Recently, ¡§Pyrene¡¨ is a well-known substitutive group because the rigid structure and hole-injection ability of pyrene units can improve the thermal and electronic properties of blue OLED materials. The aromatic ring of pyrene not only improves the thermal and hole-injection ability of derivatives, but also provides high photoluminescence (PL) efficiency and high carrier mobility. Through these characteristics we can understand that the electron-rich pyrene derivatives can enhance the properties of OLED device. In this study, we developed low-molecular-weight structures with spiro-type molecules based on 9,9-spirobifluorene and fabricated the OLED device with the structure of ITO(170 nm)/PEDOT:PSS(50 nm)/PVK:TPSBF (40%)(90 mm)/BPhen (30 nm)/ LiF(1 nm)/Al(200 nm). It exhibited a maximum luminance at 500 mA/cm2 of 4130 cd/m2 with the Commission Internationale de l'Eclairage (CIE) of (0.16 , 0.16), and the maximum current and power efficiency were 1.9 cd/A and 0.9 lm/W, respectively. We concluded that TPSBF has good emission efficiency according to device performances. The PL maximum of the thick film of TPSBF, prepared by vacuum vapor deposition appears broadband spectrum, that resulted from the aggregation of the pyrene moieties. From Atomatic Force Microscopy (AFM) results, we propose three emission mechanisms. 1. Intramolecular spectrum ¡÷ 450 nm 2. Molecular aggregation spectrum ¡÷ 500 nm 3. Longer conjugation spectrum of intermolecular ¡÷ 550 nm We could fabricate the organic white light emitting device with a single and thicker emitting layer TPSBF and the more broadband emitting spectrum can be obtained. Finally, we fabricated the organic white light emitting device with a structure of ITO(170 nm)/2T-NATA(15 nm)/NPB(65 nm)/TPSBF(50 nm)/Alq3(30 nm)/LiF(0.8 nm)/Al(200 nm). It exhibited a maximum luminance at 1300 mA/cm2 of 57680 cd/m2, the maximum current and power efficiency were 6.51 cd/A and 4.07 lm/W, respectively, and with good CIE coordinate of (0.29 , 0.36).

Arbuscular mycorrhizal fungi (AMF) can play an important role in the phytoremediation of petroleum hydrocarbon (PH)-contaminated soil. However, little is known about the effects of AMF in combination with biostimulation via fertilization or bioaugmentation with hydrocarbonoclastic microorganisms, during phytoremediation of PH in soils. This research evaluated the influence of the AMF Glomus intraradices and inorganic fertilization on growth and physiological responses of Lolium multiflorum Lam. cv. Passarel Plus during phytoremediation of soil contaminated with Arabian medium crude oil (ACO). Also determined was the interaction of AMF with the hydrocarbonoclastic bacterium, Sphingomonas paucimobilis EPA505 (Sp), and the filamentous fungus, Cunninghamella echinulata var. elegans ATCC-36112 (Ce), on growth and selected physiological responses of L. multiflorum during phytoremediation of soil contaminated with benzo[a]pyrene (BaP) or ACO. This research provides evidence that AMF enhance the phytoremediation of petroleum hydrocarbons in soils when inoculated with L. multiflorum. The concentration of petroleum hydrocarbons in soil was a determining factor of potential benefits of AMF on L. multiflorum. Low (3000 mg·kg-1) or high (15000 mg·kg-1) concentrations of ACO resulted in limited benefits of AMF on plant growth, physiology, and degradation of ACO in soil. However, when plants were exposed to an intermediate ACO concentration in soil (6000 mg·kg-1), AMF plants had enhanced growth, physiological responses, and greater ACO-degradation than non-AMF plants. The AMF symbiosis in roots of plants was observed at all concentrations of ACO-contaminated soil. This research is one of the first reports demonstrating the benefits of AMF on the degradation of benzo[a]pyrene or ACO, alone or in combination, with the hydrocarbonoclastic microorganisms. Thus, AMF resulted in a beneficial synergism with the hydrocarbonoclastic microorganisms, particularly during ACO-degradation in the rhizosphere of L. multiflorum. Hydrocarbonoclastic microorganisms had no negative effects on AMF colonization.

