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Saha, Roy Indrani. "From communism to Radical humanism : a critical study of the political thought of M N Roy". Thesis, University of North Bengal, 1991. http://hdl.handle.net/123456789/246.

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Pedrosa, Diogo Pinheiro Fernandes. "Sistema de navega??o para rob?s m?veis aut?nomos". Universidade Federal do Rio Grande do Norte, 2001. http://repositorio.ufrn.br:8080/jspui/handle/123456789/15417.

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The main task and one of the major mobile robotics problems is its navigation process. Conceptualy, this process means drive the robot from an initial position and orientation to a goal position and orientation, along an admissible path respecting the temporal and velocity constraints. This task must be accomplished by some subtasks like robot localization in the workspace, admissible path planning, trajectory generation and motion control. Moreover, autonomous wheeled mobile robots have kinematics constraints, also called nonholonomic constraints, that impose the robot can not move everywhere freely in its workspace, reducing the number of feasible paths between two distinct positions. This work mainly approaches the path planning and trajectory generation problems applied to wheeled mobile robots acting on a robot soccer environment. The major dificulty in this process is to find a smooth function that respects the imposed robot kinematic constraints. This work proposes a path generation strategy based on parametric polynomials of third degree for the 'x' and 'y' axis. The 'theta' orientation is derived from the 'y' and 'x' relations in such a way that the generated path respects the kinematic constraint. To execute the trajectory, this work also shows a simple control strategy acting on the robot linear and angular velocities
Um dos maiores problemas em rob?tica m?vel diz respeito ? sua navega??o. Conceitualmente, o ato de navegar em rob?tica consiste em guiar um rob? em um espa?o de trabalho durante um determinado intervalo de tempo, por um caminho que possa ser percorrido e que leve o rob? de uma posi??o e orienta??o iniciais para uma posi??o e orienta??o finais. Esta ? a principal tarefa que um rob? m?vel deve executar. Ela implica em subproblemas que s?o a localiza??o do rob? no espa?o de trabalho, o planejamento de um caminho admiss?vel, a gera??o de uma trajet?ria e, por fim, a sua execu??o. Al?m disso, rob?s m?veis aut?nomos com rodas possuem restri??es cinem?ticas, chamadas tamb?m de restri??es n?o-holon?micas, que fazem com que o rob? n?o possa se mover livremente em seu espa?o de trabalho, limitando a quantidade de caminhos admiss?veis entre duas posi??es distintas. Este trabalho aborda principalmente os subproblemas do planejamento de caminho e gera??o de trajet?ria aplicado a minirrob?s m?veis com rodas que atuam em um projeto de futebol de rob?s. O maior desafio para a navega??o destes ve?culos ? determinar uma fun??o cont?nua que respeite suas restri??es cinem?ticas e evolua no tempo segundo as restri??es impostas pelo problema quanto ? posi??o e orienta??o iniciais e finais e quanto ? velocidade do movimento. Prop?e-se uma estrat?gia de gera??o de caminho baseada em polin?mios param?tricos de terceiro grau em 'x' e 'y'. A orienta??o 'theta' do minirrob? ? obtida da rela??o entre 'y' e 'x' de modo que os caminhos gerados respeitem a restri??o cinem?tica imposta. Para que a trajet?ria seja executada e os resultados experimentais validados ? apresentada uma estrat?gia simples de controle que atua sobre as velocidades linear e angular desenvolvidas pelo rob? m?vel

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Dias, Samaherni Morais. "Controle adaptativo robusto para um modelo desacoplado de um rob? m?vel". Universidade Federal do Rio Grande do Norte, 2010. http://repositorio.ufrn.br:8080/jspui/handle/123456789/15138.

