The research and development of organic electron donors is essential in the discovery of photodynamic therapy photosensitizers and catalysts, as well as in the fabrication of organic-based electronic devices. Recently, [pi]-extended tetrathiafulvalenes (exTTFs) have emerged as important organic donors due to their superb electronic properties. However, in general, exTTFs lack significant absorption in the visible and near-infrared portions of the electromagnetic spectrum, thereby limiting their utility. This doctoral dissertation depicts the author's efforts to address this inherent drawback of exTTFs by extending the electronic conjugation of tetrathiafulvalene moieties through pyrrole-based chromophores. The reported findings describe the design, synthesis, properties and potential applications of exTTFs with greatly enhanced absorption profiles. The first Chapter provides a brief historical overview on the history and development of [pi]-extended tetrathiafulvalenes. The various conjugated linkers utilized in exTTF systems are reviewed. In the latter part of the Chapter, emphasis is given to the applications in which exTTFs find use. Chapter 2, as the major focus of the dissertation, details the synthesis and characteristics of a quinoidal porphyrin-bridged exTTF, termed MTTFP. Several metalated complexes, including the Zn, Co, Cu, and Ni derivatives of MTTFP are reported. Additionally, the electrochemical, photophysical, and structural properties of MTTFPs are discussed. We also detail our efforts to synthesize and characterize both the one- and two-electron oxidized forms of MTTFPs. Finally, we discuss our efforts to reversibly switch thermodynamic electron transfer from ZnTTFP to Li@C₆₀ through coordination of axial ligands. Chapter 3 describes the formation of a 2:1 supramolecular ionic porphyrin complex between the two-electron oxidized form of ZnTTFP and a tetranionic sulfonated porphyrin. The association constants and the X-ray crystal structure of the complex are reported. A brief discussion outlining the photophysical characteristics (performed in Prof. Shunichi Fukuzumi and Prof. Dongho Kim's group) of the porphyrin donor-acceptor complexes are included. Chapter 4 details the synthesis, photophysical properties, and spectroelectrochemistry of a difluoroboradiazaindacene (BODIPY) bridged exTTF. This compound is referred to as ex-BODIPY. A singlet oxygen generation study provides initial evidence that ex-BODIPY could potentially serve as a photosensitizer. All of the experimental procedures, characterization data, and X-ray crystallographic data tables are reported in Chapter 5. / text

The aims of the thesis were synthesis and studies of the properties of new solution processable electron-transporting and ambipolar donor-acceptor hybrids as well as the synthesis and investigation of the properties of dendritic charge-transporting materials possessing luminescence and redox characteristics. It is found that the newly synthesized solution processable bay carbazol-2-yl or -3-yl substituted perylene bisimides are applicable as ambipolar organic semiconductors with complementary charge-transporting properties. Bay triphenylamino substituted perylene bisimide is found to relevant for the fabrication of solution processable ambipolar organic field-effect transistor. Furthermore, electron-donor functionalized pyrene, triazine and triphenylamine core-centred organic materials exhibiting good luminescence, charge-transport and redox characteristics are appropriate for application in optoelectronic devices. / Disertacijos tikslas - naujų elektronus pernešančių ir bipolinių junginių skirtų organiniams lauko tranzistoriams sintezė ir savybių tyrimas. Taip pat dendritinių liuminescuojančių junginių, skirtų organiniams šviesos diodams, sintezė ir savybių tyrimas. Nustatyta, kad susintetinti nauji perilenbisimido dariniai su karbazol-2-il- ir karbazol-3-il pakaitais pasižymi ir teigiamų ir neigiamų krūvininkų pernašos savybėmis; pernašos efektyvumas priklauso nuo chromoforų sujungimo topologijos. Perilenbisimido darinys su trifenilamino pakaitais yra tinkamas naudoti bipoliniuse organiniuose lauko tranzistoriuose, kurių sluoksniai gaunami, liejant tirpalus. Taip pat elektronų donorinėmis grupėmis funkcionalizuoti, pireno, triazino ir trifenilamino šerdis turintys junginiai, pasižymintys liuminescensija, krūvininkų pernaša ir gali būti panaudoti organiniuose šviesos dioduose.

