Dissertations / Theses on the topic 'Selenophene'

SELENOPHENE DERIVATIVES FOR ELECTROCHROMIC APPLICATIONS Aydemir, Kadir M.S., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare February 2008, 60 pages A novel selenophene-based monomer
1,4-di(selenophen-2-yl) benzene (DSB), synthesized via Stille coupling reaction of 1,4 dibromobenzene and tributyl (2-selenophenyl) stannane and corresponding conducting homopolymer (Poly (DSB)) was electrochemically synthesized in the presence of tetrabutylammoniumhexafluorophosphate (TBAPF6) as the supporting electrolyte in dichloromethane. The resulting conducting polymer was characterized by Cyclic Voltammetry (CV), Fourier Transform Infra Red Spectrometry (FTIR) and Ultraviolet&ndash
Visible Spectrometry (UV-Vis Spectrometry). Spectroelectrochemistry analysis and kinetic studies of Poly (DSB) revealed &ndash
* transition (max) at 340 nm with almost zero percent transmittance (T%) concurrently with striking and rapid (0.6 s) absorbance change at near infrared region (1250 nm) with 35% percent transmittance, indicating that Poly (DSB) is a very suitable near infrared electrochromic material. Copolymer of selenophene with ethylenedioxythiophene (EDOT) was potentiostatically synthesized. Poly (selenophene-co-EDOT) was characterized by Cyclic Voltammetry, FTIR and UV-Vis Spectrometry. During spectroelectrochemistry studies, &ndash
* transition (max) was observed at 555 nm with a switching time of 1.4 s and 39% transmittance. Polaron and bipolaron bands were observed at 851 nm and 1299 nm, respectively. Switching time at 1299 nm was 1.8 s with a percent transmittance of 72. Copolymer of DSB with EDOT (Poly (DSB-co-EDOT)) was synthesized and characterized. max, polaron and bipolaron bands were observed at 457 nm, 696 nm and 1251 nm, respectively. A rapid switching time (0.2 s) with 12% transmittance was observed at 696 nm. At the near infrared region (1251 nm), satisfactory percent transmittance (35%) and a moderate switching time (1.75 s) were observed.

This thesis is an exploration of the synthesis and characterisation of novel selenophene-containing conjugated materials. Conjugated materials containing thiophene units are well-known and offer many exciting applications in OPV, OTFT, and flexible-electronics devices. Theory and some studies suggest that replacing thiophene units with selenophene could potentially improve optical and electronic properties of interest to device performance. This thesis comprises: • An introduction detailing the potential interest in selenophene-containing materials and the state of current research. • An investigation into the Stille polymerization process on a known thiophene-based polymer, PBTTT, testing the limits of Stille polymerization's effectiveness and the extent to which Stille polymerization can be optimized, as well as investigating the effect of alkyl chain length on the properties of a known polymer. • A systematic investigation into the effects of replacing thiophene with selenophene on the backbone of a known thiophene-based polymer, poly(terthiophene), and also selenium-bearing analogues of other well-studied polymers, showing how increasing selenophene incorporation affects properties relevant to device performance. • The synthesis and characterisation of a novel high-performance low-bandgap polyselenophene featuring DPP units, including a discussion on the synthesis of DPP-functionalised selenophene. Approaches for developing novel fused selenophene-containing materials including issues with functionalising selenophenes, the synthesis of several potentially useful intermediates, the use of a new selenium-transfer reagent, and the successful synthesis and characterisation of three novel fused selenophene-containing systems.

Ce travail est consacre a l'etude electrochimique du polymethyl-3selenophene. Lors de la synthese de ce polymere, nous avons pu mettre en evidence un phenomene de germination tridimensionnel progressif. La caracterisation du depot obtenu a ete effectuee notamment par methodes a echelons de potentiel et a surtout ete abordee en terme de coefficient de diffusion. L'importance de l'epaisseur intervient sur la stabilite electrochimique du film, sur les temps de reponse ainsi que sur son comportement en tant qu'electrode modifiee. Les perturbations capacitives du polymethyl-3selenophene ont pu etre extraites et une approche de modelisation obtenue

A novel electrically conducting polymer, poly(2-dodecyl-4,7-di(selenophen-2-yl)benzotriazole) (Poly(SBT)), containing selenophene as a strong donor and benzotriazole as a strong acceptor group was synthesized by electrochemical polymerization. Homopolymerization and copolymerization ( in the presence of 3,4-ethylenedioxythiophene (EDOT) ) was achieved in acetonitrile/ dichloromethane(95/5 v/v) with 0.1M tetrabutylammonium hexafluorophosphate (TBAPF6). The electrochemical and optical properties of homopolymer and copolymer were investigated by Cyclic voltammetry, UV-Vis, near IR Spectroscopy. Cyclic voltammetry and spectroelectrochemistry studies demonstrated that homopolymer can be reversibly reduced and oxidized (both n- and p-doped) between -1.9 V and 1.4 V, at a scan rate of 100 mV/s. Optical contrast was calculated as 32% and 56% with a switching time of 2.4 s and 0.4 s at 511 and 1200 nm respectively. Poly(SBT) exhibits a &
#955
max value of 511nm and a band gap of 1.67eV.

Au cours de ce travail, nous avons synthetise un certain nombre de polymeres en serie heterocyclique. La synthese des monomeres precurseurs est decrite dans le chapitre i. Trois series de composes sont decrites: - les 3-alkyl-thiophenes; - les 3-alkylchalcogeno-thiophenes; - les 3-alkyl-selenophenes. Dans tous les cas, la chaine alkyle est lineaire et possede un a douze atomes de carbone. Dans le chapitre ii nous decrivons: - l'analyse detaillee des conditions de polymerisation par voie electrochimique, en particulier la determination des potentiels anodiques et cathodique des monomeres; la polymerisation proprement dite: elle conduit a des materiaux conducteurs a l'etat dope. Ceux-ci ont ete ensuite etudies a l'aide de leurs voltamogrammes et de techniques physiques telles que i. R. , exafs, xanes

Synthesis of new electroactive monomers are highly desired since these compounds can be utilized as active layers in many device applications such as ECDs, LEDs and solar cells. Pyrrole and selenophene bearing polymers were also proven to be excellent candidates as electrochromic materials. Benzothiodiazole can be coupled to to pyrrole and selenophene yield materials that can be polymerized to give donor acceptor type polymers. These donor-acceptor type materials
Poly(4,7-di(1H-pyrrol-2-yl)benzo[c][1,2,5]thiadiazole P(PYBTPY) and poly(4,7-di(selenophen-2-yl)benzo[c][1,2,5]thiadiazole P(SEBTSE) were synthesized via bromination, stannylation and Stille coupling reactions. Electrochemical and electrochromic properties of the polymers were examined in detail.

