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Master's Dissertation
DOI
10.11606/D.54.1989.tde-16012008-105256
Document
Author
Full name
Carlos Alberto Fonzar Pintao
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 1989
Supervisor
Committee
Nascimento, Otaciro Rangel (President)
Carvalho, Rene Ayres
Pizani, Paulo Sérgio
Title in Portuguese
Estudo dos complexos de cobre (ii) com triptofilglicina utilizando a técnica de ressonância paramagnética eletrônica
Keywords in Portuguese
Complexo de cobre (II)
Ressonância paramagnética eletrônica
Tryptofilglicina
Abstract in Portuguese
Neste trabalho estudou-se os complexos formados pelo íon cobre (II) com o dipeptides triptofilglicina na faixa de pH=3,0 a 13,5. A caracterização dos mesmos foram realizadas através das técnicas de Ressonância Paramagnética Eletrônica (RPE) em duas temperaturas (ambiente e nitrogênio líquido) e Absorção Ótica no visível (350 a 1000 nm). As amostras em solução aquosa obedeceram a relação de 10 ligantes para 1 metal. Caracterizou-se três tipos de complexos nas faixas pHs: 4.0 a 6,0; 6,0 a 12,0 e acima de 12,0. Estes complexos foram propostos com base nos dados espectroscópicos e um conhecimento prévio dos pKs dos grupos desprotonáveis, são eles: CuL2, CuL(H2O) e CuL(OH) (H2O). Estudou-se a influência da cadeia lateral pesada nos parâmetros espectroscópicos e comparativamente ao complexo Gliciltriptofano estudado por Nascimento (1985) no mesmo intervalo de pH, foi possível mostrar que o modelo de não covalência (Brill e Bryce (1968)), é o mais adequado em explicar a diminuição da constante hiperfina Az, constatado em Ph elevado. O complexo tridentado CuL(H2O) foi cristalizado e medidas de RPE no monocristal permitiram obter o tensor giromagnético molecular. Interação de exchange e/ou dipolar, não permitiram a determinação do tensor hiperfino no complexo. Através das direções principais e valores das direções das componentes do tensor cristalino e as direções das normais aos planos de coordenação, foi possível detectar uma forte interação de exchange entre dois íons vizinhos.
Title in English
Study of complex the copper (II) with Trp-Gly by using the techinique of electronic paramagnetic resonance
Keywords in English
Complex of the copper (II)
Eletronic paramagnetic resonance
Tryptofilglicine
Abstract in English
In this work was studied the complex made by the ion copper(II) with the dipeptide tryptophilglicine in the area of pH between 3,0-13,5. The cacacterizations of them were realized by the electron paramagnet resonance (ERP) in two temperatures (room and liquid nitrogen) and Optics Absorption in the visible (between 350 - 1100 nm). The samples in aqueous solution got the rate of 10 ligand to one metal. Three species of complex were characterized: pHs between 4,0-6,0; 6,0-12,0 and above 12,0. These complexes were proposed with foundation in the spectroscope informations and a previous know of the pKs of the deprotanatable groups, they are: CuL2; CuL(H2O) and CuL(OH) (H2O). The influency of the lateral chain weighed in the spectroscopies parameter was studied, and in compere with the glyciltryptophan complex studied by Nascimentoi (1985) in the same intermission of the pH, it was possible to show that the model of no covalente (Brill and Bryce-1968) is the adequader to explain the hiperfine constant Az diminution, evidenced in heigh pH. The tridentate complex CuL(H2O) was crystallized and EPR mensures in the monocrystal allowed to get the molecular gyromagnetic tensor. Exchange and/or dipolar interaction didn't allow the determination of the hyperfine tensor of the complex. By the main directions and values of the component parts of the tensor g crystalline and the normal directions to the plans of coordination, it was possible to detect a strong interaction of exchange between to neighbour ions.
 
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CarlosPintaoM.pdf (2.18 Mbytes)
Publishing Date
2008-01-18
 
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