A systematic study of propylene polymerization using a 4th generation Ziegler-Natta catalyst is presented in this thesis. The apparent kinetic rate constants for propylene polymerization were estimated in the presence and absence of hydrogen and/or donor. The estimated activation energies for activation, propagation, and deactivation were found to be close to values previously reported in the literature for similar catalysts. The polypropylene samples were characterized using high-temperature gel permeation chromatography (GPC), carbon-13 nuclear magnetic resonance (13C NMR), and crystallization elution fractionation (CEF). The effect of hydrogen and external electron donor on polypropylene microstructure was investigated at two polymerization temperatures. In addition to the expected electron donor positive effect on tacticity, hydrogen was also found to increase polypropylene tacticity. The effect of changing these polymerization conditions on molecular weight and polydispersity was also investigated. Finally, CEF profiles show how the distribution of polypropylene crystallizability changes by adding hydrogen and electron donor to the reactor. The concentrations of hydrogen and external donor were also varied to study their effect of polymerization kinetics and polymer microstructure. The estimated activation energies were close to those found in the first part of this investigation in the presence and/or absence of donor and hydrogen. A polypropylene microstructural study showed a positive effect of hydrogen concentration on mmmm pentad at low donor concentration, likely due to an increase in stereoselectivity of the aspecific sites by hydrogen. However, increasing donor concentration over a given threshold seems to transform the aspecific sitess into stereospecific sites that are no longer significantly affected by hydrogen. These experimental results were compared to a previously developed Monte Carlo model and found to agree with the trends predicted by simulation. Finally, the effect of diisopropyldimethoxysilane (P), n-propyltrimethoxysilane (N), paraethoxyethylbenzoate (PEEB), and dicyclopentyldimethoxysilane (D) external donors on catalyst activity and stereoselectivity was investigated. P and D donors were more stereoselective than N and PEEB donors; however, D donor had the best activity among all donors investigated. Therefore, D donor was mixed with PEEB to combine its high activity with the self-extinguishing properties of PEEB. The D/PEEB 90/10 (mol/mol) mixture generated a catalyst with good stereoselectivity but poor activity. When the ratio was increased to 95/5 and 98/2, the resulting catalyst had high activity and good stereoselectivity. Interestingly, the D/PEEB combination with just a small fraction of PEEB has a positive effect on the catalysts activation term which may decrease polymerization costs with this system.

Thesis (Ph. D.)--University of New South Wales, 2000. / Includes bibliographic references. Also available online.

Thesis (Ph.D.)--University of Western Sydney, 2008. / Thesis submitted to the University of Western Sydney, College of Health and Science, School of Natural Sciences, in fulfilment of the requirements for admission to the Doctor of Philosophy. Includes bibliography.

Thesis (Ph.D.) -- Mississippi State University. Department of Chemistry. / Title from title screen. Includes bibliographical references.

Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xii, 286 p.; also includes graphics (some col.). Includes bibliographical references (p. 273-286). Available online via OhioLINK's ETD Center

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 62-66).