The purpose of this study was to treat soils contaminated by pyrene through phytoremediation. The plant species selected were Phragmites communis Trin., Typha orientalis Presl, Vetiveria zizanioides, Rohdea japonica (Thunb.) Roth et Kunth, Cyperus malaccensis. Lam. subsp. monophyllus (Vahl) T. Koyama, Bolboschoenus planiculmis (F. Schmidt) T. Koyama and Bidens pilosa respectively. The degradation efficiencies of pyrene in soils and concentration of pyrene in the plant tissues were evaluated in this study. In addition, the change of microbial biota in soils was investigated in the tests of this study. The experimental results indicated that after twenty-two weeks, soils planted with V. zizanioides, R. japonica and T. orientalis have better pyrene degradation efficiencies. Especially, after fourteen weeks the pyrene degradation efficiencies were 86%, 84% and 77% respectively, which showed that the efficiencies 10% to 20% higher than those unplanted control experiments, which was 66%. In addition, the pyrene degradation efficiencies in summer were found to be higher than those in winter. The degradation efficiencies of pyrene in sterilized soil with and without T. orientalis were found equal to 59% and 55%, respectively. These values were found lower than those in the experiment without sterilization, in which the pyrene degradation efficiencies with and without T. orientalis were 77% and 66%, respectively, after the fourteen weeks experiment. Hence the rhizospheric microorganisms had a significant effect on the degradation of pyrene in soils. The pyrene degradation efficiencies were improved with application of fertilizer (HYPONeX No.2, HYPONeX Co., USA). After fourteen weeks, it was found that the experiment with fertilizer and with or without T. orientalis planted were 7% higher, which were 84% and 73% respectively, compared to 77% and 66% with no application of fertilizer. Proper surfactants have positive effect on phytoremediation. In this study, we found that addition of the surfactant Triton X-100 or combined surfactants (Triton X-100, Tween 20 and sodium dodecylbenzene sulfonate) both presented better pyrene degradation efficiencies than the system without adding surfactant. After ten weeks, soils planted with V. zizanioides and added with surfactants showed the pyrene degradation efficiencies equal to 85% and 87% (combined) respectively, which showed that 4% and 6% higher rate than the system without adding surfactants (81% ). After twenty two weeks, soils planted with V. zizanioides and added with surfactants showed that the pyrene degradation efficiencies were 96% and 96% (combined) respectively. They were all higher than the system without adding surfactants (94%). Soils planted with R. japonica also showed the same results. In this study, it was also found that the degradation efficiencies were higher at the surface layer of the soil than subsurface layer due to better oxygen content there. Hence the activities of microorganisms in the surface layer were higher than those in the subsurface layer of soils. After twenty two weeks, soils planted with V. zizanioides showed the residual concentration of pyrene were 5.7mg/Kg (surface layer) and 10.8 mg/Kg (subsurface layer). The difference between them was about 50%. Soils planted with R. japonica, T. orientalis or unvegetation also showed the same results. The pyrene concentrations of the roots, stems and leaves were analyzed and the results showed that pyrene did not exist in the plant stems or its leaves. Since pyrene could not be absorbed into plant¡¦s tissues by plants, the phytoextraction and phytovolatilization did not occur in this study. It was concluded that the degradation of pyrene in soils was mainly in rhizoremediation. The soils planted with V. zizanioides showed that the inhibition of Lactobacillus sp, while the soils planted with R. japonica and T. orientalis showed unfavorable conditions to Rhibopus sp.. Four weeks after this experiment, both Lactobacillus sp. and Rhibopus sp. were not existent. The soils planted with V. zizanioides, R. japonica and T. orientalis showed an increase of the number of bacteria (CFU), and thus the pyrene degradation efficiency was increased.

The objective of this project is synthesizing bipyridine-derived ligands in order to study DNA conformational bending. The synthesis of bipyridine derivatives has been investigated. 6,6’-Dibromo-2,2’- bipyridine and small scale of 6,6’-diformyl-2,2’-bipyridine have been successfully synthesized in the laboratory. The synthesis of large amount of a direct precursor to 6,6’-diformyl-2,2’- bipyridine in an multiple step way has been achieved. The synthesis of mono functionalized pyrene derivatives and of 1,6-dissymmetrically functionalized pyrene derivatives has been heavily studied. Successfully methods have been reported in this thesis. The complete assembly of bipyridine and pyrene units into the final ligands and their model has also been studied. Palladium borylation and Suzuki-Miyaura cross-coupling have been used to successfully connect the bipyridine with pyrene units. In addition to Suzuki-Miyaura methodology, the direct coupling of N,N’-dioxide-2,2’- bipyridine with aromatic bromides under palladium catalysis has been investigated. This method could be an alternative way to access to mono-substituted 6-bipyridines, symmetrically or even asymmetrically 6,6’-disubstituted-2,2’-bipyridine derivatives. / Thesis (Master, Chemistry) -- Queen's University, 2009-09-06 01:06:41.646

