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Neben der Frequenz eines cues ist es dessen Zuverlässigkeit, die Kindern hilft, die an sie gerichtete Sprache zu segmentieren, Worteinheiten zu erkennen sowie diese syntaktisch zu kategorisieren. Im Deutschen weist die Subsilbe „Langvokal+Konsonant+/t/“ (z.B. in fehlt, wohnt) zuverlässig auf eine -t-flektierte Verbform hin. Die in kindgerichteter Sprache höher frequente Subsilbe „Kurzvokal+Konsonant+/t/“ (z.B. in Feld, Hemd, fällt, rund) gibt hingegen keinen derartig eindeutigen Hinweis. Es wurde der Frage nachgegangen, inwiefern diese unterschiedlichen Zuverlässigkeiten und Frequenzen der Subsilben auf die Nomen-, Verb- und Verbflexionsverarbeitung einwirken. Drei Altersgruppen wurden untersucht: achtzehn Monate alte Kinder, drei- bis fünfjährige sprachunauffällige und -auffällige Kinder sowie erwachsene Sprecher. Einflüsse der unterschiedlichen Zuverlässigkeiten und Frequenzen der ausgewählten Subsilben konnten für alle Probandengruppen gefunden werden. Die Subsilbe stellt damit eine linguistische Größe dar, die in der frühen Sprachwahrnehmung als cue dienen sowie die Sprachverarbeitung Erwachsener lenken kann und auch für die Sprachdiagnostik und -therapie sprachauffälliger Kinder berücksichtigt werden sollte.
The need to reduce humankind reliance on fossil fuels by exploiting sustainably the planet renewable resources is a major driving force determining the focus of modern material research. For this reason great interest is nowadays focused on finding alternatives to fossil fuels derived products/materials. For the short term the most promising substitute is undoubtedly biomass, since it is the only renewable and sustainable alternative to fossil fuels as carbon source. As a consequence efforts, aimed at finding new synthetic approaches to convert biomass and its derivatives into carbon-based materials, are constantly increasing. In this regard, hydrothermal carbonisation (HTC) has shown to be an effective means of conversion of biomass-derived precursors into functional carbon materials. However the attempts to convert raw biomass, in particular lignocellulosic one, directly into such products have certainly been rarer. Unlocking the direct use of these raw materials as carbon precursors would definitely be beneficial in terms of HTC sustainability. For this reason, in this thesis the HTC of carbohydrate and protein-rich biomass was systematically investigated, in order to obtain more insights on the potentials of this thermochemical processing technique in relation to the production of functional carbon materials from crude biomass. First a detailed investigation on the HTC conversion mechanism of lignocellulosic biomass and its single components (i.e. cellulose, lignin) was developed based on a comparison with glucose HTC, which was adopted as a reference model. In the glucose case it was demonstrated that varying the HTC temperature allowed tuning the chemical structure of the synthesised carbon materials from a highly cross-linked furan-based structure (T = 180oC) to a carbon framework composed of polyaromatic arene-like domains. When cellulose or lignocellulosic biomass was used as carbon precursor, the furan rich structure could not be isolated at any of the investigated processing conditions. These evidences were indicative of a different HTC conversion mechanism for cellulose, involving reactions that are commonly observed during pyrolytic processes. The evolution of glucose-derived HTC carbon chemical structure upon pyrolysis was also investigated. These studies revealed that upon heat treatment (Investigated temperatures 350 – 900 oC) the furan-based structure was progressively converted into highly curved aromatic pre-graphenic domains. This thermal degradation process was observed to produce an increasingly more hydrophobic surface and considerable microporosity within the HTC carbon structure. In order to introduce porosity in the HTC carbons derived from lignocellulosic biomass, KOH chemical activation was investigated as an HTC post-synthesis functionalisation step. These studies demonstrated that HTC carbons are excellent precursors for the production of highly microporous activated carbons (ACs) and that the porosity development upon KOH chemical activation is dependent on the chemical structure of the HTC carbon, tuned by employing different HTC temperatures. Preliminary testing of the ACs for CO2 capture or high pressure CH4 storage yielded very promising results, since the measured uptakes of both adsorbates (i.e. CO2 and CH4) were comparable to top-performing and commercially available adsorbents, usually employed for these end-applications. The combined use of HTC and KOH chemical activation was also employed