Nanopartiklar (NP) erbjuder unika möjligheter för medicinska tillämpningar, inklusive kontrollerad frisättning av cancerläkemedel, användning som bildkontrast vid avbildningsprocedurer eller hypertermisk behandling av cancerceller. Flash nanoprecipitation (FNP) producerar NPs för att kombinera dessa tillämpningar i en snabb, billig och skalbar beläggningsprocess. Användning av FNP med en Multi-Inlet Vortex Mixer (MIVM) är en lovande metod för att enkelt belägga hydrofoba oljesyra järnoxid NP (IONP) med olika biokompatibla block-copolymerer. Amfifila block-copolymerer baserade på hydrofil polyetylenglykol (PEG) och hydrofob poly(laktid) (PLA), poly(laktid-co-glykolid) (PLGA) eller poly(kaprolakton) (PCL) syntetiserades framgångsrikt. Den organiska katalysatorn 1,8-diazabicyclo[5.4.0]undec-7-en (DBU) användes för att öka biokompatibiliteten hos de resulterande polymererna PEG-PLA, PEG-PL7,5KG2,5KA och PEG2K-PCL2K. Syntes av hydroxylterminerad poly(akrylsyra) (PAA-OH) följt av polymerisation med PLGA prövades. De amfifila blockpolymererna användes i kombination med stabilisatorn polysorbat 80 (Tween80®) i FNP för att bilda nakna polymera NP med en MIVM som reaktor. DLS och STEM bekräftade partikelstorlekar mellan 50 - 100 nm. Tillsatsen av 13 ± 2 nm hydrofoba oljesyra-IONPs gav en ökning av partikelstorleken samt en ökning av partikelstabiliteten över tid. STEM-bilder visade att enstaka IONPs fästs på utsidan av de polymera NPs. Hydrofoba interaktioner mellan polymeren och oleinsyra-IONPs är möjliga. För att uppnå inkapsling av oljesyra-IONPs bör justeringar av processparametrarna för FNP övervägas i framtida forskning. Ytterligare experiment krävs för att utforska möjliga läkemedelstillsatser, frisättningsmekanismer och hypertermi hos de polymerbelagda IONP-partiklarna. / Nanoparticles (NPs) offer unique possibilities for medical applications, including the controlled release of cancer drugs, the use as imaging contrast during imaging procedures or the hyperthermic treatment of cancer cells. Flash nanoprecipitation (FNP) produces NPs to combine these applications in a fast, cheap, and scalable coating process. The use of FNP with a Multi-Inlet Vortex Mixer (MIVM) is a promising method to easily coat hydrophobic oleic acid iron oxide NPs (IONPs) with various biocompatible block-copolymers. Amphiphilic block-copolymers based on hydrophilic polyethylene glycol (PEG) and hydrophobic poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA) or poly(caprolactone) (PCL) were successfully synthesized. The organic catalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was used to increase biocompatibility of the resulting polymers PEG-PLA, PEG-PL7.5KG2.5KA and PEG2K-PCL2K. The synthesis of hydroxyl terminated poly(acrylic acid) (PAA-OH) followed by the polymerization with PLGA was attempted. The amphiphilic block-copolymers were used in combination with the stabilizer polysorbate 80 (Tween80®) in FNP to form bare polymeric NPs using a MIVM as the reactor. DLS and STEM confirmed particle sizes between 50 - 100 nm. The addition of 13 ± 2 nm hydrophobic oleic acid IONPs yielded an increase in particle size as well as increase in particle stability over time. STEM images showed attachment of single IONPs to the outside of the polymeric NPs. Hydrophobic interactions between the polymer and oleic acid IONPs are possible. To achieve encapsulation of the oleic acid IONPs, adjustments to the process parameters of FNP should be considered in future research. Additional experiments are required to explore possible drug addition, release mechanisms and hyperthermia behavior of the polymer coated IONPs particles.