Conselho Nacional de Desenvolvimento Científico e Tecnológico
The liver presents extraordinary functional diversity, particularly in the control of energy production, immune defense and volemic reserve. The human being is exposed occupationally and in the environment to a variety of hepatotoxic compounds, such as the use of paints and their derivatives (2-nitropropane, 2-NP), chemical reagents (carbon tetrachloride, CCl4) and exposure to cigarette (2-NP). Therefore, it is interesting the study of therapies to prevent or even reverse the poisoning caused by these compounds. Considering that reactive oxygen species (ROS) have an important role in various diseases, especially in liver diseases, the use of antioxidant therapies should be considered. In this context, the heterocyclic compounds containing selenium in their structures have attracted the attention of researchers. Thus, this study investigated the antioxidant activity of 3-alkynyl selenophenes in models of oxidative damage in vitro and ex vivo in rats (Wistar, male, weighing 200-300g). A class of 3-alkynyl selenophene compounds with different substitutions was tested, with the objective to assess their antioxidant profile and their possible toxic effect in vitro. As a result, 3-alkynyl selenophenes had antioxidant activity, but this activity was dependent on the presence of terminal alkynes in the molecule or easy conversion to it. The possible toxic effect of 3-alkynyl selenophenes was evaluated through the activity of the enzyme δ-aminolevulinate dehydratase (δ-ALA-D) in vitro. The results showed that none of 3-alkynyl selenophenes inhibited the activity of this enzyme, suggesting that this class of compound did not present toxicity on this enzyme. From these results, selenophene h (compound that had the best antioxidant activity in vitro) was selected for the evaluation of its protective effect against oxidative damage induced by 2-NP and CCl4 (ex vivo). Selenophene h (25 mg/kg) protected against the increase of markers of liver damage (aspartate aminotransferase (AST) and alanine aminotransferase (ALT) activities) and oxidative stress induced by administration of 2-NP in rats. 2-NP induced microscopic changes, evaluated by histopathological inspections, that were protected by this compound. Selenophene h showed a protective effect against the increase of lipid peroxidation and inhibition of activity of δ-ALA-D in animals treated with 2-NP. Selenophene h protected against oxidative damage induced by CCl4 in rats. A single dose of CCl4 caused significant hepatotoxicity, evidenced by elevated plasma enzyme activity of AST and ALT, increased incidence of histopathological lesions, increased lipid peroxidation levels and the activity of Glutathione-S-transferase (GST), decreased levels of ascorbic acid and the activity of catalase and δ-ALA-D. In conclusion, 3-alkynyl selenophene protected from all these changes, confirming its hepatoprotective effect. Considering the results, we suggest that 3-alkynyl selenophene, an antioxidant, may be a useful therapy for the oxidative damage induced by 2-NP or CCl4 .
O fígado apresenta extraordinária pluralidade funcional, destacando-se no controle de produção de energia, defesa imunológica e reserva volêmica. No meio ambiente e ocupacionalmente, o ser humano está exposto a uma variedade de compostos hepatotóxicos, como por exemplo, no uso de tintas e seus derivados (2-nitropropano, 2- NP), reagentes químicos (tetracloreto de carbono, CCl4) e na exposição ao cigarro (2-NP). Portanto, é interessante o estudo de terapias que previnam ou até mesmo revertam a intoxicação causada por estes compostos. Considerando que as espécies reativas de oxigênio (EROs) apresentam importante papel sobre diversas patologias, em especial nas doenças hepáticas, o uso de terapias antioxidantes deve ser considerada. Neste contexto, destacam-se os compostos heterocíclicos contendo selênio em sua estrutura. Deste modo, neste estudo investigou-se a atividade antioxidante de 3-alquinil selenofenos em modelos de dano oxidativo in vitro e ex vivo em ratos (Wistar, machos, pesando entre 200 300 g). Para esse fim, testou-se uma classe de compostos 3-alquinil selenofeno, com diferentes substituições na estrutura química, com o objetivo de avaliar o perfil antioxidante e seu possível efeito tóxico in vitro em ratos. Como resultado, 3- alquinil selenofenos tiveram atividade antioxidante, porém esta atividade foi dependente da presença de um alquino terminal na molécula ou da fácil conversão da molécula a um alquino terminal. Além disso, o possível efeito tóxico dos 3-alquinil selenofenos foi avaliado através da atividade da enzima δ-aminolevulinato desidratase (δ-ALA-D) in vitro. Os resultados obtidos demonstraram que nenhum dos 3-alquinil selenofenos testados inibiu a atividade desta enzima, sugerindo que esta classe de compostos não apresentou toxicidade sobre a atividade da δ-ALA-D. A partir destes resultados, selecionou-se o selenofeno h (que obteve melhor atividade antioxidante in vitro) para a avaliação do seu efeito protetor contra o dano oxidativo induzido por 2-NP e CCl4 em ratos (ex vivo). O selenofeno h (25 mg/kg) protegeu contra o aumento dos marcadores de dano hepático (aspartato aminotranferase (AST) e alanina aminotransferase (ALT)) e de estresse oxidativo induzidos pela administração do 2-NP. O 2-NP induziu alterações microscópicas avaliadas por inspeções histopatológicas as quais foram protegidas pelo composto. O selenofeno h demonstrou efeito protetor contra o aumento da peroxidação lipídica e inibição da atividade da δ-ALA-D nos animais tratados com 2-NP. Além disso, o selenofeno h protegeu contra o dano oxidativo induzido pelo CCl4 em ratos. Uma única dose de CCl4 causou significante hepatotoxicidade, evidenciada por elevação da atividade plasmática das enzimas AST e ALT, aumento da incidência de lesões histopatológicas, aumento dos níveis de peroxidação lipídica e da atividade da enzima glutationa-S-transferase (GST), bem como diminuição dos níveis de ácido ascórbico e da atividade das enzimas catalase e δ-ALA-D. A partir dos resultados demonstrados, verificou-se que o selenofeno h protegeu contra todas estas alterações, confirmando o seu efeito hepatoprotetor. Considerando os resultados obtidos, pode-se sugerir que o selenofeno h, uma molécula com atividade antioxidante, pode ser uma útil terapia contra o dano oxidativo induzido pelos hepatotoxicantes: 2-NP e CCl4.