to produce highly microporous N-doped ACs from microalgae. The hydrothermal treatment of the microalgae substrate was observed to cause the depletion of the protein and carbohydrate fractions and the near complete loss (i.e. 90%) of the microalgae N-content, as liquid hydrolysis/degradation products. The obtained carbonaceous product showed a predominantly aliphatic character indicating the presence of alkyl chains presumably derived from the lipid fractions. Addition of glucose to the initial reaction mixture was found out to be extremely beneficial, because it allowed the fixation of a higher N amount, in the algae derived HTC carbons (i.e. 60%), and the attainment of higher product yields (50%). Both positive effects were attributed to Maillard type cascade reactions taking place between the monosaccharides and the microalgae derived liquid hydrolysis/degradation products, which were in this way recovered from the liquid phase. KOH chemical activation of the microalgae/glucose mixture derived HTC carbons produced highly microporous N-doped carbons. Although the activation process led to a major reduction of the N-content, the retained N-amount in the ACs was still considerable. These features render these materials ideal candidates for supercapacitors electrodes, since they provide extremely high surface areas, for the formation of electric double-layer, coupled to abundant heteroatom doping (i.e. N and O) necessary to obtain a pseudocapacitance contribution.
Die eingehende Analyse ausgewählter Aspekte der Wort-Ton-Gestaltung in Gustav Mahlers Vokalsinfonik ist Schwerpunkt der vorliegenden Untersuchung. Prämisse ist Mahlers Ausarbeitung ideenprogrammatischer Intentionen, wobei er sich die besondere Stärke der Musik, geistige Sachverhalte in gewisser Weise präziser als Sprache (die hier ins Symbolhafte ausweichen muss) verdeutlichen zu können, offensichtlich bewusst zunutze gemacht hatte. Die Differenziertheit der musikalischen Textinterpretation, zugleich Fokus der Analysen, weist deutliche graduelle Unterschiede auf. Sie reicht vom ,Vertonungscharakter‘ bis hin zur innigsten Anverwandlung von Musik und Textaussage bzw. -semantik. Wesentlich ist das oft proportionale Verhältnis von Grad der Freiheit, die sich Mahler hinsichtlich der Beziehung der Musik zur formalen Topographie des Textes nimmt, zu Intensität und Vielschichtigkeit der musikalischen Textexegese. Je stärker sich ihre musikalische Umsetzung in Richtung ‚Semantik-Ausarbeitung‘ bewegt, verliert die äußerliche Sprache an Materialität, wobei das im Lied von der Erde zutage tretende Amalgam von sprachlicher Semantik und Musik gesondert zu nennen ist. Letztendlich wird die überwiegend eher unbestimmte Textsemantik durch Mahlers Musik denotiert und in zuvor im Bereich der Vokalsinfonik nicht erreichter Intensität zum Klingen gebracht.
One of the major problems for the implementation of water resources planning and management in arid and semi-arid environments is the scarcity of hydrological data and, consequently, research studies. In this thesis, the hydrology of dryland river systems was analyzed and a semi-distributed hydrological model and a forecasting approach were developed for flow transmission processes in river-systems with a focus on semi-arid conditions. Three different sources of hydrological data (streamflow series, groundwater level series and multi-temporal satellite data) were combined in order to analyze the channel transmission losses of a large reach of the Jaguaribe River in NE Brazil. A perceptual model of this reach was derived suggesting that the application of models, which were developed for sub-humid and temperate regions, may be more suitable for this reach than classical models, which were developed for arid and semi-arid regions. Summarily, it was shown that this river reach is hydraulically connected with groundwater and shifts from being a losing river at the dry and beginning of rainy seasons to become a losing/gaining (mostly losing) river at the middle and end of rainy seasons. A new semi-distributed channel transmission losses model was developed, which was based primarily on the capability of simulation in very different dryland environments and flexible model structures for testing hypotheses on the dominant hydrological processes of rivers. This model was successfully tested in a large reach of the Jaguaribe River in NE Brazil and a small stream in the Walnut Gulch Experimental Watershed in the SW USA. Hypotheses on the dominant processes of the channel transmission losses (different model structures) in the Jaguaribe river were evaluated, showing that both lateral (stream-)aquifer water fluxes and ground-water flow in the underlying alluvium parallel to the river course are necessary to