Tavares, P., N. Ravi, J. J. Moura, J. LeGall, Y. H. Huang, B. R. Crouse, M. K. Johnson, BH HUYNH, and I. Moura. "
{Spectroscopic properties of desulfoferrodoxin from Desulfovibrio desulfuricans (ATCC 27774).}."
Journal Of Biochemistry. 269 (1994): 10504-10510.
AbstractDesulfoferrodoxin, a non-heme iron protein, was purified previously from extracts of Desulfovibrio desulfuricans (ATCC 27774) (Moura, I., Tavares, P., Moura, J. J. G., Ravi, N., Huynh, B. H., Liu, M.-Y., and LeGall, J. (1990) J. Biol. Chem. 265, 21596-21602). The as-isolated protein displays a pink color (pink form) and contains two mononuclear iron sites in different oxidation states: a ferric site (center I) with a distorted tetrahedral sulfur coordination similar to that found in desulforedoxin from Desulfovibrio gigas and a ferrous site (center II) octahedrally coordinated with predominantly nitrogen/oxygen-containing ligands. A new form of desulfoferrodoxin which displays a gray color (gray form) has now been purified. Optical, electron paramagnetic resonance (EPR), and Mössbauer data of the gray desulfoferrodoxin indicate that both iron centers are in the high-spin ferric states. In addition to the EPR signals originating from center I at g = 7.7, 5.7, 4.1, and 1.8, the gray form of desulfoferrodoxin exhibits a signal at g = 4.3 and a shoulder at g = 9.6, indicating a high-spin ferric state with E/D approximately 1/3 for the oxidized center II. Redox titrations of the gray form of the protein monitored by optical spectroscopy indicate midpoint potentials of +4 +/- 10 and +240 +/- 10 mV for centers I and II, respectively. Mössbauer spectra of the gray form of the protein are consistent with the EPR finding that both centers are high-spin ferric and can be analyzed in terms of the EPR-determined spin Hamiltonian parameters. The Mössbauer parameters for both the ferric and ferrous forms of center II are indicative of a mononuclear high spin iron site with octahedral coordination and predominantly nitrogen/oxygen-containing ligands. Resonance Raman studies confirm the structural similarity of center I and the distorted tetrahedral FeS4 center in desulforedoxin and provide evidence for one or two cysteinyl-S ligands for center II. On the basis of the resonance Raman results, the 635 nm absorption band that is responsible for the gray color of the oxidized protein is assigned to a cysteinyl-S–>Fe(III) charge transfer transition localized on center II. The novel properties and possible function of center II are discussed in relation to those of mononuclear iron centers in other enzymes.
Lourenço, João M. Mecanismos de Suporte à Execução Concorrente de Programas em Lógica. Eds. José C. Cunha. Universidade Nova de Lisboa. Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 1994.
AbstractA evolução do hardware dos computadores para arquitecturas paralelas, incentivou a concepção de novos modelos de programação e o desenvolvimento dos sistemas de suporte à execução correspondentes, de forma a conseguir uma melhor exploração do paralelismo. A linguagem de programação Prolog, pelas suas características declarativas e operacionais, tem vindo a ser objecto de estudo nesta área, através de adaptações da linguagem e/ou da sua máquina de inferência. Este trabalho incide sobre os aspectos de concepção e implementação de um modelo de um sistema de suporte à execução de programas em Prolog, em arquitecturas de múltiplos processadores, com unidades de memória fisicamente distribuídas. O modelo propõe extensões a um executor de Prolog convencional, de forma a disponibilizar funcionalidades que permitam o controlo do paralelismo e da distribuição. Estas funcionalidades podem ser utilizadas para a implementação de modelos de linguagens lógicas concorrentes de mais alto nível, ou então serem utilizadas directamente para a programação de sistemas distribuídos, em que múltiplos executores Prolog cooperam na resolução de um golo, comunicando com base em mensagens. Para avaliar a funcionalidade do modelo proposto, concebeu-se e implementou-se um sistema de distribuição de golos Prolog, que permite recorrer a diversas estratégias para composição sequencial e paralela de golos, escondendo os aspectos de gestão explícita dos recursos efectivos. A dissertação inclui uma discussão dos aspectos mais relevantes da realização do protótipo do modelo proposto sobre uma arquitectura baseada em Transputers.
Vieira, M., Fantoni Fortunato Lavareda Martins A. E. G. "
AD-layer for spatial control of light induced degradation on pin devices."
Materials Research Society Symposium Proceedings. Vol. 336. 1994. 741-746.
AbstractIn this work we report experimental results on light induced metastability of a-Si: H p.i.n. devices with different microscopic/macroscopic structures and we discuss them in terms of improved stability through spatial control of charged defects grown during light exposure. By placing a thin (few A) intrinsic layer (i) between both p/i and i/n a-Si: H interfaces we are able to reduce the effective degradation rate through spatial modification of the electric field profile in the device. The electronic transport and the stability changes that accompany the change in microstructure (R) and hydrogen content (CH) of the i- and i′-layer, were monitored throughout the entire light induced degradation process and compared with the corresponding μT product (for both carriers) inferred through steady state photoconductivity and Flying Spot Technique (FST) measurements. Results show that the degradation rate is a function of CH and R of both layers and can be correlated with the density of microvoids and di-hydride bonding. Since the i′-layers have a higher CH bonded mainly as SiF2 radicals (R≈0.4), they act as an hindrance to the growth of the defect, in the active region, generating "gettering centers" whose localisation and density are tailored in such a way that they will control spatially the electric field profile during light exposure. Preliminary results show improvements in film's stability when the interfacial layer is included. So future progress toward more stable and efficient a-Si: H solar cells will depend on a careful engineering design of the devices. © 1994 Materials Research Society.