Este trabalho descreve a síntese, caracterização e aplicação de sistemas poliméricos baseados em polímeros condutores em sistemas de liberação controlada de drogas. Esta tese pode ser dividida em duas partes: na primeira se apresentam os resultados da aplicação de filmes de polianilina e polipirrol na liberação de drogasmodelo como a dopamina protonada e o ácido salicílico. Na liberação de salicilato utilizou-se um filme polianilina eletrosintetizado e dopado com íons cloreto. Já para a liberação de dopamina protonada (um cátion) a liberação foi conduzida a partir de um sistema bicamadas, com um filme de polianilina recoberta com uma camada de Náfion. É mostrada a liberação controlada nos dois casos, porém também se discutem limitaçãoes deste tipo de sistema que levaram ao estudo de uma forma alternativa de controle eletroquímico utilizando polímeros condutores. A segunda parte do trabalho mostra então esta nova metodologia que se baseia em compósitos de poianilina eletropolimerizada no interior de hidrogéis de poliacrilamida. É mostrado que este novo material é eletroativo e mantém as características de intumescimento dos hidrogéis, tanto necessárias ao desenvolvimento destes sistemas de liberação controlada. Mecanismos para o crescimento e distribuição da polianilina na matriz isolante e para a atuação do compósito no controle eletroquímico da liberação são propostos com base nos dados de microscopia de força atômica, Raman e eletrônica de varredura, além de testes de liberação controlada com moléculas de diferentes cargas. / This work describes the synthesis, characterization and application of polimeric systems based on contucting polymers for electrochemical release devices. The thesis is divided into two parts: frrst, results conceming the application of polyaniline and polypyrrole films in the controlled release of dopamine and salicilyc acid, are showed. An electrosyntetized polyaniline film doped with chloride ions was used in the salicilate release. On the other hand, for the controlled release of protonated dopamine, a bilayer system consisting of a polyaniline film recovered with Nafion was employed. The release control was reached in both cases, but this kind of actuator show serious limitations that lead to the conclusion that a new type of electrochemical control based in conducting polymers must be developped. The second part shows the new methodology based on composites of polyaniline grown inside polyacrylamide hydrogels. It\'s showed that this new material is electroactive and still maintains the hydrogel\'s swelling properties, which makes it an interesting and suitable material for drug delivery devices. Raman Microscopy, Scaning Electron Microscopy and Atomic Force Microscopy, and controlled release tests of different charged molecules were tools for the elucidation of polyaniline\'s growth and distribuition inside the hydrogels and for the mecanism of actuation in the controlled release.

Blendas poliméricas são misturas físicas de dois ou mais polímeros. O interesse de obtenção de blendas poliméricas, com características físicas e químicas desejadas para as mais diversas aplicações, é crescente em todo o mundo. Neste trabalho foram desenvolvidos filmes de blendas de quitosana e poli(N-vinil-2-pirrolidona) (PVP) em várias proporções. A irradiação destes filmes com radiação UV254nm gerou hidrogéis estáveis. Foram também obtidos hidrogéis a partir de co-soluções aquosas destes polímeros, em diversas proporções, com reticulação de seus componentes induzida pela radiação ultravioleta. Em ambos os casos, os materiais foram caracterizados e avaliados quanto a sua potencialidade de uso como biomaterial. Para análise e caracterização das blendas e hidrogéis utilizaram-se as técnicas de espectroscopia no infravermelho (IV), microscopia eletrônica de varredura (MEV), calorimetria exploratória diferencial (DSC), análise termogravimétrica (TGA), difratometria de raios X e transmissão de vapor de água (WVT). Os resultados mostraram que a forte interação entre PVP e quitosana leva a um aumento da insolubilidade da blenda em relação à PVP pura, mesmo com baixas quantidades de quitosana. A presença