Conducting polymer is a rapidly developing area of research due to its potential in combining the physical properties of polymers with electrical properties previously found only in inorganic systems. These conducting polymers owe their unique properties to a conjugated polymer backbone and become conducting upon oxidation or reduction. Melanin, a biopolymer, possess a conjugated backbone required of a conducting polymer, and has shown properties of an amorphous semiconductor. However, there has not been much study done in this area despite its potential, and this is partially due to the lack of processing methods as melanin is generally synthesised as an intractable powder. Thus, a better synthetic method was required, and a possible solution is the use of electrochemical synthesis. In our previous study we have shown that melanin can be synthesised electrochemically as a free-standing film, which was the first step towards the use of melanin as a bulk material. This project aims to continue from this preliminary work, investigating the various synthetic parameters and possible modifications as well as investigating possible applications for the electrochemically synthesised melanin film.

Diss. (sammanfattning) Stockholm : Karol. inst., 2005. / Härtill 4 uppsatser.

Thesis (Ph.D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2008. / Committee Chair: Tolbert, Laren; Committee Member: Collard, David; Committee Member: Lyon, Andrew; Committee Member: Srinivasarao, Mohan; Committee Member: Wilkinson, Angus

Polymer solar cells are promising in that they are inexpensive to produce, and due to their mechanical flexibility have the potential for use in applications not possible for more traditional types of solar cells. The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor material in the active layer. Understanding the connection between morphology and performance as well as how to control the morphology, is therefore of great importance. Furthermore, improving the lifetime of polymer solar cells has become at least as important as improving the efficiency.   In this thesis, the relation between morphology and solar cell performance is studied, and the material stability for blend films of the thiophene-quinoxaline copolymer TQ1 and the fullerene derivatives PCBM and PC70BM. Atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM) are used to investigate the lateral morphology, secondary ion mass spectrometry (SIMS) to measure the vertical morphology and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to determine the surface composition. Lateral phase-separated domains are observed whose size is correlated to the solar cell performance, while the observed TQ1 surface enrichment does not affect the performance. Changes to the unoccupied molecular orbitals as a result of illumination in ambient air are observed by NEXAFS spectroscopy for PCBM, but not for TQ1. The NEXAFS spectrum of PCBM in a blend with TQ1 changes more than that of pristine PCBM. Solar cells in which the active layer has been illuminated in air prior to the deposition of the top electrode exhibit greatly reduced electrical performance. The valence band and absorption spectrum of TQ1 is affected by illumination in air, but the effects are not large enough to account for losses in solar cell performance, which are mainly attributed to PCBM degradation at the active layer surface. / The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor material in the active layer. Understanding the connection between morphology and performance as well as how to control the morphology, is therefore of great importance. Furthermore, improving the lifetime has become at least as important as improving the efficiency for polymer solar cells to become a viable technology.   In this work, the relation between morphology and solar cell performance is studied as well as the material stability for polymer:fullerene blend films. A combination of microscopic and spectroscopic methods is used to investigate the lateral and vertical morphology as well as the surface composition. Lateral phase-separated domains are observed whose size is correlated to the solar cell performance, while the observed surface enrichment of polymer does not affect the performance. Changes to the unoccupied molecular states as a result of illumination in ambient air are observed for the fullerene, but not for the polymer, and fullerenes in a blend change more than pristine fullerenes. Solar cells in which the active layer has been illuminated exhibit greatly reduced electrical performance, mainly attributed to fullerene degradation at the active layer surface. / <p>Paper 2 ingick som manuskript i avhandlingen. Nu publicerad. </p>