Conselho Nacional de Desenvolvimento Científico e Tecnológico
Seizures have important consequences in terms of mortality and quality of life of the affected population, being a risk factor for the development of cognitive and behavioral abnormalities. Considering the promising pharmacological properties of molecules containing selenium, in article 1, we evaluated the anticonvulsant action of 1-(2,5-diphenylselenophen-3-yl)-3-methylpent-1-yn-3-ol, generically called 3-alkynyl selenophene (3-ASP) against seizures induced by pilocarpine (PC), pentylenetetrazole (PTZ) and kainate (KA) in 21-days-old rats. Animals were pre-treated with 3-ASP (10, 25 or 50 mg/kg; per oral, p.o.) or vehicle, 30 minutes before of intraperitoneally administration of PC (400 mg/kg), PTZ (80 mg/kg) or KA (45 mg/kg). 3-ASP pre-treatment (50 mg/kg) abolished seizures and the death induced by PC administration. 3-ASP (50 mg/kg) increased the latency to the first convulsive episode, as well as decreased the mortality and incidence of seizures caused by PTZ and KA. In article 1, the antioxidant activity of 3-ASP (10, 25 or 50 mg/kg; p.o.) against the oxidative stress induced by PC (400 mg/kg, i.p.) in 21-days-old rats was evaluated. Our results demonstrated that 3-ASP pre-treatment was effective in protecting against the inhibition of cerebral activity of superoxide dismutase, decreased ascorbic acid levels, stimulation of catalase activity and increase of reactive species levels caused by PC. Additionally, 3-ASP protected against the inhibition of acetylcholinesterase and Na+, K+-ATPase activities resulting from convulsions induced by PC. The involvement of glutamatergic and GABAergic systems in the anticonvulsant action of 3-ASP was investigated (Articles 1 and 2). The combination of sub-effective doses of 3-ASP (10 mg/kg, p.o.) and diazepam (GABA agonist; 0,5 mg/kg, i.p.), 5S,10R-(+)-5-methyl-10,11-dihydro- 5H-dibenzo[a,d]cyclohepten-5,10-imine maleate (MK-801, a non-competitive N-methyl-D-aspartate (NMDA) receptor antagonist; 0.1mg/kg, i.p.) or 6,7-dinitroquinoxaline-2,3-dione (DNQX, a non-NMDA receptor antagonist; 5 mg/kg, i.p.) was effective in increasing the latency to the first convulsive episode, as well as, in decreasing the incidence of convulsions induced by PC. On the other hand, the combination of 3-ASP and 2-methyl-6-phenylethynyl pyridine hydrochloride (MPEP, an antagonist of metabotropic glutamate receptor mGluR5; 0,5 mg/kg, i.p.) did not protect against convulsions. The oral administration of 3-ASP (50 mg/kg) caused an inhibition of 64% and 58% of GABA uptake in the cortex and hippocampus, respectively. However, no change in glutamate uptake after 3-ASP administration (50 mg/kg) was found. Additionally, in article 2, we investigated the possible interaction between sub-effective doses of 3-ASP and GABA uptake or GABA transaminase (GABA-T) inhibitors against PC-induced seizures in 21-days-old rats. To this, sub-effective doses of 3-ASP (10 mg/kg; p.o.) and DL-2,4-diamino-n-butyric acid hydrochloride (DABA, an inhibitor of GABA uptake; 2 mg/kg; i.p.) or aminooxyacetic acid hemihydrochloride (AOAA; a GABA-T inhibitor; 10 mg/kg, i.p.) were co-administrated in 21-days-old rats before of PC administration (400 mg/kg). The treatment with 3-ASP and DABA abolished the PC-induced seizures. Similar results were found when sub-effective doses of 3-ASP and AOAA were administrated in 21-days-old rats. Finally, in the article 3 we investigated the effect of 3-ASP or diazepam against convulsions, the increased susceptibility to the development of seizures and long term memory impairment resulting from febrile seizures induced by hyperthermia. 21-Days-old rats were pre-treated with 3-ASP (25, 50 or 100 mg/kg; p.o), diazepam (1 or 5 mg/kg; i.p.) or vehicle. After the treatment, animals were exposed to a stream of heated air to approximately 41°C. Thirty days after the exposure to hyperthermia, the susceptibility to the development of seizures and long term memory impairment were evaluated. We verified that the pre-treatment with 3-ASP or diazepam did not protect against stereotyped behavior, facial automatisms and body flexion induced by hyperthermia. The protective effect of 3-ASP (100 mg/kg) against the increased susceptibility to the development of seizures and long term memory impairment resulting from febrile seizures induced by hyperthermia was demonstrated. Diazepam (1 or 5 mg/kg) did not protect against long term memory impairment caused by febrile seizures. In addition, diazepam (1 mg/kg) treatment caused a significant cognitive impairment in animals kept at room temperature. These results suggest that 3-ASP had anticonvulsant action in 21-days-old rats and that this action appears to be mediated by glutamatergic and GABAergic systems. In addition, the anticonvulsant action of 3-ASP seems to be associated with its antioxidant activity. Finally, 3-ASP can represent an important tool to protect against increased susceptibility to seizures and cognitive impairment resulting from febrile seizures.
As convulsões têm conseqüências importantes em termos de mortalidade e qualidade de vida da população afetada, sendo um fator de risco para o desenvolvimento de alterações cognitivas e anormalidades comportamentais. Tendo em vista as promissoras propriedades farmacológicas das moléculas contendo selênio, no artigo 1 avaliamos a ação anticonvulsivante do (1-(2,5-difenilselenofeno-3-il)-3-metilpent-1-in-3-ol, que foi genericamente denominado de 3-alquinil selenofeno (3-ASP) frente as convulsões induzidas por pilocarpina (PC), pentilenotetrazole (PTZ) e cainato (KA) em ratos de 21 dias de vida. Os animais foram pré-tratados com 3-ASP (10, 25 ou 50 mg/kg; per oral, p.o.) ou veículo, 30 minutos antes da administração intraperitoneal (i.p.) de PC (400 mg/kg), PTZ (80 mg/kg) ou KA (45 mg/kg). Verificamos que o pré-tratamento com 3-ASP (50 mg/kg) aboliu as convulsões e a morte induzidas pela administração de PC. O 3-ASP (50 mg/kg) aumentou a latência para o primeiro episódio convulsivo, bem como, diminuiu a mortalidade e a incidência das convulsões causadas por PTZ e KA. Ainda no artigo 1, consideramos importante o estudo da ação antioxidante do 3-ASP (10, 25 e 50 mg/kg; p.o.) frente ao estresse oxidativo induzido pela PC (400 mg/kg, i.p.) em ratos de 21 dias de vida. Os resultados demonstraram que o pré-tratamento com 3-ASP mostrou-se eficaz na proteção contra a inibição da atividade cerebral da superóxido dismutase, diminuição dos níveis de ácido ascórbico, estimulação da atividade da catalase e aumento dos níveis de espécies reativas causadas pela PC. Adicionalmente, o 3-ASP protegeu contra a inibição da atividade da acetilcolinesterase e da Na+,K+-ATPase resultantes das convulsões induzidas pela PC. Em um segundo momento, o envolvimento dos sistemas glutamatérgico e GABAérgico na ação anticonvulsivante do 3-ASP foi verificado (Artigos 1 e 2). A combinação de doses sub-efetivas de 3-ASP (10 mg/kg, p.o.) e diazepam (agonista GABAérgico; 0,5 mg/kg, i.p.), 5S,10R (+)-5-metil-10,11-dihidro-5H-dibenzo [a,d] ciclohepteno -5,10- imina maleato (MK-801; antagonista não-competitivo do receptor NMDA; 0.1mg/kg, i.p.) ou 6,7-dinitroquinoxalina-2,3-diona (DNQX; antagonista de receptores não-NMDA; 5 mg/kg, i.p.) aumentou a latência para o primeiro episódio convulsivo, bem como diminuiu a incidência de convulsões induzidas pela PC. Por outro lado, a combinação de 3-ASP e 2-metil-6-feniletinil piridina hidroclorada (MPEP; antagonista do receptor glutamatérgico metabotrópico do tipo 5; 0,5 mg/kg, i.p.) não apresentou efeito protetor contra os episódios convulsivos. A administração oral de 3-ASP (50 mg/kg) causou uma inibição de 64% e 58% da captação de GABA no córtex e no hipocampo, respectivamente. Entretanto, nenhuma alteração na captação de glutamato após a administração de 3-ASP (50 mg/kg) foi observada. Adicionalmente, no artigo 2 investigamos a possível interação entre doses sub-efetivas de 3-ASP e inibidores da captação de GABA ou da GABA transaminase (GABA-T) frente às convulsões induzidas por PC em ratos de 21 dias de vida. Para isto, doses sub-efetivas de 3-ASP (10 mg/kg; p.o.) e ácido DL-2,4-diamino-n-butírico hidroclorado (DABA - um inibidor da captação de GABA; 2 mg/kg; i.p.) ou ácido aminooxiacético hemihidroclorado (AOAA um inibidor da GABA-T; 10 mg/kg, i.p.) foram co-administrados em ratos de 21 dias de vida antes da administração de PC (400 mg/kg; i.p.). A presença de episódios convulsivos foi avaliada. Verificamos que o tratamento com o 3-ASP e DABA aboliu as convulsões induzidas por PC, corroborando com nossos resultados neuroquímicos. O mesmo foi observado quando foram administradas doses sub-efetivas de 3-ASP e AOAA. Por fim, no artigo 3 investigamos o efeito do 3-ASP ou diazepam frente as convulsões, aumento da susceptibilidade ao desenvolvimento de convulsões e prejuízo na memória a longo prazo resultantes da convulsão febril induzida pela hipertermia. Os ratos de 21 dias de vida foram pré-tratados com 3-ASP (25, 50 ou 100 mg/kg; p.o), diazepam (1 ou 5 mg/kg; i.p.) ou veículo. Após o pré-tratamento, os animais foram expostos a uma temperatura de 41°C. Trinta dias após a exposição à hipertermia, avaliamos o aumento da susceptibilidade ao desenvolvimento de convulsões e prejuízo na memória a longo prazo. Verificamos que o pré-tratamento com 3-ASP ou diazepam não foi capaz de proteger contra o comportamento estereotipado, automatismos faciais e flexão corporal induzidos pela hipertermia. O efeito protetor do 3-ASP (100 mg/kg) contra o aumento da susceptibilidade ao desenvolvimento de convulsões e prejuízo na memória a longo prazo resultantes da convulsão febril induzida pela hipertermia foi verificado. O diazepam (1 ou 5 mg/kg) não protegeu contra o prejuízo na memória a longo prazo causado pela convulsão febril. Além disso, o tratamento com diazepam (1 mg/kg) nos animais mantidos a temperatura ambiente causou um significativo prejuízo cognitivo. Estes resultados sugerem que o 3-ASP apresenta ação anticonvulsivante em ratos de 21 dias de vida e que essa ação parece ser mediada pelos sistemas glutamatérgico e GABAérgico. Além disso, a ação anticonvulsivante do 3-ASP parece estar associada à sua atividade antioxidante. Por fim, o 3-ASP pode representar uma importante ferramenta para a proteção contra o aumento à susceptibilidade às convulsões e o prejuízo cognitivo resultantes das convulsões febris.