Zur Entwicklung eines effizienten Verfahrens zur CO2-Hydierung im Dreiphasensystem erfolgten in dieser Arbeit Untersuchungen zur Optimierung des Katalysatorsystems, zum Screening nach neuen geeigneten Lösungsmitteln und zum Einfluss der Prozessführung. Durch Variieren des Trägersystems und der Präparationsmethode ergaben sich sieben Kupferkatalysatoren, welche sich in ihren Eigenschaften und ihrer katalytischen Aktivität unterschieden. Zudem gelang die Immobilisierung von Kupferkatalysatoren auf Aluminiumoxid und auf Glas. Es wurde eine kontinuierliche Anlage mit Rieselbettreaktor entwickelt und in Betrieb genommen, welche die Durchführung der CO2-Hydrierung in Gasphase und im Dreiphasensystem bei bis zu 90 bar ermöglicht. Im Batchversuch zeigte sich der Einfluss der Lösungsmittel auf die Effizienz des Katalysators. Vielversprechende Lösungsmittel wurden dann zur Methanolsynthese im kontinuierlichen Prozess eingesetzt, um den Einfluss der Prozessbedingungen zu untersuchen.

Melanoidin, a high molecular-weight heterogeneous pollutant in the effluents of molasses-using industries, poses a significant threat to the environment due to its non-biodegradability, unpleasant odour, and harmful effect. Various advanced oxidation processes (AOPs) that produce reactive oxygen species (ROS) are used for the degradation of melanoidins. Heterogeneous photo-Fenton process has emerged as a promising alternative approach in wastewater treatment owing to its enhanced catalytic activity, lower hydrogen peroxide (H2O2) consumption, and reusability of the catalyst. In this work, we investigated the photo-Fenton oxidation of melanoidins using heterogeneous catalyst ZnO@SnOx@nZVI supported on a flexible substrate. The effects of reaction pH, amount of catalyst and H2O2 on color and chemical oxygen demand (COD) removal, as well as the removal kinetics, were studied. It is found that the developed heterogeneous catalyst can lead to 97.3% decolorization of melanoidin (7000 COD) after 4 hours irradiation of simulated sunlight at pH 6 with a much lower dosage of H2O2 than the stoichiometric ratio with respect to COD. The generation of ·OH free radicals and residual H2O2 were monitored to understand the mechanism of melanoidin degradation at near-neutral pH with insufficient H2O2. The findings of this work have significant implications in treatment of non-biodegradable organic pollutants, owing to the advantages in avoiding low pH treatment condition, reducing the cost of H2O2, and enhanced chemical stability of photo-Fenton catalyst. / Melanoidin, en heterogen förorening med hög molekylvikt i avloppsvatten från industrier som använder melass, utgör ett betydande hot mot miljön på grund av dess icke-biologiska nedbrytbarhet, obehagliga lukt och skadliga effekt. Olika avancerade oxidationsprocesser (AOP) som producerar reaktiva syreföreningar (ROS) används för nedbrytning av melanoidiner. Heterogen foto-Fenton-process har framstått som ett lovande alternativ för avloppsrening på grund av dess förbättrade katalytiska aktivitet, lägre väteperoxid (H2O2) förbrukning och återanvändbarhet av katalysatorn. I detta arbete undersökte vi foto-Fenton-oxidationen av melanoidiner med hjälp av heterogen katalysator ZnO@SnOx@nZVI som stöds på ett flexibelt substrat. Effekterna av reaktionens pH, mängden katalysator och H2O2 på färg och avlägsnande av kemisk syreförbrukning (COD), liksom avlägsnandets kinetik, studerades. Det visade sig att den utvecklade heterogena katalysatorn kan leda till 97,3% avfärgning av melanoidin (7000 COD) efter 4 timmars bestrålning av simulerat solljus vid pH 6 med en mycket lågre dosering av H2O2 än det stökiometriska förhållandet med avseende på COD. Generering av ·OH fria radikaler och kvarvarande H2O2 övervakades för att förstå mekanismen för nedbrytning av melanoidin vid nära neutralt pH med otillräcklig H2O2. Resultaten av detta arbete har betydande konsekvenser vid behandling av icke- biologiskt nedbrytbara organiska föroreningar, på grund av fördelarna med att undvika behandlingsförhållanden med lågt pH, minska kostnaden för H2O2 och förbättrad kemiska stabilitet hos foto-Fenton-katalysatorn.

