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Desenvolvimento de complexo de Ru(II) com 3-metilpiperidina para atuar como catalisador em reações de polimerização via metátese de olefinas cíclicas / Development of Ru (II) complex with 3-methylpiperidine to act as a catalyst in polymerization reactions via cyclic olefin metathesisPereira, João Clécio Alves 22 February 2018 (has links)
A molécula de 3-metilpiperidina (3-Mepip) foi investigada como ligante ancilar em um novo complexo do tipo [RuCl2(PPh3)2(amina)] em polimerização via metátese de olefinas ciclicas por abertura de anel (ROMP) de norborneno (NBE) e norbornadieno (NBD). A síntese do novo complexo foi realizada partindo-se do complexo precursor [RuCl2(PPh3)3], e foi caracterizado por: EPR, análise elementar de CHN, infravermelho (FTIR) e RMN de 31P. Com base nos resultados obtidos é possível propor um complexo pentacoordenado com geometria pirâmide de base quadrada (PBQ), estando os íons cloretos trans-posionados no plano equatorial da esfera de coordenação do metal, com a amina ocupando a posição apical da pirâmide devido ao seu forte caráter doador σ. As reações de ROMP dos monômeros NBE e NBD utilizando o novo complexo foram realizadas em atmosfera de argônio em função da razão molar de molar [monômero]/[Ru] (1000, 3000, 5000, 7000 e 10000), tempo (5, 30 e 60 min) e temperatura (25 e 50 °C). Com um volume de 5 µ de etildiazoacetato (EDA), 25 °C e uma razão molar de 5000 de monômero a 5 min, obteve-se 65 % de poliNBE com Mn = 0,8 x 105 e IPD igual a 1,9. Os polímeros obtidos com NBD apresentaram um rendimento em torno de 20% a 25 °C por 5 min. Reações de polimerização em atmosfera aberta resultaram em valores de rendimento próximos dos observados em atmosfera de argônio, sugerindo dessa forma que o novo complexo é resistente a processos oxidativos provocados pelo O2 da atmosfera ambiente. As reações de polimerização foram realizadas na presença de outros diazocompostos benzildiazoacetato (BDA) e tertbutildiazoacetato (TBDA) como fontes de carbenos, afim de avaliar a influência eletrônica e estérica provocada pelos diferentes grupo R desses diazocompostos. Foi observado que o etildiazoacetato (EDA) apresentou os melhores valores de rendimento dos polímeros isolados, provavelmente devido ao balanço nas características estéricas e eletrônicas desse diazo frente ao centro de Ru(II). / The 3-methylpiperidine (3-Mepip) molecule was investigated as ancillary ligand in a novel [RuCl2(PPh3)2(amine)] type complex for ring-opening metathesis polymerization (ROMP) of norbornene (NBE) and norbornadiene (NBD). The synthesis of the new complex was performed from the precursor complex [RuCl2(PPh3)3], and it was characterized by: EPR, CHN elemental analysis, infrared (FTIR) and 31P NMR (1H). From the obtained results it was possible to propose a pentacoordenado complex with square-shaped pyramid geometry (PBQ), with chloride ions trans-positioned in the equatorial plane of the coordinating metal sphere, with the amine occupying the apical position of the pyramid due to its strong σ-donor character. The ROMP reactions of NBE and NBD monomers using the new complex were performed under argon atmosphere as a function of the [monomer]/[Ru] molar ratio (1000, 3000, 5000, 7000 and 10000), reaction time (5, 30 and 60 min) and temperature (25 and 50 ° C). With a volume of 5 µL of ethyldiazoacetate (EDA), at 25 °C and a 5000 molar ratio of monomer for 5 min, 65% polyNBE was obtained with Mn = 0.8 x 105 and IPD equal to 1.9. The polymers obtained with NBD showed 20% yield at 25 °C for 5 min. The polymers obtained with norbornadiene showed a yield of about 20% at 25 °C for 5 min. Polymerization reactions in air atmosphere resulted in values close to those observed in argon atmosphere, suggesting that the complex presents resistance to oxidative processes caused by O2 from the ambient atmosphere. The polymerization reactions were performed in the presence of other diazocompounds benzyldiazoacetate (BDA) and tert-butyldiazolacetate (TBDA) as sources of carbenes. In order to evaluate the electronic and steric influence caused by the different R groups of these diazocompounds, it was observed that ethyldiazoacetate EDA) presented the best yield values of the isolated polymers, probably due to the balance in the steric and electronic characteristics of this diazo in front of the Ru(II) center.