O principal objetivo deste trabalho foi a avaliação de estratégias que viabilizassem o uso do metano como doador de elétrons para desnitrificação em ambiente anóxico, visando à aplicação de tecnologia para pós-tratamento de efluente de reatores de manta de lodo e fluxo ascendente (UASB) aplicado no tratamento de esgoto sanitário. O trabalho foi dividido em cinco etapas, sendo que em todas elas o metano foi fornecido como única fonte de carbono orgânico. Na Etapa 1, foram comparados dois inóculos, em reatores em batelada sequenciais (SBR) com biomassa imobilizada. Como inóculo, foi utilizada mistura de sedimento marinho e sedimento de mangue (SED-SBR) ou lodo de reator UASB (LAn-SBR). Na Etapa 2, foram avaliadas estratégias de enriquecimento da comunidade metanotrófica desnitrificante. Para tanto, foram operados dois SBRs: um com biomassa imobilizada (Imob-SBR) e outro com biomassa suspensa (Susp-SBR). Na Etapa 3, foi operado reator contínuo de leito fixo e estruturado e fluxo ascendente (Up-FSBR). Nas etapas 1 e 3, o metano suportou a ocorrência da desnitrificação e da manutenção celular. O consumo das formas nitrogenadas na Etapa 2 foi muito baixo e não foi possível concluir qual a melhor estratégia para enriquecimento da biomassa. Na Etapa 4, a biomassa retirada do Up-FSBR ao final da operação foi submetida a testes de endogenia. Foram operadas bateladas simples e, em cada uma, foi dosada apenas uma das formas nitrogenadas em condições com metano e sem metano. Os resultados mostraram que a redução das formas nitrogenadas é um processo paralelo à oxidação de metano. Na Etapa 5, foi avaliado o consumo de metano e de nitrato em SBR com biomassa suspensa em condições microaeradas e anóxicas. Foi observado que tanto a oxidação do metano quanto a redução do nitrato ocorrem em maior intensidade quando expostos a condições de microaerofilia. A análise dos resultados obtidos permite concluir que os organismos responsáveis pela redução de nitrato (MD) estabeleceram uma relação sintrófica com as bactérias oxidadoras de metano (MM). Observou-se que, quando as bactérias oxidadoras de metano foram estimuladas, a desnitrificação ocorreu em maior intensidade. / This work aimed to develop the methane (CH4) application as electron donor to denitrification under anoxic conditions for post-treatment of Upflow Anaerobic Sludge Blanket (UASB) effluent, applied in sewage treatment systems. The study was conducted in five stages, in which methane was provided as the sole organic carbon source. In Stage 1, methanotrophic denitrification was assessed in Sequencing Batch Reactors (SBR) inoculated with a blend of marine and mangrove sediments (SED-SBR) or anaerobic sludge (LAn-SBR). For both inocula. In Stage 2, strategies for the enrichment of methanotrophic-denitrifying community were evaluated. Two SBRs were operated: in one of them, biomass was immobilized (Imob-SBR) while the other was inoculated with suspended biomass (Susp-SBR). In Stage 3, methanotrophic denitrification was addressed in an Upflow Fixed-Structured Bed Reactor (Up-FSBR). In Stages 1 and 3, methane supported denitrification and cellular maintenance. In Stage 2, the consumption of oxidized nitrogen compounds was too low, and it was not possible to conclude which is the better strategy for enrichment of the methanotrophic-denitrifying community. In Stage 4, the biomass withdrawn from Up-FSBR was subjected to endogeny tests, in batch reactors. In each batch reactor, only nitrite or nitrate was provided, and both methane and methane-free conditions were tested. It was observed that nitrite and nitrate reduction occurred as a marginal process. In Stage 5, methane oxidation coupled to denitrification was assessed under both anoxic and microoxic conditions and both processes were stimulated under the latter. The obtained data suggest denitrifiers established a syntrophic relationship with methane-oxidizers, and when the latter was stimulated, the denitrification also occurred in greater extent.