predict streamflow and channel transmission losses, the former process being more relevant than the latter. This procedure not only reduced model structure uncertainties, but also reported modelling failures rejecting model structure hypotheses, namely streamflow without river-aquifer interaction and stream-aquifer flow without groundwater flow parallel to the river course. The application of the model to different dryland environments enabled learning about the model itself from differences in channel reach responses. For example, the parameters related to the unsaturated part of the model, which were active for the small reach in the USA, presented a much greater variation in the sensitivity coefficients than those which drove the saturated part of the model, which were active for the large reach in Brazil. Moreover, a nonparametric approach, which dealt with both deterministic evolution and inherent fluctuations in river discharge data, was developed based on a qualitative dynamical system-based criterion, which involved a learning process about the structure of the time series, instead of a fitting procedure only. This approach, which was based only on the discharge time series itself, was applied to a headwater catchment in Germany, in which runoff are induced by either convective rainfall during the summer or snow melt in the spring. The application showed the following important features: • the differences between runoff measurements were more suitable than the actual runoff measurements when using regression models; • the catchment runoff system shifted from being a possible dynamical system contaminated with noise to a linear random process when the interval time of the discharge time series increased; • and runoff underestimation can be expected for rising limbs and overestimation for falling limbs. This nonparametric approach was compared with a distributed hydrological model designed for real-time flood forecasting, with both presenting similar results on average. Finally, a benchmark for hydrological research using semi-distributed modelling was proposed, based on the aforementioned analysis, modelling and forecasting of flow transmission processes. The aim of this benchmark was not to describe a blue-print for hydrological modelling design, but rather to propose a scientific method to improve hydrological knowledge using semi-distributed hydrological modelling. Following the application of the proposed benchmark to a case study, the actual state of its hydrological knowledge and its predictive uncertainty can be determined, primarily through rejected hypotheses on the dominant hydrological processes and differences in catchment/variables responses.
This paper examines and develops matrix methods to approximate the eigenvalues of a fourth order Sturm-Liouville problem subjected to a kind of fixed boundary conditions, furthermore, it extends the matrix methods for a kind of general boundary conditions. The idea of the methods comes from finite difference and Numerov's method as well as boundary value methods for second order regular Sturm-Liouville problems. Moreover, the determination of the correction term formulas of the matrix methods are investigated in order to obtain better approximations of the problem with fixed boundary conditions since the exact eigenvalues for q = 0 are known in this case. Finally, some numerical examples are illustrated.
Carbohydrate recognition is a ubiquitous principle underlying many fundamental biological processes like fertilization, embryogenesis and viral infections. But how carbohydrate specificity and affinity induce a molecular event is not well understood. One of these examples is bacteriophage P22 that binds and infects three distinct Salmonella enterica (S.) hosts. It recognizes and depolymerizes repetitive carbohydrate structures of O antigen in its host´s outer membrane lipopolysaccharide molecule. This is mediated by tailspikes, mainly β helical appendages on phage P22 short non contractile tail apparatus (podovirus). The O antigen of all three Salmonella enterica hosts is built from tetrasaccharide repeating units consisting of an identical main chain with a distinguished 3,6 dideoxyhexose substituent that is crucial for P22 tailspike recognition: tyvelose in S. Enteritidis, abequose in S. Typhimurium and paratose in S. Paratyphi. In the first study the complexes of P22 tailspike with its host’s O antigen octasaccharide were characterized. S. Paratyphi octasaccharide binds less tightly (ΔΔG≈7 kJ/mol) to the tailspike than the other two hosts. Crystal structure analysis of P22 tailspike co crystallized with S. Paratyphi octasaccharides revealed different interactions than those observed before in tailspike complexes with S. Enteritidis