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Desenvolvimento de complexo de Ru(II) com 3-metilpiperidina para atuar como catalisador em reações de polimerização via metátese de olefinas cíclicas / Development of Ru (II) complex with 3-methylpiperidine to act as a catalyst in polymerization reactions via cyclic olefin metathesisJoão Clécio Alves Pereira 22 February 2018 (has links)
A molécula de 3-metilpiperidina (3-Mepip) foi investigada como ligante ancilar em um novo complexo do tipo [RuCl2(PPh3)2(amina)] em polimerização via metátese de olefinas ciclicas por abertura de anel (ROMP) de norborneno (NBE) e norbornadieno (NBD). A síntese do novo complexo foi realizada partindo-se do complexo precursor [RuCl2(PPh3)3], e foi caracterizado por: EPR, análise elementar de CHN, infravermelho (FTIR) e RMN de 31P. Com base nos resultados obtidos é possível propor um complexo pentacoordenado com geometria pirâmide de base quadrada (PBQ), estando os íons cloretos trans-posionados no plano equatorial da esfera de coordenação do metal, com a amina ocupando a posição apical da pirâmide devido ao seu forte caráter doador σ. As reações de ROMP dos monômeros NBE e NBD utilizando o novo complexo foram realizadas em atmosfera de argônio em função da razão molar de molar [monômero]/[Ru] (1000, 3000, 5000, 7000 e 10000), tempo (5, 30 e 60 min) e temperatura (25 e 50 °C). Com um volume de 5 µ de etildiazoacetato (EDA), 25 °C e uma razão molar de 5000 de monômero a 5 min, obteve-se 65 % de poliNBE com Mn = 0,8 x 105 e IPD igual a 1,9. Os polímeros obtidos com NBD apresentaram um rendimento em torno de 20% a 25 °C por 5 min. Reações de polimerização em atmosfera aberta resultaram em valores de rendimento próximos dos observados em atmosfera de argônio, sugerindo dessa forma que o novo complexo é resistente a processos oxidativos provocados pelo O2 da atmosfera ambiente. As reações de polimerização foram realizadas na presença de outros diazocompostos benzildiazoacetato (BDA) e tertbutildiazoacetato (TBDA) como fontes de carbenos, afim de avaliar a influência eletrônica e estérica provocada pelos diferentes grupo R desses diazocompostos. Foi observado que o etildiazoacetato (EDA) apresentou os melhores valores de rendimento dos polímeros isolados, provavelmente devido ao balanço nas características estéricas e eletrônicas desse diazo frente ao centro de Ru(II). / The 3-methylpiperidine (3-Mepip) molecule was investigated as ancillary ligand in a novel [RuCl2(PPh3)2(amine)] type complex for ring-opening metathesis polymerization (ROMP) of norbornene (NBE) and norbornadiene (NBD). The synthesis of the new complex was performed from the precursor complex [RuCl2(PPh3)3], and it was characterized by: EPR, CHN elemental analysis, infrared (FTIR) and 31P NMR (1H). From the obtained results it was possible to propose a pentacoordenado complex with square-shaped pyramid geometry (PBQ), with chloride ions trans-positioned in the equatorial plane of the coordinating metal sphere, with the amine occupying the apical position of the pyramid due to its strong σ-donor character. The ROMP reactions of NBE and NBD monomers using the new complex were performed under argon atmosphere as a function of the [monomer]/[Ru] molar ratio (1000, 3000, 5000, 7000 and 10000), reaction time (5, 30 and 60 min) and temperature (25 and 50 ° C). With a volume of 5 µL of ethyldiazoacetate (EDA), at 25 °C and a 5000 molar ratio of monomer for 5 min, 65% polyNBE was obtained with Mn = 0.8 x 105 and IPD equal to 1.9. The polymers obtained with NBD showed 20% yield at 25 °C for 5 min. The polymers obtained with norbornadiene showed a yield of about 20% at 25 °C for 5 min. Polymerization reactions in air atmosphere resulted in values close to those observed in argon atmosphere, suggesting that the complex presents resistance to oxidative processes caused by O2 from the ambient atmosphere. The polymerization reactions were performed in the presence of other diazocompounds benzyldiazoacetate (BDA) and tert-butyldiazolacetate (TBDA) as sources of carbenes. In order to evaluate the electronic and steric influence caused by the different R groups of these diazocompounds, it was observed that ethyldiazoacetate EDA) presented the best yield values of the isolated polymers, probably due to the balance in the steric and electronic characteristics of this diazo in front of the Ru(II) center.