Une grande quantité des eaux usées, particulièrement celles provenant de l'industrie minière, des fermentations et du traitement des aliments, contiennent-elles des concentrations élevées de sulfate (SO42-). SO42- réduction est une problématique sérieuse au niveau environnemental sous conditions qui ne sont pas contrôlées, cette problématique peut résulter en la libération de sulfure toxique vers l'environnement. Les caractéristiques typiques des eaux usées riches en SO42- sont 0.4-20.8 g SO42-.L-1, faible pH, élevé potentiel oxydatif, faible o négligeable demande chimique d'oxygène (DCO) et hautes concentrations de métaux lourds (drainage minier acide) que peuvent drastiquement endommager la flore et la faune des masses d'eau. L'objectif de cette thèse est d'étudier l'effet du donneur d'électrons sur le processus biologique RS par des bactéries réductrices de sulfate dans des bioréacteurs. Le processus biologique RS a été étudié à l'aide de polymères à base d'hydrate de carbone (PBHC) et biodéchets lignocellulosiques (L) comme des donneurs de libération lente d'électrons (PBCH-DLLE et L-DLLE, respectivement) dans des bioréacteurs discontinus et des bioréacteurs fonctionnant en continu inverse à lit fluidisé (ILF). Les ILF ont été rigoureusement testé pour RS sous haute vitesse et (alimentation-pénurie de nourriture) des conditions d'alimentation transitoires. Dans une autre configuration du bioréacteur, un bioréacteur séquentiel, l'effet de la concentration initiale SO42- sur le démarrage du réacteur a été étudié. Par ailleurs, l'effet de la concentration initiale du donneur d'électrons, NH4+ et SO42- ont été évalués dans des bioréacteurs de traitement par lots aussi bien. La robustesse et la résilience de RS a été démontrée dans les ILF en utilisant le lactate comme donneur d'électrons, dans lequel l'efficacité d'élimination de SO42- (EES) était comparable dans la période d’alimentation (67 ± 15%) de ILF2 aux conditions d'alimentation stables (71 ± 4%) dans même ILF2 et ILF1, le réacteur de commande (61 ± 15%). De la modélisation des réseaux de neurones artificiels et de l'analyse de sensibilité des données de fonctionnement de ILF2, il était prévu que les concentrations de SO42- influents ont affecté le rendement d'élimination de la DCO, la production de sulfure et des changements de pH. Dans un autre ILF3 à un rapport DCO:SO42- de 2.3, RS dans des conditions de taux élevés (CTE = 0.125 d) était 4,866 mg SO42- L-1 d-1 et un EES de 79% a été remporté. Par ailleurs, le second ordre Grau et les modèles d'enlèvement de substrat Stover-Kincannon équipés de la performance du réacteur à haut débit avec r2 > 0.96. Le rapport DCO:SO42- était le principal facteur affectant la RS. Dans des bioréacteurs par lots, en utilisant du papier filtre PBCH-DLLE, la RS a été réalisée à EES > 98%. Avec l'utilisation de scourer comme L-DLLE, un EES de 95% a été remporté. Cependant, lorsque la lavette est utilisée comme matériau de support de L-DLLE dans un ILF4, le RS a montré 38% (± 14) de EES entre 10-33 d de fonctionnement. La SR était limitée par le taux d'hydrolyse-fermentation et, par conséquent, la complexité de la DLLE. L'utilisation du donneur d'électrons pour le processus RS a simultanément amélioré aux concentrations de donneurs d'électrons initial décroissants / Many industrial wastewaters, particularly from the mining, fermentation and food processing industry contain high sulphate (SO42-) concentrations. SO42- reduction (SR) is a serious environmental problem under non-controlled conditions, which can result in the release of toxic sulphide to the environment. Typical characteristics of SO42--rich wastewater are 0.4-20.8 g SO42-.L-1, low pH, high oxidative potential, low or negligible chemical oxygen demand (COD) and high heavy metals concentrations (acid mine drainage), that can dramatically damage the flora and fauna of water bodies. The aim of this PhD is to study the effect of electron donor supply on the biological SR process by sulphate reducing bacteria in bioreactors. The biological SR process was studied using carbohydrate based polymers (CBP) and lignocelulosic biowaste (L) as slow release electron donors (CBP-SRED and L-SRED, respectively) in batch bioreactors and continuously operated inverse fluidized bed bioreactors (IFBB). IFBB were vigorously tested for SR under high rate and transient (feast-famine) feeding conditions. In another bioreactor configuration, a sequencing batch bioreactor, the effect of the initial SO42- concentration on the reactor start-up was investigated. Besides, the effect of the initial concentration of electron donor, NH4+, and SO42- were evaluated in batch bioreactors as well. The robustness and resilience of SR was demonstrated in IFBB using lactate as the electron donor wherein the SO42- removal efficiency (SRE) was comparable in the feast period (67 ± 15%) of IFBB2 to steady feeding conditions (71 ± 4%) in the same IFBB2 and to IFBB1, the control reactor (61 ± 15%). From artificial neural network modeling and sensitivity analysis of data of IFBB2 operation, it was envisaged that the influent SO42- concentrations affected the COD removal efficiency, the sulphide production and pH changes. In another IFBB3 at a COD:SO42- ratio of 2.3, SR under high rate conditions (HRT=0.125 d) was 4,866 mg SO42-. L-1 d-1 and a SRE of 79% was achieved. Besides, the Grau second order and the Stover-Kincannon substrate removal models fitted the high rate reactor performance with r2 > 0.96. The COD:SO42- ratio was the major factor affecting the SR. In batch bioreactors, using filter paper as CBP-SRED, SR was carried out at > 98% SRE. Using scourer as L-SRED, a 95% SRE was achieved. However, when the scourer was used as the L-SRED carrier material in an IFBB4, the SR showed 38 (± 14) % SRE between 10-33 d of operation. The SR was limited by the hydrolysis-fermentation rate and, therefore, the complexity of the SRED. Concerning sequencing batch bioreactor operation, the SR process was affected by the initial SO42- concentration (2.5 g SO42-.L-1) during the start-up. The sequencing batch bioreactor performing at low SRE (< 70%) lead to propionate accumulation, however, acetate was the major end product when SRE was > 90%. In batch bioreactors, the NH4+ feast or famine conditions affected the SR rates with only 4% and the electron donor uptake was 16.6% greater under NH4+ feast conditions. The electron donor utilization via the SR process improved simultaneously to the decreasing initial electron donor concentrations. This PhD research demonstrated that the SR process is robust to transient and high rate feeding conditions. Moreover, SR was mainly affected by the approach how electron donor is supplied, e.g. as SRED or as easy available electron donor, independently of the COD:SO42- ratio. Besides, the electron donor and SO42- utilization were affected by the lack or presence of nutrients like NH4+