In this paper we present a comparison of aerogels which are dried under different conditions. Of those, most important are the solvent, temperature, and pressure. Criteria of comparison rely mostly on results from analysis of nitrogen adsorption experiments, as well as transmission electron microscopy imaging. Platinum loaded indium oxide aerogels were picked as a model system for this study as they can be used as highly effective heterogeneous catalysts in methanol steam reforming. The compared drying methods include supercritical drying from CO2, supercritical CO2 - ethanol mixture, freeze drying from tert-butanol and ambient conditions drying from acetone and 1-Methoxyheptafluoropropane. High porosities and large specific surface areas can be achieved via supercritical, freeze- and ambient conditions drying, while retaining the original gel morphology in this system for most methods except freeze drying and ambient conditions drying from acetone.

Im Gegensatz zu „festen Säuren“ sind „feste Basen“ wesentlich seltener Untersuchungsgegenstand in ihrer Anwendung als Katalysatoren in der heterogenen Katalyse. In der vorliegenden Promotionsarbeit wurden entgegen diesem Trend die Herstellung, Charakterisierung und Anwendung basischer Oxide sowie modifizierter Oxide in ihrer Eignung als feste Basen in der Katalyse untersucht. Zu diesen Katalysatoren gehören MgO, hergestellt nach unterschiedlichen Methoden, Kalium modifiziertes ZrO2, calcinierte Mg-Al Hydrotalcite und ein neuartiges Katalysatorsystem auf der Basis von Mg(O,F)-Kompositionen, die zum ersten Mal nach einem Sol-Gel-Fluorierungsverfahren hergestellt wurden. Die Katalysatoren wurden mittels N2 Adsorptions/Desorptionsuntersuchungen (BET), XRD, FTIR, XPS, TG-DTA-DTG und MAS NMR untersucht. Die Säure-Basen-Eigenschaften der Katalysatoren wurden durch TPD, FTIR Spektroskopie und Mikrokalorimetrie charakterisiert und mit den katalytischen Eigenschaften korreliert. Calcinierte Mg-Al Hydrotalcite und Mg(O,F) waren in diesem Zusammenhang am stärksten aktiv und auch selektiv wie für die Flüssigphasenreaktion der Michael-Addition von CH aciden Verbindungen mit Methylvinylketon gezeigt wurde. / In contrast to solid acid catalysts, much fewer efforts have been made to study solid base catalysts. In this thesis, preparation, characterization and application of oxides and modified oxide as solid base catalysts were studied. The catalysts include MgO prepared by different methods, potassium-modified ZrO2, calcined Mg-Al hydrotalcites, and a novel catalyst system Mg(O,F), which was prepared by sol-gel method for the first time. The catalysts were studied by N2 adsorption/desorption measurement, XRD, FTIR, XPS, TG-DTA-DTG and NMR. Acid-base properties of the catalysts were investigated by TPD, FTIR spectroscopy and microcalorimetry to correlate with the catalytic behavior. Calcined Mg-Al hydrotalcite and Mg(O,F) are found to be highly active and selective catalysts for liquid-phase Michael additions of CH-acid compounds with methyl vinyl ketone.