de PVP aumenta a hidrofilicidade da blenda e também ocasiona a diminuição da cristalinidade da quitosana. Outro aspecto importante foi o aumento da estabilidade térmica das quitosanas, também influenciada pelo aumento da parcela de PVP nas blendas. A análise dos dados parece indicar que uma SIPN foi formada, onde a rede básica é constituída de PVP reticulada, enquanto a quitosana é mantida \"presa\" nesta rede, sem participar da mesma, mas impedida de ser extraída. O estudo da irradiação de co-soluções aquosas de PVP e quitosana gerou hidrogéis estáveis, porém restritos a baixa porcentagem de quitosana na mistura - até 30%. Este estudo revelou, também, que a presença de ácido acético na solução facilita o processo de reticulação, incluindo solução de PVP pura. A permeabilidade à água dos filmes de blendas de quitosana/PVP não irradiados e irradiados indica sua potencialidade de aplicações desses materiais em áreas medicinal e alimentícia. A literatura descreve vários métodos de produção de hidrogéis de quitosana, porém, todos baseados no uso de agentes reticulantes externos ou da enxertia de grupos reativos na cadeia de quitosana. Deve-se ressaltar que o sistema de reticulação aqui proposto não faz uso de agentes de reticulação, fotoiniciadores nem incorporação de algum grupo fotorreativo nas cadeias dos polímeros. De modo geral, os resultados obtidos dos materiais poliméricos irradiados e não-irradiados sugerem que possuem potencialidade para várias aplicações: como biomaterial, por exemplo, matrizes poliméricas para liberação controlada de fármacos, curativos para ferimentos mais leves, outros. / Polymer blends are physical mixtures of two or more polymers. The interest in obtaining polymer blends, with desired physical and chemical characteristics for the most diverse applications, is increasing in the whole world. In this work, chitosan and poly(N-vinyl-2-pyrrolidone) (PVP) blend films were developed at several ratios. Hydrogels were also obtained from co-solutions of these polymers, at diverse ratios, through crosslinking induced by ultraviolet radiation. In both cases, the materiais were characterized and evaluated in terms of their potentiality of use as biomaterial. For analysis and characterization of blends and hydrogels were utilized the techniques of infrared spectroscopy (IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffractometry (XRD), and water vapor transmission (WVT). The results have shown that the strong interaction between PVP and chitosan leads to an increase of blend insolubility in relation to pure PVP, even with low amounts of chitosan. PVP presence increases blend hydrophilicity and causes reduction of chitosan crystallinity, as well. Another important aspect was the increase of chitosan thermal stability, influenced by the increase of PVP portion in blends. Analysis of the data seems to indicate that a SIPN was formed, where the basic net is constituted of crosslinked PVP, while chitosan is kept \"imprisoned\" in this net, without participating of the same, but hindered of being extracted. The study of irradiation of PVP and chitosan aqueous co-solutions generated stable hydrogels, however restricted low chitosan percentage in the mixture - up to 30%. This study also disclosed that the acetic acid presence in the solution facilitates the crosslinking process, including pure PVP solution. Permeability to water of non-irradiated and irradiated blend films of chitrosan/PVP indicates application potentiality of these materiais in medicinal and food areas. Literature describes several methods of chitosan hydrogel production, however, all basing on the use of external crosslinkers or graft of reactive groups on chitosan chain. It must be pointed out that the crosslinking system considered here does not make use of crosslinkers, photoinitiators nor incorporation of some photoreactive group into the chains of the polymers. In a general way, the results obtained from irradiated and non-irradiated polymer materials suggest they possess potentiality for some applications: as biomaterial, for example, polymer matrices for controlled drug release, dressings for simpler wounds, others.