and S. Typhimurium octasaccharides. These different interactions occur due to a structural rearrangement in the S. Paratyphi octasaccharide. It results in an unfavorable glycosidic bond Φ/Ψ angle combination that also had occurred when the S. Paratyphi octasaccharide conformation was analyzed in an aprotic environment. Contributions of individual protein surface contacts to binding affinity were analyzed showing that conserved structural waters mediate specific recognition of all three different Salmonella host O antigens. Although different O antigen structures possess distinct binding behavior on the tailspike surface, all are recognized and infected by phage P22. Hence, in a second study, binding measurements revealed that multivalent O antigen was able to bind with high avidity to P22 tailspike. Dissociation rates of the polymer were three times slower than for an octasaccharide fragment pointing towards high affinity for O antigen polysaccharide. Furthermore, when phage P22 was incubated with lipopolysaccharide aggregates before plating on S. Typhimurium cells, P22 infectivity became significantly reduced. Therefore, in a third study, the function of carbohydrate recognition on the infection process was characterized. It was shown that large S. Typhimurium lipopolysaccharide aggregates triggered DNA release from the phage capsid in vitro. This provides evidence that phage P22 does not use a second receptor on the Salmonella surface for infection. P22 tailspike binding and cleavage activity modulate DNA egress from the phage capsid. DNA release occurred more slowly when the phage possessed mutant tailspikes with less hydrolytic activity and was not induced if lipopolysaccharides contained tailspike shortened O antigen polymer. Furthermore, the onset of DNA release was delayed by tailspikes with reduced binding affinity. The results suggest a model for P22 infection induced by carbohydrate recognition: tailspikes position the phage on Salmonella enterica and their hydrolytic activity forces a central structural protein of the phage assembly, the plug protein, onto the host´s membrane surface. Upon membrane contact, a conformational change has to occur in the assembly to eject DNA and pilot proteins from the phage to establish infection. Earlier studies had investigated DNA ejection in vitro solely for viruses with long non contractile tails (siphovirus) recognizing protein receptors. Podovirus P22 in this work was therefore the first example for a short tailed phage with an LPS recognition organelle that can trigger DNA ejection in vitro. However, O antigen binding and cleaving tailspikes are widely distributed in the phage biosphere, for example in siphovirus 9NA. Crystal structure analysis of 9NA tailspike revealed a complete similar fold to P22 tailspike although they only share 36 % sequence identity. Moreover, 9NA tailspike possesses similar enzyme activity towards S. Typhimurium O antigen within conserved amino acids. These are responsible for a DNA ejection process from siphovirus 9NA triggered by lipopolysaccharide aggregates. 9NA expelled its DNA 30 times faster than podovirus P22 although the associated conformational change is controlled with a similar high activation barrier. The difference in DNA ejection velocity mirrors different tail morphologies and their efficiency to translate a carbohydrate recognition signal into action.
In continuation of a successful series of events, the 4th Many-core Applications Research Community (MARC) symposium took place at the HPI in Potsdam on December 8th and 9th 2011. Over 60 researchers from different fields presented their work on many-core hardware architectures, their programming models, and the resulting research questions for the upcoming generation of heterogeneous parallel systems.
Wissenschaft hat einen großen Anteil daran, internationale Umweltprobleme auf die politische Tagesordnung zu bringen und Maßnahmen zu ihrer technischen Lösung zu entwerfen. Dies gilt sowohl für den Abbau der Ozonschicht als auch für den Klimawandel. So relevant die Generierung von wissenschaftlichen Erkenntnissen in diesen Feldern ist, so komplex ist die Interaktion zwischen Wissenschaft und Politik und so schwierig ist es, Verlässliches darüber zu sagen. Thomas Hickmann analysiert das Verhältnis von Wissenschaft und Politik in internationalen Umweltregimen aus einer neuen Perspektive. Er untersucht nicht den Einfluss wissenschaftlicher Erkenntnisse auf die Politik, sondern rückt die Frage in den Fokus, inwieweit Regierungen Einfluss auf die Wissenschaft nehmen, um nationale Interessen durchzusetzen. Diese Perspektive wurde in der Forschung bislang weitgehend vernachlässigt, weshalb eine systematische Analyse dieser Frage in der Literatur fehlt.