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Electrochemical Quartz Crystal Microbalance Study Of Bismuth Underpotential Deposition On Ruthenium And On Electrochemically Formed Ruthenium OxideLin, Po-Fu 12 1900 (has links)
Kinetics and thermodynamics of bismuth (Bi) underpotential deposition (UPD) on ruthenium (Ru) and on electrochemically formed Ru oxide are studied using electrochemical quartz crystal microbalance technique. The Bi UPD and Bi bulk deposition are observed both on Ru and on electrochemically formed Ru oxide electrodes. The anodic peak potential of Bi UPD shifts slightly to positive potential as the scan rate increases. The peak current ratio (IAnode/ICathode) of Bi UPD and Bi bulk increases as the scan rate increases. Bi monolayer coverage calculated from mass (MLMass) and from charge (MLCharge) with scan rates dependent are compared both in Bi UPD region and in Bi bulk region. Stability and oxidation time effects are also investigated. Bi UPD on Ru and on electrochemically formed Ru oxide are quasi-reversible, scan rate independent, oxidation time dependent, and have higher plating efficiency on Ru. However, Bi bulk deposition on Ru and on electrochemically formed Ru oxide are quasi-reversible, scan rate dependent, oxidation time independent, and have higher plating efficiency on electrochemically formed Ru oxide. Both Bi UPD adatoms and Bi bulk are unstable in 0.5M H2SO4.
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Chemical abortion in ItalyInnocenti, Paola January 2013 (has links)
In Italy, the “traditional” form of family revaluated by fascist dogma is one of the pillars of the society. Women have a central role to maintain, protect and support this form of family. Many Italian women, the State, the media and the Church, all act to safeguard this reality, seeking to remove all obstacles that can challenge the family. Abortion is considered as one of these obstacles and it has been a much debated topic in Italy over the years. Abortion was made legal in Italy in 1978 with a widely discussed law. The Italian Abortion Act, despite being the object of debates, critics and two referenda supported by all Parliamentary factions, has never been modified. In 2002, with the introduction of RU 486 at the Sant’Anna of Turin all debates about abortion started up again accompanied by a strong opposition to the implementation of the drug. The purpose of this study is to better understand the social definition of the female condition in Italy analysing the obstacles to the implementation of chemical abortion in Italy. In order to evaluate the role of both the Italian Government and society in obstructing the introduction of RU 486 in Italy, historical and secondary sociological data were collected and a series of interviews and a participant observation in a selection of Italian hospitals were conducted. A comparative study between Italy and the UK was also conducted. The results of this study seem to prove how the majority of Italian women, in opposition to feminist theory, prioritize family, femininity and maternity, considering career as necessary mainly from an economic point of view. Abortion is now considered by the young generation as something avoidable and no longer associated with women’s right to choose or as an expression of “self-determination”. This strong “traditionalistic” attitude seems to be caused by the inability of the Italian State to implement its laws and by the direct and indirect influence of the Catholic Church.
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Människosonen : en självgod messias i Tyskland efter första världskriget / av Tore Ahlbäck.Ahlbäck, Tore, January 1983 (has links)
Akademisk avhandling--Teologi--Åbo, 1983. / Bibliogr. p. 289-297.