Progress in biomedicine requires the design of functional biomaterials, in particular, 3-dimensional (3D) scaffolds. Shear thinning, β-sheet based peptide hydrogels have attracted wide interest due to their potential use in tissue engineering and biomedical applications as 3D functional scaffolds. The emergence of carbon nanomaterials has also opened the door for the construction of increasingly functional hybrid hydrogels built from nanofibres and graphene-based materials using non-covalent physical interactions. The relationship between peptide molecular structure and the formed hydrogel is important for understanding the material response to shear. In particular, the physicochemical properties of peptide based biomaterials will affect the feasibility of injecting them during medical procedures. In the first part of this work, four peptides: FEFKFEFK (F8), FKFEFKFK (FK), KFEFKFEFK (KF8) and KFEFKFEFKK (KF8K) (F - phenylalanine, E - glutamic acid, K - lysine) were designed and used at identical charge to explore the effect of lysine rich β-sheet self-assembling sequences on the shear thinning behaviour and final properties of bulk hydrogels. By varying the peptide sequence design and concentration of the peptide, the tendency of the nanofibres formed to aggregate and the balance of nanofibre junction strength versus fibre cohesive strength could be explored. This allowed the existing theory of the shear thinning behaviour of this class of materials to be extended. The relationship between molecular structures of nanofibres forming the 3D network and the nano-filler is critical to understand in order to design tuneable and functional materials. In the next part of the work, three rationally designed β-sheet peptides, which form hydrogels: VEVKVEVK (V8), FEFKFEFK (F8) and FEFEFKFE (FE) (V - valine) and five graphene-based materials: graphene oxide (GO), reduced graphene oxide (rGO), three graphene-polymer hybrid flakes: GO with polydiallyldimethylammonium chloride (GO/PDADMAC), rGO with PDADMAC (rGO/PDADMAC) and rGO with polyvinylpyrrolidone (rGO/PVP) were used to form a selection of hybrid hydrogels. Graphene derivatives of the lateral flake sizes of 16.8 ± 10.1 µm were used. Various interactions between the graphene flakes and the peptides were observed that affected the overall mechanical properties of the hydrogels. Electrostatic interactions and pie-pie stacking, when phenylalanine residues are present, were shown to play a key role in determining the dispersion of graphene materials in the peptide hydrogels and stiffness of the hybrid materials. In particular, FE with reduced graphene oxide (rGO) and FE with rGO covered with polydiallyldimethylammonium chloride (PDADMAC) thin film formed double network-like hybrid hydrogels due to strong formation of peptide nanofibrillar bridges between adjacent rGO flakes. This corresponded to the 3- and 4-fold increase in the storage modulus (Gꞌ) of these hydrogels in comparison to controls. FE hydrogels with homogeneus dispersions of graphene oxide (GO) and reduced graphene oxide (rGO) are further shown to be suitable for 3D culture of human mesenchymal stem cells (hMSCs) with no cytotoxicity. These results focus attention on the importance of understanding interactions between the nano-filler and the nanofibrillar network in forming hybrid hydrogels with tuneable mechanical and biological properties, and demonstrates the possibility of using these materials as 3D cell culture scaffolds for biomedical purposes. Furthermore, graphene oxide (GO) itself is currently used in a number of processes of technological relevance such as wet spinning, injection moulding or inkjet printing to form graphene fibres, composites and printed conductors. Typically, such processes utilise well-aligned layered GO liquid crystal (LC) structures in aqueous dispersions. Flow and confinement encountered during processing affects the alignment and stability of this phase. In the final part of this work, the alignment of GOLCs of two lateral flake sizes (42.1 ± 29.4 µm and 15.5 ± 7.5 µm) were probed under a wide range of rotational shear flow conditions that overlap with the manufacturing processes defined by angular speeds from 0.08 to 8 rad.s-1 (and corresponding maximum shear rates from 0.1 s-1 to 100 s-1), in real-time, using shear induced polarized light imaging and small angle X-ray scattering, both coupled with an in-situ rheometer (Rheo-SIPLI and Rheo-SAXS, respectively). Under certain conditions, a unique pattern in Rheo-SIPLI: a Maltese cross combined with shear banding was observed. This phenomenon is unique to GO flakes of sufficiently large lateral size. The structure formed is attributed to a helical flow arising from a combination of shear flow and Taylor-vortex type flow, which is reinforced by a mathematical model. The orientations prescribed by this model are consistent with anomalous rheopecty oberved in Rheo-SIPLI and an anomolous scattering pattern in Rheo-SAXS. With the current trend towards producing ultra-large GO flakes, evidence that the flow behaviour changes from a Couette flow to a Taylor vortex flow was provided, which would lead to undesired, or alternatively, controllable alignment of GO flakes for a variety of applications, including aligned structures for biomedical purposes.