Conselho Nacional de Desenvolvimento Científico e Tecnológico
Depression is a serious, recurrent and incapacitating psychiatric condition with a heavy social burden. The pharmacological approach to this disorder employs therapy with antidepressant drugs, which have side effects and numerous limitations. In view of the promising pharmacological properties of containing-selenium molecules, this study evaluated the effect of 3-(4-fluorophenylselenyl)-2,5-diphenylselenophene (DPS) in the mouse forced swim test (FST) and tail suspension test (TST), two models predictive of depressant activity. Since serotonin (5-HT) plays an important role in the pathophysiology of depressive disorders, the involvement of serotonergic system and 5-HT receptors in the action caused by DPS was studied. The antidepressant-like action of combined treatment with subeffective doses of both DPS plus paroxetine, a selective serotonin reuptake inhibitor (SSRI) was investigated. Further, we verified the possible mechanism responsible for antidepressant-like action of DPS. The results showed that DPS (50 and 100 mg/kg, p.o.) significantly reduced the immobility time during the FST and TST, without accompanying changes in ambulation when assessed in the open-field test. The anti-immobility effect of DPS (50 mg/kg, i.g.) in the FST was prevented by pretreatment of mice with pCPA (p-chlorophenylalanine; an inhibitor of 5-HT synthesis, 100 mg/kg, i.p., once a day for 4 consecutive days,), WAY 100635 (N-[2- [4-(2-methoxyphenyl)-1-piperazinyl]ethyl]-N-2-pyridinylcyclohexane carboxamide; 0.1 mg/kg, s.c., a selective 5-HT1A receptor antagonist), ritanserin (1 mg/kg, i.p., a 5-HT2 receptor antagonist) or ondansetron (1 mg/kg, i.p., a 5-HT3 receptor antagonist). Combined treatment with paroxetine and DPS reduced the immobility time in the FST. DPS at the dose of 50 mg/kg did not produce any change in the cerebral activity of monoamine oxidase subtypes (MAO-A or MAO-B). DPS at the dose of 50 mg/kg inhibited significantly 5-HT uptake in mouse brain synaptosomes. These results suggest that DPS produced an antidepressant-like action in the mouse FST and TST and this action seems most likely to be mediated through an interaction with serotonergic system, particularly by 5-HT reuptake inhibition.
A depressão é uma doença grave, recorrente e uma condição psiquiátrica incapacitante que gera pesados custos sociais. A abordagem farmacológica dessa desordem é feita por meio do emprego de antidepressivos, os quais apresentam efeitos adversos e numerosas limitações. Tendo em vista as promissoras propriedades farmacológicas das moléculas contendo selênio, este estudo avaliou o efeito do 3-(4-fluorofenilselenil)-2,5-difenilselenofeno (DPS) no teste do nado forçado (TNF) e no teste da suspensão da cauda (TSC) em camundongos, dois modelos preditivos de comportamento depressivo. Uma vez que a serotonina (5-HT) desempenha um importante papel na patofisiologia dos transtornos depressivos, o envolvimento do sistema serotoninérgico e dos receptores de 5-HT na ação desenvolvida pelo DPS foi estudado. A ação do tipo antidepressiva do tratamento combinado com doses subefetivas de DPS e paroxetina, um inibidor seletivo da recaptação de serotonina (ISRS) foi investigada. Além disso, o possível mecanismo responsável pela ação do tipo antidepressiva do DPS também foi verificado. Os resultados mostram que o DPS (50 e 100 mg/kg) reduziu significativamente o tempo de imobilidade durante os TSC e TNF, sem causar alterações na atividade locomotora no teste do campo aberto (TCA). O efeito anti-imobilidade do DPS (50 mg/kg, i.g.) no TNF foi prevenido pelo pré-tratamento dos animais com pCPA (p-clorofenilalanina; 100 mg/kg, i.p., administrado uma vez ao dia durante 4 dias consecutivos, um inibidor da síntese de serotonina), WAY 100635 (N-[2-[4-(2-metoxifenil)-1-piperazinil]etil]-N-2- piridinilciclohexano carboxamida; 0,1 mg/kg, s.c., um antagonista seletivo de receptores 5- HT1A), ritanserina (1 mg/kg, i.p., um antagonista seletivo de receptores 5-HT2) ou ondansetrona (1 mg/kg, i.p., um antagonista seletivo de receptores 5-HT3). O tratamento combinado com paroxetina e DPS reduziu o tempo de imobilidade no TNF. O DPS na dose de 50 mg/kg não produziu nenhuma alteração na atividade dos subtipos da monoamino oxidase (MAO-A e MAO-B) cerebral. O DPS na dose de 50 mg/kg inibiu significantemente a captação de 5-HT em sinaptossoma de cérebro de camundongos. Esses resultados sugerem que o DPS produziu uma ação do tipo antidepressiva no TSC e no TNF em camundongos e esta ação parece ser mediada por uma interação com o sistema serotoninérgico, particularmente por uma inibição da recaptação de 5-HT.