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Structure and reactivity of clean, potassium promoted and iron modified rutheniumHarrison, K. January 1987 (has links)
Various aspects of the surface chemistry of a ruthenium (1010) single crystal have been investigated under ultra-high vacuum conditions, employing the techniques of Auger Electron Spectroscopy, Low Energy Electron Diffraction, Multimass Thermal Desorption Spectroscopy, photoemission spectroscopies and work function measurements. The studies were undertaken with a view towards the applicability of ruthenium and iron-ruthenium alloys to the ammonia synthesis, though work relevant to the Fischer-Tropsch synthesis was also performed. The interactions of the gases nitrogen, hydrogen and ammonia with the clean surface were all explored. Molecular nitrogen was found to have an extremely low sticking probability of less than 10<SUP>-9</SUP> at room temperature, but surface nitrogen atoms were deposited via two separate means, using either a mixture of nitrogen ions or nitrogen atoms themselves as the impinging species. Both chemisorbed and bulk implanted states were thereby observed. Hydrogen uptake at 310 K saturated at small doses but an estimate of 256 kJ mol<SUP>-1</SUP> was made for the Ru-H bond strength from thermal desorption traces. Ammonia readily adsorbed at and above room temperature. Partial dissociation occurred at 300 K, the extent of fragmentation increasing as the crystal temperature was raised. Strong electron beam perturbations of the adlayer occurred, accelerating the rate of adsorption and resulting in the appearance of otherwise unobservable LEED patterns. The behaviour of the model promoter potassium was relatively typical of alkali metal/transition metal systems, though the anisotropic substrate potential was found to induce a series of interesting one dimensionally incoherent compressed overlayer structures. A further striking observation was the occurrence of substantial bulk dissolution of potassium following small doses at 430 K. The promoting effects of potassium on CO adsorption were investigated and interpreted interms of a recent modification of the Blyholder model, which combines indirect, through metal and direct, through space interactions. Finally, the deposition of iron on Ru(10bar 10) was studied. At 300 K the iron film grew in a metastable layer by layer mode, which rapidly rearranged on heating to either an alloy phase or a regime of 3D crystallites lying above one or two iron monolayers. Adsorption at elevated temperatures produced essentially the same results as heating layers deposited at room temperature.
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Antigestagene als Abtreibungsmethode : leichtfertiger Umgang mit ungeborenem Leben oder medizinischer Fortschritt? /Spek, Petra Christine. January 2000 (has links)
Thesis (doctoral)--Freie Universität, Berlin, 1999.
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Medidas de correlação angular gama-gama no 100 ANTPOT. Ru / Measurements of gamma-gamma angular correlation in 100RuKenchian, Garabed 08 June 1990 (has links)
Um espectrômetro automático de correlação angular Ge(Li)-Ge(Li) foi desenvolvido. O espectrômetro é movido automaticamente, controlado um microcomputador. A correlação angular direcional gama-gama entre transições coincidentes dos níveis do ANTPOT100 RU, alimentados pelo decaimento ß+ e por captura de elétrons do ANTPOT 100 R foi medida. A fonte de ANTPOT 100 Ru foi produzida na reação ANTPOT 100 Ru (p, n) Rh POT. 100 utilizando o feixe de prótons do Acelerador cíclotron. Foram medidas 30 cascatas simples e 11 cascatas triplas produzindo como resultado a assinalação do spin e paridade dos estados de 1865 kev, 1881 kev, 2099 kev, 2167 kev, 2241 kev, 2517 kev, e 3070 kev e a determinação dos valores de mistura multipolar de 21 transições sendo que 12 delas pela primeira vez. Foi medido ainda o valor da razão de mistura multipolar Q POT. 2 (E0\\E2) da transição 2+ IND. 2 2+ IND. 2 / Knowledge of the spectral distribution of radiation emitted by radiodiagnostic units provides important information, which can be applied to the Quality Assurance and Radiological Protection programs. Detectors which utilize Silicon PIN Photodiodes have been increasingly used in recent years, due to their low cost and being worked with at room temperature, the liquid nitrogen containers used with Ge and Si(Li) detectors not being necessary. Although, initially, the PIN photodiodes have a poorer energy resolution, as compared with Ge detectors, it\'s good enough for most purposes. Moreover, the development of thermoelectrically cooled systems and low noise level pre-amplifiers have resulted in PIN photodiodes achieving comparable resolutions to Ge ones. This work seeks to establish the properties of detectors made with Silicon PIN photodiodes and to develop the correctional process of the raw specffa both for the efficiency of the detector and other relevant factors, with the aim of obtaining the true spectrum emitted by radiodiagnostic equipment. The radiation spectra of radiodiagnostic equipment experimentally obtained were compared with theoretical spectra calculated from a semi-empirical model. Furthermore, mammography x-ray spectra scattered by a breast simulator were obtained. As a direct application of these experimentally measured spectra, methodologies were developed to determine the peak kilovoltage (kvp) of X-Ray tubes, to be able to calibrate kVp meters, and the half-value layer (HW) of the beams of interest.