Dans la première partie on propose un outil mathématique pour traiter les conditions aux limites dynamiques d'un problème couplé d'EDP. La simulation avec des conditions aux limites dynamiques nécessite quelques fois une condition de "switch" en temps des conditions aux limites de Dirichlet en Neumann. La méthode numérique (St DN) a été validée avec des mesures expérimentales pour le cas de la contamination croisée en industrie micro-électronique. Cet outil sera utilisé par la suite pour simuler le phénomène de « self-heating » dans les polymères et les hydrogels sous sollicitations dynamiques. Dans la deuxième partie, on s'intéresse à la modélisation du phénomène de self-heating dans les polymères, les hydrogels et les tissus biologiques. D'abord, nous nous sommes focalisés sur la modélisation de la loi constitutive de l'hydrogel de type HEMA-EGDMA. Nous avons utilisé la théorie des invariants polynomiaux pour définir la loi constitutive du matériau. Ensuite, nous avons mis en place un modèle théorique en thermomécanique couplée d'un milieu continu classique pour analyser la production de chaleur dans ce matériau. Deux potentiels thermodynamiques ont été proposés et identifiés avec les mesures expérimentales. Une nouvelle forme d'équation du mouvement non-linéaire et couplée a été obtenue (un système d'équation aux dérivées partielles parabolique et hyperbolique non-linéaire couplé avec des conditions aux limites dynamiques). Dans la troisième partie, une méthode numérique des équations thermomécaniques (couplage parabolique-hyperbolique) pour les modèles a été utilisée. Cette étape nous a permis, entre autres, de résoudre ce système couplé. La méthode est basée sur la méthode des éléments finis. Divers résultats expérimentaux obtenus sur ce phénomène de self-heating sont présentés dans ce travail suivi d'une étude de corrélations des résultats théoriques et expérimentaux. Dans la dernière partie de ce travail, ces divers résultats sont repris et leurs conséquences sur la modélisation du comportement de l'hydrogel naturel utilisé dans le domaine biomédical sont discutées. / In the first part, we propose a mathematical tool for treating the dynamic boundary conditions. The simulation within dynamic boundary condition requires sometimes ''switch'' condition in time of the Dirichlet to Neumann boundary condition (St DN). We propose a numerical method validated with experimental measurements for the case of cross-contamination in microelectronics industry. This tool will be used to compute self-heating in the polymers and hydrogels under dynamic loading. In the second part we focus on modeling the self-heating phenomenon in polymers, hydrogels and biological tissues. We develop constitutive law of the hydrogel type HEMA-EGDMA, focusing on the heat e.ects (dissipation) in this material. Then we set up a theoretical model of coupled thermo-mechanical classic continuum for a better understanding of the heat production in this media. We use polynomial invariants theory to define the constitutive law of the media. Two original thermodynamic potentials are proposed. Original non-linear and coupled governing equations were obtained and identified with the experimental measurements (non-linear parabolic-hyperbolic system with the dynamic boundary condition). In the third part, numerical methods were used to solve thermo-mechanical formalism for the model. This step deals with a numerical method of a coupled partial di.erential equation system of the self-heating (parabolic-hyperbolic coupling). Then, is step allows us, among other things, to propose an appropriate numerical methods to solve this system. The numerical method is based on the finite element methods. Numerous experimental results on the self-heating phenomenon are presented in this work together with correlations studies between the theoretical and experimental results. In the last part of the thesis, these various results will be presented and their impact on the modeling of the behavior of the natural hydrogel used in the biomedical field will be discussed.

L’objectif de ce travail était de contrôler les propriétés rhéologiques de solutions aqueuses de copolymères amphiphiles. Dans l’eau, ces copolymères s’auto-associent et leurs propriétés peuvent être contrôlées en partie par leur dynamique d’échange. Il avait précédemment était montré que cette dynamique pouvait être contrôlée par le pH et la quantité d’unités acide acrylique dans des triblocs BAB (THx) où le bloc A est du poly(acide acrylique) (PAA) et les blocs B sont des copolymères statistiques (MHx) d’acrylate de n-butyle (nBA) et d’acide acrylique (AA). Tout d’abord, l’étude de l’auto-association en solution des blocs B seuls (MHx) a montré un lien fort entre leur agrégation et celle des diblocs de type BA (DHx). Cette agrégation est contrôlée par la quantité de charge des blocs B. Par la suite, des mélanges de triblocs (BAB) THx contenant différentes proportions (x) d’unités AA ont permis la formation de réseaux hybrides dont les propriétés rhéologiques sont maîtrisées par formulation plutôt que via la chimie. Des propriétés rhéologiques similaires aux triblocs BAB (THx) ont été obtenues avec des copolymères