Conjugated Polymers have attracted a great deal of research interest in recent years due to their optoelectronic properties which makes them suitable for applications in organic light-emitting devices (OLEDs) and organic photovoltaics. Their properties are strongly dependent on the electron-electron and electron-nuclear interactions as well as the disorder which is present in almost all systems at finite temperatures. In this thesis the optical properties of electronically neutral conjugated polymers will be investigated. The results obtained are general and applicable to a wide range of parameters. In order to compare these to experiment the optical properties of poly( paraphenylene), poly(para-phenylene vinylene), and derivatives have been calculated. In these polymers the primary photoexcitations are Frenkel excitons which can be described by the Frenkel-Holstein Hamiltonian, which explicitly takes into account the exciton-nuclear coupling. Disorder can be introduced into this model both as diagonal and off-diagonal disorder within the Hamiltonian. First the optical transitions in ordered, linear conjugated polymers are investigated. It is found that the length of the polymer has a direct spectroscopic signature in the emission spectrum. When off-diagonal disorder is introduced the excitons localise on portions of the chain and the length of these portions, the conjugation length, then shows a clear emission signature. As such, a disordered polymer can be described theoretically as a chain of shorter segments, which define chromophores in a polymer context. Following from these calculations the role of conformation was investigated and effects were observed that greatly determine the optical properties of non-linear polymers. Most notable the Herzberg-Teller effect, which renders symmetrically forbidden transitions weakly allowed and greatly affects the absorption and emission spectra. The signatures observed in these spectra allow the determination of the (coarse grained) conformation of the polymer, something that has been difficult to measure directly.

xvii, 159 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Experimental studies on mix-conducting hetero-ionic junctions of anionically (PA A ) and cationically (PA C ) functionalized polyacetylene ionomers, as well as each individual ionomer, in thin-film sandwich configurations are reported for the purpose of better understanding the interaction between ionic and electronic charge transports in mixed ionic-electronic conductor (MIEC) systems. The transport of ions in both individual ionomers as well as their hetero-ionic junction was investigated via small-amplitude AC impedance spectroscopy in the absence of significant interference from the electronic charge transport. Modeling of the impedance results reveal important information about the materials such as: ion conductivity, activation energy of ion conduction, ion hopping frequency, dielectric constant, interfacial capacitance, and estimates of effective ion density. Electrochemical injection of electronic charge carriers into PA A and PA C from gold electrodes was monitored to determine the applied potentials needed to drive hole and electron injection into each ionomer. It is found that for both ionomers, the onset voltages for unipolar and bipolar charge injection are similar, and holes can be injected at close to zero bias. The responses of the complete Au|PA A |PA C |Au hetero-ionic junction, as well as each constituent ionomer layer in Au|Ionomer|Au configuration, to various stepping biases were investigated through current-voltage and impedance measurements to study the origin of the asymmetric current-voltage response observed in the hetero-ionic junction. Analysis of the results reveal a working mechanism of a mix-conducting junction that is fundamentally different from that of a purely electronic pn junction. When illuminated with light, the Au|PA A |PA C |Au junction exhibits unidirectional photovoltage and photocurrent with the PA A side at higher potential, while the Au|PA A |Au and Au|PA C |Au samples exhibit symmetric photoresponses. The efficiency of photocurrent generation in the Au|PA A |PA C |Au junction was found to be strongly dependent on the direction of illumination and on the sample thickness. These observations can be explained by the difference in the mobility of holes and electrons and the existence of a built-in ionic space charge region at the PA A |PA C interface. A mechanism of photoresponse unique to MIEC junctions was proposed, and the magnitude of built-in potential was estimated. / Committee in charge: J David Cohen, Chairperson, Physics; Mark Lonergan, Advisor, Chemistry; Roger Haydock, Member, Physics; David Strom, Member, Physics; David Tyler, Outside Member, Chemistry