Au cours de cette thèse, nous nous sommes intéressés à la synthèse d’hétérocycles arylés via l’activation de liaisons sp2 C-H d’hétéroaromatiques et à la synthèse d’alcènes arylés halo-substitués catalysée par le palladium. Les produits obtenus sont considérés comme des briques moléculaires, intéressantes pour les biochimistes, ainsi que pour la préparation de matériaux. Le système catalytique Pd(MeCN)2Cl2/Li2CO3/dioxane permet l’accès direct à une grande variété de molécules arylées à partir d’hétéroarènes ou d’alcènes et de chlorures de benzènesulfonyle. Nous avons mis au point une méthode permettant l’arylation directe en position β de sélénophènes à partir de sélénophènes et de chlorures de benzènesulfonyle. Nous avons également montré que l’utilisation de chlorures de benzènesulfonyle (poly)halogénés permet de synthétiser par des réactions pallado-catalysées des hétéroarènes arylés, des stilbènes ou des cinnamates (poly)halo-substitués
In this thesis we have been interested in the synthesis of arylated heterocycles via the activation of sp2 C-H bonds of heteroaromatics and to the synthesis of halo-substituted arylated alkenes using palladium-catalysis. The products obtained are considered to be molecular bricks which are of interest to biochemists as well as to the preparation of materials. The catalyst system Pd(MeCN)2Cl2/Li2CO3/dioxane allows the direct access to a wide variety of arylated molecules from heteroarenes or alkenes and benzenesulfonyl chlorides. We have developed a method for the direct β-arylation of selenophenes from selenophenes and benzenesulfonyl chlorides. We have also shown that the use of (poly)halogenated benzenesulfonyl chlorides makes it possible to synthesize, by Pd-catalyzed reactions, (poly)halo-substituted arylated heteroarenes, stilbenes or cinnamates

