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Microporous titanosilicates and vanadosilicates were synthesised characterized and photoreactivity studies were carried out.  The titanosilicates synthesised were the titanosilicate pharmacosiderite and AM – 18 and the vanadosilicates were AM – 6, ETVS – 10, AM – 14 and VSH -13Na.  A variety of different techniques were used in the characterisation studies including different X-Ray methods, vibrational spectroscopy, electron microscopy, and solid state NMR spectroscopy.  The studies showed that the synthesised products were homogeneous and an insight into the structures of AM – 18 and AM – 14 was obtained. Raman spectroscopy was used to assess the levels of defects in large crystals of ETS – 10 and ETS – 4 by measuring the variation in the frequency of the Ti – O band and the width of this band.  A similar study was done on large crystals of AM – 6.  Raman spectroscopy showed that Ti – O stretching bands containing Ti(V) and Ti(IV) were present in AM – 18 structure.  The frequency of the vanadyl bands in AM – 14 indicated that it could contain vanadyl chains. Photoreactivity studies using EPR spectroscopy, on the potassium titanosilicate pharmacosiderite showed an O^- species, after UV irradiation in the presence of oxygen.  When the partial pressure was reduced a superoxide and the anomalous ozonide species were observed.  On changing the cation to a proton form, a superoxide anion radical was observed but no other oxygen radicals were observed. Attempted oxidation and reduction studies on VSH – 13Na were unsuccessful and HRTEM and nitrogen adsorption studies showed that the one-dimensional channels were blocked. Oxidation and reduction studies on AM – 14 indicated that the vanadium sites were easily accessible to gas phase.

Cristais únicos de pireno, C16H10, irradiados por raios X, à temperatura ambiente, foram estudados por técnicas de RPE para determinar os radicais livres formados pela radiação. A dependência angular dos espectros de RPE medidos, foi explicada pela presença de dois tipos de radicais, com um hidrogênio adicional: 2-H2 pireno e 3-H2 pireno. Estudamos o decaimento isotérmico do sinal de RPE e foram obtidos dois valores para a energia de ativação: (1,9 ± 0,1) eV e (1,93 ± 0,03) eV. / Single crystals of pirene, C16H10, irradiated with X-rays at room temperature was investigated by EPR to determine the types of stable free radicals formed by the radiation. Angular dependence of the EPR spectra was measured and explained on the basis that 2-H2 pyrene and 3-H2 pyirene were present. The annealing behavior of EPR signal was studied and we obtained two values of activation energy: (1,9 ± 0,1) eV and (1,93 ± 0,03) eV.

Estudamos monocristais de Zn(BF4)26H2O dopados com Mn2+ no intervalo de temperatura de 94K à 353K empregando a técnica de Ressonância Paramagnética Eletrônica (RPE). Determinamos todos os parâmetros da Hamiltoniana de spin. Constatamos que o fator espectroscópico g = 2,000 ± 0,001 é constante com a temperatura. Calculamos o parâmetro D e através da curva de D versus T confirmamos a existência de uma transição de fase à 181K. Verificamos que este parâmetro D apresenta variação linear com a temperatura acima de 200K (D= (127 + 0,228T) Gauss), o que está de acordo com a previsão do modelo de Walsh. Com os espectros obtidos da variação angular do eixo c do cristal em relação ao campo magnético externo, constatamos que os resultados experimentais estão em excelente acordo com a teoria. Concluímos que o campo cristalino tem simetria trigonal em toda a faixa de temperatura pesquisada. / We have studied monocrystals of Zn(BF4)26H2O doped with Mn2+ in the range of the temperature of 94K to 353K employing the technics of Electron Paramagnetic Resonance (EPR). We have determined all the parameters of the spin Hamiltonian. We have verified that the temperature. We have calculated the parameter D and through the curve of D versus T confirmed the existence of a phase transition at 181K. We have verified that this parameter D shows linear variation with the temperature above 200K (D= (127 + 0,228T) Gauss), which agrees with the prevision of the Walshs model. With the spectra of the angular variation of the c axis of the crystal in relation to extern magnetic field, we have verified that the experimental results are in excellent agreement with the theory. We have concluded that the crystal field has trigonal symmetry in all range of temperature investigated.

Efetuamos medidas de RPE nos seguintes sais hexahidratados: fluorborato de níquel (Ni (BF IND. 4) IND. 2 6 H IND. 2 O) , perclorato de níquel (Ni(Cl O IND. 4) IND. 2 6 H IND. 2 O) e fluorsilicato de níquel (NiSi F IND. 6 6 H IND. 2 O). Os parâmetros da hamiltoniana de spin deste último sal foram redeterminados no intervalo de 100 K à 323 K. Os nossos resultados de RPE indicam a existência de anomalias no intervalo 153 K a 273 K que caracterizam uma transição de fase. Estudamos também as larguras de linha dos sais acima, separando as contribuições devido à interação spin- spin e a relaxação spin- rede. Os valores destas contribuições concordam perfeitamente com os calculados a partir de modelos teóricos. Desenvolvemos uma nova forma de linha que dá excelentes ajustes, por mínimos quadrados, das curvas experimentais. / We have performed EPR measurements in the following hexahidrated salts: nickel fluorborate (Ni(BF4)2 6H2O), nickel perchlorate (Ni(Cl04) 2 6H2O) and nickel fluorsilicate (NiSiF6 6 H20). The spin hamiltonian parameters of the last salt were determined once again in the range 100 - 323K. Our results of EPR indicate anomalies in the range 153 - 273K, which characterize a phase transition. Line widths of the above salts were also studied separating the contributions given by spin-spin interaction and spin-lattice relaxation. The values of these contributions agree with theoretical calculations. We have developped a new line form, which gives excellent fits, by least square fit, for the experimental data.

by Wong Lai-ping, Gloria. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1980. / Bibliography: leaves 136-140.