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This thesis presents a new structure of robust adaptive controller applied to mobile robots (surface mobile robot) with nonholonomic constraints. It acts in the dynamics and kinematics of the robot, and it is split in two distinct parts. The first part controls the robot dynamics, using variable structure model reference adaptive controllers. The second part controls the robot kinematics, using a position controller, whose objective is to make the robot to reach any point in the cartesian plan. The kinematic controller is based only on information about the robot configuration. A decoupling method is adopted to transform the linear model of the mobile robot, a multiple-input multiple-output system, into two decoupled single-input single-output systems, thus reducing the complexity of designing the controller for the mobile robot. After that, a variable structure model reference adaptive controller is applied to each one of the resulting systems. One of such controllers will be responsible for the robot position and the other for the leading angle, using reference signals generated by the position controller. To validate the proposed structure, some simulated and experimental results using differential drive mobile robots of a robot soccer kit are presented. The simulator uses the main characteristics of real physical system as noise and non-linearities such as deadzone and saturation. The experimental results were obtained through an C++ program applied to the robot soccer kit of Microrobot team at the LACI/UFRN. The simulated and experimental results are presented and discussed at the end of the text
Esta tese apresenta o desenvolvimento de uma nova estrutura de controlador adaptativo robusto aplicado a sistemas rob?ticos m?veis com rodas (rob? m?vel de superf?cie) e restri??es n?o-holon?micas de movimento. Este controlador atua tanto na din?mica como na cinem?tica do rob?, e pode ser dividido em duas partes distintas. A primeira parte controla a din?mica, atrav?s da utiliza??o de controladores adaptativos por modelo de refer?ncia e estrutura vari?vel. A segunda parte controla a cinem?tica do rob? atrav?s de um controlador de posi??o, cujo objetivo ? fazer com que o rob? seja capaz de atingir um ponto qualquer no plano cartesiano, sendo que este controlador cinem?tico ? baseado apenas em informa??es da configura??o do rob?. O trabalho aplica um m?todo de desacoplamento para transformar o modelo linear do rob? m?vel, que ? um sistema com m?ltiplas entradas e m?ltiplas sa?das, em dois sistemas desacoplados com apenas uma entrada e uma sa?da cada um, para reduzir a complexidade do projeto do controlador. Em seguida, aplica-se um controlador adaptativo por modelo de refer?ncia e estrutura vari?vel a cada um dos sistemas resultantes. Um controlador ser? respons?vel pelo posicionamento e o outro pela orienta??o do rob?, sendo que estes controladores utilizam como refer?ncias sinais provenientes do controlador cinem?tico de posi??o. Para comprovar o funcionamento da estrutura proposta, obteve-se resultados simulados e experimentais para o rob? m?vel com acionamento diferencial de um kit de futebol de rob?s. O simulador possui as principais caracter?sticas do sistema f?sico real, dentre as quais podem-se destacar os ru?dos de entradas e as n?o-linearidades como zona morta e satura??o. Os resultados experimentais foram obtidos atrav?s de um programa desenvolvido em C++ e aplicado a um kit de futebol de rob?s da empresa Microrobot no Laborat?rio de Acionamento, Controle e Instrumenta??o da Universidade Federal do Rio Grande do Norte (LACI/UFRN). Os resultados simulados e experimentais s?o apresentados e discutidos ao final da tese

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Santos, Pablo Vieira dos. "Utiliza??o de m?todos n?o destrutivos na avalia??o da qualidade da madeira de Cariniana legalis (Mart.) Kuntze proveniente de plantios de restaura??o florestal". Universidade Federal Rural do Rio de Janeiro, 2016. https://tede.ufrrj.br/jspui/handle/jspui/1793.

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES
Forest restoration is an important mechanism which can recover anthropized environments. In this context, the use of native species in order to wood production has become a very positive alternative in the economic viability of this activity, so that, know information about native species with potential for production of high quality wood, used in forest restoration, is an important task. Concerning this, the objective of this study was to evaluate the quality of the wood Cariniana legalis (Mart.) Kuntze from forest restoration plantings, through non-destructive methods. Were selected 20 individuals in the field through a silvicultural assessment and then were determined dendrometric characteristics: diameter at breast height (DBH), total height, tree standing volume and bark thickness. Four different non-destructive methods of assessing wood quality based on the DBH (1.30 m from the base of the tree): extensometry, resistograph, impulse tomograph and x-ray densitometry (pulling out wood samples by Pressler probe). The longitudinal residual strain (LRS) average of wood was 0.054 mm, a value lower than that found in the literature for many species, as for the Eucalyptus genus. The amplitudes generated by resistograph allowed the estimation the basic density values of wood Cariniana legalis, presenting a positive and significant correlation (r = 0.68) at 1% significance level. The average apparent density average, obtained by X-ray densitometry, was 0.528 g / cm3. In general, Cariniana legalis threes were homogeneous, with good sanity wood (without internal rot or hollow) and moderately dense density being easy workability and suitable for the furniture industry.
A restaura??o florestal ? um importante mecanismo, no qual se consegue recuperar ambientes antropizados. Neste contexto, o uso de esp?cies nativas visando a produ??o madeireira tem se tornado uma alternativa bastante positiva na viabiliza??o econ?mica desta atividade, de modo que, conhecer informa??es a respeito de esp?cies nativas com potencial na produ??o de madeira de alta qualidade, utilizadas na restaura??o florestal, ? uma tarefa de grande import?ncia. Nesse sentido, o objetivo deste trabalho foi avaliar a qualidade da madeira de Cariniana legalis (Mart.) Kuntze proveniente de plantios de restaura??o florestal, atrav?s de m?todos n?o destrutivos. Foram selecionados 20 indiv?duos no campo por meio de uma avalia??o silvicultural e em seguida determinou-se as caracter?sticas dendrom?tricas (di?metro ? altura do peito (DAP), altura total, volume da ?rvore em p? e a espessura da casca). Quatro diferentes m?todos n?o destrutivos de avalia??o da qualidade da madeira foram utilizados, sendo eles a extensometria, resistograf?a, tomografia de impulso e densitometria de raios X (retirando-se amostras do lenho por meio da sonda de Pressler), todos os ensaios tiveram como refer?ncia a altura do DAP (1,30m a partir da base da ?rvore). A deforma??o residual longitudinal (DRL) m?dia da madeira foi de 0,054 mm, valor este inferior ao encontrado na literatura para muitas esp?cies, como para o g?nero Eucalyptus. As amplitudes geradas pelo resist?grafo permitiram estimar os valores de densidade b?sica da madeira de Cariniana legalis, apresentando uma correla??o positiva e significativa (r = 0,68) ao n?vel de 1% de signific?ncia. A densidade aparente m?dia, obtida por meio da densitometria de raios X, foi de 0,528 g/cm3. De maneira geral os indiv?duos de Cariniana legalis se mostraram homog?neos, apresentando boa sanidade do lenho (sem ocos internos ou podrid?es) e densidade moderadamente densa, sendo de f?cil trabalhabilidade e indicada para a ind?stria moveleira