greffés possédant un squelette hydrophile PAA et des greffons B. Leurs propriétés rhéologiques sont principalement contrôlées par la structure chimique des blocs B, mais aussi par le taux de greffage. Ces copolymères greffés devraient être plus simples à obtenir à l’échelle industrielle que des triblocs. Pour finir, l’approche consistant à incorporer des unités hydrophiles dans les blocs hydrophobes de copolymères amphiphiles pour en contrôler la dynamique d’échange a été appliquée avec succès à des copolymères à base de méthacrylate de diméthylaminoéthyle et de méthacrylate de n-butyle. Leurs propriétés rhéologiques peuvent être contrôlées à nouveau par le pH, mais dans une gamme différente des polymères à base d’acide acrylique, et aussi dans une certaine mesure par la température. / The aim of this work was to control the rheological properties of aqueous solutions of amphiphilic copolymers. In water, these copolymers self-assemble and part of their properties can be controlled by their dynamic of exchange. As previously reported, the exchange dynamics can be controlled by the pH and the acrylic acid (AA) content for BAB triblock copolymers (THx) consisting of a poly(acrylic acid) (PAA) A block and two statistical B blocks (MHx) of n-butyl acryle (nBA) and AA.First, the study of the self-association of B blocks (MHx) alone showed a strong relationship between their aggregation and the one of BA diblocks (DHx). This aggregation was mainly controlled by the amount of charges within the B blocks.Then, mixtures of BAB triblocks (THx) with different contents of AA units, x, formed hybrid networks the rheological properties of which were controlled by formulation rather than chemistry.Similar rheological properties were obtained using graft copolymers consisting of a PAA hydrophilic backbone and B grafts. Their rheological properties were mainly controlled by the chemical structure of the B grafts and by the grafting density. Such graft copolymers should be easier to produce at an industrial scale than triblock copolymers.To finish, the strategy consisting of incorporating hydrophilic units inside the hydrophobic blocks of amphiphilic copolymers to control their exchange dynamics was successfully applied to copolymers made of dimethylaminoethyl methacraylate and n-butyl methacrylate. Their rheological properties were controlled by the pH on a different pH-range than the AA based polymers, and, to some extent, by the temperature.

The search for alternatives to the fossil-based products has dramatically surged during past few decades primarily due to the problems associated with the scarcity of these sources and global environmental concerns. Among those many alternatives, exploitation of cellulose, as a raw material to develop novel products has been a constant attempt since it has never lost its both economic and industrial impact. Cellulose is known for its significant contribution as a raw material and as a fascinating sustainable macromolecule, which exhibits wide availability and versatile chemical reactivity to discover novel derivatives for broad range of applications. Conversion of cellulose C2/C3 secondary hydroxyl groups to dialdehyde groups in the presence of periodate is an extremely useful method for regioselective oxidation of cellulose and to activate the polymer for further derivatization. This thesis is primarily focused on synthesis and characterization of wide range of cellulose derivatives exploiting facile periodate oxidation methodology. The first study investigated the use of periodate oxidation as a potential method to synthesize a novel water soluble derivative of cellulose from bleached hardwood Kraft pulp. The work focused on the effect of periodate oxidation and sulfonation reaction on water solubility, morphology and structure of cellulose fibers. The results showed a significant increase in water solubility (2.85 -28.5 g/L) and complete change in surface morphology of the fibers due to the introduction of sulfonic acid groups. In the second study, the same reaction scheme was employed on bead cellulose to prepare anionic 2,3-disulfonated beads. Due to the presence of negatively charged sulfonic acid groups, the beads were found to be agglomerated in presence of cationic starch, exhibiting their future application in chromatographic separation. In the third study, model primary amine compounds such as methyl and butyl amines were grafted to nanowhisker surfaces following periodate oxidation and reductive amination. Then, based on the grafting procedure, in the following study, gamma aminobutyric acid (spacer) and syringyl alcohol (linker) was attached to periodate oxidized nanowhiskers to synthesize a novel drug delivery system. The final study investigated the application of periodate oxidized nanowhiskers as chemical cross-linkers to stabilize gelatin gels. It was concluded that the chemical cross-linking has a significant effect on relative increase in percentage of rigid protons, reduced water uptake ability and reduced pore size of the gels. Not only did the chemical cross-linking improve the storage modulus of the gels (150%) and but it also increased the thermal resistance until 50 oC.