Der Cr2O3 ist einer der wichtigsten Katalysatoren im Chlor/Fluor (Cl/F) Austauschreaktionen für die Produktion von chlorofluorocarbon (CFC) Alternativen. Es wird als ein ausgezeichneter heterogener Katalysator für Fluorierung Reaktionen gegründet. Die Dismutierung von CCl2F2 wurde verwendet, um die Wirkung von Halogenierung von Chrom(III) Oxyd auf Cl/F-Austauschreaktionen zu untersuchen und um den Unterschied zwischen den inaktiven und aktiven Katalysatoren herauszufinden. Die heterogenen Reaktionen wurden in einem tubular-flow Ni Reaktor und auch unter simulierten Reaktionsbedingungen in einem Reaktor durchgeführt, wo nach der Reaktion die Photoelektronspektroskopie (XPS) und die Auger-Elektronspektroskopie (XAES) Analysen konnte direkt ohne Luftkontakt, unter so genannt "in - situ" Bedingungen gefolgt werden. Es wurde gezeigt, dass die Probleme der Behandlung von Cr (III) 2p Photoelektronenspektren so gelöst werden können, dass ihnen relevante Daten für die chemische Charakterisierung von Oberflächen entnommen werden können. Hochaufgelöste Photoelektronspektroskopie von Cr2O3 Pulverproben zeigte deutlich die Existenz von spektralen Strukturen, die mit Multiplet-Aufspaltungen im jeweiligen Cr 2p Spektrum verbunden sind. Das Spektrum kann durch eine Peakfit-Analyse vertieft interpretiert werden in dem die Anfangswerte für die Peakparameter der Multiplet-Strukturen den jeweiligen Cr L2,3 XANES Spektren entnommen werden. Vom theoretischen Gesichtspunkt sollte dasselbe Verfahren auch eine Analyse der Cr 2p Photoelektronenspektren von alpha-CrF3, CrCl3 und anderen Chrom (III) Verbindungen ermöglichen. Die Unterschiede, die im Experiment für die Cr2O3, alpha-CrF3 und CrCl Photoelektronenspektren beobachtet werden, deuten auf die Tatsache, dass, obwohl in all diesen Fällen dieselben Multiplet-Aufspaltungen für Cr3+ erwartet werden, individuelle Einflüsse der Symmetrie und Ligandenfelder die Endgestalt des jeweiligen Cr 2p Photoelektronenspektrums definieren. Eine Analyse von Cr 3s Spektren kann zusätzlich wertvolle Finger-print Informationen zu chemischen Zuständen von Chrom in Cr (III) Verbindungen erbringen. Sowohl ex-situ als auch ´´in-situ´´ ESCA zeigen, dass sobald CCl2F2 zu Cr2O3 an 390 °C geführt wird, Fluorierung sowie Chlorierung an der Katalysator-Oberfläche findet statt. Wenn die XPS Oberflächenzusammensetzung etwa 4 Atom - % Fluorierung und 6 Atom - %-Chlorierung erreicht, wird die maximale katalytische Aktivität erhalten. Die längeren Reaktionszeiten ändern bedeutsam die erhaltene Oberflächenzusammensetzung von aktiviertem Chrom(III) Oxyd nicht. Der Fluorierung und Chlorierung von Chrom(III) Oxyd wurden weiter durch verschiedenen HF und HCl Behandlungen ebenso untersucht. Die aktivierten Chrom(III) Oxyd Proben und Referenzproben mit der weithin bekannten chemischen Struktur wurden auch durch Kantennahe Röntegenabsorptionsuntersuchungen (XANES), Flugzeit-statischesekundärionenmassenspektroskopie (TOF-SSIMS), Rasterelektronenmikroskopie (SEM), Fluor-Festkörper-NMR, Pyridin-FTIR, Nasschemie (F und Cl) Analyse, Pulver Röntgensbeugung (XRD) und Oberflächen (BET) Analyse untersucht. Die Ergebnisse der Referenzproben Cr2O3, Cr (OH) 3, CrF2 (OH), CrF3.3H2O, Alpha-CrF3, Beta-CrF3 und CrCl3 und aktivierte Cr2O3 Proben wurden verglichen. Die angewandten Charakterisierungsmethoden schlagen vor, dass die Bildung der Chrom-Oxydchlorid-Fluorid-Arten, bzw. Chrom-Oxyd Halogenide, an der Oberfläche ist genügend die katalytische Aktivität zu versorgen. Die Anwesenheit jedes CrF3 und/oder CrCl3 Phasen auf den aktivierten Chrom(III) Oxyd Proben wurde nicht entdeckt. / The Cr2O3 is one of the most important catalysts in the chlorine/fluorine (Cl/F) exchange reactions for the production of chlorofluorocarbon (CFC) alternatives. It is established as an excellent heterogeneous catalyst for fluorination reactions. The dismutation of CCl2F2 was used to probe the effect of halogenation of chromia on Cl/F exchange reactions in order to find out the difference between the inactive and active catalysts. The heterogeneous reactions were performed in a continuous flow Ni reactor and also under simulated reaction conditions in a reactor where after the reaction the X-ray photoelectron spectroscopy (XPS) and the X-ray excited Auger electron spectroscopy (XAES) analyses could be followed directly without air contact, under so called ´´in-situ´´ conditions. In order to be able to apply the Cr(III) 2p XPS analysis in the proper manner the