Conselho Nacional de Desenvolvimento Científico e Tecnológico
Selenophenes are a promising class of heterocyclic selenium-containing compounds presenting important pharmacological properties. Based on selenium well-described role on mood regulation and since depression is a serious and prevalent disease affecting a wide part of the world s population, the main aim of this work was to investigate de antidepressant-like action of 3-(organosseleno)-2,5-diphenyl-selenophenes in mice. The pharmacological effect of these compounds was analyzed by using different experimental models of depression and results were shown by three scientific articles. Firstly, results of Article 1 demonstrated the antidepressant-like action of five selenophene compounds. H-DPS, CH3-DPS, Cl-DPS, FDPS and CF3-DPS reduced the total immobility time of mice evaluated in the forced swimming test (FST), which seems to be related to their chemical structure. The antidepressant-like action of F-DPS was observed at lower doses than other selenophenes e involves the phosphorylation of extracellular-signal-regulated kinases (ERK), whose signaling pathway is commonly modulated by antidepressant drugs. Articles 2 and 3 investigated the pharmacological effect of F-DPS in mouse models of depression induced by both neuropathic pain and chronic corticosterone administration, respectively. Both the acute and subchronic treatments with F-DPS significantly reversed the depression-related behavior produced by partial sciatic nerve ligation (PSNL), whereas pain sensibility was only reduced after repeated treatment with this selenophene. Besides, repeated administration of the glucocorticoid hormone corticosterone induced behavior, endocrinal and neurochemical changes similar to those clinically observed in depression, which were also reversed by treatment of animals with F-DPS. Based on these data, the mechanisms of pharmacological action of this organoselenium compound seem to involve, at least in part, a modulation of glutamatergic and serotonergic systems, the hypothalamic-pituitary-adrenal (HPA) axis regulation and changes on neuronal pathways related to the synaptic plasticity. Together, the results shown in this thesis suggest the pharmacological properties of selenophene compounds, particularly F-DPS, as an interesting tool in the study and development of future therapies for depressive disorders.
Os selenofenos são uma classe de compostos heterocíclicos aromáticos com promissoras propriedades farmacológicas. Tendo em vista o importante papel do selênio na regulação do humor e a grande prevalência populacional das doenças depressivas, o principal objetivo deste estudo foi investigar a ação do tipo antidepressiva de 3-(organosseleno)-2,5-difenilselenofenos em camundongos. A fim de atender a este objetivo, o efeito farmacológico destes compostos foi analisado pelo uso de diferentes modelos experimentais de depressão e os resultados foram apresentados em três artigos científicos. Primeiramente, os resultados do Artigo 1 demonstraram a ação do tipo antidepressiva de cinco representantes da classe dos selenofenos. Os compostos H-DPS, CH3-DPS, Cl-DPS, F-DPS e CF3-DPS reduziram significantemente o tempo total de imobilidade de camundongos avaliados no teste do nado forçado (TNF), efeito este que parece estar relacionado às suas estruturas químicas. A ação do tipo antidepressiva do F-DPS foi observada em menores doses em comparação aos outros selenofenos e envolve a fosforilação da proteína quinase regulada por sinal extracelular (ERK), cuja via de sinalização é comumente modulada por drogas antidepressivas. Os Artigos 2 e 3 investigaram o efeito farmacológico do F-DPS em modelos crônicos de depressão induzida pela dor neuropática e pela administração crônica de corticosterona em camundongos, respectivamente. Tanto o tratamento agudo como o subcrônico com F-DPS reverteram significantemente o comportamento do tipo depressivo produzido pela ligação parcial do nervo ciático (LPNC), enquanto que a sensibilidade à dor foi reduzida somente após a terapia prolongada com este composto. Por sua vez, a administração repetida do hormônio glicocorticoide corticosterona induziu alterações comportamentais, endócrinas e neuroquímicas similares às observadas clinicamente na depressão e que também foram revertidas pelo tratamento dos animais com F-DPS. Com base nestes resultados, acredita-se que os mecanismos de ação farmacológica deste composto orgânico de selênio envolvam, pelo menos em parte, a modulação dos sistemas glutamatérgico e serotonérgico, a regulação da atividade do eixo hipotálamo-pituitária-adrenal (HPA) e modificações em vias neuronais relacionadas à plasticidade sináptica. Juntos os resultados apresentados nesta tese de doutorado sugerem que o estudo das propriedades farmacológicas de compostos selenofenos, particularmente do F-DPS, parece ser interessante no desenvolvimento de futuras terapias para o tratamento dos distúrbios neurológicos relacionados às doenças depressivas.

Na primeira parte deste trabalho, desenvolvemos duas metodologias para a preparação de α-dicloroteluro cetonas. A primeira utiliza a reação direta de tricloretos de ariltelúrio com cetonas e a segunda envolve a reação do mesmo reagente com éteres enólicos de silício de cetonas. As dicloroteluro cetonas preparadas foram transformadas em α-halo cetonas pela reação com cloro ou bromo, ou utilizando condições de termólise sob pressão reduzida. Dados de ressonância magnética nuclear de 1H e de 13C, de difração de raios-X e de espectros no infra-vermelho foram utilizados na determinação estrutural dos compostos preparados. Numa segunda arte foram preparados α-halo-α-seleno alcanos através da adição de HBr a selenetos vinílicos obtidos por reação de acetilenos aromáticos com selenofenol. Os α-halo-α-seleno alcanos foram transformados em α-selenofenil acetaldeídos por reação de solvólise em DMSO.
In the first parto of this work two methodologies for the synthesis of α-dichlorotelluroketones were developed. The first one employs the reaction of aryltellurium tricholorides with ketones and the second one involves the reaction of the same reagent with silylenol ethers of ketones. The α-dichlorotelluroketones prepared were transformed into α-halo ketones by means of the reaction with chlorine or bromine or by pyrolysis at reduced pressure. 1H and 13C nuclear magnetic ressonance, x-ray difraction and infrared data were used in the structure elucidations of the compounds prepared. In the second part of the work α-halo- α-seleno-alkanes were prepared by addition of hydrogen bromide to vinylic selenides which were prepared by reacting aromatic acetylenes with selenophenol. The α-halo-α-seleno-alkanes were transformed into α-selenophenyl acetaldehydes by solvolysis in DMSO.

博士
國防醫學院
生命科學研究所
100
D-501036 is a selenophene compound that exhibits potent anti-proliferative activity against various types of human cancers through the induction of double strand DNA breaks in cells. In order to investigate drug resistance mechanism of this compound, a human cervical cancer cell line KB-derived D-501036-resistant (S4) cells were established. S4 cells were 45-fold more resistant to D-501036 than its parental KB cells. D-501036 induced less DNA damage responses in S4 cells were less than in KB cells. Further study revealed that S4 cells exhibited higher DNA rejoining ability than KB cells through non-homologous end joining (NHEJ) machinery. Silencing Ku80 expression by siRNA reduced global DNA repair ability thus restored drug sensitivity to D-501036 in S4 cells. Furthermore, combination of D-501036 and X-ray irradiation was demonstrated to have synergistic anti-cancer effect in NSCLC cell lines A549, H460, and H358. However, Annexin V assay suggested that combined treatment could produce synergistic effect only in H460 cells. In vivo xenograft studies revealed that effective dose of both X-ray irradiation and D-501036 was reduced through combined treatment. Taken together, these results indicate that enhancement of NHEJ activity plays an important role in the development of D-501036 resistance. The results of combined treatment also provide valuable information for future design of clinical trial in development of D-501036. 4