Diese Publikation einer Masterarbeit leistet einen Beitrag, die bestehende Forschungslücke hinsichtlich der Rolle rechtspopulistischer Parteien in Regierungsbildungsprozessen zu füllen. Warum haben sich etablierte Parteien und Rechtspopulisten für eine bestimmte Konstellation entschieden? Welche Probleme traten durch den spezifisch rechtspopulistischen Charakter bei der Regierungsbildung auf? Welche Alternativen gibt es? Mittels eines vergleichenden Ansatzes werden dabei als Fallbeispiele die Regierungsbildungsprozesse nach drei Wahlen zu nationalen Parlamenten im Jahr 2010 in Belgien, den Niederlanden und Schweden analysiert.
Der Gewaltige und der Poet
(2012)
Der Herr Major
(2012)
Ein alter Major stößt zu einer Reisegesellschaft, die sich auf einem Dampfer nach Hallig Hooge befindet. Durch seine verbalen Ausfälle und seine Trunksucht verspielt der Major allmählich die Achtung, die ihm anfangs entgegengebracht wurde. Eine genaue Beobachtung von gesellschaftlicher Gruppendynamik und unterschiedlichen Rollenverhalten in der Konfrontation mit einem Außenseiter.
"Hinnerk Pick und der Steernkieker" ist ein poetischer Text, der sich mit dem Astronomen J. J. Sievers, der an der Altonaer Sternwarte tätig war, befasst. J. J. Sievers (1804-1881) stammte aus Stafstedt (Kreis Rendsburg-Eckernförde), einem Dorf in der Nähe von Luhnstedt, dem Heimatdorf von F. E. Peters. Er wird beschrieben als märchenhaft geheimnisvolle Gestalt und zugleich liebenswerter Sonderling, in dessen Augen sich eine Pascalsche Scheu vor der Unendlichkeit des Raumes widerspiegelt. "Immer aber wird mir der Steernkieker teuer bleiben als ein Zeugnis dafür, dass aus der Enge eines holsteinischen Dorfes zum Geist geführt werden kann, wen der Geist gerufen hat. Am Ende ist eines Menschen Drang ins Weite doch vergeblich, wenn er sie nach unruhigen Jahren des Suchens nicht findet in sich selbst." In den Mund des Astronomen Sievers ("de ool Steernkieker", "de ool Klooksnacker") legt Peters am Anfang der "Baasdörper Krönk" die berühmte Beschreibung von Baasdorp und der Anlage des Dorfes in drei sozial definierte konzentrische Kreise (reiche Bauern; Halbhufner und kleine Bauern; schließlich Handwerker und Katenbauern).
Das Opfer
(2012)
Der alte Timm Wieben sieht die natürliche gottgewollte Ordnung durch den Fortschritt, d. h. den Bau eines Bahndammes in seinem Dorf, gefährdet. Er prophezeit die Notwendigkeit eines Menschenopfers, das die Erde besänftigen soll: "Es muss etwas Lebiges in die Grund". Daraufhin ereignet sich ein schwerer Unfall. Der aus dem Nachlass veröffentlichte Text gehört eindeutig zu dem Umfeld der "Baasdörper Krönk". Er kontrastiert Aberglaube und aufgeklärtes Denken, , ohne in Schwarz-Weiß-Malerei zu verfallen. In Peters' Autobiographie Preis der guten Mächte (1940) erscheint der Großvater als ein Fürsprecher des Rationalismus und, wie Hans Lohse in der Erzählung, als ein Gegenentwurf zu Timm Wieben ("Dat geiht all natürlich to"). Aber auch er erkennt trotz allem die Macht des Übernatürlichen an. Für Peters löst sich der Gegensatz zwischen Licht und Dunkel, Aufklärung und Dämonie in der Religion auf: "Und wenn wir auch den beschränkten Geltungsbereich unserer Leuchte erkennen, so haben wir dennoch die Pflicht, sie ins Dunkel hinauszutragen bis an den alleräußersten Rand unseres Vermögens. Wer aber vor dem letzten, undurchleuchtbaren Dunkel steht, der suche seine Zuflucht nicht bei verdächtigen Mächten des Zaubers, sondern fasse die Hand Gottes, die sich ihm aus der deutschen Bibel Martin Luthers hilfreich entgegenstreckt." (Ausgewählte Werke, Bd II, Hamburg, Hoffmann und Campe, S. 111)
This thesis aims at a better mechanistic understanding of animal communities. Therefore, an allometry- and individual-based model has been developed which was used to simulate mammal and bird communities in heterogeneous landscapes, and to to better understand their response to landscape changes (habitat loss and fragmentation).