spectroscopic features of the chromium(III) compounds of O, F and Cl were re-investigated. Latest generation of XPS spectrometers, which are able to analyze non-conductive powders with ultimate energy resolution, were used to reveal multiplet splitting features and satellite emission in the Cr 2p spectra. The energy positions of the multiplets were determined by total electron yield (TEY)- X-ray absorption near edge structure (XANES) spectroscopy. Using both high resolution XPS and XANES spectra a peak-fit analysis, which is also applicable for normally resolved Cr 2p XPS spectrum, was proposed. In order to overcome the known background problem by drawing the background in the broad Cr 2p window including the high binding energy satellite, a modified Shirley background, which is a combination of a linear and Shirley function, was used. Moreover, the spectroscopic features of the Cr(III) 3s XPS spectrum, which is relatively simpler than the Cr 2p one, were also surveyed. An alternative chemical analysis was proposed by using chemical state plots for Cr 3s. Both ex- and in-situ ESCA show that as soon as Cr2O3 is conducted to CCl2F2 at 390 °C fluorination as well as chlorination takes place at the catalyst surface. When the XPS surface composition reaches approximately 4 atom-% fluorination and 6 atom-% chlorination, maximum catalytic activity is obtained. Applying longer reaction times do not change significantly the obtained surface composition of the activated chromia. The fluorination and chlorination of chromia was further investigated by various HF and HCl treatments as well. The activated chromia samples and reference samples with well known chemical structure were also characterized by XANES, time of flight - static secondary ion mass spectroscopy (TOF-SSIMS), scanning electron microscopy (SEM), fluorine solid state NMR, pyridine-FTIR, wet chemical (F and Cl) analysis, X-ray powder diffraction (XRD) and surface area (BET) analysis. The results for the references Cr2O3, Cr(OH)3, CrF2(OH), CrF3.3H2O, alpha-CrF3, beta-CrF3 and CrCl3 and activated Cr2O3 samples were compared. The applied characterization methods suggest that the formation of chromium oxide chloride fluoride species, e.g. chromium oxide halides, at the surface is sufficient to provide catalytic activity. The presence of any CrF3 and/or CrCl3 phases on the activated chromia samples was not detected.

The aim of the present work was to screen the main methods for the synthesis of conjugated polymers for their suitability in the preparation of conductive polymer brushes. The main focus was put on the grafting of intrinsically soluble substituted regioregular polyalkylthiophenes because of their excellent optoelectronic properties. The resulting polymer films were characterized and their optoelectrical properties studied. For the first time, a synthesis of conductive polymer brushes on solid substrates using “grafting-from” method was performed. The most important, from my opinion, finding of this work is that regioregular head-to-tail poly-3-alkylthiophenes – benchmark materials for organic electronics - can be now selectively grafted from appropriately-terminated surfaces to produce polymer brushes of otherwise soluble polymers - the architecture earlier accessible only in the case of non-conductive polymers. In particular, we developed a new method to grow P3ATs via Kumada Catalyst Transfer Polymerization (KCTP) of 2-bromo-5-chloromagnesio-3-alkylthiophene. Exposure of the initiator layers to monomer solutions leads to selective chain-growth polycondensation of the monomers from the surface, resulting into P3AT brushes in a very economical way. The grafting process was investigated in detail and the structure of the resulting composite films was elucidated using several methods. The obtained data suggests that the grafting process occurs not only at the poly(4-bromstyrene) (PS-Br)/polymerization solution interface, but also deeply inside the swollen PS-Br films, penetrable for the catalyst and for the monomer The grafting process was investigated in detail and the structure of the resulting composite film was elucidated using ellipsometry, X-ray Photoelectron Spectroscopy (XPS), Rutherford backscattering spectroscopy (RBS), and Conductive atomic force microscopy (C-AFM). The obtained data suggests that the grafting process occurs not only at the poly(4-bromostyrene), PS-Br/polymerization solution interface, but also deeply inside the swollen PS-Br