碩士
國立交通大學
應用化學系碩博士班
106
In this study, in order to develop a series of organic photovoltaic (OPV) materials with high performance, three selenophene-incorporating naphthobisthiadiazole-based donor-acceptor copolymers (OD-series), PNT2Th2Se-OD, PNT2Se2Th-OD and PNT4Se-OD, have been successfully tailored and synthesized. PNT2Th2Se-OD and PNT2Se2Th-OD hybridize two thiophenes and two selenophenes as the donor with different isomeric main-chain placement while thiophene-free PNT4Se-OD uses quaterselenophene as the donor. In comparison with the thiophene-based polymer, the selenophene-based polymer is prone to forming quinoidal character that enhances the planarity of the polymer, increases effective conjugation length and strengthens intermolecular interctions. Due to above-mentioned properties, the polymers containing selenophenes possess narrower optical bandganp, broader absorption range and enhancement of charge mobilities. However, the selenophene with the strong intermolecular force results in lower solubility. Herein, three polymers (DT-series) with same polymer backbone, PNT2Th2Se-DT, PNT2Se2Th-DT and PNT4Se-DT, have been additionally synthesized by side-chain variations. PNT2Th2Se-OD, PNT2Se2Th-OD and PNT4Se-OD exhibited gradually red-shifted and extensive absorptions, which cover the whole visible light and part of infrared area. The DT-series polymer demonstrated the similar polymeric properties. PNT2Se2Th-OD exhibited more red-shifted absorption due to stronger intramolecular charge transfer between NT-unit and selenophenes. Moreover, PNT4Se-OD consisting of quaterselenophene showed the narrowest bandgap and highest HOMO energy level. Furthermore, these six polymers revealed temperature-dependent aggregation in temperature-gradient absorption spectrum. By changing the selenophene/thiophene arrangement and the number of selenophene in the polymer to systematically fine-tune and investigate the isomeric properties, all the six polymers show good light-harvesting ability, strong intermolecular aggregation, high crystallinity, and high charge mobilities. Bulk-heterojunction solar cells with inverted architecture (ITO/ZnO/polymer: PC71BM/MoO3/Ag), incorporating these selenophene-containing polymers have exhibited promising photovoltaic performance. The device with the PNT2Th2Se-OD:PC71BM blend showed a highest PCE of 9.47 % with an impressive Jsc of 20.69 mA/cm2. The device with PNT2Se2Th-DT:PC71BM blend performed a PCE of 8.42 % with a Jsc of 19.70 mA/cm2. In addition, the device with PNT2Se2Th-DT:PC71BM blend exhibited a PCE of 8.25 % with a 43% improvement compared to PNT2Se2Th-OD.

碩士
國立臺灣大學
化學研究所
103
In this study, we report two conjugated copolymers, combined with indacenodithiophene- (IDT) and fluorinated quinoxaline- (FQ) based monomers, while using thiophene and selenophene as π-bridge in both, yielding pIDTTFQ and pIDTSFQ, respectively. In an aim to apply them into polymer photovoltaics and achieve better power conversion efficiencies (PCEs), alternating variant π-space to harness the photochemical properties of conjugated copolymers has been one of the strategies in modifying present copolymer combinations. Theoretical calculations reveal that the usage of selenophene reliefs the intramolecular repulsion and the corresponding twist, with the decrease of dihedral angle. Compared with pIDTTFQ, the absorption edge of pIDTSFQ in solid state is extended from 685nm to 742nm, while the EHOMO was increased from -5.37eV to -5.31eV. Considering the decreased Voc and the enhanced Jsc, the optimized pIDTTFQ- and pIDTSFQ-based devices achieve PCE values of 2.0±0.1% and 2.6±0.5%, respectively. However, the two polymers exhibit similar devices performance but much different absorption ranges, which signifies the potential of choosing selenophene as π-bridge to achieve better device performance.

碩士
國立交通大學
應用化學系碩博士班
105
Selenophene has several advantages such as high polarizability and high quinoidal population which endow many selenophene-based materials with narrower optical bandgap, enhance light-harvesting ability and higher crystallinity. These beneficial properties lead to the improved charge carrier mobiliies in transistor devices or higher photocurrents in OPV devices. The traditional method to synthesize 3-alkyl selenophene is quite complicated and costly. We successfully design an efficient way to simplify the synthesis of selenophene. We utilize selenophene to synthesize three donor-acceptor copolymers consisting of 5,6-difluorobenzo[2,1,3]thiadiazole (FBT) and selenophene called PFBT2Th2Se, PFBT2Se2Th and PFBT4Se, respectively. Selenophene has higher intramolecular charge transfer ability with FBT than thiophene. Therefore, the polymers containing selenophene display more red-shifted absorption. The selenophene-containing polymers also show temperature-dependent absorption spectrum, indicating that the incorporation of selenophene does not affect the crystalline behavior of the polymers. Furthermore, the results from differential scanning calorimeter (DSC) confirm that these three polymers have crystalline behavior since it shows the obvious melting point upon heating and the clear crystallization point upon cooling. The combination of these characteristics enhances the charge transport efficiency. Hence, the devices which utilize these selenophene-containing polymers can obtain impressive current density (>20 mA/cm2). To gain a deeper insight into the nanoscale morphology and orientation of the photoactive layers, the grazing-incidence wide-angle X-ray diffraction (GIWAXD) was employed. The results suggest that the three polymers blended with PC71BM adopt face-on orientation which is beneficial for charge carrier transport in the vertical direction in the active layer. Organic photovoltaic devices are fabricared with inverted atchitecture (ITO/ZnO/Active layer/MoO3/Ag). The device using PFBT2Th2Se:PC71BM shows a PCE of 8.68 % with a Voc of 0.68 V, an FF of 69.1 %, and a high Jsc of 18.46 mA/cm2. Under similar conditions, the device using the PFBT2Se2Th:PC71BM blend presents a PCE of 9.02% with a Voc of 0.66 V, an FF of 65.0 %, and an impressive Jsc of 21.02 mA/cm2. Furthermore, the device with PFBT4Se displays a PCE of 8.92 % with a Voc of 0.62 V, FF of 63.6 %, and a superior Jsc of 22.63 mA/cm2 which represents one of the highest current densities from PSCs reported in the literature.

碩士
國立交通大學
應用化學系碩博士班
104
In this study, two series of conjugated polymers were synthesized for the application of organic thin film transistors (OTETs) and organic solar cells (OSCs). For the first series, perylene and dithienylbenzothiadiazole (DTBT) were introduced to the side chain of poly(5,6-difluoro-benzo-2,1,3-thiadiazole co-quaterthiophene) (PTh4FBT) to obtain two types of copolymers, i.e. PTh4FBT-PERY, PTh4FBT-DTBT. The obtained polymers were characterized by UV, CV, DSC, TGA, X-ray diffraction and their performance in OTFTs and OSCs. Both PTh4FBT-PERY and PTh4FBT-DTBT show the mobilities of 4.04 × 10-1 cm2 V-1 s-1 and 1.08 × 10-1 cm2 V-1 s-1 respectively. The mobility of PTh4FBT-PERY is higher than that (2.89 × 10-1 cm2 V-1 s-1) of PTh4FBT. The PCE values of PTh4FBT-PERY and PTh4FBT-DTBT based OPV devices are 5.0% and 4.97% respectively. For the second series, silolo[3,2-b:4,5-b']bis(selenophene)(DSS) were used as an electron donor unit and it was copolymerized with dithienodiketopyrrolopyrrole (DPP) containing octyl and 2-ethylhexyl side chains to obtain two alternating copolymers, i.e. PDSSDPP-C2C6 and PDSSDPP-C8. The obtained polymers were characterized by UV, CV, DSC, TGA, X-ray diffraction and their OTFTs performance. Both PDSSDPP-C2C6 and PDSSDPP-C8 show the mobilities of 2.67 × 10-2 cm2 V-1 s-1 and 2.47 × 10-2 cm2 V-1 s-1 respectively.Both values are higher than that (3.89 × 10-3 cm2 V-1 s-1) of homologue PDTSDPP-C8.