The microbial degradation of pyrene, a 4-ring polycyclic aromatic hydrocarbon (PAH), has been elucidated with the increasing number of pyrene-degrading bacteria that have been isolated in recent years. A pyrene degrading bacterium identified as Mycobacterium sp. strain S65, was isolated from a jet-fuel contaminated site in Sept-Iles, northern Quebec, Canada. S65 utilized pyrene, phenanthrene, and fluoranthene as sole carbon and energy sources, but did not degrade naphthalene, anthracene, and fluorene. Pyrene mineralization was enhanced by adding benz[a]anthracene, benzy[a]pyrene, or phenanthrene as cosubstrates. When added to PAH contaminated soil as a potential bioaugmentation agent, S65 did not appear to survive well, nor was it effective at degrading PAHs under these conditions. / Pyrene catabolic genes in S65 were partially characterized by Southern hybridization using a probe constructed from the naphthalene inducible pyrene dioxygenase gene, nidA, from the pyrene-degrading bacterium, Mycobacterium sp. strain PYR-1.

Organic photovoltaics (OPVs) are mainly based on organic semiconducting small molecules, macromolecules, and polymers, which form an active layer in photovoltaics. They act as an active material in absorbing light and causing charge mobility to generate electricity from sunlight. This thesis describes the molecular systems derived from fused arenes such as anthracene, pyrene, carbazole and thiophene for use as either a donor or an acceptor component of the active layer of OPVs. Two novel molecular systems (9- anthracenecarboxy-1-methylpyrene, (1) and Py-bi-TH-ANT, (2) were prepared using Steglich esterification and Grignard metathesis followed by Kumada coupling. The molecular structure of each was confirmed by 1H-NMR and IR analysis respectively. The photophysical properties of the products were also evaluated in solution. The potential applicability of these two novel systems for OPVs will be studied in the future.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants. There are numerous studies reporting developmental cardiac toxicity in multiple fish species due to PAH exposure. However, there are relatively few instances where the effects of acute PAH exposure in adult fish have been characterized. Furthermore, the majority of experiments comparing PAH toxicity with exposure route in adult fish focus on CYP1A gene expression or enzyme activity, while there is a lack of information about the possible pathophysiological effects. Therefore, the overall objective of this thesis was to characterize the sublethal effects of benzo[a]pyrene (BaP), a prototypical PAH, on adult zebrafish (Danio rerio) cardiorespiratory function and fitness following acute exposure by two different routes. In the first experiment, adult zebrafish were intraperitoneally (i.p.) injected twice (one injection/24 hr) with increasing concentrations of BaP (0.1, 10, and 1000 μg/kg) and compared to corresponding dimethylsulfoxide (DMSO) controls. In a second set of experiments, adult zebrafish were aqueously exposed to BaP (static, renewal at 24 hr; 16.2 and 162 μg/L) and compared to DMSO controls. Following 48 hr exposure, one group of fish (n=10/treatment group) were subjected to swimming performance tests to assess critical swimming speed (Ucrit), oxygen consumption rate (MO2), cost of transport (COT), standard metabolic rate (SMR), active metabolic rate (AMR), and factorial aerobic scope (F-AS). Another group of fish (n=12/treatment group) were subjected to echocardiography following 48 hr BaP exposure to evaluate cardiac function. Following echocardiography analysis, samples were collected for parent compound (BaP) body burden and CYP1A mRNA induction analysis. 48 hr BaP injection resulted in significant sublethal effects on adult zebrafish cardiorespiratory function. Oxygen consumption (MO2) was increased at three swimming speeds in injected BaP groups compared to control. In contrast, aqueously BaP-exposed fish showed increased MO2 only at the single lowest swim speed. COT was also similarly increased for both exposure routes. SMR was elevated with both exposure routes, while AMR remained unchanged. This resulted in a significant decrease in F-AS for all treatment groups compared to corresponding controls with both exposure routes. Cardiac function was significantly affected by both routes of BaP exposure. Ventricular heart rate was significantly decreased in BaP-exposed fish, both injected and aqueously-exposed. However, stroke volume was decreased only in fish aqueously exposed to BaP, which resulted in significantly reduced cardiac output with that exposure route. In contrast, the ratio of atrial to ventricular heart rate (AV ratio) was increased only in fish i.p. injected with BaP, indicating the possibility of cardiac arrhythmias occurring. Analysis of BaP body burdens in fish tissue allowed for identification of an overlapping dose group between exposure routes, through which comparisons of cardiotoxicity were then made. This comparison revealed slight differences in cardiotoxicity between exposure routes. BaP-injected fish suffered from more severe bradycardia than aqueously exposed fish. Furthermore, cytochrome P4501A (CYP1A) mRNA levels in liver and heart tissue showed more significant increases in injected fish, while skeletal muscle CYP1A was increased only following aqueous exposure. In conclusion, acute BaP exposure caused metabolic alterations and impaired cardiorespiratory function in adult zebrafish regardless of exposure route. Interestingly, the primary mechanism behind these effects appeared to differ slightly with exposure route. These results suggest that acute BaP exposure may have negative effects on adult fish survivability in the environment. Overall, this work provides valuable insight into the pathophysiogical consequences of acute PAH exposure in adult stage fish.