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Silva, Alane de Medeiros. "Padr?o de distribui??o e caracteriza??o morfol?gica de fibras seroton?rgicas nos n?cleos da linha M?dia/ intralaminares do t?lamo do moc? (Kerodon rupestris)". Universidade Federal do Rio Grande do Norte, 2013. http://repositorio.ufrn.br:8080/jspui/handle/123456789/17343.

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Funda??o de Apoio ? Pesquisa do Estado do Rio Grande do Norte
The midline/intralaminar nuclei form a remarkable group of nuclei of the medial and dorsal thalamus. The midline nuclei, in rats, comprises the paratenial nuclei (PT), paraventricular (PV), intermediodorsal (IMD), reuniens (Re) and rhomboid (Rh). The intralaminar nuclei comprises the central medial (CM), paracentral (PC), central lateral (CL) and parafascicular (PF). Such nuclei have dense serotonergic innervation originating from the brainstem, especially from the so-called ascending activation system. These nuclei, in turn, send projections to various cortical and subcortical areas, specifically to limbic areas, which suggests the important role of this neurotransmitter in the limbic circuitry. The aim of this study was to characterize the distribution pattern and morphology of serotonin fibers in the nuclei of the midline and intralaminar thalamic of rocky cavy (Kerodon rupestris), a tipical rodent from brazilizan northeast. To reach this aim we used four rock cavies adults. Following the transcardially perfusion with paraformaldehyde and brain microtomy steps was performed immunohistochemistry for serotonin (5-HT), Nissl technique and subsequent achievement and image analysis to characterize the cytoarchitecture of these nuclei and the serotonergic fibers visualized. An analysis was made of Relative Optical Density (ROD) to semi-quantify the concentration of serotonin fibers in the areas of interest. Thus, we observed a cytoarchitectonic arrangement of these nuclei similar to that found in rats. In case of fibers distribution, those immunoreactive to 5-HT were presented in a higher concentration according as ROD in the midline nuclei relative to intralaminar; Re being the core which has a higher pixel value followed by the PV , Rh, IMD and PT. In intralaminar CL showed higher pixels, followed by nuclei CM, PC and PF. The serotonergic fibers were classified as number of varicosities and axon diameter, therefore find three types of fibers distributed through this nuclear complex: fibers rugous, granular and semi-granular. In PV fibers predominated rugous; in PT fibers predominated granular; IMD, CL and PF fibers were represented by semi-granular and Re, Rh, PC and CM fibers showed granular and semi-granular. Morphological characterization of serotonergic fibers and differences in density between the nuclei may suggest different patterns of synaptic organization of this neurotransmitter beyond confirming his large repertoire functional
O complexo nuclear da linha m?dia/intralaminar forma um not?vel grupo de n?cleos da parte medial e dorsal do t?lamo. Os n?cleos da linha m?dia, em ratos, s?o compreendidos pelos n?cleos paratenial (PT), paraventricular (PV), intermediodorsal (IMD), reuniens (Re) e romb?ide (Rh). J? os intralaminares compreendem os n?cleos central medial (CM), paracentral (PC), central lateral (CL) e parafascicular (PF). Tais n?cleos apresentam densa inerva??o seroton?rgica oriunda do tronco encef?lico, a partir, principalmente, do denominado sistema de ativa??o ascendente. Esses n?cleos, por sua vez, emitem proje??es para diversas ?reas corticais e subcorticais, mais especificamente para ?reas l?mbicas, o que prop?e o importante papel desse neurotransmissor na circuitaria l?mbica. O objetivo desse trabalho foi caracterizar o padr?o de distribui??o e morfologia das fibras de seroton?rgicas nos n?cleos da linha m?dia e intralaminares do t?lamo do moc? (Kerodon rupestris), um roedor t?pico da regi?o Nordeste. Para isso, foram utilizados 4 moc?s adultos jovens. Ap?s etapas de perfus?o e microtomia, foi realizada imunoistoqu?mica para serotonina (5-HT), t?cnica de Nissl e posterior coleta e an?lise de imagens a fim de caracterizar a citoarquitetura desses n?cleos, bem como as fibras de 5-HT neles visualizadas. Foi realizada ainda uma an?lise de Densidade ?ptica Relativa (DOR) para semiquantificar a concentra??o de fibras de 5-HT nas ?reas de interesse. Sendo assim, observamos uma distribui??o citoarquitet?nica desses n?cleos semelhante ao observado em ratos. Em se tratando da distribui??o de fibras, aquelas imunorreativas a 5-HT apresentaram-se em maior concentra??o, conforme a DOR, nos n?cleos da linha m?dia em rela??o aos intralaminares, sendo o Re o n?cleo que apresenta maior valor de pixels, seguido do PV, Rh, IMD e PT. Nos intralaminares o CL apresentou maior valor de pixels, seguido dos n?cleos CM, PC e PF. As fibras seroton?rgicas foram classificadas conforme n?mero de varicosidades, bem como di?metro axonal. Assim, encontramos tr?s tipos de fibras distribu?das atrav?s desse complexo nuclear: fibras rugosas, granulares e semi-granulares. No PV predominaram fibras rugosas; PT predominaram fibras granulares; IMD, CL e PF foram representados por fibras semi-granulares e Re, Rh, PC e CM apresentaram fibras granulares e semi-granulares. A caracteriza??o morfol?gica das fibras seroton?rgicas encontradas e as diferen?as de densidades entre os n?cleos permite sugerir diferentes padr?es de organiza??o sin?ptica deste neurotransmissor al?m de confirmar seu grande repert?rio funcional