The interface between tendon/ligament and bone tissue is a complex transition of biochemical, cellular, and mechanical properties. Investigating computational and tissue engineering models that imitate aspects of this interface may supply critical design parameters for designing future tissue replacements to promote increased biochemical and mechanical integration between tendon/ligament and bone. Strategies for modeling this tissue have typically focused on the development of heterogeneous structures to create gradients or multiphasic materials that mimic aspects of the transition. However, further work is required to elucidate the role of specific mechanical and material stimuli in recapitulating features of the tendon/ligament-bone insertion. In particular, in constructs that exhibit variation in both mechanical and biochemical properties, the interplay of mechanical, material, and chemical signals can complicate understanding of the particular factors at work in interface formation. Thus, the overall goal of this dissertation was to provide insight into the role of mechanical strain and scaffold degradability on cell behavior within heterogeneous biomaterials. Specifically, a method for determining cell vertical position within a degradable gel through a laminated interface was developed. A computational model was created to examine possible variation in local mechanical strain due to heterogeneity in mechanical properties and different interface geometries. Finally, the influence of biomaterial degradability on changes in encapsulated human mesenchymal stem cell morphology under response to cyclic mechanical strain was explored. Together, these studies provide insight into mechanical and material design considerations when devising tissue engineering strategies to regenerate the tendon/ligament-bone interface.

Vor dem Hintergrund des weltweit wachsenden Bedarfes an Bodenverbesserungsmitteln, durch die Humus-, Nährstoff- und Wassermangel auf Problemstandorten kompensiert werden sollen, war es das Ziel der vorliegenden Arbeit, Bodenwasser-speicher auf Basis der nachwachsenden Biopolymere Stärke und Lignin zu entwickeln. Durch Derivatisierung der Stärke wurde deren Hydrophilie deutlich gesteigert, was Voraussetzung für die Bildung von Hydrogelen war. Es konnte gezeigt werden, dass durch Vernetzung der wasserlöslichen Stärkederivate Carboxymethylstärke und Monostärkemonophosphat mit Di-/Tricarbonsäuren quellfähige Hydrogele erzeugt werden, deren Quellungsvermögen und rheologische Eigenschaften über die Wahl des Vernetzers und die Vernetzerstoffmenge gezielt eingestellt werden können. Die Modifizierung von Lignin wurde durch Oxidation mit Wasserstoffperoxid, z.T. in Kombination mit Fe(II)- bzw. Mn(II)-Chloriden realisiert. Dadurch wurde die Vernetzbarkeit von Lignin deutlich verbessert, was auf oxidativ bedingte Strukturänderungen des Lignins zurückzuführen war. Diese bestanden im Wesentlichen in der Spaltung und Oxidation der Lignin-Seitenkette sowie der Hydroxylierung der Seitenkette und aromatischer Strukturen. Die Vernetzung von Lignin mit Poly-(ethylenglycol)-diglycidylether ergab quellfähige Hydrogele, deren Wasseraufnahmevermögen und rheologische Materialfunktionen von der eingesetzten Vernetzerstoffmenge abhängig sind. Es konnte gezeigt werden, dass durch den Einsatz von Stärkephosphat- und Lignin-Hydrogelen das Wasserspeichervermögen erhöht und die Evaporationsraten eines entsprechend behandelten Sandbodens verringert werden. Im Wachstumsversuch wurden die Frischmasseerträge von Gelbsenf (Sinapis alba) durch Behandlung eines Sandbodens mit Hydrogelen gesteigert. / Soil degradation leading to a lack of humus, nutrients and water especially on exploited sites causes the worldwide need in soil amendments. Aim of the work was the development of hydrogels from renewable biopolymers starch and lignin improving water retention especially in degraded soils. A significant increase of hydrophilic properties of starch was obtained by chemical modification with the objective of forming starch based hydrogels. Swellable hydrogels were formed by cross-linking of water soluble starch derivatives like carboxymethyl starch and monostarch monophosphates with di- and tricarboxylic acids. Swelling capacity and rheological properties of the starch gels were selective adjusted by variation of cross linking agent and whose amounts. Modification of lignin was realized by oxidation with hydrogen peroxide partly in combination with ferrous and manganese chlorides, respectively. In consequence of oxidative structural changes which were cleavage and oxidation of side chain as well as aliphatic and aromatic hydroxylation, gelation of lignin was improved significant. Lignin hydrogels with different swelling capacities and rheological functions were formed by cross-linking lignin with different amounts of poly (ethylene glycol) diglycidyl ether. Application of hydrogels based on starch and lignin causes increased water storing capacity/field capacity and decreased evaporation of a sandy soil as well as an increased biomass yield of yellow mustard (Sinapis alba).