Os compostos carbonílicos no estado triplete (CCT) são considerados espécies reativas de oxigênio uma vez que possuem comportamento químico semelhante ao de radicais alcoxil. Quando formadas em sistemas biológicos, estas espécies podem estar envolvidas tanto em processos benéficos quanto deletérios ao organismo, como é o caso da lipoperoxidação, onde CCT não só são gerados como também iniciam ou amplificam o processo. Visando estudar a capacidade de dienos conjugados de suprimir a energia triplete de tais compostos, de forma a diminuir seus efeitos deletérios, determinou-se as constantes de supressão, para quatro diferentes dienos, de acetona triplete gerada pela da termólise do tetrametil-1 ,2- dioxetano e pelo sistema enzimático isobutanal/ \"horseradish peroxidase\"/O2 Todos os dienos apresentaram constantes de supressão de ordem difusional. Foi analisada também a forma pela qual os dienos suprimem a acetona triplete e concluiu-se que tanto dienos com hidrogênios alílicos (2,4-hexadienoato e seu éster etílico), potencialmente abstraíveis, quanto dienos sem estes hidrogênios (2 ,4-pentadienoato e seu éster metílico), suprimem a acetona por um processo físico de transferência de energia, que leva à sua fotoisomerização cis,trans. A reatividade destes dienos frente a espécies reativas de oxigênio comumente formadas em sistemas de lipoperoxidação, como o oxigênio singlete, radicais hidroxil, peroxil e superóxido, foi também testada, mostrando que nenhum dos dienos apresenta atividade sequestradora destas espécies. Experimentos preliminares de lipoperoxidação em sistemas biomiméticos (mitocôndrias e microssomos isolados de fígado de rato), mostraram que o trans, trans-2,4-hexadienoato de etila é capaz de inibir o inchamento mitocondrial induzido por benzofenona triplete e de suprimir a quimiluminescência de microssomos induzida por Fe2+/ ascorbato. Concluiu-se assim que dienos conjugados, contendo ou não hidrogênios alílicos, podem ser usados como supressores específicos de compostos carbonílicos triplete em sistemas biológicos e contribuir para o esclarecimento dos mecanismos de reação destes processos. / Triplet carbonyls can be named reactive oxygen species once they behave chemically as alkyloxyl radicals and therefore can potentially drive beneficial and deleterious processes in biological systems. In the case of lipid peroxidation, these species have been found not only to be reaction products but also to amplify the radical chain by hydrogen abstraction of polyunsatured lipid molecules. With the aim of finding efficient and reliable chemical probes for triplet carbonyls, we studied here the quenching properties of conjugated dienes, namely 2,4-hexadienoate and 2,4- pentadienoate anions and corresponding alkyl esters, upon triplet acetone generated either chemically (thermolysis of tetramethyl-1 ,2-dioxetane) or enzymically (aerobic oxidation of isobutanal/horseradish peroxidase). As expected, the quenching rate constants were found to be diffusion controlled, although those for the pentadienoate derivatives were 3-fold lower than those measured for the hexadienoates. Therefore, independently of the presence of allylic hydrogens in the diene probe, the triplet acetone quenching occurred by a physical process followed by cis,trans-isomerization, without hydrogen abstraction from the quencher. The reactivity of the studied dienes towards oxygen reactive species known to be formed during lipid peroxidation, such as singlet oxygen, and peroxyl, hydroxyl and superoxide radicals, was also investigated to assure they would not interfere with the radical lipoperoxidation chain. Indeed, none of the dienes showed antioxidant activity on classical model systems. Preliminary experiments with model systems widely used to study lipid peroxidation showed that the trans, trans-ethyl sorbate can inhibit the mitochondrial swelling induced by enzymically formed triplet benzophenone and to quench the chemiluminescence of microsome preparations challenged with iron/ascorbate. This is in agreement with reported work showing that the lipid peroxidation chain associated with mitochondria permeabilization and polyunsaturated fatty acid peroxidation is amplified by intermediate triplet carbonyl products. Altogether our data indicate that conjugated dienes can be used as specific quenchers of triplet carbonyls formed in biological systems without reacting with other reactive intermediates.