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Vestin, Albin y Gustav Strandberg. "Evaluation of Target Tracking Using Multiple Sensors and Non-Causal Algorithms". Thesis, Linköpings universitet, Reglerteknik, 2019. http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-160020.

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Today, the main research field for the automotive industry is to find solutions for active safety. In order to perceive the surrounding environment, tracking nearby traffic objects plays an important role. Validation of the tracking performance is often done in staged traffic scenarios, where additional sensors, mounted on the vehicles, are used to obtain their true positions and velocities. The difficulty of evaluating the tracking performance complicates its development. An alternative approach studied in this thesis, is to record sequences and use non-causal algorithms, such as smoothing, instead of filtering to estimate the true target states. With this method, validation data for online, causal, target tracking algorithms can be obtained for all traffic scenarios without the need of extra sensors. We investigate how non-causal algorithms affects the target tracking performance using multiple sensors and dynamic models of different complexity. This is done to evaluate real-time methods against estimates obtained from non-causal filtering. Two different measurement units, a monocular camera and a LIDAR sensor, and two dynamic models are evaluated and compared using both causal and non-causal methods. The system is tested in two single object scenarios where ground truth is available and in three multi object scenarios without ground truth. Results from the two single object scenarios shows that tracking using only a monocular camera performs poorly since it is unable to measure the distance to objects. Here, a complementary LIDAR sensor improves the tracking performance significantly. The dynamic models are shown to have a small impact on the tracking performance, while the non-causal application gives a distinct improvement when tracking objects at large distances. Since the sequence can be reversed, the non-causal estimates are propagated from more certain states when the target is closer to the ego vehicle. For multiple object tracking, we find that correct associations between measurements and tracks are crucial for improving the tracking performance with non-causal algorithms.

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Hung, Sheng-Wei y 洪聖威. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M (Por)(L)n, M = Tl and Zn ,Por = (N-p-NSO2C6H4OCH3-tpp) ; M = Ni ,Por =(N-NHCO-(p-OCH3)C6H4-tpp); M = Zn , Por =". Thesis, 2009. http://ndltd.ncl.edu.tw/handle/41094063881905130727.

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Chen, Chun-Yi y 陳鈞義. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Zn , Por = (N-NCO(o-Cl)C6H4-tpp)M = Cu , Por = (N-NCO-CH=CH-C6H5-tpp)". Thesis, 2007. http://ndltd.ncl.edu.tw/handle/37198835961666755595.

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Liu, Wei-Chin y 劉偉欽. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Tl and Ni , Por = (N-NCOCH=CHC6H5-tpp)". Thesis, 2006. http://ndltd.ncl.edu.tw/handle/01451059784642287182.

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Chen, Kwan-Tin y 陳冠廷. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Tl、Cd, Por = (N-NCO(o-Cl)C6H4-tpp)". Thesis, 2008. http://ndltd.ncl.edu.tw/handle/66051650339135519568.