Structuring process models
(2012)
One can fairly adopt the ideas of Donald E. Knuth to conclude that process modeling is both a science and an art. Process modeling does have an aesthetic sense. Similar to composing an opera or writing a novel, process modeling is carried out by humans who undergo creative practices when engineering a process model. Therefore, the very same process can be modeled in a myriad number of ways. Once modeled, processes can be analyzed by employing scientific methods. Usually, process models are formalized as directed graphs, with nodes representing tasks and decisions, and directed arcs describing temporal constraints between the nodes. Common process definition languages, such as Business Process Model and Notation (BPMN) and Event-driven Process Chain (EPC) allow process analysts to define models with arbitrary complex topologies. The absence of structural constraints supports creativity and productivity, as there is no need to force ideas into a limited amount of available structural patterns. Nevertheless, it is often preferable that models follow certain structural rules. A well-known structural property of process models is (well-)structuredness. A process model is (well-)structured if and only if every node with multiple outgoing arcs (a split) has a corresponding node with multiple incoming arcs (a join), and vice versa, such that the set of nodes between the split and the join induces a single-entry-single-exit (SESE) region; otherwise the process model is unstructured. The motivations for well-structured process models are manifold: (i) Well-structured process models are easier to layout for visual representation as their formalizations are planar graphs. (ii) Well-structured process models are easier to comprehend by humans. (iii) Well-structured process models tend to have fewer errors than unstructured ones and it is less probable to introduce new errors when modifying a well-structured process model. (iv) Well-structured process models are better suited for analysis with many existing formal techniques applicable only for well-structured process models. (v) Well-structured process models are better suited for efficient execution and optimization, e.g., when discovering independent regions of a process model that can be executed concurrently. Consequently, there are process modeling languages that encourage well-structured modeling, e.g., Business Process Execution Language (BPEL) and ADEPT. However, the well-structured process modeling implies some limitations: (i) There exist processes that cannot be formalized as well-structured process models. (ii) There exist processes that when formalized as well-structured process models require a considerable duplication of modeling constructs. Rather than expecting well-structured modeling from start, we advocate for the absence of structural constraints when modeling. Afterwards, automated methods can suggest, upon request and whenever possible, alternative formalizations that are "better" structured, preferably well-structured. In this thesis, we study the problem of automatically transforming process models into equivalent well-structured models. The developed transformations are performed under a strong notion of behavioral equivalence which preserves concurrency. The findings are implemented in a tool, which is publicly available.
Arabische Brüche
(2012)
Können Araber Demokratie? Im Jahr II des Arabischen Frühlings werden erste zarte Triebe der Hoffnungen, die in diese Richtung neigten, von Soldatenstiefeln und flüchtenden Demonstranten zertreten. Die versiegelte Zeit brach auf, doch was ist erreicht worden? In der neuen Ausgabe ziehen wir eine Bilanz, die ebenso sachlich wie zwiespältig ist. Sie zeigt Erfolge, ohne zu beschönigen. Probleme werden sichtbar gemacht, aber auch Wege zu ihrer Lösung. Auch Europa ist gefragt: Wir müssen zu einem neuen, partnerschaftlichen Verhältnis mit den sich wandelnden arabischen Nationen finden!
Krieg in Sicht?
(2012)
Säbelrasseln und Bombendrohungen am Persischen Golf. Israelische Politiker sprechen sich für Angriffe auf iranische Nuklearanlagen aus, bevor es zu "spät" sei. US-Verteidigungsminister Panetta hält einen Angriff Israels auf den Iran im Frühling für wahrscheinlich, während sein Präsident abwiegelt: Israel habe noch keine Entscheidung getroffen, man müsse den Sanktionen mehr Zeit geben. Mittlerweile werden aber die Instrumente scharf gemacht. Die 5. Flotte überwacht den Golf; in der Region sind etwa 40.000 US-Soldaten stationiert. Der Iran setzt auf Seemanöver.