Ce travail de thèse concerne l'élaboration de nouveaux copolymères à faible bande interdite de type « push-pull », constitués par une unité donneuse d'électrons (push) et une unité acceptrice d'électrons (pull) en modulant les relations structures-propriétés par stratégie de synthèse. Des copolymères constitués par des unités acceptrices d'électrons (dérivées du benzothiadiazole ou du thienopyrrolodione) et donneuses d'électrons (3,6-carbazole, 2,7-carbazole, dialkoxybezodithiophène) ont été obtenus par différentes méthodes de couplage carbone carbone (C-C). Des études physico-chimiques par des techniques de spectroscopie (UV-visible), d'électrochimie (voltampérométrie cyclique), de diffraction de rayon X et d'analyses thermogravimétriques ont été utilisées pour élucider les propriétés fondamentales des copolymères pour des applications dans le domaine du photovoltaïque organique. Des études de RPE sous éclairement couplées avec de la simulation théorique ont permis l'étude des différents transferts électroniques dans les copolymères push-pull en mélange avec deux types de matériaux accepteurs d'électrons (le PCBM et les nanocristaux de CuInS2). Des calculs de DFT ont mis en évidence une bonne corrélation avec les résultats expérimentaux. Des tests préliminaires en hétérojonctions volumiques sur les (co)polymères ont étés réalisés mettant en évidence les facteurs clés limitant les performances des dispositifs de photovoltaïques organiques. / In this work, the attention was focused on the synthesis of new low-band gap polymers and on the adopted chemical strategy aims on developing the so called push-pull copolymers: formed by a donor (push) and an acceptor (pull) electron unit in the polymer backbone. It was demonstrated that exploited building block approach can lead to copolymers with tunable physical properties. By selecting acceptor (benzothiadiazole or thienopyrrolodione derivatives) and donor (3,6-carbazole, 2,7-carbazole, dialkoxybenzodithiophene) units of different DA strength, it is possible to prepare copolymers through several C-C coupling methods. Detailed physico-chemical studies using complementary spectroscopic, electrochemical, diffraction and thermal techniques enabled the determination of synthesized push-pull copolymers properties, which are crucial for their photovoltaic application. Detailed studies on EPR under illumination and EPR tracing allowed the characterization of various electronic transfers in the presented and particularly designed push-pull copolymers, blended with two types of electron acceptor materials: PCBM and CuInS2 nanocrystals. DFT calculations supported the experimental results. Preliminary tests on synthesized copolymers were carried out taking into account all limiting factors concerning the device fabrication.

Made available in DSpace on 2014-06-11T19:28:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-25Bitstream added on 2014-06-13T19:16:09Z : No. of bitstreams: 1 pivaro_tm_me_jabo.pdf: 588445 bytes, checksum: 95df0e35e0500ea8feeb836651cb1172 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / No presente trabalho, avaliou-se o efeito do processo de maturação na qualidade da carne do músculo Longissimus de 35 tourinhos da raça Nelore confinados por 96 dias e abatidos com peso de 532,17 ± 30,25kg e 24 meses de idade. Os animais foram alimentados com uma dieta controle sem a adição de óleo e outras quatro dietas contendo diferentes fontes de óleo (soja ou linhaça) protegido ou não da degradação ruminal. Após o abate e 24 horas de resfriamento foram retirados 3 bifes de 2,5cm de espessura entre a 12a e 13a costelas do músculo Longissimus, posteriormente embalados à vácuo e maturados em estufa B.O.D. à temperatura de 2oC durante 7, 14 e 21 dias. Em seguida, foram analisadas as seguintes características: força de cisalhamento, ph, cor, perdas na maturação e composição química da carne assada. Após liofilização, o extrato etéreo foi extraído, metilado e as leituras realizadas por cromatografia gasosa. O delineamento estatístico utilizado foi em blocos casualizados, sendo 5 tratamentos, em 7 blocos e utilizadas 4 medidas repetidas no tempo. As variáveis foram avaliadas por meio de análise de variância e teste t Student à 5% de probabilidade e para as características sensoriais da carne foi utilizado o teste não paramétrico de Kruskal-Wallis. Houve efeito significativo para as variáveis matéria seca, extrato etéreo e matéria mineral. A força de cisalhamento apresentou diferenças entre os grupos de bifes maturados, (5,97; 4,31; 3,25 e 2,96kgf/cm2, para 0, 7, 14 e 21 dias de maturação, respectivamente), sendo que o tempo 14 e 21 foram mais macios que o tempo 7, e este, mais macio que o tempo 0. O ph apresentou diferença entre a carne in natura e os períodos de maturação. Houve efeito significativo para a maturação das variáveis luminosidade, intensidade da cor vermelha e intensidade da cor amarela. As perdas por exsudação na maturação... / In this study, we assess the effect of the ageing process in the meat quality of Longissimus muscles from 35 Nellore bulls young bulls confined for 96 days and slaughtered weighing 532.17 ± 30.25 kg and 24 months of age. The animals were fed with five different diets: the first one was a control diet, without oil and the other four diets containing different oil sources (soy or flaxseed) protected or not from ruminal degradation. After slaughter and 24 hours of cooling, 3 samples with 2.5 cm thickness were removed between the 12th and 13th ribs of Longissimus muscles and subsequently vacuum packaged and aged in an environmental chamber at a temperature of 2o C for 7, 14 and 21 days. We assess the characteristics: shear force, pH, color, ageing losses, chemical composition and fatty acids of meat. The fatty acids were assess by gas chromatography. Variables were evaluated by analysis of variance and Student t test at 5% probability and the sensory characteristics of meat was used nonparametric Kruskal-Wallis test. Shear force differed between the ageing groups, (5.97; 4.31, 3.25 and 2.96 Kgf/cm2 to 0, 7, 14 and 21 days) the period 14 and 21 were softer than the period 7. The pH was different between the fresh beef and the other periods. There was a significant effect on the variable lightness, red color intensity and intensity of yellow color. The losses were larger as the period of ageing increased, and the period of 21 days showed 5.58% of losses. The sensory evaluation showed the difference to variable smoothness for the period of 7 days.. There was a significant effect on concentration of myristic acids (C14: 0), miristoleico \ (C14: 1), pentadecanoic (C15: 0), palmitic (C16: 0), palmitoleic (C16: 1) vacênico (C18: 1 n7) and oleic (C18: 1 n9). In contrast there was an increase in the levels of stearic (C18: 0), linoleic (C18: 2 n6) eicosenoic (C20: 1 n9), eicosadienoico (C20: 2) ... (Complete abstract click electronic access below)