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碩士
國立中興大學
化學系所
96
We use (N-NHCO(o-Cl)C6H4-Htpp) to react with Tl(OAc)3 and Cd(OAc)2 and form (Tl(N-NCO(o-Cl)C6H4-tpp)(OAc)•H2O) and Cd(N-NCO(o-Cl)C6H4-tpp)(OAc)•CH2Cl2). Because (Zn(N-NCO(o-Cl)C6H4-tpp)(MeOH)) and (Zn(N-NHCO(o-Cl)C6H4-tpp)(Cl)) have been synthesized, we use 1H-1H COSY、HSQC、HMBC(heteronuclear multiple bond coherence) and DEPT to analyse the NMR data and X-ray Single-Crystal Diffractometer to determine the structure and compare the differences.

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Shil, Wei-Zhil y 施偉志. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Ni and Tl , Por = (N-NCO-2-C4H3O-tpp)". Thesis, 2006. http://ndltd.ncl.edu.tw/handle/02074321887732352657.

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Tsai, Chia-Jung y 蔡佳蓉. "Synthesis,Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single- Crystal Determination On Metalloporphyrins: M(Por)(L)n, M=Tl and Cu, Por = (N-NHCO-(p-OCH3)C6H4-tpp)". Thesis, 2010. http://ndltd.ncl.edu.tw/handle/88912934374837887211.

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Chien, Ting-Yuan y 簡廷原. "Synthesis, Characterization and Molecular Structure Studies by NMR, EPR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Ga、Mn, Por = (N-NCO(o-O)C6H4-tpp)". Thesis, 2009. http://ndltd.ncl.edu.tw/handle/73333720642139834090.

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碩士
國立中興大學
化學系所
97
We use (N-NHCO(o-OH)C6H4-tpp) to react with Ga2O3 and MnCl2 and form (Ga(N-NCO((o-O) C6H4-tpp)) •0.5CHCl3•MeOH) and (Mn(N-NCO((o-O) C6H4-tpp)) •CH2Cl2•MeOH). Because (Ni(N-NCO((o-OH)- C6H4-tpp)) •0.6CHCl3), (Cu(N-NCO((o-OH) C6H4-tpp)) •C6H5CH3) and (Zn(N-NCO((o-OH) C6H4-tpp)) •C6H5CH3) have been synthesized, we use 1H-1H COSY、HSQC、HMBC(heteronuclear multiple bond coherence) and DEPT to analyse the NMR data and X-ray Single-Crystal Diffractometer to determine the structure and compare the differences.

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Cheng, Ching-Wen y 鄭景文. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Hg、Cd and Fe , Por = (N-NHCO-2-C4H3S-tpp)". Thesis, 2006. http://ndltd.ncl.edu.tw/handle/09233334095421768157.

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Hsieh, Hua-Yu y 謝化宇. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Ni、Cu and Zn , Por = N-NHCO-(o-OH)C6H4-tpp". Thesis, 2007. http://ndltd.ncl.edu.tw/handle/57179945564294884728.

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Hsieh, Hsi-Ying y 解熙英. "Synthesis and Molecular Structure Studies of Metalloporphyrins : M(Por)(L)n, M=Hg, Ni and Mn by single-crystal X-ray determination, NMR and EPR Spectroscopy". Thesis, 2008. http://ndltd.ncl.edu.tw/handle/84156073093603476981.

