os tecidos hospedeiros, contribuindo assim para a redução de falhas na reabilitação com implantes ósseos.

Despite emerging water shortages, most water is only used once, and often with low efficiency. However, with appropriate treatment, water can be re–used to reduce the demand on freshwater sources. The Department of Water Affairs, South Africa, promotes industries to reduce discharges into water resources in order to sustain an overall good water quality of all water systems. All of this ultimately leads to industries striving towards zero effluent discharge. Primary Column Bottoms (PCBs) is a wastewater stream derived from the Fischer–Tropsch Gas to Liquid process and consists mainly of organic acids, but no nitrogen or phosphorous, which by implication excludes possible biodegradation. In the operation of cooling towers in industrial processes, cooling water quality has a direct impact on the cooling performance of the system, where nutrient levels may affect fouling, scaling and corrosion observed in the cooling towers. Fouling, scaling and corrosion affect the operating efficiency of cooling water systems and may necessitate the addition of chemical agents to control these phenomena. This has a financial and labour time impact on the operation of these systems. In this study a mini cooling tower test rig was operated with a synthetic PCB effluent as cooling water and various cycles of concentration, pH and linear flow velocities (LFVs). A constant delta temperature of 10 °C was maintained. Cycles of concentration (COC) evaluated included 2, 4 and 6 cycles of concentration and linear flow velocities evaluated was 0.6 m/s, 0.9 m/s and 1.2 m/s. Fouling, scaling and corrosion rates were determined using corrosion coupons and heat exchanger tubes for mild steel and stainless steel. Besides the evaluation of the various operational parameters for fouling, scaling and corrosion, the possibility for chemical oxygen demand (COD) removal by operating the cooling tower as a bioreactor was also evaluated. To this end nutrient correction was applied to the reactor to allow for a CNP ratio of 100:10:1. With regard to fouling, scaling and corrosion, mild steel was more affected by fouling, scaling and corrosion compared to stainless steel where almost no fouling, scaling and corrosion was observed. Overall increased linear flow velocities resulted in higher fouling and scaling rates, whereas lower linear flow velocities resulted in decreased corrosion rates. In terms of cycles of concentration, increased COC resulted in higher fouling, scaling and corrosion rates. Despite the high nutrient removal levels, the accompanying fouling, scaling and corrosion was still below the particular industry’s guidelines. Besides physical–chemical evaluation of the towers under the various operational conditions, culture–dependent and culture–independent methods were also employed. Concerning culture–dependent approaches the study demonstrated that aerobic and anaerobic organisms are present in both the planktonic and sessile phase of the cooling tower reactors. Heterotrophic aerobes were found to be the most abundant under all the operating conditions. Sulphate reducing bacteria were more abundant in the sessile phase of the cooling towers, and the presence of high sulphate levels in the experiments could be indicative of the sulphate reducing bacteria actively participating in the microbial community. Lower than expected corrosion levels, however, suggest that a combination of the organisms in the biofilm rather than sulphate reducing bacteria alone, contributed to the corrosion rates observed. Culture–independent methods, specifically phospholipid fatty acid analysis supported the results from the culture–dependent methods. Furthermore results demonstrated that linear flow velocity had a greater effect on the community structure than cycles of concentration. Finally molecular methods, specifically denaturing gradient gel electrophoresis, found that increasing cycles of concentration resulted in increased microbial community diversity, while increasing linear flow velocity resulted in decreased microbial community diversity. Regarding COD removal, nutrient correction of the synthetic PCB effluent achieved 89.35 % COD removal at 2 COC and 1.2 m/s LFV, while 80.85 % COD removal was achieved at 4 COC at 1.2 m/s LFV. From these results it was recommended that the operation of the cooling tower should be at 4 COC and 1.2 m/s, which despite slightly lower % COD removal, were characterised by fouling, scaling and corrosion rates well within guidelines.<br>Thesis (M. Environmental Science)--North-West University, Potchefstroom Campus, 2012.

This thesis describes the difference between the baseline composition of Diamondback moth (Plutella xylostella L.) insect colonies' gut microbiomes collected from field- and laboratory-reared populations. Results indicates that variation of gut bacterial community composition between individual insect influences baseline microbiome composition estimates at the population scale. The gut bacteria diversity and functional composition change in response to external challenges, and those changes reflect on insect development. This explains the need to discover the specific symbiotic gut bacteria that respond to environmental variables - such findings will be essential for controlling insect hosts, and this knowledge can be applied to develop insect pest management and control.

Alopecia areata (AA) is a putative autoimmune hair loss disorder. It mainly affects the scalp hair but can also involve body hair, and can also affect the nail and the eye. While there are may be several lines of evidence to support the autoimmune basis of AA, there is still very little information on the hair follicle autoantigen(s) involved in its pathogenesis. In this project, serum antibodies (AA=10, control=10) were used to immunoprecipitate AA-relevant target antigens from normal human scalp hair follicle extracts. These immunoprecipitates were analysed by LC-MALDI-TOF/TOF mass spectrometry for target protein identification. This part of the project involved substantial methods development. Trichohyalin was immunoprecipitated by all AA sera, but by only 5 normal sera. Importantly, the mean Mascot scores of the AA group was significantly higher than the normal group (p=0.005). Keratin 16 was also identified from immunoprecipitates as another potential AA-relevant target antigen. Functional studies by ex vivo whole hair follicle organ culture using commercial antibodies to trichohyalin and keratin 16 significantly inhibited hair fibre elongation compared to controls. Indirect immunofluorescence studies revealed that AA sera contained higher immunoreactivity against normal human scalp anagen hair follicles compared to normal sera. Immunoreactivities were mainly in the outer root sheath and inner root sheath, and less so to the medulla and hair bulb matrix. Double immunofluorescence studies of AA and normal serum with anti-trichohyalin antibody (AE15) revealed co-localisation of 9 of the AA sera antibodies with trichohyalin in the inner root sheath (mostly in Henle's, less in Huxley's/inner root sheath cuticle), but only weakly in 3 normal sera. This study supports the involvement of an antibody response to anagen-specific hair follicles antigens in AA. Moreover, there may be some evidence that these antibodies may have a pathogenic role.