film, which is penetrable for the catalyst and the monomer. The process results in an interpenetrated PS-Br/P3HT network, in which relatively short poly(3-hexylthiophene), P3HT grafts emanate from long, cross-linked PS-Br chains. A further method investigated during our work was to covalently graft regioirregular P3HT to substrates modified by macromolecular anchors using oxidative polymerization of 3HT with FeCl3. P3HT layers with variable thicknesses from 30 nm up to 200 nm were produced using two steps of polymerization reaction. The P3HT obtained by oxidative polymerization had always an irregular structure, which was a result of the starting monomer being asymmetric, which is undesired for electronic applications. The third method for the production of conductive polymer brushes was to graft regioregular poly(3,3''-dioctyl-[2,2';5',2'']terthiophene) (PDOTT) by electrochemical oxidative polycondensation of symmetrically substituted 3,3''-dioctyl-[2,2';5',2'']terthiophene (DOTT). A modification of the supporting ITO electrode by the self-assembled monolayers (SAMs) of compounds having polymerizable head-groups with properly adjusted oxidative potentials was found to be essential to achieve a covalent attachment of PDOTT chains. The polymer films produced show solvatochromism and electrochromism, as well as the previous two methods. After polymerization, the next step towards building organic electronic devices is applying the methods obtained in nano- and microscale production. Block copolymers constitute an attractive option for such surface-engineering, due to their ability to form a variety of nanoscale ordered phase-separated structures. However, block copolymers containing conjugated blocks are less abundant compared to their non-conjugated counterparts. Additionally, their phase behaviour at surfaces is not always predictable. We demonstrated in this work, how surface structures of non-conductive block copolymers, such as P4VP-b-PS-I, can be converted into (semi)conductive P4VP-b-PS-graft-P3HT chains via a surface-initiated polymerization of P3HT (Kumada Catalyst Transfer Polymerization (KCTP) from reactive surface-grafted block copolymers. This proves that our method is applicable to develop structured brushes of conductive polymers. We believe that it can be further exploited for novel, stimuli-responsive materials, for the construction of sensors, or for building various opto-electronic devices. The methods developed here can in principle be adapted for the preparation of any conductive block copolymers and conductive polymers, including other interesting architectures of conductive polymers, such as block copolymers, cylindrical brushes, star-like polymers, etc. To this end, one needs to synthesize properly-designed and multi-functional Ni-initiators before performing the polycondensation.

Within process or manufacturing industries, the production of goods and services or the products themselves may have negative side effects such as pollution. An important task for environmental policy is to control and limit these pollutions, for example via regulatory measures. Although, the efficiency of such measures vary greatly between different industries and an increasingly important task for environmental policy is then to encourage companies to engage in environmentally motivated innovation. Governments can utilize other measures than regulation to indirectly decrease pollution. This thesis aims to analyze such activities and how it affects the innovativeness of wastewater treatment, refrigeration and automobile manufacturing industries. The aim is also to investigate how environmental policy is shaped by opinion, technology and relationships within and to an industry. In each of the cases, the current technical system was a major determinator for what could be accomplished in an industry. This was more or less dependent on foreign conditions, such as market, opinion and policy, but the domestic level of technical advancement was critical. The geographical breadth of the issue at hand was a major factor. Also, all three cases showed that each industry has, for good or bad, dominating players that either dictates or largely influences the pace of adoption of environmentally motivated innovation. Government agencies must understand these facts, inventively use the array of policy tools at hand and include both industry representatives and foreign piers to speed up environmentally motivated innovation.