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博士
國立中興大學
化學系所
96
1.The reaction of PhHgOAc with N–NHCO-2-C4H3S-Htpp (5) and N–p-HNSO2C6H4tBu-Htpp (4) gave a mercury (II) complex of (phenylato) (N-2-thiophenecarboxamido-meso-tetra phenylporphyrinato)mercury(II) 1.5 methylene chloride solvate [HgPh(N–NHCO-2-C4H3S-tpp)•CH2Cl2•0.5C6H14; 6•CH2Cl2•0.5C6H14] and a bismercury complex of bisphenylmercury(II) complex of 21-(4-tert-butyl-benzenesulfonamido)-5,10,15,20,- tetraphenylporphyrin, [(HgPh)2 (N–p-NSO2C6H4tBu-tpp); 7], respectively. The crystal structures of 6•CH2Cl2•0.5C6H14 and 7 were determined. The coordination sphere around Hg(1) in 6•CH2Cl2•0.5C6H14 and Hg(2) in 7 is a sitting-atop derivative with a seesaw geometry, whereas for the Hg(1) in 7, it is a linear coordination geometry. Both Hg(1) in 6•CH2Cl2•0.5C6H14 and Hg(2) in 7 acquire 4-coordination with four strong bonds [Hg(1)-N(1) = 2.586(3) Å, Hg(1)-N(2) = 2.118(3) Å, Hg(1)-N(3) = 2.625(3) Å, and Hg(1)-C(50) = 2.049(4) Å for 6•CH2Cl2•0.5C6H14; Hg(2)-N(1) = 2.566(6) Å, Hg(2)-N(2) = 2.155(6) Å, Hg(2)-N(3) = 2.583(6) Å, and Hg(2)-C(61) = 2.064(7) Å for 7]. The plane of the three pyrrole nitrogen atoms [i.e., N(1)-N(3)] strongly bonded to Hg(1) in 6•CH2Cl2•0.5C6H14 and to Hg(2) in 7 is adopted as a reference plane 3N. For the Hg2+ complex in 6•CH2Cl2•0.5C6H14 , the pyrrole nitrogen bonded to the 2-thiophenecarboxamido ligand lies in a plane with a dihedral angle of 33.4° with respect to the 3N plane, but for the bismercury(II) complex in 7, the corresponding dihedral angle for the pyrrole nitrogen bonded to the NSO2C6H4tBu group is found to be 42.9°. In the former complex, Hg(1)2+ and N(5) are located on different sides at 1.47 and -1.29 Å from its 3N plane, and in the latter one, Hg(2)2+ and N(5) are also located on different sides at -1.49 and 1.36 Å form its 3N plane. The Hg(1)•••Hg(2) distance in 7 is 3.622(6) Å. Hence, no metallophilic Hg(II)•••Hg(II) interaction may be anticipated. NOE difference spectroscopy, HMQC and HMBC were employed to unambiguous assignment for the 1H and 13C NMR resonances of 6•CH2Cl2•0.5C6H14 in CD2Cl2 and 7 in CDCl3 at 20°C. The 199Hg chemical shift δ for a 0.05 M solution of 7 in CDCl3 solution is observed at -1074 ppm for Hg(2) nucleus with a coordination number of four and at -1191 ppm for Hg(1) nucleus with a coordination number of two. The former resonance is consistent with that chemical shift for a 0.01 M solution of 6 in CD2Cl2 having observed at -1108 ppm for Hg(1) nucleus with a coordination number of four. 2.The crystal structures of diamagnetic N-p-tert-butylbenzenesulfonylimido- meso-tetraphenylporphyrinatonickle(II) [Ni(N-p-NSO2C6H4tBu-tpp); 8] and paramagnetic acetato-[N-p-tert-butylbenzenesulfonylimido-meso- tetraphenylporphyrinato]manganese(III) [Mn(N-p-NSO2C6H4 tBu-tpp)(O2CCH3); 9] were determined. The coordination sphere around Ni2+ in 8 is described as four-coordinated distorted square planar, whereas, for the Mn3+ ion in 9, it is a five-coordinate distorted square-based pyramid in which the unidentate CH3COO- ligand occupied the axial site. By the ‘‘degree of trigonality’’ principle ,the penta-coordinated Mn(III) complex is best described as a distorted trigonal bipyramid (or a squarebased pyramidal distorted trigonal bipyramid, SBPDTBP) The magnetic moment of 9 clearly shows a plateau equal to 4.57 µB, which is close to the expected value of 4.90 µB for a quintet high-spin state (S = 2).The g value of 12.6 (or 8.8) measured from the parallel polarization (or perpendicular polarization) of X-band EPR spectra at 77 K is consistent with a high spin manganese(III) (S = 2) in 9. The magnitude of axial (D) zero-field splitting (ZFS) in 9 were determined approximately as –1.1 cm-1, by paramagnetic susceptibility measurements and EPR spectroscopy.

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17

YU, CHO KUAN y 卓冠宇. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Zn, Tl, Ga, Cd, Hg and Mg, Por = (N-p-NSO2C6H4tBu-tpp) and (p-Br)4tpp". Thesis, 2005. http://ndltd.ncl.edu.tw/handle/56002867048654147868.

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碩士
國立中興大學
化學系
93
Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M(Por)(L)n, M = Zn, Tl, Ga, Cd, Hg and Mg, Por = (N-p-NSO2C6H4tBu-tpp) and (p-Br)4tpp

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18

Peng, Cheng-Chi y 彭正吉. "Synthesis, characterization and molecular structure studies by NMR spectroscopy and X-ray single-crystal determenation on metalloporphyrind:M(Por)(L)n, M-Tl, Zn and Ni, Por=(N-NCOC4H3S-tpp)". Thesis, 2005. http://ndltd.ncl.edu.tw/handle/81564710894270907194.

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碩士
國立中興大學
化學系
93
The crystal structure of N-2-thiophenecarboxamido-meso-tetraphenylporphyrin (1) was determined. The free energy of activation at the coalescence temperature Tc are determined to be G‡273 = 52.4 kJ/mol and G‡283 = 58.4 kJ/mol for the internal rotation of ortho protons of 1 along C(17)-C(39) [or C(12)-C(33)] and C(2)-C(21) [or C(7)-C(27)] bond in CD2Cl2, respectively. The free energy of activation at the coalescence temperature Tc for the internal rotation along C(17)-C(39) [or C(12)-C(33)] bond in 1 in CD2Cl2 solvent is found to be G‡273 = 52.4 kJ/mol whereas rotation along C(2)-C(21) [or C(7)-C(27)] bond turns out to be G‡283 = 58.4 kJ/mol.