As diferentes formas com que o hidrogênio pode ocorrer nos vidros alumino-boratos de bário, ora na formação de ligações covalentes, ora ocupando posições intersticiais formando centros atômicos foram investigados por ressonância paramagnética eletrônica (RPE) e por medidas complementares de absorção no infravermelho. O estudo de cinética do centro de hidrogênio intersticial H IND. i revelou a presença de três tipos de armadilhas, com energias de ativação de (O,32±O,06}eV; (O,15±0,02}eV e (0,10±0,02}eV. Um estudo experimental da cinética do centro de elétron do boro (BEC), descoberto por D.L. Griscom, também foi realizado, incluindo o decaimento do BEC por exposição à luz visível, o que produziu o aumento de centros H IND. i observados por RPE, indicando a presença de centros H IND. i, ou prótons. Por outro lado, medidas de absorção no infravermelho de vidro hidrogenado revelaram a presença de pontes O-H...O. As distâncias entre átomos de oxigênio que encontramos são 2,69; 2,71 e 2,715 A SOB. 0. Sugerimos que a cada distância corresponde o lado de um polígono da cadeia de B-O, formadora do vidro. Propomos um modelo para o centro H IND. i, no qual os átomos de hidrogênio são capturados pelos polígonos por meio de forças atrativas de van der Waals. Avaliando a energia de van der Waals para polígonos de n lados e 2,70 A SOB. 0 de aresta, comparamos os resultados com as energias de ativação fornecidas por RPE, para determinar os números de lados dos polígonos (n = 5, 6 e 7). Acrescentamos a este trabalho um estudo de RPE de centros de prata em vidros alumino-boratos de bário irradiados com raios X a 77K. Em contraste com o que acontece com o hidrogênio, a presença de prata nos vidros altera consideravelmente as dimensões dos anéis de B-O. A constatação da ausência de centros sugere que a prata encontra dificuldade para difundir nestes vidros. / The different ways in which hydrogen can occur in barium alumino-borate glasses, either forming covalent bonds, or occupying interstitial positions forming atomic centers, were investigated by electron paramagnetic resonance (EPR) and complementary infrared absorption measurements. A study of the kinetics of interstitial hydrogen centers Hi0 revealed the presence of the three kinds of traps, whose activation energies are (.32 ± .06) eV; (.l5±.02)eV and (.l0±.02)eV. An experimental study of the kinetics of boron electron centers (BEC) was also carried out, including the decay of BEC when exposed to visible light. This exposure produced an increase of Hi0 centers, as observed by EPR, indicating the presence of Hi+ centers, or protons. On the other hand, I.R. absorption measurements of hydrogenated glass revealed the presence of O-HO bonds. The distances between oxygen atoms were found to be 2.69; 2.71; and 2.715 A. We suggest that each of these distances corresponds to a side of a polygon of the chain of B-O in the glass network. We propose a model for the Hi0 center where the hydrogen atoms are trapped by the polygons by means of attractive van der Waals forces. Evaluating the van der Waals energy for polygons of n sides, each side measuring 2.70 A, we compared the results with activation energies given by EPR, to determine the number of sides of the polygons (n= 5, 6 and 7). We studied, in addition, the EPR spectra of silver centers in barium alumino-borate glasses irradiated with X-rays at 77 K. In contrast to the behavior of hydrogen, the presence of silver in the glasses produces considerable alterations in the dimensions of the rings of B-O. The absence of Ag2+ suggests that silver has difficulty in diffusing in these glasses.

Pulsed electron-electron double resonance (PELDOR) is an emerging technique for nanometre distance measurements in nano-sized assemblies and between specific sites of molecules. Most commonly nitroxide radicals are used as probes for EPR distance measurements because they are easy to introduce in biological systems such as soluble and membrane proteins or nucleic acids. PELDOR distance measurements currently rely on data processing software which has been proven to accurately extract inter-spin distances from the dipolar coupling between two paramagnetic centres. However, when the dipolar coupling is affected by contributions from other close-by unpaired electrons inaccuracies as broadening effects and artefacts are introduced in the distance distributions derived. This challenge, commonly referred as multi-spin effects, has been affecting the extraction of accurate distance information from PELDOR measurements in chemical and biological systems with multiple spin labels. The aim of this project is to approach, identify and suppress inaccuracies introduced in PELDOR-based distance distributions by multi-spin effects. This is achieved through the synthesis of multiply labelled model systems which would allow for assessment of the impact of multi-spin effects on distance measurements of simple geometries whose behaviour can be easily predicted and modelled. In this work existing methods for suppression of multi-spin effects are tested, together with their efficiency and limitations. The results are used to devise better sets of parameters including alternative settings for extraction of accurate distances from multi-spin systems and to explore their efficiency and limitations. Additional effects influencing distance measurements by pulsed EPR are also examined; in particular the effects of orientation selection and their interplay with multi-spin effects is studied in depth. Studies on rigid symmetric and asymmetric chemical model systems together with heptameric channel membrane proteins allow for outlining of recommendations for PELDOR distance measurements settings on systems presenting similar structural features, including symmetries and inter-spin distances.