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.

Die Funktionalisierung von tetra-PEG Makromolekülen mit fotoreaktiven Gruppen und die anschließende Umsetzung zu Hydrogelen durch fotochemische Vernetzung werden beschrieben. Die Funktionalisierung der Makromoleküle wird mittels UV-Vis- und NMR-Spektroskopie nachgewiesen, während der Verlauf der Vernetzung über die dynamische Lichtstreuung und IR-Spektroskopie betrachtet wird. Die hergestellten Hydrogele werden hinsichtlich des Sol-Anteils und der Quelleigenschaften untersucht. Über den Umsatz wird die Konzentration der Netzketten theoretisch berechnet. Einen weiteren Schwerpunkt bildet die Charakterisierung der Hydrogele hinsichtlich der mechanischen Eigenschaften. Über den Speichermodul wird die Konzentration der Netzketten experimentell bestimmt. Mittels dynamischer Lichtstreuung werden die kooperativen Diffusionskoeffizienten und Maschenweiten der Hydrogele bestimmt.

Artikulärer Knorpel weist ein geringes Selbstheilungspotential auf und aktuelle Methoden zur Therapie von Knorpeldefekten resultieren meist im Aufbau fibrösen, mechanisch inferioren Regenerationsgewebes. Deshalb wird stetig versucht neue Therapiemethoden zu entwickeln, die häufig auf Tissue Engineering basieren. Ein Ansatz sind biogedruckte Tissue Engineering Konstrukte, die es ermöglichen durch das „Eindrucken“ vitaler Zellen die komplexen zellulären Strukturen des Knorpelgewebes nachzubilden. Trotz vielsprechender Ergebnisse in vitro, scheitert die langfristige Regeneration von Knorpeldefekten mittels Tissue Engineering jedoch häufig an der mangelnden Fixierung und Integration der Konstrukte in das umliegende Gewebe. Besonders um biogedruckte Hydrogelkonstrukte, für die viele gängigen Fixierungsoptionen ungeeignet sind, für das Knorpel Tissue Engineering nutzbar zu machen, müssen daher neue Fixierungs- und Integrationsmethoden entwickelt werden. Als Ansatz zur Verbesserung der osteochondralen Integration von Knorpelersatzmaterialien wurde im Rahmen dieser Arbeit ein GDF-5 beladener Gewebekleber getestet. GDF-5, ein Knorpelmorphogenetisches Protein, kann die chondrogene Differenzierung sowie die Hypertrophie von Vorläuferzellen fördern. Durch den Einsatz eines GDF-5 beladenen Gewebeklebers sollen in den Defekt einwandernde, wirtseigene Progenitorzellen zur chondrogenen Differenzierung und Mineralisierung angeregt werden, mit dem Ziel eine mineralisierte Knorpelgewebsschicht zwischen der subchondralen Knochen-platte und dem implantierten Tissue Engineering Konstrukt zu generieren und so dessen Integration zu verbessern.

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.

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).

Active membranes with switchable pores that are based on hydrogels can be used to measure the cell size distribution in blood samples. The system investigated in the present research is based on a polyethylene terephthalate (PET) membrane that is surface polymerized with poly (N-isopropyl acrylamide) (PNiPAAm) to form active pores of arbitrary geometry. The PET membrane provides the functionality of a backbone for mechanical rigidity, while the soft PNiPAAm hydrogel forms the active pores. Modeling and simulation of the active hydrogel behavior proved to adequately predict the opening and closing of the pores under application of an activating stimulus, e.g. temperature. The applied model is called Temperature-Expansion-Model and uses the analogy of thermal expansion to model the volume swelling of hydrogels. The Normalized Extended Temperature-Expansion-Model can englobe arbitrary hydrogels and large geometric displacements. Studies of pore opening - performed by using commercial finite element tools - show good agreement of the experimentally measured shape change of active pores. Based on these studies, the particulate fluid flow through the switchable pores is analyzed. Through application of a membrane process, i.e. a given variation of applied pressure and switching stimulus for the hydrogel, the size profile of the blocking particles can be measured directly using the flux difference under constant pressure. This allows the measurement of the cell size distribution in blood samples, e.g. to detect circulating tumor cells or anomalies in the distribution that hint to anemia.

An environment is defined by a set of field values, such as temperature, electro-magnetic field, light intensity, air humidity and air composition. Smart materials, such as hydrogels, are able to react to these kinds of stimuli. The spatial and time development of environmental values is governed by transport equations. Hence the reaction, i.e. actuation or sensing, of the smart material can be described based on the same assumptions. The displacement, here swelling and deswelling, of the material depends on the combination of the environmental parameters. Smart materials are called multi-sensitive, when more than one parameter is purposely used (i) to manipulate the material, i.e. as an actuator or (ii) to measure the quantities, i.e. as a (multi-)sensor. However, the material can also perform (iii) the objective of a logic processing unit in addition to (i) and (ii). In the current work, we present a device that realizes this concept: An automatic window opener that senses environmental parameters (light-level and air temperature) and reacts accordingly. The hydrogel material that is included in the simplistic device simultaneously acts as sensor, logic processing unit and actuator.

In engineering, materials are chosen from databases: Engineers orient on specific parameters such as Young's modulus, yield stress or thermal expansion coefficients for a desired application. For hydrogels, the choice of materials is rather tedious since no generalized material parameters are currently available to quantify the swelling behavior. The normalization of swelling, which we present in the current work, allows an easy comparison of different hydrogel materials. Thus, for a specific application like a sensor or an actuator, an adequate material can be chosen. In the current work, we present the process of normalization and provide a course of action for the data analysis. Special challenges for hydrogels like hysteresis, conditional multi-sensitivity and anisotropic swelling are addressed. Then, the Temperature Expansion Model is shortly described and applied. Using the derived normalized swelling curves, a nonlinear expansion coefficient β(F) is derived. The derived material behavior is used in an analytical model to predict the bending behavior of a beam made of thermo-responsive hydrogel material under an anisotropic temperature load. A bending behavior of the beam can be observed and the impact of other geometry and material parameters can be investigated. To overcome the limitations of the one-dimensional beam theory, the material behavior and geometry can be implemented in Finite Element analysis tools. Thus, novel applications for hydrogels in various fields can be envisioned, designed and tested. This can lead to a wider use of smart materials in sensor or actuator devices even by engineers without chemical background.