In this thesis, different aspects within the research field of protein spectro- and electro-chemistry on nanostructured materials are addressed. On the one hand, this work is related to the investigation of nanostructured transparent and conductive metal oxides as platform for the immobilization of electroactive enzymes. On the other hand the second part of this work is related to the immobilization of sulfite oxidase on gold nanoparticles modified electrode. Finally direct and mediated spectroelectrochemistry protein with high structure complexity such as the xanthine dehydrogenase from Rhodobacter capsulatus and its high homologues the mouse aldehyde oxidase homolog 1. Stable immobilization and reversible electrochemistry of cytochrome c in a transparent and conductive tin-doped and tin-rich indium oxide film with a well-defined mesoporosity is reported. The transparency and good conductivity, in combination with the large surface area of these materials, allow the incorporation of a high amount of electroactive biomolecules (between 250 and 2500 pmol cm-2) and their electrochemical and spectroscopic investigation. Both, the electrochemical behavior and the immobilization of proteins are influenced by the geometric parameters of the porous material, such as the structure and pore shape, the surface chemistry, as well as the protein size and charge. UV-Vis and resonance Raman spectroscopy, in combination with direct protein voltammetry, are employed for the characterization of cytochrome c immobilized in the mesoporous indium tin oxide and reveal no perturbation of the structural integrity of the redox protein. A long term protein immobilization is reached using these unmodified mesoporous indium oxide based materials, i.e. more than two weeks even at high ionic strength. The potential of this modified material as an amperometric biosensor for the detection of superoxide anions is demonstrated. A sensitivity of about 100 A M-1 m-2, in a linear measuring range of the superoxide concentration between 0.13 and 0.67 μM, is estimated. In addition an electrochemical switchable protein-based optical device is designed with the core part composed of cytochrome c immobilized on a mesoporous indium tin oxide film. A color developing redox sensitive dye is used as switchable component of the system. The cytochrome c-catalyzed oxidation of the dye by hydrogen peroxide is spectroscopically investigated. When the dye is co-immobilized with the protein, its redox state is easily controlled by application of an electrical potential at the supporting material. This enables to electrochemical reset the system to the initial state and repetitive signal generation. The case of negative charged proteins, which does not have a good interaction with the negative charged indium oxide based films, is also explored. The modification of an indium tin oxide film with a positive charged polymer and the employment of a antimony doped tin oxide film were investigated in this work in order to overcome the repulsion induced by similar charges of the protein and electrode. Human sulfite oxidase and its separated heme-containing domain are able to direct exchange electrons with the supporting material. A study of a new approach for sulfite biosensing, based on enhanced direct electron transfer of a human sulfite oxidase immobilized on a gold nanoparticles modified electrode is reported. The spherical gold nanoparticles were prepared via a novel method by reduction of HAuCl4 with branched poly(ethyleneimine) in an ionic liquid resulting in particles of about 10 nm in hydrodynamic diameter. These nanoparticles were covalently attached to a mercaptoundecanoic acid modified Au-electrode and act as platform where human sulfite oxidase is adsorbed. An enhanced interfacial electron transfer and electrocatalysis is therefore achieved. UV-Vis and resonance Raman spectroscopy, in combination with direct protein voltammetry, were employed for the characterization of the system and reveal no perturbation of the structural integrity of the redox protein. The proposed biosensor exhibited a quick steady-state current response, within 2 s and a linear detection range between 0.5 and 5.4 μM with high sensitivity (1.85 nA μM-1). The investigated system provides remarkable advantages, since it works at low applied potential and at very high ionic strength. Therefore these properties could make the proposed system useful in the development of bioelectronic devices and its application in real samples. Finally protein with high structure complexity such as the xanthine dehydrogenase from Rhodobacter capsulatus and the mouse aldehyde oxidase homolog 1 were spectroelectrochemically studied. It could be demonstrated that different cofactors present in the protein structure, like the FAD and the molybdenum cofactor, are able to directly exchange electrons with an electrode and are displayed as a single peak in a square wave voltammogram. Protein mutants bearing a serine substituted to the cysteines, bounding to the most exposed iron sulfur cluster additionally showed direct electron transfer which can be attributable to this cluster. On the other hand a mediated spectroelectrochemical titration of the protein bound FAD cofactor was performed in presence of transparent iron and cobalt complex mediators. The results showed the formation of the stable semiquinone and the fully reduced flavin. Two formal potentials for each single electron exchange step were then determined.