Made available in DSpace on 2014-06-11T19:22:54Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-08-30Bitstream added on 2014-06-13T19:49:15Z : No. of bitstreams: 1 pereira_cj_me_sjrp.pdf: 4585703 bytes, checksum: 2f751deb0c13952d939c128cd3139b81 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Esta dissertação de mestrado apresenta um estudo sobre as propriedades de foto-geração de portadores de carga e sua condução em dispositivos optoeletrônicos orgânicos construídos em estruturas de diodo tipo sanduíche – ITO/Polímero/Metal – sendo empregados como sua camada ativa dois polímeros orgânicos conjugados distintos, o poly[2-methoxy-5-(3’,7’-dimethyloctyloxy)-1,4-phenylene vinylene) ou MDMO-PPV, e o copolímero fenil substituído do poli(p-fenileno vinileno) conhecido como Super Yellow® ou SY-PPV. As características da foto-geração e de transporte de cargas dos dispositivos foram determinada através da análise de medidas de corrente-tensão (I-V) em regime d.c., e de espectroscopia de impedância/capacitância no regime da frequência (1Hz-1MHz). As propriedades elétricas dos dispositivos foram estudadas com os dispositivos iluminados em diferentes faixas de comprimentos de onda na região do visível, a diferentes intensidades, e comparadas com as propriedades dos dispositivos no escuro. Para iluminação através do eletrodo transparente (ITO), tanto um efeito fotovoltaico quanto fotocondutivo foram claramente observados. Em particular, o efeito da foto-geração no espectro de capacitância em função da frequência foi estudado em maiores detalhes. Um modelo semiempírico, levando em conta as distribuições de cargas espaciais devidas à foto-geração de portadores de carga e propriedades de transporte como, por exemplo... / This dissertation presents a study on the properties of photo-generation and conduction of charge carriers in organic optoelectronic devices built in sandwich diode structures – ITO/Polymer/Metal – with the active layer comprised by two different organic conjugated polymers: poly[2-methoxy-5-(3’,7’-dimethyloctyloxy)-1,4-phenylene vinylene) MDMO-PPV, and a phenyl-substituted copolymer of poly(p-phenylene vinylene) known as Super Yellow®, SY-PPV. The photo-generation and charge transport properties have been determined from the analysis of current-voltage (I-V) measurements in the d.c. regime and impedance/capacitance spectroscopy in the regime of frequency (1Hz-1MHz). The electrical properties of the devices were studied with the devices under illumination, in different ranges of wavelength in the visible region, at different intensities and compared with the properties of devices in the dark. By illuminating the devices through the transparent electrode (ITO), both photovoltaic and photoconductive effects were clearly observed. Particularly, the photo-generation effect in the frequency-dependent capacitance spectrum was studied in detail. A semiempirical model taking into account the spatial distribution of charges due the photo-generation and material properties... (Complete abstract click electronic access below)