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19

Peng, Cheng-Chun y 彭政鈞. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M1(Por1)(L)n, M1 = Tl and Zn , Por1 = (N-m-NSO2C6H4NO2-tpp) ; M2(Por2)(L)n, M2 = Hg , Por2 = (N-NCOCH=CHC6H5-tpp)". Thesis, 2008. http://ndltd.ncl.edu.tw/handle/20152890695499893002.

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碩士
國立中興大學
化學系所
96
chapter 1 We use N-m-NSO2C6H4NO2-Htpp (3) to react with [Zn(OAc)2·2H2O] and form Zn(N-m-NSO2C6H4NO2-Htpp)(4). Then we use 1H-1H COSY、HSQC、HMBC(heteronuclear multiple bond coherence) and DEPT to analyse the NMR data and X-ray Single-Crystal Diffractometer to determine the structure and compare the differences. chapter 2 We use (N-m-NSO2C6H4NO2-Htpp(3) to react with Tl(OAc)3 and form Tl(N-m-NSO2C6H4NO2-Htpp)(OAc)(5). Then we use 1H-1H COSY、HSQC、HMBC(heteronuclear multiple bond coherence) and DEPT to analyse the NMR data and X-ray Single-Crystal Diffractometer to determine the structure and compare the differences. chapter 3 We use N-NHCO-HC=CH-C6H5-Htpp (7) to react withPhHgOAc and form Hg(N-NCOCH=CH-C6H5-tpp)(Phenyl)(8). X-ray Single-Crystal Diffractometer to determine the structure and compare the differences.

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20

Cho, Cheng-Hsiung y 卓禎祥. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-Ray Single-Crystal Determination On Metalloporphyrins : M1(Por1)(L)n, M1 = Ni, Cu , Por1 = (N-m-NSO2C6H4NO2-tpp) ; M2(Por2)(L)n , M2 =Co，Por2 = (N-NCO(o-O)C6H4-tpp)". Thesis, 2009. http://ndltd.ncl.edu.tw/handle/04581760862479012344.

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21

Lo, Yun-Nan y 羅勻男. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-ray Single-Crystal Determination on Metalloporphyrin : M(por)(L)n, M1 = Hg，por1 = N-p-NHCOC6H4NO2-tpp；M2 = Cd，por2 = N-NHCO-HC=CH-C6H5-tpp". Thesis, 2007. http://ndltd.ncl.edu.tw/handle/66725205523506685938.

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22

Guo, Chih-Wei y 郭智維. "Synthesis, Characterization and Molecular Structure Studies by NMR Spectroscopy and X-ray Single-Crystal Determination on Metalloporphyrin : M(por)(L)n, M1 = Tl，por1 = N-NCO-HC=CH-C6H5-tpp；M2 = Cd，por2 = N-NHCO-C4H3O-tpp". Thesis, 2006. http://ndltd.ncl.edu.tw/handle/89341232834663077825.

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23

Kuo, I.-Chih y 郭益志. "Synthesis,Characterization and Molecular Structure Studies by NMR Spectroscopy and X-ray Single-Crystal Determination On Metalloporphyrins : M(por)(L)n , M1=Tl、Cu，por1=(N-NHCO-2-C4H3O-tpp)；M2=Ga，por2 =(N-NHCO-2-C4H3S-tpp)". Thesis, 2007. http://ndltd.ncl.edu.tw/handle/77705992484235709351.

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24

Young, Fuh-An y 楊富安. "Synthesis, Characterization and Molecular Structure Studies by EPR, NMR Spectroscopy and X-Ray Single-Crystal Determination on Metalloheteroporphyrins: M(Por)(L)n, M1= Tl、Zn、Cu，por1 = (tpp-N-O)；M2,3 = Hg，por2 = N-NCOC6H5-tpp，por3 =2-NCH3NCtpp". Thesis, 2007. http://ndltd.ncl.edu.tw/handle/34763667529563597167.