A bifunctional imidazolium linker was used for the production of highly crosslinked element organic frameworks by Suzuki-coupling with tetrafunctional boronic acids. The resulting porous materials are good heterogeneous organocatalysts in the N-heterocyclic carbene-catalyzed conjugated umpolung of α,β-unsaturated cinnamaldehyde. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

The aim of the present work was to screen the main methods for the synthesis of conjugated polymers for their suitability in the preparation of conductive polymer brushes. The main focus was put on the grafting of intrinsically soluble substituted regioregular polyalkylthiophenes because of their excellent optoelectronic properties. The resulting polymer films were characterized and their optoelectrical properties studied. For the first time, a synthesis of conductive polymer brushes on solid substrates using “grafting-from” method was performed. The most important, from my opinion, finding of this work is that regioregular head-to-tail poly-3-alkylthiophenes – benchmark materials for organic electronics - can be now selectively grafted from appropriately-terminated surfaces to produce polymer brushes of otherwise soluble polymers - the architecture earlier accessible only in the case of non-conductive polymers. In particular, we developed a new method to grow P3ATs via Kumada Catalyst Transfer Polymerization (KCTP) of 2-bromo-5-chloromagnesio-3-alkylthiophene. Exposure of the initiator layers to monomer solutions leads to selective chain-growth polycondensation of the monomers from the surface, resulting into P3AT brushes in a very economical way. The grafting process was investigated in detail and the structure of the resulting composite films was elucidated using several methods. The obtained data suggests that the grafting process occurs not only at the poly(4-bromstyrene) (PS-Br)/polymerization solution interface, but also deeply inside the swollen PS-Br films, penetrable for the catalyst and for the monomer The grafting process was investigated in detail and the structure of the resulting composite film was elucidated using ellipsometry, X-ray Photoelectron Spectroscopy (XPS), Rutherford backscattering spectroscopy (RBS), and Conductive atomic force microscopy (C-AFM). The obtained data suggests that the grafting process occurs not only at the poly(4-bromostyrene), PS-Br/polymerization solution interface, but also deeply inside the swollen PS-Br film, which is penetrable for the catalyst and the monomer. The process results in an interpenetrated PS-Br/P3HT network, in which relatively short poly(3-hexylthiophene), P3HT grafts emanate from long, cross-linked PS-Br chains. A further method investigated during our work was to covalently graft regioirregular P3HT to substrates modified by macromolecular anchors using oxidative polymerization of 3HT with FeCl3. P3HT layers with variable thicknesses from 30 nm up to 200 nm were produced using two steps of polymerization reaction. The P3HT obtained by oxidative polymerization had always an irregular structure, which was a result of the starting monomer being asymmetric, which is undesired for electronic applications. The third method for the production of conductive polymer brushes was to graft regioregular poly(3,3''-dioctyl-[2,2';5',2'']terthiophene) (PDOTT) by electrochemical oxidative polycondensation of symmetrically substituted 3,3''-dioctyl-[2,2';5',2'']terthiophene (DOTT). A modification of the supporting ITO electrode by the self-assembled monolayers (SAMs) of compounds having polymerizable head-groups with properly adjusted oxidative potentials was found to be essential to achieve a covalent attachment of PDOTT chains. The polymer films produced show solvatochromism and electrochromism, as well as the previous two methods. After polymerization, the next step towards building organic electronic devices is applying the methods obtained in nano- and microscale production. Block copolymers constitute an attractive option for such surface-engineering, due to their ability to form a variety of nanoscale ordered phase-separated structures. However, block copolymers containing conjugated blocks are less abundant compared to their non-conjugated counterparts. Additionally, their phase behaviour at surfaces is not always predictable. We demonstrated in this work, how surface structures of non-conductive block copolymers, such as P4VP-b-PS-I, can be converted into (semi)conductive P4VP-b-PS-graft-P3HT chains via a surface-initiated polymerization of P3HT (Kumada Catalyst Transfer Polymerization (KCTP) from reactive surface-grafted block copolymers. This proves that our method is applicable to develop structured brushes of conductive polymers. We believe that it can be further exploited for novel, stimuli-responsive materials, for the construction of sensors, or for building various opto-electronic devices. The methods developed here can in principle be adapted for the preparation of any conductive block copolymers and conductive polymers, including other interesting architectures of conductive polymers, such as block copolymers, cylindrical brushes, star-like polymers, etc. To this end, one needs to synthesize properly-designed and multi-functional Ni-initiators before performing the polycondensation.