碩士
國立交通大學
應用化學系碩博士班
101
This research is aimed to enhance the performances of low band gap (LBG) polymer in the optoelectronic applications, such as organic field-effect transistors (OFETs) and organic polymer photovoltaics (OPVs). Two strategies were used to design high performance LBG polymers, including promoting of the intermolecular non-covalent interaction strength and effect of congeners of the state-of-art LBG polymers. In the first part of this study, 5,6-difluoro-benzo-2,1,3-thiadiazole acceptor unit was copolymerized with quaterthiophene donor unit (PTh4FBT). This fluorinated unit was used to enhance the non-covalent interaction and the packing order of polymer chains in the aggregation state. The best OPV device based on this obtained polymer shows the power conversion efficiency (PCE) value of 6.82% and its OFET mobility of 0.29 cm2v-1s-1. In the second part of this study, furan and selenophene units were used to replace two thiophene units in the copolymers to study the effect of congeners. Other two copolymers (PTh2OFBT and PTH2SeFBT) were synthesized. Reduction of the bandgap and increase of crystallinity were observed in the selenophene containing polymer. Therefore, the device performances of PTh2SeFBT were the highest among the three polymers. The OPV and OFET devices based on PTh2SeFBT reveals the PCE value of 7.34% and 0.36 cm2v-1s-1. However, PTh2OFBT shows increase of the bandgap and reduction of crystallinity. So the OPV and OFET devices based on PTh2OFBT shows PCE value of 0.21% and mobility of 10-3 cm2v-1s-1.

博士
中國醫藥大學
藥物化學研究所博士班
100
In our prior work, the phosphorylation of two promising lead 2-arylquinoline (2AQ) analogues, 2-(2-fluorophenyl)-6,7-methylenedioxy-quinolin-4-one (2AQ-1) and 2-(3-fluorophenyl)-5-hydroxy-6-methoxy-quinolin-4-one (2AQ-2) led to the production of two anticancer drug candidates. In order to develop additional new lead compounds among 2AQ analogues and elucidate structure-activity relationships (SAR), 2- selenophenylquinoline and related compounds were synthesized as target compounds and evaluated for in vitro anticancer activity against HL-60, Hep 3B, and H460 cancer cell lines. Comparison of the 6,7-methylenedioxy-2- (substituted selenophenyl)quinolin-4-ones (52, 55, 58 and 70), with their thiophenyl (53, 56, 59 and 71) and furanyl isosteres (54, 57, 60 and 72) gave the following rank order of potency: selenophenyl derivatives ?l thiophenyl derivatives > furanyl derivatives. The anticancer activity of 5,6-substituted-2-(substituted selenophenyl)quinolin-4-ones (61, 63, 65, 67, 68, 75, 77, 79, 73, 74 and 81) was ranked in the following order: 5-hydroxy-6-methoxy derivatives > 6-methoxy derivatives > 5,6-dimethoxy derivatives. Among all tested compounds, 6,7-methylenedioxy-2-(5- methylselenophen-2-yl)quinolin-4-one (55) was found to be the most promising anticancer agent. In screening against NCI’s 60 human tumor cell line panel, compound 55 exhibited highly selective cytotoxicity activity against HL-60 leukemia. Furthermore, the results of COMPARE analysis suggested that 55 is an antimitotic agent with a different mechanism of action not only from the conventional antimitotic agents, such as colchicine, vincristine、vinblastine and paclitaxel, but also from 2AQ-1 and 2AQ-2, which have the same quinolin-4-one scaffold as 55. Therefore, compound 55 was identified as a new lead compound that merits further optimization.

碩士
國立中央大學
化學工程與材料工程學系
103
A practical and convenient Co-catalyzed alkylation method targeting on the facile introduction of various alkyl chains into organic-electronically significant heteroaryls including thiophenes, furans, selenophenes, and pyrroles is reported. Under well-optimized reaction conditions, a wide range of alkylated heteroaryls are efficiently prepared in moderate to good isolated yields. Notably, 2- or 3-alkylthiophenes, as playing a decisive role in polymer chemistry and organic materials, are step-economically synthesized for the first time by present reductive-coupling methodology using inexpensive cobalt salts as catalyst. This straightforward synthetic method avoids the preparation of moisture-unstable organometallic reagents (RMgX or RZnX) and the use of precious catalysts ([Pd] or [Ni]) required in conventional alkylation protocols.

碩士
國立中山大學
化學系研究所
90
(1) Flash vacuum pyrolysis (FVP) of (5-methyl-2-selenophenyl)methyl benzoate gave 4-methylene-4H-selenopyran. The structure was confirmed by trapping experiment. The mechanism for the 4-methylene-4H-selenopyran will be discussed. (2) Flash vacuum pyrolysis of 2-Azidomethylselenophene, via a nitrene intermediate, gave a trimer (N,N’-di-2-selenophenylmethylidene-2-selenophenylmethylidene diamine).

碩士
國立交通大學
應用化學系碩博士班
105
New D-A systemic copolymers based on 3,6-bis(2-bromothieno-[3,2-b]thiophen-5-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]-pyrrole-1,4-(2H,5H)-dione (TTDPP) combined with three different electron-donating strength monomer bithiophene (BT), di(2-thienyl)ethene (TVT), di(selenophen-2-yl)ethene (SVS) were synthesized. These three polymers’ optical band gap, electrochemical properties and organic thin-film transistors (OTFTs) device performance were systematically investigated. PBTTDPP-BT containing flexible moiety BT and long conjugated chain could modulate the polymer’s energy level and show the good packing on X-ray Diffraction (XRD). In order to get the better molecular packing, the strategy of using double bond as backbone moiety was used to create TVT as a donor unit. PBTTDPP-TVT copolymer showed better packing ability. It showed that OFET mobility of PBTTDPP-BT and PBTTDPP-TVT were 0.0882 cm2 V-1 s-1, 0.0945 cm2 V-1 s-1, respectively. Sequentially, we replaced the sulfur atom with the selenium atom in TVT unit. SVS was also copolymerized with TTDPP to form the polymer PBTTDPP-SVS. PBTTDPP-SVS had smallest d-spacing among three copolymers in lamellar direction. It implied that PBTTDPP-SVS had better intrachain transport charge transfer. Furthermore, PBTTDPP-SVS had suitable HOMO level to help carrier inject into Au electrode from polymer. As a result, PBTTDPP-SVS showed the highest hole mobility of 0.196 cm2V-1s-1 and the lowest threshold voltage -3.60 V in this study.