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Medidas de correlação angular gama-gama no 100 ANTPOT. Ru / Measurements of gamma-gamma angular correlation in 100RuGarabed Kenchian 08 June 1990 (has links)
Um espectrômetro automático de correlação angular Ge(Li)-Ge(Li) foi desenvolvido. O espectrômetro é movido automaticamente, controlado um microcomputador. A correlação angular direcional gama-gama entre transições coincidentes dos níveis do ANTPOT100 RU, alimentados pelo decaimento ß+ e por captura de elétrons do ANTPOT 100 R foi medida. A fonte de ANTPOT 100 Ru foi produzida na reação ANTPOT 100 Ru (p, n) Rh POT. 100 utilizando o feixe de prótons do Acelerador cíclotron. Foram medidas 30 cascatas simples e 11 cascatas triplas produzindo como resultado a assinalação do spin e paridade dos estados de 1865 kev, 1881 kev, 2099 kev, 2167 kev, 2241 kev, 2517 kev, e 3070 kev e a determinação dos valores de mistura multipolar de 21 transições sendo que 12 delas pela primeira vez. Foi medido ainda o valor da razão de mistura multipolar Q POT. 2 (E0\\E2) da transição 2+ IND. 2 2+ IND. 2 / Knowledge of the spectral distribution of radiation emitted by radiodiagnostic units provides important information, which can be applied to the Quality Assurance and Radiological Protection programs. Detectors which utilize Silicon PIN Photodiodes have been increasingly used in recent years, due to their low cost and being worked with at room temperature, the liquid nitrogen containers used with Ge and Si(Li) detectors not being necessary. Although, initially, the PIN photodiodes have a poorer energy resolution, as compared with Ge detectors, it\'s good enough for most purposes. Moreover, the development of thermoelectrically cooled systems and low noise level pre-amplifiers have resulted in PIN photodiodes achieving comparable resolutions to Ge ones. This work seeks to establish the properties of detectors made with Silicon PIN photodiodes and to develop the correctional process of the raw specffa both for the efficiency of the detector and other relevant factors, with the aim of obtaining the true spectrum emitted by radiodiagnostic equipment. The radiation spectra of radiodiagnostic equipment experimentally obtained were compared with theoretical spectra calculated from a semi-empirical model. Furthermore, mammography x-ray spectra scattered by a breast simulator were obtained. As a direct application of these experimentally measured spectra, methodologies were developed to determine the peak kilovoltage (kvp) of X-Ray tubes, to be able to calibrate kVp meters, and the half-value layer (HW) of the beams of interest.
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noneKuo, Haiang-lin 18 January 2006 (has links)
Ru-Shih Liu was a famous and respectable poet in the 17th Century (from 1618 to 1664) in China. Because of her special background, extremely excellent writing techniques and creative thinking, she was very active in the history of literature and left many theses. Her first poetry publication was published at the age of 21. Zu-Loong Chen helped her to write the introduction and promoted her a lot. The next year, her friend invited her to travel to Hangchow, where her second poetry publication was published. Most of her poems¡¦ ideas were from her travel experiences, so this poetry publication was named ¡§Grass of lake¡¨. At that time she was only twenty-two years old. Because of her special life experience, her study presented a kind of excellent art style and worthy literature.
The purpose of this research is to analyze the poetry of her second publication as the main subject and research her creative thinking characteristics and artistic performance. The background of her writing and thoughts can be understood by her biography. Six topics were set to analyze the purpose and essence of her creations. Writing styles were concluded by the skills of writing: such as purports of time, purports of space, purports of humanity and purports of nature. The value and style of her poetry was investigated by the evaluation of later literature and analyses of her poetry. Moreover, Ru-Sheih Liu and her poetry influenced female literature development, the exaltation of national integrity and the promotion of life spirit during the late Ming Dynasty.
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