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博士
中興大學
化學系所
95
Chapter 1 The crystal structures of Tl(tpp-N-O)(OAc) 3 and acetato-N-p-tert-butylbenzensulfonylimido-meso-tetraphenylporphyrinatothallium(III) Tl(N-p-NSO2C6H4tBu-tpp)(OAc) 5 were determined. The coordination sphere around Tl3+ is a distorted square-based pyramid in which the apical site is occupied by a bidentate chelating OAc‾ group for 3 and 5. The plane of three pyrrole nitrogen atoms [i. e., N(1), N(2), and N(3)] strongly bonded to Tl3+ in 3 and 5 is adopted as a reference plane, 3N. The porphyrin ring is severely distorted and the pyrrole ring N(4) bonding to the oxygen and NSO2C6H4tBu group makes a dihedral angle of 46.5° and of 46.7° with the 3N plane for 3 and 5, respectively. In 3, Tl3+ and O(1) are located on the same side at 1.11 and 1.34 Å from its 3N plane, while in 5, Tl3+ and N(5) are still located on the same side at 1.15 and 1.30 Å from its 3N plane. The free energy of activation at the coalescence Tc for the intermolecular acetate exchange process of 3 and 5 in CD2Cl2 is found to be ΔG‡184 = 39.3 and ΔG‡208 = 44.1 kJ/mol, respectively, through 1H NMR variable temperature measurements. An electronegative substituent, O(1), bonded to Tl in 3 causes a significant negative contribution up to 145 Hz for Δ3J(Tl-C, O) and 79 Hz for Δ2J(Tl-C, O) of OAc‾ in 3. Chapter 2 The crystal structures of the dimer form of copper(II) tetraphenylporphyrin N-oxide [Cu(tpp–N–O)]2 (3-dimer) and zinc(II) tetraphenylporphyrin N-oxide [Zn(tpp–N–O)]2 (4-dimer) were established. The geometry at the copper ion in 3-dimer is essentially square-pyramidal with one oxygen bridge [O(1A)] occupying the apical site giving much larger Cu–O bond distance compared to those at the basal plane. The Cu•••Cu distance and Cu–O–Cu angle in the core of 3-dimer lie at 3.987(4) Å and 148.1(3)°. The Zn(1) atom in 4-dimer has a distorted square-pyramidal [4 + 1] coordination geometry that gives a τ value of 0.19. The Zn•••Zn distance and Zn–O–Zn angle in the dimeric unit of 4-dimer are 4.025(3) A and 148.1(2)°. The 3-dimer displays axial X-band EPR spectral features (Es = 0) in the powder state at 4 K giving g�� = 2.51 [A��, s = (9.6 ± 0.2) × 10–3 cm–1], g⊥= 2.11 and in the same powder state at 293 K giving Ds = 0.0731 cm–1 (as derived from ΔMs = 1 lines) or 0.0743 cm–1 (as derived from the ΔMs = 2 lines). In addition, 3-dimer displays a ΔMs = 2 transition at g = 4.17 indicating the presence of spin-exchange coupling. The anisotropic exchange interaction (Ds(ex)= 0.132 cm–1) gives the main contribution to Ds in 3-dimer. The theoretical fit of the susceptibility and effective magnetic moment data of 3-dimer in the temperature range 5 – 300 K gives 2J = 68 cm–1, g = 2.01, p = 0.06 and temperature independent paramagnetism TIP = 10–6 cm3/mol. This magnetic susceptibility data indicates that the copper(II) ions in 3-dimer are coupled in a ferromagnetic manner with the ground-spin triplet stabilized by 68 cm–1 with regard to the singlet. Chapter 3 Reaction of PhHgOAc with N-NHCOC6H5-Htpp gave a bismercury(II) complex of [((benzamido-κN)phenylmercury-κHg-N21, N22)-meso-tetraphenylporphyrinato-N23, N24]phenylatomercury(II) toluene solvate [Hg(Ph)(N21, N22-(Ph)-Hg-N(COPh)tpp•C6H5CH3; 3•C6H5CH3] with Hg(1)-N(5) as a N21, N22 –bridged atoms. The crystal structure of 3•C6H5CH3 was determined. The Hg(1)· · · Hg(2) distance is 3.611(7) A. Hence, no metallophilic Hg(II)···Hg(II) interaction may be anticipated. 3 in CDCl3 was characterized by 1H, 13C, and 199Hg NMR. The 199Hg NMR for a 0.2 M solution of 3 in CDCl3 at 20°C is observed at -1088.3 ppm for Hg(2) nucleus with 3J(Hg-H) = 188 Hz and an effective coordination number of five and at -1118.6 ppm for Hg(1) nucleus with 3J(Hg-H) = 177 Hz and an effective coordination number of four. This fact explained that the 199Hg signal of the Hg(2) nucleus with an effective coordination number of five lies at a downfield of 30 ppm from that of the Hg(1) nucleus with a smaller effective coordination number of four. The 199Hg in CDCl3 solution clearly reveals that there are two different Hg nuclei, i.e. Hg(1) and Hg(2), in 3 and this NMR data provides an evidence that 3 remains as a bismercury species in CDCl3 solution. The proton and 199Hg spectra clearly show 3J(Hg-H) coupling and this coupling indicates a slow ligand exchange for 3 in CDCl3. Chapter 4 The reaction of PhHgOAc with 2-NCH3NCTPPH (2) gave a mercury (II) complex of (phenylato)(4-aza-4-methyl-5, 10, 15, 20-tetraphenyl-2-carbaporphyrinato-N,N’,N” )-mercury(II), [HgPh(4-NCH3NCTPP); 6]. The crystal structure of 6 was determined and the coordination sphere around Hg(1) in 6 was a four-coordinate derivative with a seesaw geometry. Dipole-dipole (DD) interaction governs the longitudinal relaxation rate for Hg(1)-Ph-H2,6 of 6 in CDCl3 (0.01 M) at 599.95 MHz.

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