Stimuli sensitive polymers and hydrogels respond with large property changes to small physical and chemical stimuli (e.g. temperature, pH, ionic strength). The bulk behavior of these polymers is widely studied and they show an isotropic swelling. However, thin hydrogel layers of polymers on a substrate show a swelling behavior, which is constrained in some way. Therefore, size, confinement, patternability, response time and transition temperature of thin hydrogel layers are the most important parameters in technological applications and this study focuses on the investigation of these above-mentioned parameters. The aim of this study involves synthesis, characterization and application of thin photo-crosslinked hydrogel layers. Dimethylmaleimide (DMI) moiety was incorporated in the polymers chains and was used to introduce photo-crosslinking by [2+2] cyclodimerization reaction in the presence of UV irradiation. The following photo-crosslinkers based on DMI group were synthesized ? - Acrylate photo-crosslinker (DMIAm) - Acrylamide photo-crosslinker (DMIAAm) - Polyol photo-crosslinker (DMIPA, DMIPACl) The conventional free radical polymerization of above listed photo-crosslinker with its respective monomer resulted in formation of photo-crosslinkable polymers of (a) HEMA, (b) DMAAm, (c) NIPAAm/DMAAm, (d) NIPAAm/Cyclam. The properties of these polymers were investigated by NMR, UV-VIS spectroscopy, GPC and SPR. Thin hydrogel layers were prepared by spin coating on gold-coated LaSFN9 glass. The covalent attachment to the surface was achieved through an adhesion promoter. Swelling behavior of the thin polymer layers was thoroughly investigated by Surface Plasmon Resonance (SPR) Spectroscopy and Optical Waveguide Spectroscopy (OWS). SPR and OWS gave a wide range of information regarding the film thickness, swelling ratio, refractive index, and volume degree of swelling of the thin hydrogel layer. For hydrophilic photo-crosslinked hydrogel layers of HEMA and DMAAm, it was observed that the volume degree of swelling was independent of temperature changes but was dependent on the photo-crosslinker mol-% in the polymer. These surface attached thin hydrogel layer exhibited an anisotropic swelling. For NIPAAm photo-crosslinked hydrogel layers with DMAAm as a hydrophilic monomer, it was observed that both transition temperature (Tc) and volume degree of swelling increases with increase in the mol-% of DMAAm. To study the effect of film thickness on Tc and volume degree of swelling, hydrogels with wide range of film thickness were prepared and investigated by SPR. These results provided vital information on the swelling behavior of surface attached hydrogel layer and showed the versatility of SPR instrument for studying thin hydrogel layers. Later part of project involved synthesis of multilayer hydrogel assembly involving a thermoresponsive polymer and a hydrophilic polymer. The combination of two layers with photo-crosslinkable DMAAm polymer as base layer and photo-crosslinkable NIPAAm polymer as top layer formulate a multilayer assembly where, the base layer only swells in response to temperature and the top layer shows temperature dependent swelling. Photo-crosslinked hydrogel layers of NIPAAm, DMAAm and HEMA shows a high-resolution patterns when irradiated by UV light through a chromium mask. At last this study focused on an important application of these hydrogel layers for cell attachment processes. Cell growth, proliferation and spreading shows a biocompatible nature of these hydrogel surfaces. Such thermoresponsive photo-crosslinkable multilayer structure forms bases for future projects involving their use in actuator material and cell-attachment processes.

The main goal of this work is design and synthesis of novel composite hydrogel-based core-shell microparticles and their application for fabrication of coatings, which provide the “inverse-switching” behaviour to the surface, namely, to become more hydrophobic in water environment. Since contact angle of heterogeneous surfaces is dependent on the nature and ratio of surface components, an increase of amount of more hydrophobic component on the surface will cause the reducing of surface wettability. It was suggested that core-shell particles having water-swellable hydrogel core and hydrophobic, but permeable for water shell when deposited on the hydrophilic substrate should increase the total amount of hydrophobic component on the surface when the cores of particles will swell in water. During the work different approaches to obtain freely dispersed and surface-immobilized core-shell particles with required structure were developed. Obtained particles were applied for preparation of coatings with ability to display “inverse-switching” behaviour. It was demonstrated that properly designed and properly prepared core-shell particles could be successfully used for creation of smart adaptive coatings having the ability to alter the surface properties upon changing of the environment.