Orientador: Teresa D. Z. Atvars / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T07:47:01Z (GMT). No. of bitstreams: 1 Baldi_LeonardoDelaColeta_M.pdf: 4843408 bytes, checksum: 8a861f165970d1fd6ff07a8b5889c676 (MD5) Previous issue date: 2004 / Mestrado / Físico-Química / Mestre em Química

Abstract The tumour suppressor gene TP53 is the most commonly mutated gene in human cancers. The protein it codes, p53, becomes activated as a response to stress signals. When activated, p53 binds to DNA and affects the transcription of its target genes. They then cause cell cycle arrest, DNA repair and/or induction of programmed cell death, thus preventing mutations and cancer. Specific mutations in TP53 are associated with exposure to certain carcinogens, such as polycyclic aromatic hydrocarbons (PAHs). These environmental chemical carcinogens are formed through incomplete combustion of organic material. Benzo(a)pyrene (BP) is commonly used as a model compound for PAH carcinogenesis. BP causes accumulation of p53, but the mechanism of accumulation is not known. The aim of this study was to gain more insight into the p53 protein in the first phases of PAH carcinogenesis in vivo in mouse, using BP as the model compound. Mice from the inbred C57BL/6 strain were treated topically or intraperitoneally with BP or were exposed to cigarette smoke inhalation. The amount of p53 protein was studied by immunoblotting, immunohistochemistry and immuno electron microscopy, and the mdm2, p21 and p19ARF proteins were studied by immunoblotting. The binding of BP to DNA was measured by synchronous fluorescence spectrophotometry. The p53 protein was induced in vivo in skin and lung after BP treatment and in lung after cigarette smoke treatment. An increase in p53 was associated with an increase in the amount of BP-DNA adducts. In skin, the induction of p53 was accompanied by induction of the p21 and mdm2 proteins, which are transcriptional targets of p53. This indicates that the in vivo induced p53 is a wild-type protein and functional. In lungs, the induction of p53 was accompanied by a decrease of mdm2 and an increase of p19ARF. These results confirm that BP is metabolized and binds to DNA in mouse tissues and indicate that BP-DNA adducts are the trigger for p53 protein induction. The in vivo regulation of the p53 protein is different in different tissues of C57BL/6 mouse.

Yunnan, southwestern China, represents a modern biodiversity center for Rubus (Rosaceae). The history for this high modern diversity remains poorly known due to the lack of fossil evidence. In this report, fossil pyrenes of Rubus are taxonomically studied from the late Pliocene (Piacenzian) of Lanping County, northwestern Yunnan. These pyrenes show a greater morphological variation than that of extant Rubus pyrenes within the same species, indicating that they belong to different taxa of Rubus. Based on comparisons with both modern and other fossil species, our fossil pyrenes are assigned to five taxa, including a newly established one, Rubus lanpingensis nov. sp. These fossils suggest a somewhat high species diversity of Rubus in Lanping, a small area in northwestern Yunnan, during the late Pliocene. This provides the first fossil perspective for an understanding of the historical background of the modern Rubus diversity in a limited geographic area of Yunnan. The inferred palaeobiodiversity is probably associated with a large environmental heterogeneity in a limited area of Yunnan at that time.